Optical Properties of Solids 2nd Ed by Mark Fox

Name: Tapas Banerji
Email: mybirthday29thjune@gmail.com
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Optical Properties of Solids

Second Edition
Mark Fox
Oxford University Press, 2010
SOLUTIONS TO EXERCISES
These notes contain detailed solutions to the Exercises at the end of each
chapter of the book, for the benefit of class instructors. Please note that figures
within the solutions are numbered consecutively from the start of the document
(e.g. Fig. 1) in order to distinguish them from the figures in the book, which
have an additional chapter label (e.g. Fig. 1.1). A similar convention applies to
the labels of tables.
The author would be very grateful if mistakes that are discovered in the solutions would be communicated to him. He is also very appreciative of comments
about the text and/or the Exercises. He may be contacted at the following
address:
Department of Physics and Astronomy
University of Sheffield
Hicks Building
Sheffield, S3 7RH
United Kingdom.
email: mark.fox@shef.ac.uk
c Mark Fox 2010
Address: C-3/144,Vikrant Khand, Gomtinagar, Lucknow, UP 226010, IND
Name: Tapas Banerji
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Chapter 1
Introduction
(1.1) Glass is transparent in the visible spectral region and hence we can assume
= = 0. The reflectivity is calculated by inserting n = 1.51 and = 0
into eqn 1.29 to obtain R = 0.041. The transmission is calculated from
eqn 1.9 with R = 0.041 to obtain T = 92%.
(1.2) From Table 1.4 we read that the refractive indices of fused silica and
dense flint glass are 1.46 and 1.746 respectively. The reflectivities are then
calculated from eqn 1.29 to be 0.035 and 0.074 respectively, with = 0
in both cases because the glass is transparent. We thus find that the
reflectivity of dense flint glass is larger than that of fused silica by a factor
of 2.1. This is why cutglass products made from dense flint glass have a
sparkling appearance.
(1.3) We first use eqns 1.25 and 1.26 to convert r to n
, giving n = 3.01 and
= 0.38. We then proceed as in Example 1.2. This gives:
v = c/n = 9.97 107 m s1 ,
= 4/ = 9.6 106 m1 ,
R = [(n 1)2 + 2 ]/[(n + 1)2 + 2 ] = 25.6%.
(1.4) The antireflection coating prevents losses at the airsemiconductor interface, and 90% of the light is absorbed when exp(l) = 0.1 at the
operating wavelength. With = 1.3 105 m1 at 850 nm, we then find
l = 1.8 105 m = 18 m.
(1.5) We are given n = 3.68 and we can use eqn 1.19 to work out = /4 =
0.083. We then use eqn 1.29 to find R = 0.328. Since l = 2.6, we do not
need to consider multiple reflections and we can just use eqn 1.8 to find
the transmission. This gives: T = (1 0.328)2 exp(1.3 2) = 0.034.
The optical density is calculated from eqn 1.11 as 0.434 1.3 2 = 1.1.
(1.6) 99.8% absorption in 10 m means exp(l) = 0.002, and hence = 0.62 m1 .
We use eqn 1.19 to find = /4 = 3.5 108 . We thus have n
=
1.33 + i 3.5 108 . The real and imaginary parts of r are found from
eqns 1.23 and 1.24 respectively, and we thus obtain r = 1.77+i 9.2108 .
(1.7) The filter appears yellow and so it must transmit red and green light, but
not blue. The filter must therefore have absorption at blue wavelengths.
(1.8) (a) In the incoherent limit, we just add the intensities of the beams. The
intensities of the beams transmitted after multiple reflections are shown
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incident light R1
I0
R2
e-al
I0(1-R1)
I0(1-R1)e-a l
I0R1
I0(1-R1)R2e
I0(1-R1)R2e-a l
I0(1-R1) R2R1e-3a l
I0(1-R1)2R2e-2a l
I0(1-R1)2 R22R1 e-4a l
transmitted light
-2a l
I0(1-R1) R2R1e-2a l
I0(1-R1) R22R1e-4a l
I0(1-R1) (1-R2) e-a l
I0(1-R1) R22R1e-3a l
I0(1-R1) R22R12e-5a l
I0(1-R1) R22R12e-4a l
I0(1-R1) (1-R2) R2R1 e-3a l
I0(1-R1) R23R12e-5a l
reflected light
I0(1-R1) (1-R2) R22R12 e-5a l

Figure 1: Multiple reflections in the incoherent limit, as considered in Exercise
1.8.
in Fig. 1. The transmitted intensity is given by:
It
= I0 (1 R1 )(1 R2 )el + I0 (1 R1 )(1 R2 )R1 R2 e3l

+ I0 (1 R1 )(1 R2 )R12 R22 e5l +
= I0 (1 R1 )(1 R2 )el 1 + R1 R2 e2l + (R1 R2 )2 e4l + ,
X
= I0 (1 R1 )(1 R2 )el
(R1 R2 e2l )k ,
k=0
= I0 (1 R1 )(1 R2 )e
where we used the identity
transmissivity is thus:
T =
1
,
1 R1 R2 e2l
P
k=0
xk = 1/(1 x) in the last line. The
It
(1 R1 )(1 R2 )el
=
.
I0
1 R1 R2 e2l
(b) We have an air-medium-air situation, and so it will be the case that

R1 = R2 R. We need to compare the exact formulae given in eqns 1.6
and 1.9 with the approximate one that neglects multiple reflections given
in eqn 1.8.
(i) With = 0 the extinction coefficient will also be zero. We then
calculate the reflectivity from eqn 1.29 to be:
R=
2.42
(3.4 1)2
=
= 0.30 .
(3.4 + 1)2
4.42
2
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Hence the exact transmission from eqn 1.9 is given by:

Texact =
1 0.30
0.70
=
= 54% .
1 + 0.30
1.30
The approximate result with multiple reflections neglected is found from

eqn 1.8 with = 0:
Tapprox = (1 R)2 = (1 0.30)2 = (0.70)2 = 49% .
Thus by neglecting multiple reflections, the transmission is underestimated
by a factor of about 10%.
(ii) If we assume n , we can ignore the terms in in the formula for
the reflectivity (eqn 1.29) and so just obtain R = 0.30 as in part (a). The
exact transmission is calculated from eqn 1.6 to be:
Texact =
(1 0.30)2 e1
= 18.2% .
1 0.302 e2
The formula with multiple reflections neglected (eqn 1.8) gives:

Tapprox = (1 0.30)2 e1 = 18.0% .
The transmission is thus underestimated by a factor of 1%.
(iii) Following the same method as in part (b)(i), we find:
R
Texact
Tapprox
= 0.772 /2.772 = 0.077 ,

= (1 0.077)/(1 + 0.077) = 85.7% ,
= (1 0.077)2 = 85.2% .
The error is thus 0.6%.

(c) It is intuitively obvious that it is valid to neglect multiple reflections
when the absorption is strong (i.e. l & 1), since the reflected beams will
be very weak. Part (b)(ii) confirms this.
For the case of transparent materials (i.e. = 0), it will be valid to
neglect multiple reflections when R is small, since then it will be valid
to approximate 1/(1 + R) as (1 R), and eqn 1.8 with = 0 will be
equivalent to eqn 1.9. The reflectivity will be small when (n 1) is small
(see eqn 1.29), and so we conclude that multiple reflections are insignificant
for small (n 1). This point is illustrated by comparing parts (b)(i) and
(iii).
(1.9) In contrast to the previous exercise, we must now add up the electric field
amplitudes of the beams and consider their relative phases. Let r and t
be the amplitude reflection and transmission coefficients for going from
air to the medium, and r0 and t0 be the equivalent quantities for going
from the medium to air. If the absorption coefficient is , the amplitude
will decay by a factor of el/2 during a single pass of the medium, since
I E 2 . For simplicity we define x = el/2 ei/2 , where = 4nl/ is
the round-trip phase shift, so that the complex amplitude changes by a
3
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r
incident
amplitude
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t'
r'
x = eif/2 e-al / 2
E0
t E0
tx E0
r E0
tx2r' E0
txr' E0
tx2r'2E0
tx3r'2E0
tx4r'3 E0
tx3r'3E0
tx4r'4 E0
tx5r'4 E0
transmitted
amplitude
tt'x E0
tt'x2r'E0
tt'x4r'3E0
reflected
amplitude
tx5r'5 E0
tt'x3r'2E0
tt'x5r'4 E0
Figure 2: Multiple reflections in the coherent limit, as considered in Exercise

1.9.
factor x after one pass through the medium.
(a) With the definitions above, the transmitted amplitude E t is given by
(see Fig. 2):
Et
=
=
=
tt0 xE 0 + tt0 x3 r02 E 0 + tt0 x5 r04 E 0 + ,

tt0 xE 0 (1 + x2 r02 + x4 r04 + ) ,
X
tt0 xE 0
(x2 r02 )k ,
k=0
tt0 x
E0
,
1 x2 r02
P
where we used k=0 ak = 1/(1 a) in the last line. The transmitted
intensity is then given by:
I t E t (E t ) = |E 0 |2
(1
|x|2 |tt0 |2
.
x2 r02 )
x2 r02 )(1
Now x2 = el ei , r = r0 (due to the phase shift on going from a more

dense to a less dense medium), tt0 = 1 r2 , and r2 = r02 = R. Therefore
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we have:
T
=
=
=
=
It
|E t |2
=
,
I0
|E 0 |2
(1 R)2 el
,
l
(1 Re ei )(1 Rel ei )
(1 R)2 el
,
l
(1 Re (ei + ei ) + R2 e2l )
(1 R)2 el
,
(1 2Rel cos + R2 e2l )
where we used ei + ei = 2 cos in the last line.

(b) For the reflectivity, we proceed as in part (a). From Fig. 2 it is apparent
that the reflected amplitude E r is given by:
Er
= rE 0 + tt0 x2 r0 E 0 + tt0 x4 r03 E 0 + ,

= E 0 (r + r0 tt0 x2 [1 + x2 r02 + x4 r04 + ]) ,
r0 tt0 x2
= E0 r +
,
1 x2 r02
P
where we again used k=0 ak = 1/(1 a). On inserting r0 = r and
tt0 = 1 r2 = 1 R, we find:
x2 (1 R)
1 x2
Er = E0 r 1
=
E
r
.
0
1 x2 R
1 x2 R
Therefore, with x2 = el ei , and again using ei + ei = 2 cos , we
find:
reflectivity
|E r |2
,
|E 0 |2
(1 el ei )(1 el ei )
= R
,
(1 Rel ei )(1 Rel ei )
(1 2el cos + e2l )
= R
.
(1 2Rel cos + R2 e2l )
(c) In the limit with = 0, the reflectivity and transmission formulae

just reduce to the standard ones for a FabryPerot etalon (see e.g. Hecht
chapter 9):
(1 R)2
,
lim0 (T ) =
(1 2R cos + R2 )
lim0 (reflectivity) =
2R(1 cos )
.
(1 2R cos + R2 )
Note that in this 0 limit, conservation of energy requires that the

transmission and reflection coefficients must sum to unity. This can be
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proven as follows. We have I t = T I0 and I r = reflectivity I0 . Hence:

It + Ir
(1 R)2
2R(1 cos )
+ I0
(1 2R cos + R2 )
(1 2R cos + R2 )
(1 R)2 + 2R(1 cos )
I0
.
(1 2R cos + R2 )
(1 2R + R2 + 2R 2R cos )
I0
,
(1 2R cos + R2 )
(1 + R2 2R cos )
,
I0
(1 2R cos + R2 )
I0 .
= I0
=
=
=
=
(d) If l 1, then el 1. Since R 1, we can neglect the second and

third terms in the denominator, and so the transmission is just:
T = (1 R)2 el ,
as in eqn 1.8.
(e) For negligible absorption, we expect to observe thin-film fringes. The
transmission will be as given in part (c):
lim0 (T ) =
(1 R)2
.
(1 2R cos + R2 )
When = 2m, where m is an integer, we have constructive interference,

with:
(1 R)2
(1 R)2
T =
=
= 1.
(1 2R + R2 )
(1 R)2
Since = 4nl/, this constructive interference condition occurs when
2nl = m, that is, the round trip path length is equal to an integer
number of wavelengths. The other extreme occurs when = (2m + 1):
T =
(1 R)2
(1 R)2
=
.
(1 + 2R + R2 )
(1 + R)2
At this point, we have 2nl = (m + 1/2)0 , so that the waves from each
round trip are out of phase and interfere destructively. Therefore, as
the wavelength is scanned, the transmission oscillates between unity and
(1 R)2 /(1 + R)2 , as in a FabryPerot etalon.
(1.10) This problem is meant to be a rough attempt to model the optical properties of GaAs near its band edge. The band gap is taken to be 1.42 eV,
as appropriate for GaAs at room temperature, and the form of the absorption is meant to be rough fit to the data in Fig. 3.9, with C chosen to
give the correct absorption around 2 eV, namely 4 106 m1 .
The reflectivity and transmissivity have to be calculated from the two formulae given in parts (a) and (b) of the previous exercise. In principle, for
wavelengths below the band edge, we have to work out the extinction coefficient from the absorption via eqn 1.19, and then work out the reflection
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1.0
Transmission or Reflectivity
Name: Tapas Banerji
0.8
Transmission
Reflectivity
0.6
0.4
0.2
0.0
600
700
800
900
1000
Wavelength (nm)
Figure 3: Transmission and reflectivity of a 2m thick platelet, as considered

in Exercise 1.10.
coefficient from eqn 1.29 with both the terms in n and included. However, the maximum value of in this exercise is only 0.19, which occurs
at 600 nm, where = 4 106 m1 , and (0.19)2 is negligible compared to
(3.5 1)2 . Therefore, in fact we can just work out R from the real part of
the refractive index and use R = 2.52 /4.52 = 0.31 at all wavelengths. The
transmissivity and reflectivity calculated in this way are plotted in Fig. 3.
For wavelengths below the band edge (i.e. 8701000 nm), the medium is
transparent, and we observe FabryPerot fringes. Peaks in the transmission with T = 1 occur at wavelengths that satisfy 2nl = m, (m =
integer), i.e. at 875 nm (m = 16), 933 nm (m = 15), and 1000 nm
(m = 14). The reflectivity at these wavelengths is equal to zero. Peaks
in the reflectivity and minima in the transmission are observed in between the transmission maxima. The minimum value of the transmission
is (1 R)2 /(1 + R)2 = 0.28, implying that the maximum value of the
reflectivity is 0.72.
For wavelengths below the band edge, the absorption increases rapidly,
and the interference fringes are rapidly damped, with multiple reflections
becoming negligible. The reflectivity settles to the value determined by
the front surface (i.e. 31%), while the transmission decreases exponentially
according to eqn 1.8. The transmissivity at 600 nm where = 4106 m1
is (0.69)2 exp(8) = 1.6 104 .
(1.11) In the incoherent limit, the transmissivity of a transparent plate is given
by eqn 1.9 as (1 R)/(1 + R), while the reflectivity is obtained from
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eqn 1.29, which becomes R = (n 1)2 /(n + 1)2 when = 0. Now:

1R=1
(n 1)2
(n + 1)2 (n 1)2
4n
=
=
.
(n + 1)2
(n + 1)2
(n + 1)2
Similarly:
1+R=1+
(n 1)2
(n + 1)2 + (n 1)2
2(n2 + 1)
=
=
.
2
2
(n + 1)
(n + 1)
(n + 1)2
We therefore have:
T =
1R
4n
(n + 1)2
2n
=
= 2
.
2
1+R
(n + 1)
2(n2 + 1)
(n + 1)
(1.12) The reflection coefficient for the interface between two transparent media
with refractive indices of n1 and n2 is (see eqn A.55):
R=
(n1 n2 )2
.
(n1 + n2 )2
Note that this reduces to R = (n 1)2 /(n + 1)2 for the case of an airmedium interface with n1 = 1 and n2 = n. (cf. eqn 1.29 with = 0.) For
the three cases considered here we have:
air film: n1 = 1, n2 = 2.5, so R = (1.5/3.5)2 = 18%.
film substrate: n1 = 2.5, n2 = 1.5, so R = (2.5 1.5)2 /(2.5 +
1.5)2 = (1/4)2 = 6%.
substrate air: n1 = 1.5, n2 = 1, so R = (0.5/2.5)2 = 4%.
(1.13) For a thick sample it is appropriate to use eqn 1.8 for the transmission.
We take the log10 of eqn 1.8 to obtain (using log10 x = loge x/ loge 10):
log10 (T ) = 2 log10 (1 R) + l/ loge 10 .
We can then substitute l/ loge 10 from eqn 1.11 to obtain the required
result.
If the medium is transparent at 0 then we will have that T0 = (1
R)/(1 + R) for the incoherent limit, where R is the reflectivity at 0 . We
assume that the reflectivity varies only weakly with wavelength. This is
a reasonable assumption for most materials if we choose 0 sensibly, for
example, just above the absorption edge we are trying to measure. With
this assumption, we can work out the value of R from a measurement
of the transmission at 0 , and then use this value in the formula derived
in the exercise to work out the optical density from a measurement of
the transmission at . Measurements of T () and T (0 ) thus allow the
optical density to be determined. The absorption coefficient can then be
determined from the optical density by using eqn 1.11.
(1.14) With = 6.6 107 1 m, and = 1.88 1013 rad/s, we find r =
r + i 3.97 105 . The imaginary part of r is very large, and hence the
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approximation
2
1 is a good one. In this approximation, we have

(with i = (1 + i)/ 2):
p
n
= r = (3.97 105 )1/2 i = 445(1 + i) .
By inserting n = = 445 into eqn 1.29, we then obtain R = 99.6 %.
(1.15) We use the same formula for the complex dielectric constant as in the
previous exercise. With = 1.88 1013 rad/s, we find
n
2 = r = 1 + i 2.94 105 .
Since 2 1 , this implies:
p
n
= r = (2.94 105 )1/2 i = 383(1 + i) .
We then find from eqn 1.19 that = 4/ = 4.8 107 m1 . Beers law
means that we set exp(l) = 0.5 for a drop in intensity by a factor of 2,
giving l = 1.4 108 m = 14 nm.
(1.16) It is apparent from eqn 1.29 that R = 1 when n = 1 and = 0. For zero
reflectivity we thus require r = (n + i)2 = 1.
(1.17) (a) We convert wavelengths to photon energies using E = hc/ to obtain
the energy level scheme shown in Fig. 4. It is thus apparent that 0.294 eV
of energy is dissipated during each absorption / emission process.
(b) When the quantum efficiency is 100%, every absorbed photon produces a luminescent photon. The ratio of the light energy emitted to that
absorbed is then simply given by the ratio of the relevant photon energies.
The emitted power is thus (1.165/1.459) 10 = 8 W, and the dissipated
power is 2 W.
(c) For a luminescent quantum efficiency of 50% the number of photons
emitted drops by a factor of 2 compared to part (b), and so the light
power emitted falls to 4 W. The remaining 6 W of the absorbed power is
dissipated as heat.
relaxation (0.294 eV)

absorption
1.459 eV
emission
1.165 eV
Figure 4: Energy level scheme for Exercise 1.17.

(1.18) This is an example of Raman scattering, which is discussed in detail in
Section 10.5. Conservation of energy in the scattering process is satisfied
when
h out = h in h phonon .
With = c/, we then find out = 521 nm.
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(1.19) The transmission is given by eqn 1.12, with the wavelength dependence
of the scattering cross section given by eqn 1.13. At 850 nm we have 10%
transmission, so that N s l = 2.30. Since s 4 , the scattering crosssection is 11.1 times larger at 850 nm than at 1550 nm, and so we have
N s l = 2.30/11.1 = 0.21 at the longer wavelength, implying a transmission of 81 %.
In general, the scattering losses decrease as the wavelength increases, and
hence the propagation losses decrease. Longer wavelengths are therefore
preferable for long range communication systems. At the same time, the
fibres start to absorb in the infrared due to phonon absorption. 1550 nm is
the longest practical wavelength for silica fibres before phonon absorption
becomes significant.
(1.20) We again use eqn 1.12 to calculate the transmission, setting exp(N s l) =
0.5. This gives N s l = 0.69, which implies l = 3.5 m for the given values
of N and s .
If the wavelength is reduced by a factor of two, Rayleighs scattering law
(eqn 1.13) implies that s increases by a factor of 16. The length required
for the same transmission is thus smaller by a factor of 16: i.e. l =
3.5/16 = 0.22 m.
(1.21) Birefringence is an example of optical anisotropy as discussed in Section 1.5.1, and also in Section 2.5. Ice is a uniaxial crystal, and therefore
has preferential axes, making optical anisotropy possible. Water, by contrast, is a liquid and has no preferential axes. The optical properties must
therefore be isotropic, making birefringence impossible.
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Chapter 2
Classical propagation
(2.1) We envisage two displaced masses as shown in Fig. 5. The spring is
extended by a distance (x1 x2 ) and so the force on the masses are
Ks (x1 x2 ). The equations of motion are therefore
m1
d2 x1
= Ks (x1 x2 )
dt2
and
d2 x2
= Ks (x2 x1 ) .
dt2
Divide the equations by m1 and m2 respectively and subtract them to
obtain:
1
1
d2
(x
x
)
=
K
+
(x1 x2 ) .
1
2
s
dt2
m1
m2
m2
On defining the relative displacement x = x1 x2 and introducing the

reduced mass , where 1/ = 1/m1 + 1/m2 , we then have:
d2 x
= Ks x .
dt2
This is the equation of motion of an oscillator of angular frequency (Ks /)1/2 .
m1
rest
x1
displaced
m2
x2
Figure 5: Displacement of two masses as described in Exercise 2.1

(2.2) The solution is simpler if complex exponentials are used. We therefore
write the force as the real part of F0 eit , and look for solutions of the
form x(t) = x0 eit . On substituting into the equation of motion we then
obtain:
m( 2 i + 02 )x0 eit = F0 eit ,
which implies:
x(t) =
F0
1
eit .
m (02 2 i)
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The phase factor comes from the factor of [02 2 i]1 . On multiplying the top and bottom by the complex conjugate, we find:
02
1
( 2 2 ) + i
= 20 2 2
.
2
i
(0 ) + ()2
On writing this in the form:

a + ib = rei r(cos + i sin ) ,
we then see that the phase factor is given by:
tan = 2
.
(0 2 )
This implies that the displacement of the oscillator is of the form:
x(t) ei eit = ei(t) ,
which shows that the oscillator has a relative phase lag of:
= tan1 [/(02 2 )] .
(2.3) By applying the Lorentz oscillator model of Section 2.2.1, we realize that
the refractive index will have a frequency dependence as shown in Fig. 2.4,
with 0 corresponding to 500 nm. (i.e. 0 = 3.8 1015 rad/s.) For
frequencies well above the resonance, we will just have the contribution of
the undoped sapphire crystal:
n n( 0 ) = 1.77 ,
which implies = (1.77)2 . The refractive index well below the resonance
can be worked out from eqn 2.19. On using the value of N given in the
exercise, we find st = 2.23 103 . We thus have:
nst = st = [(1.77)2 + 2.23 103 ]1/2 .

We thus find nst n = 6.3 104 .
(2.4) We again use the Lorentz oscillator model of Section 2.2. The Exercise
is similar to Example 2.1, because we are dealing with a relatively small
number of absorbers and the overall refractive index will be dominated
by the host crystal. We can therefore assume n = 1.39 throughout the
Exercise. On the other hand, the host crystal is transparent at 405 nm, and
so the absorption will be determined by the impurity atoms. The other
factor we have to include is the low oscillator strength of the transition.
We therefore modify the first equation in Example 2.1 to:
(0 ) =
2 (0 )
N e2
1
=
f,
2n
2n0 m0 0
where f = 9 105 is the oscillator strength. For the absorption line

we have 0 = 2c/405 nm = 4.65 1015 rad/s, and = = 2 =
5.15 1014 s1 . With N = 2 1026 m3 and n = 1.39, we then find
(0 ) = 8.6 106 . We finally obtain the absorption at the line centre
(405 nm) from eqn 1.19 as 270 m1 .
This Exercise is broadly based on the results presented in the paper by
Iverson and Sibley in J. Luminescence 20, 311 (1979).
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(2.5) The result of this Exercise works in the limit where the contribution of
the particular oscillator to the dielectric constant is relatively small, as in
Example 2.1 and the previous exercise. In this limit we have 2 1 , and
therefore (0 ) = 2 (0 )/2n, where n = 1 , and 1 (0 ) = 1+. We then

2
see from eqn 2.16 that 2 (0 ) = N e /0 m0 0 , so that the absorption is
(cf. eqn 1.19):
(0 ) =
4(0 )
2 (0 )
N e2
= 4
(2c/0 ) =
.
2n
n0 m0 c
This shows that it is the linewidth that determines the peak absorption
strength per oscillator. The oscillator strength is, of course, also important.
(2.6) The data can be analysed by comparison with Fig. 2.4 with the assumption
that the oscillator strength is unity.
(a) The low frequency refractive index corresponds to st . With n = 2.43

for 0 from the data, we find st = 5.9.
(b) The resonant frequency is the mid point of the wiggle, i.e. 5.0
1012 Hz.
(c) The natural frequency is given by eqn 2.2, which implies Ks = 02 .
The reduced mass is given by:
1/ = 1/m1 + 1/m2 = 1/23 + 1/35.5 amu1 ,
which gives = 14 amu = 2.33 1026 kg. With 0 = 20 = 3.1
1013 rad/s, we find Ks = 23 kg s2 . The restoring force is given by F =
Ks x, which implies |F | = 23 N for x equal to unity.
(d) The oscillator density can be found from eqn 2.19. st = 5.9 has been
found in part (a), and can be read from the graph for 0 as
= n2 = (1.45)2 = 2.10. We thus have st = 3.8. Using the values
of 0 and worked out previously, we then find N = 3.0 1028 m3 .
(e) is equal to the shift between the maximum and minimum in the refractive index in angular frequency units. We can only make a rough estimate of because the data does not follow a simple line shape. The damping rate depends strongly on the frequency, which is why the resonance
line is asymmetric. By comparison with Fig. 2.4 we find 11012 Hz,
and hence = 2 6 1012 s1 .
(f) The result of Exercise 2.5 tells us that = N e2 /n0 c at the line
centre for a weak absorber. This limit does not really apply here, but we
can still use it to get a rough answer. On inserting the values of N , and
found above, and taking n 2, we find 1 106 m1 .
(2.7) We start by re-writing eqn 2.25 as:
1
dk
=
.
vg
d
13
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IP: 129.82.195.78
We then substitute k = n/c and v = c/n to obtain:
1
1
dn
=
n+
,
vg
c
d
n
dn
=
1+
,
c
n d
1
dn
=
1+
.
v
n d
The first relationship in eqn 2.26 follows immediately by taking the reciprocal.
The second relationship in eqn 2.26 is obtained by substituting = 2c/
so that
dn
dn d
2 dn
=
=
,
d
d d
2c d
and hence:
vg = v[1 + (2c/n)(2 /2c)dn/d]1 = v[1 (/n)dn/d]1 .
(2.8) We consider three separate frequency regions.
(i) < 0 : In this frequency region r is real, and increases with frequency.
Since n = r , it is apparent that dn/d is positive, so that from eqn 2.26

we see that vg < v. Since r > 1, n > 1, and hence v = c/n < c. Therefore
vg < c.
(ii) 0 < < (02 + N e2 /0 m0 )1/2 : In this frequency region, r is negative.
The refractive index is purely imaginary and the wave does not propagate.
This is an example of the Reststrahlen effect discussed in Section 10.2.3.
(iii) > (02 + N e2 /0 m0 )1/2 : In this region r is positive and increases
with frequency, approaching unity asymptotically. dn/d is therefore positive, but we cannot use the same line of argument as part (i) because
n < 1 and therefore v > c. We must therefore work out vg explicitly using
eqn 2.26. With n = r , we obtain:

dn
d
=
d
d
1/2
N e2
1
1 N e2
1+
=
.
2
2
2
0 m0 0
n 0 m0 (0 2 )2
Hence
1
vg
=
=
=
n
N e2
2
+
,
c
nc0 m0 (02 2 )2
N e2
2
1
n2 +
,
nc
0 m0 (02 2 )2
N e2
1
2
r +
.
nc
0 m0 (02 2 )2
On substituting for r from the exercise, we find:
1
1
N e2
02
=
1+
,
vg
nc
0 m0 (02 2 )2
14
Name: Tapas Banerji
and hence:
IP: 129.82.195.78
1
N e2
02
vg = nc 1 +
.
0 m0 (02 2 )2
The denominator is greater than unity, and n < 1, so vg < c.

(2.9) (a) Consider a dipole p placed at the origin. The electric field generated
at position vector r is given by:
E(r) =
3(p r)r r2 p
.
40 r5
The electric field generated at the origin by a dipole p at position vector

r is therefore given by:
E(r) =
3(p (r))(r) r2 p
3(p r)r r2 p
=
.
40 r5
40 r5
Consider the ith dipole within the sphere illustrated in Fig. 2.8. We
assume that the dipole is oriented parallel to the z axis so that we can
write pi = (0, 0, pi ). Then, on writing r i = (xi , yi , zi ) in the formula for
E, we find that the z component of the field at the origin from the ith
dipole is:
pi (3zi2 ri2 )
Ei =
.
40 ri5
We now sum over the cubic lattice of dipoles within the sphere. By symmetry, the x and y components sum to zero, giving a resultant field along
the z axis of magnitude:
E sphere =
1 X 3zi2 ri2
,
pi
40 i
ri5
as required.
(b) If all the dipoles have the same magnitude p, then the resultant field
is given by:
p X 2zi2 x2i yi2
E sphere =
.
40 i
ri5
The x, y and z axes are equivalent for the cubic lattice within the sphere,
and so we must have:
X y2
X z2
X x2
i
i
i
=
=
5
5
5 .
r
r
r
i
i
i
i
i
i
It is thus apparent that
X 2z 2 x2 y 2
i
ri5
= 0.
The net field is therefore zero.

(c) Consider a hollow sphere of radius a placed within a polarized dielectric
medium as illustrated in Fig. 6. (cf. Fig 2.8.) We assume that the polarization is parallel to the z axis. The surface charge on the sphere must
15
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balance the normal component of the polarization P . With P = (0, 0, P ),

the normal component at polar angle is equal P cos , as shown in Fig. 6.
Hence the surface charge density at angle is equal to P cos . The
charge contained in a circular element at angle subtending an incremental angle d as defined in Fig. 6 is then given by:
dq = dA = P cos (2a sin a d) = 2P a2 cos sin d .
The x and y components of the field generated at the origin by this incremental charge sum to zero by symmetry, leaving just a z component,
with a magnitude given by Coulombs law as:
dE z =
dq
P cos2 sin d
cos
=
+
.
40 a2
20
On integrating over , we then obtain:

Z
Z
P
P
Ez =
dE z =
cos2 sin d =
.
20 0
30
=0
Since P is parallel to the z axis, and the x and y components of E are
zero, we therefore have:
P
E=
,
30
as required for eqn 2.28.
-- - - -
dq
P cosq
dq
+ + +
Figure 6: Definition of angles and charge increment as required for Exercise

2.9(c).
(2.10) If r 1 is small, the left hand side of the ClausiusMossotti relationship
becomes equal to (r 1)/3, and we then find:
r = 1 + N a 1 + ,
where = N a , as in eqn A.4. It is apparent that r 1 will be small
if either N is small or a is small. This means that we either have a low
density of absorbing atoms (as in a gas, for example), or we are working
at frequencies far away from any resonances.
16
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(2.11) We are working with a gas, and we can therefore forget about ClausiusMossotti. At s.t.p. we have NA (Avogadros constant) molecules in a
volume of 22.4 litres. Hence N = 2.69 1025 m3 . We then find a from:
a = (r 1)/N = 2.2 1029 m3 .
The atomic dipole is worked out from
p = 0 a E .
The displacement of an electron by 1
A produces a dipole of 1.61029 C m.
11
Hence we require a field of 0.810 V/m. The field acting on an electron
at a distance r from a proton is given by Coulombs law as:
e
E=
.
40 r2
, we find E = 1.4 1011 V/m. It is not surprising
On substituting r = 1 A
that these two fields are of similar magnitude because the external field
must work against the Coulomb forces in the molecule to induce a dipole.
(2.12) We are given that (E) = 0 for E2 E E1 , where E is the photon
energy, and (E) = 0 at all other energies. By using eqn 1.19 we then
have:
(E) =
(E) =
c~0 /2E , E2 E E1 ,
0 , elsewhere .
We can then find the refractive index from eqn 2.36 as follows:
Z
2 E2 /~ 0 ( 0 )
n(E) = 1 +
d 0 ,
E1 /~ 02 2
Z
2 E2 E 0 (E 0 )
= 1+
dE 0 .
E1 E 02 E 2
Note that we do not have to worry about taking principal parts because
(E) = 0 when E 0 = E if E < E1 . On substituting for (E 0 ) we find:
Z
c~0 E2
1
n(E) = 1 +
dE 0 .
02 E 2
E
E1
Now:
1
dx
x2 a2
=
=
Hence:
n(E)
Z
1
1
1
dx ,
2a
xa x+a
xa
1
ln
.
2a
x+a
0
E2
E E
c~0 1
,
ln
= 1+
2E
E 0 + E E1

c~0
E2 E
E1 E
= 1+
ln
ln
,
2E
E2 + E
E1 + E
c~0
(E2 E)(E1 + E)
= 1+
ln
,
2E
(E2 + E)(E1 E)
as required.
17
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(2.13) (a) If we are far away from resonance frequencies, we can ignore the
damping term, and write eqn 2.24 as:
r n2 = 1 +
N e2 X
fj
2 2 .
0 m0 j 0j
On substituting = 2c/, this becomes:

n2 = 1 +
N e2
1 X fj 2j 2
,
0 m0 (2c)2 j 2 2j
where j = 2c/0j . This is of the Sellmeier form if we take:

Aj = N e2 fj 2j /4 2 0 m0 c2 .
(b) With the approximations stated in the exercise, we have:
n2 = 1 +
A1 2
= 1 + A1 (1 21 /2 )1 .
2 21
With x 21 /2 1, we can expand this to:

n2 = 1 + A1 (1 + x + x2 + ) ,
which implies:
n
= [(1 + A1 ) + A1 (x + x2 + )]1/2
= (1 + A1 )1/2 [1 + A1 /(1 + A1 )(x + x2 + )]1/2
= (1 + A1 )1/2 [1 + (1/2)A1 /(1 + A1 )(x + x2 ) (1/8)(A1 /(1 + A1 ))2 (x + x2 )2 + ]
A1
A
A21
1
x2 +
= (1 + A1 )1/2 +
x+
8(1 + A1 )3/2
2 1 + A1
2 1 + A1
On re-substituting for x, we then find:
4
21
A1
A21
A1
1
,
n = (1 + A1 )1/2 +
2
3/2
4
8(1 + A1 )
2 1 + A1
2 1 + A1
which shows that:
C1
C2
= (1 + A1 )1/2 ,
= A1 21 /2(1 + A1 )1/2 ,
C3
= A1 (4 + 3A1 )41 /8(1 + A1 )3/2 .
Note that the Cauchy formula generally applies to transparent materials

(eg glasses) in the visible spectral region. In this situation, the dispersion
is dominated by the electronic absorption in the ultraviolet. We should
then take 1 as the wavelength of the band gap, and the approximation
21 /2 1 will be reasonable, as we are far away from the band gap
energy.
18
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(2.14) (a) On neglecting the 4 term in Cauchys formula, we have

n = C1 + C2 /2 .
On inserting the values of n at 402.6 nm and 706.5 nm and solving, we find
C1 = 1.5255 and C2 = 4824.7 nm2 , so that we have:
n = 1.5255 + 4824.7/2 ,
where is measured in nm.
(b) The values are found by substituting into the result found in part (a)
to obtain n = 1.5493 at 450 nm and n = 1.5369 at 650 nm.
(c) Referring to the angles defined in Fig. 7, we have
sin in
sin out
=
= n,
sin 1
sin 2
from Snells law. Furthermore, for a prism with apex angle , we have
1 + 2 = . With in = 45 and = 60 , we then find out = 57.17 for
n = 1.5493 (450 nm) and out = 55.91 for n = 1.5369 (650 nm). Hence
out = 1.26 .
60
qin
qout
q1
q2
Figure 7: Angles required for the solution of Exercise 2.14.

(2.15) The transit time is given by:
=
L
dk
=L
,
vg
d
which, with k = n/c, becomes:

=
L
c
dn
n+
.
d
We introduce the vacuum wavelength via = 2c/, and write:

dn
dn d
2 dn
=
=
.
d
d d
2c d
We then have (cf. eqn 2.26 with = L/vg ):
L
dn
=
n
.
c
d
The difference in the transit time for two wavelengths separated by ,
where , is given by:
=
d
.
d
19
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On using the result for above, we find:

L d2 n
d
= 2,
d
c d
which implies:
= L
d2 n
= L D ,
c d2
where D is the material dispersion parameter defined in eqn 2.40. We

therefore finally obtain:
d2 n
= L |D| .
| | = L
c d2
The timebandwidth product of eqn 2.39 implies that a pulse of light
contains a spread of frequencies and therefore a spread of wavelengths.
In a dispersive medium, the different wavelengths will travel at different
velocities, and this will cause pulse broadening. The precise amount of
broadening depends on the numerical value of the timebandwidth product assumed for the pulse. For a 10 ps pulse with t = 1, we have
= 1011 Hz. With = c/, we have || = (2 /c)||, so that
|| = 0.8 nm in this case. We thus find:
| | = L|D| = 1 km 17 ps km1 nm1 0.8nm = 14 ps .
e-ray
polarization
vector
direction of
propagation
ne
q
n(q )
no
no
index ellipsoid
ne
Figure 8: Index ellipse for the eray of a wave propagating at an angle to the
optic (z) axis of a uniaxial crystal, as required for Exercise 2.16.
(2.16) It is apparent from eqn 2.50 that 11 /0 = 22 /0 = n2o and 33 /0 = n2e .
Hence we can re-cast the index ellipsoid in the form:
x2
y2
z2
+ 2 + 2 = 1.
2
no
no
ne
Owing to the x-y symmetry about the optic (z) axis, we can choose the
axes of the index ellipsoid so that the x axis coincides with the polarization
20
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vector of the oray as in Fig 2.13(a). The polarization of the eray will
then lie in the yz plane, as in Fig. 2.13(b). The projection of the index
ellipsoid onto the plane that contains the direction of propagation and the
polarization vector of the eray thus appears as the ellipse drawn in Fig. 8.
The refractive index n() that we require is the distance from the origin
to the point of the ellipse where the E-vector cuts it. The co-ordinates of
this point are x = 0, y = n() cos and z = n() sin . On substituting
into the equation of the index ellipsoid, we then have:
0+
n()2 cos2 n()2 sin2

+
= 1,
n2o
n2e
which implies:
1
cos2 sin2
=
+
,
n()2
n2o
n2e
as required.
(2.17) The condition for total internal reflection for a mediumair interface is
that the angle of incidence should exceed the critical angle c given by:
sin c = 1/n ,
where n is the refractive index of the medium. We see from Table 2.1
that no = 1.658 and ne = 1.486 for calcite. The critical angles for the
o- and e-rays are therefore 37.1 and 42.3 respectively. For the polarizer
to work, we want the o-ray to suffer total internal reflection, but not the
e-ray. With normal incidence as shown in Fig. 2.14, this will occur if the
apex angle lies in the range 37.1 42.3 .
y
Input
E-vector
(a)
Input
E-vector
direction
(b)
Ey
q
Ez
Ez
optic axis (z)
q
-Ey
front surface of
wave plate
optic axis (z)
Output
E-vector
Figure 9: (a) Input polarization vector for light propagating along the x direction, relative to the crystal axes, as required for the solution of Exercise 2.18(a).
(b) Output polarization of the half-wave plate.
(2.18) (a) We resolve the input polarization into two components, one along the
optic axis, and one orthogonal to it, as shown in Fig. 2.15(b). We define
our axes so that z lies along the optic axis, and y lies in the plane of the
front surface of the waveplate, as shown in Fig. 9(a). The x axis is taken
21
Name: Tapas Banerji
IP: 129.82.195.78
to be the direction of propagation. If the input beam has amplitude E 0 ,

the input polarization has components:
E in
z
E in
y
= E 0 cos ,
= E 0 sin .
The component along z is the e-ray and the one along y is the o-ray.
In a half-wave plate, the phase of the o-ray is shifted by relative to the
e-ray at the output of the retarder plate. This means that the output
polarizations will be given by:
E out
z
E out
y
= E 0 cos = E in
z ,
= E 0 ei sin = E 0 sin = E in
y ,
as shown in Fig. 9(b). The resultant E-vector points at an angle with

respect to the optic axis. Hence the output polarization is rotated by an
angle 2 with respect to the input polarization.
(b) If we set = 45 , the input polarization will be given by:
E in
= E 0 cos 45 = E 0 / 2 ,
z
E in
= E 0 sin 45 = E 0 / 2 .
y
The quarter-wave plate introduces a phase difference of /2 between the
e-ray and o-rays. The output polarization will therefore be:
E out
= E 0/ 2 ,
z
E out
= (E 0 / 2)ei/2 = i E 0 / 2 .
y
The output therefore consists of two orthogonal linearly polarized components of equal amplitude with a phase difference of 90 between them.
This is circularly-polarized light.
(c) When 6= 45 , the amplitudes of the e- and o-rays will be different.
The quarter-wave plate still introduces a phase shift of 90 between them,
and so the output consists of two orthogonal linearly polarized components
with unequal amplitude and with a 90 phase difference between them.
This is elliptically polarized light.
(2.19) We follow Example 2.4, but set the phase difference to be /2 because
we have a quarter-wave plate instead of a half-wave plate. We therefore
require:
2|n|d
,
= =
2
which implies d = /4|n|. In this case we have |n| = 0.0091 and

= 500 nm, and so we require d = 1.4 105 m.
In this exercise we have neglected the optical activity of the quartz plate
because the thickness is very small. In a thicker multiple-order waveplate
(i.e one with = (2m + /2), where m is an integer) a small correction
would have to be introduced to account for the optical activity.
22
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(2.20) The crystal will be isotropic if the medium has high symmetry so that
the x, y and z axes are equivalent. If not, it will be birefringent. For the
crystals listed in the Exercise we have:
Crystal
(a) NaCl
(b) Diamond
(c) Graphite
(d) Wurtzite
(e) Zinc blende
(f) Solid argon
(g) Sulphur
Structure
cubic (fcc)
cubic
hexagonal
hexagonal
cubic
cubic (fcc)
orthorhombic
x, y, z equivalent ?
yes
yes
no
no
yes
yes
no
Birefringent ?
no
no
yes
yes
no
no
yes
The two hexagonal crystals are uniaxial, with the optic axis lying along the
direction perpendicular to the hexagons. Sulphur has the lowest symmetry
and is the only biaxial crystal included in the list.
(2.21) (a) The birefringent phase shift for a refractive difference of n is given
by eqn 2.46. For a half wavelength shift, this is equal to . On substituting
for the Kerr-induced birefringence from eqn 2.51, we obtain:
==
2|n|d
2(KE 2 )d
=
= 2KE 2 d .
On solving for the field, we then find:
E /2 = 1/ 2Kd ,
as required.
(b) We substitute for K and d to find:
p
E /2 = 1/ 2 (8.7 1014 ) 0.02 = 1.7 107 V/m .
The field is dropped across a distance of 5 mm, and so the voltage required
is V/2 = E /2 0.005 = 85 kV.
As Table 2.2 shows, the value of K for the chalcogenide considered here
is large for a glass, but the voltage required to make a Kerr cell is still
very high. Practical Kerr cells use liquids with larger Kerr constants, for
example, nitrobenzene.
(2.22) (a) Set up axes so that z corresponds to the direction of propagation and
x to the input polarization. With these definitions the input polarization
can be written as:
E in = E 0 x
,
where E 0 is the amplitude of the light.
Circular polarization consists of two orthogonally polarized waves of equal
amplitude with a 90 phase difference between them, and so we can write
left and right circular light as:
+ = E 0 (
x + i
y)/ 2 ,
= E 0 (
x i
y)/ 2 ,
23
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where the factor of i ei/2 represents the 90 phase shift. This allows
us to re-write the input polarization in terms of the left and right circular
light as:
E in = E 0 ( + + )/ 2 .
An optically-active medium will introduce a phase difference between
the left- and right-circular components, where:
=
2
n d .
Here, is the vacuum wavelength, n = (nR nL ) is the difference of the

refractive indices for right- and left-circular light, and d is the thickness
of the medium. The output wave will therefore be of the form:
E out = E 0 ( + + ei )/ 2 .
We revert to the linear basis by substituting for + and and re-writing
this as:
E out = E 0 (
x + i
y) + ei (
x i
y) /2 .
Collecting the terms in x
and y
, we find:
E out = E 0 (1 + ei )
x + i(1 ei )
y) /2 ,
= E 0 ei/2 (ei/2 + ei/2 )

x + i(ei/2 ei/2 )
y) /2 ,
=
=
E 0 ei/2 (2 cos(/2) x
+ i(2i sin(/2)) y
) /2 ,
E 0 ei/2 (cos(/2) x
+ sin(/2) y
) .
This shows that the output polarization is linearly polarized at an angle /2 with respect to the x axis. The polarization rotation angle is
therefore equal to /2, and so we find:
=
d
= n d =
(nR nL ) .
2
(b) Using the result from part(a), we find that the rotatory power of an
optically-active medium is given by:
RP = |/d| = |n|/ .
For quartz we thus find
RP = (7.1 105 )/589 109 = 379 rad/m = 21.7 /mm .
(2.23) We apply a Lorentzian model according to the theory in Section 2.2. The
Lorentzian lineshapes are shifted for + and light due to the Zeeman
effect, which shifts the energy of the transition from ~0 to ~0 B B
according to the circular polarization.
(a) The Faraday rotation is caused by the difference of the real part of
the refractive index for + and light. Figure 10(a) plots the refractive
indices for two Lorentzian lines shifted from each other by 2B B and their
24
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1.04
0.04
Dn
1.02
0.02
1.00
0.00
0.98
nn+
-0.02
Dn
-0.04
Dn
Refractive index n
(a)
0.96
0.6
0.8
1.0
1.2
1.4
Angular frequency (w/w0)

0.06
Extinction coefficient k
Name: Tapas Banerji
0.04
kk+
(b)
0.02
Dk
0.00
-0.02
-0.04
Dk
-0.06
0.6
0.8
1.0
1.2
1.4
Angular frequency (w/w0)

Figure 10: Lorentzian model calculation of Faraday effect and magnetic circular
dichroism, as considered in Exercise 2.23. (a) Faraday rotation. (b) Magnetic
circular dichroism.
difference. The lines are plotted against the normalized angular frequency
(/0 ) for a Lorentzian line with = 0.050 . The value of B B/~ is set
to be equal to . The value of n = Re(
n+ n
), and hence the Faraday
rotation is negative above and below the line, and positive near 0 . The
rotation decays as the frequency is tuned away from resonance.
(b) The magnetic circular polarization is found by calculating the difference of the imaginary part of (
n+ n
). This is shown in Fig. 10 for
the same Lorentzian line as in part (a). We see that the magnetic circular
dichroism follows a dispersive lineshape, with a negative signal below 0
that peaks at 0 B B/~, and a positive signal above 0 that peaks at
0 + B B/~. The signal precisely at 0 is zero.
(2.24) We require a Faraday rotation of /4 at a magnetic field of 0.5 T. The
Faraday rotation is given by eqn 2.53, and so the thickness of glass is given
25
Name: Tapas Banerji
IP: 129.82.195.78
by:
/4
=
= 0.17 m = 17 cm .
Vb
9.0 0.5
This long length is impractical, and real Faraday isolators use specialist
glasses or crystals with larger Verdet coefficients.
d=
26
Name: Tapas Banerji
IP: 129.82.195.78
Chapter 3
Interband absorption
(3.1) The Bornvon Karman boundary conditions are satisfied when:
kx L
ky L
kz L
=
=
=
nx L ,
ny L ,
nz L ,
where nx , ny and nz are integers. The wave vector is therefore of the

form:
k = (2/L)(nx , ny , nz ) .
The allowed values of k form a grid as shown in Fig. 11. Each allowed k
state occupies a volume of k space equal to (2/L)3 . This implies that
the number of states in a unit volume of k space is L3 /(2)3 . Hence a
unit volume of the material would have 1/(2)3 states per unit volume of
k space.
In most calculations we actually require the density of states in k space as
given in eqn 3.15. This is found by calculating the number of states within
the incremental shell between k vectors of magnitude k and k + dk, as
shown in Fig. 11. This volume of the incremental shell is equal to 4k 2 dk,
and contains 4k 2 dk 1/(2)3 = k 2 dk/2 2 states. Hence g(k) = k 2 /2 2 .
ky
dk
k
kx
2p/L
Figure 11: Grid of allowed values of k permitted by the Bornvon Karman

boundary conditions, as considered in Exercise 3.1. The points of the grid are
separated from each other by distance 2/L in all three directions, giving a
volume per state of (2/L)3 . Note that the diagram only shows the x-y plane
of k space. The incremental shell considered for the derivation of eqn 3.15 is
also shown.
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Name: Tapas Banerji
IP: 129.82.195.78
(3.2) With E(k) = ~2 k 2 /2m , we have:

~2 k
dE
= .
dk
m
On inserting into eqn 3.1415 and substituting for k, we find:
g(E) = 2
k 2 /2 2
m k
m
= 2 2 = 2 2
2
~ k/m
~
~
2m E
~2
1/2
=
1
2 2
2m
~2
3/2
E 1/2 ,
as required.
(3.3) (a) The parity of a wave function is equal to 1 depending on whether
(r) = (r). Atoms are spherically symmetric, and so measurable
properties such as the probability amplitude must possess inversion symmetry about the origin: i.e. |(r)|2 = |(r)|2 . This is satisfied if
(r) = (r). In other words, the wave function must have a definite parity.
(b) r is an odd function, and so the integral over all space will be zero
unless the product f i is also an odd function. This condition is satisfied
if the two wave functions have different parities (parity selection rule).
Since the wave function parity is equal to (1)l , the parity selection rule
implies that l is an odd number.
(c) In spherical polar co-ordinates (r, , ) we have:
x =
y =
z =
r sin cos = r sin (ei + ei )/2 ,

r sin sin = r sin (ei ei )/2i ,
r cos .
The selection rules on m can be derived by considering the integral over

. For light polarized along the z axis we have:
Z 2
0
M
eim 1 eim d ,
=0
since z is independent of . The integral is zero unless m0 = m. The

selection rule for z-polarized light is therefore m = 0.
For x or y polarized light we have:
Z 2
0
M
eim (ei ei ) eim d ,
=0
which is zero unless m0 = m1. We thus have the selection rule m = 1

for light linearly polarized along the x or y axis.
(d) From eqn A.40 we have that:
E+
E
= E 0 (
x + i
y)/ 2 ,
= E 0 (
x i
y)/ 2 ,
28
Name: Tapas Banerji
IP: 129.82.195.78
where E are the electric fields for polarizations. With x = r sin cos
and y = r sin sin , we therefore find:
E + = E 0 r sin (cos + i sin )/ 2 e+i ,
E = E 0 r sin (cos i sin )/ 2 ei .

On inserting these into the matrix element, we have for + light:
Z 2
0
M+
eim e+i eim d ,
=0
which is zero unless m0 = m + 1. Similarly, for light we have:

Z 2
0
M
eim ei eim d ,
=0
which is zero unless m0 = m 1. With circularly polarized light we therefore have m = +1 for + polarization and m = 1 for polarization.
(3.4) The apparatus required is basically the same as for Figs 3.1415, but with
modifications to take account of the fact that the required energy range of
0.30.6 eV corresponds to a wavelength range of 24 m. This means that
a detector with a band gap smaller than 0.3 eV must be used, e.g. InSb.
(See Table 3.3.) As InSb array detectors are not available, a scanning
monochromator with a single channel detector would normally be used.
A thermal source would suffice as the light source.
Another point to consider is that standard glass lenses do not transmit
in this wavelength range, and appropriate infrared lenses would have to
be used, e.g. made from CdSe. (See Fig. 1.4(b).) Also, since the data is
taken at room temperature, no cryostat is needed.
Figure 12 gives a diagram of a typical arrangement that could be used.
computer
white light
source
InAs sample
:
InSb
detector
infrared lenses
scanning
monochromator
Figure 12: Apparatus for measuring infrared absorption spectra in the range
24 m, as discussed in Exercise 3.4.
(3.5) The type of band gap can be determined from an analysis of the variation
of the absorption coefficient with photon energy. The material is direct
or indirect depending on whether a graph of 2 or 1/2 against ~ is a
29
IP: 129.82.195.78
straight line. Other factors to consider are that the absorption is much
stronger in a direct gap material, and that the temperature dependence
of is expected to be different. In an indirect gap material, phonon
absorption mechanisms will freeze out as the temperature is lowered.
(3.6) Plot 2 and 1/2 against ~ as shown in Fig. 13. In the range 2.2 ~
2.7 eV, the graph of 2 is a straight line with an intercept at 2.2 eV. We
thus deduce that GaP has an indirect band gap at 2.2 eV. For ~ > 2.7 eV,
the graph of 1/2 is a straight line with an intercept at 2.75 eV, which
implies that GaP has a direct gap at 2.75 eV. The huge difference in the
two axis scales of Fig. 13 is a further indication of the indirect nature of
the transitions below 2.75 eV, and their direct nature above 2.75 eV. We
thus conclude that the conduction band has two minima: one away from
k = 0 at 2.2 eV, and another at k = 0 at 2.75 eV.
1000
80
60
600
40
400
20
200
0
a2 (1012 m-2)
800
a1/2 (m-1/2)
Name: Tapas Banerji
2.2
2.4
2.6
2.8
Energy (eV)
3.0
Figure 13: Analysis of GaP absorption data as required for Exercise 3.6.
(3.7) A wavelength of 1200 nm corresponds to a photon energy of 1.03 eV. This
is above the direct gap of germanium at 0.805 eV, and thus the absorption
will be given by (cf. eqn 3.25):
= C(~ 0.805)1/2 .
The scaling coefficient C can be determined from the data in Fig. 3.11:
6 105 m1 at 0.86 eV implies that C 2.5 106 m1 eV1/2 . With
this value of C, we then find 1.2 106 m1 at 1.03 eV.
(3.8) (a) We consider transitions 1 and 2 in Fig. 3.5. The k vectors for the
transitions can be worked out from eqn 3.23. The appropriate parameters
are read from Table D.2 as follows: Eg = 1.424 eV, me = 0.067me , mhh =
0.5me , and mlh = 0.08me . For the heavy-hole and light-hole transitions we
find from eqn 3.22 that hh = 0.059 me and lh = 0.036 me respectively.
Hence for ~ = 1.60 eV, we find k = 5.3 108 m1 for the heavy holes
and k = 4.1 108 m1 for the light holes.
(b) The air wavelength of the photon is 775 nm. The wavelength inside
the crystal is reduced by a factor n. The photon wave vector inside the
30
Name: Tapas Banerji
IP: 129.82.195.78
crystal is therefore given by:

k=
2
= 3.0 107 m1 .
(/n)
This is more than an order of magnitude smaller than the electron wave
vector, and hence the approximation in eqn 3.12 is justified.
(c) Equation 3.24 shows that the joint density of states is proportional to
3/2 . Hence the ratio of the joint density of states for heavy- and light-hole
transitions with the same photon energy is equal to:
(hh /lh )3/2 = (0.059/0.036)3/2 = 2.1 .
(d) It is apparent from Fig. 3.5 that the lowest energy (i.e. k = 0) split-off
hole transition occurs at ~ = Eg + . Reading a value of = 0.34 eV
from Table C.2, we find ~ = 1.76 eV, which is equivalent to = 704 nm.
(3.9) Consider a + transition. By referring to Fig. 3.8, we see that in a heavyhole transition we start from the |J, MJ i = |3/2, 3/2i sublevel. For
heavy holes we must therefore insert J = 3/2 and MJ = 3/2 into the
matrix element for + transitions. This gives:
|hJ 1, MJ + 1| + |J, MJ i|2
1
2
1
2
=
=
(J MJ )(J MJ 1)C ,
(3/2 (3/2))(3/2 (3/2) 1)C ,

= 3C.
For light holes we start from the |J, MJ i = |3/2, 1/2i sublevel in a +
transition, and so the matrix element is given by:
|hJ 1, MJ + 1| + |J, MJ i|2
= 21 (J MJ )(J MJ 1)C ,
= 21 (3/2 (1/2))(3/2 (1/2) 1)C ,
= C.
The ratio of the squares of the matrix elements is therefore 3C : C = 3 : 1.

The argument is the same for transitions. For heavy holes we start
from the |J, MJ i = |3/2, +3/2i sublevel, and so the heavy-hole matrix
element is given by:
|hJ 1, MJ 1| |J, MJ i|2
1
2
1
2
(J + MJ )(J + MJ 1)C ,
(3/2 + (+3/2))(3/2 + (+3/2) 1)C ,
=
= 3C.
For light holes we have |J, MJ i = |3/2, +1/2i, and hence:

|hJ 1, MJ 1| |J, MJ i|2
1
2
1
2
=
=
=
(J + MJ )(J + MJ 1)C ,
(3/2 + (+1/2))(3/2 + (+1/2) 1)C ,
C.
The ratio is therefore 3 : 1 again.
31
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(3.10) Linearly polarized light can be considered as a superposition of two oppositely circularly polarized waves. (See eqn A.41.) The + part of the
wave will create negative spin polarization, while the part will create
an identical positive spin polarization. Hence the net spin polarization is
always equal to zero.
(3.11) The main issue to think about is the effect of the split-off hole band.
A split-off hole transition with + polarization will generate a spin up
electron, and thus start to cancel the negative spin polarization created
by the heavy-hole transitions. The matrix element squared for split-off
holes transitions is twice that of the light-hole transitions, [see eg Meier &
Zacharchenya (1984), p.24] so that the combined strength of the (light-hole
+ split-off hole) transitions is equal to that of the heavy-hole transition.
This means that the net spin polarization will ultimately go to zero when
split-off hole transitions become significant. Thus we expect that the
electron spin polarization will be constant at 50% for Eg ~ (Eg +
), where is the spinorbit energy, and then to drop for higher photon
energies. This is in fact observed experimentally.
The spin polarization is effectively zero for ~ (Eg + ). One way to
understand this is to realize that the electric field of the light only interacts
with the orbital motion of the electron and does not interact directly with
its spin. Therefore, if spin polarization is being generated optically, it
must be through the spinorbit interaction. Hence we expect the effect to
disappear when the electron energy is larger than the spinorbit energy
.
(3.12) (a) The lowest conduction band states of silicon are plike at the point
(i.e k = 0). The spinorbit splitting is small, and the J = 1/2 and
J = 3/2 conduction bands states are degenerate at k = 0, but not for
finite k. Electric dipole transitions from the plike valence band states
are forbidden to these plike conduction band states at k = 0. The first
dipole allowed transition is to the slike antibonding state at 4.1 eV.
Hence the direct gap at the point is equal to 4.1 eV.
(b) The discussion of the atomic character of bands given in Section 3.3.1
only applies at the point where k = 0 and we are considering stationary
states. This means that electric dipole transitions can be allowed at the
zone edges, even though they are forbidden at k = 0.
(3.13) At low temperatures, phonon absorption is impossible, and the indirect
transition must proceed by phonon emission, with a threshold energy of
Egind + ~. The band structure diagram of germanium given in Fig. 3.10
shows that the indirect gap occurs at the L point of the Brillouin zone. We
therefore need a phonon with a wave vector equal to the k vector at the
L point. The energies of these phonons are given in Table 3.1. The lowest
energy energy phonon is the TA phonon with an energy of 0.008 eV. The
absorption threshold would thus occur at Egind + 0.008 eV, i.e. at 0.75 eV,
as indeed demonstrated by the data in Fig. 3.11(a).
(3.14) The absorption coefficient with a field applied is given by eqn 3.26. The
absorption decreases exponentially for ~ < Eg , and this produces an exponential absorption tail below Eg . Although there is no clear absorption
32
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IP: 129.82.195.78
edge as for the case at zero field, a reasonable point to take is when the
absorption has decayed by a factor e1 from its value at Eg . This occurs
when
4 2me
(Eg ~)3/2 = 1 .
3|e|~E
We are looking for the field at which this condition is satisfied for ~ =
(Eg 0.01) eV. We thus need to solve:
4 2me
(0.01 eV)3/2 = 1 .
3|e|~E
With me = 0.067me , we find E = 1.8 106 V/m.
v
F
B
w
r
Figure 14: Force acting on a particle moving in a magnetic field pointing into
the paper, as required for Exercise 3.15. The charge is assumed to be positive.
(3.15) We consider a particle of charge q, mass m and velocity v moving in a
magnetic field B. The particle experiences the Lorentz force F = qv B
which is at right angles both to the velocity and the field, as shown in
Fig. 14. This perpendicular force produces circular motion at angular
frequency with radius r. We equate the central force with the Lorentz
force to obtain, with v = r:
m 2 r = qrB ,
which, with |q| = e, implies:
= eB/m ,
as required.
With a magnetic field pointing in the z direction, the motion in the x-y
plane is quantized, but the motion in the z direction is free. We have
seen above that, in the classical analysis, the field causes circular motion.
The quantized motion will therefore correspond to a quantum harmonic
oscillator. These quantized states are called Landau levels. The Bloch
wave functions of eqn 3.78 are therefore modified to the form:
n (r) u(r) n (x, y) eikz z ,
where n is a harmonic oscillator function, and n is the quantum number
of the Landau level. The selection rule for transitions between the Landau
levels can be deduced by repeating the derivation in Section 3.2 with the
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IP: 129.82.195.78
modified wave functions. For x-polarized light, the matrix element is now
given by:
Z
0
M
uf (r)n0 (x, y)eikz z x ui (r)n (x, y)eikz z d3 r ,
Z
uf (r) x ui (r) d3 r hn0 |n i ,
unit cell
where we assumed kz0 = kz as usual in the second line. The electric dipole
matrix element is therefore proportional to the overlap of harmonic oscillator wave functions with different values of n. Now harmonic oscillator
functions form an orthonormal set, and so the wave functions of differing
n are orthogonal. Hence the matrix element is zero unless n0 = n, i.e.
n = 0.
(3.16) (a) Let z be the free direction. Apply Bornvon Karman boundary conditions as in Exercise 3.1 to show that kz = 2n/L, where n is an integer.
There is therefore one k state in a distance 2/L, so that the density of
states in k space is 1/2 per unit length of material. For free motion in
the z direction we have E = ~2 k 2 /2m for a particle of mass m, which
implies:
p
dE/dk = ~2 k/m = ~ 2E/m .
The density of states in energy space is then worked out from eqn 3.14:
g1D (E) = 2
1/2
g(k)
=2 p
= (2m/Eh2 )1/2 .
dE/dk
~ 2E/m
We thus see that g1D (E) E 1/2 .

(b) The threshold energy will be equal to the band gap Eg of the semiconductor as for a 3-D material. Fermis golden rule indicates that the
absorption is proportional to the density of states. Since g1D (E) E 1/2 ,
we therefore expect (~ Eg )1/2 , for ~ > Eg . See Fig. 15(i).
6
Absorption (a.u.)
Absorption (a.u.)
Name: Tapas Banerji
(i)
4
2
0
6
(ii)
4
2
0
0
2
4
6
8
10
Energy relative to Eg in arb. units
0
1
2
3
Energy in units of h wL relative to Eg
Figure 15: (i) Absorption of a one-dimensional semiconductor as discussed in

Exercise 3.16(b). (ii) Absorption for a system with quantized Landau levels in
two directions and free motion in the third. L is the Landau level angular
frequency, as discussed in Exercise 3.16(c).
(c) The magnetic field quantizes the motion in two dimensions to give
Landau levels, leaving the particle free to move in the third dimension.
34
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Optical transitions are possible between Landau levels with the same value
of n. (See Exercise 3.15.) These will occur at energies given by (cf. eqn
3.32):
En = Eg + (n + 1/2)~L ,
where
L = eB/me + eB/mh = eB/ .
Each Landau level transition has a 1-D density of states due to the free
motion parallel to the field. Hence for each Landau level we expect:
(~ En )1/2 .
The total absorption is found by adding the absorption for each Landau
level transition together, as shown in Fig. 15(ii).
When comparing to the experimental data in Fig. 3.7, we expect (~) to
diverge each time the frequency crosses the threshold for a new value of
n. These divergences are broadened by scattering. We therefore see dips
in the transmission at each value of ~ that satisfies eqn 3.32.
(d) Minima in the transmission occur at 0.807 eV, 0.823 eV, 0.832 eV and
0.844 eV, with an average separation of 0.012 eV. We equate this separation
energy to e~B/, and hence find = 0.035me . If mh me , we will have
= me , and hence we deduce me 0.035me . The lowest energy transition
occurs at Eg + (1/2)e~B/, which implies Eg = 0.80 eV.
The values we have deduced refer to the point of the Brillouin zone.
(See Fig. 3.10.) The indirect transitions for ~ > 0.66 eV are too weak to
be observed compared to the direct transitions above 0.80 eV.
(3.17) The responsivity is calculated by using eqn 3.39. The device will be most
efficient if it has 100% quantum efficiency, and so we set = 1, giving:
Responsivitymax =
e
(1 el ) .
~
On inserting the values given in the Exercise, we find responsivities of

0.46 A/W at 1.55 m and 1.05 A/W at 1.30 m.
(3.18) (a) The pin diode structure is described in Appendix E. The p- and
n-regions are good conductors, whereas the i-region is depleted of free
carriers and therefore acts like an insulator. We thus have two parallel
conducting sheets separated by a dielectric medium, as in a parallel plate
capacitor.
(b) The capacitance of a parallel-plate capacitor of area A, permittivity
r 0 and plate separation d is given by:
C=
Ar 0
.
d
In applying this formula to a pn junction, we should use the depletion

region thickness for d. In the case of a pin diode, we assume that the
depletion lengths in the highly doped p- and n-regions are much smaller
than the i-region thickness, so that can set d = li . We then find C = 10 pF
for a silicon pin diode with A = 106 m2 , r = 11.9 and li = 105 m.
35
Name: Tapas Banerji
IP: 129.82.195.78
(c) The electric field for an applied bias of 10 V can be calculated from
eqn E.3 as:
1.1 (10)
= 1.1 106 V/m .
E=
105
The electron and hole velocities can be calculated from the field and the
respective mobilities:
v = E .
This gives v = 1.7 105 m/s for the electrons and v = 5 104 m/s for
the holes. The drift time is finally calculated from t = li /v, which gives
60 ps for the electrons and 200 ps for the holes.
Note that velocity saturation effects have been neglected here. The linear
relationship between the velocity and field breaks down at high fields,
and the velocity approaches a limiting velocity called the saturation drift
velocity. The field in this example is quite large, and the transit times will
actually be slightly longer than those calculated from the mobility due to
the saturation of the velocity.
(d) With R = 50 and C = 10 pF, we find RC = 500 ps. To obtain the
same transit time, we need a velocity of
v = li /t = 105 /5 1010 = 2 104 m/s .
This velocity occurs for an electric field of v/e = 1.3 105 V/m. We
finally find the voltage from eqn E.3:
E = 1.3 105 =
|1.1 V |
,
105
which gives V = 0.2 V. We therefore need to apply a reverse bias of

0.2 V.
The point about this last part of the question is to make the students
think about the factors that limit the response time of the photodetector.
In most situations, the time constant will be capacitance-limited because
the transit time is much shorter than the RC time constant. It is only in
small-area, low-capacitance devices that we need to worry about the drift
transit time.
36
Name: Tapas Banerji
IP: 129.82.195.78
Chapter 4
Excitons
(4.1) The Hamiltonian for the hydrogen atom has three terms corresponding to
the kinetic energies of the proton and electron, and the Coulomb attraction
between them. On writing the position vectors of the electron and proton
as r 1 and r 2 , the Hamiltonian thus takes the form:
2
2
e2
= ~ 2 ~ 2
H
,
2m1 1 2m2 2 40 |r 1 r 2 |
where m1 = me , m2 = mp , and
2i =
2
2
2
+
+
.
x2i
yi2
zi2
We introduce the relative co-ordinate r and the centre of mass co-ordinate

R according to:
r
R
= r1 r2
m1 r 1 + m2 r 2
=
.
m1 + m2
Now
x1
x2
=
=
x
X
m1
+
=
+
x1 x x1 X
x m1 + m2 X
x
X
m2
+
=
+
,
x2 x x2 X
x m1 + m2 X
which implies
2
x21
2
2m1
2
+
+
x2
m1 + m2 xX
2
x21
2
2m2
2
+
2
x
m1 + m2 xX
m1
m1 + m2
m2
m1 + m2
2
2
2
X 2
2
.
X 2
It is then apparent that:

1 2
1 2
+
=
2
m1 x1
m2 x22
1
1
+
m1
m2
2
1
2
+
.
2
x
m1 + m2 X 2
Similar results may be derived for the other co-ordinates, so that we have:
1 2
1
1
1
1 2
1 +
2 =
+
2r +
2
m1
m2
m1
m2
m1 + m2 R
37
Name: Tapas Banerji
IP: 129.82.195.78
On introducing the total mass M and reduced mass according to:

M
1
=
=
m1 + m2 ,
1
1
+
,
m1
m2
and substituting into the Hamiltonian, we then find

2
2
2
= ~ 2R ~ 2r e
.
H
2M
2
40 |r|
The three terms in the Hamiltonian now represent respectively:

the kinetic energy of the whole atom,
the kinetic energy due to relative motion of the two particles,
the Coulomb attraction, which depends only on the relative co-ordinate.
The Hamiltonian thus breaks down into two terms:
=H
whole atom + H
relative ,
H
where:
whole atom
H
relative
H
~2 2
2M R
~2
e2
= 2r
.
2
40 |r|
=
These two terms correspond respectively to the motions of:

a free particle of mass M moving with the centre of mass co-ordinate,
a particle of mass experiencing the Coulomb force and moving
relative to a stationary origin.
The Hamiltonian is thus separable into the free kinetic energy of the atom
as a whole and the bound motion of the electron relative to the nucleus.
For the latter case, we describe the motion by using the reduced mass ,
rather than the individual electron mass. The reduced mass correction
does not make much difference for hydrogen itself, where m2 m1 and
hence m1 , but it is very important for excitons, where the electron
and hole masses are typically of the same order of magnitude.
(4.2) (a) The Hamiltonian describes the relative motion of the electron and hole
as they experience their mutual Coulomb attraction within the semiconductor. The kinetic energy of the exciton as a whole is not included. As
explained in Exercise 4.1, the appropriate mass is the reduced electronhole mass , and the co-ordinate r is the position of the electron relative
to the hole. The first term represents the kinetic energy, and the second is
the Coulomb potential. The inclusion of r in the Coulomb terms accounts
for the relative permittivity of the semiconductor.
(b) We substitute into the Schrodinger equation with the 2 operator
written in spherical polar co-ordinates:
1
2
1
2
2
r
+ 2
sin
+ 2 2
.
= 2
r r
r
r sin
r sin 2
38
Name: Tapas Banerji
IP: 129.82.195.78
Since does not depend on or , the Schrodinger equation becomes:
~2 1
e2
2
= E .
2
2 r r
r
40 r r
On substituting = C exp(r/a0 ), we obtain:
~2
e2
~2
+
= E .
2a20
a0 r 40 r r
The wave function is therefore a solution if
+
e2
~2
= 0,
a0 r 40 r r
which implies
40 r ~2
m0
r
aH ,
2
e
is the hydrogen Bohr radius. With this value of a0 , we then

a0 =
where aH
find:
e4
~2
1
= 2 2 2
RH ,
2
2a0
8r 0 h
m0 2r
where RH is the hydrogen Rydberg energy.
E=
The normalization constant is found by solving:

Z Z Z 2
r2 sin drdd = 1 .
r=0
This gives:
=0
Z
4C 2
=0
r2 e2r/a0 dr = 4C 2
r=0
which implies:
C=
1
a30
a30
= 1,
4
1/2
.
In the language of atomic physics, the wave function considered here is a

1s state.
(4.3) The radial probability density P (r) is proportional to r2 |R(r)|2 , where
R(r) is the radial part of the wave function. For the 1s wave function of
Exercise 4.2 we then have:
P (r) r2 e2r/a0 .
On differentiating, we find that this peaks at a0 .
The expectation value of r is found from
Z Z Z 2
hri =
r r2 sin drdd ,
r=0 =0 =0
Z
1
= 4
r3 e2r/a0 dr ,
a30
r=0
= (3/2)a0 .
The peak of the probability density and the expectation value thus differ
by a factor of 3/2.
39
Name: Tapas Banerji
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(4.4) The purpose of this exercise is to familiarize the student with the variational method and demonstrate that it works. This will be useful to us
later for obtaining an estimate of the wave function and binding energy
of the excitons in quantum wells. (See Exercise 6.9.)
(a) We require a spherically-symmetric wave function with a functional
forms that makes the probability density peak at some finite radius and
then decay to zero for large values of r. The given wave function satisfies
these criteria. It is actually a correctly normalized 1s-like atomic wave
function, but with a variable radius parameter .
(b) We substitute into the Hamiltonian with the 2 written in spherical
polar co-ordinates, as in Exercise 4.2. Since again depends only on r,
this gives:
~2 1
e2
2
H =
r
.
2 r2 r
r
40 r r
On evaluating the derivatives, we find:
2

1/2
2
2
1
1
= ~ + ~ e
H
er/ .
2 2
40 r r
3
The expectation value is then given by:
Z Z Z 2
r2 sin drdd
hEi =
H
r=0
=0
1
3
=0
~2
e2
.
2
2
4r 0
r=0
~2 2
r +
2 2
~2
e2
40 r

r e2r/ dr
(c) On differentiating hEi with respect to , we find a minimum when =

40 r ~2 /e2 . The value of hEi at this minimum is hEi = e4 /8h2 20 2r .
(d) The value of that minimizes hEi is equal to a0 , and the minimum
value of hEi is the same energy as that found in Exercise 4.2.
The variational method gives exactly the right energy and wave function
here because our guess wave function had exactly the right functional
form. In other situations, this will not be the case, and the energy and
wave functions obtained by the variational method will only be an approximation to the exact ones. The accuracy of the results will depend on how
good a guess we make for the functional form of the trial wave function.
(4.5) (a) The electron performs circular motion around the nucleus with quantized angular momentum equal to n~. The orbits are stable, and photons
are only emitted or absorbed when the electron jumps between orbits.
(b) The central force for the circular motion is provided by the Coulomb
attraction, and the electron velocity v must therefore satisfy:
v 2
e2
=
,
r
40 r r2
40
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where r is the radius of the orbit and is the reduced mass. (See Exercises
4.1 and 4.2 for a discussion of why it is appropriate to use the reduced
mass here.) The Bohr assumption implies that the angular momentum is
quantized:
L = vr = n~ .
On eliminating v from these two equations we find:
r=
40 r ~2 2
m0
r n2 aH ,
n
2
e
where aH = 40 ~2 /m0 e2 is the hydrogen Bohr radius. The energy is

found from:
1
e2
.
E = v 2
2
40 r r
On solving for v and substituting, we find:
E=
e4
1 RH
,
8h2 20 2r n2
m0 2r n2
where RH = m0 e4 /8h2 20 is the hydrogen Rydberg energy. These are the

same results as in eqns 4.1 and 4.2.
(c) E is identical to the exact solution of the hydrogen Schrodinger equation.
(d) The radius for n = 1 corresponds to the peak in the radial probability
density for the ground state 1s wave function. For higher atomic shells, the
Bohr radius corresponds to the peak radial density of the wave function
with the highest value of the orbital quantum number l, namely l = n 1.
(4.6) The binding energies and radii can be calculated from eqns 4.1 and 4.2
respectively. The reduced mass is calculated from eqn 3.22 to be =
0.179m0 , and with r = 7.9 we then find RX = 39.1 meV and aX = 2.3 nm.
Hence we obtain E(1) = 39.1 meV, E(2) = 9.8 meV, r1 = 2.3 nm and
r2 = 9.3 nm.
We expect the excitons to be stable if E(n) > kB T . At room temperature
kB T = 25 meV, so that we would expect the n = 1 exciton to be stable,
but not the n = 2 exciton.
(4.7) The reduced mass is calculated from eqn 3.22 to be 0.056m0 , and hence
we calculate RX = 4.9 meV from eqn 4.1 using r = 12.4. Equation 4.4
gives the wavelengths of the n = 1 and n = 2 excitonic transitions as
873.7 nm and 871.4 nm respectively. Hence = 2.3 nm.
(4.8) We assume that the exciton has a Lorentzian line with a centre energy of
1.5149 eV and a full width at half maximum of 0.6 meV. We then expect
the absorption and refractive index to follow a frequency dependence as
in Fig. 2.5. This implies that the maximum in the refractive index would
occur at 0 /2, i.e. [1.5149 (0.6/2)] = 1.5146 eV.
The peak value of the refractive index can be worked out from eqns 2.15
21. At line centre, we have from eqns 1.19 and 1.28:
=
42
4
=
,
2n
41
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which implies 2 (0 ) = 1.37 if we assume that n 3.5 (i.e. the excitonic

contribution to the refractive index is relatively small.) From eqn 2.21 we
have
1.5149
0
= (st )
,
2 (0 ) = 1.37 = (st )
0.6
implying (st ) = 5.4 104 . With st = (3.5)2 = 12.25, we can
then find the dielectric constant at (0 /2) using eqns 2.2021. This
gives (0 /2) = 12.93 + 0.685i. We finally find n from eqn 1.25 to be
3.60. This justifies the approximation n 3.5 in the calculation of 2 (0 )
above.
(4.9) The n = 1 and n = 2 excitons have energies of Eg RX and Eg
RX /4 respectively. Hence the n = 1 2 transition occurs at a photon
energy of 3RX /4. We calculate RX = 4.2 meV from eqn 4.1, and hence
conclude that the transition energy is 3.15 eV. This occurs at a wavelength
of 394 m.
(4.10) The magnitude of the electric field between an electron and hole separated by a distance of r in a medium of relative permittivity r is given
by Coulombs law as:
e
E=
.
40 r r2
In the Bohr model we have (see e.g. Exercise 4.5):
|E(n)| =
e4
8(0 r hn)2
and
40 r ~2 n2
.
e2
It is thus apparent that for n = 1 we have:
2
2|E(1)|
2RX
e
e2
e
=
=
=
.
er1
eaX
40 r 0 r h2
40 r r2
rn =
Hence E = 2RX /eaX .

(4.11) We use eqn 3.22 to find = 0.028m0 , and then use eqns 4.12 with
r = 16 to calculate E(1) = 1.5 meV and r1 = 31 nm. Then, using the
result of the previous exercise, we find that the internal field in the exciton
has a magnitude of 9.7 104 V/m. We expect the excitons to be ionized
whenever the applied field exceeds this value. The voltage at which this
occurs can be worked out from eqn 4.5. With Vbi = 0.74 V and li =
2 106 m, we find E = 9.7 104 V/m for V0 = +0.55 V. Hence we need
to apply a forward voltage of 0.55 V. The excitons will therefore only be
observed for forward bias voltages above about 0.5 V. At zero bias and in
reverse bias, the excitons will be ionized.
(4.12) The cyclotron energy is given by eqn 4.6 and the exciton Rydberg by
eqn 4.1. The condition ~c = RX can thus be written:
RH
e~B
=
,
m0 2r
42
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which, on solving for B, gives:

B=
2 RH
.
m0 2r e~
On inserting the numbers for GaAs we find B = 1.8 T.

(4.13) The magnetic field is related to the vector potential by
B = A.
Thus for A = (B/2)(y, x, 0), we obtain:
0
y
B x
y
x = 0 .
B=
2
z
0
B
In the analysis following eqn B.17, we neglected the term in A2 because
the magnetic vector potential of a light wave is small. However, we are
now considering the interaction between an exciton and a strong magnetic
field, and it is precisely the term in A2 that gives rise to the diamagnetic
shift. It is then apparent from eqn B.17 that the diamagnetic perturbation
for a vector potential of A = (B/2)(y, x, 0) is given by:
2 2
2 2
0 = e A = e B (x2 + y 2 ) .
H
2m0
8m0
The diamagnetic energy shift is calculated from

2 2
0 |i = e B h|(x2 + y 2 )|i .
E = h|H
8m0
In the case of an exciton, the wave functions are spherically symmetric so

that:
hx2 i = hy 2 i = hz 2 i = hr2 i/3 = rn2 /3 .
The total shift is obtained by summing the energy shifts of the electrons
and holes to obtain:
E =
e2 B 2 2rn2
e2 B 2 2rn2
e2 B 2 rn2
+
=
.
8me 3
8mh 3
12
(4.14) It is shown in Example 4.1 that the radius of the ground state exciton in
GaAs is 13 nm. Hence for = 0.05m0 we calculate E = +4.9 105 eV
at B = 1 T. The wavelength shift can be calculated from:
=
hc
d
E = 2 E = 0.026 nm .
dE
E
(4.15) The effective masses given imply that = 0.17m0 from eqn 3.22, so
that we can calculate r1 = 3.1 nm and r2 = 12.3 nm from eqn 4.2 for
r = 10. The Mott densities are estimated from eqn 4.8. Hence we obtain
NMott = 8.1 1024 m3 and 1.3 1023 m3 for the n = 1 and n = 2
excitons respectively.
43
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(4.16) The classical theory of equipartition of energy states that we have a

thermal energy of kB T /2 per degree of freedom. A free particle has three
degrees of freedom corresponding to the three velocity components. Hence
the total thermal kinetic energy is given by:
3
p2
= kB T .
2m
2
This implies a thermal de Broglie wavelength of:
deB =
h
h
=
.
p
3mkB T
The particle density at the BoseEinstein condensation temperature is

given by eqn 4.9. On setting N = 1/r3 , where r is the average interparticle distance, we find
1
1/3 2mkB T
= (2.612)
.
r
h
Hence:
r
deB
1
(2.612)1/3
3
= 0.50 .
2
(4.17) BoseEinstein condensation refers to the quantization of the kinetic energy due to free translational motion. In applying this to excitons, we need
to consider the centre of mass motion of the whole exciton, which behaves
as a composite boson. The appropriate mass to use to calculate the condensation temperature is therefore the total mass of the exciton, namely
(me + mh ) = 1.7m0 . On substituting into eqn 4.9 with N = 1 1024 m3
and solving for Tc , we find Tc = 17.2 K.
(4.18) The excitonic radii calculated from eqn 4.2 are r1 = 0.85 nm and r2 =
3.4 nm. For the n = 1 exciton, the radius is comparable to the unit cell
size a and thus the Wannier model is invalid. On the other hand, the
n = 2 exciton satisfies the condition r a, and the Wannier model is
valid.
44
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Chapter 5
Luminescence
(5.1) Indirect transitions involve the absorption or emission of a phonon to conserve momentum. This means that they have a low transition probability,
and hence low quantum efficiency. See Section 5.5.2.
(5.2) This occurs because the electrons can relax very rapidly to the bottom
of the conduction band by emission of phonons, and similarly for holes.
The relaxation processes occur on a much faster timescale (ps) than
the radiative recombination (ns). Hence all the carriers have relaxed
before emission occurs, and it makes no difference where they were initially
injected. See Section 5.3.1.
(5.3) In the 2p 1s transition, the upper 2p level has n = 2, l = 1 and m = 1,
0 or +1, while the lower 1s level has n = 1, l = 0 and m = 0. The Einstein
A coefficient is therefore given from eqn B.31 as:
e2 3 1 X
A=
|h2p, m|r|1si|2 ,
30 ~c3 3 m=1,0,1
where the factor of 1/3 accounts for the triple degeneracy of the 2p state.
(It is not necessary to consider the spin degeneracies here because they
cancel out.) We write:
,
r = xi + yj + z k
so that:
|hri|2 = |hxi|2 + |hyi|2 + |hzi|2 .
Now atoms are spherically symmetric, and so it must be the case that:
|hxi|2 = |hyi|2 = |hzi|2 .
We therefore only have to evaluate one of these, and we chose hzi because
the mathematics is easier. Written explicitly, with z = r cos , we have:
Z Z Z 2
hzi =
2p r cos 1s r2 sin drdd .
r=0
=0
=0
This has to be evaluated for each of the three possible m values of the 2p
state. However, since z has no dependence on , and the dependence of
the wave functions is determined only by m, the integral is only non-zero
for the m = 0 level of the 2p state. Hence we only have to evaluate one
integral. On inserting the explicit forms of the wave functions, we then
have:
Z
Z Z 2
hzi =
R21 rR10 r dr
Y1,0
cos Y0,0 sin dd ,
r=0
1
6a4H
=0
=0
r4 exp(3r/2aH ) dr
r=0
Z Z 2
3
cos2 sin dd .
4 =0 =0
45
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This gives:
24
hzi =
6
5
2
1
aH = 0.745 aH = 3.94 1011 m .
3
3
Then, with |hri|2 = 3|hzi|2 , we obtain:

A=
e2 3 1
e2 3
2
3|hzi|
=
|hzi|2 .
30 ~c3 3
30 ~c3
The 2p 1s transition in hydrogen has an energy of (3/4)RH = 10.2 eV,

and therefore = 1.55 1016 rad/s. Hence we obtain A2p1s = 6.27
108 s1 . We then see from eqn 5.2 that the radiative lifetime R = 1/A =
1.6 ns. This agrees with the experimental value.
(5.4) It follows from eqn 5.4 that:
1
1
1
=
+
,
R
NR
where 1/NR is the non-radiative recombination rate. Hence the excited
state lifetime can be shorter than the radiative lifetime. The radiative
lifetime R would normally be independent of T , since it depends only on
the electron wave functions. However, the non-radiative recombination
rate 1/NR generally increases with T due to increased non-radiative recombination by phonon emission or thermally-activated traps. Hence
decreases with T . The quantum efficiency can calculated from eqn 5.5 to
be equal to /R . At 300 K we find R = 79 %, while at 350 K we find
R = 56 %.
(5.5) Semiconductors emit light at their band gap energy. We are therefore looking for a semiconductor with Eg = 2.3 eV. Inspection of Table C.3 suggest
two possibilities: ZnTe or GaP. The latter has an indirect band gap and
would therefore not be very efficient. Hence the most likely candidate material is ZnTe. Note, however, that we could also make an emitter at this
wavelength by using an alloy, for example: Inx Ga1x N. (See Fig. 5.11.)
Linear extrapolation between the GaN and InN band gaps would suggest
that a composition with x 0.41 would emit at 540 nm.
(5.6) (a) Consider an incremental beam slice at a position z within the absorbing
material as shown in Fig. 16. Let A be the area of the slice, dz its thickness,
I the incoming intensity (power per unit area), and I the loss of intensity
due to absorption within the slice. From Beers law (eqn 1.3) we have:
I = Idz .
We assume that each absorbed photon generates an electron-hole pair.
The number of electron-hole pairs generated within the slice per unit time
is therefore equal to AI/h. Hence the carrier generation rate G per unit
volume is given by:
G=
AIdz/h
I
AI/h
=
=
.
Adz
Adz
h
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(b) The rate equation for the carrier density N is

dN
N
I N
=G
=
,
dt
where the first term accounts for carrier generation and the second for
carrier recombination. In steady-state conditions we must have that
dN
= 0.
dt
Hence:
N=
I
.
h
(c) We calculate the laser intensity from:

I=
P
1 mW
=
= 1.3 105 Wm2 .
A
(50 m)2
The sample is antireflection coated, and so this is also the intensity inside
the sample. We can then calculate the carrier density using the result
from part (b) with the values of and given in the exercise. Hence we
find N = 6.6 1020 m3 for h = 2.41 eV. Note that this is the carrier
density at the front of the sample. The intensity will decay exponentially
(cf. eqn 1.4) and the carrier density will follow a similar exponential decay.
dz
Incoming
intensity
I(z)
Incoming
photon number
N (z)
Outgoing
intensity
I - dI
Outgoing
photon number
N-dN
A
z
Figure 16: An incremental slice of a laser beam at a position z within an

absorbing material. A is the area of the slice and dz its thickness. In Exercise 5.6
we consider a continuous laser beam with an intensity I(z), whereas in Exercise
5.7 we consider a pulse with a photon number of N(z).
(5.7) (a) The argument proceeds along similar lines as for the previous exercise.
Consider again an incremental beam slice of area A and thickness dz, as
shown in Fig. 16. Since we are now dealing with a pulse rather than a
continuous beam, we need to consider the photon number rather than the
intensity. Let N be the incoming photon number, and N the number of
photons absorbed within the slice. From Beers law (eqn 1.3) we have:
N = Ndz .
We assume that each absorbed photon generates an electron-hole pair.
Furthermore, we assume that the pulse is so short that no recombination takes place while the material is being excited. Hence the number
47
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of electron-hole pairs generated is just equal to the number of photons

absorbed. The carrier density generated is then given by:
N=
N
Ndz
N
=
=
.
Adz
Adz
A
Now the number of photons N in the pulse is just equal to E/h, where
E is the pulse energy. Hence we obtain:
N=
E
.
Ah
On inserting the relevant numbers from the exercise, we find N = 1.9

1024 m3 .
(b) The pulse excites the carrier density calculated in part (a) at time
t = 0. The carriers then recombine and the carrier density decreases
according to
N (t) = N0 exp(t/ ) ,
where is the total decay rate including both radiative and non-radiative
recombination. (See eqn 5.4.) With = (1/R + 1/NR )1 = 0.89 ns, we
find N (t) = N0 /2 at t = 0.62 ns.
(c) The quantum efficiency is calculated from eqn 5.5 as R = 89%. Each
laser pulse contains E/h photons. We are told that the crystal is thick,
and so we can assume that all the laser photons are absorbed in the crystal.
The number of photons re-emitted by luminescence is therefore ER /h =
3.5 1010 photons.
Ee
Eg
hn
Eh
k=0
Figure 17: Definition of energies as required for Exercise 5.8.

(5.8) The emission rate is proportional to the probability that the upper level
is occupied and that the lower level is empty. These probabilities can
be calculated from the FermiDirac functions for the electrons and holes,
with fe as the electron occupancy of the upper level and fh as the hole
occupancy of the lower level (i.e. the probability that the lower level is
empty.) Hence the emission probability is proportional to fe fh .
48
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In the classical limit, the occupancy factors follow Boltzmann statistics

with:
fe,h exp(Ee,h /kB T ) ,
where Ee and Eh are the electron and hole energies within the conduction
or valence band, respectively. (See Fig. 17.) Hence:
fe fh exp(Ee /kB T ) exp(Eh /kB T ) = exp[(Ee + Eh )/kB T ] .
Now it is apparent from Fig. 17 that
h = Eg + Ee + Eh ,
and hence that (Ee + Eh ) = h Eg . We therefore conclude that:
I(h) fe fh exp[(h Eg )/kB T ] .
(5.9) The number of electrons in the conduction band is given by eqn 5.6. In the
classical limit, we have (E EF ) kB T , so that the electron occupancy
factor is given by:
fe (E) =
1
exp[(EF E)/kB T ] .
exp[(E EF )/kB T ] + 1
On using the density of states given in eqn 5.7, we then obtain:

1
Ne =
2 2
2me
~2
3/2
exp
EF
kB T
1/2
(E Eg )
Eg
exp
E
kB T
dE .
On introducing the variable x = (E Eg )/kB T we then obtain:

1
Ne =
2 2
2me kB T
~2
3/2
exp
(EF Eg )
kB T
x1/2 exp(x) dx .
The final result is obtained by setting (EF Eg ) EFc , where EFc is the
electron Fermi energy measured relative to the bottom of the conduction
band.
For the case of GaAs at 300 K, we can insert the effective mass and
temperature, and use the definite integral given in the Exercise to obtain:
c
EF
(4.4 1023 ) m3 .
Ne = exp
kB T
In part (a) we then find EFc = 0.216 eV 8.4kB T , whereas in part (b)
we find EFc = +0.021 eV +0.83kB T . The approximations are therefore
valid for part (a) because we have (E EF ) kB T for all states in the
conduction band, but not for part (b), where the Fermi level comes out
above the conduction band minimum.
The aim of this exercise is to get the students to think about the conditions
under which the use of Boltzmann statistics is valid.
49
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(5.10) At T = 0 we have f (E) = 1 for E < EF and f (E) = 0 for E > EF .

We can therefore cut off the integral at the relevant Fermi energy, and
replace the Fermi function by unity up to this energy. With the energies
measured relative to the band edge, we then find:
3/2 Z EFc
2me
1
E 1/2 dE ,
Ne =
2 2
~2
0
for the electrons and similarly for the holes.
On evaluating the integral we find:
3/2
1
2
2me
Ne =
(EFc )3/2 ,
2 2
~2
3
and similarly for the holes. Equation 5.13 then follows by simple rearrangement.
(5.11) We use eqn 5.13 to evaluate the Fermi energies. In part (a) we find
EFc = 0.36 meV for the electrons, and EFv = 0.073 meV for the holes. In
part (b) we find EFc = 36 meV for the electrons, and EFv = 7.3 meV for the
holes.
For the conditions of degeneracy to apply, we need EF kB T . In part (a),
the electrons will be degenerate for T 4.2 K, while the holes will be
degenerate for T 0.9 K. In part (b), the electrons will be degenerate for
T 420 K, while the holes will be degenerate for T 85 K. This shows
that it is much easier to obtain degenerate statistics for the electrons than
the holes because they are lighter.
(5.12) The Fermi wave vector kF is, in general, related to the Fermi energy EF
by:
~2 kF2
EF =
.
2m
With EF given by eqn 5.13, we then find:
kF = (3 2 N )1/3 ,
where N = Ne or Nh as appropriate. In a photoluminescence experiment,
we excite equal numbers of electrons and holes, so that Ne = Nh . Hence
the Fermi wave vectors of the electrons and holes are identical. The fact
that the mass does not appear in the formula for the Fermi wave vector
is a consequence of the fact that the density of states in k-space does not
depend on the mass. (See eqn 3.15.)
(5.13) (a) The solid angle subtended by an object of area dA at a distance r is
given by (See Fig 18(a)):
dA
d = 2 .
r
The lens will be positioned at a distance equal to its focal length from the
sample, and so we set r = 100 mm in this case. We then find:
d =
(25 mm/2)2
= 0.049 .
(100 mm)2
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dA
qinside
dW
qoutside
medium
n
(a)
air
n=1
(b)
Figure 18: (a) Definition of solid angle d for an object of area dA at a distance
of r, as required for Exercise 5.13. (b) Emission of a ray at angle inside from a
source S embedded within a medium of refractive index n.
(b) Consider a ray emitted by a source embedded within a medium of
refractive index n as illustrated in Fig. 18(b). The ray is refracted at the
surface according to Snells law, with:
sin outside
= n.
sin inside
The light is being collected by a lens of radius 12.5 mm positioned 100 mm
from the surface, and therefore only those rays that satisfy outside
12.5/100 will be collected (assuming small angles). By Snells law we
deduce that only those rays within a cone with inside 0.125/n will be
collected.
The source emits uniformly over all 4 steradians within the medium.
The fraction F of the photons emitted that can be collected by the lens is
worked out by considering a circle of radius rinside placed at a distance
of r from the source:
F =
dA
r2 (inside )2
(inside )2
(outside )2
=
=
.
4r2
4r2
4
4n2
Finally, we have to consider that some of the photons will be reflected

at the surface. The reflectivity is calculated from eqn 1.29 to be 21% for
n = 2.7. Hence the final fraction collected is 0.79F = 4.2 104 .
(c) The semiconductor absorbs photons of energy 2.41 eV and emits luminescent photons at the band gap energy of 1.61 eV with a probability
equal to R . Hence the power emitted is equal (1.61/2.41)R times the
power absorbed. The incoming laser will be partially reflected at the
surface, and so the maximum power that can be absorbed is equal to
(1 R) Pincident = 0.79 1 mW. Hence the maximum luminescent
power is equal to:
Plum =
1.61
R 0.79 1 mW = 0.53 R mW .
2.41
(d) We obtain the luminescent power collected by the lens by multiplying

51
Name: Tapas Banerji
IP: 129.82.195.78
the total luminescent power by the collected fraction:

P collected = 0.53 R 4.2 104 mW = 0.22 R W .
(5.14) (a) The electron Fermi energy is calculated from eqn 5.13 to be 0.14 eV.
(b) The hole Fermi energy is calculated from:
Z
Nh
v
EF
[ghh (E) + glh (E)] dE
3/2
2
1
3/2
3/2
(mhh + mlh ) E 1/2 dE
2
2
2
~
0
3/2
1
2
3/2
3/2
(mhh + mlh ) (EFv )3/2 .
2
3
~2
Z
=
=
v
EF
Hence for Nh = 2 1024 m3 we obtain EFv = 0.012 eV.

(c) The carriers will be degenerate if EF > kB T . At 180 K we have kB T =
0.018 eV, and so the electrons are degenerate, but not the holes.
(d) When both the electrons and holes are degenerate, we expect emission
from the band edge up to the Fermi energies as illustrated in Fig. 5.7.
We then expect emission from the band gap to Eg + EFc + EFv . At T = 0
we would have a sharp cut-off at this energy, but at finite T the edge is
broadened over kB T . The luminescence would then be expected to fall
to 50 % of its peak value at Eg + EFc + EFv . On inserting the calculated
Fermi energies, and the value of the band gap, we expect the 50% point
at around 0.95 eV. This can be compared to the experimental value of
0.94 eV. The agreement between the experiment and model is thus
good.
(e) The luminescence spectrum at 250 ps given in Fig. 5.8 is consistent
with a value of the electron Fermi energy of 0.035 eV. This implies from
eqn 5.13 that the carrier density is Ne 3 1023 m3 . The electrons are
still degenerate at this density for T = 55 K. The lifetime is estimated
from:
N (t) = N0 exp(t/ ) ,
which implies N (24)/N (250) = exp(226/ ), where is the lifetime in
ps. On inserting the two values, we find 120 ps = 0.12 ns.
(5.15) We consider a zincblende IIIV semiconductor with the band structure
shown in Fig. 3.8. As explained in Section 3.3.7, the heavy-hole transitions are three times as strong as the light-hole transitions. The selection
rules are MJ = 1 for light, as indicated in Fig. 19. Note that
these selection rules are the opposite way around to those for absorption,
because we are now considering emission.
Consider the situation after excitation with + light resonant with the
band gap. There will be three times as many electrons in the MJ = 1/2
state as the +1/2 state. On the other hand, the holes will be equally distributed between all four possible sub-levels due to fast spinorbit mixing.
The transitions that are possible are indicated in Fig. 19. The intensity
52
Name: Tapas Banerji
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E
Eg
conduction
band
3N
s+
hh
-D
J = 1/2
s+
3
0
s-
lh
slh
so
so
hh
J = 3/2
J = 1/2
valence band
-3/2
-1/2
+1/2
+3/2
MJ
Figure 19: Optical transitions after excitation with + photons, as required for
Exercise 5.15. The relative weights of the transitions are indicated.
will be proportional to the population of the initial electron state and the
transition weight (i.e. |M |2 ).
From the MJ = 1/2 electron state with population 3N we have two
transitions:
A + transition to the MJ = 3/2 hh level: relative intensity =
3 3 = 9.
A transition to the MJ = +1/2 lh level: relative intensity =
3 1 = 3.
From the MJ = +1/2 electron state with population N we also have two
transitions:
A + transition to the MJ = 1/2 lh level: relative intensity =
1 1 = 1.
A transition to the MJ = +3/2 hh level: relative intensity =
1 3 = 3.
The total relative + intensity I + is therefore 9 + 1 = 10, while the total
relative intensity I is 3 + 3 = 6. The polarization is then given by
eqn 5.14 as:
10 6
4
I+ I
=
=
= 25% .
P = +
I + I
10 + 6
16
The argument works equally well for excitation.
(5.16) We see from eqn 5.16 that P (B)/P (0) = 1/2 when TS = 1. Hence at
B1/2 we have (from eqn 5.17):
TS =
ge B B1/2 TS
= 1.
~
53
Name: Tapas Banerji
IP: 129.82.195.78
Hence (cf eqn 5.18):

ge B B1/2
1
1
1
+
=
.
TS
S
~
Now from eqn 5.15 we have that:
P (0)
1
=
,
P0
1 + /S
which implies:
1
1
1 P0
= +
.
P (0)
Hence:
ge B B1/2
1 P0
=
,
P (0)
~
which gives:
=
P0
~
.
ge B B1/2 P (0)
We can then work out S from:

ge B B1/2
1
1
=
,
S
~
which implies:
S =
~
ge B B1/2
1
P (0)
1
.
P0
Note that P0 is expected to be 25% for a bulk III-V semiconductor, as

shown in Exercise 5.15.
(5.17) We follow Example 5.1. We extrapolate linearly between the direct gaps
of GaP and GaAs to find that:
Egdirect (x) = 1.42 + 1.36x eV .
(a) The LED will cease to function efficiently when the gap becomes indirect, i.e. for x > 0.45, where the conduction band minimum at the
Brillouin zone edge drops below the conduction band minimum at k = 0.
Hence the minimum wavelength occurs for x = 0.45, where Eg = 2.03 eV.
This corresponds to a wavelength of 610 nm.
(b) We require a direct band gap equivalent to 670 nm, namely 1.85 eV.
On substituting into the formula for the direct gap, we find x = 0.316.
Note that this is less than 45%, so that the alloy will have a direct gap
and hence be an efficient emitter.
(5.18) (a) The reflectivity is calculated from eqn 1.29 to be 31% for n = 3.5.
(b) The cavity mode frequency is given by eqn 5.20, and implies a mode
spacing of = c/2nl. With n = 3.5 and l = 1 mm, we find =
4.3 1010 Hz.
54
Name: Tapas Banerji
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(c) The threshold gain can be calculated from eqn 5.24. We are told to
ignore background absorption and scattering, and so we set b = 0. The
coated facet has a reflectivity of 95%, while the other facet will just have
the natural reflectivity of 31%. Hence we find:
th =
1
ln(0.95 0.31) = 610 m1 .
2 103 m
(5.19) (a) The maximum possible power would be obtained if one photon is
emitted for each electron that flows through the device. The power is
then equal to the electron flow rate multiplied by the photon energy:
100 mA
Pmax = h
= 150 mW .
e
(b) The electrical power input is equal to IV = 0.1 1.9 = 0.19 W =
190 mW. With a power output of 50 mW, the power conversion efficiency
is therefore equal to (50/190) = 26 %.
(c) The power output will vary as shown in Fig. 5.15(a). The slope efficiency is calculated from eqn 5.26 as (50/(100 35) = 0.77 mW/mA =
0.77 W/A. The differential quantum efficiency is calculated from eqn 5.26
to be 51 %.
(5.20) The incident primary electron flux per unit area is equal to J/e electrons m2 . Each primary electron will generate N eh electron hole pairs in
a distance Re from the surface, where N eh is given by eqn 5.27 and Re is
the penetration depth. The generation rate per unit volume of crystal is
thus given by:
J
J
Ep
G=
N eh =
(1 ) i .
e Re
e Re
E
The rate equation for the number of electronhole pairs is thus given by:
dN
N
=G
,
dt
where is the lifetime. In steady state conditions we must have N = 0

(cf Exercise 5.6), and we thus have:
N = G =
J
Ep
(1 ) i .
e Re
E
55
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Chapter 6
Quantum confinement
(6.1) Substitute into eqn 6.3 with x = 106 m and m = 0.1m0 to obtain
T . 0.01 K.
(6.2) The energy difference between the n = 1 and n = 2 levels is worked out
from eqn 6.13 to be 3~2 2 /2m d2 . On setting this energy difference to be
equal to kB T /2, we then derive the required result, namely
s
3~2 2
d=
.
m kB T
On substituting into this formula with T = 300 K, we find d = 9.3 nm for
m = m0 , and d = 30 nm for m = 0.1m0 .
On comparing with eqn 6.4, it is apparent that d = 3 2 x. This shows

that the two criteria used to determine when quantum size effects are
important give the same answer, apart from a numerical factor of 5.
The differing numerical factor is to be expected, given the approximate
nature of the criteria.
ky
dk
k
kx
(2p/L)2
Figure 20: Grid of allowed k states in a two-dimensional material of area L2 ,

as required for the solution of Exercise 6.3.
(6.3) The x and y components of the k vector must each satisfy the criterion
exp(ikL) = 1, which implies k = integer 2/L. The possible values of
the k vector therefore form a regular grid in k-space as shown in Fig. 20,
with a grid-spacing of 2/L. The area per k-state is (2/L)2 , and the
56
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density of states for an area L2 is therefore L2 /(2)2 . This implies that

the density of states in k-space for a unit area of crystal is 1/(2)2 .
It is also apparent from Fig. 20 that the area of k-space enclosed by the
increment k k + dk is 2kdk. If we call the number of k-states enclosed
by this area g L (k)dk, we then find:
g L (k)dk =
2kdk
L2
kdk .
=
2
(2/L)
2
Hence for a unit area of crystal we have:

g2D (k)dk =
k
dk .
2
The density of states in energy space can be found from eqns 3.1314. (The
factor or two accounts for the fact that spin 1/2 particles have two spin
states for each k-state.) With E(k) = ~2 k 2 /2m, we have dE/dk = ~2 k/m,
and hence
2g2D (k)
2k/2
m
g2D (E) =
= 2
=
,
dE/dk
~ k/m
~2
as required.
(6.4) In one dimension the k states must all lie on a single axis (say the x
axis). Let L be the length of the wire. The Bornvon Karman boundary
conditions require that exp(ikL) = 1, and hence that k = integer 2/L.
The density of states in k space for a sample of unit length is therefore
1/2. We thus have:
1
g1D (k)dk =
dk .
2
The density of states in energy space is then found from eqns 3.1314 with
E = ~2 k 2 /2m. This gives:
g1D (E) =
m 1/2
2g1D (k)
2/2
m
= 2
=
=
E 1/2 ,
dE/dk
~ k/m
~2 k
2~2 2
as required.
(6.5) The depth of the potential well enters eqn 6.26 via , which is defined in
eqn 6.27. The
function on the right handside of eqn 6.26 decreases from
(mw /mb )1/2 at x = 0 to zero at x = . (See, for example, Fig. 6.5,
for the case with = 13.2.) The function on the RHS of eqn 6.26 will
therefore always cross the x tan x function between 0 and /2, no matter
how small is.
(6.6) We follow the method of Example 6.1. We have
and
=
mw
mb
1/2
0.34
0.5
1/2
= 0.82 ,
0.34m0 (108 )2 0.15 eV

= 33.5 .
2~2
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IP: 129.82.195.78
y = x tan x
y = 0.82 (33.5-x2)1/2
x = 1.30
Name: Tapas Banerji
Figure 21: Graphical solution required for Exercise 6.6.

Hence we must solve:
x tan x = 0.82
p
33.5 x2 .
The two functions are plotted in Fig. 21, which shows that the solution is
x = 1.30. The energy is then found from
E=
2~2 x2
= 7.6 meV ,
mw d2
for d = 10 nm. The equivalent energy for an infinite well is calculated

from eqn 6.13 to be 11 meV.
(6.7) (a) The wave functions of an infinite potential well form a complete orthonormal basis, with
Z +
n n0 dz = nn0 ,
where nn0 is the Kronecker delta function:

nn0
=
=
1 if n = n0
0 if n 6= n0 .
It is apparent from eqn 6.11 that the wave functions depend only on n
and are therefore identical for electrons and holes with the same n. Hence
the orthonormality condition applies irrespective of whether n and n0
are electron or hole wave functions, or a mixture. Hence:
Mnn0
= 1 if n = n0
= 0 if n =
6 n0 .
This result can also be derived by explicit (and somewhat tedious) substitution of the wave functions from eqn 6.11 into the formula for Mnn0 .
(b) This result follows from parity arguments. The wave functions of
a finite well have well-defined parities as a consequence of the inversion
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IP: 129.82.195.78
symmetry about the centre of the well. Wave functions with odd n have
even parity, while those with even n have odd parity. Hence the product
en hn0 has even parity if n n0 is even and has odd parity for odd n n0 .
The integral of an odd function from + is zero, and so the
overlap integral is zero if n is equal to an odd number.
n
1
2
Electron
225
898
Heavy hole
30
120
Light hole
188
750
Table 1: Confinement energies in meV calculated for an infinite quantum well

of width 5 nm, as required for Exercise 6.8.
(6.8) The confinement energies of the electrons, heavy holes and light holes
calculated from eqn 6.13 are given in Table 1. With an infinite well, we
only need consider n = 0 transitions. The threshold photon energies for
these transitions are given by eqn 6.39, or the equivalent for higher values
of n or for the light holes. Two transitions fall in the range 1.4 2.0 eV:
Heavy hole 1 electron 1 at 1.679 eV,
Light hole 1 electron 1 at 1.837 eV.
For each transition we expect a step at the threshold energy as in Fig. 6.9.
In 2-D materials the joint density of states is proportional to the electronhole reduced mass (see eqn 6.41), and hence the relative height of the
heavy-hole and light-hole transition steps is in proportion to their reduced
masses, that is 0.059 : 0.036. Hence the final spectrum would appear as in
Fig. 22.
1.837 eV
Absorption (arb. units)
Name: Tapas Banerji
0.1
1.679 eV
lh1 e1
hh1 e1
0.0
1.4
1.6
1.8
Photon energy (eV)
2.0
Figure 22: Absorption spectrum for Exercise 6.8

(6.9) (a) In finite wells the confinement energies are reduced compared to those
of an infinite well of the same width. Hence the transition energies would
be lower. Furthermore, transitions that are forbidden in infinite wells
become weakly allowed, such as the hh3 e1 transition. This transition
would fall within the observed energy range, as might also some n = 2
transitions.
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(b) Peaks would appear below the steps in the absorption spectrum due
to excitonic absorption. The difference in energy between the peak and
the continuum absorption would be equal to the exciton binding energy.
RR
dA = 1. For the
(6.10) (a) To prove normalization, we must show that
given wave function we have:
Z Z 2
Z Z 2
2
rdrd =
exp(2r/) rdrd ,
2
r=0 =0
r=0 =0
Z
2
2
exp(2r/) rdr ,
=
2
r=0
= 1,
as required.
on , using the fact that / = 0:
(b) We first compute the effect of H
~2 d
d
e2
H
=
r
,
2r dr
dr
40 r r
2
~
e2
~2
.
=
2 2
2 2
40 r r
We can then calculate hEivar from:
Z
hEivar
=
r=0
Z
rdrd ,
H
=0
Z 2
~
e2
~2
rdrd ,

2
2
2
2
40 r r
r=0 =0
2
Z Z 2
Z Z 2
~2
~
e2
=
rdrd +
drd ,
2 2 r=0 =0
2 2
40 r
r=0 =0
2
~2
~
e2
2
=
1+
,
2
2
2
2
40 r
e2
~2
= +
.
2 2
20 r
=
(c) On differentiating hEivar with respect to , we find that hEivar achieves

its minimum value of Emin = e4 /8(0 r ~)2 for = 2~2 0 r /e2 . The
minimum energy is four times larger than the bulk exciton binding energy
found in Exercise 4.4.
(d) In part (c) we found min = 2~2 0 r /e2 . This can be written in
terms of the bulk exciton radius aX defined in eqn 4.2 as:
min = aX /2 .
Hence the radius of the exciton in 2-D is half the radius of the bulk.
(6.11) At d = we have bulk GaAs, while at d = 0 we have bulk AlGaAs.
For intermediate values of d, we have a GaAs quantum well exciton with
an enhanced binding energy. In an ideal 2D system we would expect
60
IP: 129.82.195.78
four times the binding energy of bulk GaAs (i.e. 16 meV), but in realistic
systems, the enhancement might be smaller due to the imperfect quantum
confinement of the finite-height AlGaAs barriers. Thus as d is reduced
from , the binding energy increases from 4 meV, going through a peak,
and then dropping to 6 meV as d 0. The height of the peak might
typically be around 10 meV.
hh1 e1 band edge

1.0
hh1 e1
exciton
PLE intensity
Name: Tapas Banerji
0.0
lh1 e1
exciton
lh1 e1
band edge
1.58
1.60
1.62
Energy (eV)
1.64
Figure 23: Interpretation of the data in Fig. 6.23 as required for Exercise 6.12.
(6.12) (a) See Section 5.3.5.
(b) The interpretation of the principal features in the data is shown in
Fig. 23. For both heavy- and light-hole transitions, we expect to observe a
peak due to excitonic absorption followed by a step at the band edge. The
two strong peaks observed in the data correspond to the excitons for the
hh1 e1 and lh1 e1 transitions, while the flat absorption bands above
both excitons correspond to the interband transitions. These interband
absorption bands are flat because the density of states is independent of
the energy in 2-D systems (see eqn 6.41.)
(c) The hh1 e1 interband continuum starts at 1.592 eV. In the infinite
well model, the transition energy is given by eqn 6.42 with n = 1, which,
on using Eg = 1.519 eV, me = 0.067m0 and mhh = 0.5m0 , implies d =
9.3 nm. The real well width would be smaller, because the infinite well
model overestimates the confinement energy.
(d) The binding energies can be read from Fig. 6.23 as the energy gap
between the exciton peak and the appropriate band edge. With the transitions identified as in Fig. 23, we find binding energies of 11 meV for the
heavy holes and 12 meV for light holes. For a perfect 2-D system we would
expect 4 RX for GaAs, i.e. 16.8 meV. The experimental values are lower
because a real quantum well is not a perfect 2-D system.
(6.13) By considering Fig. 6.12 we would expect three different regimes to apply.
1. For photon energies in the range set by eqn 6.43, that is:
Eg + Ee1 + Ehh1 ~ < Eg + Ee1 + Elh1 ,
we can only excite hh1 e1 transitions. These only create MJ =
1/2 spin down electrons, and so we expect e = 100%.
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2. For photon energies in the range:

Eg + Ee1 + Elh1 ~ < Eg + Ee1 + Eso1 ,
where Eso1 is the confinement energy of the first split-off hole band,
we can excite both hh1 e1 and lh1 e1 transitions, which create
oppositely polarized electrons. Hence we expect the magnitude of the
electron spin polarization to decrease. If the matrix elements are the
same as in the bulk, the heavy-hole transitions will be three times
stronger than the light-hole transitions, and this gives an electron
spin polarization of 50%. (See Section 3.3.7.)
3. For photon energies in the range:
~ > Eg + Ee1 + Eso1 ,
we expect that no spin polarization will be be created. The extra
contribution of the split-off hole band exactly cancels the net polarization created by the stronger weight of the heavy-hole transition.
This can be understood in general terms by realizing that the electron spin polarization is created by spinorbit coupling, so that when
the excess photon energy exceeds the spinorbit interaction energy
, then the effect will be negligible.
Experimental data showing these effects may be found in Vi
na, J. Phys.:
Condens. Matter 11, 5929 (1999), Fig. 2. The basic trends discussed
above are reproduced in the experimental data, although there are some
important differences. This is because we really should work in the excitonic rather than single-particle picture, and also because the relative
weight of the heavy- and light-hole transitions is not exactly 3:1. See the
discussion in Vi
nas article for further details.
(6.14) (a) With H 0 = +ezE z , we have:
Z
E (1) = eE z
z dz .
Since z is an odd function, and ||2 is an even one, the integral is

zero.
(b) With H 0 = +ezE z , the second-order energy shift is given by:
E (2) = e2 E 2z
X
|h1|z|ni|2
.
E1 En
n=2
Since the wave functions have parity (1)n+1 , and z is an odd parity
operator, all the terms with odd n are zero. Hence we have:
E (2) = e2 E 2z
|h1|z|4i|2
|h1|z|2i|2
+ e2 E 2z
+ .
E1 E2
E1 E4
Now the terms with n 4 are much smaller than the term with n = 2.
(This can be verified by working through the integrals, but it is fairly
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Name: Tapas Banerji
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obvious given the larger denominator.) Hence we only need to consider

the first term:
|h1|z|2i|2
.
E (2) = e2 E 2z
E1 E2
On substituting the energies for an infinite well from eqn 6.13, this becomes:
2e2 E 2z m d2
|h1|z|2i|2 .
E (2) =
3~2 2
Now, on redefining the origin so that the quantum well runs from z = 0
to z = +d, we have:
Z +
h1|z|2i =
1 z 2 dz ,
Z d
=
=
2
d
sin(z/d) z sin(2z/d) dz ,
0
16d
.
9 2
Hence we find
E
(2)
2
6 2 2 4
2e2 E 2z m d2 16d
e Ezm d
2
=
2 = 24
,
3~2 2
9
3
~2
as required.
(6.15) (a) Figure 6.13 predicts that the energy of the hh1e1 transition will
shift from 1462.4 meV to 1438.5 meV in a 10 nm quantum well on increasing the field from zero to 1 107 V/m. This corresponds to a red
shift of 14.1 nm. This can be compared to the experimental red shift of
10.5 nm for a 9 nm well for a voltage change of 10 V. Excitonic effects
are not included in the calculation of Fig. 6.13, but this is not expected
to make a large difference. Two main factors account for the difference
between the experimental and theoretical results.
The well width for the experiment was smaller by a factor of 0.9.
From eqn 6.47 we would then expect the Stark shift to be smaller by
a factor (0.9)4 = 0.66.
For the experimental data, we can calculate the field from eqn 6.52.
From this we find that E z changes from 0.15 107 V/m to 1.15
107 V/m, which should be compared to the theoretical data, which
corresponds to changing E z from 0 1 107 V/m. The field change
is the same in both cases, but because the Stark shift is quadratic at
low fields, we do not expect the Stark shifts to be the same. If the
Stark shift remained quadratic at all field strengths, we would expect
the experiment shift to be larger by a factor (1.152 0.152 )/(12 02 ) =
1.30.
Putting these two factors together, we expect the experimental Stark shift
to be smaller than the theoretical one by a factor of 0.94 1.3 = 0.85. The
actual ratio is (10.5/14.1) = 0.74. This difference is easily explained by
63
Name: Tapas Banerji
IP: 129.82.195.78
the fact that the Stark shift does not remain quadratic at all fields, and
so the factor due to the different fields should be smaller.
(b) We assume that the Stark shift is quadratic, and hence that E
E 2z . We work out the field strength from eqn 6.52, which implies E z =
11.5 MV/m at 10 V and E z = 6.5 MV/m at 5 V. For small shifts we have
E, and so we find:
(5 V) =
6.5
11.5
2
(10 V) = 0.32 10.5 nm = 3.4 nm .
(c) The wavelength red shift of 10.5 nm corresponds to an energy shift of

18 meV. This energy shift is related to the net electron-hole displacement
hzi by:
E = pz E z = ehziE z .
With E z = 11.5 MV/m, we thus obtain hzi = 1.6 nm.
E z (MV/m)
3
6
9
Sample A
Ecalc Eexp
1.5
1
5.9
5
13
13
Sample B
Ecalc Eexp
15
6
62
27
139
54
Table 2: Comparison of the calculated and measured Stark shifts (in meV) for
the two samples discussed in Exercise 6.16.
(6.16) The experimental data is taken from Polland et al., Phys. Rev. Lett. 55,
2610 (1985). We analyse it by using the energy shift calculated by secondorder perturbation theory in Exercise 6.14(b). Since we are considering
an electron-hole transition, we must add together the Stark shifts of the
electrons and holes, giving:
(2)
= 24
2
3
e2 E 2z d4
(me + mhh ) .
~2
The calculated shifts using me = 0.067m0 and mhh = 0.5m0 are compared
to the experimental ones in Table 2. It is apparent that the model works
well for sample A, but not for sample B. The model breaks down when the
size of the Stark shift becomes comparable to the energy splitting of the
unperturbed hh1 and hh2 levels. This is essentially the same criterion as
for the transition from the quadratic to the linear Stark effect in atomic
physics. In sample B, we are in this regime at all the fields considered.
(6.17) At E z = 0 the quantum well is symmetric about the centre of the well.
The electron and hole states therefore have a definite parity with respect
to inversion about z = 0. The parity is (1)(n+1) , and the electronhole
overlap given by eqn 6.36 is zero if n is odd: see Exercise 6.7(b). At
finite E z , the inversion symmetry is broken, and the states no longer have
a definite parity. Therefore, the selection rule based on parity no longer
holds.
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(6.18) With the confinement energy E d2 , we have dE/dd 2/d3 , and

hence we expect:
E
d
= 2
.
E
d
A 5% change in d is thus expected to give E/E = 10%. With
E = 0.1 eV, we then expect a full-width broadening of 0.02 eV. This is
comparable to the linewidth observed in the 10 K data shown in Fig. 6.16.
A 5% variation in d corresponds more or less to a fluctuation of one
atomic layer. Such monolayer fluctuations are unavoidable in the crystal
growth. The linewidth at room temperature is further broadened by the
thermal spread of the carriers in the bands.
(6.19) We assume infinite barriers and use eqn 6.53 to calculate the emission
energy. With ~ = 0.80 eV, Eg = 0.75 eV, and = 0.038m0 , we find
d = 14 nm. In reality, the quantum well would have to be narrower to
compensate for the imperfect confinement of the barriers.
(6.20) (a) z is an odd function with respect to inversion about z = 0. The
integral from to + will therefore be zero unless n n0 is also an
odd function, which requires that the wave functions must have different
parities. Since the wave functions have parities of (1)n+1 , the condition
is satisfied if n is an even number and n0 odd, and vice versa. Hence n
must be equal to an odd number.
(b) The strength of the intersubband transitions is proportional to the
square of the matrix elements. These matrix elements can be evaluated
by substituting the wave functions from eqn 6.11. On redefining the origin
so that the quantum well runs from z = 0 to z = +d, we find:
2
h1|z|2i =
d
and
2
h1|z|4i =
d
sin(z/d) z sin(2z/d) dz =
0
sin(z/d) z sin(4z/d) dz =
0
16
d,
9 2
4
d.
45 2
Hence the 1 4 transition is weaker than the 1 2 transition by a factor

[(4/45)/(16/9)]2 = [1/20]2 = 2.5 103 .
It is apparent from Fig. 6.17 that the wavelength of the 1 2 transition
is given by
hc
3 2 ~2
= E2 E1 =
,
2me d2
where we used the infinite well energies of eqn 6.13 in the second equality.
On inserting me = 0.067m0 and d = 20 nm, we find hc/ = 0.042 eV, and
hence = 29 m.
(6.21) Consider a ray incident at angle to the normal as shown in Fig. 24.
The ray will be refracted according to Snells law, with
sin
= n,
sin 0
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n=1
semiconductor, refractive index n
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q
E
quantum well
Figure 24: Refraction of light entering a semiconductor containing a quantum

well, as discussed in Exercise 6.21.
where 0 is the angle inside the crystal. For intersubband transitions, we
are interested in the z component of the electric field of the light at the
quantum well, namely:
E z = E 0 sin 0 = E 0 sin /n .
If I0 is the incident intensity, and there are no intensity losses at the
surface, then the intensity in the z component at the quantum well is
given by
Iz = I0 (sin /n)2 ,
since the intensity is proportional to E 2 . Hence the fraction of the power
of the beam in the z polarization at the quantum well is (sin /n)2 . This
fraction has a maximum value of 1/n2 for = 90 . Therefore even if we
completely absorb all the z polarized light by intersubband transitions,
and we use glancing incidence, we can only remove a fraction of 1/n2 of
the power in the incident beam. This fractional absorption is equal to 9%
if n = 3.3.
nx
1
2
2
3
2
3
3
ny
1
1
2
1
2
2
2
nx
1
1
1
1
2
1
2
(n2x + n2y + n2z )

3
6
9
11
12
14
17
g
1
3
3
3
1
6
3
Table 3: Quantum numbers of the energy levels for a cubic quantum dots in order of increasing energy, as discussed in Exercise 6.22. g denotes the degeneracy
excluding spin.
(6.22) For a cubic dot, the energies of the quantized levels are given by eqn 6.54
with dx = dy = dz = d, implying:
E(nx , ny , nz ) =
2 ~2
(n2 + n2y + n2z ) ,
2m d2 x
where nx , ny and nz are integers with a minimum value of 1. As demonstrated by Table 3, the quantized levels occur at energies of 3, 6, 9, 11,
12, 14, 17,. . . in units of h2 /8m d2 .
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The degeneracy factor g is worked out by finding the number of permutations of (nx , ny , nz ) that can give the same energy. The ground
state is unique, but for the first excited we can have (2, 1, 1), (1, 2, 1)
and (1, 1, 2), and similarly for the levels at 9, 11, and 17 h2 /8m d2 . The
level at 14 h2 /8m d2 has a degeneracy of 6 because there are 3! = 6 ways
of arranging the numbers 3, 2 and 1.
(6.23) The radial equation for a spherical dot is given by eqn 6.57. If the confining potential is V0 , then we can put V (r) = V0 for r R0 . Therefore,
when the particle is inside the dot (i.e. r R0 ), the radial wave function
for states with l = 0 must satisfy:
~2 1 d
d
2
r2
V0 R(r) = E R(r) .
2m r dr
dr
Now
1 d
r2 dr
sin kr
sin kr
2 d
2
r
= k
.
dr
r
r
Hence if R(r) = sin kr/r, then substitution into the radial equation gives:
~2 k 2
R(r) V0 R(r) = E R(r) ,
2m
which implies that
~2 k 2
.
2m
For an infinite well it must be the case the R(r) = 0 for r R0 . Therefore
at r = R0 we require that sin kR0 /R0 = 0, which implies that kR0 = n,
where n is an integer. Hence:
E = V0 +
E = V0 +
~ 2 n2 2
.
2m R02
The confinement energy relative to the bottom of the potential well at

V0 is thus:
~2 n2 2
En =
.
2m R02
(6.24) For the dots to have the same volume, we require that:
d3 =
4 3
R ,
3 0
where d is the cube size and R0 is the radius of the spherical dot. This
implies that (R0 /d) = (3/4)1/3 . From Exercise 6.22 we find that the
confinement energy of the first level in a cubic dot with infinite barriers
is E1cubic = 3~2 2 /2m d2 . For a spherical dot eqn 6.58 gives E1spherical =
~2 2 /2m R02 for C10 = 1, as appropriate for infinite barriers. Hence:
E1cubic
E1spherical
~2 2
3~2 2
=3
2
2m d
2m R02
R0
d
=3
3
4
2/3
= 1.15 .
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The reason why the cube has the higher energy can be understood by
reference to Fig. 25. In the infinite well approximation, the wave functions
are proportional to sine waves with nodes at the edges for both the cube
and the sphere. It is apparent from Fig. 25 that if the cube and sphere
have the same volume, then the wavelength of the sine wave in the cube
will be smaller. This corresponds to a larger k vector, and hence larger
confinement energy, since E = ~2 k 2 /2m inside the dot in both cases.
Figure 25: Comparison of cube and sphere of the same volume, as discussed in
Exercise 6.24. The wave functions have nodes at the edges.
(6.25) (a) In Cartesian co-ordinates, the Schrodinger equation for a 2D harmonic oscillator takes the form:
2
2
1
~2
2 2
2
+ 2 + me 0 (x + y ) (x, y) = E(x, y) .
2me x2
y
2
On writing (x, y) = X(x)Y (y) and substituting, we find:
~2 d2 X
1
~2
d2 Y
1
Y + me 02 x2 XY
X 2 + me 02 y 2 XY = EXY .
2
2me dx
2
2me dy
2
On dividing by XY and re-arranging this gives:
~2 1 d2 Y
~2 1 d2 X
1
1
2 2
x
=
E
+
+
m
me 02 y 2 .
e
0
2me X dx2
2
2me Y dy 2
2
The left hand side is a function of x, and the right hand side a function
of y, and so they both must equal a constant. On calling this constant C
and rearranging we have:
1
~2 d2 X
+ me 02 x2 X
2
2me dx
2
~2 d2 Y
1
+ me 02 y 2 Y
2me dy 2
2
= CX
= (E C)Y .
Both of these are standard harmonic oscillator equations. The one for x
implies C = (nx + 1/2)~0 , where nx is an integer, while the one for y
implies that (E C) = (ny + 1/2)~0 , where ny is another integer. Hence:
E = C + (ny + 1/2)~0 = (nx + ny + 1)~0 (n + 1)~0 ,
where n = nx + ny .
The degeneracies are found by working out the different possible permutations of nx and ny to get the same energy:
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Ground state: E = ~0 , n = 0, (nx , ny ) = (0, 0), degeneracy = 1.

1st excited state: E = 2~0 , n = 1, (nx , ny ) = (1, 0) or (0,1), degeneracy = 2.
2nd excited state: E = 3~0 , n = 2, (nx , ny ) = (2, 0), (1,1) or (0,2),
degeneracy = 3.
3rd excited state: E = 4~0 , n = 3, (nx , ny ) = (3, 0), (2,1), (1,2) or
(0,3), degeneracy = 4.
4th excited state: E = 5~0 , n = 4, (nx , ny ) = (4, 0), (3,1), (2,2),
(1,3) or (0,4), degeneracy = 5.
It is thus apparent that the degeneracy is equal to n. This results can also
be worked out by considering the m states: there are n states from n to
+n in steps of 2.
(b) In polar co-ordinates, the Schrodinger equation for a 2D harmonic
oscillator takes the form:
~2 1
1 2
1
2 2
r
+ 2 2 + me 0 r (r, ) = E(r, ) .
2me r r
r
r
2
On writing (r, ) = R(r)() and substituting, we find:
~2 1 d
dR
R d2 1
r
+ 2
+ me 02 r2 R = ER .
2me r dr
dr
r d2
2
On multiplying through by r2 /R and re-arranging, this gives:
~2 r d
dR
1
1 d2
r
+ me 02 r4 Er2 =
.
2me R dr
dr
2
d2
The left hand side is a function of r, and the right hand side a function
of , and so they both must equal a constant. On calling this constant C
and rearranging we have:
d2
= C ,
d2
which has solutions () = eim , where m2 = C. Now the wave function
must be single valued for each value of and so we require:
() = ( + 2) ,
which implies that eim2 = 1 and hence that m must be an integer. Therefore, the wave functions are of the form (r, ) = R(r)eim , where m is
an integer.
(c) The fact that m is equal to n to +n in steps of 2 can be proved
mathematically, but requires a lot of work. (See, for example, Pauling &
Wilson, Introduction to quantum mechanics, 1935.) We thus restrict our
efforts here to justifying this result for the first three levels. From part (a)
we know that the wave function for the state with energy (n+1)~ has the
form nx (x)ny (y), where n = nx +ny . We can draw up a correspondence
69
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Energy
~
2~
3~
Polar co-ordinates
n = 0, m = 0
n = 1, m = 1
n = 2, m = 2, 0, +2
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Cartesian co-ordinates
(nx , ny ) = (0, 0)
(nx , ny ) = (1, 0) or (0, 1)
(nx , ny ) = (2, 0), (1, 1) or (0, 2)
Table 4: Equivalence of the states of a 2D harmonic oscillator in polar and

Cartesian co-ordinates, as considered in Exercise 6.25(c).
between the Cartesian and polar co-ordinates as shown in Table 4. We
consider each energy state in turn.
Ground state with energy ~
This state is easy. There is only one possibility with (nx , ny ) = (0, 0). The
wave function in polar co-ordinates is therefore of the form:
0,0 (r, ) = 0 (x)0 (y) exp(x2 /2) exp(y 2 /2) = exp(r2 /2) ,
as required.
First excited state with energy 2~
We now have two possibilities, and the wave functions must be linear
combinations of each other, that is:
1,m (r, ) = C1 1 (x)0 (y) + C2 0 (x)1 (y) .
It is apparent that if we take
1,m (r, ) 1 (x)0 (y) i0 (x)1 (y) ,
then we have:
1,m (r, ) (x iy) exp(x2 /2) exp(y 2 /2) .
Now x = r cos and y = r sin . Therefore:
1,m (r, ) r(cos i sin ) exp(r2 /2) = r ei exp(r2 /2) .
This shows that m = 1 for the state with energy 2~. Note that the
radial form is as given in the Exercise.
Second excited state with energy 3~
We now have three possibilities, and the wave functions must be linear
combinations of each other, that is:
2,m (r, ) = C1 2 (x)0 (y) + C2 1 (x)1 (y) + C3 0 (x)2 (y) .
Consider the combination 2 (x)0 (y) + 0 (x)2 (y). This can be written:
2,m (r, )
(1 2x2 ) exp(x2 /2) exp(y 2 /2)
+ exp(x2 /2) (1 2y 2 ) exp(y 2 /2) ,

2(1 x2 y 2 ) exp((x2 + y 2 )/2) ,
2(1 r2 ) exp(r2 /2) .

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This clearly has no dependence on and so it must correspond to the

state with m = 0. Note that the radial form is correct for this state. We
can thus write:
2,0 (r, ) 2 (x)0 (y) + 0 (x)2 (y) .
Now consider the combination: 2 (x)0 (y) 2i1 (x)1 (y)+0 (x)2 (y).
By carefully considering the normalization constants in front of the harmonic oscillator functions, we find that this gives:
2,m (r, )
(1 + 2x2 4ixy + (1 2y 2 )) exp((x2 + y 2 )/2) ,

2(x2 y 2 2ixy) exp(r2 /2) ,
(r2 cos2 r2 sin2 2ir2 cos sin ) exp(r2 /2) ,
r2 ((cos2 sin2 ) 2i cos sin ) exp(r2 /2) ,
r2 (cos 2 i sin 2) exp(r2 /2) ,
r2 e2i exp(r2 /2) .
By comparing with the radial functions given in the Exercise, we then

conclude that
2,2 (r, ) 2 (x)0 (y) + 2i1 (x)1 (y) + 0 (x)2 (y) ,
2,2 (r, ) 2 (x)0 (y) 2i1 (x)1 (y) + 0 (x)2 (y) .

This shows that the allowed values of m for n = 2 are indeed 2, 0 and
+2. It can be verified
that these three wave functions are orthogonal, i.e.
R
that they satisfy d2 r = 0.
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Chapter 7
Free electrons
(7.1) The method for determining the electron Fermi energy was considered in
Exercise 5.10, and the formula for EF is given in eqn 5.13:
EF =
~2
(3 2 N )2/3 ,
2m
which implies:
3/2
1
2mEF
.
3 2
~2
On substituting this form of N into the formula for the plasma frequency
in eqn 7.6, we then obtain
4
92 ~2 ~p
EF3 = 0
.
8m
e
N=
(7.2) We expect 100% reflectivity below the plasma frequency and transmission
at higher frequencies. (See Fig. 7.1.) Hence we can set p /2 = 3 MHz
in this example. On substituting into eqn 7.6 and solving for N , we find
N 1011 m3 . (n.b. The electron density calculated here is just a typical
one. The value of N varies somewhat due to atmospheric conditions.)
(7.3) The formula for the skin depth is given in eqn 7.20. On inserting the
value of for salt water we find 0.5 m for /2 = 200 kHz. This
shows that electromagnetic waves of this frequency penetrate less than
1 m from the surface of the sea. To obtain a skin depth of 30 m as required
for communication with a submarine submerged at this depth, we require
/2 = 70 Hz. Even lower frequencies are required for deeper depths. The
data transmission rate is very low at these small carrier frequencies.
(7.4) From Table 7.1 we read N = 0.91 1028 m3 for cesium, while the transmission edge at 440 nm implies p = 440 nm, and hence:
p = 2c/p = 4.3 1015 rad/s .
On substituting into eqn 7.6 and solving for m, we find me = 1.4
1030 kg 1.6 m0 .
(7.5) This Exercise closely follows Example 7.3. We read p = 1.36 1016 rad/s
from Table 7.1, and work out = 4.0 1014 s from eqn 7.14 using the
value of N from Table 7.1 and the value of 0 given in the exercise. At
500 nm we have = 3.77 1015 rad/s, and the relative permittivity at
this wavelength is then given by eqns 7.1617 as:
r = 12.0 + 0.086i .
We finally use eqns 1.2526 to calculate n
= 0.012 + 3.5i, and substitute
n = 0.012 and = 3.5 into eqn 1.29 to obtain R = 99.6 %.
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(7.6) We first use eqn 7.14 to find = 1.2 1013 s, taking N = 5.9 1028 m3
from Table 7.1, and then proceed as in Example 7.3 to find the extinction
coefficient . With p = 1.37 1016 rad/s (cf. Table 7.1), and =
2c/ = 1.88 1015 rad/s, we find from eqns 7.1617 that r = 52.1 +
0.235i, and hence = 7.22 (see eqn 1.26). This value of implies, through
eqn 1.19, an absorption coefficient = 9.1 107 m1 . The transmission
is given by Beers law (see eqn 1.4) as exp(z) = 0.16 for z = 20 nm.
Note that the skin depth approximation in eqns 7.1820 is not valid here
because we have = 230 for = 1 m ( = 1.9 1015 rad/s), and
hence we do not satisfy 1. The absorption coefficient estimated
from eqn 7.19 is wrong by approximately one order of magnitude.
(7.7) Based on the plasma frequency of gold given in Table 7.1, we expect high
reflectivity above 140 nm. The low reflectivity up to 600 nm is caused by
interband transitions as illustrated schematically in Fig 7.4. The energy
gap between the d bands and the Fermi energy can be read from the
data as the energy equivalent of 520 nm, i.e. 2.4 eV. It is apparent
from the reflectivity spectrum that gold reflects red, orange and yellow
light stronger than green and blue. This accounts for its characteristic
yellowish colour.
(7.8) It is apparent from eqn 1.29 that R = 0 when n
= 1, and hence r = 1.
The relative permittivity of a doped semiconductor is given by eqn 7.22,
and light damping implies that we take = 0. Hence we shall have zero
reflectivity when: (see eqn 7.24 for p ):
!
p2
N e2
1 = opt
= opt 1 2 .
m 0 2
Equation 7.25 is then derived by solving this formula for 2 .

N (1024 m3 )
(R = 0) (m)
(R = 0) (1013 rad/s)
me /m0
0.35
0.62
1.2
2.8
4.0
33
27
22
16
14
5.7
7.0
8.6
12
13
0.020
0.028
0.036
0.044
0.048
Table 5: Effective masses of n-type InSb calculated from the data in Fig 7.7 as
required for Exercise 7.9.
(7.9) The easiest way to determine the effective mass from the spectra is to read
the wavelength at which R = 0 from the data. We then use eqns 7.2425
to write:
N e2
,
m =
0 (opt 1) 2
where is the angular frequency corresponding to R = 0. The values
of the effective masses found in this way with opt = 15.6 are given in
Table 5.
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It is apparent from Table 5 that me increases strongly with N , rising from

0.020 m0 at 3.5 1023 m3 to 0.048 m0 at 4 1024 m3 . This increase
in the effective mass with carrier density is caused by non-parabolicity in
the conduction band of InSb. The effective mass approximation assumes
that the bands are parabolic in shape as in Fig 3.5. However, a glance at
the band structure of a real III-V semiconductor (eg GaAs, see Fig 3.4)
indicates that this approximation only holds near k = 0. To get a good
fit to the energy bands for larger values of k (but still below the maxima),
we have to re-write eqn 3.17 as:
Ec (k) = Eg +
~2 k 2
,
2m (k)
where m (k) = me for small k, but then increases at larger values of k. As

we dope the semiconductor with more electrons, the Fermi energy increases
(see eqn 5.13) and we are probing states of the conduction band with larger
values of E and k. It is therefore to be expected that the effective mass
should increase with the doping density. The band non-parabolicity is
particularly strong in some narrow gap semiconductors such as InSb.
(7.10) The free carrier absorption coefficient in the limit 1 is given by
eqn 7.28. At 10 m we have = 1.9 1014 rad/s, and on inserting the
relevant values into eqn 7.28 we find = 1.0 ps. This implies 200,
so that the approximations used to derive eqn 7.28 are justified.
(7.11) The laser beam generates free carriers in the conduction and valence
bands which can then induce free carrier absorption. The carrier density
generated by a continuous laser beam is given by (see Exercise 5.6):
N=
I
,
~
where I is the intensity, is the absorption coefficient, is the carrier

lifetime, and ~ is the photon energy. On inserting the appropriate values
as given in the Exercise, we find N = 1.9 1022 m3 . This is the density
of electrons in the conduction band and holes in the valence band, both
of which cause free carrier absorption. At = 10.6 m we have =
1.8 1014 rad/s, and hence = 36 for the electrons and = 9 for
the holes. We thus have 1 in both cases, and we can therefore
calculate the free carrier absorption coefficients by using eqn 7.28. This
gives = 130 m1 for the electrons and = 70 m1 for the holes. Hence
the total free carrier absorption coefficient is 200 m1 .
Here are a few points to note about this exercise:
Students should be careful not to confuse the two different usages of
. In the calculation of the carrier density, represents the carrier
lifetime, whereas in eqn 7.28 it represents the momentum scattering
time.
Intervalence band absorption has been neglected here. However, with
only 1022 m3 holes, it is probable that intervalence band absorption will be insignificant. (See the next exercise.)
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This exercise is actually an example of a nonlinear optical effect: the

light beam at 633 nm induces changes in the optical properties. The
mechanism is that the beam creates carriers which then alter the
optical properties. These types of nonlinear effects are called free
carrier nonlinearities for obvious reasons. See Chapter 11 for more
information on nonlinear optics.
E
max,min
min
EF
max
min
max
lh
hh
kF
kF
Figure 26: Intervalence band transitions as required for the solution of Exercise
7.12. The Fermi energy is not drawn to scale: with the parameters given in the
Exercise, the Fermi energy is just above the split-off band. The labels (1), (2)
and (3) refer to the lhhh, SOlh, and SOhh transitions as in Fig. 7.9.
(7.12) (a) The holes are distributed between the heavy- and light-hole bands,
and so we can find the Fermi energy from (see eqn 3.16):
Z
N
EF
(ghh + glh ) dE
0
23/2
3/2
3/2
(m + mlh )
2 2 ~3 hh
EF
E 1/2 dE .
With mhh = 0.5 m0 and mlh = 0.08 m0 we then find EF = 0.032 eV for
N = 1 1025 m3 . Note that this is smaller than the spinorbit energy
and so our neglect of the occupancy of the split-off band is justified. The
wave vector at the Fermi energy is worked out from:
EF =
~2 kF2
.
2m
This give kFhh = 6.5 108 m1 and kFlh = 2.6 108 m1 for the heavy and
light holes respectively. (See Fig. 26.)
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(b) The energies of the three types of intervalence band transitions indicated in Fig. 7.9 can be calculated by using eqns 3.1820:
1
~2
1
k2 ,
(1) lh hh : ~ = |Elh (k) Ehh (k)| =
2 mlh
mhh
~2
1
1
(2) SO lh : ~ = |Eso (k) Elh (k)| = +
k2 ,
2 mso
mlh
1
~2
1

k2 ,
(3) SO hh : ~ = |Eso (k) Ehh (k)| = +
2 mso
mhh
where k is the wave vector at which the transition occurs. Transitions can
only take place from occupied states to empty ones. The upper and lower
limits of the transition energies are therefore set by the Fermi wave vectors
as indicated in Fig. 26. The energy limits calculated using the Fermi wave
vectors from part (a) are therefore as follows:
1. lhhh transitions: The lower and upper limits are set by kFlh and
kFhh respectively. On inserting the into (1) above, we find a transition
range of 0.03 0.17 eV.
2. SOlh transitions: Since the light hole effective mass is smaller than
the split-off mass, the lower and upper limits correspond to the transitions at kFlh and k = 0 respectively. On inserting into (2) above we
find a range 0.32 0.34 eV.
3. SOhh transitions: The lower limit is set by the transition at k = 0,
and the upper limit by the one at kFhh , giving a range of 0.34
0.42 eV.
(7.13) (a) The energies of the 2p0 , 3p0 and 4p0 transitions can be read from
Fig. 7.11 as 34.0, 40.1, and 42.4 meV respectively. These energies fit well
to the formula:
h = R 1 2 ,
n
with R = 45.2 meV. This is consistent with eqn 7.30 if we set me =
0.85 m0 for the donor levels.
(b) The energies of the 2p , 3p , 4p and 5p transitions can be read
from Fig. 7.11 as 39.2, 42.4, 43.3 and 44.1 meV respectively. The np
transitions correspond to transitions from np hydrogenic states to the 1s
state, with energies given by:
h = |E1s Enp | .
The 1s energy is just equal to the value of R found in the part (a), and
so we can identify R0 = R = 45.2 meV. The value of R

is then found
by fitting the transition energies. A good fit is found with R

25 meV.
(7.14) These are donor level transitions as shown in Fig. 7.10(a). Their transition energies are given by eqn 7.30. It is apparent that they depend only
on the effective mass and relative permittivity of the host crystal, and
not on any of the properties of the dopant atom. The reason why this is
so is that the donor levels are formed by the interaction between a band
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electron and an ionized impurity. The donor atoms are chosen so that
they have a single excess electron, and so they are all singly ionized. The
donor level energies are therefore hydrogenic with the relevant mass and
permittivity of the band electron.
On comparing with eqn 7.30, we see that we must have R = (me /m0 2r )
RH . On setting this equal to 2.1 meV we find me = 0.036 m0 for r = 15.2.
conduction band
Eg
acceptor
levels
valence band
Figure 27: Acceptor to conduction band transitions in a p-type semiconductor

as discussed in Exercise 7.15. Note that this figure is not drawn to scale: the
acceptor energies are much smaller than the band gap.
(7.15) Doping with acceptors creates a p-type semiconductor with a series of
acceptor levels just above the valence band as indicated in Fig. 27. The
energy of the acceptor levels relative to the top of the valence band will
be given by eqn 7.29 with me replaced by mh . Electrons from the valence
band can be thermally excited to fill the acceptor levels, giving rise to
the possibility of acceptor to conduction band transitions as indicated in
Fig. 27. These transitions occur at a photon energy of Eg EA . The absorption edge of a p-type semiconductor will therefore decrease on doping
from Eg to Eg EA , where EA is the energy of n = 1 acceptor level. A
wavelength shift from 5.26 m to 5.44 m corresponds to an energy shift
of 8 meV, and hence we deduce EA 8 meV.
This exercise is based on experimental data for zinc acceptors in InSb.
See Figure 2 in Impurity and Exciton Effects on the Infrared Absorption
Edges of III-V Compounds, E.J. Johnson H.Y. Fan, Phys. Rev. 139,
A1991A2001 (1965).
(7.16) The peak is caused by Raman scattering from plasmon modes, as shown
in Fig. 7.13. The energy of the scattered photons is given by eqn 7.49.
In this exercise, we are clearly considering the case of plasmon emission
where the sign is appropriate. We thus deduce:
~p = ~in ~out = (2.410 2.321) eV = 0.089 eV .
On substituting into eqn 7.24 with opt = n2 and the given value of m , we
find N = 4.2 1024 m3 . Note that we would also expect Raman signals
from optical phonons, but these would occur at smaller energy shifts with
300 cm1 37 meV. (See Fig. 10.11.)
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Name: Tapas Banerji
(7.17) We set
p =
N e2
opt 0 me
IP: 129.82.195.78
1/2
= LO ,
with opt = n2 and solve for N . A wave number of 297 cm1 implies
= 2c = 5.6 1013 rad/s, and hence we find N = 7.2 1023 m3 . A
mixed plasmonphonon mode is formed at this doping density because the
two longitudinal excitations couple strongly together if their frequencies
are the same.
(7.18) We first calculate p using eqn 7.6. With N = 1 1029 m3 , we find
p = 1.8 1016 rad/s. Next, we work out vF from:
EF =
1
mv 2 .
2 F
With EF = ~2 (3 2 N )2/3 /2m (cf. eqn 5.13), we then find:

vF =
~
(3 2 N )1/3 ,
m
which gives vF = 1.7 106 m/s.

A wave vector of 0.1/a has a magnitude of 7.9 108 m1 if a = 4
A. We
then have:
3 (1.7 106 )2 (7.9 108 )2

p 1 +
= 1.002 p .
10 (1.8 1016 )2
We thus see that the term in k 2 only makes a difference of 0.2%. It can
therefore safely be ignored in most circumstances.
(7.19) In an electron energy loss experiment on a metal, we expect to observe
peaks from both the surface and bulk plasmons. On inserting d = 1 into
eqn 7.61 as appropriate for
air, we expect the two plasmons to differ in
frequency by a factor of 2 = 1.41. The data fits this model quite well,
with the experimental ratio being 1.49. The 10.3 eV and 15.3 eV series
are thus the surface and bulk plasmons respectively. The bulk plasma
energy of 15.3 eV implies p /2 = 3.7 1015 Hz. It is then apparent from
Table 7.1 that the metal is aluminium.
This Exercise is based on the electron energy loss spectroscopy data shown
in Kittel (7th edition), Chapter 10, Figure 8.
(7.20) (a) At this point, we ignore the imaginary part of m , and put d = 1
and m = 18 into eqn 7.62. With /c = 2/, this gives:
kzd
2
600 109
kzm
2
600 109
12
18 + 1
1/2
(18)2
18 + 1
= 2.5 106 m1 ,
1/2
= 4.6 107 m1 .
Hence lzd = (kzd )1 = 394 nm and lzm = (kzm )1 = 22 nm.

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Name: Tapas Banerji
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(b) The propagation length in the x direction is determined by the imaginary part of kx and so in this part of the exercise we do have to include
the imaginary part of m . On substituting d = 1 and m = (18 + i) into
eqn 7.58 with /c = 2/, we find:
2
kx =
600 109
18 + i
17 + i
1/2
= 1.05 107 (1.03 + 1.7 103 i) m1 .
On writing the real and imaginary parts of kx as k 0 and k 00 respectively,

we then obtain k 00 = 1.8 104 m1 . The wave therefore propagates with:
E(x) = E 0 exp[ikx x] = E 0 exp[(i(k 0 + ik 00 )x] = E 0 exp(ik 0 x) exp(k 00 x) .
The intensity is proportional to EE , and therefore decays with x according
to I(x) = I0 exp (2k 00 x). The propagation distance is therefore given by
(2k 00 )1 = 28 m.
(7.21) Equation 7.63 shows that the resonance in the polarizability of a colloidal
metal nanoparticle occurs when m = 2d . On setting d = n2 for the
dielectric, and using the standard frequency dependence of m for a metal
(cf. eqn 7.7), we see that this resonance occurs when:
1
p2
= 2n2 .
2
On rearranging, this gives:

(1 + 2n2 ) 2 = p2 ,
and hence:
=
p
.
1 + 2n2
When the dielectric is air, we have n = 1, and hence = p / 3.

(7.22) (a) As shown in the discussion of eqn 7.63, the resonance occurs when
m = 2d . When m is complex, as is the case considered here, this
resonance condition is satisfied when the real part of m , namely 1 , is
equal to 2d . This is because d is real, and so the denominator of
eqn 7.63 is smallest when 1 + 2d = 0. For water we have d = n2 = 1.77,
and so we require 1 = 3.5. A linear fit to the data given in Table 7.3
indicates that this condition is satisfied at about 517 nm.
(b) The result derived in Exercise 7.21 predicts a resonance wavelength
given by:
p
2c
1 + 2n2
=
=
= 1 + 2n2 p ,
p /2
where p is the wavelength corresponding to p . On using the value of p
for gold given in Table 7.1, namely 138 nm, we predict = 294 nm, which
differs significantly from the correct value obtained in part (a).
The reason for the discrepancy is that the undamped Drude formula given
in eqn 7.7 is not a good approximation for gold in the optical frequency
range. For example, the Drude model would predict high reflectivity up to
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Name: Tapas Banerji
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the plasma wavelength of 138 nm, but this is not observed in experimental
reflectivity data. (See Fig. 7.20.) At optical frequencies the d-band transitions are very strong, and this modifies the relative permittivity very
significantly.
In fact the situation is more complicated. Equation 7.63 only applies
to spherical nanoparticles. Furthermore, it predicts that the resonance
frequency should be independent of the nanoparticle size, which is not
actually the case: see Maier (2007) for details. This becomes apparent
when attempting to fit the data in Fig. 7.17. With d = 2.5, we would
expect the resonance to occur when 1 = 5. Table 7.3 gives 1 = 5 at
538 nm for gold, but the peak actually occurs at 580 nm. This shows that a
more detailed model is required to get a good fit to the data. Equation 7.63
does, however, explain the basic phenomenon, and correctly explains the
red shift of the resonance with increasing d .
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Name: Tapas Banerji
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Chapter 8
Molecular materials
(8.1) This is a standard example covered in all elementary quantum mechanics
texts. On substituting 1 into the Schrodinger equation, we obtain:
~2 x2
1
1
1 + m2 x2 1 = E1 1 ,
4
2
2m a
a
2
which can be re-arranged to give:
~2
~2
1
2
2
m
x
+
1 = E1 1 .
1
2
2ma4
2ma2
1 is therefore a solution if we set a = (~/m)1/2 to eliminate the first
term. We can then deduce:
E1 =
~2
1
= ~ .
2ma2
2
By a similar method we can show that 2 and 3 are solutions with

E2 = (3/2)~ and E3 = (5/2)~ respectively, and with a again equal to
(~/m)1/2 .
(8.2) The energy levels for a particle of mass m in an infinite potential well of
width d are given by eqn 6.13 as:
En =
h2 n 2
.
8md2
Selection rules permit transitions with n equal to an odd number. (See

the discussion of intersubband transitions in Section 6.7.) The lowest
energy transition occurs for n = 1 2, with h = 3h2 /8md2 . On setting
m = m0 for the -electron, and h = 2.5 eV, we find d = 6.7 1010 m.
This corresponds to about six carboncarbon bonds.
Note that this model should not be taken too seriously, since it predicts
that the transition energy scales as d2 . The data in Fig. 8.11 show that
the actual scaling is much weaker, with E d0.4 .
(8.3) The ratio of the number of molecules with one vibrational quantum excited
compared to those with none is given by Boltzmanns law as exp(h/kB T ),
where is the frequency of the vibration. The calculated ratios for the
three modes at 300 K are:
= 2 1013 Hz: 4 102 ,
= 4 1013 Hz: 1.6 103 ,
= 7 1013 Hz: 1.4 105 .
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The point of this exercise is to make the student appreciate that it is a

good approximation to assume that all the molecules are in the vibrational
ground state at room temperature.
(8.4) The energy of isolated hydrogen atoms is given by the standard Rydberg
formula with En = RH /n2 . The energy required to promote one of the
atoms from a 1s to a 2p state is therefore (3/4)RH = 10.2 eV. This is
smaller than the equivalent transition in the H2 molecule. The reason is
that the energy of a diatomic molecule is given by:
E molecule = E atom1 + E atom2 E binding ,
where E atomi is the energy of the isolated atoms, and E binding is the
binding energy of the molecule. Now the ground state of the molecule
is more strongly bound than the excited state, and the transition includes
the difference of the two binding energies. Hence in the molecule the
transition energy is:
h = (3/4)RH + E binding .
We can then account for the molecular transition energy of 11.3 eV if we
assume that the difference of the binding energies of the 1s1s and 1s2p
molecular configurations is 1.1 eV.
1.0
0.8
0.6
U(r)
Name: Tapas Banerji
0.4
0.2
0.0
r
0.5
1.0
1.5
2.0
-0.2
Figure 28: LennardJones potential for A = B = 1, as considered in Exercise

8.5.
(8.5) (a) The attractive r6 term is caused by the van der Waals interaction,
which is the main attractive force between neutral molecules. This is a
dipole-dipole interaction. A fluctuating dipole p1 on molecule 1 generates
an electric field of strength E 1 p1 /r3 at molecule 2. This induces a
dipole of magnitude p2 E 1 p1 /r3 on molecule 2, which then generates
a field E 2 p2 /r3 p1 /r6 at molecule 1. The interaction energy is then
p1 E 2 (p1 )2 /r6 . Although the time average of p1 will be zero, the time
average of (p1 )2 is not. Hence the dipole-dipole mechanism generates an
attractive potential r6 .
(b) The Lennard-Jones potential is plotted for the case A = B = 1 in
Fig. 28. The potential is attractive at large r, but the repulsive term
dominates for small r. This gives a minimum at a well-defined value of r,
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Name: Tapas Banerji
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which we call r0 . The position of the minimum energy can be calculated

by setting:
dU
12A 6B
= 13 + 7 = 0 ,
dr
r
r
at r = r0 , which implies r0 = (2A/B)1/6 .
(c) The Taylor expansion for U (r) near r0 is:
dU
1 d2 U
U (r) = U (r0 ) +
(r r0 ) +
(r r0 )2 + ,
dr
2 dr2
where the derivatives are evaluated at r = r0 . If r0 is the position of the
minimum, then the first derivative will be zero, and U(r) reduces to:
1 d2 U
U (r) = U (r0 ) +
(r r0 )2 + .
2 dr2
Now
d2 U
156A 42B
= + 14 8 ,
2
dr
r
r
which, with r = r0 = (2A/B)1/6 , gives:

18B 2
d2 U
=
2
dr
A
B
2A
1/3
.
Thus:
U (r) =
1/3
18B 2 B
(r r0 )2 + ,
A
2A
1
U (r0 ) + 2 (r r0 )2 .
2
U (r0 ) +
Hence 2 = (18B 2 /A)(B/2A)1/3 .

(8.6) (a) This result follows directly from the FranckCondon principle. We
are at T = 0 and so the initial state of the system will be the lowest
vibrational level of the lower state, i.e. the n = 0 vibrational level of the
electronic ground state. The initial wave function is therefore 0 (Q Q0 ).
Transitions are possible to any of the vibrational levels of the excited state,
as shown in Fig. 8.7. The energy of the transition to the nth level is given
by eqn 8.3 and can be written:
~n = ~0 + n~ .
We are at T = 0 and thus expect negligible broadening of the transitions.
The probability for the transition is given by the FranckCondon factor
(eqn 8.12), which in this case takes the form:
Z
P (n, 0) =
n (Q
Q00 )
0 (Q Q0 ) dQ |hn, Q00 |0, Q0 i|2 .
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IP: 129.82.195.78
The spectrum will therefore be given by a series of sharp transitions to

each vibrational level, with their relative weight given by P (n, 0). This is
conveniently expressed in Dirac delta function notation as:
I(~)
n=0
P (n, 0)(~ ~n )
|hn, Q00 |0, Q0 i|2 (~ ~0 n~) .
n=0
as required.
S=0
Intenmsity (arb units)
Name: Tapas Banerji
S=1
S=5
2 4 6 8 10 12 14
(hw - hw0) in units of hW
Figure 29: Vibronic spectra, as considered in Exercise 8.6.

(b) We substitute for the FranckCondon factor to obtain:
I(~)
X
exp(S)S n
(~ ~0 n~) .
n!
n=0
This defines a Poisson distribution. The spectra are shown in Fig.29.

(i) If S = 0, then the only non-zero term is the one with n = 0. The
spectrum therefore just consists of the zero-phonon line at ~0 .
(ii) When S = 1, the strongest two transitions are the ones with n = 0
and n = 1. The intensity drops sharply with increasing n.
(iii) We now have a bell-shaped distribution peaked
at n = 5. The half
width of the distribution is given approximately by 2 5 5. In the limit
of large S, the spectrum is Gaussian.
More details about how the HuangRhys factor determines the vibronic
line shape may be found, for example, in Henderson & Imbusch, Optical
spectroscopy of inorganic solids (Oxford, 1989) or Hayes & Stoneham,
Defects and defect processes in nonmetallic solids (Wiley, 1985).
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Transition energy (eV)
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5.4
5.2
5.0
4.8
4.6
0
Quantum number n
Figure 30: Analysis of transition energies of benzene as considered in Exercise
8.7.
(8.7) The absorption spectrum will consist of a series of vibronic lines with
energies given by eqn 8.3. The longest wavelength will correspond to
the transition with n = 0, and the others to increasing values of n. The
transition energies are plotted against this assignment of n in Fig. 30. The
good linear fit confirms the assignment. The fitting parameters that come
out of the analysis are ~0 = 4.65 eV and ~2 = 0.113 eV. On making the
reasonable assumption that ~|2 1 | (E2 E1 ), we then deduce from
eqn 8.4 that E2 = E1 +4.65 eV. We thus identify the energy of the S1 state
relative to the S0 ground state as 4.65 eV, and find /2 = 2.7 1013 Hz.
E
0.13 eV
S2
0.11 eV
n=6
S1
7.3 eV
n=5
5.7 eV
Name: Tapas Banerji
S0
Q0
Figure 31: Configuration diagram for ammonia deduced from the data of Fig. 8.9
as considered in Exercise 8.8.
(8.8) The absorption spectrum shows a progression of vibronic lines obeying
eqn 8.3 with at least two excited electronic states. The first progression
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Name: Tapas Banerji
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starts at 5.7 eV, and has a vibrational splitting of 0.11 eV. The intensity
of the lines peaks for n = 6. The second progression starts at 7.3 eV, has
a vibrational splitting of 0.13 eV, and has maximum intensity for n = 5.
We thus deduce that we have two excited states:
S1 at energy 5.7 eV with ~ = 0.11 eV,
S2 at energy 7.3 eV with ~ = 0.13 eV.
The line with the maximum intensity tells us about the relative values of
Q0 for the states. The intensity peaks when the overlap of the vibronic
states is largest. The wave function of the ground state S0 peaks at Q0 ,
while for the excited states the wave function gradually peaks more and
more at the classical turning points. The potential minima of S1 and S2
therefore occur so that the edge of their sixth and fifth vibronic levels align
respectively with Q0 for S0 . We thus obtain the schematic configuration
diagram given in Fig. 31.
(8.9) The spinorbit interaction introduces a coupling mechanism between the
spin and orbital angular momenta S and L. It is therefore possible to have
an interaction between different S states via their spinorbit interaction
with a common L state. This interaction produces a small mixing of the
wave functions, so that triplet states contain a small admixture of singlet
character. This small singlet admixture gives a finite probability for a
triplet-to-singlet transition, which would otherwise be totally forbidden if
the spin states were pure.
Spin-orbit coupling is now routinely used to increase the intensity of phosphorescence in organic LEDs. A heavy metal (eg platinum) is introduced
into the molecule, and this increases the spinorbit interaction, because the
spinorbit coupling generally scales as Z 2 , where Z is the atomic number.
The use of heavy-metal dopants strongly enhances the triplet-to-singlet
transition rate, and hence the overall light emission efficiency. This is
especially important in electrically-pumped devices, which are otherwise
limited to a maximum efficiency of 25%. (See Exercises 8.16 and 8.17.)
(8.10) The weak nature of the emission and the long radiative lifetime indicates
that we are dealing with phosphorescence from a triplet state. The energy
level scheme for pyrromethene 567 would be qualitatively similar to that
for anthracene shown in Fig. 8.12(b). From the spectra shown in Fig. 8.10
we deduce that the S1 level has an energy of 2.3 eV, while the wavelength
of the phosphorescence indicates that the triplet lies at an energy of 1.6 eV.
In the case of optical excitation, the phosphorescence could be caused by
intersystem crossing from excited singlet states.
(8.11) The assignment of the vibronic peaks of the solution is given in Fig. 8.13.
The energies of the vibronic peaks are plotted in Fig. 32 and a good
straight line is obtained. The linear fit according to eqn 8.3 gives the
vibrational energy as 0.16 eV.
In the case of the crystal, we have first to identify the various peaks in the
absorption spectrum. A strong vibronic progression with energies of 3.13,
3.30, 3.46 and 3.61 eV is observed in the data. These can be identified as
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4.4
solution
Energy (eV)
Name: Tapas Banerji
crystal
4.0
3.6
3.2
0
2
4
Vibronic number
Figure 32: Analysis of the vibronic peaks of anthracene shown in Fig. 8.13 as
considered in Exercise 8.11.
the 00, 01, 02, and 03 transitions, and a linear fit according to eqn 8.3
gives the vibrational energy as 0.18 eV. (See Fig. 32.)
Two other features can also be identified in the absorption spectrum of
the crystal at 3.18 and 3.35 eV. These have the same splitting as the other
progression and therefore involve similar types of vibrations. The most
probable cause is a splitting of the electronic states in the crystal due to
its lower symmetry, eg by the Davydov effect. (See Pope and Swenberg,
Electronic processes in organic crystals and polymers, 2nd edn, Oxford
University Press, 1999, Section I.D.5, pp 5966.)
(8.12) When the mirror symmetry rule works, we expect the emission spectrum
to be a mirror image of the absorption spectrum about the 00 transition.
(See, for example, Figs 8.10 or 8.17.) We thus expect a broad vibronic
band extending downwards from the 0-0 transition at 3.13 eV. The width
of the band will be about 1 eV. A series of vibronic peaks will occur with
energies given by h (3.13 n~), with ~ 0.18 eV. We would thus
expect peaks at 3.13, 2.95, 2.77, 2.59 eV .
(8.13) The S1 absorption band has a 00 transition at 1.9 eV and extends to
2.8 eV. The emission band would thus have a 00 transition at 1.9 eV
and extend down to about 1.0 eV. The 01 vibronic peaks occurs at 2.1 eV
in the absorption spectrum, which implies a vibrational energy of 0.2 eV,
and hence a 01 transition in emission at around 1.7 eV.
(8.14) As discussed for the PDA data in Fig. 8.16, the difference between the
absorption and photoconductivity edges is caused by excitonic effects. The
absorption edge corresponds to the creation of tightly-bound (Frenkel)
excitons. Since excitons are neutral particles, they do not contribute to
the photoconductivity. The photoconductivity edge therefore corresponds
to the band edge where free electrons and holes are first created. The
difference in the two edges gives the exciton binding energy, which works
out to be 1.1 eV.
It is important to realize that this is a different situation to that encountered for weakly-bound (Wannier) excitons. Weakly-bound excitons can
87
Name: Tapas Banerji
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be easily ionized to produce free electrons and holes, and hence produce
a photocurrent. (See, for example, Figs 4.5 and 6.15.)
(8.15) The dominant vibrational frequency can be deduced by analysing the vibronic progression of either the absorption or emission spectra in Fig. 8.17
according to eqns 8.3 or 8.5 as appropriate. This gives ~ 0.17 eV, implying 2.6 1014 rad/s. With = 2.98 1015 rad/s, we then find
Raman = ( ) = 2.72 1015 rad/s, which is equivalent to a wavelength
of 693 nm.
Two points could be made here:
The molecule will have other vibrational modes, and these will give
additional Raman lines.
Not all vibrational modes are Raman-active, (see Section 10.5.2) and
it is not immediately obvious that the 0.17 eV mode responsible for
the vibronic spectra will show up in the Raman spectrum. In fact,
these modes are observed in the experimental Raman spectra, but it
requires a careful analysis by group theory to prove that this is so.
(8.16) Optical excitation creates only singlets because the ground state is a
singlet and optical transitions do not change the spin. With only singlet
states excited, the recombination of the electrons and holes is optically
allowed for all the carriers.
Wave function
e h
(e h + e h )/2
(e h e h )/ 2
e h
Sz
+1
0
0
1
S
1
1
0
1
State
triplet
triplet
singlet
triplet
Table 6: Possible arrangements of relative electron-hole spins as discussed in

Exercise 8.16.
On the other hand, with electrical injection there is no control of the
relative spin of the electrons and holes. The spins can be either parallel or
anti-parallel, and this gives rise to four possible total spin wave functions,
as indicated in Table 6. Three of these are triplets and only one is a
singlet state. The relative number of triplet and singlet excitons created
by electrical injection is therefore in the ratio 3:1, which implies that only
25% of the excitons are in singlet states. The remaining 75% are in triplet
states with very low emission probabilities. Hence the emission is expected
to be weaker than that for optical excitation by a factor of four.
The creation of triplets in electrically-driven organic LEDs is a serious
issue that limits their efficiency. One way to enhance the efficiency is
to increase the spinorbit interaction to encourage inter-system crossing.
This is typically done by including a heavy metal atom in the molecule.
(See Exercise 8.9.)
(8.17) (a) As we have seen in Exercise 8.16, we expect that 75% of the excitons
created will be in triplet states with very low emission probabilities. Hence
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Name: Tapas Banerji
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the maximum quantum efficiency that we can expect corresponds to the

number of singlet excitons that we create, namely 25%.
(b) The number of electrons and holes flowing into a device carrying a
current i is equal to i/e. The quantum efficiency is defined as the ratio of
photons out to electrons in, and so the number of photons emitted will be
equal to i/e. The power emitted is then equal to h i/e, and we have:
P = 2.25 eV 25% 10 mA/e = 5.6 mW .
(c) The electrical power consumed by the device is equal to iV = 50 mW.
The power conversion efficiency is thus equal to 5.6/50 = 11 %. The
efficiency of a real device would be much lower, mainly due to the difficulty
of collecting the photons, which are emitted in all directions (ie over 4
solid angle). Only a small fraction of these would be collected by the
optics. This latter point is exacerbated by the high refractive index of the
molecular material, which tends to limit the effective collection efficiency
even further. (See Exercise 5.13.)
a
30
q
n1 a
a1
n 2a 2
60
a2
(a)
n2 |a2| sin 60
(b)
n2 |a2| cos 60
Figure 33: (a) Analysis of the lattice vectors of graphene, as considered in in

Exercise 8.18(a). (b) Evaluation of the chiral angle , as required in Exercise 8.18(c).
(8.18) (a) The unit cell of graphene and its lattice vectors are shown in Fig. 33(a).
From inspection of this figure, we see that:
|a1 | = 2 a cos 30 = 2a 3/2 = 3a ,

where a is the length of the hexagon edge. The result for |a2 | is identical
by symmetry.
(b) We first find the length of the chiral vector c defined in eqn 8.14 by
evaluating its scalar product:
c2 c c = (n1 a1 + n2 a2 ) (n1 a1 + n2 a2 ) ,
= n21 a1 a1 + 2n1 n2 a1 a2 + n22 a2 a2 .
Now a1 a1 = a2 a2 = a20 and a1 a2 = |a1 | |a2 | cos 60 = a20 /2. Hence
c2 = a20 (n21 + n1 n2 + n22 ) .
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Since c is the circumference, the tube diameter d is then given by:

q
c
a0
d= =
n21 + n1 n2 + n22 ,
as required.
(c) The chiral angle for a nanotube with the chiral vector defined in
eqn 8.14 can be evaluated by reference to Fig. 33(b). It is apparent that:
tan =
n2 |a2 | sin 60
.
n1 |a1 | + n2 |a2 | cos 60
On noting that |a1 | = |a2 |, this simplifies to:
n2 sin 60
3n2 /2
3n2
tan =
=
=
.
n1 + n2 cos 60
n1 + n2 /2
2n1 + n2
Equation 8.16 follows immediately.
(8.19) (a) Symmetry requires that the electron wave function should be singlevalued on rotating the tube by 2. The phase change of the electron wave
function for a rotation through 2 is given by:
= k |c| k c
where k is the component of the wave vector in the direction perpendicular to the tube axis and c is the chiral vector. This must be equal
to an integer multiple of 2 in order that the electron wave function is
single-valued. Hence we require:
k c = 2m ,
where m is an integer.
(b) The tube will be metallic if the k vector corresponding to the K point
of the Brillouin zone is one of the allowed wave vectors of the nanotube.
This will be the case if the condition derived in part (a) is satisfied when
k corresponds to the K point, that is if:
K c = 2m ,
where K = (k1 k2 )/3. Now the reciprocal lattice vectors are defined
by:
a1 k1 = a2 k2
= 2 ,
a2 k1 = a1 k2
= 0.
Hence
K c = (k1 k2 ) (n1 a1 + n2 a2 )/3 = (2n1 2n2 )/3 ,
and therefore
2(n1 n2 )/3 = 2m ,
which implies n1 n2 = 3m.
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(8.20) We treat the nanotube as a 1D quantum wire of length L with its axis
along the z direction, and apply periodic boundary conditions so that
(x, y, z) = (x, y, z + L) .
The electrons are assumed to have free motion along the z axis and so
their wave function is of the form:
(x, y, z) = (x, y) exp ikz .
The periodic boundary condition requires that:
exp ik(z + L) = exp ikz .
This means that exp ikL = 1, and hence that k = 2m/L, where m is an
integer. The density of states in k space is therefore L/2. We can thus
write the density of states per unit length in k space as
g(k) = 1/2 .
The density of states per unit length in energy space is worked out from:
g(E) = 2
2g(k)
.
dE/dk
The additional factor of two here compared to eqn 3.14 comes from the
fact that the +k and k velocity states are degenerate. We assume that
we have a free electron moving in a band with energy En associated with
the quantized motion in the (x, y) directions. The total energy is then
given by:
~2 k 2
E(k) = En +
,
2m
so that
2 1/2
dE
~2 k
2~
= =
(E En )1/2 .
dk
m
m
The density of states is thus given by:
g(E) = 4
1
2
1/2
m
2~2
(E En )1/2 =
2m
(E En )1/2 ,
~
as required for eqn 8.20.

(8.21) The radiative quantum efficiency is given by eqn 5.5. The decay route
via intersystem crossing to the T1 level is non-radiative, and so we can
take NR = 1.2 ns. The radiative lifetime R is given as 1.8 s. Hence:
R =
1
1
=
= 6.7 104 .
1 + R /NR
1 + (1.8 106 /1.2 109 )
The radiative quantum efficiency is therefore only 0.07%.
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Chapter 9
Luminescence centres
(9.1) The solution for a one-dimensional potential well with infinite barriers
is given in Section 6.3.2. In a cube the motion is quantized in all three
dimensions, and the energies for the x, y and z directions just add together.
For each direction, we have (cf eqn 6.13):
E=
~2 2
n2
2m (2a)2
where n is the quantum number. The quantum numbers for the three
degrees of freedom are independent of each other, and we derive eqn 9.4
by adding the quantized energies for the x, y and z directions together.
Note that the similar case of a quantum dot was considered previously in
Section 6.8.1. See especially eqn 6.54.
(9.2) Equation 9.5 predicts E = 0.28/a2 . The experimental energies are lower
because a real F-centre is not a rigid cubic box, and hence it would be
more appropriate to use a finite rather than infinite potential well model.
As discussed in Section 6.3.3, the quantization energies of finite potential
wells are smaller than those of infinite wells of the same dimension.
(9.3) We can set a = 0.33 nm and calculate h = 2.6 eV from eqn 9.5. Alternatively, we can just read h 2 eV from Fig. 9.4.
2a
b
2a
b
+ F2+ + - + - +
+ - + - + - + - + - + - + - +
2b
(a)
(b)
Figure 34: (a) An F+

2 centre in an alkali halide with cell size 2a, as considered
in Exercise 9.4. The colour centre is modelled as a rectangular box with square
cross-section as shown in part (b).
(9.4) The energy of the electron will be given by eqn 6.54 with dx = dy = b and
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dz = 2b. We therefore have:

~2 2
E=
2m0
n2y
n2x
n2z
+
+
b2
b2
4b2
!
.
We can apply this model to the F+

2 centre by taking the appropriate value
of b. The rectangle equivalent to the F+
2 centre is sketched in Fig. 34. If
the
cubic unit cell size is 2a, then the
square
end
of
the
box
has
dimension
2a,
and the longer dimension is 2 2a. We therefore need to take b = 2a for
an F+
2 transition,
2 centre. The lowest energy transition is the nz = 1
which has an energy of h = 3h2 /32m0 b2 . With b = 2a, this gives
h = 3h2 /64m0 a2 , which is half the value given in eqn 9.5.
The experimental absorption peak of KF:F+
2 occurs at 1.1 eV (see Fig. 9.5),
while that of KF:F occurs at 2.9 eV (see Fig. 9.4.) The experimental ratio is thus 0.4, which is close to the predicted value of 0.5. This is
remarkably good agreement considering the simplicity of the model.
(9.5) (a) By applying Boltzmanns law to the two levels, we see that the occupancy of the MS = 1 upper level relative to the MS = 0 lower level is
given by:
N2
g2
E
=
exp
,
N1
g1
kB T
where g2 and g1 are the level degeneracies (i.e. g2 = 2, g1 = 1), and E/h
is given in Fig 7.9(a) as 2.9 GHz. We thus find N2 /N1 = 1.87 for T = 2 K,
which means that 1/2.87 = 35% of the centres are in the MS = 0 level,
and 65% of them are in the MS = 1 level.
(b) We require N1 /(N1 + N2 ) = 80%, which implies N2 /N1 = 0.25. We
thus solve:
N2
g2
E
=
exp
= 0.25 ,
N1
g1
kB T
for T . This gives T = 0.07 K.
(9.6) The emission spectrum shows four clear peaks within the vibronic band:
the zero-phonon line at 638 nm, and three phonon sidebands at 660, 685,
and 708 nm. These are assigned to multiple-phonon emission processes.
A fit of these energies to eqn 9.2 is shown in Fig. 35. The phonon energy
is 0.064 eV.
(9.7) (a) For the 3d electron we have n = 3 and l = 2, which implies hri3d =
(21/2)aH /Z, while for the 4f electron we have n = 4 and l = 3 and hence
hri4f = 18 aH /Z. We thus find:
7 Z4f
hri3d
=
.
hri4f
12 Z3d
As a crude estimate we use average values for the atomic numbers of the
relevant series: i.e. we take Z = 25 for the transition metals, and Z = 64
for the rare earths. This implies
7
64
hri3d
1.5 .
hri4f
12 25
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E = 1.941 - 0.0636 n
1.95
1.90
1.85
1.80
1.75
0
1
2
Sideband number n
Figure 35: Fit to the phonon sidebands in Fig. 9.7(b) using eqn 9.2, as required
for Exercise 9.6.
This shows that the 3d series is expected to have a larger radius by a
factor of 1.5.
It is instructive to compare the radial probability densities (i.e. r2 |R(r)|2 )
derived from the radial wave functions:
2
r
Z 7/2 4
Zr
R3d (r) =
exp
,
3/2
3aH
aH 81 30 aH
3
Z 9/2
1
r
Zr
R4f (r) =
exp
.
3/2
4aH
768 35 aH
a
H
Figure 36 compares r2 R(r)2 for a 3d wave function with Z = 25 with that

for a 4f wave function with Z = 64. It is apparent that the 3d orbital has
the larger average radius.
Radial probability density (a.u.)
Name: Tapas Banerji
4f (Z = 64)
4
3
3d (Z = 25)
2
1
0
0.0
0.2
0.4
0.6
0.8
1.0
1.2
r / aH
Figure 36: Radial probability densities for the 3d orbitals of a transition-metal
ion and the 4f orbitals of a rare-earth ion, as considered in Exercise 9.7.
It should be stressed that these arguments are not totally convincing because they take no account of the screening effect of the inner shells, which
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will reduce the effective value of Z experienced by the electron. However,

the more accurate calculations of the wave functions do confirm the general trends predicted by this argument.
(b) The 3d transition metal ions have lost the 4s electrons, and so the 3d
electrons are the outermost orbitals. By contrast, the 4f orbitals in the
rare earths are inside the filled 5s and 5p orbitals. The 5s and 5p orbitals
have n = 5 and l = 0 & 1 respectively. They therefore have larger radii
than the 4f shell on account of the fact that hri is proportional to n2 and
decreases with l.
smaller
distance
x
z
x, y
y
x, y
x
(a)
(b)
(c)
(d)
Figure 37: Discussion of p orbitals as required for Exercise 9.8. (a) A pz orbital.
(b) pz , px and py orbitals in an octahedral lattice, as seen in the x-z and x-y
planes. (c) pz , px and py orbitals in a uniaxially-distorted lattice, as seen in the
x-z and x-y planes. (d) Splitting of the p orbitals in the distorted lattice, with
negative nearest neighbours.
(9.8) (a) The three p orbitals are dumb-bell shaped as shown in Fig. 37(a) for
the case of the pz orbital. In an octahedral lattice, the x, y and z directions
are all equivalent. This implies that the px , py and pz orbitals must all
experience the same interaction with the crystal. This is apparent from
Fig. 37(b), which shows that the distance from the electron cloud to the
ions is the same for the pz , px and py orbitals. Hence they will experience
identical Coulomb interactions.
(b) In a uniaxial crystal, the octahedral symmetry is lost and the z direction is now different. This means that the pz orbitals are closer to the ions
than the px or py orbitals. (See Fig. 37(c).) The Coulomb interactions
between the electron cloud will now be different for the pz orbital and the
other two, and so its energy will be different. On the other hand, the x
and y directions remain equivalent (see lower half of Fig. 37(c)), and so
the px and py orbitals are still degenerate. Hence the triplet p state splits
into a singlet and a doublet.
(c) If the nearest neighbour ions are negative, the pz electrons will experience a stronger repulsive interaction with the lattice because of the
smaller distance to the ion. Hence the pz states will have a larger energy
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than the px and py states. This will give a splitting as shown in Fig. 37(d),
with the singlet at higher energy.
(9.9) (a) We write the potential in the form:
V (r, , ) =
6
+ f (r)[f1 () + f2 ()(e+i4 + ei4 )] ,
a
and evaluate the matrix element from:

ZZZ
hm|V |m0 i =
m
V m0 r2 sin dr d d .
It is immediately obvious that the constant term 6/a can only give nonzero terms if m0 = m by wave function orthogonality. Consider the integral
over for the remaining terms. This is of the form:
Z 2
0
I=
eim [f1 () + f2 ()(e+i4 + ei4 )] eim d .
0
Now it is apparent that

Z 2
00
0
eim eim eim d = 2m,(m0 +m00 ) ,
0
where i,j is the Kronecker delta function. Hence the only non-zero matrix
elements are those with m0 = m, m0 = m 4 or m0 = m + 4.
P2
(b) A general state of the system may be written as =
i=2 ci |ii,
which may be expressed as the column vector:
c2
c1
=
c0 .
c1
c2
In this basis, and with the notation introduced in the Exercise, the crystalfield Hamiltonian matrix takes the form:
A 0 0 0 D
0 B 0 0 0
Hcf =
0 0 C 0 0 .
0 0 0 B 0
D 0 0 0 A
The eigenenergies and states are found by diagonalizing the Hamiltonian.
It is apparent that the central part of the matrix is already diagonal, and
so immediately we find three eigenstates, namely:
| 1i with energy B,
|0i with energy C,
| + 1i, also with energy B.
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The states | 2i and | + 2i separate into a submatrix, with:
A D
c2
c2
=
.
D A
c2
c2
The solutions are: c2 = c2 , = A D. We thus find the final two
eigenstates, namely:
(|2i + | 2i)/ 2 with energy A + D,
(|2i | 2i)/ 2 with energy A D.

(c) The explicit calculation of the matrix elements A, B, C and D, and
hence the demonstration that A + D = C and A D = B, may be found
in Henderson & Imbusch (1989), 2.6.
If A+D = C, then the eigenstates |0i and (|2i+|2i)/ 2 are degenerate,
and if A D = B, then the eigenstates | 1i, | + 1i and (|2i | 2i)/ 2

are degenerate.
We thus identify the two d states with the |0i and (|2i +
| 2i)/ 2 states, or a linear combination of them. Similarly, we identify
the three d states with the eigenstates | 1i, | + 1i and (|2i | 2i)/ 2,
or a linear combination of them.
It is simplest to see the connection between these states and those given
in the Exercise by working backwards from the Cartesian versions, and
relating them to the spherical harmonic functions given in part (a) of the
exercise.
2z 2 x2 y 2
= 2r2 cos2 r2 sin2 cos2 r2 sin2 sin2 ,

= r2 (2 cos2 sin2 [cos2 + sin2 ]) ,
= r2 (2 cos2 sin2 ) ,
= r2 (3 cos2 1) ,
C2,0 (, ) ,
|0i ;
x2 y 2
=
=
=
=
r2 sin2 cos2 r2 sin2 sin2 ,

r2 sin2 (cos2 sin2 ) ,
r2 sin2 cos 2 ,
r2 sin2 (ei2 + ei2 )/2 ,
(C2,2 + C2,2 ) ,
(|2i + | 2i)/ 2 .
We thus identify the wave functions 2z 2 x2 y 2 and x2 y 2 with the

two d states.
Similarly:
xy
= r2 sin2 cos sin ,

= r2 sin2 sin 2/2 ,
= r2 sin2 (ei2 ei2 )/4i ,
(C2,2 C2,2 ) ,
(|2i | 2i)/ 2 ;
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yz
= r2 sin sin cos ,

= r2 cos sin (ei ei )/2i ,
(C2,1 C2,1 ) ,
(|1i | 1i)/ 2 ;
zx
= r2 cos sin cos ,

= r2 cos sin (ei + ei )/2 ,
(C2,1 + C2,1 ) ,
(|1i + | 1i)/ 2 .
We thus identify the wave functions xy, yz and zx with the three d states.
(a)
(b)
(c)
q = -Ze
d xy
d x2 - y 2
d z2
Figure 38: Probability densities for the d and d states, as considered in Exercise 9.9(d): (a) dxy , (b) dx2 y2 , and (c) dz2 . The circles on the axes represent
the anions, which have charge Ze. The probability densities for the dyz and
dzx states are obtained by exchanging the axis labels.
(d) The probability densities for the d and d states are plotted in Fig. 38.
The d state with wave function 2z 2 x2 y 2 is labelled dz2 . The dxy ,
dyz and dzx states have zero probability along the axes, and have high
probability between the axes. On the other hand, the dx2 y2 and dz2
states have high probability densities along the axes, but not along the
diagonal directions.
For a d1 configuration the ion has a single d electron. In the d states
the electron probability density is high along the crystalline axes, and so
the electron experiences a strong repulsion from the negatively-charged
anions. The d states, by contrast, have a smaller probability density
close to the anions and thus experience a smaller repulsion. The two d
states therefore have the higher energy, and hence the doublet lies above
the triplet.
The argument is reversed for a d9 configuration, which can be considered
as a single hole in the filled d shell. The charge cloud is now positive rather
than negative, and the two d states experience a stronger attraction
rather than repulsion. They therefore have the lower energy.
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(9.10) The 1064 nm line in a Nd:YAG crystal corresponds to a transition from

the 11 502 cm1 level as shown in Fig. 9.9(b). The relative populations of
the 11 502 cm1 and 11 414 cm1 levels of the 4 F3/2 term are proportional
to the Boltzmann factor:
N (11502 cm1 )
E
= exp
,
N (11414 cm1 )
kB T
where E = 88 cm1 . This ratio equals 0.19 at 77 K and 0.66 at 300 K.
The spontaneous emission rate increases in proportion to these factors,
and therefore the relative intensity of the 1064 nm line increases with T .
(9.11) The transition rates between the two levels are governed by the Einstein
coefficients, the populations of the levels, and the light energy density.
(See Section B.1 in Appendix B.) Three types of transitions are possible,
namely spontaneous emission, stimulated emission, and absorption. For
gain, we need that the stimulated emission rate should exceed the absorption rate. (Spontaneous emission is negligible at high light intensities.)
The condition for this to occur is (see eqns B.5 and B.6):
B21 N2 u() > B12 N1 u() ,
which implies:
N2
B12
>
.
N1
B21
On substituting from eqn B.10, we derive the condition for net gain:
N2
g2
>
,
N1
g1
where g2 and g1 are the degeneracies of the two levels. This condition is
called population inversion.
(9.12) (a) When the pump is turned off, all of the atoms will be in the ground
state, so that:
N0
N2
= N,
= 0,
where N is the total number of atoms. When the pump is turned on, N
atoms will be pumped to the upper laser level via level 1, so that:
N0
N N .
N2
= N .
For population inversion, we require N2 > N0 , which implies N > (N

N ), i.e. N > N/2. Population inversion is therefore only achieved
when more than 50% of the atoms are pumped to the excited state.
(b) In this particular example, we have N2 = 0.6N at t = 0, and we
have seen in part (a) that the laser will stop oscillating when N2 = 0.5N .
The sequence of events is therefore as shown in Fig. 39. The number of
atoms that make stimulated radiative transitions (and hence the number
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of photons emitted) during the laser pulse is therefore 0.1N . This gives a
pulse energy of 0.1N h, where h is the laser photon energy, namely
1.79 eV. On inserting the appropriate numbers we find:
Epulse = 0.1 (1025 106 ) 1.79 eV = 0.3 J .
60%
50%
2
laser pulse
emitted
40%
50%
0
t=0
after pulse
Figure 39: Sequence of events for the ruby laser considered in Exercise 9.12(b).
(9.13) (a) The optical intensity I(t) is proportional to |E(t)|2 , and hence if we
have a Gaussian pulse as defined in the exercise, we have a time-varying
electric field of the form (note the extra factor of two):
E(t) = E 0 exp(t2 /2 2 ) ei0 t ,
where 0 is the centre angular frequency. The spectrum of the pulse is
found by first taking the Fourier transform of E(t):
Z +
1
E() =
E(t) eit dt ,
2
Z +
E0
exp(t2 /2 2 ) ei(0 )t dt ,
=
2
= E 0 exp[ 2 ( 0 )2 /2] ,
where we used the standard integral:
Z +
F () =
exp(t2 / 2 )eit dt = exp( 2 2 /4) ,
in the last line. The final result is obtained by using:

I() |E()|2 exp[ 2 ( 0 )2 ] .
(b) The full width at half maximum (FWHM) of the pulse in the time
domain is found by finding the times for which I(t) = I0 /2, i.e. by solving:
exp(t2 / 2 ) = 0.5 .
This gives t = ln 2 , so that t = 2 ln 2 . The FWHM of the pulse

in the frequency domain is likewise found by solving:
exp[ 2 ( 0 )2 ] = 0.5 ,
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which gives ( 0 ) = ln 2/ , and hence = 2 ln 2/ . We then

obtain:
t = t/2 = 2 ln 2/ = 0.441 .
(9.14) The crystal-field shifts of the energy levels depend on the local environment of the ion. For example, small perturbations to the atomic positions
affect the energy levels of the ion through the alterations to the local electric field the ion experiences. There will be much larger inhomogeneity in
the local environment in a glass than in a crystal, due to the lack of longrange order. Hence we expect much larger inhomogeneous broadening of
the crystal-field split transitions in a glass than in a crystal.
If we assume a Gaussian pulse, we expect a time-bandwidth product of
0.441, and hence tmin = 60 fs. Other pulse shapes would give comparable
minimum pulse durations.
(9.15) The subscript g stands for gerade and implies even parity. A gg
transition therefore involves no parity change and is forbidden for electricdipole transitions. (See Section B.3.) The transition will therefore have
a lower probability than for an electric-dipole allowed process, and hence
have a long excited state lifetime ( 4 s). Since the lifetime is long, the
radiation would be classified as phosphorescence rather than fluorescence.
(See Section B.3.)
(9.16) The excited state lifetime is determined by both radiative and nonradiative processes. It follows from eqn 5.4 that:
1
1
1
=
+
.
R
NR
The radiative lifetime is governed by atomic transition probabilities and
is not expected to vary significantly with the temperature. On the other
hand, the non-radiative transition rate is governed by phonon-assisted
processes and is expected to increase strongly with T . On substituting
R = 1.8 ms into the equation above, we find NR = 6.3 ms at 77 K
and 0.062 ms at 300 K. This implies, through eqn 5.5, that the radiative
quantum efficiency is 78% at 77 K and 3% at 300 K. The radiative efficiency
is too low at 300 K to allow lasing.
(9.17) The level scheme for Ti:sapphire is shown in Fig. 9.13. If we assume that
the laser threshold is low, and that the slope efficiency is 100% (i.e. one
laser photon emitted for each pump photon absorbed), then the ratio of
the output power to the input power would just be proportional to the
ratio of the respective photon energies, which implies:
Pout =
1/800
hout
Pin =
Pin = 3.2 W .
hin
1/514
In this case, the remaining 1.8 W of power produces phonons (i.e. heat)
in the crystal. Note that a substantial amount of heat is generated in
the crystal even for the ideal case of 100% quantum efficiency due to the
difference in the photon energies of the argon and Ti:sapphire lasers.
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In reality, a Ti:sapphire laser typically gives about 1 W for a pump power

of 5 W at 500 nm. This reduction of the power from the ideal value is
caused by a number of factors:
The laser threshold will be significant, and the output power is proportional to (Pin Pth ) rather than to just Pin (cf. Fig 5.15(a));
the quantum efficiency is less than 100% due to significant nonradiative decay;1
the absorption of the pump laser in the crystal is not perfect, and so
not all of the pump power is absorbed;
there might be optical losses within the cavity.
(9.18) The energy conversion efficiency is calculated by assuming that we obtain
one emitted photon from the phosphor for each photon absorbed from the
LED. The intrinsic energy conversion efficiency is then just determined by
the ratio of the photon energies:
=
hout
in
=
,
hin
out
where in and out are the wavelengths of the photons absorbed and emitted, respectively. In this case we have out = 650 nm. Hence:
(a) = 54% for in = 350 nm;
(b) = 69% for in = 450 nm.
1 The
operating temperature of the laser crystal will be above room temperature due to
the heat generated within it, and this further increases the non-radiative decay rate. Cooling
of the laser rod is therefore essential.
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Chapter 10
Phonons
(10.1) The phonon modes of purely covalent crystals do not give rise to infrared
absorption because the atoms are neutral and do not interact with the
electric field of the light wave. Of the five materials listed, germanium
and argon are elemental, and must therefore have neutral atoms with nonpolar bonds, and hence no infrared absorption. The other three, namely
ice, ZnSe and SiC, are polar, and would therefore have some infrared-active
phonons.
(10.2) It is apparent from eqn 1.29 that R = 0 when n
= 1, and hence r = 1.
For an undamped oscillator, r () is given by eqn 10.15. We thus solve:
r () = + (st )
2
TO
2 2) = 1 ,
(TO
for . Rearrangement gives:
st 1
1
2
TO
,
leading to the result quoted in the exercise.

(10.3) The exercise follows Example 10.1(a). We calculate LO = 20 THz from
the LST relationship, and hence that the Reststrahl band runs from 9.2
to 20 THz, i.e. 15 m to 33 m.
(10.4) The exercise closely follows Example 10.1(b). The relative permittivity
is given by eqn 10.10 as:
r () = 10 +
210
,
100 i 0 /2
2
where is measured in THz and 0 = /1012 . We calculate LO = 11 THz

from the LST relationship, so that the Reststrahl band runs from 10 to
11 THz. We thus need to evaluate r at = 10.5 THz.
(a) With = 1011 s1 , we find r = 10.48+0.336i at 10.5 THz, and hence
that n = 0.0519 and = 3.238 from eqns 1.2526. Then from eqn 1.29 we
find R = 0.98.
(b) With = 1012 s1 , we find r = 9.958+0.252i and n
= 0.509+3.196i
at 10.5 THz, and hence that R = 0.84.
(10.5) (a) We identify the Reststrahl band from the region of high reflectivity
from 3032 m. (See Fig. 40(a).) On equating the upper and lower wavelength limits with TO and LO respectively, we find TO 9.5 THz and
LO 10 THz.
103
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nTO
1.00
0.8
Reflectivity
1.0
Reflectivity
Name: Tapas Banerji
(a)
AlSb
0.6
0.4
R()
R(0)
0.2
0.0
16
(b)
0.96
0.92
0.88
0.84
20
24 28 32 36
Wavelength ( mm)
40
0.0
0.4
0.8
1.2
g (1012 s-1)
1.6
Figure 40: (a) Interpretation of the data in Fig. 10.14 as required for Exercise
10.5(a) and (b). (b) Calculated reflectivity versus damping constant, as required
for Exercise 10.5(c).
(b) The high- and low-frequency permittivities can be deduced from the
asymptotic reflectivities. (See Fig. 40(a).) The low-frequency limit gives
st from (see eqn 1.29, with n = r ):

R(0) =
st 1 2
.
st + 1
At 0, there is no absorption, and so r will be real. On reading

R 0.30 R(0) at long wavelengths, we deduce st 12. On similarly
equating the short wavelength limit of R, namely 26%, with R(), we
deduce 9.5.
(c) The peak reflectivity is about 90%, and is limited by , which in turn
is determined by the lifetime of the TO phonons. The middle of the
Reststrahl band occurs at 9.75 THz. We thus need to evaluate r from
(see eqn 10.10, with measured in THz and 0 = /1012 ):
r () = + (st )
2
(TO
2
TO
225
= 9.5 +
,
2
2
) i/2
90 i 0 /2
at = 9.75 THz. We split this into the real and imaginary parts, compute
n and from eqns 1.2526, and R from eqn 1.29. The reflectivity calculated in this way is plotted as a function of in Fig. 40(b). It is apparent
that we have R = 0.9 for = 8.6 1011 s1 . This implies, from = 1/ ,
that = 12 ps.
The values of LO and TO found in part (a) can be compared to the
LyddaneSachsTeller relationship, which predicts LO /TO = 1.11. The
experimental ratio is slightly smaller. The values given here are only
approximate, and depend on how exactly they are extracted from the
data. The departure from LST is therefore not very significant.
(10.6) The exercise closely follows Example 10.1(c). We first use eqn 10.17
to find r at TO , which gives r = 10 + 132i for = 1012 s1 and
r = 10 + 1320i for = 1011 s1 . We then use eqn 1.26 to find and
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eqn 1.19 to find .

(a) For = 1012 s1 we find = 7.8 and = 3.4 106 m1 .
(b) For = 1011 s1 we find = 26 and = 1.1 107 m1 .
Note that the peak absorption increases for the smaller value of the damping, as normal for a damped oscillator.
(10.7) The peak reflectivity is governed by the damping constant . (See, for
example, Fig. 40(b) above.) As the temperature increases, we expect
to increase, and hence R to decrease, due to the increased probability
of anharmonic decay processes of the type illustrated in Fig. 10.13. The
reason why anharmonic phonon decay increases with T is that phonons are
bosons, and the probability for phonon emission increases as the thermal
population of the final state increases. (n.b. This contrasts with fermions,
for which the transition probabilities decrease with increasing occupancy
of the final state.)
(10.8) With negligible damping, we can use eqn 10.15 to calculate r = 21.5 at
8 THz. We then substitute this value of r into eqn 10.18 to compute the
wave vector. This gives:
r
21.5 2 8 1012
q=
=
= 7.8 105 m1 .
c
3 108
(10.9) (a) The condition for cyclotron resonance is given in eqn 10.24. In a
polar material, the mass that is measured is the polaron mass m . We
thus obtain:
eB
m =
= 0.097 m0 .
2c
(b) The rigid lattice mass m can be calculated from eqn 10.21. On
inserting the relevant values into eqn 10.19, we find ep 0.33 for CdTe.
Then from eqn 10.21 we find that m = 0.097 m0 implies m = 0.092 m0 .
(10.10) The Raman spectra for a number of III-V crystals are shown in Fig. 10.11.
In each case we observe two peaks: one for the TO phonons and the other
for the LO phonons. These two phonon modes have different frequencies
because III-V compounds have polar bonds with partially charged atoms.
They therefore interact with light, and obey the LST relationship. The
situation in diamond is different because it is a purely covalent crystal,
with neutral atoms that do not interact with the light. The LST analysis
does not apply, and the optical phonons are degenerate at q = 0. The
Raman spectrum therefore has only one peak for the optical phonons.
(10.11) Silicon, like diamond in the previous exercise, is covalent, and its LO
and TO phonons are degenerate at q = 0. The two peaks correspond to
the Stokes and anti-Stokes lines from these degenerate optical phonons.
The line at 501.2 nm is shifted up in frequency compared to the laser and
is thus the anti-Stokes line, while that at 528.6 nm is the Stokes line. The
phonon frequency can be worked out from eqn 10.27, which gives, for the
case of the Stokes line:
/2 =
c
c
= 15.5 THz .
514.5 nm 528.6 nm
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The relative intensities of the lines are given by eqn 10.29:
I(501.2 nm)
h 15.5 1012
= exp
= 0.08 .
I(528.6 nm)
kB T
(10.12) NaCl has an inversion centre and so the mutual exclusion rule applies. It
is apparent from Fig. 41 that the TO mode has odd parity under inversion.
The TO mode is therefore IR active but not Raman active.
invert
Figure 41: Inversion of a TO mode in an ionic crystal, as considered in Exercise

10.12. The inversion centre is circled.
(10.13) The energies of the phonon modes can be deduced directly from the
Raman spectra by applying eqn 10.27, with the + sign as appropriate for
a Stokes shift. This shows that the Raman shift is exactly equal to the
phonon frequency. For each crystal, two lines are observed. The lower
frequency line comes from the TO phonons, while the higher frequency
line originates from the LO phonons. The Raman shifts in cm1 from
Fig. 10.11 are given in Table 7, together with the energies deduced according to:
E (meV) = 0.124 Raman shift (cm1 ) .
Crystal
GaAs
InP
AlSb
GaP
Raman line 1
cm1
262
299
312
364
Raman line 2
cm1
286
341
332
403
TO phonon energy
meV
32.5
37.1
38.7
45.1
LO phonon energy
meV
35.5
42.3
41.1
50.0
Table 7: Raman shifts deduced from the data in Fig. 10.11, as considered in
Exercise 10.13.
On comparing the frequencies of the TO and LO phonons of GaAs in
Table 7 with those deduced from the infrared reflectivity data in Fig. 10.5,
we see that there is a small shift of a few wave numbers between the two
sets of data. This is caused by the slight decrease of the optical phonon
frequencies between 4 K and 300 K.
(10.14) Equation 10.28 implies that momentum is conserved during the Raman scattering process so that the vectors form a triangle as depicted in
Fig. 42(a). In the case of inelastic scattering by acoustic phonons, the
frequency shift of the photon is very small because . This implies
that the magnitude of the photon wave vector hardly changes, so that we
can approximate:
n
.
|k1 | = |k2 | k =
c
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k2
k1
k2
k1
q/2
(a)
(b)
Figure 42: (a) Conservation of momentum during Raman scattering by a phonon

of wave vector q, as as considered in Exercise 10.14. (b) Back-scattering geometry.
It is then apparent from Fig. 42(a) that:
q
= k sin =
sin .
2
2
c
2
On writing q = /vs as appropriate for acoustic phonons, we derive the
result in the exercise. Equation 10.32 then follows by writing:
= |2 1 | = .
(10.15) In back-scattering geometry, we have = 180 , so that q = 2k. (See
Fig. 42(b) with |k1 | = |k2 | = k.) It then follows from eqn 10.32 with
sin(/2) = 1 that:
c
vs =
=
.
2n
2n
On inserting the data given in the exercise, we find vs = 813 m s1 .
(10.16) (a) The negative term in r1 is the attractive potential due to the
Coulomb interaction between the ions. The Madelung constant accounts
for the summation of the contributions of the positive and negative ions
over the whole crystal. The positive term in r12 represents the short
range repulsive force due to the Pauli exclusion principle when the electron
wave functions overlap.
(b) The graph of U (r) is qualitatively similar to that for the LennardJones
potential, being attractive for large r, repulsive for small r, and with a
minimum at some intermediate value of r, labelled r0 . (cf. Fig. 28.) The
value of r0 is found by differentiating U (r):
dU
12
e2
= 13 +
,
dr
r
40 r2
and finding the value of r for which dU/dr = 0, namely:
12
e2
=
,
r013
40 r02
which implies r011 = 12 40 /e2 .
(c) The Taylor series for U (r) expanded about r0 is:
U (r) = U (r0 )+
3
dU
1 d2 U
2 1d U
(rr0 )+
(rr
)
+
(rr0 )3 + .
0
dr r=r0
2 dr2 r=r0
6 dr3 r=r0
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Now U (r) has a minimum at r0 , and the first derivative is therefore zero,
so that:
U (r) = U (r0 ) +
1 d2 U
1 d3 U
2
(r
r
)
+
(r r0 )3 + .
0
2 dr2 r=r0
6 dr3 r=r0
We can reconcile this with eqn 10.33 by taking x = r r0 and U (x) =

U (r) U (r0 ). It is then apparent that:
C2
C3
1 d2 U
,
2 dr2 r=r0
1 d3 U
.
6 dr3 r=r0
At r = r0 we have
d3 U
dr3
6e2
2184
= 15 +
,
r
40 r04
02
6e
2184 1
,
=
11
40
r0
r04
176e2
=
,
40 r04
where we used the result of part (b) to derive the last line. Hence:
C3 = 22e2 /30 r04 .
(10.17) If the Raman spectrum is lifetime-broadened, we shall have a Lorentzian
line shape with:
1
t =
.
2
Hence with t = , and = c, we have:
=
1
.
2c
On inserting the data given in the exercise, we find = 6 ps. This value
agrees with the lifetime measured by time-resolved Raman scattering. See:
von der Linde et al., Phys. Rev. Lett. 44, 1505 (1980).
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Chapter 11
Nonlinear optics
(11.1) In the Bohr model for hydrogen, the radius of the electron in the nth
quantum level is given by:
rn =
40 ~2 n2
n2
=
aH .
me2 Z
Z
The magnitude of the electric field is given by the standard Coulomb

formula:
Ze
E=
,
40 r2
which, on inserting rn from the Bohr formula, gives:
E=
e
Ze
Z3
=
.
40 rn2
40 a2H n4
For the outer 3s and 3p electrons in atomic silicon, use n = 3 and an

effective nuclear charge Z 4.2 We then obtain a value of E = 5
1011 V m1 . The field for the conduction electrons in crystalline silicon
would, of course, be different due to the high relative permittivity and the
low effective mass.
(11.2) We can relate the optical intensity to the electric field by using eqn A.44.
(a) The optical intensity is found from:
I=
P
Epulse /pulse
1 108
2
=
=
= 5.1 1012 W/m .
A
r2
(2.5 103 )2
Hence with n = 1 for air, we find from eqn A.44 that E = 6.2107 V m1 .
(b) The optical intensity is found from:
I=
P
103
2
=
= 5 107 W/m .
A
20 1012
Then with n = 1.45 as appropriate for the fibre, we find from eqn A.44
that E = 1.6 105 V m1 .
(11.3) With no external field applied, the gas is isotropic and therefore possesses
inversion symmetry. Hence (2) = 0, and no frequency doubling will occur.
With the electric field applied, the gas is no longer isotropic as the electron
clouds of the atoms will be distorted along the axis defined by the field.
This means that inversion symmetry no longer holds, so that (2) 6= 0 and
frequency doubling can, in principle, occur. However, it would give a very
weak signal due to the low density of atoms.
2Z
eff
is the difference between the nuclear charge and the total number of inner shell
electrons that screen the valence electrons from the nucleus. i.e. Zeff = 14 10, where 10 is
the total number of electrons in the 1s, 2s and 2p shells.
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(11.4) The second-order nonlinear susceptibility is zero if the material has an

inversion centre. We must therefore consider the microscopic structure to
see if the material has inversion symmetry or not.
(a) NaCl is a face-centred cubic crystal with inversion symmetry: (2) = 0.
(b) GaAs has the zinc-blende structure, which is similar to the diamond
structure except that the bonds are asymmetric. It does not possess inversion symmetry and therefore (2) 6= 0.
(c) Water is a liquid and is therefore isotropic; hence inversion symmetry
applies and (2) = 0.
(d) Glass is amorphous and has no preferred axes; inversion symmetry
applies and (2) = 0.
(e) Crystalline quartz is a uniaxial crystal with the trigonal 3m structure.
It does not possess inversion symmetry, so that (2) 6= 0.
(f) ZnS has the hexagonal wurtzite structure (6mm), without inversion
symmetry. Hence (2) 6= 0.
(11.5) (a) Consider the absorption and stimulated emission transitions as indicated in Fig. 11.2. (Spontaneous emission can be neglected if u is sufficiently large.) The absorption and stimulated emission rates are equal
to N1 B12 u g() and N2 B21 u g() respectively. (See eqns B.56 with the
additional factor of g() explained in the discussion of eqn 11.30.) If the
levels are non-degenerate, then eqn B.10 tells us that B12 = B21 . At t = 0,
all the atoms are in level 1, and there is net absorption, which increases
N2 and decreases N1 . As the atoms are pumped to level 2, the stimulated emission rate becomes increasingly significant. Eventually, we reach
a stage where N1 = N2 = N0 /2, and the stimulated emission and absorption rates are identical. There is therefore no net absorption or emission,
and N2 cannot increase further. The maximum value of N2 that can be
achieved is therefore N0 /2.3
(b) If we only have two levels and we neglect spontaneous emission, then
the rate equations for N1 and N2 are:
dN1
dt
dN2
dt
= B12 N1 u g() + B21 N2 u g() ,

= +B12 N1 u g() B21 N2 u g() .
On setting B12 = B21 as appropriate for non-degenerate levels, and subtracting, we find:
dN
d
(N1 N2 ) =
= 2B12 u g()N ,
dt
dt
where N = N1 N2 . Integration yields:
N (t) = N (0) exp(2B12 u g()t) ,
which, with N (0) = N0 , gives the required result.
3 This shows that it is not possible to achieve population inversion (i.e. N > N ) in a
2
1
two-level system: three or more levels are required. This is why lasers, in which population
inversion is essential, are always classified as either three or four-level systems.
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The result quantifies the way the laser pumps atoms from level 1 to level
2, and hence reduces the net absorption. The equation implies that the
populations will eventually equalize no matter how weak the laser beam
is. This unphysical result arises from neglecting spontaneous emission and
transitions to other levels that occur in real atoms.
y
direction of propagation
q
Figure 43: Propagation and polarization vectors for the light wave considered
in Exercise 11.6.
(11.6) With the beam propagating in the x-y plane and with its polarization in
the same plane, the light must be linearly polarized as shown in Fig. 43.
The z-component of the electric field is therefore zero. The nonlinear
polarization, for the given nonlinear optical tensor, is found from eqn 11.43
to be:
E xE x
(2)
EyEy
Px
0 0 0 d14 0
0
2d14 E y E z
EzEz
(2)

Py = 0 0 0 0 d25 0
2E y E z = 2d25 E z E x .
(2)
0 0 0 0
0 d36
2d14 E y E z
Pz
2E z E x
2E x E y
On setting E z = 0, we obtain:
(2)
Px
0
(2)
.
0
Py =
(2)
2d
E
E
14 y z
Pz
(2)
Only Pz is non-zero, and therefore the second harmonic beam must be

polarized along z.
We assume that the direction of propagation makes an angle with respect
to the x axis as shown in Fig. 43 and that the light has an electric field
of magnitude E 0 . It will then be the case that E x = E 0 cos and E y =
E 0 sin , and hence that:
Pz(2) = 2d36 E 20 cos sin = d36 E 20 sin 2 .
This is maximized when 2 = 90 : i.e. = 45 .
(11.7) This exercise closely follows Example 11.2, and the phase-matching angle
is found by substituting the appropriate refractive indices into eqn 11.52.
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With the data given in the exercise, this gives:

1
sin2
cos2
=
+
.
2
2
(1.506)
(1.490)
(1.534)2
On using cos2 = 1 sin2 and re-arranging, we find sin2 = 0.626 and
hence = 52.3 .
(11.8) (a) In the absence of the field, the index ellipsoid given in eqn 11.54 is
of the form:
x2 + y 2
z2
+
= 1.
n2o
n2e
On substituting into eqn 11.60 with E x = E y = 0 and E z = E, we find
that the only non-zero changes to the index ellipsoid induced by the field
are as follows:

1
1
=
= r13 E ,
n2 1
n2 2

1
= r33 E .
n2 3
From eqn 11.56 we then see that the modified index ellipsoid is:
1
1
1
2
2
+ r13 E x +
+ r13 E y +
+ r33 E z 2 = 1 ,
n2o
n2o
n2e
which can be written in the form :
x2 + y 2
z2
+
= 1,
no (E)2
ne (E)2
where:
1
n2o (E)
1
n2e (E)
=
=
1
+ r13 E ,
n2o
1
+ r33 E .
n2e
This implies:
no (E) =
ne (E) =
no (1 + n2o r13 E)1/2 ,

ne (1 + n2e r33 E)1/2 .
We assume that the field-induced changes are small and use the approximation (1 + x)1/2 = (1 x/2) for small x to obtain the final result:
1
no (E) = no n3o r13 E ,
2
1
ne (E) = ne n3e r33 E .
2
(b) The geometry of the crystal is shown in Fig. 44. If the light is propagating along the y axis, and is polarized along the z direction, then it
112
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L
z
y
V
Figure 44: Experimental geometry of the electrooptic phase modulator considered in Exercise 11.8.
will experience a refractive index of ne (E). From part (a) we know that
ne (E) = ne n3e r33 E/2, and hence the refractive index change when the
field is applied. The phase change associated with the change in ne is
therefore given by
(E) =
2
ne L = n3e r33 EL/ .
The argument would work equally well if the light were polarized along x
instead of z. In this case the phase change would be given by:
(E) =
2
no L = n3e r13 EL/ .
In the case of LiNbO3 , r33 3r13 (see Table 11.3), and so it is convenient
to use the z polarization, but this is not necessarily true for other crystals.
(c) It is apparent from part (b) that the electric field produces a linear
modulation of the phase. Hence the application of a voltage modulates
the phase in proportion to the voltage. This is a phase modulator.
L
x
x y
z
y
V
Figure 45: Experimental geometry of the electro-optic crystal considered in

Exercise 11.9.
(11.9) We consider an electro-optic crystal with axes as defined in Fig. 45. The
voltage is applied so as to produce an electric field of magnitude E z along
z axis.
(a) If the light propagates along the z axis, the polarization vector will
lie in the x-y plane, or equivalently, in the x0 -y 0 plane. We resolve the
113
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light polarization vector into its components along the x0 and y 0 axes.
The phase shift induced by a refractive index change n in a medium of
length L is, in general, given by:
2
nL ,
where is the vacuum wavelength. On applying this to the two components along the x0 and y 0 axes, we then have:
x0
y0
2L
Ln30 r41
nx0 =
Ez
2L
Ln30 r41
ny0 =
Ez ,
where nx0 and ny0 are the field-induced refractive index changes along
the x0 and y 0 axes as given in the exercise. The phase difference is
thus given by (with E z = V /L):
= x0 y0 =
2Ln30 r41 E z
2n30 r41 V
=
.
Note that the phase change is independent of the length in this longitudinal
geometry.
(b) On setting = , we find:
V =
.
2n30 r41
With the appropriate figures for CdTe given in the exercise, we obtain
V = 44 kV.
(11.10) The phase change is given by eqn 11.62. For a crystal of length L, the
field strength at voltage V is equal to V /L. Hence the phase change is:
=
2 3
n r63 (V /L)L = 2n3o r63 V / .
o
The transmission will be equal to 50% when = /2, since this means
that the crystal acts like a quarter wave plate. In these circumstances, the
output of the crystal is circularly polarized, so that half of the intensity is
transmitted through the second polarizer. This occurs when:
V = /2n3o r63 = /4n3o r63 .
On inserting the values of no and r63 for = 633 nm, we find V = 4.2 kV.
(11.11) In a third-order nonlinear medium, the change in the relative permittivity is given by (see eqn 11.69):
r = 1 + i2 = (3) E 2 .
We therefore have 2 = Im((3) )E 2 and hence that 2 Im((3) )I
because I E 2 . It follows from eqns 1.19 and 1.24 that 2 .
Hence, in a medium with Im((3) ) 6= 0, we expect
Im((3) )I .
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A saturable absorber has an absorption coefficient that obeys eqn 11.37.

In the limit of small intensities, this is of the form:
(I) = 0 0 I/Is = 0 ,
where = 2 I and 2 = 0 /Is . We thus have an intensity dependence
exactly as described above, and we therefore conclude that the saturable
absorber must have Im((3) ) 6= 0.
(11.12) We can choose our axes as we please in an isotropic medium. Therefore
choose z as the direction of propagation, and x as the polarization vector,
so that the electric field is given by:
E = (E x , 0, 0) .
The third-order nonlinear polarization is given by eqn 11.11, and, with
E y = E z = 0, the nonlinear polarization is of the form:
(3)
Px
xxxx
(3)
3
Py = 0 E x yxxx .
(3)
zxxx
Pz
However, we see from Table 11.6 that yxxx = zxxx = 0. Hence we find
P = 0 xxxx E 3x (1, 0, 0) ,
which means that P is parallel to E.
(11.13) This exercise is very similar to Example 11.4. From eqn 11.76, we
require that:
2
nonlinear =
n2 IL = ,
which implies:
I=
1.55 106
=
= 3.9 1012 W m2 .
2n2 L
2 2 1020 10
The optical power to produce this intensity is given by:

P = IA = 3.9 1012 (2.5 106 )2 = 76 W .
This is a large power level for a continuous-wave laser, but not for a pulsed
laser. Consider, for example, a mode-locked laser with an average power
of Pav , pulse repetition rate f , and pulse width tp . The peak power is
given by:
Pav
Epulse
=
.
Ppk =
tp
f tp
On inserting typical values, namely Pav = 10 mW, f = 100 MHz, and
tp = 1 ps, we find Ppk = 100 W.
115
Name: Tapas Banerji
IP: 129.82.195.78
(11.14) It is apparent from Fig. 11.10 that the presence of electrons causes the
states in the conduction band up to EFc to be filled up, and likewise for
the holes in the valence band. The absorption between Eg and (Eg + EFc +
EFv ) will therefore be blocked, and the new absorption edge will occur at
(Eg + EFc + EFv ). The shift in the absorption edge is therefore (EFc + EFv ).
The Fermi energy in the conduction band can be calculated from eqn 5.13.
On inserting me = 0.067m0 , we find EFc = 0.054 eV. In the case of the
valence band, we must consider the occupancy of both the heavy and light
hole bands. On using the result of Exercise 5.14(b), we have:
1
Nh =
3 2
2
~2
3/2
3/2
3/2
(mhh + mlh ) (EFv )3/2 ,
which gives EFv = 0.007 eV for mhh = 0.5m0 and mlh = 0.08m0 . Hence the
absorption edge will shift to higher energy by 0.054 + 0.007 = 0.061 eV.4
(11.15) If we treat the exciton as a classical oscillator, we can use the results
derived in Chapter 2. If we assume that the contribution of the exciton to
the refractive index is small compared to the non-resonant value, (which
is indeed the case, as we shall show below,) then we expect a refractive
index variation as in Fig. 2.5. The refractive index will thus have local
maxima and minima just below and above the centre of the absorption
line. It is this extra contribution that we are considering in this exercise.
The magnitude of the excitonic contribution can be calculated by following
the method of Example 2.1. In part (a) of Example 2.1 it is shown that
max =
N e2
,
2n0 m0 0
where max is the extinction coefficient at the line centre, while in part (c)
it is shown that:
1/2
N e2
nmax = +
.
20 m0 0
It then follows, with = n2 , that:
max 1/2
nmax = n 1 +
,
n
where nmax is the maximum value of the refractive index. If we assume,
as is demonstrated below, that max n, we then find:
nmax = n + max /2 .
Now we know from eqn 1.19 and the data given in the exercise that
max =
max
847 109 8 105
=
= 0.054 .
4
4
4 In
a real experiment, the behaviour would be more complicated due to many-body effects
such as band gap renormalization. This causes a shift of Eg N 1/3 , which reduces the blue
shift of the absorption edge.
116
Name: Tapas Banerji
IP: 129.82.195.78
We thus deduce that there is a local maximum in the refractive index

just below the absorption line with (nmax n) = 0.027. If the exciton
absorption is saturated, this local maximum will disappear. Hence the
maximum change in the refractive index is 0.027.
(11.16) (a) The saturation density for the excitons is equal to the Mott density
given in eqn 4.8. We consider here only the n = 1 exciton, since this is
the ground state of the system and has the highest stability. For InP we
have:
= (1/me + 1/mh )1 0.06m0
for me = 0.077m0 and mh 0.3m0 (i.e. a mean of mhh and mlh ).
Equation 4.2 then gives r1 = 12.5 aH /0.06 = 11 nm, and we hence find
NMott 1.8 1023 m3 .
(b) We first calculate the energy of the n = 1 exciton. We see from eqn 4.4
that the n = 1 exciton absorption line will occur at
h = Eg RX ,
where Eg is given in Table D.2 as 1.42 eV. With = 0.06m0 and r = 12.5,
we find from eqn 4.1 that RX = (0.06/12.52 )RH = 5.2 meV. The exciton
energy is thus 1.41 eV at low temperatures. (We consider low temperatures
here because the exciton would be ionized at room temperature.)
The saturation intensity Is is the optical intensity required to produce the
Mott density worked out in part (a). By using the result of Exercise 5.6(b),
namely:
I
N=
,
h
we then find
Is =
h
1.41 eV
NMott = 6
(1.8 1023 ) 4 107 W m2 .
10 109
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Name: Tapas Banerji