2010 - 65 Years of ZnO Research - Old and Very Recent Results

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Phys. Status Solidi B 247, No. 6, 1424–1447 (2010) / DOI 10.1002/pssb.200983195 b
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basic solid state physics
65 years of ZnO research – old Review Article

and very recent results
Claus Klingshirn*, J. Fallert, H. Zhou, J. Sartor, C. Thiele, F. Maier-Flaig, D. Schneider, and H. Kalt
Institut für Angewandte Physik, Karlsruher Institut für Technologie (KIT), Wolfgang Gaede Str. 1, 76131 Karlsruhe, Germany
Received 17 September 2009, revised 12 January 2010, accepted 13 January 2010

Published online 28 April 2010
Keywords excitons, photoluminescence, ZnO nanostructures
* Corresponding author: e-mail claus.klingshirn@kit.edu, Phone: þ49 (0)721 608 3417, Fax: þ49(0)721 608 8480
The research on ZnO has a long history but experiences an properties identical to bulk samples and end in several cases
extremely vivid revival during the last 10 years. We critically with data on quantum wells or nano crystallites. Since it is a
discuss in this didactical review old and new results concen- didactical review, we present explicitly misconceptions found
trating on optical properties but presenting shortly also a few frequently in submitted or published papers, with the aim to
aspects of other fields like transport or magnetic properties. We help young scientists entering this field to improve the quality of
start generally with the properties of bulk samples, proceed then their submitted manuscripts. We finish with an appendix on
to epitaxial layers and nanorods, which have in many respects quasi two- and one-dimensional exciton cavity polaritons.
ß 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
1 Introduction Zinc oxide (ZnO) is a wide gap This huge number of publications makes it completely
semiconductor [Eg(0 K) ¼ (3.441 0.003) eV; Eg(300 K) impossible to cite or even to read all relevant ones for this
¼ (3.365 0.005) eV]. It belongs to the group of IIb-VI contribution. We restrict ourselves therefore to a small,
compound semiconductors. It crystallizes almost exclu- partly arbitrary selection of references, refer the reader for
sively in the hexagonal wurtzite type structure (point group more e.g. to the databases mentioned above or the more recent
C6v or 6 mm, space group C46v or P63mc). Compared to ones of the reviews and apologize for this shortcoming.
similar IIb–VI (e.g. ZnS) or III–V (e.g. GaN) semiconductors After this introduction, we shortly review some aspects
it has a relatively strong polar binding and a relatively large of present and future applications, growth, doping, electronic
exciton binding energy of (59.5 0.5) meV. Due to the light transport, band structure and deep centre luminescence.
mass of oxygen, the up most LO phonon has a relatively high Then we present in more detail linear and nonlinear optical
energy of 72 meV. The density of ZnO is 5.6 gcm3 properties close to the fundamental absorption edge,
corresponding to 4.2 1022 ZnO molecules per cm3. including lasing and stimulated emission as well as
These data can be found e.g. in a recent data collection dynamics. The contribution closes with a short outlook,
[1] and references therein. followed by an appendix in which we comment recent work
ZnO is a long known semiconductor, with research going on quasi one- and two-dimensional cavities.
back to the first quarter of the last century. The time
mentioned in the title of this paper is simply based on the fact 2 Applications The present world wide research
that the oldest references which are cited here are from the activities on ZnO, its alloys Zn1xAxO (with A ¼ Cd, Mg
year 1944. or Be) and on nano- or quantum structures based on them, are
The research history, with peaks occurring from time to driven by various hopes. The predominant one is possibly
time, is documented apart from many scientific papers by a the hope to obtain a material for optoelectronics covering the
large number of review articles and books, from which we give spectral range from the green (A ¼ Cd) over the blue to the
here a selection [2–10, 12–16]. During the last 5 to 10 years, the near UV (A ¼ Mg or Be), especially to obtain light emitting
research on ZnO experiences a very vivid renaissance (or (LED) or laser diodes (LD) in these spectral ranges. ZnO
hype) with more than 2 000 ZnO relevant papers per year. could in case of success supplement or replace the GaN-
The total number of these papers exceeds 26 000 as indicated based devices. The main problem here is still a high, stable,
e.g. by the databases INSPEC or web of science. reproducible p-type doping.
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Phys. Status Solidi B 247, No. 6 (2010) 1425
There are many reports on LED involving both temperature (RT) are due to the doped or alloyed ZnO itself
homojunctions based on ZnO and its alloys and heterojunc- or to precipitates and clusters of other phases or even of the
tions in which generally electrons from n-type ZnO are substrate alone [14, 22, 25]. For a short list of pro and contra
injected into a p-type material like GaN, SiC etc. including papers see e.g. Ref. [24] and references therein. Note that the
even organic semiconductors. For a few examples see absence of diffraction orders other than ZnO related ones in
Refs. [8–17] and references therein. There are up to now only XRD is a necessary but by no means sufficient criterion to
very few claims of electrically pumped LDs [18, 19]. exclude other phases. Raman scattering revealed e.g. other
A common feature is the fact that the luminescence yield phases, which have not been seen in XRD [26].
is in all cases in these L(E)D very low and the emission The observation of ferromagnetism immediately trig-
spectrum has frequently large contributions from deep centre gered heavy speculations to use ZnO:X in spintronics or even
emission. For a LD a light output of 0.5 mW has been in quantum computing. The facts that the para- or
reported for a forward current of 60 mA at Ub 20 V [19]. If ferromagnetic magnetization is tiny (apart from the sign
we calculate the efficiency h in the favourable way as frequently of the same order of magnitude as diamagnetism
[27] and that the resulting magnetic flux densities B can only
h ¼ photon flux out=electronhole flux in (1) be measured with high sensitive SQUID arrangements and
are orders of magnitude smaller than the magnetic field of the
we find h 105 even neglecting in this definition the fact earth, shed serious doubt on this field of applications [28].
that the forward bias voltage Ub is considerably higher than Other future hopes of application which are partly
the emitted photon energy. The present situation is (possibly already in use or close to it are:
unintentionally) very well characterized by the cover photo
of [15] which shows presumably the optically pumped blue/ – transparent electronics, based on the large band gap of ZnO,
UV emission from a ZnO sample in the upper half and a e.g. in the form of field effect transistors (FET) or
LED in the lower which is still dark. Hopefully, it will emit (transparent) thin film transitions (TFT or TTFT, respec-
bright blue/UV light in the future. tively), which do not necessarily require a p–n junction
Another aspect driving the present research is the strong [29, 30],
tendency of ZnO to self-organized growth in the form of – the use of ZnO:Y (with Y ¼ Al but also In or Ga) as a highly
nano rods [10–13] and references therein. For an example of conductive transparent oxide (TCO), in addition to the
regular growth on a prepatterned surface see Fig. 1. Such more expensive and poisonous ITO [30, 31],
nanostructures could help to develop nano lasers etc. – the use of ZnO as a gas sensor, due to the strong sensitivity
Apart from more or less well aligned ensembles of of its (surface-) conductivity on the surrounding gas
nanorods, there are other self organized nanostructures, like atmosphere [32],
nano cabbages, corals etc. which are frequently nothing but – the use of pointed nanorods as field emitters [33],
unsuccessful attempts to grow a good epitaxial layer or nano – the use as material for random lasers as discussed in Section
rods. 10 below with Refs. [109–111],
Still another driving force for the ZnO revival is the fact – the application in solar cells. [11]
that diluted magnetic or even ferromagnetic samples can be
grown by doping ZnO:X with ‘magnetic’ ions like Mn, Fe,
Co, Ni, V or even with nonmagnetic ones like Ag, Cu, N or Actually ZnO is used already by 100 000 tons per year as
with intrinsic defects [22, 23]. It is still an open question if the additive to concrete or to the rubber of tires and in smaller
resulting hysteresis loops observed partly up to room quantities as additive to human and animal food, as UV
blocker in sun crèmes, as anti-inflammatory component in
crèmes and ointments, as white pigment in paints and glazes,
as catalyst etc. [14–16].
3 Growth After this short tour d’horizon on appli-

cations a few words on growth.
Bulk ZnO has been grown by gas transport methods
[34], hydrothermal growth [35] or from melt [36]. High
quality epitaxial layers or quantum wells (QW) can be
grown by molecular beam epitaxy (MBE), metal organic
vapour phase epitaxy (MOVPE) or pulsed laser deposition
(PLD). For large area growth or coatings also magnetron
sputtering, spray pyrolysis and other techniques are used
also including the oxidation of a film of metallic zinc [14,
15, 22].
Figure 1 An ensemble of nanorods grown on a prepatterned sur- Nano rods are frequently grown on substrates prepat-
face, according to H.Z. in Ref. [21]. terned with small dots of Au or other metals in a way known
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1426 C. Klingshirn et al.: 65 years of ZnO research – old and very recent results
as vapour–liquid–solid process (VLS): ZnO is reduced to Zn

vapour at elevated temperatures by graphite or hydrogen.
This vapour is transported by an inert gas to the heated
substrate and reacts with Au, forming a low melting eutectic.
From this liquid phase the ZnO rods grow if oxygen is
admitted. If the intermediate liquid state is not used one
speaks about vapour–solid process (VS). An example has
been shown already with Fig. 1 above. For an early example
see the work by Fuller in Ref. [21].
4 Doping Doping ZnO n-type is easy with group III

elements on Zn-place [37]. Doping levels up to
n ¼ 1021 cm3 can be reached. Doping with group VII
elements on the anion site, which proved very efficient in
ZnSe and other IIb–VI compounds ([38] and references
therein) is much less investigated in ZnO.
Doping ZnO p-type is as mentioned already notoriously
difficult. Group I elements (Li, Na, K) on Zn place form deep
acceptors, resulting in high resistivity material but not in
efficient p-type conductivity. Group V elements (N, P, As,
Sb) on oxygen place result sometimes in p-type conductivity Figure 2 Strongly Li-doped samples (concentrations in the range
sometimes also in n-type. Li may form a complex, resulting above 1020 cm3) which are showing platelet type defects (a) and
in p-type conductivity. Some authors claim also the cracks in the sample (b) and precipitates originating from these
observation of p-type after incorporation of Ag, Cu, C and cracks (c). The height of the tree-like precipitates in (c) is about
other elements. See for a few older and more recent papers 100 mm. Partly according to Ref. [41].
[39, 40].
Unfortunately, p-type conductivity is often claimed from (dimensions of several mm in all directions) for 18 days in
Hall or van der Pauw measurements, however on samples, ambient atmosphere at 870 8C in a ‘sarcophagus’ made from
which are inhomogeneous in their plane or into the depth sintered ZnO containing about 1% of LiOH. The tree-shaped
which opens the door for misinterpretations. Furthermore Zn precipitates grew obviously from the cracks in one direction
may act as a p-type dopant for some substrates (e.g. for GaAs only.
or Si) and/or enhancement-, depletion- or inversion- layers Homogenous concentrations around or even above 1%
may form at the interface to the substrate. The change of should be considered as alloys and no longer as doping with
conductivity in FET-like structures in dependence of the the usual consequences of impurity bands or localized tail
polarity of the gate voltage on the other hand gives support states, showing up in absorption or emission or in the
to the claim of p-type doping [40]. Sometimes p-type is occurrence of a mobility edge [42].
claimed only from the observation of excitons bound to In contradiction to these expectations, frequently narrow
neutral acceptors or free-to-bound or donator–acceptor pair luminescence features are reported at low temperatures
recombination in luminescence. Another point of concern in indicating that the density of incorporated species is orders of
p-type doping is that concentrations of the dopant in the ingot magnitude lower in the regions from which the luminescence
or in the produced samples are claimed in the range up to originates than the claimed doping levels.
5 to 10%, i.e. up to 4 1021 cm3 while the resulting hole Despite some success, it is still fair to say again that
concentration is generally only in the 1016 to 1017 cm3 p-type doping is still an unsolved problem concerning
range. This means that most of the doping material does not stability, reproducibility and efficiency. Neither group I nor
act as the desired shallow acceptor but forms something else group V dopants nor co-doping with either two different
e.g. precipitates [26] if it is incorporated into the sample at acceptors or with an acceptor and a donor species brought
all. A detailed analysis of this aspect and of the solubility is until now the breakthrough to high, stable and reproducible
frequently missing but important, especially if dopants are p-type conductivity. However, it does not need much of a
introduced with different ion radii or valence states. prophetic gift to predict that application oriented ZnO
In Ref. [41] it has been shown that Li concentrations in research will decay if this problem can not be solved in the
the range of 3 000 ppm (or 1020 cm3) lead already to near future.
precipitates with pan-cake like shape and diameters in the
range of 2 mm, which are seen in anisotropic light scattering. 5 Electronic transport The Hall mobility of elec-
Even higher concentrations lead to macroscopic cracks and trons has been measured by many authors [43]. The mobility
precipitates in the samples as shown in Fig. 2 or in Ref. [41]. in good bulk samples, epilayers or nanorods is about 200 to
The sample in Fig. 2b and c has been diffusion doped by 500 cm2/Vs at RT, limited by the intrinsic process of
annealing a nominally undoped ZnO bulk sample scattering with LO phonons. It goes with decreasing
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temperature through a maximum of a few 1 000 cm2/Vs ordering has been (quietly) accepted by many authors since
around 100 K and decays at lower temperature due to then [49]. The idea of the normal VB ordering has been
scattering with (ionized) impurities. revived with the renaissance of ZnO research, partly by the
In quasi two-dimensional QWs and heterojunctions, this same authors [50]. It has been shown that both the old and the
latter process can be reduced and values between 3 000 and new arguments in favour of the normal VB ordering in ZnO
10 000 cm2/Vs have been obtained in the 1 K region [46]. lack stringency [51]. These arguments against the normal
These values are sufficient to observe the integer quantum- ordering have been written up several times [9, 14, 16].
Hall effect (IQHE) in ZnO [46]. Therefore it is not necessary to repeat them here. In
If scattering at grain boundaries comes additionally agreement with [15] we state that the inverted VB-ordering
into play, e.g. in pressed and sintered samples or in has been adopted in the meantime by the majority of
(epi-)layers consisting of small grains, the mobility may be scientists and use it throughout in the following.
significantly reduced, at RT to values as low as a few ten
cm2/Vs [43, 44] or even below. 7 Deep centre luminescence Similarly to other
The hole mobility is generally considerably lower than wide gap semiconductors, ZnO has a lot of defect levels in
the electron mobility. Typical values reported at RT range the forbidden gap. Many of them can give rise to
from a few to some ten cm2/Vs [45]. luminescence and absorption bands covering the spectral
range from the violet over the whole visible to the IR [52]. A
6 Band structure and band alignments The band colour photograph published in Refs. [11, 14] illustrates
structure is shown schematically in Fig. 3. As stated already, some of these emission bands. In the past many of these
ZnO is a wide, direct gap semiconductor. The conduction emission bands have been attributed to extrinsic defects like
band (CB) with symmetry G7 including spin originates from substitutional Cuzn (giving a green emission band with a well
the empty 4s levels of Znþþ or the antibonding sp3 hybrid pronounced phonon structure) [52, 53] which has also been
states, adapting the views of ionic or covalent binding, partly attributed to Vanadium [54]. In the red to yellow
respectively. The valence band (VB) results in this sense spectral range recombination via deep Li and Na acceptors
from the occupied 2p levels of O– or the bonding sp3 states. It has been identified. This identification was very thoroughly
is split by the hexagonal crystal field and by spin orbit made based on optical spectroscopy, doping experiments,
coupling into three, two fold degenerate sub-VBs, which are EPR and thermo luminescence studies. See the work of D.Z.
called from top to bottom A, B and C VB in all wurtzite type in Ref. [39] or Refs. [52, 55].
semiconductors. The usual ordering is AG9, BG7 and CG7. In In recent years intrinsic defects have been stressed more,
ZnO the inverted VB ordering has been introduced in Ref. with the exception of an unstructured green emission band,
[47] and since then there is a discussion about ‘normal’ or which has been attributed since decades to an oxygen
‘inverted’ VB ordering in ZnO [48]. The inverted VB vacancy V0 [56]. Now many of these emission bands
including one in the violet are attributed to all types of
intrinsic defects like vacancies or interstitials or anti-site
defects. However, these interpretations are still strongly
controversial [57] and the arguments for the identification
are often less stringent, so that more detailed results are
required, to come to clear assignments.
The external luminescence yield of deep centres (and of
the near edge luminescence) is typically around or below
10% at low temperatures and decreases with increasing
temperature [58]. Very weak deep centre luminescence can
be a sign of good sample quality or of the presence of fast non
radiative recombination centres like Co, Fe or Ni [59] but
also Cu at higher concentrations.
8 Free excitons and the Urbach tail According to

the band-structure in Fig. 3 there are three series of excitons
labelled according to the involved hole.
The selection rules for dipole allowed transitions without
spin flip result in strong oscillator strengths for the nB ¼ 1 A
and BG5 excitons for E?c and for the CG1 excitons in Ejjc as
Figure 3 (online colour at: www.pss-b.com) Schematic of the band shown in Fig. 4 where we show in reflection the series of A, B
structure of ZnO. A k-linear term possible for G7 states for k and C exciton with main quantum numbers nB ¼ 1, 2, 3 in
perpendicular to c is shown schematically for the AG7 valence their respective polarizations and a close-up of the nB ¼ 1
band. The polarizations of the band-to-band transitions which states with some line-shape fits. Further examples are found
are dipole allowed and do not involve a spin flip are indicated. e.g. in Refs [1, 6, 7, 60].

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Table 1 Some properties of the nB ¼ 1 excitons with large oscil-

lator strength in ZnO at low temperatures (T 5 K), namely the
transverse eigen energies and the longitudinal–transverse splitting.
Data according to Refs [1, 7, 47, 49, 60, 104].
state E0 (eV) DLT (meV)
AG5 3.37550.001 2.00.2

BG5 3.38150.001 111
CG1 3.4200.001 121
Note that the longitudinal-transverse splitting DLT is in

the case of two close lying resonances not directly
proportional to the oscillator strength f. The value of DLT
of the energetically lower resonance is reduced, that of the
higher one increased. See e.g. Refs [28, 61]. This situation is
met for the A and BG5 excitons which have roughly equal
values of f but significantly different ones for DLT. See also
Table 1.
The longitudinal eigen energies hvL are situated slightly
below the reflection minima which occur at the spectral
position, where the refractive index of the UPB has the value
1, the transverse ones, named frequently hv0 or hvT , are
slightly below the reflection maximum. Their precise
positions can only be determined by an advanced line shape
fit. See Fig. 4 for an example.
Note further that the reflection spectra are strongly
polarized. The observation of nB ¼ 1 AG5, BG5 and CG1 at
10 K excitons in reflection for Ejjc with approximately equal
signal strength as reported e.g. in Ref. [62] is not possible.
The same is true for the absence of the CG1 exciton for
unpolarized light. Either a poor sample with differently
oriented crystal domains has been used or the notation of the
states of polarization is not correct. But even if the dotted line
in the cited Figures would correspond to unpolarized light
and the solid one to E ? c the shape of the dotted spectrum
remains strange. At higher temperatures, the A and B G5
signals may merge to one as is evidently the case in Ref. [63].
See also [14].
The free exciton resonances can also be seen in
absorption as demonstrated in Fig. 5 for low temperatures
and RT and for the two polarizations.
Again the different widths of the nB ¼ 1 A and BG5
features are obvious at low temperatures. At higher energies
follow states with nB ¼ 2, 3 and structures connected with
LO-phonons, which are also known as exciton–phonon
bound states [28]. At RT, the absorption spectra broaden. See
e.g. also [4, 65]. The position of the energy gap can be easily
deduced from the absorption spectra in Fig. 5. It is situated
by the exciton binding energy above the exciton peak i.e. at
3.37 eV for T ¼ 295 K.
Figure 4 The A, B and C exciton series (upper panels), and Note that the widths of the reflection and absorption
the nB ¼ 1 states with some fits (lower panels), according to Ref. features do not reflect the homogeneous broadening of the
[7] and the work by Hümmer in [49]. exciton resonances at low temperatures but are rather
given by DLT. Only at higher temperatures the damping
G dominates the width of the absorption spectra. G varies

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first exciton resonance, the so-called Urbach tail [67]. It can

be described by [28]
aðhv; TÞ ¼ a0 exp½sðTÞðEoo hvÞ=kB T

(2)
for hv < ET :
The quantities a0 and Eoo are material parameters. Eoo is

situated slightly above the transverse exciton eigen energy at
low T. The function s(T) varies only weakly with T. In
disordered systems like amorphous semiconductors or alloys
there is an additional, essentially temperature independent
contribution to this Urbach tail. In quantum structures (wells,
superlattices, wires and dots) fluctuations of the geometrical
sizes can additionally contribute to disorder and broadening.
This tail is frequently misinterpreted in submitted or
published manuscripts to determine the energy gap (some-
times also called the optical gap). Usually one finds in these
texts plots like Eq. (3a, b)
a2 ðhvÞ ¼ f ðhvÞ; (3a)
or
ðhvÞ2 a2 ðhvÞ ¼ gðhvÞ: (3b)
They are fitted by a straight line and the intersection of

this line with the x-axis is claimed to be the gap or the optical
gap. Examples are found e.g. for pure ZnO in Ref. [68] and
the references therein. A first hint that this approach is wrong,
is the observation, that the linear fit of the data generally
holds for a rather small interval of a2(hv) only. The
next argument is the fact that the absorption coefficient at
the thus determined ‘gap’ is still rather small (i.e. the sample
is still almost transparent) in contrast to values of
a(hv ¼ Eg ) 105 cm1. See e.g. Fig. 5. A third point is that
many authors state in the beginning of their manuscript
correctly that Eg is in ZnO at RT at (3.365 0.05) eV but
based on the misinterpretation of their data came up later
with values around 3.25 to 3.28 eV [68], frequently without
bothering about this discrepancy.
The approach of Eq. (3a) is based on a so-called square-
root absorption edge. See e.g. Ref. [28] or the discussion in
Ref. [15] with e.g. (3.59).
aðhvÞ ¼ constðhv Eg Þ1=2 for hv Eg (4)

and aðhvÞ ¼ 0 for hv < Eg :
This behaviour is expected if one assumes simple

vertical band-to-band transitions without any electron-hole
Coulomb correlation (i.e. without exciton states) and without
Figure 5 The A, B and C exciton series seen in absorption in their
respective polarizations and for 4.2 and 295 K, according to Ref. [64]. broadening mechanics. This simple approach is never
observed in semiconductors and it is in stark contradiction
with the correct statement frequently given in the introduc-
from values G 1 meV < DLT at 4 K to G 20 meV tion of the same papers that the exciton binding energy is in
(HWHM) > DLT at RT. See Fig. 8 or Refs. [14, 66]. ZnO with a value of 60 meV relatively large. Actually the
An exponential tail develops in the absorption spectra approach (4) goes back to the middle of the last century [69]
with increasing temperature on the low energy side of the when not much was known about the optical properties of

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semiconductors. It is not clear to the authors, why such an

outdated approach is now revived.
The approach of Eq. (3b) is valid in the so-called Tauc-
regime in the absorption spectrum of disordered (e.g.
amorphous) semiconductors. It is connected with the
concept of a mobility edge and occurs only at photon
energies and absorption coefficients beyond the Urbach tail.
See Ref. [28] and references therein. To make it explicitly
clear, a valid fit of the absorption spectrum with (3b)
extrapolates to a characteristic energy then correctly named
‘optical gap’ only if it is situated energetically around the
upper end of the Urbach tail, not somewhere at its beginning.
The use of this approach for disordered semiconductors
strongly contrasts again with the statement frequently given
in the same paper that the used ZnO samples are of ‘high
crystalline quality’ as deduced e.g. from XRD rocking
curves, HRTEM and other methods.
The energy which is determined with the above methods
gives in some way the onset of the absorption edge. But even
to analyse this region, a fit with the Urbach tail would be
much more adequate.
The free excitons and their LO-phonon satellites can also
be seen in (photo-) luminescence. Figure 6 shows the
dispersion relation and the low temperature luminescence of
the nB ¼ 1AG5 exciton polariton for the orientations E?c and
k?c (Fig. 6 a, b) or kjjc (Fig. 6c, d). The influence of the k-
linear term in the A VB for k?c is obvious, which mixes the
AG5 spin singlet with the A(G1 þ G2) spin triplet states and
gives them a k?c-dependent oscillator strength. For Ejjc
(Fig. 6e, f) one observes the spectrally much narrower
luminescence signal from the AG1 state, which has a much
lower oscillator strength because it involves a spin flip,
though being dipole allowed in this orientation. It is evident
from Fig. 6 that the assignments in Fig. 1 of Refs. [62a] or in
Refs. [62b] are open for discussion, which attribute two
emission peaks to the transverse nB ¼ 1AG5 exciton and to its
lower polariton branch (LPB) separately, while the triplet
(AG6 in the band structure notation of Ref. [62]) is situated Figure 6 The polariton dispersion and the luminescence of the zero
phonon exciton polaritons for various orientations at 1.8 K, accord-
above the LPB and is of comparable intensity and width.
ing to the work of Hümmer in Refs. [49] and [14].
At higher temperatures the zero phonon emission of A
and BG5 excitons may be fitted with Lorentzians. See Fig. 7.
Their LO-phonon replica can be modelled including the by reabsorption through the Urbach tail at higher tempera-
square-root density of states of effective mass particles tures as shown in Fig. 7 for 290 K. The analysis of the
(here the excitons), a Boltzmann occupation probability and luminescence spectra allows determining the homogenous
the proper dependence of the transition probability on k, the width of the A and BG5 excitons as a function of temperature
whole result folded with the Lorentzian used already for the (see Fig. 8 for the HWHM data) and the shift of the band gap
zero phonon line. The exciton temperature is assumed to (see Fig. 9) where a fit using the theory of Ref. [70] is shown.
be identical to the lattice temperature. This is a valid The equations derived there are more complicated than the
assumption for low excitation levels, small excess energy frequently used Varshni formula and are therefore not
and the temperature range covered in Fig. 7. For more details reproduced here.
see Ref. [66] and references therein. Note that there is no We already stated that the optical properties of good
physical reason for a fit with one or several Gaussians. epilayers and of nano rods are essentially identical to the ones
The LO phonon energy is found in the distance of the free of good bulk samples with possibly two differences.
exciton to the low energy side of the LO phonon satellites Absorption and reflection spectra may be difficult to measure
(not to the maxima which are influenced by the thermal on nano rods and the details of their optical properties may be
kinetic energy of the excitons), roughly the point of influenced by their waveguide properties. (See Section 10).
inflection. Furthermore the luminescence may be influenced To verify this general statement we show in Fig. 10 the

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Figure 8 The homogeneous width (HWHM) of the free A and B

excitons as a function of temperature, according to Refs. [66, 71].
temperature at low temperatures faster to the red than the

band gap does. This region is followed by a temperature
interval in which a blue-shift dominates caused by thermal
population of higher states, followed again by a red-shift
following then essentially the temperature dependence of the
gap. If this dependence is plotted over the temperature, the
resulting curve looks like a badly written small ‘n’. Strange
enough, this dependence is called in the literature frequently
an ‘s’-shaped behaviour.
In Fig. 11 we show a set of spectra of MgxZn1xO at
4.2 K as an example. For x ¼ 0 the broadened (A þ B) G5
nB ¼ 1 exciton resonance can be seen at 3.375 eV and above
the onset of band-to-band absorption. The full triangles
indicate the LO phonon replica in luminescence. The full
circles in the insert give the exciton energies.
Figure 7 (online colour at: www.pss-b.com) The luminescence of

the free exciton polariton and of its LO-phonon satellites for various
temperatures, according to Refs. [14, 66, 71].
photoluminescence of a single nano rod for two different

temperatures, which looks very much like the luminescence
of a good bulk sample.
In alloys the emission and absorption features broaden
inhomogeneously due to alloy disorder, resulting in a
substantial Stokes shift between the two and an overall shift
due to the dependence of the gap and of the exciton binding
energy on the composition. Furthermore an ‘n-shaped’
dependence of the luminescence maximum can be observed
with increasing T which results from temperature dependent
relaxation processes in the tail states [28]. This ‘n-shaped’ Figure 9 The dependence of the band gap on temperature as
dependence means, as in other semiconductor alloys [28], deduced from luminescence and absorption spectroscopy, according
that the emission maximum shifts with increasing to Refs. [66, 71].

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Figure 10 (online colour at: www.pss-b.com) The luminescence

of a single nano rod at 10 K and 50 K (a) and a close up to the free and
bound excitons at 10 K (b). The LO phonon replica of the BEC are
marked by vertical arrows. According to Ref. [72].
In quantum structures there is in addition to alloy

disorder in the well and/or the barrier also a further
contribution to inhomogeneous broadening due to well
width fluctuations. For some examples see Ref. [74].
9 Bound exciton complexes, free-to-bound and

donor–acceptor pair transitions The low temperature Figure 11 Luminescence and absorption spectra of a set of
(T 50 K) near edge luminescence of high quality bulk MgxZn1xO films. According to Ref. [73].
samples, epilayers and nanorods is dominated by radiative
recombination of bound exciton complexes (BEC or BE).
See Fig. 10 or Refs. [75–80] for an example. The width of Refs. [76] or [79]. Furthermore excited states have been
individual lines can be at low temperatures (T 1.8 K) as observed for these BEC in photoluminescence excitation
narrow as 100 meV [77]. In lower quality samples, they are spectroscopy containing one or two holes from the B-VB
broader and the whole BEC emission spectrum may merge [79]. The latter is only possible for A0X. Later on even a
into one inhomogeneously broadened band. See e.g. the majority of the BEC lines has been attributed to A0X [80],
comparison of the luminescence spectra in Ref. [63]. which is surprising to some extend, since nominally undoped
The bound exciton lines have been labelled by Reynolds ZnO is always n-type. Presently there is agreement that both
as I0 to I10 from higher to lower emission energies [75]. In the D0X and A0X may occur in the low energy part of the BEC
meantime many more lines have been observed, labelled e.g. spectrum, i.e. in the range from I8 down to I12 [78]. This
as I6a etc. [78]. means that a decision between D0X and A0X cannot be made
The simplest, straight forward assignment of these lines from the spectral position alone.
would be to attribute those with the lowest binding energies On the low energy side of the BEC there are further
to excitons bound to ionized donors DþX (e.g. I2 and I3) the contributions to the near edge emission, from which we
next to excitons bound to neutral donors D0X (e.g. I4, I6, I8, mention some in the following.
and I9) and the deepest ones to A0X (e.g. I9, I10, and I12). There are the LO-phonon satellites of BEC and of free
Excitons do not form a bound state with ionized acceptors in excitons. See e.g. Fig. 10. Then there are the two electron
ZnO. For some of the D0X the chemical nature of the centre satellites (TES) in the interval from 3.29 to 3.33 eV. The
could be identified (I4:H, I6:Al, I8:Ga and I9:In). See the work origin of these TES is the radiative recombination of a D0X
by Meyer in Ref. [76]. The search for and interpretation of with simultaneous transfer of the electron of the remaining
D0X and A0X states has varied with time. First the lines I9 D0 into an excited state like 2s or 2p. The observation allows
and I10 have been attributed to A0X based on the to determine the binding energy of the electron to the donor
thermalization properties in a B-field and on doping EDb , assuming a hydrogen like series of states, and to verify
experiments with Li and Na. See the work by Tomzig in the so-called Haynes-rule [81] which relates EDb with the

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binding (or localization) energy of the exciton in the BEC

EDb 0 via
X
EDb 0 X ¼ a þ b EDb ; (5)

originally formulated with a ¼ 0. The constants a and b can
be determined from experiment resulting in a ¼ 3.8 meV
and b ¼ 0.365 [76].
Furthermore, there are excitons bound to deep centres
e.g. iso-electronic traps or to structural defects e.g. the
Y-band or so-called surface excitons. These are excitons
bound to centres at or close to the surface, i.e. in a surface
layer with a thickness comparable to the exciton radius [82] Figure 12 The spatially directed stimulated emission from a ZnO
(not to be confused with surface exciton-polaritons [83]). sample just above(left) and well above threshold (right), according to
Free-to-bound transitions describe the recombination of Ref. [85].
a free carrier (in ZnO usually an electron) with a bound one
(in ZnO frequently a hole bound to an acceptor). Therefore
the band is also known as eA0. The thermal distribution of emission of one or two LO phonons [86, 87]. A photographic
the free carrier is seen in the luminescence spectrum because plate has been attached just outside the cryostat window
k-conservation is relaxed by the localized carrier. The eA0 (Ø 4 cm, distance to the ZnO sample about 10 cm) without
emission may dominate in less pure samples up to RT. any further optics except a filter, which blocked the pump-
Frequently its zero-phonon band coincides with the first light.
LO-phonon replica of the free exciton. As a first approach, the gain processes can be grouped
Donor–acceptor pair recombination occurs at a photon as limiting cases into excitonic ones and the recombina-
energy given by tion in an inverted (or degenerate) electron hole plasma
(EHP) [28].
hv¼Eg EDb 0 EAb 0 mhvLO þ e2 =ð4pee0 rDA Þ:
(6) The excitonic ones include the recombination of a free
exciton under emission of one or more LO-phonons
The last term in Eq. (6) describes the Coulomb energy of (X-mLO). The X-mLO process has relatively low threshold
the ionized donor and acceptor after the recombination and gain. Therefore it is observed preferentially if large
process. It results in a blue shift of the emission with volumes with low losses are excited e.g. by two-photon
increasing (excitation-) density i.e. with decreasing (aver- absorption as in Fig. 12 [85–87] the positions of the emission
age) distance rDA. maxima of the X-mLO process can be approximated by
The assignment of various luminescence features to
these above-mentioned processes is not unique and still a hvmax ¼ Eg ðTÞ EbX mhvLO þ aðmÞkB T; (7)
point of controversial discussion as outlined by Waag in Ref.
as long as reabsorption by the Urbach tail (see above) can be
[16] chapter 5. Therefore we give here only one more
neglected. In Eq. (7) Eg(T) is the temperature dependent
reference as an example [84].
gap energy (see Fig. 9), EbX the exciton binding energy (in
In alloys and QWs the BEC emission merges usually
ZnO (59.5 0.5) meV), hvLO the LO-phonon energy (in ZnO
with the recombination of excitons in localized tail states so
72 meV), kB Boltzmann’s constant and a(1) ¼ 3/2 and
that an easy distinction between an exciton localized ‘only’
a(m > 1) ¼ 1/2. See for details of a line shape analysis also
by disorder or bound ‘additionally’ to some defect is hardly
the explanations above with Fig. 7 and [66, 71, 87].
possible.
The next process is the inelastic exciton–exciton
scattering (X–X) in which one of the excitons is scattered
10 Stimulated emission The processes for stimu-
onto the photon-like LPB and appears as a luminescence
lated emission are in ZnO essentially the same for high
quantum while the other reaches under energy and
quality bulk samples, epilayers, nano rods, nano-crystals and
momentum conservation a higher state with main quantum
partly also QWs.
number nB ¼ 2..1, resulting in the emission bands P2 to P1.
Stimulated emission is usually characterized by a
The process is called inelastic, because the total energy is
threshold behaviour of the input/output characteristics
conserved, but not the kinetic energy, the conservation of the
ILum ¼ f(Iexc) (see e.g. Ref. [28] or Fig. 19), a narrowing of
latter being the definition of elastic scattering. For a
the emission spectrum or the appearance of a mode pattern
hydrogen-like exciton series the emission maxima are
(see e.g. Figs. 19 and 20) and spatially directed emission. See
situated around [87]
Fig. 12.
The photo of Fig. 12 has been obtained under two-photon hvmax ¼ Eg ðTÞ ð2 1=n2B Þ EbX þ d3kB T; (8)
excitation of a rather large volume of several mm3 with
pulses from a Q-switched ruby laser. Under these conditions where Eg(T) is again the temperature dependent gap energy,
the laser process is the recombination of excitons under EbX the exciton binding energy, kB Boltzmann’s constant and

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Figure 13 The luminescence spectrum of the X–X process (P2 and

P1 bands) under one photon excitation at 60 K, according to Ref.
[87].
d has a value of 0 < d < 1, (typically d 0.5). The laser

emission occurs in this, like in many other processes [88],
often on the low energy side of the maximum. The X–X
process has been observed in many semiconductors Figure 14 The schematic presentation of various excitonic recom-
including ZnO [28, 91]. In Fig. 13 we give an example. bination processes in the intermediate density regime, according to
With increasing temperature the nB 2 states become Refs. [28, 87, 93].
thermally populated resulting in reabsorption and an increase
of the threshold with temperature. This increase is even more In Fig. 15 we show the temperature dependence of
pronounced, when part of the excitons become ionized several (stimulated) emission maxima.
thermally. Then (for ZnO at T 100 K) a new process sets in, The solid lines in Fig. 15 give the temperature
namely an inelastic scattering between a free exciton and a dependence of the free A and B exciton energies and of
free carrier, in ZnO generally an electron [28]. From energy their LO phonon replica. The BEC and their LO replica are
and momentum conservation one can deduce that the indicated in grey (red). The dashed lines give the Pi (i ¼ 2,1)
maximum of this X-e emission process shifts with increasing bands for T below approximately 100 K and the X-e process
temperature faster to lower energies than the band-gap does above. These data are confirmed by experiment [87]. The
e.g. according to [87] as
hvmax ¼ Eg ðTÞ EbX

3kB T½M=me 1 þ 2gðM=me Þ1=2 =2; (9)
where M is the free exciton mass, me the electron mass and g

again around 1.
The temperature dependences of the thresholds of the
various processes mentioned above have been calculated and
verified experimentally for CdS and partly for ZnO [89],
though the absolute densities in the calculation for CdS are
most probably too high, since they reach well into the EHP
regime. The thresholds of the various processes depend
trivially on the losses. For the X-mLO and the X–X processes
it increases above approximately 100 to 150 K due to
reabsorption, while the one of the X-e process decreases in
this temperature interval due to thermal ionization of free
carriers
Some other excitonic processes involve the formation
and decay of biexcitons (for bulk and QWs see Refs. [9, 90])
or the participation of bound exciton complexes, e.g. their
acoustic phonon side band [92, 93].
All the intrinsic processes mentioned above are shown
schematically in Fig. 14. A small selection on theory and Figure 15 The temperature dependence of the emission maxima of
experimental results is found in Refs. [28, 87, 93] and the various processes. See text. According to Ref. [14]. The references
references given therein. [4–8,10,22] in the inset correspond to [94–100] here.

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Figure 17 The density dependencies of the BGR DEg, the exciton

energy and of the chemical potential m(np,T ¼ 300 K). According to
Refs. [14, 102].
Figure 16 Schematic representation of the recombination in an

energy E0X b (np) is smaller than the HWHM value of the
inverted (or degenerate) EHP. According to Ref. [14]. homogeneous width.
The last quantity which we introduce with Figs. 16
and 17 is the chemical potential of the electron–hole pair
open and closed symbols are more recent experimental data. system m(np,T). This is the energetic distance between the
We will come back to them later. quasi Fermi levels of electrons and holes describing the
Most of the excitonic processes can be mapped on a four distribution of the various carriers in their respective bands.
level laser system (except for the X-e process) with ideally The quantity m(np,T) depends strongly on both variables.
vanishing threshold at low T. The X-LO process is inverted if Population inversion and optical gain are reached, if
there is one exciton in the sample and no LO phonon, the
biexciton recombination is inverted if there is one biexciton mðnp ; TÞ > Eg0 ðnp Þ: (10)
and no exciton etc. Finite losses require of course finite
threshold densities. At low temperatures the condition (10) is fulfilled
If the electron–hole pair density np is increased, various already at np ¼ nM. In Fig. 16 we show the situation for T!0
things are happening: The gap is normalized due to exchange and in Fig. 17 for RT. Optical gain occurs in the interval
and correlation effects. This means that Eg0 ðnp Þ decreases
monotonically with increasing np. This band gap renorma- Eg0 ðnp Þ hv mðnp ; TÞ: (11)
lization (BGR) is essentially temperature independent [101].
The experimentally observed BGR in various II-VI semi- In simplest approximation the spectral shape of the gain
conductors (Fig 21.2 in Ref. [28]) is somewhat larger than the spectrum g(hv) is given above E0 g(np) by the square root
calculated data in Ref. [101]. In Fig. 17 the solid and dashed dependence of the density of states of the free carriers and the
curves correspond to theory and an average over the II-VI quasi Fermi functions according to
data.
The next thing is that the exciton binding energy gðhvÞ ¼ const½hv Eg0 ðnp Þ1=2
(12)
decreases with increasing np due to Coulomb screening ½fe ðnp ; TÞ þ fh ðmðnp ; TÞ 1;
and Pauli blocking, i.e. the exciton state shifts closer to
Eg0 ðnp Þ. The BGR and the decrease of E0X b (np) almost and zero below. Actually there are some modifications: at
compensate each other with the consequence that the the low energy side a tail forms due to final state damping
exciton energy remains in absolute terms almost constant, and Fermi sea shake up [93, 101] and [103], at the high
but its homogeneous width increases as shown by the energy side an enhancement of the oscillator strength occurs
hatched area in Fig. 17. At a density nM called Mott density due to the residual electron–hole Coulomb correlation [93,
E0Xb (np) tends to zero, i.e. excitons do no longer exist as 101].
individual quasi particles and a new collective phase is In Fig. 18 we show gain spectra obtained for bulk
formed, the EHP. For ZnO one finds from Fig. 17 nM ¼ 4 to samples, platelet type ones and epilayers, measured with the
9 1017 cm3. Due to the finite damping, excitons will no variation of the excitation stripe length (Fig. 18a and c) or by
longer be good quasi particles at RT already at densities np pump-and probe techniques (Fig. 18b). The parameter is the
around 1017 cm3 because then their renormalized binding pump power. The lattice temperature is around 5 K but the

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Figure 19 (online colour at: www.pss-b.com) Stimulated emission

of a single nano rod pumped at 11 K with 5 ns pulses at 3.495 eV.
According to Refs. [102, 115].
temperature of the EHP may be higher. The variation of the

low energy side of the gain spectra reflects the density
dependence of the BGR. The high energy side is determined
by the density and temperature dependent chemical
potential. Note that in thicker samples both quantities may
have a spatially inhomogeneous distribution. The absolute
values of the gain depend on the filling factor of the excited
volume with an EHP [104] and on the overlap of the light
field with the pumped volume. Especially in thin epilayers
this overlap may be substantially below unity.
For the broadest gain spectrum in Fig. 18c, the gain
extends from 3.34 eV down to 3.20 eV. See also the vertical
bar in Fig. 15 labelled EHP. The BGR is from 3.341 eV for
np ¼ 0 cm3 down to 3.24 eV i.e. by about 200 meV resulting
with Fig. 17 in np 1019 cm3. The variation of the pump
power was limited on the high energy side by the damage
threshold of the sample.
After the discussion of the limiting cases we now come to
the transition region. Since the short electron–hole pair
lifetime prevents the formation of a liquid-like EHP state,
even well below the expected critical temperature for such a
van der Waals gas like phase separation into an EHL in the
form of droplets surrounded by a gas of free carriers, excitons
and biexcitons, there is a continuous transition from the
optical properties of an exciton gas to an EHP [28, 106].
The situation is even more intriguing at RT and above.
We discuss this situation with Figs. 15 and 17 along the lines
Figure 18 (online colour at: www.pss-b.com) Gain spectra of EHP already given in Refs [14, 66]. The more recent data points in
recombination at low temperatures and for various excitation inten- Fig. 15 start together with the old ones at low T in the range of
sities (in all cases ca. 5 ns excitation pulse duration and band-to-band P1 and X-LO and follow at T 100 K to some extend the
transition excitation), for a bulk sample (a), a platelet (b) and an dashed X-e line. At RT stimulated emission and gain have
epilayer (c). The pump powers were 0.24, 1 and 4 MW cm2 in (a) been observed by various authors in the range from 3.2 eV
and 3.8 MWcm2 in (b). According to Refs. [104, 105]. down to 3.05 eV. One group claims stimulated emission via
two different processes up to 550 K [95].
The np values given by most of the authors (or deduced
from the experimental data) are for the appearance of

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stimulated emission in the range between a few times are presented and discussed in Refs. [110, 111] and in an
1017 cm3 to a few times 1018 cm3. Surprisingly most of the invited contribution [113] to this conference [112]. For hints
recent authors claim the gain mechanism for RT stimulated towards random lasing in disordered ensembles of nano rods
emission to be inelastic X–X scattering. The energetic see Ref. [114].
scattering of the data at RT in Fig. 15 immediately makes To conclude this section we give a few words on claims
clear that different processes are involved. of stimulated emission under optical pumping with power
The inspection of Fig. 17 shows that excitons do no densities as low as 10 Wcm2 [116, 117].
longer exist at these densities at RT as individual quasi- An excitation power of 10 Wcm2 results with reason-
particles since the remaining (or renormalized) binding able values for lifetime (1 ns, see below) and excitation
energy is smaller than the homogeneous width. Therefore the depth (1 mm) determined essentially by diffusion in a density
assignment of gain at RT to excitonic processes will be in np ¼ 5 1014 cm3. This value is too low to produce an EHP
most cases a misconception. The data given by open full stars [116] or significant X–X scattering [117]. The appearance of
are assigned in Ref. [95] to recombination in an inverted modes observed in Ref. [116] may also occur for spon-
EHP. This interpretation is most probably a wrong one. At taneous emission [118] and slopes above one [117] can be
450 K the BGR had to be at least 300 meV resulting in np explained without stimulated emission by simple (e.g.
values well beyond 1020 cm3. These values are neither quadratic) recombination kinetics [28] as well.
compatible with the experimental excitation conditions nor
with the damage threshold of the sample. 11 Dynamics The luminescence decay time of ZnO
On the other hand it is an experimental fact that bulk samples and nano structures has been measured by
stimulated emission is observed at RT in the density regime many research groups. See e.g. Refs. [9, 119] and [120] and
mentioned above though neither excitons exist as good quasi references therein for some examples for bulk, epilayers,
particles nor is an EHP inverted. Therefore we proposed in rods, QWs and nano crystallites. There are also data given on
Refs. [14, 66] and [107] two other recombination processes, dephasing and intra- or inter (sub-) band relaxation. We
which can occur already in a non-degenerate EHP, which has concentrate here mainly on the lifetime. The decay dynamics
some residual Coulomb correlation between the carriers. We is frequently not exponential, so that one cannot speak about
note first that in this density regime the position of the a luminescence decay constant, but only about an effective
renormalized gap E0 g(np) coincides approximately with the decay time tl valid for the given density interval. Frequently
exciton energy at low densities. One of the two processes is the decaying intensity is followed in the experiments only
the recombination of an electron–hole pair in the EHP under over one order of magnitude or even less. This interval is by
emission of a photon and of one or two LO phonons (or more far not sufficient to claim a single or even multi-exponential
accurately plasmon–phonon mixed state quanta). This decay. Fitting with a power law or a stretched exponential is
suggestion is supported by the fact that the data given by usually also possible and partly physically even more
the open stars in Fig. 15 extrapolate the X-2LO process reasonable. To claim a single exponential decay, the signal
observed at lower temperatures and densities. The full stars should be followed at least over three orders of magnitude
in contrast extrapolate beautifully the X-e line and could [121]. The value of tl varies from sample to sample, with
therefore be explained by a process in which again an temperature and with the excitation conditions. Both for free
electron–hole pair recombines in the EHP under emission of and bound excitons and their LO-phonon replica tl is found
a photon and simultaneously transfers part of its energy and generally in the interval
its momentum to a third carrier, most probably another
electron. A detailed many-particle calculation is necessary to 0:1 ns tl 3 ns: (13)
verify or to falsify these concepts.
The explanation developed above may be valid for bulk Differences in tl may already occur between the upper
samples, platelets, epilayers, micro- and nano-rods, for nano and LPBs [122]. Since the (external) luminescence yield h of
crystals and even in QWs. the near edge emission is typically around 0.1 in high quality
Nano rods have a pronounced wave guide property and samples at low temperatures and tends to decrease towards
mode structure. We show in Fig. 19 the stimulated emission higher T [58] this luminescence decay time is significantly
from a single rod at 11 K under band-to-band excitation with different from the radiative lifetime tr. To identify tl with tr is
5 ns pulses from the 3rd harmonic of a Nd-YAG laser. The only correct if h is close to one. However, this precondition is
laser modes are clearly visible. They show mode competition generally not verified.
with increasing excitation (see inset and Fig. 20c) and a Under conditions of stimulated emission the decay time
small blue shift. We will come back to these aspects later. may become much shorter than the range indicated by Eq.
If there is no mode available for a certain emission process (13) reaching down to 10 ps.
(e.g. the X–X process at low temperatures) this process may We show in Fig. 20 a rather illustrative example. A single
be suppressed [108]. nano rod has been excited in the band-to-band transition
Random lasing has been observed in ZnO powders [109]. region with 150 fs pulses. The luminescence was spectrally
Recent results of this topic including the observation of the and temporally resolved by the combination of a spec-
coexistence of spatially extended and more confined modes trometer with a streak camera. At low cw-excitation the

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sample shows a well resolved near edge emission similar to

Fig. 10. At the lowest fluence F in Fig. 20 the emission
appears mainly in the M-band region. For possible origins of
this band apart from biexciton decay see Ref. [93]. With
increasing F the spectrum broadens and shifts to the red. At
F ¼ 0.35 mJ cm2 it is at least at the beginning due to
recombination in an EHP. With further increasing F sharp
laser modes develop.
We qualitatively discuss the prominent features seen in
Fig. 20 in the following:
Overall, the spectrum broadens and shifts to the red with
increasing F. This fact is due to the increase of the carrier pair
density np in the EHP and the resulting increase of BGR and
band filling. Which of the two effects dominates depends on
np and on T. This means that there is no such thing like a
simple Burstein-Moss shift of the absorption edge (and of
other spectral features) to the blue due to filling of states.
Secondly one sees that every individual mode shifts to
the blue with increasing F. See also Fig. 20c. In the transition
to an EHP first the exciton resonances are bleached and
disappear [104, 123] and then the lower end of the band-to-
band transitions is blocked between Eg0 ðnp Þ and m(np,T).
This bleaching of absorption leads via Kramers–Kronig
relations to a decrease of the real part of the refractive index
n(np). Since the geometrical length of the rod remains
unchanged, the vacuum wavelength must have become
shorter i.e. the photon energy must increase so that the
number of half waves fitting in the rod length remains
constant for a given mode.
Finally, it can be seen that within every trace the modes
shift with time back towards the red. This fact results simply
from recombination of the carriers and the resulting recovery
of the refractive index.
12 Conclusion and outlook We mentioned at the

beginning that the main driving force for the present
renaissance of ZnO research is the hope to obtain green/
blue/near UV light emitting (LED) or LD. Though p-type
doping is not yet solved in a stable and reproducible way,
several reports exist on electrically pumped, ZnO-based
LEDs and a few on LDs. For a small selection see Refs. [8–
17, 18] and [19]. Partly the structures are made entirely of
ZnO and its alloys with MgO, BeO and CdO, partly hetero
structures are grown with n-type ZnO and p-type GaN, SiC
etc.
Common features of almost all examples are at present as
already partly mentioned in chapter 2:
– a low luminescence yield. See e.g. data given in the

introduction
Figure 20 (online colour at: www.pss-b.com) Time resolved emis- – an emission spectrum which contains a lot of deep centre
sion spectra of a single rod at 15 K excited with 150 fs pulses from the luminescence or is partly even dominated by it
second harmonic of a TiSa laser for various excitation fluences F. – no information exists on the lifetime of the devices.
Every horizontal trace covers a time interval of 60 ps (a), the intensity
of the modesas a function of F (b) and the shift of themodes with F (c). Because of the low valence band in ZnO [124] electrons
According to Ref. [115]. are generally injected in heterojunctions from ZnO into the
other material and not holes into ZnO. This has the

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unfortunate consequence that the luminescence originates while only kz can be varied (quasi-) continuously in the limit
not from the ZnO, but either from a spatially indirect of a very long rod [129–131].
transition across the interface or from the other material of We start with a relatively trivial point. It has been
the hetero-junction. These materials have partly an intrinsi- claimed that the dispersion of the empty cavity modes (i.e. of
cally low luminescence yield if they have an indirect gap the cavity containing no QW) and being described by the
(like SiC) or they can also be doped n-type themselves (like constant refractive index of air or better of the barrier
GaN), thus casting some doubt on the technical relevance of material of the well nb is parabolic [28, 129]. This statement
the heterostructures. is wrong. The intersection of a light cone defined over the
To conclude we may state that beautiful old and new kk k? plane by
physics can be investigated in ZnO, its alloys and nano
structures and that many applications for ZnO exist or are E2 ðkk ; k? Þ ¼ ðhvÞ2 ¼ ðk2k þ k2? Þc2 h2 =n2b ; (14a)
emerging. The question if ZnO will see a major breakthrough
with the plane given by
in (opto-) electronics depends strongly on the availability of
high, efficient, stable and reproducible p-type doping and of k? ¼ mp=d; (14b)
efficient LEDs and LDs based on it in the next (very few!!)
years to come. results in a hyperbola and not a parabola. See e.g. Fig. 17.1d
in Ref. [28]. The curvature of this hyperbola is in its
minimum given by
Acknowledgements The authors want to thank the
Deutsche Forschungsgemeinschaft for financial support in an @ðhvÞ=@kk2 ¼ ch k? =nb ; (15)
individual grant (Kl 354/23) and through the CFN and the Landes-
stiftung Baden-Württemberg through the Kompetenznetz
If one translates this curvature into an effective mass meff
‘Funktionelle Nanostukturen’ Project A1.
one obtains
Appendix The fact that the deadline for the paper meff ¼ hv=c2 nb : (16)
submission to the proceedings of the 14th International
Conference on II-VI Compounds was about 3 weeks after the This means that the effective mass in the minimum is just
end of the conference has an advantage. Some thoughts about given by a modified Einstein relation
contributions to the conference can be included in this
review. It is clear to the main author of this appendix (CK) E ¼ hv ¼ meff c2 : (17)
that not all of the ideas presented below are yet mature. Partly
This corresponds indeed to the very low effective mass
they even contradict present state theoretical modelling.
quoted usually in connection with claims of Bose Einstein
They are therefore meant as a stimulus for discussion in the
condensation (BEC) of cavity polaritons. However, it must
scientific community.
be kept in mind that for a hyperbolic dispersion meff is not
We consider here some aspects of exciton cavity
constant, but increases rapidly for finite kjj and asymptoti-
polaritons in quasi two-dimensional and quasi one-dimen-
cally reaches the value infinity in the linear part of the
sional systems, which are both relevant for ZnO [125–131]
hyperbola. Possibly one could think to introduce a concept of
and compare them to bulk material. Quasi two-dimensional
meff based on the first derivative as used e.g. in metal physics
systems are in the present context Fabry–Perot resonators
around the Fermi energy [28]
with plane, highly reflecting mirrors on both sides (generally
Bragg reflectors) containing in this cavity one or a few QW, meff ¼ h2 k=ð@E=@kÞ: (18)
with the exciton resonance of these QW overlapping
energetically with the two-dimensional dispersion E(kjj,k? ) The next aspect is excitonic or polaritonic Bose-Einstein
of the cavity modes without these QW, the so-called empty condensation (BEC). At least one of the authors of this
cavity. The value of k? is quantized by the cavity modes to review (CK) is notoriously sceptic about excitonic BEC [28],
mp/d where d is the geometrical thickness of the cavity and because he has seen in the 35 or more years of his scientific
m ¼ 1, 2, 3. . .. The in-plane wave vector is given by career too many claims of excitonic BEC appearing and
kjj ¼ kxex þ kyey where ex and ey are the unit vectors in the disappearing again. See for some recent examples e.g. Refs.
plane of the cavity. Without loss of generality we can choose [133, 134] and the references therein. However, the results
ky ¼ 0 for a system isotropic in the x–y plane. Examples are presented at this conference [126–128] start to be convinc-
e.g. GaAs, ZnO or CdTe based cavities [28, 126–128] and ing, especially since both thermal quasi-equilibrium con-
[132]. A good overview of this field is found in Ref. [138] and ditions in the BEC ground state have been reached and the
the references therein. differences to polariton lasing have been worked out and also
The quasi one-dimensional situation has been realized in to a process analogous to two-photon or hyper-Raman
ZnO micro rods of some micrometers in diameter and some scattering in bulk samples [93] under a so-called magic
10 mm in length by whispering gallery modes (WGM), in angle. The first difference i.e. polariton lasing is a very
which the k vector is quantized in the two-dimensional plane common phenomenon in semiconductors [14, 93] and
perpendicular to the growth-, z- or c-axis of the micro rod, includes among other processes the inelastic polariton–

pss b
solidi
physica
status
polariton (or exciton–exciton) scattering which results in the lz is much smaller than the width of the cavity d
Pi-bands (i ¼ 2,3. . .1). See above or Ref. [28]. This positive
statement about BEC of cavity polaritons is made being 10 nm lz d 500 nm: (19)
aware of the implications (or difficulties) of BEC in a quasi
two-dimensional system, which has in meff–approximation This means that only a small fraction of the cavity
ideally a Heavyside function for the density of states instead volume contains the exciton resonance. The Q-value or
of the square root one and in reality tail states resulting from finesse of the cavity and the dephasing time T2 of the exciton
inhomogeneous and homogeneous broadening induced e.g. can be varied independently. The strong coupling regime
by width fluctuations of both the QW and of the cavity and with the pronounced non-crossing behaviour between the
from scattering processes e.g. with phonons. dispersion curves of the empty cavity mode and of the
A third point addresses the concepts of strong and exciton is reached if T2 is several times the round trip time tr
weak coupling between cavity modes and exciton resonance, of the light in the cavity, typically requiring T2 1 ps.
since we think that there are significant differences in the Furthermore, the small volume fraction occupied by the QW
three- and quasi two- and one-dimensional systems dis- has the advantage that the absorption of the QW hardly
cussed here. affects the finesse of the cavity. Even with a ¼ 105 cm1 and
In a bulk sample, the coupling between light and exciton lz ¼ 10 nm one obtains an optical density of only a lz ¼ 0.1.
resonances is an intrinsic feature and so is the resulting The Rabi splitting is then given in the case of strong coupling
exciton polariton dispersion curve. Consequently, one is for by the minimal energetic distance between the lower and
excitons in direct gap semiconductors generally in the strong upper polariton branches of the cavity exciton polariton
coupling limit. Even for damping zero one has a significant resulting from the (quantum-mechanical) non-crossing rule.
imaginary part of k or k [28] between the transverse and It can be much higher than in bulk samples.
longitudinal exciton eigen-energies, which makes the In the case of weak coupling, the exciton resonance is so
direct observation of the dispersion in this spectral range a strongly (in-) homogeneously broadened (and so is the
non-trivial problem. Frequently processes of nonlinear contribution of this resonance to the whole system consisting
optics are used for its experimental verification like two- of cavity mode and exciton) that it hardly influences the
photon absorption or hyper-Raman scattering [28]. In linear hyperbolic empty cavity dispersion. Also this behaviour is
optics the polariton dispersion can be deduced by the favoured by the small volume fraction occupied by the QW.
refraction at a thin prism, from resonant Brillouin scattering The situation is now significantly different for the quasi
or from the Fabry–Perot modes of thin platelets. See for one-dimensional longitudinal cavity formed by the micro rod
some references [28]. Care has to be taken for the or for the transverse WGM and starts to resemble again the
observability of the dispersion between the transverse and situation of bulk material, since in this case the whole cavity
longitudinal eigen energies of the bulk exciton polariton is formed by and filled with the medium containing the
resonances that the optical density of the platelet type exciton resonance and is described by its complex index of
samples a(£v)d remains below or around 1, despite the fact refraction
that the reflectivity for the intensity under normal incidence n~ðvÞ ¼ nðvÞ þ ikðvÞ: (20)
reaches values around 0.8 for a single surface on the LPB.
This value is almost comparable to the one of real Bragg
mirrors and results from the fact that the real part n(£v)of the This means that these cavity modes are determined
complex index of refraction reaches values beyond 10 in the completely by this ñ(v). The absorption coefficient a( hv)
above mentioned range. See e.g. Figs 13.17 and 20 in Ref. reaches in ZnO throughout the whole cavity values
[28]. If a(£v)d grows considerably beyond unity, the a(hv) 2 105/cm in the spectral range between the
observability of the Fabry–Perot modes becomes quenched transverse and longitudinal eigen energies of the bulk
simply by absorption, though one is still in the strong exciton. See Fig. 5. Consequently, alz ¼ ad ¼ 20 already
coupling limit. for d ¼ 1 mm. This fact has the consequence that the visibility
For Fabry–Perot (i.e. micro-cavity) modes on one side of the micro rod cavity modes is completely quenched when
and WGM on the other, the situations are different, too, since approaching this spectral range. Actually, to the memory of
several round trips of the light are necessary to form the one of the authors (CK), no cavity modes where visible in
polariton. Strong losses in the cavity caused e.g. by a large Refs. [129–131] around 3.31 eV, the position of the A and B
optical density necessarily destroy the modes [28]. See G5 nB ¼ 1 exciton resonances at RT, but only a broad
above. luminescence band from the free exciton and its LO-phonon
For the quasi two-dimensional case, the cavity is replica. See Fig. 7.
essentially filled with the barrier material of the QW, which Towards lower photon energies where ZnO becomes
has in the spectral region of interest – the exciton resonances transparent, the one-dimensional exciton cavity polariton
of the QW – an almost constant refractive index nb and dispersion became visible in the beautiful experiments
negligible absorption. The exciton of the QW has a mentioned above, with an energetic distance and curvature
dispersion with much higher effective mass mex ¼ me þ mh increasing with decreasing energy of the branch due to the
than the empty cavity. The thickness of the QW in the cavity decrease of n(v) below the exciton resonance towards lower

Review
Article
photon energies. The increasing curvature leads for finite kjj surfaces but should become transparent and show well-
to a crossing between the dispersion curves of adjacent resolved WGM if the light circulates in these modes.
branches and in case of coupling between them to an avoided As mentioned already, in the ZnO rods it is not possible
crossing. Since photons in vacuum do not interact, this to vary the finesse of the resonator and the damping of the
coupling is based on the excitonic part of the polariton wave exciton resonance within wide limits independently as in the
function (more generally the electronic parts, which include case of a QW exciton in a micro cavity formed by two Bragg
also the band-to-band transitions or the presence of an EHP, mirrors, but the whole system remains determined by ñ(v).
see below). The wave function of an exciton polariton has This remains true if the exciton resonance is broadened by
substantial exciton-like character about more than ten times increasing temperature T or if an increasing density np of
the longitudinal-transverse DLT splitting below and above electron–hole pairs lead to increasing screening of the
the exciton energy [135]. Since the sum of DLT is for the exciton up to the limit of an EHP where excitons do no longer
(A þ B)G5 excitons more than 10 meV, the exciton like exist as individual quasi particles. Also in this situation the
character of the polariton wave function extends quite a bit system is described by ñ(v,T, np). The influence of the
below the resonance. This fact is confirmed by the density dependent changes of the refractive index on the
observation of luminescence from the cavity polariton longitudinal modes in a nano rod has been presented already
modes, since an empty cavity does not show luminescence. above with Fig. 20, including the onset of recovery with time
The fact that the dispersion and visibility of the WGM is after pulsed excitation. The same phenomenon was obvi-
completely determined by the complex index of refraction ously observed in Ref. [129] when the spectral position of the
ñ(v) ¼ n(v) þ ik(v) remains true, if the (in-) homogeneous WGM shifted in the case of stimulated emission. Their
broadening G(T) increases from about 1 meV at 2 K to values properties are then simply determined by ñ(v, T, np) and the
of above 20 meV HWHM at RT. This effect influences the geometry of the micro rod.
dispersion of the exciton cavity polariton only close to In bulk, the dispersion of light in ZnO in the presence of
resonance in the strongly absorbing regime but not below, an EHP would be simply given by a modified polariton
where cavity polaritons remain clearly visible. The width of equation
the cavity modes in the transparent regime is determined by
the finesse or Q-factor of the cavity (or by the photonic decay c2 k2 =v2 ¼ n~2 ðv; T; np Þ ¼ eðv; k; T; np Þ: (21)
time) and the residual absorption, both being directly
determined by ñ(v). In the context of micro or nano rods we consider the
If a phenomenological damping constant is introduced in WGM in micro rods and the longitudinal modes in nano rods
the Lorentz oscillator model, the damping of the polariton as two limiting cases with a continuous transition between
i.e. the absorption coefficient or the imaginary part of ñ(v) them in the following sense: For the fundamental longi-
decreases strongly with increasing energetic distance below tudinal modes in a nano rod the wave vector is almost
the resonance as is also obvious for bulk exciton polaritons. completely determined by the quantized kjj, while k? is
See Fig. 5 above or Figs 4.5 and 13.9 in Ref. [28]. Therefore marginal. This situation changes if one goes to higher
the spectral width of the cavity polaritons decreases, too. For transversal modes [108]. Then k? increases at the expense of
more detailed considerations of the damping of cavity kjj for constant energy of the light quanta or the modes shift to
polaritons see e.g. Ref. [139]. In a microscopic model one the blue for fixed kjj. For WGM one has the opposite
may consider scattering processes e.g. with phonons or with situation. In a mode, which circulates completely in the
other polaritons to describe damping. The steep decrease of hexagonal cross section of the rod, k? is quantized and makes
the damping especially below the bulk exciton resonance up the whole wave vector. For observation under an oblique
may then be attributed to the small DOS of both bulk and angle to the rod- or c-axis kjj increasingly comes into play
cavity polaritons. It should be noted that at RT the damping now at the expense of k? . In principle it should be possible to
of the exciton resonances is in ZnO mainly determined by give a general description of modes in a hexagonal rod for all
scattering with LO phonons. See the experimental data in (k? ,kjj) which includes the above limiting cases.
Fig. 8 or Ref. [66]. To conclude this appendix, one may ask if it makes sense
A huge Rabi splitting of more than 300 meV (i.e. more to separate the strong and weak coupling limits in ZnO rods?
than five times the exciton binding energy) has been claimed A situation where one sits spectrally on the bulk exciton
in Ref. [129] from a fitting procedure. It is not clear to the resonance and still has a high finesse cavity is not possible for
author to which extend this value corresponds to a real the rods as mentioned above. At this resonance, where the
splitting between the lower and upper polariton branches at coupling between electromagnetic field and the exciton is
the WGM exciton polariton resonance in the sense strongest, one has necessarily strong damping and low
introduced above, because the WG is opaque in the range finesse and in the transparent region below the exciton the
of A and BG5 excitons and of their higher states including the finesse and the width of the modes get better, but the coupling
ionization continuum, or if it is simply a fitting parameter between excitons and electromagnetic field decreases.
deduced from the low energy data in the transparent region of A more detailed theoretical treatment of this problem
the sample. It is difficult to imagine that a micro rod is opaque [136, 137] came to a Rabi splitting for WGM of the order of
in a simple transmission measurement through two opposite 200 meV in agreement with the value cited above as a new

pss b
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physica
status
energy scale, which is larger than the exciton binding energy, T. Minami et al., SPIE Proc. 5274, 399 (2003). P. Chen,
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and B. Mallik, Nanotechnology 19, 495202 (2008). L. Ae,
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Chen Jie, and M. C. Lux-Steiner, Nanotechnology 47,
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Yu. Quing-Xuan et al., Appl. Phys. Lett. 83, 4713 (2003).
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2010 - 65 Years of ZnO Research - Old and Very Recent Results

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65 years of ZnO research – old Review Article

Received 17 September 2009, revised 12 January 2010, accepted 13 January 2010

Keywords excitons, photoluminescence, ZnO nanostructures

ß 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

ß 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

Phys. Status Solidi B 247, No. 6 (2010) 1425

3 Growth After this short tour d’horizon on appli-

www.pss-b.com ß 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

as vapour–liquid–solid process (VLS): ZnO is reduced to Zn

4 Doping Doping ZnO n-type is easy with group III

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Phys. Status Solidi B 247, No. 6 (2010) 1427

8 Free excitons and the Urbach tail According to

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Table 1 Some properties of the nB ¼ 1 excitons with large oscil-

AG5 3.37550.001 2.00.2

Note that the longitudinal-transverse splitting DLT is in

ß 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim www.pss-b.com

Phys. Status Solidi B 247, No. 6 (2010) 1429

first exciton resonance, the so-called Urbach tail [67]. It can

aðhv; TÞ ¼ a0 exp½sðTÞðEoo hvÞ=kB T

The quantities a0 and Eoo are material parameters. Eoo is

a2 ðhvÞ ¼ f ðhvÞ; (3a)

ðhvÞ2 a2 ðhvÞ ¼ gðhvÞ: (3b)

They are fitted by a straight line and the intersection of

aðhvÞ ¼ constðhv Eg Þ1=2 for hv  Eg (4)

This behaviour is expected if one assumes simple

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semiconductors. It is not clear to the authors, why such an

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Phys. Status Solidi B 247, No. 6 (2010) 1431

Figure 8 The homogeneous width (HWHM) of the free A and B

temperature at low temperatures faster to the red than the

Figure 7 (online colour at: www.pss-b.com) The luminescence of

photoluminescence of a single nano rod for two different

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Figure 10 (online colour at: www.pss-b.com) The luminescence

In quantum structures there is in addition to alloy

9 Bound exciton complexes, free-to-bound and

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Phys. Status Solidi B 247, No. 6 (2010) 1433

binding (or localization) energy of the exciton in the BEC

EDb 0 X ¼ a þ b EDb ; (5)

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Figure 13 The luminescence spectrum of the X–X process (P2 and

d has a value of 0 < d < 1, (typically d 0.5). The laser

hvmax ¼ Eg ðTÞ EbX

where M is the free exciton mass, me the electron mass and g

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Phys. Status Solidi B 247, No. 6 (2010) 1435

Figure 17 The density dependencies of the BGR DEg, the exciton

Figure 16 Schematic representation of the recombination in an

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Figure 19 (online colour at: www.pss-b.com) Stimulated emission

temperature of the EHP may be higher. The variation of the

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Phys. Status Solidi B 247, No. 6 (2010) 1437

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sample shows a well resolved near edge emission similar to

12 Conclusion and outlook We mentioned at the

– a low luminescence yield. See e.g. data given in the

aðhv; TÞ ¼ a0 exp½sðTÞðEoo hvÞ=kB T

aðhvÞ ¼ constðhv Eg Þ1=2 for hv Eg (4)