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Chng 1: Cc cht bn dn khi




1.1 M u

1.2 Cu trc tinh th v cu trc vng nng lng ca cc cht bn dn
khi
1.3 Cc tnh cht quang, in ca cc cht bn dn khi
1.3.1 Tnh cht quang
1.3.2 Tnh cht in
1.4 ng dng ca vt liu bn dn khi
1.5 Cng ngh ch to cc cht bn dn khi
1.6 Phn loi cc cht bn dn

Cc cht bn dn c cu trc nan
(nanostructured semiconductors)
GS. TS. Phan Hng Khi
E-mail: phkhoi@ims.vast.ac.vm
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1.1 M u
3
Cht bn dn (ting Anh: Semiconductor) l vt liu trung gian gia
cht dn in v cht cch in.

Cht bn dn hot ng nh mt cht cch in nhit thp v c
tnh dn in nhit phng.

Gi l "bn dn" (ch "bn" theo ngha Hn Vit c ngha l mt
na), c ngha l c th dn in mt iu kin no , hoc mt
iu kin khc s khng dn in.
Cht bn dn
4

Thnh tu ca cng ngh vi in t bn dn :

Transitor bn dn ( Bell-lab, 1947)
Vi mch tch hp (IC- Integrated Circuit)
Cng ngh planar (Texas Instruments, 1958)
MOSFET (RCA- USA, 1960)
B nh RAM (IBM, 1966)
Laser bn dn (1970)
B vi x l CPU tc 4 GHz
Trung bnh s lng transitor/chip tng gp i sau 18 thng
Kch thc linh kin ngy cng b, tin gn n gii hn vt l
Nhiu tnh cht vt l mi xut hin
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H. 1.1: Ba nh hoa hc Walter Brattain, William Shockley v
John Bardeen - nhng ngi c trao tng gii Nobel
v Ha hc cho pht minh ca h vo nm 1956. nh minh
ha t www.porticus.org
H. 1.2: Mu transistor u tin.
nh Bell Labs, porticus.org
H. 1.3: 3 mu transistor ca nhng nm thuc th k
20. nh Bell Labs, porticus.org
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S bng bn dn trong mt chip:

o Chip u tin ca Intel 4004 (nm 1971) c 2.300 transistor. Cc my tnh IBM
PC u tin:
o Loi 8086 (nm 1978): 29.000 transistor.
o Loi i486 (nm 1989): 1.200.000 transistor.
o Pentium III (nm 1999): 9.500.000 transistor.
o Pentium IV (nm 2000): 42.000.000 transistor.
o Penryn (cng b ngy 12/11/2007:): 820.000.000 transistor.

Cc loi chip v cng ngh sn xut:

o 1993: Pentium 800 nm
o 1999: Pentium III 250 nm
o 2002: Pentium IV 130 nm
o 2003: Centrino 130 nm
o 2005: Pentium D 90 nm
o 2006: Core 2 Duo 65 nm
o 2007: Core 2 Duo th h sau 45 nm (cn gi l Penryn)

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H. 1.4: S tng trng mt transito trn 1 chip v lng bit trn mt cm
2
theo nm v
nh lut Moor
8
H. 1.5: S tng trng s lng transistor trn cc
mch vi in t theo nm
H. 1.6: nh TEM ca transitor MOS
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H. 1.7: Tin s Moore c trong tay bn gc tp
ch ln u tin ng bi vit v nh lut ca
ng. (hin ang sng Hawaii)
H. 1.8: K s David Clark ti qun Surrey (Anh), gi cc n phm ca tp ch Electronics
Magazine trong sut 15 nm qua, k cho c v ni n qung chng i. V by gi, h ang n mng
trc mn tin thng hp dn ca Intel.. Ti dnh c bui sng lc tung c ln v
khng nhn thy chng trong sut 15 nm. Khi lin h vi Intel, ti vn khng ngh h s tin li ti,
Clark k li.
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H.1.9: Gordon Moore gii thiu mt tm wafer (dng
lm chip) ti tr s Intel Santa Clara, California
(M).
nh lut Moore (mt trong 7 k quan ca cng ngh my tnh)

Thin nhin c 7 k quan th gii v hin nhin, chng ta cng mun bit th gii cng ngh c
nhng k quan no? nh lut Moore l mt trong 7 tuyt tc trong th gii @ do tp ch CNTT
PCMag bnh chn.

nh lut Moore l mt bc ngot ln trong ngnh cng ngh in t. nh lut c xy
dng bi Gordon Moore - mt trong nhng sng lp vin ca tp on sn xut chip my tnh
ni ting Intel. nh lut ni rng, tc ca b vi x l, hay cn gi l s lng transistor trn
mi n v inch vung s tng ln gp i. iu ny cho n nay vn lun lun ng.

nh lut Moore cng l mt ng lc kch thch cho ngnh cng nghip in t duy tr s pht
trin mnh m trong hng thp k qua.
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Di y l trao i ca Gordon Moore vi mt s hng tin cng ngh quc t:

nh lut Moore bt ngun t u?

o Nm 1965 tp ch Electronics t chc k nim 35 nm. Vo thi im , mch vi in t
ln nht c khong 30 linh kin bn trong. Ti ln ngc li lch s th thy con s bt u
t 4,8,16...v c nh vy tng gp i mi nm. Lc y ti cng khng ngh iu ny thc s
l chnh xc v bn thn ti ch mun c lm r rng mi th s tr nn ngy cng tinh vi v
r tin hn. Cui cng, ha ra iu m ti vit li chnh xc hn c mc bn thn ti c th
tin. Mt ngi bn ca ti l gio s Carver Mead thuc hng Cal Tech t lun tn cho
pht hin ny l nh lut Moore v c th ngi ta gi n nh vy. Sut 20 nm ti thm ch
khng th t tin s dng ci tn v mi v sau mi thy chp nhn c. Nm 1975, ti
thay i mt s ni dung trong nh lut v mi th c gi nguyn cho n hin nay. Vo
thi im ny, ti vit mt bi bo v tng lai ca cc linh kin bn dn trong vng 10 nm
tip theo. Ti mun trnh by tng v vic cc mch tch hp (IC) s l cha kha to ra
nhng thit b r tin hn. V th, ti t ra php ngoi suy v sau tr thnh nh lut nhn
i s transistor l xp x 24 thng.

ng cm nhn nh th no v ngha ca qu trnh nhn i transistor ny cng nh nhng
c hi m n cho php to ra?

o Ti c li bi bo mnh vit v nhn thy nhng vn nhc n trong lin quan n
my tnh gia nh. Ti rt ngc nhin khi thy chnh mnh tm ra tnh quy lut nh vy.
Thnh thc m ni ti khng bit mnh d bo mt iu mang tnh l thuyt vo nm .
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Mi th ang i n gii hn v tc nhn i bng bn dn chm dn. Nhng vt liu
mi c th cho php ngnh cng nghip my tnh vt qua ngng gii hn?

o Vi bt c vt liu no lm t nguyn t th u c mt gii hn c bn m bn khng th
lm nh hn. Ti thay i chu k nhn i t 1 nm ln 2 nm v dn dn c th s l 3-
4 nm.

bao nhiu ln ngi ta d bo s kt thc ca nh lut Moore v bao nhiu ln ng thc
s tin rng iu s xy ra?

o Trong 10 nm qua, ti c rt nhiu bi bo vit v s chm dt ca tin trnh nhn i
transistor trn chip. C thi im ti ngh rng 1 micromet (1 phn triu met) s l gii
hn cui cng nhng ri mc nhanh chng b vt qua. Sau , ti li tin rng 1/4
micromet s l du chm ht nhng mi th vn tip din. Gi y chng ta ang mc
di 1/10 micromet v ang tin n mc 1/65. Qu trnh nhn i khng th ko di mi
mi nhng s chm ht s ch n trong t nht 10-20 nm na v cng l khong thi
gian m chng ta c th d bo.

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Th g c th thay th silicon?

o C th l in ton lng t hay cng ngh nano Thc s m ni th ti vn rt hoi
nghi v vic nhng th c kh nng thay th hon ton silicon k thut s. Bn c th d
dng to ra mt transistor cc nh bng nhng cng ngh ny vi tn sut rt cao nhng
kh c th kt ni hng t th li vi nhau. chnh l vn . Mi vic khng n
thun ch l lm ra mt transistor tht nh.
Ti coi cng ngh pht trin xoay quanh mch tch hp IC l phng php c bn xy
dng cc vi kin trc phc tp. Thay v b thay th, n thc s ang xm nhp vo rt
nhiu lnh vc khc. Chng hn nh chip gene. Silicon l mt cng ngh rt mnh m s
cn c s dng rng ri. Ti cha thy bt c th g c tim nng thay th n.
Tuy nhin, iu khng c ngha l nhiu pht minh mi s khng th c tch hp li,
chng hn vic tch hp cc ng nano carbon vo nhiu lp kim loi hoc tng t nh vy.
Du sao, ti vn cha thy l mt gii php thay th bng bn dn silicon.

ng c d bo nh lut g mi cho 40 nm ti?

o Thi, ti xin chu. Mt vng nguyt qu cho nh lut Moore ny ri. Tt nhin,
cng c th c mt nh lut Moore phin bn 2 nhng ngi ra n s khng phi l ti.

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H.1.11: Apple iPhone: my nghe nhc, in thoi di
ng
H. 1.10: Nintendo Wii l game console thu ht
nhiu s quan tm nht trong th gii game th.
H.1.12: Lade gip cc my nghe nhc s v a quang hc hin th hnh nh vi nt cao
Cc k quan ca cng ngh my tnh
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H.1.15: My tnh cm ng b mt ca Microsoft
H. 1.14: Cng ngh mn hnh phng H.1.13: Apple Inc. nh iPod, iTunes, Macsintosh
v mi y nht l tn binh iPhone
Cc k quan ca cng ngh my tnh
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1.2. Cu trc tinh th v cu trc
vng nng lng ca cc cht bn dn
khi
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Cu trc tinh th:

Hu ht cc cht bn dn c cu trc tinh th lp phng tp mt (fcc). Chng c 2 nguyn t trong
mt c s. To ca hai nguyn t c s l: (000) v ( a/4, a/4, a/4). Nu hai nguyn t cng loi:
mng tinh th kim cng (DI) v d: Si, Ge (H. 1.4); nu hai nguyn t khc loi: mng tinh th
Zinc-Blend (ZB), tn c t theo tn ca tinh th ZnS. GaAs, GaP thuc loI ny (H. 1.5)
Nhiu vt liu bn dn c th c hn mt loi cu trc tinh th. Cc bn dn hp cht trong c
GaAs, GaN, ZnS c th c cu trc lp phng hoc cu trc lc gic (hexogonal). SiC c th c cu
trc lp phng, hoc mt trong nhiu cu trc lc gic khc. Tinh th lp phng c c trng
bi mt thng s mng duy nht, hng s mng a, trong khi tinh th lc gic c c trng bi
ngoi hng s mng a cn bi khong cch gia hai mt lc gic c
H. 1.16: Mng tinh th kim cng (Si, Ge) .
Mng gm hai mng tinh th Fcc lng vo
nhau. Mt dch dc theo trc ng cho so
vi mng kia mt khong cch l (a/4,a/4,a/4).
H. 1.17: Mng tinh th Zinc
Blend (GaAs, GaP)
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+ + + +
+ + + + +
+ +
+ +
+
+
+
+
+
+
- - - - - -
- - - - -
-
-
- - - - -

+ +
+ + + + +
+ + +













C-axis
a
1

a
2

a
3

H. 1.19: Cc v tr ca mng tinh th
hcp (ZnS, CdS)
Tinh th hcp

Qu cu lp 1
+
Tm qu cu lp 2
-
Tm qu cu lp 3
H. 1.18: Sp xp cc nguyn t 3 lp ca mng
tinh th hcp (ZnS, CdS)
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Tnh cht dn in ca cc vt liu rn c gii thch nh l thuyt vng nng
lng.

Nh ta bit, in t tn ti trong nguyn t trn nhng mc nng lng gin on
(cc trng thi dng).

Nhng trong cht rn, khi m cc nguyn t kt hp li vi nhau thnh cc khi,
th cc mc nng lng ny b ph ln nhau, v tr thnh cc vng nng lng v
s c ba vng chnh.
Cu trc vng nng lng:
Xc nh ph nng lng in t hay s quan h gia nng lng E v vector
sng K E= E(k), thng qua gii phng trnh Schrodinger tm biu thc:



Trong : H - Haminltonian ca tinh th,
, E - Hm sng v nng lng ca tinh th.
E H =

(1.1)
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y e v h l hai ch s ch in t v l trng, m- khi lng hiu dng, r vector
v tr, r
eh
=|r
e
- r
h
|, c
o
v c l hng s in mi chn khng v cht bn dn. S dng
gn ng khi lng hiu dng ta gii phng trnh trn cho bn dn khi v tm
c:
(1.2)
(1.3)
H. 1.21:
21
Bn dn Kim loi
Mc li
Mc li
Vng ho tr
Vng dn
E
g
: Vng cm
i lc in t Cng thot eu
Nng lng chn khng
Cu trc vng nng lng ca kim loi v bn dn
H. 1.22: Gin cc vng nng lng ca kim loi v bn dn
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Vng ha tr (Valence band): L vng c nng lng thp nht theo thang
nng lng, l vng m in t b lin kt mnh vi nguyn t v khng linh
ng.

Vng dn (Conduction band): Vng c mc nng lng cao nht, l vng m
in t s linh ng (nh cc in t t do) v in t vng ny s l in t
dn, c ngha l cht s c kh nng dn in khi c in t tn ti trn vng
dn. Tnh dn in tng khi mt in t trn vng dn tng.

Vng cm (Forbidden band): L vng nm gia vng ha tr v vng dn,
khng c mc nng lng no do in t khng th tn ti trn vng cm.
Nu bn dn pha tp, c th xut hin cc mc nng lng trong vng cm
(mc pha tp). Khong cch gia y vng dn v nh vng ha tr gi l
rng vng cm, hay nng lng vng cm (Band Gap). Ty theo rng vng
cm ln hay nh m cht c th l dn in hoc khng dn in.

Nh vy, tnh dn in ca cc cht rn v tnh cht ca cht bn dn c th l
gii mt cch n gin nh l thuyt vng nng lng nh sau:

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Kim loi c vng dn v vng ha tr ph ln nhau (khng c vng cm) do
lun lun c in t trn vng dn v th m kim loi lun lun dn in.

Cc cht bn dn c vng cm c mt rng xc nh. khng tuyt i (0
o
K), mc Fermi nm gia vng cm, c ngha l tt c cc in t tn ti vng
ha tr, do cht bn dn khng dn in. Khi tng dn nhit , cc in t s
nhn c nng lng nhit (kB.T vi kB l hng s Boltzmann) nhng nng
lng ny cha in t vt qua vng cm nn in t vn vng ha tr.
Khi tng nhit n mc cao, s c mt s in t nhn c nng lng ln
hn nng lng vng cm v n s nhy ln vng dn v cht rn tr thnh dn
in. Khi nhit cng tng ln, mt in t trn vng dn s cng tng ln,
do , tnh dn in ca cht bn dn tng dn theo nhit (hay in tr sut
gim dn theo nhit ). Mt cch gn ng, c th vit s ph thuc ca in tr
cht bn dn vo nhit nh sau:
vi: R0 l hng s, Eg l rng vng cm. Ngoi ra, tnh dn ca cht bn dn
c th thay i nh cc kch thch nng lng khc, v d nh nh sng. Khi chiu
sng, cc in t s hp thu nng lng t photon, v c th nhy ln vng dn nu
nng lng ln. y chnh l nguyn nhn dn n s thay i v tnh cht ca
cht bn dn di tc dng ca nh sng (quang-bn dn).
(1.4)
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H. 1.23: Cu trc vng nng lng ca bn dn Si (vng cm xin) v GaAs khi (Vng cm
thng)
in t
dn
L
trn
g
L
trn
g
in t
dn
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B. 1.1: Cu trc tinh th v cu trc vng nng lng ca cc cht bn dn khi
Vt liu Cu trc tinh
th
rng vng
cm (eV)
Hng s in
mi
Hng s
mng (A
o
)
Khi lng
ring (g.cm
-3
)
C
Si
SiC
Ge
AlN

AlP
AlAs
GaN

GaP
GaAs
GaSb
InN
DI
DI
ZB
DI
W

ZB
ZB
W

ZB
ZB
ZB
W

5,50 I
1,1242 I
2,416 I
0,664 I
6,2 D

2,45 I
2,153 I
3,44 D

2,272 I
1,424 D
0,75 D
1,89 D
5,570
11,9
9,72
16,2
c =

9,14

9,8
10,06
c
||
= 10,4
c

= 9,5
11,11
13,18
15,69
-
3,5668
5,431
4,3596
5,658
a = 3,111
c = 4,981
5,4636
5,660
a = 3,5446
c = 5,158
5,4505
5,653
6,0959
a = 3,5446
c = 8,7034
3,5153
2,3290
3,166
5,323
3,255

2,401
3,760
6,095

4,138
5,318
5,6137
6,81

DI: Diamond; R: Rocksalt. W: Wurtzite; ZB: Zinc-Blend;
*
Gap Tnh ti im L; D: vng cm
thng (Direct); I: vng cm Xing (Indirect); c
||
: song song trc C; c
:
Vung gc trc C.
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Vt liu Cu trc tinh
th
rng vng
cm (eV)
Hng s in
mi
Hng s
mng (A
o
)
Khi lng
ring (g.cm
-3
)
InP
InAs
InSb
ZnS
ZnS

ZnSe
ZnTe
CdS

CdS
CdSe

CdTe
PbS
PbSe
PbTe
ZB
ZB
ZB
ZB
W

ZB
ZB
W

ZB
W

ZB
R
R
R
1,344 D
0,354 D
0,230 D
3,68 D
3,9107 D

2,822 D
2,394 D
2,501 D

2,50 D
1,751 D

1,475 D
0,41 D
*
0,278 D
*
0,310 D
*
12,56
15, 15
16,8
8,9
c = 9,6

9,1
8,7
c = 9,38

-
c
||
= 10,16
c

= 9,29
10,2
169
210
414
5,8687
6,058
6,479
5,4102
a = 3,8226
c = 6,6205
5,668
6,104
a = 4,1362
c = 6,714
5,818
a = 4,2999
c = 7,0109
6,482
5,936
6,117
6,462
4,81
5,667
5,775
4,079
4,084

5,266
5,636
4,82

-
5,81

5,87
7,597
8,26
8,219
D: Diamond; R: Rocksalt. W: Wurtzite; ZB: Zinc-Blend;
*
Gap Tnh ti im L; D: vng cm
thng (Direct); I: vng cm Xing (Indirect); c
||
: song song trc C; c
:
Vung gc trc C.
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Bn dn thun (Pure semiconductor or intrinsic semiconductor)

Hu ht cc cht bn dn u c cc nguyn t sp xp theo cu to tinh th.
Hai cht bn dn c dng nhiu nht trong k thut ch to linh kin in t
l Silicium v Germanium. Mi nguyn t ca hai cht ny u c 4 in t
ngoi cng kt hp vi 4 in t ca 4 nguyn t k cn to thnh 4 lin kt
ha tr. V vy tinh th Ge v Si nhit thp l cc cht cch in
H. 1.24:
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Nu ta tng nhit tinh th, nhit nng s lm tng nng lng mt s in t
v lm gy mt s ni ha tr. Cc in t cc ni b gy ri xa nhau v c
th di chuyn d dng trong mng tinh th di tc dng ca in trng. Ti
cc ni ha tr b gy ta c cc l trng (hole). V phng din nng lng, ta
c th ni rng nhit nng lm tng nng lng cc in t trong di ha tr.
H. 1.25:
29
Khi nng lng ny ln hn nng lng ca di cm (0,7eV i vi Ge v
1,12eV i vi Si), in t c th vt di cm vo di dn in v cha li
nhng l trng (trng thi nng lng trng) trong di ha tr). Ta nhn thy s
in t trong di dn in bng s l trng trong di ha tr.

Nu ta gi n l mt in t c nng lng trong di dn in v p l mt
l trng c nng lng trong di ha tr. Ta c:n=p=ni

Ngi ta chng minh c rng:
n
i
2
= A
0
.T
3
. exp(-EG/KT)
Trong : A0 : S Avogadro=6,203.1023
T : Nhit tuyt i ( Kelvin)
K : Hng s Bolzman=8,62.10-5 eV/0K
EG : Chiu cao ca di cm.
(1.5)
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Ta gi cht bn dn c tnh cht n = p l cht bn dn ni bm hay cht bn dn thun.
Thng thng ngi ta gp nhiu kh khn ch to cht bn dn loi ny.
H. 1.26
31
Bn dn thun (Intrinsic Semiconductor):

Mt trng thi hiu dng
2
1/2
(m
*
dos
)
3/2
(E E
c
)
1/2

N(E) =
t
2
h
3

Nng ht ti thun

n
i
= p
i
= 2(k
B
T/2th
2
)
3/2
(m
e
*
m
h
*
)
3/2
exp(-E
g
/2k
B
T)

E
Fi
=

(E
c
+ E
v
)/2 + 3/4k
B
Tln(m
h
*
/m
e
*
)
Vt liu Mt trng thi
hiu dng vng dn
(N
c
)
Mt trng thi
hiu dng vng ho
tr (N
v
)
Nng ht ti
thun (n
i
= p
i
)
Si (300K)
Ge (300K)
GaAs (300K)
2,78x10
19
cm
-3

1,04x10
19
cm
-3

4,45x10
17
cm
-3

9,84x10
18
cm
-3
6,00x10
18
cm
-3

7,72x10
19
cm
-3

1,50x10
10
cm
-3

2,33x10
13
cm
-3

1,84x10
196
cm
-3

(1.6)
(1.7)
(1.8)
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Cht bn dn pha tp

Cht bn dn loi p (hay dng ngha ting Vit l bn dn dng) c tp cht l
cc nguyn t thuc nhm III, dn in ch yu bng cc l trng (vit tt cho
ch ting Anh positive', ngha l dng).

Cht bn dn loi n (bn dn m - Negative) c tp cht l cc nguyn t thuc
nhm V, cc nguyn t ny dng 4 electron to lin kt v mt electron lp
ngoi lin kt lng lo vi nhn, y chnh l cc electron dn chnh

C th gii thch mt cch n gin v bn dn pha tp nh vo l thuyt vng
nng lng nh sau: Khi pha tp, s xut hin cc mc pha tp nm trong vng
cm, chnh cc mc ny khin cho in t d dng chuyn ln vng dn hoc
l trng d dng di chuyn xung vng ha tr to nn tnh dn ca vt liu.
V th, ch cn pha tp vi hm lng rt nh cng lm thay i ln tnh cht
dn in ca cht bn dn.
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Cht bn dn loi N: (N - type semiconductor)

Gi s ta pha vo Si thun nhng nguyn t thuc nhm V ca bng phn loi tun
hon nh As (Arsenic), Photpho (p), Antimony (Sb). Bn knh nguyn t ca As gn
bng bn knh nguyn t ca Si nn c th thay th mt nguyn t Si trong mng
tinh th. Bn in t ca As kt hp vi 4 in t ca Si ln cn to thnh 4 ni
ha tr, Cn d li mt in t ca As. nhit thp, tt c cc in t ca cc
ni ha tr u c nng lng trong di ha tr, tr nhng in t tha ca As
khng to ni ha tr c nng lng ED nm trong di cm v cch dy dn in
mt khang nng lng nh chng 0,05eV.
H. 1.27
34
Gi s ta tng nhit ca tinh th, mt s ni ha tr b gy, ta c nhng l trng
trong di ha tr v nhng in t trong di dn in ging nh trong trng hp
ca cc cht bn dn thun. Ngoi ra, cc in t ca As c nng lng ED cng
nhn nhit nng tr thnh nhng in t c nng lng trong di dn in. V
th ta c th coi nh hu ht cc nguyn t As u b Ion ha (v khang nng
lng gia ED v di dn in rt nh), ngha l tt c cc in t lc u c nng
lng ED u c tng nng lng tr thnh in t t do.0,05eV.
Nu ta gi N
D
l mt nhng nguyn t As pha vo
(cn gi l nhng nguyn t cho donor atom).Ta c:

n = p + N
D

Vi n - mt in t trong di dn in; p - mt l
trng trong di ha tr.

Ngi ta cng chng minh c: n.p = n
i
2
(n < p)
n
i
: mt in t hoc l trng trong cht bn dn
thun trc khi pha.

Cht bn dn nh trn c s in t trong di dn in
nhiu hn s l trng trong di ha tr gi l cht bn
dn loi N.
(1.9)
H. 1.28
35
Cht bn dn loi P: (P - type semiconductor)

Thay v pha vo Si thun mt nguyn t thuc nhm V, ta pha vo nhng nguyn t
thuc nhm III nh Indium (In), Galium (Ga), nhm (Al),... Bn knh nguyn t In
gn bng bn knh nguyn t Si nn n c th thay th mt nguyn t Si trong
mng tinh th. Ba in t ca nguyn t In kt hp vi ba in t ca ba nguyn t
Si k cn to thnh 3 ni ha tr, cn mt in t ca Si c nng lng trong di
ha tr khng to mt ni vi Indium. Gia In v Si ny ta c mt trang thi nng
lng trng c nng lng EA nm trong di cm v cch di ha tr mt khong
nng lng nh chng 0,08eV.
H. 1.29
36
Thay v pha vo Si thun mt nguyn t thuc nhm V, ta pha vo nhng nguyn t
thuc nhm III nh Indium (In), Galium (Ga), nhm (Al),... Bn knh nguyn t In gn
bng bn knh nguyn t Si nn n c th thay th mt nguyn t Si trong mng tinh th.
Ba in t ca nguyn t In kt hp vi ba in t ca ba nguyn t Si k cn to thnh
3 ni ha tr, cn mt in t ca Si c nng lng trong di ha tr khng to mt ni
vi Indium. Gia In v Si ny ta c mt trang thi nng lng trng c nng lng EA
nm trong di cm v cch di ha tr mt khong nng lng nh chng 0,08eV.
H. 1.30
37
nhit thp (T=00K), tt c cc in t u c nng lng trong di ha tr. Nu ta
tng nhit ca tinh th s c mt s in t trong di ha tr nhn nng lng v
vt di cm vo di dn in, ng thi cng c nhng in t vt di cm ln chim
ch nhng l trng c nng lng EA.
H. 1.31
38
Nu ta gi N
A
l mt nhng nguyn t In pha vo (cn c gi l nguyn t
nhn), ta cng c:

p = n + N
A

p: mt l trng trong di ha tr.
n: mt in t trong di dn in.

Ngi ta cng chng minh c:

n.p = n
i
2
(p>n)

ni l mt in t hoc l trng trong cht bn dn thun trc khi pha.
Cht bn dn nh trn c s l trng trong di ha tr nhiu hn s in t trong
di dn in c gi l cht bn dn loi P.
Nh vy, trong cht bn dn loi p, ht ti in a s l l trng v ht ti in thiu
s l in t.
(1.10)
(1.11)
39
Cht bn dn hn hp:

Ta cng c th pha vo Si thun nhng nguyn t cho v nhng nguyn t nhn
c cht bn dn hn hp. Hnh sau l s nng lng ca cht bn dn hn hp.












Trong trng hp cht bn dn hn hp, ta c:

n+N
A
= p+N
D

n.p = ni
2

Nu N
D
> N
A
=> n>p, ta c cht bn dn hn hp loi N.
Nu N
D
< N
A
=> n<p, ta c cht bn dn hn hp loi P.

(1.12)
(1.13)
H. 1.32
40
H. 1.33: Cc mc tp cht trong bn dn Si v GaAs
41
Vng thun
Vng ngoi lai
Vng lnh
Mt in t (cm
-3
)
Nhit (K)
H. 1.34: S thay i mt in t theo nhit
ca bn dn Si c nng tp cht cho (Donor)
10
15
cm
-3
H. 1.35: Mc fermi ca Si v GaAs c nng
tp 10
15
cm
-3
ph thuc vo nhit
42
H. 1.36: S ph thuc in tr sut cu Si v GaAs vo nng pha tp nhit phng

in tr sut
nng pha tp (10
15
cm
-3

43
1.3. Cc tnh cht quang,
in ca cc cht bn dn
khi
44
Bc sng (m)
Nng lng Photon (eV)
0.01 0.1 0.2 0.39 1 1.5 6 10 40 100 1000
0.3 0.77
Rt xa Xa Gn Trung bnh Xa Rt xa
Tm Xanh L cy Vng Cam

0.39 0.45 0.492 0.577 0.597 0.622 0.77
100 10 1 0.1 0.01 0.001
c hc 1.24
= = = m
v hv hv(eV)
T ngoi Nhn thy Hng ngoi
1.3.1. Cc tnh cht quang
(1.14)
45






E
2

E
1

E
2

E
2

E
2

E
1

hv
12

hv
12

hv
21

hv
12
hv
21
(ng pha)
a) Hp th
c) Pht x cng bc
b)Pht x ngu nhin
Mt ht ti iu kin cn bng nhit


H s pht x cwngx bc + H s pht x ngu nhin = H s hp th
n
2
/n
1
= exp-(E
2
-E
1
)/kT = exp- hv
12
/kT
B
21
n
2
(hv
12
) + A
21
n
2
= B
12
n
1
(hv
12
)
(1.15)
(1.16)
46
Tc pht x cng bc B
2

=
(hv
12
)
Tc pht x ngu nhin A
21

pht x cng bc vt hn hn pht x ngu nhin, mt nng lng
photon (hv
12
) phi ln. c mt ny, ngi ta dng bung cng
hng quang hc (optical resonator cavity) tng trng photon. Ta c:
Tc pht x cng bc B
21
n
2

=
x
Tc hp th B
12
n
1
pht x cng bc cc photon tri hn hp th photon, chng ta phi c
mt in t mc nng lng cao nhiu hn so vi mt in t
mc nng lng thp hn. Trng thi ny gi l trng thi o mt
(population inverse).
(1.17)
(1.18)
47




E
g

a)
b)
c)
E
t

E
v

E
c

hv
H. 1.37: Hp th quang trong cc cht bn dn a) hv = E
g
, b) hv > E
g
, v c) hv <E
g
Vng dn
Vng ho tr
48
d u(x)
u(x +Ax) - u(x) = Ax = - ou(x) Ax; where o = f (v).

dx

d u(x)
Ax = - ou(x); u(x) = u(0)exp(ox);
dx

u(x) = u
0
exp(ox); y u(x) = u
0
at x = 0 and u(W) = u(0)exp(oW);
u(x) u(x +Ax) u
0
Ax
W
u
0
u
0
exp(ox);
0 x W
H. 1.38: Hp th quang a) Bn dn khi chiu sng, b) S tt dn ca chm
phton theo hm Exp.
a)
b)
(1.18)
(1.19)
(1.20)
49
0,2 0,6 1 1,4 1,8
0,7 1 1,5 2 3
10
10
2

10
3

10
4

10
5

10
6

GaP
GaAs
InP
Ga
0,3
In
0,7
As
0,64
P
0,36

InGaAs
Si
Ge
o (cm
-1
)
H. 1.39: H s hp th ca
mt s cht bn dn
Nng lng
photon (eV)
Bc sng photon (m)
50
1.3.2. Tnh cht in
Di tc dng ca in trng, cc in t v trng l di chuyn vi vn tc trung
bnh

V
n
= n
n
E v v
p
=
p
pE

S in t v l trng di chuyn thay i theo mi thi im, v ti mi thi im c
mt s in t v l trng c sinh ra di tc dng ca nhit nng. S in t sinh
ra trong mi n v thi gian gi l n v trong khi di tc sinh to g. Nhng in t
ny c i sng trung bnh chuyn in t c th gp mt l trng c cng nng
lng v ti hp vi l trng ny. Nu gi n l mt in t, trong mt n v thi
gian s in t b n. Ngoi ra, trong cht bn dn, mt i v s ti hp l n/ s phn
b ca mt in t v l trng c th khng u, do c s khuch tn ca in
t t vng c nhiu in t sang vng c t in t.

Xt mt mu bn dn khng u c mt in t c phn b nh hnh v. Ti
mt im M trn tit din A, s in t i ngang qua tit din ny (do s khuch tn)
t l vi dn/dx, vi din tch ca in t v vi tit din A.
(1.22)
51
1.4 ng dng ca vt liu bn dn khi
52
Phm cht linh kin mong mun Cu trc vng nng lng cn c
Linh kin in t pht
cng sut cao
Linh kin in t
tn s cao
Linh kin pht sng
Lade thng tin ng di
(1,55 m, 1,3 m)
ng dng hin th
, xanh l cy, xanh bin
Pht sng ngn cho cc b nh
quang v my in
Nhn m/ghi nh nhit
Vng cm rng
(GaN, SiC,C)
Khi lng hiu dng nh, phn
cch cc valley ln (InAs, InGaAs)
Vt liu c vng cm thng
(A
III
B
V)
rng vng cm khong 0,8 eV
(InGaAsP)
rng vng cm t 1,6 3,6 eV
(AlGaAs, InGaN)
Vng cm rng
(GaN, AlN)
Vt liu vng cm hp
(InSb, HgCdTe)
53
1.5. Cng ngh ch to cc cht bn dn khi
54
Cc khu cng ngh c bn ch to vt liu bn dn
vt liu ban u
Bn dn a tinh th
Bn dn n tinh th
Phin
Si/SiO
2
GaAs/Ga, As
Chng ct v lng ng
Tng hp
Nui n tinh th Nui n tinh th
Mi, ct, nh bng Mi, ct, nh bng
55
1.5.1 Cng ngh ch to cc cht bn dn khi Si
a) Vt liu ban u:

Ct SiO
2
c t vo l nung vi cc cacbon di dng than, cok.., xy ra
phn ng:

SiC (rn) + SiO
2
(rn) Si (rn) + SiO (hi) + CO (hi)

Si to ra c cht lng luyn kim c sch khong 98%.
Bc tip theo Si c nghin nh v x l trong HCl to thnh
trichlorosilane (SiHCl)
3:

Si (rn) + 3HCl (hi) (300
o
C) SiHCl
3
+ H
2
(hi)

nhit phng (SiHCl)
3
dng lng (nhit si 32
o
C). Bng cch chng ct
c th loi mt s tp cht. Sau khi chng ct lm sch, (SiHCl)
3
cho phn ng
trong kh H
2
to thnh Si a tinh th c sch in t (EGS)

(SiHCl)
3
(hi)

+ H
2
Si (rn) + 3HCl (hi)

56
b) Phng php Czochralsski
H. 1.40: M t nguyn l nui n tinh th bng phng php Czochralsski
57
c) Phng php nng chy vng
Thanh a
tinh Si
Cun t
cao tn
n tinh
th Si
Mm Si
G
Vng
nng
chy
H. 1.41: M t nguyn l nui n tinh th bng Phng php nng chy vng
58
H. 1.42: Phin Si c ct, mi, nh bng t thi n tinh th
59
1.5.2 Cng ngh ch to cc cht bn dn khi GaAs
a) Vt liu ban u:
Ga, As: sch ho hc
Gin pha h Ga - As
200
400
600
800
1000
1200
1400
(T
1
, x) T
1

810
o
C
C
l
C
m

29,5
Pha lng Pha lng
Ga + Pha lng GaAs + As
GaAs + Ga
GaAs + Pha lng
T
b
s
x
% nguyn t As
T
o
(C)
0 10 20 30 30 50 60 70 80 90 100
H. 1.43:
60
b) Nui n tinh th GaAs:

Mm tinh th GaAs nng chy
Vng 2 Vng 1
As
600
800
1000
1200
1242 1260
o
C
610 620
o
C
T
o
(C)
Phng php Bridgman
Phng php Czochralsski (tng t nh nui tinh th Si)
H. 1.44: M t nguyn l nui n tinh GaAs th bng phng php Bridgman
61
1.6. Phn loi cc cht bn dn
62
Group IV (Elemental) Crystalline
Materials (Periodic Table, Column IV)
C (carbon)
Diamond Structure: Kim cng (diamond!!), bn dn (semiconductor)
Graphite: kim loi (metal), dng thng dng nht (most common form)
Fullerenes (buckminsterfullerene): bucky balls, nanotubes, .
Clathrates (new form ?): bn dn (semiconductor), hp cht (compounds),
recent research

Si (silicon)
Diamond Structure: bn dn (semiconductor), dng thng dng nht
(common form)
Clathrates (new form): bn dn (semiconductor), cc hp cht
(compounds), nghin cu mi (recent research)
63
Group IV Materials
Ge (germanium)
Diamond Structure: semiconductor, common form
Clathrates (new form) semiconductor, compounds, current research

Sn (tin)
Diamond Structure (gray tin or -Sn): semimetal
Body Centered Tetragonal Structure (white tin or -Sn): metal,
common form
Clathrates (new form): semiconductor, compounds, current research

Pb (lead) Face Centered Cubic Structure: metal
64
Group IV Materials
(Diamond Structure Band Gaps)
Khe nng lng gim rng vng cm (Decreasing bandgap) E
g
-
Khong cch gia cc nguyn t t ng (increasing interatomic distance)

C 6 eV
+
Si 1.1 eV
+
Ge 0.7 eV
+
Sn Bn kim loi (semimetal) 0 eV

Pb Kim loi, khng phi cu trc kim cng (metal, not
diamond structure!)
65
Cc cht bn dn n cht
(Elemental Semiconductors)
Mainly, Column IV elements
C (diamond), Si, Ge, Sn (gray tin or -Sn)
Tetrahedrally bonded in diamond crystal structure.
Each atom has 4 nearest-neighbors.
Bonding: sp
3
covalent bonds.

Also! Some Column V & Column VI elements are
semiconductors!
P, 3-fold coordinated lattice
S, Se, Te 5-fold coordinated lattices


66
III-V Compounds
(Periodic Table Columns III & V)
Column III Column V
B N
Al P
Ga As
In Sb
Tl not used Bi
BN, BP, BAs; AlN, AlP, AlAs, AlSb
GaN, GaP, GaAs, GaSb; InP, InAs, InSb,.

67
III-V Compounds
Applications: IR detectors, LEDs, switches
BN, BP, BAs; AlN, AlP, AlAs, AlSb
GaN, GaP, GaAs, GaSb; InP, InAs, InSb,.

Bandgap decreases & interatomic distance increases as we go
down the periodic table

Tetrahedral coordination! Most: zincblende crystal structure.
Some (B compounds & N compounds): wurtzite crystal
structure

Bonding: Not pure covalent! Charge separation due to valence
difference Partially ionic!
68
II-VI Compounds
(Periodic Table Columns II & VI)
Column II Column VI
Zn O
Cd S
Hg Se
Mn : sometimes Te
not used Po
ZnO, ZnS, ZnSe, ZnTe; CdS, CdSe, CdTe
HgS, HgSe, HgTe, some compounds with Mn.
69
II-VI Compounds
Applications: IR detectors, LEDs, switches
ZnO, ZnS, ZnSe, ZnTe; CdS, CdSe, CdTe
HgS, HgSe, HgTe (semimetals); compounds with Mn
Bandgap decreases & interatomic distance increases as we
go down the periodic table
Large bandgaps! Except for Hg compounds, which are
semimetals with zero gaps.
Tetrahedral coordination! Some zincblende & some
wurtzite crystal structures.
Bonding: Charge separation due to valence difference is
large.
More ionic than covalent!
70
IV-IV Compounds
(Periodic Table Column IV)
Column IV
C
Si
Ge
Sn
SiC
Other compounds: GeC, SnC, SiGe, SiSn, GeSn cannot be
made or cannot be made without species segregation or are
not semiconductors.
SiC: zincblende (semiconductor), & hexagonal close
packed (large gap insulator).
Also MANY other crystal structures!
71
IV-VI Compounds
(Periodic Table Columns IV & VI)
Column IV Column VI
C O
Si S
Ge Se
Sn Te
Pb
PbS, PbTe, PbSe, SnS
Others: SnTe, GeSe, cant be made, cant be made
without segregation, arent binary compounds, or arent
semiconductors.
72
IV-VI Compounds
Applications: IR detectors, switches

PbS, PbTe have zincblende crystal structure

Others: 6-fold coordination
~ 100% ionic bonding
Small bandgaps (IR detectors)

73
I-VII Compounds
(Periodic Table Columns IV & VI)
Mostly insulators: NaCl, CsCl,

No tetrahedral coordination! 6 or 8 fold coordination.
~ 100% ionic bonding

NaCl and CsCl crystal structures
Large bandgaps
74
Hp cht oxide (Oxide Compounds)
a s l cht in mi c rng vng cm ln (Most are
good insulators with large bandgaps)

C t cht bn dn oxide: CuO, Cu
2
O, ZnO
Cha c hiu tt (Not well understood)
C rt t ng dng (Very few applications)
Except for ZnO (ultrasonic transducer)

nhit thp mt s oxide tr thnh siu dn La
2
CuO
4
(T
c
~ 135K)
75
Mt s cht bn dn khc
(Some Other Semiconductor Materials)
Alloy mixtures of elemental materials (binary alloys):
Si
x
Ge
1-x
,... (0 x 1)
Alloy mixtures of binary compounds (ternary alloys):
Ga
1-x
Al
x
As, GaAs
1-x
P
x
, (0 x 1)
Alloy mixtures of binary compounds with mixtures on
both sublattices (quaternary alloys):
Ga
1-x
Al
x
As
1-y
P
y
, .., (0 x 1, 0 y 1)

Vary x & y varies bandgap & other properties.
BANDGAP ENGINEERING!
76
Exotic Semiconductors
Layered compounds: PbI
2
, MoS
2
, PbCl
2
,
Covalent bonding within layers
weak Van Der Waals bonding between layers
Effectively 2 dimensional solids
Electronic & vibrational properties have ~ 2 dimensional
character.

Organic semiconductors
Polyacetyline: (CH
2
)
n

Great promise for future applications
(Has been said for > 25 years!)
Not well understood
77
Other Semiconductors
Bn dn t (Magnetic semiconductors)
Cc hp cht c cha Mn & / or Eu v cc ion t khc
(& other magnetic ions)
Va c tnh cht bn dn va c tnh cht t (Both
semiconducting & magnetic)
EuS, Cd
x
Mn
1-x
Te,
Cc b bin iu quang hc (Optical modulators)
Cc cht bn dn khc (Others)
I-II-(VI)
2
& II-IV-(V)
2
compounds
AgGaS
2
, ZnSiP
2
, ., Tetrahedral bonding
Cc hp cht V
2
-(VI)
3

As
2
Se
3
.

78
Cu hi n tp chng 1:
1. Cu trc tinh th v cu trc vng nng lng ca cc cht bn
dn khi Si, A
III
B
V
v

A
II
B
VI
.
2. Tnh cht quang ca cc cht bn dn khi.
3. Tnh cht in ca cc cht bn dn khi.
4. Cc phng php ch to vt liu bn dn khi
5. Phn loi cc cht bn dn

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