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AZO
BQ95001
BQ95002
BQ95038
BQ95074
DEPARTMENT OF ELECTRONIC ENGINEERING
HSIU-PING INSTITUTE OF TECHNOLOGY
(DC)(AZO)
DC AZO
DC (380nm ~ 780nm)
80%
XRD ZnO(002) FESEM
DC
.
1.1
1.2
2.1 .
2.1.1
2.1.2
2.1.3
2.2
2.2.1
2.2.2
2.2.3
3.1
3.2
3.2.1
3.2.2
3.3
3.3.1 (-step)
3.3.2 X
3.3.3
3.3.4
3.3.5 UV-VIS
4.1
4.2
4.2.1 DC
4.3
4.3.1 DC
1.1
e
(3C )
2054
[1]
2006 25.4 2007
27 [2]
(ITO)
ITO
600 USD/kg
1.2
: ()
()ZnO p
n () ZnO UV
ZnO AlInGaNGaN (excition)
GaN
[?]()
ZnO ZnO ()
AZO (RF)
AZO (DC) AZO
()
AZO (RF)+(DC)
AZO
2.1
2.1.1
( 380 ~ 780 nm) 80%
(liquid crystal display, LCD)
(Plasma display panel, PDP)
(touch panel)
: ()()
()
100 100
:
(surface effect)
(mean free path)
5 - 10
[?]
1907
Badeker[3](Cd)
[3]
Optical band gap 3ev
()
ITO [4,5] ATO [6,7]
FTO [8,9]
(non-stoichiometric)
2.1
2.1 [10]
2.1.2
(transparent conductive oxide thin film, TCO)
(Magnetron Sputtering)
(Pulsed Laser Deposition)
(CVD) (SprayPyrolysis)(Solgel)TCO
2.2 TCO
2. 2 TCO [11]
Application Material Process
Wavelength-Selective Doped SnO2
In2O3
ITO
ZnO:Al
Spray
Evaporation
CVD/Spray/Sputtering/
Evaporation
CVD/Sputtering
Solar Cell SnO2
In2O3
ITO
ZnO
Spray/Sputtering
Sputtering
Spray/Sputtering
Spray/CVD
Gas Sensors SnO2/Doped SnO2
ITO
CVD/Sputtering
Sputtering
Display Devices ITO Sputtering
2.1.3
LCD ITO
PDA
2.3
2.3 [3]
SnO2:F 3 m
AgTiN 1 m
SnO2:F
ITO
SnO2:F
(electrochromic, EC)
ITO
ITOZnO
ITOAg
Ag-Cu
alloy
SnO2
SnO2
ITOSnO2
AgITO
Ag/ZnO UV
2.2
2.2.1
Zinc Oxide, ZnO Wurzite hexagonal
structure( 2.1) N
3.1~3.6 eV
1975
UV 2.4
2. 1 Wurzite hexagonal structure
a = 3.2495 c = 5.2069
Zine
Oxygen
c
a
2. 4 [12]
Property
Mineral name zincite
Band gap Eg (eV) 0K: 3.436 300K: 3.2
Melting point () 1975
Heat of formation (eV) 3.6
Density (g/cm3) 5.67
Relative permittivity 8.1
Effective electron mass (m*/me) 0.28
Dopants B, Al, In, Ga, Si, Sn, F
Crystal structure hexagonal, wurtzite
Space group P63/mc
Lattice parameters (nm) a: 0.325 c: 0.5207
Thermal expansion (300K)
(10-6K-1) //c: 2.92 c: 4.75
Melting point of Zn metal () 420
2.2.2
3.1~3.6 eV
(UV cut off)
(Band edge)
Burstein-Moss shift(BM
)[13,14,15,16,17] 2.2(Eg0 Eg
)
BM
BM AZO
UV
cut off
2.2 -(Burstein-Moss)[17]
2.2.3
oxygen vacanciesinterstitial znic
shallow donor levels[2]
Al Zn Al Zn
(ionized impurity scattering centres)
[18]
(electrical conductivity)
:
J = E (2.1)
J ()
(A/m2)E (V/m)
(Siemens/m) S/m
(resistivity) -cm ohm-cm
J=Nev (2.2)
N ( cm-3)e
(=1.602210-19)v
(mobility cm2/V-s):
=Vd/E (2.3)
Vd(drift velocity)E
()(random)
(
)
(2.3) Vd(2.2) v
(2.1)(2.3)
=Ne (2.4)
I R
A W
T 2.3
R=L/A =L/WT (2.5)
L=W()
Rs=/T (2.6)
(sheet resistance) Rs
/square (WL T)
2.3 L A
(2.6)
(
)
3.1
1.
(AZO)(GFE)
30.125
98:2 wt%(98%ZnO,2%Al2O3) 99.99%
2.
: Corning 1737 glass
0.7mm
3.
:99.99%
: 99.99%
:99.99%
3.2
3.2.1
Corning 1737
(2cm2cm)
3.1
()
3.1
(acetone)
10
(IPA)
10
10
10
3.2.2
(1) 510-6 torr
(2) 510-6 torr(
)
(3) (Ar)
(4) DC power turn on 20 turn off
DC power
(5)
3.3
3.3.1 (-step)
stylus
(Max.
Scan Length) 10mm (Scan Speed) 2um/sec ~
200um/sec (Max. Vertical Range)0~2000um
(Sampling Rate) 50Hz100Hz200HzVertical
Range/Resolution13um/1A300 um/25A
Alpha-step500 3.3
-step
-step
3.2 Alpha-step500
substreas
3.3.2 X
X (XRD) X
() X X
(
)
2
40 kV 20 mA 20 - 60
4
AZO [27 , 28]:
Dp 1/2 the full width at half maximum of the
diffraction peak X-ray (=0.154041 nm), peak
3.3 X Rigaku PC-2000
3.3.3
(Hall effect measurement)
ECOPIA HMS-2000 3.4
3.4 ECOPIA HMS-2000
3.3.4
(I)(V)
(Sheet Resistance)
R = (L/A)
R L A
Wt
LR = (L)/(WT)
L=W
R = / T
S1=S2=S3=1 mm
s= CFV/I= CF(L)/(TW) =sT
s L T W CF
T
I
substart
S1 S2 S3
V
3.5 SR300DLCT 3000
3.3.5 UV-VIS
UV-VIS
( 190
350 nm 330 2700 nm)
()
()
band gap
[29]:
t T ( )2
[13]
3.6 UV-VIS-NIR Jasco V-670
4.1
AZO
( GFE AZO
)
4.2
4.2.1 DC
4.1 ~ 4.3 UV-VIS
AZO (380 nm ~ 780 nm) 80%
(absorption edge)(blue-shift)
Eg:
h=A(h-Eg)n
[30](direct transition) n=0.5
(indirect transition) n=2 A
h (h)1/n h
(h)1/n=0 Eg0
(band gap)
4.1 210-3 torr 3.3 ~ 3.48 eV 4.2
410-3 torr3.27 ~ 3.52 eV4.3610-3 torr3.28 ~ 3.48
eV 4.5-4.6 (optical band gap)
BM (Burstein-Moss
shift)[31,32] BM [33]
(carrier concentration) 2/3
-
4.1 210-3 torr (Refractive index)
1.9 ~ 1.81410-3 torr 1.9 ~ 1.8610-3 torr 1.9 ~ 1.7
300 400 500 600 700 800
0
20
40
60
80
100
Tra
nsm
itta
nce(%
)
Wavelength(nm)
225oC
250oC
275oC
300oC
325oC
4.1 210-3 torr
300 400 500 600 700 800
0
20
40
60
80
100
Tra
nsm
itta
nce(%
)
Wavelength(nm)
225oC
250oC
275oC
300oC
325oC
4.2 410-3 torr
300 400 500 600 700 800
0
20
40
60
80
100
Tra
nsm
itta
nce(%
)
Wavelength(nm)
225oC
250oC
275oC
300oC
325oC
4.3 610-3 torr
3.0 3.1 3.2 3.3 3.4 3.5 3.6 3.7 3.8 3.9 4.00
1x105
2x105
3x105
Ab
sorp
tio
n c
oeff
icie
nt(
cm
-2)
Energy(eV)
225oC-2x10
-3torr
3.0 3.1 3.2 3.3 3.4 3.5 3.6 3.7 3.8 3.9 4.00
1x105
2x105
3x105
Ab
sorp
tio
n c
oeff
icie
nt(
cm
-2)
Energy(eV)
250oC-2x10
-3torr
(a) (b)
3.0 3.1 3.2 3.3 3.4 3.5 3.6 3.7 3.8 3.9 4.00
1x105
2x105
3x105
4x105
Ab
sorp
tio
n c
oeff
icie
nt(
cm
-2)
Energy(eV)
275oC-2x10
-3torr
(c)
3.0 3.1 3.2 3.3 3.4 3.5 3.6 3.7 3.8 3.9 4.00
1x105
2x105
3x105
Ab
sorp
tio
n c
oeff
icie
nt2
(cm
-2)
Energy(eV)
300oC-2x10
-3torr
3.0 3.1 3.2 3.3 3.4 3.5 3.6 3.7 3.8 3.9 4.00
1x105
2x105
3x105
Ab
sorp
tio
n c
oeff
icie
nt(
cm
-2)
Energy(eV)
325oC-2x10
-3torr
(d) (e)
4.4 210-3 torr (a)225 (b)250
(c)275 (d)300 (e)325
3.0 3.1 3.2 3.3 3.4 3.5 3.6 3.7 3.8 3.9 4.00.0
2.0x105
4.0x105
6.0x105
Ab
sorp
tio
n c
oeff
icie
nt(
cm
-2)
Energy(eV)
225oC-4x10
-3torr
3.0 3.1 3.2 3.3 3.4 3.5 3.6 3.7 3.8 3.9 4.00
1x105
2x105
Ab
sorp
tio
n c
oeff
icie
nt(
cm
-2)
Energy(eV)
250oC-4x10
-3torr
(a) (b)
3.0 3.1 3.2 3.3 3.4 3.5 3.6 3.7 3.8 3.9 4.00
1x105
2x105
3x105
Ab
sorp
tio
n c
oeff
icie
nt(
cm
-2)
Energy(eV)
275oC-4x10
-3torr
(c)
3.0 3.1 3.2 3.3 3.4 3.5 3.6 3.7 3.8 3.9 4.00
1x105
2x105
3x105
Ab
sorp
tio
n c
oeff
icie
nt(
cm
-2)
Energy(eV)
300oC-4x10
-3torr
3.0 3.1 3.2 3.3 3.4 3.5 3.6 3.7 3.8 3.9 4.00
1x105
2x105
Ab
sorp
tio
n c
oeff
icie
nt(
cm
-2)
Energy(eV)
325oC-4x10
-3torr
(d) (e)
4.5 410-3 torr (a)225 (b)250
(c)275 (d)300 (e)325
3.0 3.1 3.2 3.3 3.4 3.5 3.6 3.7 3.8 3.9 4.00
1x105
2x105
3x105
Ab
sorp
tio
n c
oeff
icie
nt(
cm
-2)
Energy(eV)
225oC-6x10
-3torr
3.0 3.1 3.2 3.3 3.4 3.5 3.6 3.7 3.8 3.9 4.00
1x105
2x105
3x105
Ab
sorp
tio
n c
oeff
icie
nt(
cm
-2)
Energy(eV)
250oC-6x10
-3torr
(a) (b)
3.0 3.1 3.2 3.3 3.4 3.5 3.6 3.7 3.8 3.9 4.00
1x105
2x105
3x105
4x105
Ab
sorp
tio
n c
oef
fici
ent(
cm-2
)
Energy(eV)
275oC-6x10
-3torr
(c)
3.0 3.1 3.2 3.3 3.4 3.5 3.6 3.7 3.8 3.9 4.00
1x105
2x105
3x105
Ab
sorp
tio
n c
oeff
icie
nt(
cm
-2)
Energy(eV)
300oC-6x10
-3torr
3.0 3.1 3.2 3.3 3.4 3.5 3.6 3.7 3.8 3.9 4.00.0
2.0x103
4.0x103
6.0x103
Ab
sorp
tio
n c
oeff
icie
nt(
cm
-2)
Energy(eV)
325oC-6x10
-3torr
(d) (e)
4.6 610-3 torr (a)225 (b)250
(c)275 (d)300 (e)325
4.1 210-3 torr
4.2 410-3 torr
4.3 610-3 torr
4.3
4.3.1 DC
4.21 210-3
torr 1.2310-2 ~ 3.4210-4 .cm410-3 torr
1.2310-2 ~ 4.0610-4 .cm610-3 torr 9.6510-3 ~ 3.8710-4
.cm
Y.Igasaki[34]
4.22 210-3 torr 2.83 ~ 14.77
(1020/cm3)410-3 torr 2.74 ~ 12.36(1020/cm3)610-3 torr
3.43 ~ 15.54(1020/cm3)[34]
4.23 210-3 torr (carrier mobility)
1.8 ~ 12.37(cm2/Vs)410-3 torr 1.84 ~ 12.43(cm2/Vs)610-3
torr 1.87 ~ 10.51(cm2/Vs)
4.244.254.26 210-3 torr410-3
torr610-3 torr
4.124.13 4.14
225 250 275 300 32510
-4
10-3
10-2
10-1
Resi
stiv
ity
(.c
m)
Temperature(oC)
2x10-3torr
4x10-3torr
6x10-3torr
8x10-3torr
1x10-2torr
4.7
225 250 275 300 325
0
2
4
6
8
10
12
14
16
18
Co
ncen
trati
on
(10
20/c
m3)
Temperature(oC)
2x10-3torr
4x10-3torr
6x10-3torr
8x10-3torr
1x10-2torr
4.8
225 250 275 300 325
0
2
4
6
8
10
12
14
Mo
bil
ity
(cm
2/V
s)
Temperature(oC)
2x10-3torr
4x10-3torr
6x10-3torr
8x10-3torr
1x10-2torr
4.9
225 250 275 300 325
0
20
40
60
80
100
120
140
0
2
4
6
8
10
12
14
16
0
2
4
6
8
10
12
14
Resi
stiv
ity
(10
-4
.cm
)
Temperature(oC)
resistivity
Co
ncen
trati
on
(10
20/c
m3)
concentration
Mo
bil
ity
(cm
2/V
s)
mobility
4.10 210-3 torr
225 250 275 300 325
0
20
40
60
80
100
120
140
0
2
4
6
8
10
12
14
0
2
4
6
8
10
12
14
Resi
stiv
ity
(10
-4
.cm
)
Temperature(oC)
resistivity
Co
ncen
trati
on
(10
20/c
m3)
concentration
Mo
bil
ity
(cm
2/V
s)
mobility
4.11 410-3 torr
225 250 275 300 325
0
20
40
60
80
100
120
0
2
4
6
8
10
12
14
16
18
20
0
1
2
3
4
5
6
7
8
9
10
11
Resi
stiv
ity
(10
-4
.cm
)
Temperature(oC)
resistivity
Co
ncen
trati
on
(10
20/c
m3)
concentration
Mo
bil
ity
(cm
2/V
s)
mobility
4.12 610-3 torr
4.4
4.4.1 DC
XRD 4.13 ~ 4.15 2=35o
ZnO(002)
AZO
(002)
4.10 ~ 4.12
SEM
AZO
X
20 30 40 50 60
0
10000
20000
30000
40000
50000
Inte
nsi
ty(a
.u.)
2(o)
(002)
225oC
250oC
275oC
300oC
325oC
4.13 210-3 torr XRD
20 30 40 50 60
0
50000
100000
150000
200000
250000
300000
Inte
nsi
ty(a
.u.)
2(o)
(002)
225oC
250oC
275oC
300oC
325oC
4.14 410-3 torr XRD
20 30 40 50 60
0
10000
20000
30000
40000
50000
60000
70000
80000
90000
100000
110000
120000
130000
140000
150000
160000
170000
Inte
nsi
ty(a
.u.)
2(o)
225oC
250oC
275oC
300oC
325oC
(002)
4.15 610-3 torr XRD
4.16 210-3 torr SEM
4.17 410-3 torr SEM
4.18 610-3 torr SEM
(DC) AZO
:
1.DC (380 nm ~ 780 nm) 80%
2.DC AZO
3. DC AZO
AZO
(DC) AZO