ITO

TEL:(04)25318899 ext. 7751

e-mail: cphwang@wintek.com.tw

2006.06.07

Outline
1. ITO
(Transparent Conductive Oxide, TCO)

2. TCO
3. TCO
4. TCO
5. TCO

Section 1

1.

ITO

3. TCO
4. TCO
5. TCO
2. TCO

?

"flat panel display )
"solar cell )

" (resistivity) <10-4 cm

80 % 110-4
cm

AgPtCuAlCrPdRh< 10nm

9
9
9 Au

100

Au

90

Ag
Cu

T% 80

Pt
Al

70

Cr

60
380
18 thickness

480

580
680
Wavelength(nm)

780


(TCO)

a. ()In2O3SnO2ZnOCdO TiN
b. In2O3:Sn (ITO)ZnO:In (IZO)
ZnO:Ga (GZO)ZnO:Al (AZO)
SnO2:F TiO2:Ta

c. In2O3-ZnOCdIn2O4Cd2SnO4
Zn2SnO4

-- ITO

Indium Tin OxideITO

(Tin-doped Indium Oxide)
1934
ITO
TCO75%

(heat reflecting mirror)

History of TCO
1907CdO
photovoltaic cells.

Spray Pyrolysis CVD SnOx

.
1970 Evaporation Sputtering InOx
ITO.
1980 magnetron sputtering

ITO.
1990TCO DC
ITOTCO
.
2000 ITO
ITO.
1940

Why choose ITO ?

TCO ()

()
()
?

ITO
ITO In2O3/SnO2 = 90/10

(mOhm cm)

@550 nm (%)

SnO2

(%)

ITO
ITO In2O3/SnO2 = 90/10

Etching Rate (/min)

Etching Rate (/min)

SnO2

(%)

200C

ITO

SnO2

(%)

RT

ITO

M
ar
Ja 02'
M n0
ar 3 '
ch
M 03'
ay
Ju 03'
l
Se y 03
pt '
.
N 03'
ov
0
Ja 3'
M n0
ar 4 '
ch
M 04
ay '
Ju 04'
l
Se y 04
pt '
.
N 04'
ov
0
Ja 4'
M n0
ar 5 '
ch
M 05
ay '
Ju 05'
ly
Se 05
pt '
.
N 05'
ov
Ja 05'
n
06
'

Why Consider other TCO then ITO?

1000

800

gK
/$
SU
600

400

200

UMICORE

(In)

70%

5%

8%

5%

12%

TCO -ZnO

-cm)
ZnO:In (IZO) (2~4 10-4 -cm , )
ZnO:Ga(GZO) (1.210-4 -cm, MOCVD )
ZnO:Al (AZO) (1.310-4 -cm, )

ZnO

(3~5 10-4

ZnO:Ti

2. ITO (> 200% cost saving)

3. AZO100% Ar
3. ITO CrCo ZnO

1. ZnO

 CrAZO

AZO:Cr

ITO Patterning (Photo-etching)

By acid solution

By base solution

TCO -ZnO

(Low-E)
.

Resistivity (.cm)

IZO

RT

350 C
ZnO/(In2O3+ZnO) ratio

Section 2
1. ITO

2. TCO

4. TCO
5. TCO
3. TCO

TCO
(n-type TCO)

Ec
Dorner level (Ed)

Eg

Ev
Absent
O atom

SnIn Sn+In + e-

V +1/2 O
V V + 2e
Sn V doner
Oo
o

2(g)

In

O
Sn-interstitial
Sn-substitutional

In

ITO
(n-type TCO)
In2O3SnO2

In2O3(Oxygen vacancy)

Band gap (Eg) > 3.5eV
Crystallized at T > 150 C

(a) Amorphous ITO (b) Crystallized-ITO

TCO

= ne

n = (TCO
)
e
mobility

ITO10
10 ~10 cm

TCO
~1019 cm-3

18

22

~23

-3

TCO
mobility ()
= e/om*

relaxation time (

m*
o

mobility
) TCO TCO defect
(extrinsic effect)
) m* TCO (intrinsic effect)

TCO
(, ) (conductivity, )
= 1/ ohm-cm

(surface resistance, ) or (sheet resistance, Rs)

Rs = (L/DW) ohms

= /D (ohms/ )
Rs = (L/W)
L = W Rs =

D
L

ITO ()

ITO (D)
-Step

ITO

TCO
ITO

= /D

ITO

Ag

210-4 ohm-cm

1.810-6 ohm-cm

10 ohm/

D = /

10 ohm/

2 10-5 cm (2000 )

1.8 10-7 cm (18 )

92
90
88
Ag

%T 86

ITO

84
82
80
380

480

580
Wavelength(nm)

680

780


= /D
ITO ()

Section 3

2. TCO
1. ITO

3. TCO

5. TCO
4. TCO

TCO
TCO (energy gap)
( plasma frequence)
p

gap

TCO
In2O3SnO2ZnO
SnAlSb

= (ne / m*)

EELS for ITO

1/2

n
e

m*
o

()
AZO (antimony doped tindioxide)

SnO2

Sb

Transmittance

Sb

3.98 10 -cm
Sb2O5

-3

Wavelength

ITO

= x
( = x D)
) ITO
)
nd=(2m+1) /4m=1,2,3,4.
94
m
n0 92
55 90
) 88
%
(t
ne 86
ra 84
ps
na 82
r 80
T
78
0

30

60

90

0
12

0
15

0
18

ITO thickness

0
21

0
24

0
27

0
30

Section 4

2. TCO
3. TCO
1. ITO

4. TCO
5. TCO

TCO
TCO
1.
2.
3.
4.
5.
6.
7. Pin hole
8. Hill lock

Thin films

Zone-1

Zone-T

Zone-3

From : Thornton, J. Vac. Sci. Technol. 11, p.666, 1974

Zone-2

Intensity (Arb. Units)

ITO

50 C

125 C

180 C

2 (deg.)
J. Vac. Sci. Technol. A, Vol. 10, No. 4 P1682

Intensity (Arb. Units)

IZO

2 (deg.)
IDIXO

IZO

Intensity (Arb. Units)

ITO

0.08 Pa

0.18 Pa
0.31 Pa
0.50 Pa
0.76 Pa

2 (deg.)
Thin Solid Films 303 (1997) p151

ITO
STN-LCD
ITO300 ~ 400 C
Color filterITO
< 220 C

From J. Vac. Sci. Technol. A, Vol.8, p. 1399

ITO


In2O3
(trivalent)

2InO + O
(bivalent)

Color filter
ITO
RF+DC sputtering

From J. Vac. Sci. Technol. A, Vol.8, p. 1399

From J. Vac. Sci. Technol. A, Vol.8, p. 1399


86.8

86.6

86.4

86.2

86

Transmittance (%)

Resistivity (X 10-4 cm)

85.8

O2 flow rate (SCCM)

O2

10

O2

From J. Vac. Sci. Technol. A, Vol.8, p. 1399

Target

From J. Vac. Sci. Technol. A, Vol.8, p. 1399

Nodules formed on ITO Target

SEM micrograph of nodules formed on ITO

targets at high power density

From : B.G. Lewis, Brown Univ., SVC Conference 1994

Mechanism of Nodules Formation

Redeposited ITO
Particulate Contamination

SID 96 DIGEST p31

Nodules formed on ITO Target

In OX 1 x 1.5 ,

Ar

Particulate
> 99%

Target

(V)

(nm/min)

nodule

(%)

nodule
CP (Cold Press)

HP (Hot Press)

ITO

()

ITO

HP

()
Iron

CP

MMF

nodule
MMF (Mitsui Membrane Filter)

+ DIW (Slurry)

ITO

AL alloy

Mitsui Mining Smelting Co., Ltd.

nodule
ITO Target

MMF

(g/cm)
7.11

CP

7.08

99.5
99.0

HP

6.44

90

Mitsui Mining Smelting Co., Ltd.

(%)

nodule
MMFCP

9 MMF & d=98 CP

9 cathodes

Mitsui Mining Smelting Co., Ltd.

ITO
Wet Etching

Plasma Etching
ITO

Glass

Isotropic Etching

HBr
FeCl3/HCl

HCl/HNO3

(COOH)2

ITO

Glass

Anisotropic Etching
Reactive-Ion Etching (RIE)

ITO
ITO

ITO & IZO

(nm/sec)

(nm/sec)

Etchant : HCl/FeCl3

(C)

(C)

Sputter AZO

ZnO & AZO

Sputter
RF power
mobility() (n)()

Section 5

2. TCO
3. TCO
4. TCO
1. ITO

5. TCO

TCO
ITO

(/ )
500

300
40
10

(/)
< 1000
40 ~ 300

15 ~ 40
<10

EL

(LCD)

Display Application
PM LCD

Transparent electrode

Transparent electrode

Display Application
AM LCD

Source Drain

Gate

ITO

Display Application
AM LCD

Display Application
OLED

Active Matrix OLED

Display Application
PDP

Bus

MgO

Address

Touch Panel

Plastic Touch Panel for PDA/handheld devices

Five-wire Touch Panel for POS, Kiosk, Industrial control system

Solar cell ()

 (EMI shielding)

5 / give a shielding
performance of -30 dB
(at 1 GHz)

Electrochromic Window
()

ZnO/Ag/ZnO,
SnO2/Ag/SnO2,
SnO2:F
< 1 / required

Electrochromic Window
()

TCO

SnO2:F

Ag TiN
SnO2:F
SnO2:F

IZO
ITOAg

ITO

Ag-Cu alloy

SnO2
SnO2
SnO2

Ag ITO

(low-E) 2 m ()
(low-E) 1 m ()

EC windows

()

()

ITOTCO
ITO
&

()

ITO
ITO + AR Coating
ITO layer
Low index layer
High index layer
Glass

Low index : SiO2 (1.46)MgF2(1.38)

High index : TiO2 (2.3) Nb2O5(2.2)

Ta2O5(2.2)
SrF2(1.44)

ITO
Index matched ITO (IMITO)
Thin Film Devices

ITO

IMITO match to LC
Glass
Glass

IMITO match to Epoxy

ITO layer
H/L index dielectric layer

Contact material

&
STN display(<3/ )&
ITO>5000 < 70%

1. ITO/Ag/ITOITO/AP/ITO for display

2. ZnO/Ag/ZnO for low-E window
3. GZO/AP/GZO
4. Doping Ag in ITO target
5. High density ITO target
6. Low voltage (<200 V) sputtering
7. Pulsed power supply to avoid nodule growth and arcing

& -ITO/Ag/ITO Stack

50 nm
50 nm

From : FEP internal report, Sept. 2000

& -ZnO/Ag/ZnO Stack

ZnO 40 nm
Ag
ZnO 16 nm

substrate

3-layer stack

ZnO 40 nm
Ag
ZnO 100 nm
Ag
ZnO 40 nm

substrate

5-layer stack
250 C, 30 min annealing
From : J. Appl. Phys. Vol. 39, 2000, p.4884.

& -

SnSn4+In3+

(Mo6+)
IMO
1.

2.
3.

ITO

O
Sn-interstitial
Sn-substitutional


OLED application
Rough surface cause current leakage of OLED devices
Metal (Cathode)
EIL
Point
Discharge

Organic Layer
Spike

ITO film

Leakage Current


CMP

(Ra~30)

(Ra<3)

AFM images of ITO films for original (left) and with CMP process (right)


Application :

Benefit :
Lower-temperature processing (<50c)
Smoother film surfaces (<1nm rms)
Good conductivity (<2 x 10-4 -cm )
Better adhesion (>1000 psi)

substrate

M-

OLED Device
Plastic based Display

Mo

M-

Ar+

CS+

Cesium
injector

Cesium injection
CS+

target
magnets

Negative Sputter
Ion Beam

Magnetron cathode


New ionized PVD, Negative Ion Source (NIS) technology
for super-smooth ITO deposition

Normal Sputtering
(Ra ~ 20 )

NIS Sputtering
(Ra ~ 7 )


()

Flexible display
Large area display

DC+RF sputtering
PLD method
Ion-beam assisted
Post-annealing
From Pacific Northwest National Lab., USA

Flexible OLED

Roll-to roll coater -ITO film

Multi-chamber for multilayer

sputtering by roll coater

ITO
Dimensional stability of plastic substrate
Heat damage of plastic substrate by plasma
irradiation
Outgassing from plastic substrate
Adhesion of coating layer with substrate
Thermal stress and internal stress
- CTE, elongation,
- Bending property


: Tensile and compressive stress

f > sub

f < sub

Tensile stress

Compressive stress


Annealing

The XRD pattern of (a) In2O3 (b) ITO films annealed at

different temperature.

ITO
(Rrms = 0.29 nm)

ITO

140 C

(Rrms = 0.48 nm)

ITO Rrms 2nm

Conclusion
Transparent Conductive material is a key
point in the development of optical-electronic
device in future.
Approach higher light transmittance.
Approach lower electric resistance.
Approach more process feasibility.
Approach low cost material.