Surface and Coatings Technology 132 Ž2000.

45᎐48

Electrical and optical properties of electron beam evaporated

ITO thin films

Joseph George, C.S. MenonU

School of Pure and Applied Physics, Mahatma Gandhi Uni¨ ersity, Kottayam, Kerala, India 686 560

Received 17 February 2000; accepted in revised forn 19 May 2000

Abstract

Indium tin oxide ŽITO. thin films were prepared on glass substrates by an electron beam evaporation technique from a mixture
of In2 O3 and SnO2 . The films were annealed in air for 30 min at 350⬚C. The electrical and optical properties of these films were
investigated as a function of the substrate temperature. The films were deposited at substrate temperatures ranging from 50 to
350⬚C at an oxygen partial pressure of 5 = 10y5 mbar. The dopant concentration, resistivity, electrical conductivity, activation
energy, optical transmission and band gap energy were investigated. It was found that the activation energy decreased with an
increase in the film thickness. A transmittance value of 92% in the visible region of the spectrum and a resistivity of 3 = 10y6 ⍀ m
was obtained at a substrate temperature of 350⬚C. Structural studies showed that the films were polycrystalline. 䊚 2000 Elsevier
Science S.A. All rights reserved.

Keywords: A: Thin films; D: Electronic transport; D: Optical properties

1. Introduction films prepared by electron beam evaporation have been

Sn-doped In2 O3 ŽITO. is an n-type, highly degener-
ated, wide-gap semi-conductor w1x. Due to its relatively
low resistivity Ž; 10y6 ⍀ m. and its high transmittance
Ž; 80%. of visible light, ITO finds applications in opto-
electronic devices, such as transparent electrodes for
flat panel display devices and for solar cells w2x. ITO
films with an even lower resistivity are required to
satisfy commercial demands for flat panel displays with
a large size and higher image quality. Various deposi-
tion techniques such as sputtering w3x, spray pyrolysis
w4x, reactive thermal evaporation w5x, and electron beam
evaporation w6,7x were applied. In this paper, the elec-
trical and optical properties of indium tin oxide thin
U
Corresponding author. Tel.: q91-481-597-923; fax: q91-481-597-
494.
E-mail address.: spapforum@vsnl.com ŽC.S. Menon..
presented.
2. Experimental details
A 12-inch vacuum coating unit with an electron
beam gun was used for the evaporation of indium tin
oxide ŽITO. thin films. Spectroscopically pure indium
oxide powder and tin oxide powder Ž99.99%., taken in
wt.% proportions, were mixed well using a pestle and
mortar. The mixture was sintered in a furnace for 6 h
at a temperature of 800⬚C. The mixture was pressed
into pellets, which were used as source material for
evaporation. The vacuum chamber was evacuated to a
base pressure of 1 = 10y6 mbar. Pure oxygen was
admitted to the chamber. A steady-state chamber pres-
sure of 5 = 10y5 mbar was reached by adjusting the
needle valve for oxygen. Glass slides were used as
substrates. A calibrated thermocouple was attached to

0257-8972r00r$ - see front matter 䊚 2000 Elsevier Science S.A. All rights reserved.
PII: S 0 2 5 7 - 8 9 7 2 Ž 0 0 . 0 0 7 2 6 - X
46 J. George, C.S. Menon r Surface and Coatings Technology 132 (2000) 45᎐48

the substrate. The substrates were cleaned using a

liquid detergent, then they were kept in dilute nitric
acid for some time. These substrates were agitated
ultrasonically in acetone after cleaning in distilled
water. They were then rinsed in isopropyl alcohol and
dried in hot air. Inside the bell jar, the substrates were
subjected to ionic bombardment for 5 min as the final
cleaning before using them for deposition. The sub-
strate temperature was varied by means of a substrate
heater.
The evaporation conditions were: Ž1. a vacuum of
5 = 10y5 mbar; Ž2. an accelerating voltage of 6 kV; and
Ž3. electron beam current 10᎐15 mA. The rate of
evaporation was controlled within the range 13᎐15
nmrmin.
The thickness of this film was controlled by using a
quartz crystal thickness monitor. The thickness was Fig. 1. Resistivity vs. tin concentration.
counter-checked by means of the multiple beam inter-
ference technique w8x. The deposited films were an-
with more tin are more non-stoichiometric than the
nealed in a furnace for 30 min at 350⬚C in air.
optimum film and, hence, highly resistive w10x. The
The electrical conductivity of the sample was mea-
initial decrease in the film resistivity may be explained
sured by means of conductivity cell and a Keithly
on the basis of the gradual incorporation of the tin
programmable electrometer Žmodel no: 617.. The ohmic
impurity into the indium lattice. The increase in the
contacts were made by pre-evaporated silver electrodes
resistivity above 20% tin oxide may be attributed to the
and silver paste. The conductivity measurements were
higher concentration of tin impurity than the optimum
carried out in vacuum Ž- 10y3 mbar. to eliminate the
value, which allows more tin ions to occupy the nearest
contamination of the film. A double-beam spectropho-
neighboring sites, compensating the donor action. This
tometer ŽSchimadzu 160A. was used for recording the
leads to disordered crystallites, as explained by
UVrvis spectrum. XRD spectra of these samples were
Mizuhashi w11x.
recorded by means of the Schimadzu-610XD X-ray
ITO thin films ŽIn2 O3rSnO2 s 80%:20%. deposited
diffractometer.
at different substrate temperatures and resistivity are
shown in Fig. 2, which gives the plot of resistivity vs.
substrate temperature ŽTs .. The thickness of the film
3. Results and discussion
was 150 nm. A sudden drop in resistivity was obtained
in the temperature range between 50 and 250⬚C. The
3.1. Electrical properties
lowest resistivity obtained was 3 = 10y6 ⍀ m at a sub-
strate temperature of 350⬚C. The decrease in resistivity
In Fig. 1 the resistivity Ž␳ . vs. the percentage of tin
for films deposited at room temperature is presented.
The thickness of the film was 100 nm. It was found that
the resistivity was lowest when the sample was com-
posed of 80% In2 O3 and 20% SnO2 by wt.%. In this
study, the resistivity was 7.6= 10y3 ⍀ m. When the
concentration of SnO2 increased, the resistivity in-
creased, and at 40% SnO2 the resistivity was 1.92=
10y2 ⍀ m. Further increased doping did not show a
considerable change in resistivity.
The electrical conductivity of ITO is considered to
be due to oxygen vacancies and the incorporation of a
higher valency cation Žtin. in the host In2 O3 w9x. Non-
stoichiometry and the incorporation of impurities con-
tribute to the generation of carriers in the film. Al-
though the resistivity of ITO decreases to some extent
with an increasing number of vacancies, excess non-
stoichiometry may result in lattice structural disorder,
which reduces mobility of carriers. ITO films deposited Fig. 2. Resistivity vs. substrate temperature.
 J. George, C.S. Menon r Surface and Coatings Technology 132 (2000) 45᎐48 47

with increasing substrate temperature could be at-

tributed to the improved crystalline nature of these
films. The increase in substrate temperature may have
led to oxygen-deficient films, resulting in an increase in
carrier density. When tin is added to indium oxide, the
carrier density further varies for any particular sub-
strate temperature, due to the availability of more tin
to become ionized and donate electrons.
The activation energy is obtained using the relation:

␴ s ␴o exp Ž y ⌬ ErkT . Ž1.

where ␴ is the conductivity, ⌬ E is the activation en-

ergy, k is the Boltzmann constant, and T is the tem-
perature in Kelvin. The conductivity studies on films
deposited at a substrate temperature of 50⬚C showed
that two activation energies existed at different temper-
ature regions. The activation energy in the lower region
Ž30᎐130⬚C. for a film thickness of 100 nm was 0.033
eV, and in the higher region Ž130᎐220⬚C. it was 0.125
eV. The activation energies varied for films of different
thicknesses, as listed in Table 1. The results indicated
the presence of two donor levels, one deep and one
shallow, near the bottom of the conduction band w12x.
Both of these levels depended on the film thickness,
and were found to decrease with increasing thickness.
An increase in film thickness improved the film crys-
tallinity. Shigesato and Paine w3x suggested that an
increase in carrier density with increasing film thick-
ness was associated with increasing oxygen vacancies.
3.2. Optical properties
Thermally evaporated ITO thin films have a slightly
metallic appearance and become transparent by post-
deposition annealing w13x. The optical transmission
spectra corrected for the attenuation of the glass sub-
strate from 300 to 800 nm for ITO films deposited at
different substrate temperatures is shown in Fig. 3.
Before annealing the ITO film, only 50% of the inci-
dent light was transmitted. For the annealed samples
with Ts s 350⬚C, the average transmission in the visible
region goes up to 92%. The absorption edge was clearly
evident for all substrate temperatures in the 400᎐500-
Fig. 3. Percentage of transmission with wavelength for films de-
posited at various substrate temperatures.
nm range. There was a shift in the absorption edge to
shorter wavelength with the substrate temperature,
which was due to the Burstein᎐Moss shift w14x. The
direct band-gap of the film was calculated from the
transmission data in the lower wavelength region using
the assumption that the transition probability becomes
constant near the absorption edge, and that the absorp-
tion coefficient for the direct allowed transition can be
described as a function of photon energy:
␣ A Ž h␯ y Eg . 1r2 Ž2.
where ␣ is the absorption coefficient, Eg is the energy
gap, and h␯ is the photon energy. The photon energy
dependence of ␣2 for the tin-doped In2 O3 films with a
thickness of 100 nm was studied. The plots of ␣2 vs. h␯
had a linear region, and extrapolation of the straight
line to zero absorption gave the energy gap for differ-
ent substrate temperatures, which are listed in Table 2.
The energy gap values obtained are in good agreement
with the other reported values w15,16x.
By varying the substrate temperature during deposi-
tion, a wide spectrum of transmittance and resistivity
was obtained. The results of ITO films prepared by a

Table 1
Table 2
Variation of activation energy with thickness for ITO films deposited
Variation of energy gap with substrate temperature.
at 50⬚C.
Substrate temperature Band gap
Thickness Activation energy
Ts Ž⬚C. ŽeV.
Žnm.
⌬ E1 ⌬ E2
Ž30᎐130⬚C. Ž130᎐220⬚C. 50 3.29
100 3.30
80 0.038 0.152 150 3.31
100 0.033 0.125 200 3.30
120 0.026 0.107 250 3.36
150 0.013 0.076 300 3.41
48 J. George, C.S. Menon r Surface and Coatings Technology 132 (2000) 45᎐48

Table 3
Comparison of ITO films prepared by different researchers.

Technique Resistivity Transmittance in Ref.

␳ the visible region
Ž ⍀ m. Ž T %.

Electron beam evaporation 3.0= 10y6 92 Present work

Reactive evaporation 7.0= 10y6 80 w5x
Pulsed laser deposition 4.0= 10y6 85 w17x
Thermal deposition 9.1= 10y6 80 w18x
dc Magnetron sputtering 4.0= 10y5 97 w19x

variety of techniques are presented in Table 3 along
with the results of ITO films prepared in our labora-
tory. It was observed that our films exhibited low resis-
tivity and high transparency compared to the values
reported by others.
XRD spectra of the ITO film deposited at a sub-
strate temperature of 50⬚C before and after annealing
were studied. Before annealing, the film showed an
amorphous nature, and the same film showed a poly-
crystalline nature after annealing. The main peaks were
identified by ASTM powder data and were analyzed.
The peak at 2␪ s 30.5⬚ corresponded to the reflection
from the Ž222. plane. The other peaks were due to
reflections from the Ž400., Ž431. and Ž440. planes. None
of the spectra indicated any characteristic peaks of Sn,
SnO or SnO2 , which means that the tin atoms were
doped substitutionally into the In2 O3 lattice w20x.
4. Conclusion
ITO films of high electrical conductivity and high
visible transmittance were obtained by varying the tin
concentration and substrate temperature. The opti-
mum target composition for high conductivity was 80
wt.% In2 O3 q 20 wt.% SnO2 . The activation energies
were calculated to be 0.033 and 0.125 eV for a film
thickness of 100 nm and deposited at a substrate tem-
perature of 100⬚C. High quality films with resistivity as
low as 3 = 10y6 ⍀ m and a transmittance over 92%
were obtained by controlling the deposition parame-
ters. The optical band gap was found to vary from 3.29
to 3.41 eV with increasing substrate temperature. The
film exhibited the reflection from the Ž222. plane as the
most predominant peak in the X-ray diffraction pat-
tern. The crystallinity of the film was improved by
annealing.
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