Surface Treatment of Indium Tin Oxide (ITO) Thin Films Synthesized by Chemical Solution Deposition

Journal of Ceramic Processing Research. Vol. 5, No. 4, pp.
395~398 (2004)
J O U R N A L O F
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Surface treatment of Indium Tin Oxide (ITO) thin films synthesized by chemical
solution deposition
Young-Hoon Yun, Jin-Woo Choi and Sung-Churl Choi*
Dept. of Ceramic Engineering, Hanyang University, Seoul 133-791, Korea
Indium tin oxide (ITO) thin films were synthesized on glass substrates by chemical solution deposition from starting materials
of Indium (III) acetylacetonate and Tin (IV) iso-propoxide. The ITO films were fired in a temperature range of 400 oC to
600 oC and annealed under N2 gas at 500 oC. The effects of surface chemical treatment on the sheet resistance of ITO films
were investigated with AFM surface morphology and sheet resistance. The spin-coated ITO thin films, which was etched with
KOH solution for 20 seconds, exhibited a sheet resistance value of approximately 352 Ω/square. The AFM surface
morphologies of ITO thin films revealed a difference of surface roughness and morphology between the as-received films and
the etched films. Also, ITO thin films showed an optical transmittance of about 90% in the range of 800 nm.
Key words: Indium tin oxide (ITO) thin films, Chemical solution deposition, Sheet resistance, Surface treatment.
Introduction taminations in the surface region would deteriorate the

conductivity and homogeneity of ITO thin films, thus it
Indium tin oxide (ITO) thin films have been applied is required to minimize the influences of these obstacles
to conductive transparent films for optoelectronic devices, for the conduction behavior and device operation
since they have high electrical conductivity and trans- through such additional treatments as chemical etching.
mittance in the range of visible light [1, 2]. Presently, In the present study, ITO thin films were prepared by
ITO films have become one of the essential materials in a chemical solution deposition method, an XRD pattern
flat panel displays (FPD). Generally, ITO films have of the ITO thin film was taken and optical transmi-
been fabricated by such diverse techniques as sputter- ttance of the film was measured in the region of visible
ing [3], chemical vapor deposition [4] and a sol-gel light. Then, surface treatment of the ITO thin film after
process [5-7]. Mostly a magnetron sputtering method is annealing was carried out by chemical etching with
selected as a commercial fabrication process, although KOH solution. The sheet resistance and AFM morpho-
a sol-gel method [5] has several advantages of a simple logies of the as-received film and the etched film were
and low cost process and film preparation of large examined.
areas. Because ITO thin films, which were prepared
through a chemical solution method show rather low Experimental
conductivity compared to those obtained by physical
processes, their practical use as the transparent conduc- Indium (III) acetylacetonate (99.99+%, Aldrich, USA),
ting materials is limited [8, 9]. Tin (IV) iso-propoxide (98%, Alfa Aesar (USA), A
Therefore, there have been persistent attempts to Johnson Matthey Co., UK) and 2-metoxyethanol (99.0
enhance the conductivity of ITO thin films fabricated %, Kanto Chemical Co., Japan) were used as starting
by various deposition processes. Annealing techniques materials. The Sn/In ratio of the solutions used was
using reducing atmospheres have been utilized to fixed at 8 wt.%. Cleaned soda-lime silicate glass plates
obtain ITO thin film with low resistivity. These studies (200 × 200 × 1 mm) were used as a substrate for film
were concerned mainly with the optimization of micro- deposition. The precursor solution containing In and Sn
structure and the creation of free electrons by oxygen sources was coated on the substrate by the repetition (5
vacancy formation in the thin film. On the other hand, times) of the spinning (500 rpm: 10s and 2000 rpm:
the chemical etching has been used to remove the 20s) and drying process. The solvent in the mixed
carbon content or reduce the surface roughness on ITO solution was removed by drying at 150 oC for 10
thin films [10-12]. Generally, the roughness and con- minutes. The ITO thin films were fired at 400-600 oC
for 30 minutes in air and cooled down to room
*Corresponding author: temperature, and annealed at 500 oC for 30 minutes
Tel : +82-2-2290-0505 under N2 gas. Also, the annealed ITO thin films were
Fax: +82-2-2291-6767 etched with KOH solution (15%) for 20s to 80s. The
E-mail: choi0505@hanyang.ac.kr
crystal structure of the ITO films was examined by X-
395
396 Young-Hoon Yun, Jin-Woo Choi and Sung-Churl Choi
ray diffraction (RAX-10, Rigaku, Japan). Surface micro- of the ITO phase. A (111) preferred orientation for ITO
structural morphologies of ITO thin films were observed thin films has been reported in other cases using several
by FE-SEM (JSM-6430F. JEOL, Japan) and AFM (AP- fabrication processes such as a sputtering method [3]
1090, Park Scientific Ins., USA). The sheet resistance and an evaporation method [13].
of ITO films was measured by a four-point probe method The variation of sheet resistance of ITO thin films
(Jandel Eng. Ltd., England). The optical transmittance according to the firing temperature is shown in Fig. 2.
of ITO thin films in the wavelength range of 300 nm to ITO thin films exhibited a noticeable decline in sheet
800 nm was examined with an UV/vis spectrometer resistance by increasing the firing temperature from
(Lambda 25, Perkin-Elmer Ins. Co. Ltd., USA). 400 oC to 500 oC. The sheet resistance of ITO thin film,
which was fired at 500 oC and annealed at 500 oC under
Results and Discussion a N2 atmosphere, was approximately 570 Ω/square.
Thus, it was suggested that the relation between sheet
Indium tin oxide (ITO) thin films with 8 wt% Sn resistance and firing temperature is connected with the
were prepared on glass substrates by a sol-gel spin crystallization behavior, namely the organic thermal
coating technique and subsequently firing & annealing decomposition of the starting materials in the deposited
processes. The thin films exhibited a typical XRD films. Meanwhile, the difference of crystallization behavior
pattern of cubic bixbyite structure (Fig. 1), whose according to the firing temperature would have
largest (222) peak indicates a (111) preferred orientation influenced densification behavior during the annealing
process, which is a major factor for sheet resistance of
ITO film
On the other hand, ITO thin film, which was etched
for 20 s with KOH solution, showed a relatively low
sheet resistance value (352 Ω/square) compared to that
of the as-received film (Fig. 3) and a marked change in
AFM surface morphologies (Fig. 4). Also, the average
surface roughness of the ITO thin film decreased
through the surface treatment (Fig. 5). But the ITO thin
film after chemical etching for 40 s showed an increase
of sheet resistance (407 Ω/square), which was considered
to be due to the surface damage on the thin film.
Actually, ITO thin film, which was etched for 80 s,
showed excessive damage in surface morphology as
well as a higher surface roughness in the central region
of the thin film. As a result, the surface chemical
Fig. 1. XRD pattern of ITO thin film fired (500 oC) and annealed
etching for 20 s brought down the sheet resistance of
(500 oC) in a N2 atmosphere. the ITO thin film through modification of the surface
roughness and morphology. Concerning the surface
treatment of ITO thin films and their electrical properties,
Fig. 2. Sheet resistane of the ITO films with firing temperature. Fig. 3. Sheet resistance of the etched ITO thin films. (Firing at
(Annealed at 500 oC in a N2 atmosphere). 500 oC, annealing at 500 oC in a N2 atmosphere).
Surface treatment of Indium Tin Oxide (ITO) thin films synthesized by chemical solution deposition 397
Fig. 4. AFM images of the non-etched film and the etched ITO thin films. (Firing at 500 oC, annealing at 500 oC in a N2 atmosphere).
Fig. 6. Optical transmittance of ITO thin film. (Firing at 500 oC,

annealing at 500 oC in a N2 atmosphere).
Fig. 5. Average surface roughness of ITO thin films with etching

time. (Firing at 500 oC, annealing at 500 oC in a N2 atmosphere). Conclusions
it has already been reported that the removal of carbon Transparent conductive indium tin oxide (ITO) thin
from the ITO film surface through chemical etching could films were deposited on soda-lime silicate glass sub-
increase the carrier mobility [12]. In conclusion, it was strates by a sol-gel process using a spin-coating
thought that the decrease of sheet resistance of ITO thin method. The crystal structure of thin film showed a
films after chemical etching was accomplished through typical XRD pattern of the cubic bixbyite structure. It
either the carbon removal or a reduction in surface was known that the sheet resistance of ITO thin film
roughness of the ITO thin film. Also, it was inferred for was controlled by the firing temperature. ITO thin
etching over 40 s that the sheet resistance increased by the films etched with KOH solution showed a rather low
creation of surface damage and an enhancement of sheet resistance and smaller average roughness of the
roughness on the over-etched thin film (Fig. 4). thin films as compared with the as-received ITO
The optical transmittance of the ITO thin films films. In conclusion, the modification of the surface
between 300 nm to 800 nm is shown in Fig. 6. The morphology and roughness through such a simple
optical transmittance of ITO film was about 90% at chemical treatment could decrease somewhat the
800 nm, which is a sufficiently high value for sheet resistance of ITO thin films prepared by a sol-
application in transparent conduction devices. gel spin coating process.
398 Young-Hoon Yun, Jin-Woo Choi and Sung-Churl Choi
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Journal of Ceramic Processing Research. Vol. 5, No. 4, pp.

Introduction taminations in the surface region would deteriorate the

Fig. 6. Optical transmittance of ITO thin film. (Firing at 500 oC,

Fig. 5. Average surface roughness of ITO thin films with etching

References 7. S.J. Wen, G. Campet, J. Portier, G. Couturier, and J.B.

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