Thin Solid Films, 33 (1976) L5-L7 Elsevier Sequoia S.A.

, Lausanne -- Printed in Switzerland

L5

Letter

Etching methods for indium oxide/tin oxide films

G. BRADSHAW and A. J. HUGHES Royal Radar Establishment, Maivern, Worcs. WR14 3PS (Gt. Britain)

Received February 2, 1976; accepted February 20, 1976) Methods are described for etching patterns in conducting indium-tin oxide films on glass substrates. For patterns requiring maximum definition and resolution hydriodic acid is preferred, whereas hydrofluoric acid or zinc and hydrochloric acid are useful for other purposes.
1. Introduction Thin films of mixtures of indium oxide and tin oxide on glass substrates are commonly used as transparent electricalconductors in liquid crystal and other displays. This letter compares several etching techniques for producing the required electrode configurations. The firstfour methods used hydrochloric acid to which zinc was added in various forms. The zinc/acid reaction produces hydrogen which reduces the oxides, the residue being attacked directly by the acid. The other two methods used hydriodic and hydrofluoric acid which required no activating additions. It is well known that the etch rate decreases as the Sn:In ratio is increased. These tests were performed mainly on 1500 A films sputtered from a 4 : 1 mixture of In2Os :SnO2. A few results were obtained on other commercial films. Test patterns for etching, consisting of 2 2 m m squares 0.5 mm apart, were produced b y photolithography in t y p e AZ 1350 H photoresist. A postdevelopment bake at 120 C for 90 min improved resist adhesion and durability. The etchant temperature was limited less than to 50 C to avoid attack of t h e resist. F o r spatial resolution tests a Pattern containing narrow (~2 ~m) gaps was used. In all cases etching was stopped b y quenching the substrates in cold water.
2. E t c h i n g m e t h o d s

In m e t h o d 1 dry zinc p o w d e r was sprinkled from a " p e p p e r p o t " dispenser uniformly over the dry substrate. This was then immersed horizontally in dilute hydrochloric acid (1 volume acid to 2 volumes water) at 20 C. Etching was s t o p p e d when the zinc layer lifted o f f the substrate. The etch rate was a b o u t 150 A s - 1 .

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Method 2 used a thin slurry of zinc powder in water painted onto the substrate which was then etched as in m e t h o d 1. The etch rate was 150 A
S-1 "

With method 3 a few drops of the zinc slurry were added directly to dilute hydrochloric acid (1 volume acid to 4 volumes water) at 45 C. The substrate was immersed vertically and used to stir the etchant. By viewing through the solution etching could be stopped as soon as the oxide was removed. The etch rate was a b o u t 10 A s-1. In m e t h o d 4 solid zinc pellets, approximately 4 mm in diameter, were dropped individually into dilute hydrochloric acid (1 volume acid to 1 volume water) at 40 C. The etchant was magnetically stirred and the substrate was immersed vertically. The etch rate was a b o u t 10 A s -1 . For m e t h o d 5 the substrate was immersed vertically in 55% hydriodic acid (HI) at room temperature. The etch rate was a b o u t 25 A s -1 . Method 6 was similar, using hydrofluoric acid (HF) in place of HI.
3. Results and discussion In comparing results many aspects may be considered, including ease and safety of use, control of process time, uniformity of etching, undercutting of the photoresist, and the resolution and definition obtainable. The general conclusion was that the quality of the finished substrate improved significantly with each step from m e t h o d I to m e t h o d 5. There was considerable variability of the results obtained with each method, however, particularly where zinc powder was used. When rapid etching is required and quality is unimportant m e t h o d 2 is preferable. With methods 1 and 2 there was no means of observing the progress of etching, which usually resulted in some over-etching and undercutting of the resist, as shown in Figs. 1 and 2. With many substrates treated this way some small areas of oxide proved very persistent and this caused unavoidable over-etching of the rest of the substrate. The cause of persistent patches was n o t identified b u t they were less of a problem with methods 3 - 6 . Methods 3 and 4 permitted etching progress to be viewed through the acid, thus avoiding over-etching. The etch rate was low since less hydrogen was being liberated close to the substrate. With m e t h o d 3 occasional agglomerations of zinc particles contacted the oxide and caused severe local over-etching. Normally, however, undercutting was very slight and edge definition good. Method 5 proved the most successful. Etch rates were adequate and, although etching progress could n o t be viewed through the brown solution, it was easy to rinse and inspect the sample at intermediate stages. A typical result is shown in Fig. 3. Undercutting was reduced to less than 2 ~m and was uniform over the substrate. In Fig. 4 are shown the results of a high resolution etching test in which a gap of 3 ~m is clearly resolved. Similar resolution was obtained with m e t h o d 4, b u t n o t with methods 1, 2 or 3. Using the "squares" pattern method 6 produced similar edge quality to method 5 b u t the glass substrates were attacked b y the H F giving the

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- - 5 0 0 IJm -~

~SOOpm.---

substrate partly

oxide
etched

Fig. 1. Results of method 1, showing over 1 5/~m undercutting. Fig. 2. Results of method 2, showing the ragged oxide edges caused by localized overetching.
0-500 pm---

~tO01Jm

"

100 pm

I substrate

I oxide

I substrate

I
oxide

Fig. 3. A typical result of method 5. Fig. 4. High resolution test with method 5, showing a 3/~m gap. Fig. 5. Typical result of method 6, showing the frosted appearance of the substrate.

"f~osted" effect shown in Fig. 5, which may be o f use in some display applications. This and the advantage of visual observation during etching, m a y compensate for the extra safety precautions required. Finally, these methods have also been tried on commercial films of u n k n o w n composition. In general the relative performance of the methods was similar to that reported above. Nesvadba and Phillips I have used HI successfully to etch patterns in pyrolytically deposited tin oxide which had proved difficult to etch b y m e t h o d 2.

L8 The authors are grateful to P. Lloyd and T. Bosley of RRE for deposit. ing the majority of the oxide films used in this work. The paper is published by courtesy of the Controller, HMSO, London, 1976.
1 P. Nesvadba and S. V. Phillips, personal communication, 1975.