FILM-FORMING COMPOSITION COMPRISING INDIUM AND TIN COMPOUNDS

Abstract: A film-forming composition comprises a mixture of (a) an organic solvent solution of an inorganic indium salt (e.g. chloride or nitrate) in amount of 0.5 to 30 wt% as InO, and an inorganic tin salt (e.g. chloride) in amount of 0.5 to 30 wt% of tin: indium, and (b) a nonaqueous 1 to 20 wt% silica sol, e.g. containing SiO₂ particles of size 0.02 to 0.1 µm added in amount of 1 to 200 wt% of SiO₂:InO. Cellulosic compounds may be included as thickener. The composition is coated or printed on a flat substrate, e.g. glass plate, and air-dried at 40 to 250°C and baked at 400° to 900°C to form a transparent film composed of an upper InSn oxide layer and lower SiO₂ layer which is strongly adherent and absorbs no Na ions from soda glass and having good electrical conductivity (exemplified resistivities of 400 to 1500 ohms per square).

Description: FILM-FORMING COMPOSITION COMPRISING IND-IUM AND TIN COMPOUNDS The present invention relates to a composition which is capable of forming a transparent electrically conductive metal oxide film on a substrate plate and a method for forming such transparent conductive film. Electrode materials which are transparent to light have been widely used for electrodes in display devices, such as liquid crystal display devices, electroluminescense, etc., and photosensitive devices, such as photo-cells, image pick-ip tubes, etc., as well as anti-clouding or antifreezing electrodes for window glass of automobiles, aeroplanes, buildings and the like. As such transparent electrode materials, a tin oxide-antimony oxide type, an indium oxide-tin oxide type and the like are well known. These metal oxides can form a film on a glass or ceramic plate to provide a transparent conductive film. The well-known methods for forming atransparent conductive film includes (1) a vacuum evaporation method, (2) a sputtering method, (3) a chemical vapor deposition method, and (4) a coating method. However, each of the above-described methods (1), (2) and (3) has problems in that: equipments used therefor are so complicated that these methods are inferior in processability; and in usual cases, etching should be carried out after film formation in order to form patterns. The above-described method (4) offers a possibility of solving the aforesaid problems associated with the methods (1) to (3), but there still is a problem that it is difficult to obtain a transparent conductive thin film which can withstand practical use. For example, a method of using an organic solution of an inorganic salt, e.g., InC13, ln(N03)3, SnC14, etc., involves disadvantages =such as causing milky turbidity of the resulting conductive film or insufficient mechanical strength to easily get scratches. A method of using an indium salt of an organic acid having a strong ionic bond, such as ilium octylate, involves a disadvantage such as causing gelation of the coating composition because of tendency to readily hydrolyze and easily occur chemical change. A method of using an organic complex of indium or tin involves a disadvantage such as hindrance in homogenization of the baked film upon thermal decomposition of the coated film formed on the substrate plate, thus causing nonuniformity or insufficient sheet resistivity. Moreover, in any of the above described cases, when a transparent conductive film is formed on a soda glass substrate plate, silica coating must be performed on the soda glass substrate plate to prevent elution of sodium ions from the soda glass plate. An object of the present invention is to provide a novel composition which is capable of forming a transparent conductive film. Another object of the present invention is to provide a composition which needs no silica coating procedure to preventelution of sodium ion from the soda glass. A further object of the present invention is to provide a method for producing a transparent conductive film having a two-layered structure and a strong adhesion strength to a substrate plate. The composition of the present invention is a mixture of an organic solution of an indium salt of an inorganic acid and a tin salt of an inorganic acid with a non-aqueous silica sol. The method for forming a transparent conductive film of the present invention comprises: (1) coating the composition on a substrate plate, (2) drying the thus coated substrate plate, and then (3) heat baking the dried substrate plate. An important characteristic of the present invention resides in that the composition contains a non-aqueous silica sol. The non-aqueous silica sol contains hyperfine particles each having on the surface thereof a silanol group capable of imparting a thixotropic effect. The non-aqueous silica sol provides an improved wettability to the consosi- tion, whereby the transparent conductive film obtained can show excellent transmittance, conductivity and adhesion property. The coated film formed by coating the composition, drying and then heat baking according to the method of the present invention has a completely two-layered structure. That is, the upper layer consists of indium tin oxide and the lower layer consists of silica. This structure was identified by the following surface analyses. The presence of the upper layer (referred to as ITO layer" hereinafter) was confirmed by electron spectroscopy for chemical analysis and X-ray diffraction analysis of the surface of the coated film as well as chemical analysis of a solution obtained by hydrochloric acid-etching of the surface. Further, the presence of the lower layer (referred to as "six2 layer" hereinafter) was confirmed by the same spectrographic and X-ray analyses of the etched surface as well as chemical analysis of a solution obtained by hydrofluoric acid-etching of the etched surface. Therefore, according to the method of the present invention, it is possible to omit a silica coating procedure so far necessary to thereby minimize the total cost. The composition of the present invention will be described below in more detail. The indium salt of an inorganic acid that can be used in the present invention is generally an indium salt of a mineral acid such as indium chloride or indium nitrate. The content of the indium salt is generally about 0.5% to about 30% by weight, preferably about 1% to about 20% by weight (calculated as indium oxide), in order to obtain a transparent conductive film showing low resistivity. The tin salt of an inorganic acid that can be used in the present invention is generally a tin salt of a mineral acid such as stannic chloride. The content of the tin salt is generally about 0.5% to about 30% by weight, preferably about 1% to about 20% by weight, in terms of the proportion of tin to indium, in order to lower the resistivity of a transparent conductive film. The indium salt and tin salt may be each a hydrate thereof. The non-aqueous silica sol that can be used in the present invention is not particularly limited, but a silica sol obtained by hydrolyzing orthoethyl silicate in the presence of a catalyst and a silica sol obtained by reacting tetrachlorosilane with acetic anhydride, followed by hydrolyzing in the presence of a catalyst can be preferably used. More preferably, an organic solution of silicic acid prepared by liquid-phase neutralization of an aqueous solution of sodium silicate with a mineral acid such as sulfuric acid, followed by subjecting the neutralized solution to salting-out with a salting-out agent and extraction with an extractant, can be used. Examples of the extractant include organic solvents such as tetrahydrofuran, isopropyl alcohol and t-butancl. Examples of the salting-out agent include sodium chloride and ammonium chloride. The thus prepared non-aqueous silica sol is inexpensive and can be prepared easily. The non-aqueous silica sol as prepared above is a transparent solution which shows excellent stability with a lapse of time and contains silica particles having a particle size of about 0.02 pm to about 0.1 Vm. The concentration of the silica in the non-aqueous silica sol is not particularly limited, but it is usually in the range of from about 1% to about 20% by weight as Six2. The content of the non-aqueous silica sol added in the composition is about 1% to about 200% by weight, preferably about 10% to about 100% by weight, in terms of the proportion of SiO2 to indium oxide. The organic solvent used is selected taking into account solubilities of the indium salt and the tin salt, compatibility with the non-aqueous silica sol, and solubility of a cellulose compound described below. The organic solvent is not particularly limited but includes acetone, tetrahydrofuran, methanol, ethanol, isopropyl alcohol, tbutanol, ethylene glycol, diethylene glycol, ethyl cellosolve and ethyl carbitol. These organic solvents can be used singly or in combination. As a thickened, cellulose compounds may be added to the composition of the present invention to thereby increase its thixotropy and obtain a transparent conductive film having superior properties. The particular cellulose compound added to the composition of the present invention is not particularly limited, but it is selected taking into account solubility in the organic solvent, thickening property, dispersability, thermoplastic property, pyrolysis property and the like. Examples of the cellulose compound include ethyl cellulose, nitrocellulose, cellulose acetate, hydroxypropyl cellulose and ethyl hydroxyethyl cellulose. Among them, nitrocellulose, cellulose acetate, hydroxypropyl cellulose and ethyl hydroxyethyl cellulose can be preferably used because they prevent a hygroscopic phenomenon of the coating composition under high temperature and humidity atmosphere. Therefore, addition of the cellulose compound is effective for preventing the hindrance in homogenization of the coating composition and milky turbidity of the conductive film. The content of the cellulose compound in the composition of the present invention is not particularly limited but generally ranges from about 0.1% to about 5% by weight for the dipping and spinning methods and from about 10% to about 5C% by weight for the screen and offset printing methods, respectively. The composition of the present invention thus pr- pared shows an excellent stability with a lapse of time, and even when allowed to stand for 3 months, it undergoes no gelation. Further, the film obtained by coating the composition on a substrate plate, drying, and then heat baking the substrate plate suffers no impairment of these properties The method for forming a transparent conductive film of the present invention will be described below. Coating of the composition of the present invention can be carried out by commonly employed coating techniques, such as dipping, spinning, screen printing, offset printing, etc. The thus coated composition is generally subjected to a drying treatment at about 400C to about 2500C and then to a heat baking treatment at about 4000C to about 9000 C, to thereby form a transparent conductive film. The heat baking should be performed in an oxygen-containing gas atmosphere in order to provide a sufficient amount of oxygen to the composition. The present invention will now be illustrated in greater detail with reference to the following examplesr EXAMPLE 1 Prescribed amounts of indium chloride and stannic chloride were dissolved in tetrahydrofuran, and the solution was mixed with a non-aqueous silica sol having a concentration of 5% by weight (as SiO2) The non-aqueous silica sol mixed was prepared by neutralizing an aqueous solution containing sodium silicate with sulfuric acid and subjecting the neutralized solution to salting-out with ammonium chloride and extraction with tetrahydrofuran. Then, a prescribed amount of a cellulose compound shown in Table 1 was added to the solution and stirred well. There were thus prepared compositions shown in Table 1. Table 1 Composition Converted Converted Converted Composition to basis to basis to basis Cellulose Compound No. InCl3 of InO3 SnCl4 of Sn/In SiO2 of SiO2/In2O3 Name Amount (wt%) (wt%) (wt%) (wt%) (wt%) (wt%) (wt%) A 6.4 4.0 0.7 9.6 1.6 40 hydroxypropyl 1.0 cellulose B 6.4 4.0 0.7 9.6 1.6 40 nitrocellulose 1.0 C 3.2 2.0 0.4 11.0 0.8 40 cellulose acetate 1.0 D 8.0 5.0 0.4 9.9 2.0 40 ethyl hydroxyethyl 1.0 cellulose E 6.4 4.0 0.7 9.6 2.0 40 ethyl cellulose 1.0 F 10.0 6.3 1.1 9.7 2.5 40 - - Each of the compositions shown in Table 1 was coated on a well-cleaned soda glass substrate by the dipping method under the conditions shown in Table 2. The coated substrate plate was dried in air at 800C for 15 minutes and then baked at 5000C for 1 hour in air, to thereby obtain a transparent conductive film. The properties of the resulting transparent conductive film are shown in Table 2. Each of the thus obtained transparent conductive films had a two-layered structure and showed low resistivity and excellent transmittance. The adhesion strength of the film to the substrate plate was sufficient to stand the peeling test with an adhesive tape. Thus it is evident that the properties of the film were improved by -addition of the cellulose compound to the composition. Table 2 Coating Atmosphere Properties of Baked Film Composition Draw Speed Thickness of Thickness of Sheet No. in Dipping Temperature Humidity ITO layer SiO2 Layer Resistivity Transmittance (cm/min) ( C) (%) ( ) ( ) (#/#) (% at 550 nm) A 45 15 50 1200 1600 400 85 50 30 74 1200 1600 400 85 B 45 15 50 1100 1450 500 86 50 30 74 1100 1450 500 86 C 25 15 50 1300 1700 300 82 30 30 74 1300 1700 300 82 D 50 15 50 1100 1450 600 86 36 30 74 1100 1450 600 86 E 45 15 50 1200 1600 400 85 60 30 74 1200 1600 600 74 F 50 15 50 1200 1600 800 84 60 30 74 1200 1600 1500 70 EXAMPLE 2 Prescribed amounts of indium chloride and stannic chloride were dissolved in ethanol, and the solution was mixed with a non-aqueous silica sol having a concentration of 8% by weight (as Six2). The non-aqueous silica sol mixed was prepared by neutralizing an aqueous solution containing sodium silicate with sulfuric acid and subjecting the neutralized solution to salting-out with ammonium chloride and extraction with isopropyl alcohol. Then, a prescribed amount of ethyl cellulose was added to the solution and stirred well. There were thus prepared paste-like compositions shown in Table 3. Each of the resulting compositions was screen printed on a well-cleaned quartz substrate plate at temperature of 15 C and at a humidity of 50%. The coated substrate plate was dried in air at 1000C for 15 minutes and then baked at 5000C for 1 hour in air, to thereby obtain a transparent conductive film. The properties of the resulting transparent conductive film are shown in Table 3. Table 3 Properties of Composition Baked Film Converted Converted Converted Thickness to basis to basis to basis Ethyl Isopropyl of ITO Sheet InCl3 of In2O3 SnCl4 of Sn/In SiO2 of SiO2/In2O3 Cellulose Alcohol Ethanol Layer Resistivity (wt%) (wt%) (wt%) (wt%) (wt%) (wt%) (wt%) (wt%) (wt%) ( ) (#/#) 8.0 5.0 9.9 9.6 1.6 40 10.0 23.0 56.1 1000 800 8.0 5.0 9.9 9.6 1.6 40 18.0 23.0 48.1 2000 400 As is apparent from the above-described examples, the composition of the present invention is very useful as a composition for forming a transparent conductive film which shows low sheet resistivity and excellent adhesion strength to a substrate plate.

Claims: CLAIMS 1. A composition for forming a transparent conductive film comprising a mixture of (a) an organic solvent solution of an indium salt of an inorganic acid and a tin salt of an inorganic acid with (b) a non-aqueous silica sol. 2. A composition as claimed in Claim 1, wherein said composition contains 0.5% to 30% by weight of said indium salt calculated as indium oxide, 0.5% to 30% by weight of said tin salt in terms of the proportion of tin to indium, and 1% to 200% by weight of said non-aqueous silica sol in terms of the proportion of silica to indium oxide. 3. A composition as claimed in Claim 1 or 2, wherein said non-aqueous silica sol is one prepared by liquidphase neutralization of an aqueous solution containing sodium silicate with a mineral acid and subjecting the neutralized solution to salting-out with a salting-out agent and extraction with an organic solvent. 4. A composition as claimed in Claim 1, 2 or 3, wherein a cellulose compound is added to said composition as a thickener in an amount of 0.1% to 50% by weight in said composition. 5. A method for producing a transparent conductive film which comprises: (1) coating a composition as claimed in any preceding claim on the surface of a plate, (2) drying the coated plate, and (3) heat baking the coated substrate plate. 6. A transparent conductive film, produced by a process as claimed in Claim 5.

Inventors: HASHIMOTO, TADANORI, HATA, SHIGENAO, NAKAZONO, AKIKO, YOSHITAKE, HIROSHI
Applicants: SUMITOMO CHEMICAL COMPANY, LIMITED
Application year: 1984
Main classification: H01B1
IPC codes: H01L33, H01L31, H01B1