JPH0528834A - Composition and method for forming transparent electroconductive film - Google Patents

Composition and method for forming transparent electroconductive film

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Publication number
JPH0528834A
JPH0528834A JP3184422A JP18442291A JPH0528834A JP H0528834 A JPH0528834 A JP H0528834A JP 3184422 A JP3184422 A JP 3184422A JP 18442291 A JP18442291 A JP 18442291A JP H0528834 A JPH0528834 A JP H0528834A
Authority
JP
Japan
Prior art keywords
compound
organic
indium
composition
transparent conductive
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
JP3184422A
Other languages
Japanese (ja)
Other versions
JP3208794B2 (en
Inventor
Akiyoshi Hattori
章良 服部
Akihiko Yoshida
昭彦 吉田
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Panasonic Holdings Corp
Original Assignee
Matsushita Electric Industrial Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Matsushita Electric Industrial Co Ltd filed Critical Matsushita Electric Industrial Co Ltd
Priority to JP18442291A priority Critical patent/JP3208794B2/en
Priority to DE69223186T priority patent/DE69223186T2/en
Priority to EP92112620A priority patent/EP0524630B1/en
Publication of JPH0528834A publication Critical patent/JPH0528834A/en
Priority to US08/478,342 priority patent/US5578248A/en
Priority to US08/697,512 priority patent/US5998011A/en
Application granted granted Critical
Publication of JP3208794B2 publication Critical patent/JP3208794B2/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/1204—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds
    • C23C18/1208—Oxides, e.g. ceramics
    • C23C18/1216—Metal oxides
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/125—Process of deposition of the inorganic material
    • C23C18/1283—Control of temperature, e.g. gradual temperature increase, modulation of temperature

Abstract

PURPOSE:To provide an electroconductive film having a low resistance and a high transitivity by heating and partially hydrolyzing an organic solution consisting of an inorganic In compound, an organic Sn compound, and an organic compound which can be coordinated with any of the In and Sn, mixing the resultant with poly-hydric alcohols, and applying it to a base board followed by drying and baking. CONSTITUTION:An organic solution is subjected to a heating process, which consists of an inorganic In compound, an organic Sn compound, and an organic compound which can be coordinated with any of the In and Sn. This generates reactions of a crystalline water contained by the inorganic In compound with the organic 80 compound and inorganic. In compound where the organic compound is partially coordinated. These reactions hydrolyze the organic Sn compound partially and form an intermediate composite compound of In and Sn, to which poly-hydric alcohols are added to increase the viscosity of the solution, and this resultant solution is applied to a base board followed by drying and baking. Thus transparent electroconductive films of low resistance and high transmissivity can be produced stably.

Description

【発明の詳細な説明】Detailed Description of the Invention

【０００１】[0001]

【産業上の利用分野】本発明は、透明導電膜形成用組成
物と透明導電膜の形成方法に関し、特にガラス，セラミ
ックスなどの基板上に、透明導電膜を形成するための透
明導電膜形成用組成物と透明導電膜の形成方法に関す
る。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a composition for forming a transparent conductive film and a method for forming a transparent conductive film, and particularly for forming a transparent conductive film on a substrate such as glass or ceramics. The present invention relates to a composition and a method for forming a transparent conductive film.

【０００２】[0002]

【従来の技術】液晶表示素子，エレクトロルミネッセン
ス（ＥＬ）表示素子などの表示素子類の電極や、自動
車，航空機，建築物などの窓ガラスの防曇または氷結防
止のための発熱抵抗体において、可視光に対して高透過
性を有する電極材料が使用されている。2. Description of the Related Art Visible in electrodes of display elements such as liquid crystal display elements and electroluminescence (EL) display elements, and in heating resistors for preventing fogging or icing of window glass of automobiles, aircraft, buildings, etc. An electrode material having high transparency to light is used.

【０００３】このような透明導電性材料として、酸化錫
・酸化アンチモン系（ＡＴＯ）や、酸化インジウム・酸
化錫系（ＩＴＯ）などが知られており、これらの金属酸
化物はガラスまたはセラミック基板上に容易に被膜を形
成し、透明導電膜とすることができる。Known examples of such transparent conductive materials include tin oxide / antimony oxide (ATO) and indium oxide / tin oxide (ITO). These metal oxides are formed on a glass or ceramic substrate. It is possible to easily form a film on the transparent conductive film.

【０００４】透明導電膜の形成方法としては、次の方法
が知られている。 （１）真空蒸着法 （２）スパッタリング法 （３）ＣＶＤ法 （４）塗布法The following methods are known as methods for forming a transparent conductive film. (1) Vacuum evaporation method (2) Sputtering method (3) CVD method (4) Coating method

【０００５】[0005]

【発明が解決しようとする課題】しかし、上記の
（１），（２），（３）の方法は、装置が複雑かつ高価
で、コストと量産性に問題がある。また、（４）の方法
は、上記の（１），（２），（３）の方法の問題点を解
決する可能性を有しているものの、実用に耐えうる膜を
形成することが困難であった。However, in the above methods (1), (2) and (3), the apparatus is complicated and expensive, and there are problems in cost and mass productivity. Further, the method (4) has a possibility of solving the problems of the above methods (1), (2), and (3), but it is difficult to form a practically usable film. Met.

【０００６】例えば、硝酸インジウム，塩化インジウ
ム，塩化第２錫などの無機化合物の有機溶液を使用した
場合は、形成された膜に白濁を生じたり、得られた膜の
機械的強度が不足で、容易に傷がつくなどの欠点があ
る。また、オクチル酸インジウムなどのイオン結合性の
強い有機酸インジウムを用いる方法においては、有機酸
インジウムが加水分解しやすく、比較的容易に化学変化
するために、塗布液のゲル化が生じるなどの欠点があ
る。さらに、インジウムや錫の有機錯体を使用する方法
も提案されているが、この方法では基板に塗布した後の
塗膜の熱分解時において、錫化合物の蒸散などにより、
膜の均一化が阻害されるために、低抵抗の均質膜が得ら
れないなどの欠点がある。For example, when an organic solution of an inorganic compound such as indium nitrate, indium chloride or stannic chloride is used, the formed film becomes cloudy or the mechanical strength of the obtained film is insufficient. There are drawbacks such as being easily scratched. Further, in the method of using an organic acid indium having a strong ionic bond such as indium octylate, the organic acid indium is easily hydrolyzed and undergoes a chemical change relatively easily. There is. Further, a method using an organic complex of indium or tin has been proposed, but in this method, when the tin compound evaporates at the time of thermal decomposition of the coating film applied on the substrate,
Since the homogenization of the film is hindered, there is a defect that a low resistance homogeneous film cannot be obtained.

【０００７】本発明は、上記課題を解決するもので、低
抵抗で高透過率の透明導電膜を安定して形成することが
可能な透明導電膜形成用組成物と透明導電膜の形成方法
を提供することを目的とする。The present invention solves the above problems, and provides a composition for forming a transparent conductive film and a method for forming a transparent conductive film, which enables stable formation of a transparent conductive film having low resistance and high transmittance. The purpose is to provide.

【０００８】[0008]

【課題を解決するための手段】本発明の透明導電膜形成
用組成物と透明導電膜の形成方法は、上記目的を達成す
るために、無機インジウム化合物と有機錫化合物と、イ
ンジウムと錫のいずれとも配位可能な有機化合物を主体
とする有機溶液を加熱処理して部分的に加水分解させ、
前記有機溶液に多価アルコール類を混合して得られ、さ
らに、この透明導電膜形成用組成物を、基板に塗布・乾
燥した後、焼成するものである。In order to achieve the above object, the composition for forming a transparent conductive film and the method for forming a transparent conductive film according to the present invention are either an inorganic indium compound, an organic tin compound, indium or tin. And an organic solution mainly composed of coordinable organic compounds are heat-treated to partially hydrolyze,
It is obtained by mixing polyhydric alcohols with the organic solution, and further, the composition for forming a transparent conductive film is applied to a substrate, dried, and then baked.

【０００９】[0009]

【作用】この構成により本発明の透明導電膜形成用組成
物と透明導電膜の形成方法は、無機インジウム化合物と
有機錫化合物と、インジウムと錫のいずれとも配位可能
な有機化合物を主体とする有機溶液を加熱処理すること
により、有機化合物が１部配位した無機インジウム化合
物と、有機錫化合物と、無機インジウム化合物が含有す
る結晶水と反応し、有機錫化合物が部分的に加水分解さ
れて、インジウムと錫の中間複合化合物を形成し、これ
によって従来の課題であった錫の蒸散による膜の不均一
化を抑え、得られる膜に低抵抗率と高透過率を与えるも
のである。また、多価アルコール類の添加により、溶液
の増粘効果と、前記組成物を基板に塗布・乾燥して得ら
れる被膜の安定性を与えるものである。With this structure, the composition for forming a transparent conductive film and the method for forming a transparent conductive film of the present invention are mainly composed of an inorganic indium compound, an organic tin compound, and an organic compound capable of coordinating both indium and tin. By heat-treating the organic solution, the organic compound reacts with the inorganic indium compound in which one part is coordinated, the organic tin compound, and the crystallization water contained in the inorganic indium compound, and the organic tin compound is partially hydrolyzed. By forming an intermediate composite compound of indium and tin, this suppresses the non-uniformity of the film due to the evaporation of tin, which has been a conventional problem, and imparts a low resistivity and a high transmittance to the obtained film. In addition, the addition of polyhydric alcohols imparts a thickening effect to the solution and stability of a coating film obtained by coating and drying the composition on a substrate.

【００１０】[0010]

【実施例】以下に、本発明の実施例の透明導電膜形成用
組成物と透明導電膜の形成方法について図面に基づいて
詳細に説明する。EXAMPLES The composition for forming a transparent conductive film and the method for forming a transparent conductive film according to examples of the present invention will be described in detail below with reference to the drawings.

【００１１】本実施例の透明導電膜形成用組成物は以下
のようにして合成される。まず最初に、無機インジウム
化合物をインジウムと錫のいずれとも配位可能な有機化
合物と混合する。ここで、前記無機インジウム化合物
は、インジウムや錫と配位可能な有機化合物と、置換で
きるような配位子を持つものであればよい。例えば、硝
酸インジウム，塩化インジウムが挙げられ、さらに結晶
水を有しているものが好ましい。また、インジウムと錫
のいずれとも配位可能な有機化合物は、インジウムと錫
に１部配位して、それらの中間化合物の形成を助け、有
機溶剤に対する溶解性をもたせるために必要であり、例
えば、β−ジケトン類、αまたはβ−ケトン酸類、前記
αまたはβ−ケトン酸類のエステル類、αまたはβ−ア
ミノアルコール類が挙げられる。The transparent conductive film-forming composition of this example is synthesized as follows. First, an inorganic indium compound is mixed with an organic compound capable of coordinating both indium and tin. Here, the inorganic indium compound may have an organic compound capable of coordinating with indium or tin and a ligand capable of substituting. Examples thereof include indium nitrate and indium chloride, and those having crystal water are preferable. Further, an organic compound capable of coordinating with indium and tin is necessary for coordinating with indium and tin in a part to assist formation of an intermediate compound thereof and to have solubility in an organic solvent. , Β-diketones, α or β-ketone acids, esters of the α or β-ketone acids, and α or β-amino alcohols.

【００１２】次に、前記溶液に有機溶剤と有機錫化合物
を加え、それらの有機溶液を加熱処理する。ここで、前
記有機錫化合物としては、空気中では比較的安定である
が、加熱処理により容易に加水分解しやすいものであれ
ばよい。例えば、カルボン酸錫やジカルボン酸錫が挙げ
られ、炭素数が小さい、ぎ酸錫，酢酸錫，しゅう酸錫が
好ましい。また、前記有機溶剤としては、本実施例で用
いる有機化合物や無機化合物を溶解するものであればよ
い。例えば、トルエン，キシレンなどの芳香族炭化水
素、エタノール，イソプロパノールなどのアルコール
類、酢酸エチル，酢酸ブチルなどの酢酸エステル類、ア
セトン，ジエチルケトンなどのケトン類、メトキシエタ
ノール，エトキシエタノールなどのエーテル類、テトラ
ヒドロフランなどが挙げられる。さらに、加熱処理の温
度としては、無機インジウム化合物と有機錫化合物と、
それらと配位可能な有機化合物を主体とする有機溶液の
還流温度もしくは還流温度付近が好ましい。Next, an organic solvent and an organic tin compound are added to the solution, and the organic solution is heat-treated. Here, the organotin compound may be any one as long as it is relatively stable in air but easily hydrolyzed by heat treatment. Examples thereof include tin carboxylate and tin dicarboxylate, and tin formate, tin acetate, and tin oxalate having a small carbon number are preferable. Further, the organic solvent may be any solvent that dissolves the organic compound or the inorganic compound used in this example. For example, aromatic hydrocarbons such as toluene and xylene, alcohols such as ethanol and isopropanol, acetic acid esters such as ethyl acetate and butyl acetate, ketones such as acetone and diethyl ketone, ethers such as methoxyethanol and ethoxyethanol, Tetrahydrofuran etc. are mentioned. Furthermore, as the temperature of the heat treatment, an inorganic indium compound and an organic tin compound,
The reflux temperature of the organic solution containing an organic compound capable of coordinating with them as a main component is preferably at or near the reflux temperature.

【００１３】そして、加熱処理後の有機溶液を室温付近
まで冷却し、多価アルコール類を加えて、混合した有機
溶液を透明導電膜形成用組成物とする。ここで、多価ア
ルコール類は、有機溶液の増粘効果と、透明導電膜形成
用組成物を基板に塗布・乾燥して得られる被膜に安定性
を与えるものであり、例えばグリコール類や３価のアル
コール類が挙げられるが、炭素数が小さく、熱分解時の
炭素残留の恐れの少ない、エチレングリコールやグリセ
リンが好ましい。Then, the organic solution after the heat treatment is cooled to around room temperature, polyhydric alcohols are added, and the mixed organic solution is used as a composition for forming a transparent conductive film. Here, the polyhydric alcohols provide the thickening effect of the organic solution and the stability of the coating film obtained by coating and drying the composition for forming a transparent conductive film on the substrate. For example, glycols and trihydric alcohols are used. Examples of alcohols include ethylene glycol and glycerin, which have a small number of carbon atoms and are less likely to cause carbon residue during thermal decomposition.

【００１４】このようにして、得られた透明導電膜形成
用組成物を基板に塗布・乾燥した後、焼成して、透明導
電膜を形成する。ここで、透明導電膜形成用組成物の塗
布には、スクリーン印刷法，ロールコート法，ディップ
コート法，スピンコート法などを用いることができる
が、ディップコート法，スピンコート法が好ましい。ま
た、焼成温度としては、透明導電膜形成用組成物が分解
する温度以上で、かつ基板の変形温度以下であればよ
く、４００〜７００℃が好ましい。The composition for forming a transparent conductive film thus obtained is applied to a substrate, dried, and then baked to form a transparent conductive film. Here, a screen printing method, a roll coating method, a dip coating method, a spin coating method, or the like can be used to apply the composition for forming a transparent conductive film, and the dip coating method or the spin coating method is preferable. The firing temperature may be higher than or equal to the temperature at which the composition for forming a transparent conductive film is decomposed and lower than the deformation temperature of the substrate, and is preferably 400 to 700 ° C.

【００１５】以下、さらに詳細な実施例によって本発明
を説明するが、本発明はこれらの実施例によって限定さ
れるものではない。Hereinafter, the present invention will be described with reference to more detailed examples, but the present invention is not limited to these examples.

【００１６】（実施例１）１リットルの三角フラスコ
に、４５ｇの硝酸インジウム〔Ｉｎ（ＮＯ3）3・３Ｈ2
Ｏ〕を秤量し、５０ｇのアセチルアセトンを加えて、室
温で混合・溶解させた。その溶液に、しゅう酸第１錫
（ＳｎＣ2Ｏ4）を、しゅう酸第１錫中の錫含有量と硝酸
インジウム中のインジウム含有量の合計量に対するしゅ
う酸第１錫中の錫含有量が０，５，１０，１５，２０，
３０wt％となるように、０，１．３５，２．７，４．０
５，５．４，８．１ｇと、アセトンを加えて還流した。
その還流後の溶液を、室温付近まで冷却し、１０ｇのグ
リセリンを加えて、攪拌・混合し、透明導電膜形成用組
成物を合成した。その透明導電膜形成用組成物に、Ｓｉ
Ｏ 2コート並ガラス基板を６０cm／minの引き上げ速度で
ディップコートした。その基板を５分間室温で放置し、
１００℃で５分間乾燥した後、５００℃で１時間焼成し
た。得られた膜の厚みは０．０５μｍであり、その電気
特性を図１に示す。(Example 1) 1-liter Erlenmeyer flask
45 g of indium nitrate [In (NO3)3・ 3H2
[O] was weighed, 50 g of acetylacetone was added, and
Mix and dissolve at temperature. Stannous oxalate was added to the solution.
(SnC2OFour) The tin content in stannous oxalate and nitric acid
The total amount of indium contained in indium
The tin content in stannous oxalate is 0, 5, 10, 15, 20,
0, 1.35, 2.7, 4.0 so as to be 30 wt%
5,5.4,8.1 g and acetone were added and the mixture was refluxed.
The solution after the reflux was cooled to around room temperature and 10 g of g
Add lyserine, stir and mix, and set for transparent conductive film formation
The product was synthesized. The composition for forming the transparent conductive film contains Si
O 2Coat glass substrate at a pulling speed of 60 cm / min
I did a dip coat. Leave the substrate for 5 minutes at room temperature,
After drying at 100 ° C for 5 minutes, baking at 500 ° C for 1 hour
It was The thickness of the obtained film is 0.05 μm,
The characteristics are shown in FIG.

【００１７】図１に示すように、硝酸インジウムと、し
ゅう酸第１錫の配合比が、しゅう酸第１錫中の錫含有量
と硝酸インジウム中のインジウム含有量の合計量に対す
るしゅう酸第１錫中の錫含有量が５〜２０％の範囲にあ
るとき低いシート抵抗（Ω／□）を示した。As shown in FIG. 1, the compounding ratio of indium nitrate and stannous oxalate is such that the total content of tin in stannous oxalate and indium nitrate in stannous oxalate is equal to that of stannous oxalate. When the tin content in tin was in the range of 5 to 20%, low sheet resistance (Ω / □) was exhibited.

【００１８】（実施例２）無機インジウム化合物とし
て、塩化インジウム（ＩｎＣｌ3・３Ｈ2Ｏ）を、有機錫
化合物として、しゅう酸第１錫を用い、しゅう酸第１錫
中の錫含有量と塩化インジウムのインジウム含有量の合
計量に対するしゅう酸第１錫中の錫含有量が１０wt％と
なるように塩化インジウムとしゅう酸第１錫を配合し
た。他は実施例１に同じ。Example 2 Indium chloride (InCl 3 .3H 2 O) was used as the inorganic indium compound, and stannous oxalate was used as the organotin compound. The tin content in the stannous oxalate and the chloride Indium chloride and stannous oxalate were blended so that the tin content in stannous oxalate was 10 wt% with respect to the total indium content of indium. Others are the same as in Example 1.

【００１９】（実施例３）有機錫化合物として、酢酸第
１錫〔Ｓｎ（ＣＨ3ＣＯＯ）2〕を用い、酢酸第１錫中の
錫含有量と硝酸インジウム中のインジウム含有量の合計
量に対する酢酸第１錫中の錫含有量が１０wt％となるよ
うに酢酸第１錫と硝酸インジウムを配合した。他は実施
例１に同じ。(Example 3) Stannous acetate [Sn (CH 3 COO) 2 ] was used as the organotin compound, with respect to the total content of tin in stannous acetate and indium indium nitrate. Stannous acetate and indium nitrate were blended so that the tin content in stannous acetate was 10 wt%. Others are the same as in Example 1.

【００２０】（実施例４）インジウムと錫のいずれとも
配位可能な有機化合物として、２−アミノアルコールを
用いた。他は実施例１に同じ。Example 4 As the organic compound capable of coordinating both indium and tin, 2-amino alcohol was used. Others are the same as in Example 1.

【００２１】（実施例５）多価アルコールとして、エチ
レングリコールを用いた。他は実施例１に同じ。Example 5 Ethylene glycol was used as the polyhydric alcohol. Others are the same as in Example 1.

【００２２】（比較例１）１リットルの三角フラスコ
に、塩化第２錫（ＳｎＣｌ4・５Ｈ2Ｏ）の錫含有量と、
硝酸インジウム中のインジウム含有量の合計量に対する
塩化第２錫中の錫含有量が１０wt％になるように、４５
ｇの硝酸インジウムと、５．４ｇの塩化第２錫とアセト
ンを加えて、攪拌・混合し、透明導電膜形成用組成物を
合成した。その透明導電膜形成用組成物を、ＳｉＯ2コ
ート並ガラス基板に、６０cm／minの引き上げ速度でデ
ィップコートした。その基板を５分間室温で放置し、１
００℃で５分間乾燥した後、５００℃で１時間焼成し
た。Comparative Example 1 In a 1 liter Erlenmeyer flask, the tin content of stannic chloride (SnCl 4 .5H 2 O) was added.
The tin content in stannic chloride is 10 wt% with respect to the total indium content in indium nitrate.
g of indium nitrate, 5.4 g of stannic chloride and acetone were added, stirred and mixed to synthesize a composition for forming a transparent conductive film. The transparent conductive film-forming composition was dip-coated on a SiO 2 -coated glass substrate at a pulling rate of 60 cm / min. Leave the substrate at room temperature for 5 minutes, then
After drying at 00 ° C for 5 minutes, it was baked at 500 ° C for 1 hour.

【００２３】（表１）に実施例２〜５、比較例１の結果
を示す。Table 1 shows the results of Examples 2 to 5 and Comparative Example 1.

【００２４】[0024]

【表１】 [Table 1]

【００２５】[0025]

【発明の効果】以上の実施例の説明により明らかなよう
に、本発明の透明導電膜形成用組成物と透明導電膜の形
成方法を用いることにより、導電性と可視領域における
透過性に優れた透明導電膜を容易にかつ安価で得ること
ができ、表示素子や発熱抵抗体などの透明電極などの用
途に適するものである。As is apparent from the above description of the examples, by using the composition for forming a transparent conductive film and the method for forming a transparent conductive film of the present invention, excellent conductivity and transparency in the visible region are achieved. The transparent conductive film can be obtained easily and inexpensively, and is suitable for applications such as display elements and transparent electrodes such as heating resistors.

【図面の簡単な説明】[Brief description of drawings]

【図１】本発明の透明導電膜形成用組成物と透明導電膜
の形成方法における透明導電膜中のＳｎとＩｎの組成比
〔Ｓｎ／（Ｓｎ＋Ｉｎ）×１００〕とシート抵抗の関係
を示すグラフFIG. 1 is a graph showing the relationship between the composition ratio of Sn and In in the transparent conductive film [Sn / (Sn + In) × 100] and the sheet resistance in the composition for forming a transparent conductive film of the present invention and the method for forming a transparent conductive film.

───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.5 識別記号 庁内整理番号 ＦＩ 技術表示箇所 // Ｈ０１Ｌ 29/40 Ａ 7738−4Ｍ ─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 5 Identification code Office reference number FI technical display location // H01L 29/40 A 7738-4M

Claims (6)

【特許請求の範囲】[Claims] 【請求項１】無機インジウム化合物と有機錫化合物と、
インジウムと錫のいずれにも配位可能な有機化合物を主
体とする有機溶液を加熱処理して部分的に加水分解さ
せ、前記有機溶液に多価アルコール類を混合して得られ
る透明導電膜形成用組成物。1. An inorganic indium compound and an organic tin compound,
For forming a transparent conductive film obtained by heat-treating an organic solution mainly composed of an organic compound capable of coordinating with indium and tin to partially hydrolyze it and mixing a polyhydric alcohol with the organic solution. Composition. 【請求項２】無機インジウム化合物と有機錫化合物の配
合比が、前記有機錫化合物中の錫含有量と、前記無機イ
ンジウム化合物中のインジウム含有量の合計量に対する
前記有機錫化合物中の錫含有量が５〜２０wt％の範囲に
ある請求項１記載の透明導電膜形成用組成物。2. The compounding ratio of the inorganic indium compound and the organotin compound is such that the tin content in the organotin compound relative to the total amount of the tin content in the organotin compound and the indium content in the inorganic indium compound. The composition for forming a transparent conductive film according to claim 1, wherein the content is in the range of 5 to 20 wt%. 【請求項３】無機インジウム化合物が、硝酸インジウム
または塩化インジウムである請求項１記載の透明導電膜
形成用組成物。3. The composition for forming a transparent conductive film according to claim 1, wherein the inorganic indium compound is indium nitrate or indium chloride. 【請求項４】有機錫化合物が、カルボン酸塩またはジカ
ルボン酸塩である請求項１記載の透明導電膜形成用組成
物。4. The composition for forming a transparent conductive film according to claim 1, wherein the organotin compound is a carboxylic acid salt or a dicarboxylic acid salt. 【請求項５】配位可能な有機化合物が、β−ジケトン
類、αまたはβ−ケトン酸類、前記αまたはβ−ケトン
酸類のエステル類、αまたはβ−アミノアルコール類か
らなる群から選ばれるものである請求項１記載の透明導
電膜形成用組成物。5. A coordinating organic compound selected from the group consisting of β-diketones, α or β-ketone acids, esters of the α or β-ketone acids, and α or β-amino alcohols. The composition for forming a transparent conductive film according to claim 1, which is 【請求項６】無機インジウム化合物と有機錫化合物と、
インジウムと錫のいずれにも配位可能な有機化合物を主
体とする有機溶液を加熱処理して部分的に加水分解さ
せ、前記有機溶液に多価アルコール類を混合して得られ
る透明導電膜形成用組成物を、基板に塗布・乾燥した
後、焼成する透明導電膜の形成方法。6. An inorganic indium compound and an organic tin compound,
For forming a transparent conductive film obtained by heat-treating an organic solution mainly composed of an organic compound capable of coordinating with indium and tin to partially hydrolyze it and mixing a polyhydric alcohol with the organic solution. A method for forming a transparent conductive film, which comprises applying a composition to a substrate, drying the composition, and then baking the composition.
JP18442291A 1991-07-24 1991-07-24 Composition for forming transparent conductive film and method for forming transparent conductive film Expired - Lifetime JP3208794B2 (en)

Priority Applications (5)

Application Number Priority Date Filing Date Title
JP18442291A JP3208794B2 (en) 1991-07-24 1991-07-24 Composition for forming transparent conductive film and method for forming transparent conductive film
DE69223186T DE69223186T2 (en) 1991-07-24 1992-07-23 Composition for use in a transparent electroconductive film and process for producing the same
EP92112620A EP0524630B1 (en) 1991-07-24 1992-07-23 Composition for use in a transparent and electrically conductive film and a method for making the film
US08/478,342 US5578248A (en) 1991-07-24 1995-06-07 Composition for use in a transparent and electrically conductive film and a method for making the film
US08/697,512 US5998011A (en) 1991-07-24 1996-08-26 Composition for use in a transparent and electrically conductive film and a method for making the film

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP18442291A JP3208794B2 (en) 1991-07-24 1991-07-24 Composition for forming transparent conductive film and method for forming transparent conductive film

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JPH0528834A true JPH0528834A (en) 1993-02-05
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1306522C (en) * 2002-06-28 2007-03-21 日亚化学工业株式会社 Composition, solution and method for forming transparent conductive film
JP2008013653A (en) * 2006-07-05 2008-01-24 Nissha Printing Co Ltd Ink for forming transparent conductive film and its manufacturing method
JP2008270170A (en) * 2007-04-23 2008-11-06 Samsung Sdi Co Ltd Organic light emitting device and its manufacturing method
JP2015008181A (en) * 2013-06-24 2015-01-15 株式会社ニケ・ウィング Solar cell module and manufacturing method of the same

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1306522C (en) * 2002-06-28 2007-03-21 日亚化学工业株式会社 Composition, solution and method for forming transparent conductive film
JP2008013653A (en) * 2006-07-05 2008-01-24 Nissha Printing Co Ltd Ink for forming transparent conductive film and its manufacturing method
JP2008270170A (en) * 2007-04-23 2008-11-06 Samsung Sdi Co Ltd Organic light emitting device and its manufacturing method
JP2015008181A (en) * 2013-06-24 2015-01-15 株式会社ニケ・ウィング Solar cell module and manufacturing method of the same

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