JPH05166414A - Transparent conductive film and forming method thereof - Google Patents

Transparent conductive film and forming method thereof

Info

Publication number
JPH05166414A
JPH05166414A JP3327309A JP32730991A JPH05166414A JP H05166414 A JPH05166414 A JP H05166414A JP 3327309 A JP3327309 A JP 3327309A JP 32730991 A JP32730991 A JP 32730991A JP H05166414 A JPH05166414 A JP H05166414A
Authority
JP
Japan
Prior art keywords
transparent conductive
conductive film
indium
compound
tin
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
JP3327309A
Other languages
Japanese (ja)
Other versions
JP3049890B2 (en
Inventor
Akihiko Yoshida
昭彦 吉田
Akiyoshi Hattori
章良 服部
Atsushi Nishino
西野  敦
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 JP3327309A priority Critical patent/JP3049890B2/en
Priority claimed from DE69223186T external-priority patent/DE69223186T2/en
Publication of JPH05166414A publication Critical patent/JPH05166414A/en
Application granted granted Critical
Publication of JP3049890B2 publication Critical patent/JP3049890B2/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

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Classifications

    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C18/00Chemical 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
    • C23C18/02Chemical 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
    • C23C18/12Chemical 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
    • C23C18/1204Chemical 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
    • C23C18/1208Oxides, e.g. ceramics
    • C23C18/1216Metal oxides

Abstract

PURPOSE:To realize low resistance and also high permeability of a film by making the film of oxide particles of indium and tin whose grain sizes are 30-100nm. CONSTITUTION:An organic solution made up of an inorganic indium compound and an organic compound coordinatable with any of indium and tin is heated so that the organic solution is made to partially hydrolyze and further, polyhydric alcohols are mixed in the organic solution. Next, a composition for forming transparent conductive film is coated to a substrate and dried, and thereafter, baked at a temperature-up speed of 20 deg.C/min or more. In this case, the composition is constituted of oxide particles of indium and tin whose grain sizes are 30nm-100nm and also the ratio of an average grain size and a film thickness should be 0.7 or less. The baking should be performed under a pressure atmosphere of steam, and the mixing ratio of an organic tin compound to an inorganic indium compound should be set such that (Sn/(In+ Sn)X100) is within the range of 5-20wt. It is thereby possible to improve conductivity and the permeability in a visible region.

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ELなどの面光源や液晶
の電極に用いることのできる透明導電膜およびその形成
方法に関する。
BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a transparent conductive film which can be used for a surface light source such as EL and an electrode of liquid crystal, and a method for forming the same.

【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 defrosting or preventing freezing 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、酸化ス
ズ、酸化スズ・酸化アンチモン系(ATO)、酸化イン
ジウム・酸化スズ系(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。
As such transparent conductive materials, tin oxide, tin oxide / antimony oxide (ATO), indium oxide / tin oxide (ITO), etc. are known, and these metal oxides are glass or ceramic. A film can be easily formed on the substrate to form a transparent conductive film.

【0004】透明導電膜には、その形成方法によって、
次のように分類される。 (1) 真空蒸着法 酸化スズをEB法などにより直接基板に蒸着成膜する方
法である。 (2) スパッタリング法 ITOなどをターゲットにしてRFスパッタリング法で
成膜する方法である。 (3) CVD法・熱分解法 SnCl2などを加熱した基板に塗布する事によりSn
2膜などを形成する方法である。 (4) 塗布法 SnやInの有機化合物をバインダなどを添加して増粘
しペースト状にしてこれをスクリーン印刷熱分解する方
法である。
The transparent conductive film is formed according to its forming method.
It is classified as follows. (1) Vacuum evaporation method This is a method in which tin oxide is directly deposited on a substrate by an EB method or the like. (2) Sputtering method This is a method of forming a film by an RF sputtering method using ITO as a target. (3) CVD method / pyrolysis method SnCl 2 is applied to a heated substrate to apply Sn.
This is a method of forming an O 2 film or the like. (4) Coating method This is a method in which an organic compound such as Sn or In is thickened by adding a binder or the like to form a paste, and this is subjected to screen printing thermal decomposition.

【0005】[0005]

【発明が解決しようとする課題】上記の(1)、(2)、(3)
の方法による膜は、針状結晶子を有する密度の高い均質
膜が得られるが、製膜のための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、針状結晶相を持つ
ために、a)膜の導電性に異方性が見られる、b)膜の機械
強度が弱い、c)比表面積が大きく湿度などのガスが吸着
し易く抵抗値の経時変化が大きい、などの問題点があ
る。
[Problems to be Solved by the Invention] Above (1), (2), (3)
The film by the method of (1) can obtain a high-density homogeneous film having acicular crystallites, but the apparatus for film formation is complicated and expensive,
There are problems in cost and mass productivity. In addition, because of the acicular crystal phase, a) the conductivity of the film has anisotropy, b) the mechanical strength of the film is weak, c) the specific surface area is large, and gases such as humidity easily adsorb and the resistance value There is a problem that the change over time is large.

【0006】また、(4)の方法で得られた膜は、上記の
(1)、(2)、(3)の方法よりも安価に製膜できるが、未だ
実用に耐えうる膜を形成することが困難であった。
The film obtained by the method (4) has the above-mentioned structure.
Although it is possible to form a film at a lower cost than the methods (1), (2), and (3), it is still difficult to form a film that can be used practically.

【0007】例えば、硝酸インジウム、塩化インジウ
ム、塩化第2スズ等の無機化合物の有機溶液を使用した
場合は、粒径の不均一な粒子や針状結晶子から成る膜し
か得ることができず、その結果、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等の欠
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, only a film composed of particles having nonuniform particle diameters or needle-like crystallites can be obtained, As a result, the film becomes cloudy,
There is a defect that the obtained film has insufficient mechanical strength and is easily scratched.

【0008】オクチル酸インジウム等のイオン結合性の
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易く、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等の欠点がある。さ
らに、インジウムやスズ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、スズ化合物の蒸散等により、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
い等の欠点がある。これらの欠点はいずれも得られた膜
の構造が、構成粒子径や形の不均一性に起因しているも
のである。
In the method of using indium organic acid having a strong ionic bond such as indium octylate, the organic acid indium is easily hydrolyzed and undergoes a chemical change relatively easily, resulting in gelation of the coating solution. There are drawbacks. Furthermore, a method using an organic complex of indium or tin has also been proposed, but in this method, during the thermal decomposition of the coating film applied to the substrate, the evaporation of the tin compound or the like prevents the film from becoming uniform. Therefore, there is a defect that a low resistance homogeneous film cannot be obtained. All of these drawbacks are due to the nonuniformity of the constituent particle size and shape in the structure of the obtained film.

【0009】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に関するもので、その最適
な構成と、これを安定して形成することが可能な透明導
電膜の形成方法とを提供することを目的とする。
The present invention solves the above problems, and relates to a transparent conductive film having a low resistance and a high transmittance. The optimum structure of the transparent conductive film and a transparent conductive film capable of stably forming the same are provided. And a forming method.

【0010】[0010]

【課題を解決するための手段】本発明は、上記目的を達
成するためのもので、粒子径が30nm〜100nmの
インジウムと錫との酸化物粒子から構成される、透明導
電膜である。
The present invention is for achieving the above object, and is a transparent conductive film composed of oxide particles of indium and tin having a particle diameter of 30 nm to 100 nm.

【0011】また、無機インジウム化合物と有機スズ化
合物と、インジウムとスズのいずれにも配位可能な有機
化合物とからな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、20℃/分以上の昇温速度で焼成することを特
徴とする透明導電膜の形成方法である。
Further, an organic solution comprising an inorganic indium compound, an organic tin compound, and an organic compound capable of coordinating with indium and tin is heat-treated to be partially hydrolyzed to give a polyvalent solution to the organic solution. A method for forming a transparent conductive film, which comprises applying a composition for forming a transparent conductive film obtained by mixing alcohols to a substrate, drying the composition, and then firing the composition at a temperature rising rate of 20 ° C./minute or more. ..

【0012】[0012]

【作用】本発明は、粒子径が30nm〜100nmのイ
ンジウムと錫との酸化物粒子から構成される透明導電膜
であり、この範囲の酸化物粒子が非常に緻密に充填され
て膜を構成するために膜の電気抵抗が小さく高い可視光
透過性が達成される。
The present invention is a transparent conductive film composed of oxide particles of indium and tin having a particle size of 30 nm to 100 nm, and the oxide particles in this range are extremely densely filled to form a film. Therefore, the electric resistance of the film is small and high visible light transmittance is achieved.

【0013】この高い性能は、無機インジウム化合物と
有機スズ化合物と、インジウムとスズのいずれとも配位
可能な有機化合物とからな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
合物と有機スズ化合物と無機インジウム化合物が含有す
る結晶水が反応し、有機スズ化合物が部分的に加水分解
されて、インジウムとスズ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スズの蒸散による膜の
不均一化を抑え、得られる膜の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。
This high performance is obtained by heat-treating an organic solution containing an inorganic indium compound, an organic tin compound, and an organic compound capable of coordinating indium and tin. The water of crystallization contained in the indium compound, the organic tin compound and the inorganic indium compound reacts, the organic tin compound is partially hydrolyzed to form an intermediate composite compound of indium and tin,
This suppresses the nonuniformity of the film due to the evaporation of tin, which has been a problem in the past, and gives the obtained film a low resistivity and a high transmittance. 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.

【0014】[0014]

【実施例】本発明の具体的な実施例を示す前に本発明の
技術的な特徴を以下に述べる。
EXAMPLES The technical features of the present invention will be described below before showing specific examples of the present invention.

【0015】図1は膜を構成するインジウムと錫との酸
化物の、膜中での平均粒子径と電気抵抗値および可視光
透過率(550nmにおける)との関係を示すものであ
る。この図からわかるように粒子径が30nmから10
0nmの範囲では電気抵抗値が低くこの範囲より外側で
は抵抗値が大きくなる。粒子径が100nm以上の領域
では粒子同志の接触抵抗が大きくなり膜中に高い充填率
で粒子が存在し得なくなる。逆に粒子径が30nm以下
の領域では膜の強度が小さくなり抵抗値も大きくなる。
このことは膜を構成する粒子の平均粒子径が均一なほど
強度の高い膜が得られることを示唆しており種々検討し
た結果、中心粒径の±3σの範囲に90%含まれる粒径
分布を有している条件を満たすときに非常に低い抵抗値
を有する膜が得られることが判明した。
FIG. 1 shows the relationship between the average particle size of the oxide of indium and tin constituting the film, the electrical resistance value and the visible light transmittance (at 550 nm). As can be seen from this figure, the particle size is from 30 nm to 10
The electric resistance value is low in the range of 0 nm, and the resistance value is large outside the range. In the region where the particle diameter is 100 nm or more, the contact resistance between the particles becomes large, and the particles cannot exist in the film at a high filling rate. On the contrary, in the region where the particle diameter is 30 nm or less, the strength of the film becomes small and the resistance value becomes large.
This suggests that a film having higher strength can be obtained as the average particle size of the particles constituting the film becomes more uniform. As a result of various studies, a particle size distribution of 90% within ± 3σ of the central particle size is obtained. It has been found that a film having a very low resistance value can be obtained when the condition satisfying is satisfied.

【0016】また、平均の粒子径(A)と膜厚(B)と
の比A/Bが0.7以下である場合に、膜強度が優れた
ものになった。これは、膜の厚さ方向に直列に並ぶ粒子
の数が膜の強度と深く関係するためである。
Further, when the ratio A / B between the average particle size (A) and the film thickness (B) is 0.7 or less, the film strength becomes excellent. This is because the number of particles arranged in series in the thickness direction of the film is deeply related to the strength of the film.

【0017】次に、本発明の実施例を詳細に説明する。
本発明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
ウムとスズ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
やスズ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、インジウムとスズのいずれ
とも配位可能な有機化合物は、インジウムとスズに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。
Next, embodiments of the present invention will be described in detail.
The composition for forming a transparent conductive film of the present invention 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 both indium and tin is necessary for coordinating in part with indium and tin to assist formation of an intermediate compound thereof and to have solubility in an organic solvent. ,
Examples thereof include β-diketones, α- or β-ketone acids, esters of the above ketone acids, and α- or β-amino alcohols.

【0018】次に、前記溶液に有機溶剤と有機スズ化合
物を加え、それらの有機溶液を加熱処理する。ここで、
前記有機スズ化合物としては、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易いものであ
ればよい。例えば、カルボン酸スズやジカルボン酸スズ
が挙げられ、炭素数が小さい、ギ酸スズ、酢酸スズ、シ
ュウ酸スズが好ましい。また、前記有機溶剤としては、
本発明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、キシレン等の芳香族
炭化水素、、エタノール、イソプロパノール等のアルコ
ール類、酢酸エチル、酢酸ブチル等の酢酸エステル類、
アセトン、ジエチルケトン等のケトン類、メトキシエタ
ノール、エトキシエタノール等のエーテル類、テトラヒ
ドロフラン等が挙げられる。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スズ化合物と、そ
れらと配位可能な有機化合物とからなる有機溶液の還流
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 compound as long as it is relatively stable in the 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, as the organic solvent,
Any material capable of dissolving the organic compound or the inorganic compound used in the present invention may be used. 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,
Examples thereof include ketones such as acetone and diethyl ketone, ethers such as methoxyethanol and ethoxyethanol, and tetrahydrofuran. Further, the temperature of the heat treatment is preferably at or near the reflux temperature of the organic solution containing the inorganic indium compound, the organic tin compound, and the organic compound capable of coordinating with them.

【0019】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の安定性
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。
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 alcohol provides 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. 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.

【0020】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、スピンコート法等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、40
0〜700℃が好ましい。
The transparent conductive film-forming composition thus obtained is applied to a substrate, dried, and then baked to form a transparent conductive film. Here, for the coating of the composition for forming a transparent conductive film, a screen printing method, a roll coating method, a dip coating method, a spin coating method or the like can be used.
The dip coating method and the spin coating method are preferable. Also,
The baking 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, 40
0-700 degreeC is preferable.

【0021】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.

【0022】(実施例1)1(l)の三角フラスコに、60
gの硝酸インジウム(In(NO3)3・3H2O)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、10gのシュウ酸第1スズ(SnC2O4)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、撹拌・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、SiO2コート並ガラス基板を60cm/m
in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、水蒸気
加圧下500℃で1時間焼成した。昇温速度は20℃/
分。得られた膜の厚みは0.07μmであった。
(Example 1) 1 (1) Erlenmeyer flask, 60
g of indium nitrate (In (NO 3 ) 3 / 3H 2 O) is weighed, and 50 g
Of acetylacetone was added and mixed and dissolved at room temperature. 10 g of stannous oxalate (SnC 2 O 4 ) and acetone were added to the solution and the mixture was refluxed. The solution after the reflux was cooled to around room temperature, 10 g of glycerin was added, and the mixture was stirred and mixed to synthesize a composition for forming a transparent conductive film. The transparent conductive film forming composition was coated with a SiO 2 coated glass substrate at 60 cm / m 2.
Dip-coated at a pulling rate of in. The board 5
After leaving at room temperature for 5 minutes and drying at 100 ° C. for 5 minutes, it was baked at 500 ° C. for 1 hour under steam pressure. Temperature rising rate is 20 ° C /
Minutes. The thickness of the obtained film was 0.07 μm.

【0023】(実施例2)実施例1において昇温を30
℃/分の速度で行う。
(Embodiment 2) In Embodiment 1, the temperature is raised to 30
Perform at a rate of ° C / min.

【0024】(実施例3)実施例1において昇温を50
℃/分の速度で行う。
(Embodiment 3) In Embodiment 1, the temperature is raised to 50
Perform at a rate of ° C / min.

【0025】(比較例1)1lの三角フラスコに、50g
の硝酸インジウム(In(NO3)3・3H2O)と6.0gの塩化第2
スズ(SnCl4・5H2O)とアセトンを加えて、撹拌・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、SiO2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。(表1)に実施例1〜3、比較例1の結
果を示す。
(Comparative Example 1) 50 g in a 1 l Erlenmeyer flask
Of indium nitrate (In (NO 3) 3 · 3H 2 O) and the second chloride 6.0g
Tin (SnCl 4 .5H 2 O) and acetone were added, and the mixture was stirred and mixed to synthesize a composition for forming a transparent conductive film. The transparent conductive film forming composition was coated with a SiO 2 coated normal glass substrate at 60 cm / min.
The dip coating was performed at the pulling speed of. The substrate is left at room temperature for 5 minutes, dried at 100 ° C for 5 minutes, and then at 500 ° C for 1 minute.
Burned for hours. Table 1 shows the results of Examples 1 to 3 and Comparative Example 1.

【0026】[0026]

【表1】 [Table 1]

【0027】[0027]

【発明の効果】本発明の粒子径が30nm〜100nm
で均一な粒径分布を持ったインジウムと錫との酸化物粒
子から構成される透明導電膜は、導電性と可視領域にお
ける透過性に優れ、表示素子や発熱抵抗体等の透明電極
等の用途に適するものである。
The particle size of the present invention is 30 nm to 100 nm.
A transparent conductive film composed of oxide particles of indium and tin with a uniform particle size distribution is excellent in conductivity and transparency in the visible region, and is used for transparent electrodes such as display elements and heating resistors. It is suitable for.

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

【図1】本発明の透明導電膜を構成する粒子の平均粒子
径と膜の電気抵抗および可視透過率との関係図
FIG. 1 is a diagram showing the relationship between the average particle size of particles constituting the transparent conductive film of the present invention and the electric resistance and visible transmittance of the film.

Claims (8)

【特許請求の範囲】[Claims] 【請求項1】粒子径が30〜100nmのインジウムと
錫との酸化物粒子から構成される透明導電膜。
1. A transparent conductive film composed of oxide particles of indium and tin having a particle diameter of 30 to 100 nm.
【請求項2】平均の粒子径(A)と膜厚(B)との比A
/Bが0.7以下であることを特徴とする請求項1記載
の透明導電膜。
2. A ratio A of average particle diameter (A) to film thickness (B).
/ B is 0.7 or less, The transparent conductive film of Claim 1 characterized by the above-mentioned.
【請求項3】無機インジウム化合物と有機スズ化合物
と、インジウムとスズのいずれにも配位可能な有機化合
物とからな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、20℃/分以上の昇温速度で焼成することを特徴と
する透明導電膜の形成方法。
3. An organic solution comprising an inorganic indium compound, an organic tin compound, and an organic compound capable of coordinating with indium and tin is heat-treated to partially hydrolyze, and a polyvalent solution is added to the organic solution. A method for forming a transparent conductive film, which comprises applying a composition for forming a transparent conductive film obtained by mixing alcohols to a substrate, drying the composition, and then firing the composition at a temperature rising rate of 20 ° C./minute or more.
【請求項4】焼成が水蒸気の加圧雰囲気下で行うことを
特徴とする請求項34記載の透明導電膜の形成方法。
4. The method for forming a transparent conductive film according to claim 34, wherein the baking is performed in a pressurized atmosphere of water vapor.
【請求項5】透明導電膜形成用組成物において、無機イ
ンジウム化合物に対する有機スズ化合物の配合比(Sn/
(In+Sn)×100)が5〜20Wt%の範囲にあることを特徴と
する請求項3記載の透明導電膜の形成方法。
5. In the composition for forming a transparent conductive film, the compounding ratio of the organic tin compound to the inorganic indium compound (Sn /
The method for forming a transparent conductive film according to claim 3, wherein (In + Sn) × 100) is in the range of 5 to 20 Wt%.
【請求項6】有機スズ化合物が、カルボン酸塩またはジ
カルボン酸塩であることを特徴とする請求項3記載の透
明導電膜の形成方法。
6. The method for forming a transparent conductive film according to claim 3, wherein the organic tin compound is a carboxylate or a dicarboxylate.
【請求項7】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ことを特徴とする請求項3記載
の透明導電膜の形成方法。
7. A coordinating organic compound is selected from the group consisting of β-diketones, α- or β-ketone acids, esters of said ketone acids, and α- or β-amino alcohols. The method for forming a transparent conductive film according to claim 3, wherein
【請求項8】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ことを特徴とする請求項3
記載の透明導電膜の形成方法。
8. The inorganic indium compound is indium nitrate or indium chloride.
The method for forming a transparent conductive film as described above.
JP3327309A 1991-12-11 1991-12-11 Method for forming transparent conductive film Expired - Fee Related JP3049890B2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP3327309A JP3049890B2 (en) 1991-12-11 1991-12-11 Method for forming transparent conductive film

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
JP3327309A JP3049890B2 (en) 1991-12-11 1991-12-11 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

Publications (2)

Publication Number Publication Date
JPH05166414A true JPH05166414A (en) 1993-07-02
JP3049890B2 JP3049890B2 (en) 2000-06-05

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ID=18197698

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Country Link
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JP2009238549A (en) * 2008-03-26 2009-10-15 Panasonic Electric Works Co Ltd Method of forming conductor pattern and conductor pattern
JP2010105217A (en) * 2008-10-28 2010-05-13 Panasonic Electric Works Co Ltd Method for manufacturing printing intaglio plate, printing intaglio plate and conductor pattern
WO2010095672A1 (en) * 2009-02-18 2010-08-26 東洋紡績株式会社 Metal thin film production method and metal thin film

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005078986A (en) * 2003-09-02 2005-03-24 Tdk Corp Conductive film for transfer, forming method of transparent conductive membrane using it, and transparent conductive membrane
US7488894B2 (en) 2003-09-02 2009-02-10 Tdk Corporation Conductive film for transfer, method for forming transparent conductive film using same, and transparent conductive film
JP2009238549A (en) * 2008-03-26 2009-10-15 Panasonic Electric Works Co Ltd Method of forming conductor pattern and conductor pattern
JP2010105217A (en) * 2008-10-28 2010-05-13 Panasonic Electric Works Co Ltd Method for manufacturing printing intaglio plate, printing intaglio plate and conductor pattern
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JP4853590B2 (en) * 2009-02-18 2012-01-11 東洋紡績株式会社 Metal thin film manufacturing method and metal thin film

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