JPH07320541A - Composition for forming transparent conductive film and method for producing transparent conductive film - Google Patents
Composition for forming transparent conductive film and method for producing transparent conductive filmInfo
- Publication number
- JPH07320541A JPH07320541A JP6105583A JP10558394A JPH07320541A JP H07320541 A JPH07320541 A JP H07320541A JP 6105583 A JP6105583 A JP 6105583A JP 10558394 A JP10558394 A JP 10558394A JP H07320541 A JPH07320541 A JP H07320541A
- Authority
- JP
- Japan
- Prior art keywords
- transparent conductive
- conductive film
- composition
- forming
- polyhydric alcohol
- 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.)
- Pending
Links
Landscapes
- Chemically Coating (AREA)
- Non-Insulated Conductors (AREA)
- Manufacturing Of Electric Cables (AREA)
- Surface Treatment Of Glass (AREA)
Abstract
(57)【要約】
【目的】 低抵抗で高透過率の透明導電膜を得られる透
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。
【構成】 硝酸インジウム、多価アルコールの縮合体お
よび活剤を有機溶剤に溶解してなる透明導電膜形成用組
成物。これを基板に塗布・焼成することにより、経時変
化の少ない、低抵抗で高透過率の透明導電膜が得られ
る。(57) [Summary] [Object] To provide a composition for forming a transparent conductive film and a method for forming a transparent conductive film, which can obtain a transparent conductive film having low resistance and high transmittance. A composition for forming a transparent conductive film, which is obtained by dissolving indium nitrate, a condensate of polyhydric alcohol and an activator in an organic solvent. By coating and baking this on a substrate, a transparent conductive film having a low resistance and a high transmittance, which is less likely to change with time, can be obtained.
Description
【０００１】[0001]
【産業上の利用分野】本発明は、ガラス、セラミックス
等の基板上に、透明導電膜を形成するための組成物及び
透明導電膜の形成方法に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a composition for forming a transparent conductive film on a substrate such as glass or ceramics and a method for forming the 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。このような透明導電性材
料として、酸化スズ・酸化アンチモン系（ＡＴＯ）や酸
化インジウム・酸化スズ系（ＩＴＯ）などが知られてい
る。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。2. Description of the Related Art Electrodes for display elements such as liquid crystal display elements and electroluminescence display elements, and heating resistors for preventing fogging or icing of window glass of automobiles, aircraft, buildings, etc. Therefore, an electrode material having high transparency is used. Known examples of such transparent conductive materials include tin oxide / antimony oxide (ATO) and indium oxide / tin oxide (ITO). A film of these metal oxides can be easily formed on a glass or ceramic substrate to form a transparent conductive film.
【０００３】導電膜の形成方法としては、真空蒸着法、
スパッタリング法、ＣＶＤ法などが知られている。しか
し、これらの方法を実施するには、装置が複雑かつ高価
となるので、コストと量産性に問題がある。これらより
簡便な方法として、インジウム塩等の溶液を塗布し、熱
分解する方法がある。As a method of forming a conductive film, a vacuum vapor deposition method,
The sputtering method, the CVD method and the like are known. However, in order to carry out these methods, the apparatus becomes complicated and expensive, and there is a problem in cost and mass productivity. As a simpler method than these, there is a method of applying a solution of indium salt or the like and thermally decomposing it.
【０００４】[0004]
【発明が解決しようとする課題】前記の塗布・熱分解法
は、実用に耐えうる膜を形成することが困難であった。
例えば、硝酸インジウム、塩化インジウム、塩化第二ス
ズ等の無機化合物の有機溶剤溶液を使用した場合は、形
成される膜に白濁を生じたり、得られる膜の機械的強度
が不足で容易に傷がついたりする等の欠点がある。ま
た、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。It has been difficult for the above-mentioned coating / pyrolysis method to form a film that can withstand practical use.
For example, when an organic solvent solution of an inorganic compound such as indium nitrate, indium chloride or stannic chloride is used, white turbidity occurs in the formed film, or the mechanical strength of the obtained film is insufficient and scratches easily occur. There are drawbacks such as sticking. In addition, in the method using indium octoate or other organic acid indium having a strong ionic bond property, the organic acid indium is easily hydrolyzed and undergoes a chemical change relatively easily, so that a gelling of the coating solution occurs. There is.
【０００５】さらに、硝酸インジウムや硝酸スズとβ−
ジケトン等との金属錯体を使用する方法も提案されてい
る。しかし、この方法では硝酸インジウムや硝酸スズと
β−ジケトン等との金属錯体が経時変化を生じ、最終的
にインジウムやスズのβ−ジケトン錯塩になる。このた
め、基板に塗布した後の塗膜の熱分解時において、前記
錯塩が昇華しやすいために膜中の組成ズレや組成の不均
一が生じ、低抵抗の均質膜が得られない。また、前記錯
塩中のβ−ジケトンの数が増加すると、熱分解時に生じ
る炭酸ガス等の量が増加して、得られる膜の密度が減少
し、充分な膜強度が得られない等の欠点がある。Further, indium nitrate, tin nitrate and β-
A method using a metal complex with a diketone or the like has also been proposed. However, in this method, a metal complex of indium nitrate or tin nitrate with β-diketone changes with time, and finally becomes a β-diketone complex salt of indium or tin. Therefore, when the coating film is thermally decomposed after being applied to the substrate, the complex salt is easily sublimated, so that composition deviation or composition nonuniformity occurs in the film, and a low resistance homogeneous film cannot be obtained. Further, when the number of β-diketones in the complex salt increases, the amount of carbon dioxide gas and the like generated during thermal decomposition increases, the density of the obtained film decreases, and sufficient film strength cannot be obtained. is there.
【０００６】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を提供することを目的と
する。本発明はまた、低抵抗で高透過率の透明導電膜を
得る方法を提供することを目的とする。The present invention is intended to solve the above problems, and an object of the present invention is to provide a composition for forming a transparent conductive film capable of stably forming a transparent conductive film having low resistance and high transmittance. . Another object of the present invention is to provide a method for obtaining a transparent conductive film having low resistance and high transmittance.
【０００７】[0007]
【課題を解決するための手段】本発明の透明導電膜形成
用組成物は、硝酸インジウム、多価アルコールの縮合体
および活剤を有機溶剤に溶解して構成される。ここで、
多価アルコールの縮合体としては、ジエチレングリコー
ルおよびトリエチレングリコールよりなる群から選ばれ
るものが好ましい。また、活剤は、金属ジカルボン酸塩
が好ましい。The composition for forming a transparent conductive film of the present invention is constituted by dissolving indium nitrate, a condensate of polyhydric alcohol and an activator in an organic solvent. here,
The polyhydric alcohol condensate is preferably selected from the group consisting of diethylene glycol and triethylene glycol. Further, the activator is preferably a metal dicarboxylic acid salt.
【０００８】本発明の透明導電膜の製造方法は、硝酸イ
ンジウム、多価アルコールの縮合体および活剤を有機溶
剤に溶解して透明導電膜形成用組成物を調製する工程、
および前記組成物を基板に塗布し、焼成して基板上に透
明導電膜を生成させる工程を有する。また、前記組成物
を調製する工程は、硝酸インジウムを多価アルコールの
縮合体に溶解する工程、および前記で得られた溶液に活
剤と有機溶剤を加えて加熱する工程からなることが好ま
しい。The method for producing a transparent conductive film of the present invention comprises the steps of dissolving a condensate of indium nitrate, a polyhydric alcohol and an activator in an organic solvent to prepare a composition for forming a transparent conductive film,
And applying the composition to a substrate and baking the composition to form a transparent conductive film on the substrate. Further, the step of preparing the composition preferably comprises a step of dissolving indium nitrate in a polyhydric alcohol condensate, and a step of adding an activator and an organic solvent to the solution obtained above and heating the solution.
【０００９】[0009]
【作用】多価アルコールの縮合体は、硝酸インジウムと
反応してこれを溶解し、硝酸インジウムの加水分解を抑
制するとともに、有機溶剤に対する溶解性をもたせる作
用をする。The polyhydric alcohol condensate has a function of reacting with indium nitrate to dissolve it, suppress hydrolysis of indium nitrate, and have solubility in an organic solvent.
【００１０】本発明者らは、無機インジウム塩を沸点の
低い有機溶剤に溶解させ、前記有機溶剤中に安定に存在
させるために、無機インジウム塩を多価アルコールの縮
合体に溶解し、それらを反応させることにより、前記有
機溶剤中に無機インジウム塩と多価アルコールの縮合体
を共存させることを試みた。その結果、硫酸インジウム
塩は多価アルコールの縮合体と反応せず、多価アルコー
ルの縮合体に溶解しなかった。また、塩化インジウムは
多価アルコールの縮合体と反応して、多価アルコールの
縮合体に溶解した。しかし、塩化インジウム塩と多価ア
ルコールの縮合体との反応生成物と活剤とを有機溶剤に
溶解した溶液を基板に塗布し、焼成したところ、得られ
た膜は白濁を生じ、電気特性、機械特性のいずれも実用
に供しうる膜は得られなかった。それに対し、本発明に
よると、透過率が良く、電気特性、機械特性のいずれも
優れ、実用に供しうる透明導電膜が得られる。The present inventors dissolve the inorganic indium salt in an organic solvent having a low boiling point, and in order to make it stably exist in the organic solvent, the inorganic indium salt is dissolved in a polyhydric alcohol condensate, and these are dissolved. An attempt was made to make a condensate of an inorganic indium salt and a polyhydric alcohol coexist in the organic solvent by reacting. As a result, the indium sulfate did not react with the polyhydric alcohol condensate and did not dissolve in the polyhydric alcohol condensate. Indium chloride reacted with the polyhydric alcohol condensate and was dissolved in the polyhydric alcohol condensate. However, a solution obtained by dissolving a reaction product of an indium chloride salt and a polyhydric alcohol condensate and an activator in an organic solvent was applied to a substrate and baked, and the resulting film was clouded to give an electrical property, No film was obtained that could be put to practical use in any of its mechanical properties. On the other hand, according to the present invention, it is possible to obtain a transparent conductive film which has good transmittance and is excellent in both electric properties and mechanical properties and which can be put to practical use.
【００１１】本発明の透明導電膜形成用組成物は、以下
のようにして合成するのが好ましい。まず、硝酸インジ
ウムを多価アルコールの縮合体に溶解させる。ここで、
硝酸インジウムの結晶水の量は少ない方が好ましい。そ
の理由は、有機溶剤を用いた透明導電膜形成用組成物の
場合、前記組成物中の水分量と、得られる透明導電膜中
のピンホール量との間に相関がみられるためである。ま
た、多価アルコールの縮合体は、硝酸インジウムと反応
して、硝酸インジウムを溶解し、硝酸インジウムの加水
分解を抑えるとともに、有機溶剤に対する溶解性をもた
せるために必要である。多価アルコールの縮合体として
は、エチレングリコールの縮合体であるジエチレングリ
コール、トリエチレングリコールが好ましい。次に、前
記溶液に有機溶剤と活剤を加える。なお、前記活剤の溶
解度が低い場合には、それらを室温から前記有機溶剤の
還流温度の間で加熱処理してもよい。The composition for forming a transparent conductive film of the present invention is preferably synthesized as follows. First, indium nitrate is dissolved in a polyhydric alcohol condensate. here,
It is preferable that the amount of water of crystallization of indium nitrate is small. The reason is that in the case of the composition for forming a transparent conductive film using an organic solvent, there is a correlation between the amount of water in the composition and the amount of pinholes in the obtained transparent conductive film. Further, the polyhydric alcohol condensate is necessary for reacting with indium nitrate to dissolve indium nitrate, suppress hydrolysis of indium nitrate, and have solubility in an organic solvent. As the polyhydric alcohol condensate, diethylene glycol and triethylene glycol, which are condensates of ethylene glycol, are preferable. Next, an organic solvent and an activator are added to the solution. If the solubility of the activator is low, they may be heat-treated between room temperature and the reflux temperature of the organic solvent.
【００１２】ここで、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、メタノール、エタノール、イソプロパノー
ル等のアルコール類、アセトン、メチルエチルケトン、
ジエチルケトン等のケトン類、テトラヒドロフラン等の
エーテル類、２−メトキシエタノール、２−エトキシエ
タノール等のエーテルアルコール類が挙げられる。ま
た、活剤は、透明導電膜としての電気特性を向上させる
目的で添加されるものであり、例えば、マグネシウム、
カドミウム、亜鉛、チタン、スズ、テルル、セリウム、
ジルコニウム等の金属塩が挙げられるが、良好な導電性
を与えるものとして、スズ塩が最も好ましい。さらに、
塩として、無機塩では硝酸塩、塩化物塩、硫酸塩等が、
有機塩ではカルボン酸塩、ジカルボン酸塩が挙げられる
が、なかでもジカルボン酸塩が好ましく、特に炭素数の
小さいシュウ酸塩が好ましい。Here, the organic solvent may be any one which can dissolve the organic compound or the inorganic compound used in the present invention. For example, alcohols such as methanol, ethanol, isopropanol, acetone, methyl ethyl ketone,
Examples thereof include ketones such as diethyl ketone, ethers such as tetrahydrofuran, and ether alcohols such as 2-methoxyethanol and 2-ethoxyethanol. Further, the activator is added for the purpose of improving the electric characteristics of the transparent conductive film, for example, magnesium,
Cadmium, zinc, titanium, tin, tellurium, cerium,
Examples thereof include metal salts such as zirconium, but tin salts are most preferable as they provide good conductivity. further,
As salts, inorganic salts include nitrates, chlorides, sulfates, etc.
Examples of organic salts include carboxylates and dicarboxylates. Of these, dicarboxylates are preferable, and oxalates having a small number of carbon atoms are particularly preferable.
【００１３】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、３
００〜８００℃が好ましい。焼成雰囲気は、酸素中や空
気中など酸素を含む雰囲気が一般的である。この焼成後
さらに、不活性ガスや還元ガス雰囲気中で熱処理するこ
とにより、得られる透明導電膜の電気特性と信頼性を一
層向上することができる。この熱処理の雰囲気は、窒素
ガスなどの不活性ガスや、不活性ガスと水蒸気を混合し
た還元ガス雰囲気が好ましい。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, 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 or equal to the deformation temperature of the substrate.
The temperature is preferably 00 to 800 ° C. The firing atmosphere is generally an atmosphere containing oxygen such as oxygen or air. After the firing, a heat treatment is further performed in an atmosphere of an inert gas or a reducing gas, whereby the electrical characteristics and reliability of the obtained transparent conductive film can be further improved. The atmosphere for this heat treatment is preferably an inert gas such as nitrogen gas or a reducing gas atmosphere in which an inert gas and water vapor are mixed.
【００１４】焼成後の膜の抵抗値は数時間程度で一定と
なるが、前記の不活性ガスや還元ガス雰囲気での熱処理
後の抵抗値は、一定になるのに数日を要する。このよう
な膜の抵抗値変化の挙動は、一般には、焼成時に吸着し
た酸素ガスによるものと考えられている。すなわち、熱
処理後の抵抗値が一定となるまでに長時間を要するの
は、熱処理によりいったん脱着した部分に再び酸素ガス
が吸着されるためである。従って、得られた膜の密度が
高いほど、表面積が減少し、酸素ガスや吸着水等による
膜の抵抗値の経時変化は小さくなると考えられる。The resistance value of the film after baking becomes constant in about several hours, but it takes several days for the resistance value after heat treatment in the above-mentioned inert gas or reducing gas atmosphere to become constant. It is generally considered that such a behavior of the resistance change of the film is due to the oxygen gas adsorbed at the time of firing. That is, it takes a long time for the resistance value after the heat treatment to become constant because the oxygen gas is adsorbed again to the portion that is once desorbed by the heat treatment. Therefore, it is considered that the higher the density of the obtained film, the smaller the surface area and the smaller the change with time of the resistance value of the film due to oxygen gas, adsorbed water, or the like.
【００１５】[0015]
【実施例】以下に、本発明の実施例を詳細に説明する。 ［実施例１］１リットルの三角フラスコに、３６ｇの硝
酸インジウムＩｎ（ＮＯ3）3・３Ｈ2Ｏを秤量し、ジエ
チレングリコールＨＯＣＨ2ＣＨ2ＯＣＨ2ＣＨ2ＯＨを３
２ｇ（硝酸インジウムに対するモル比３）加えて、室温
で混合・溶解させた。その溶液に、０〜８．１ｇのシュ
ウ酸第一スズＳｎＣ2Ｏ4と６５ｇの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、透
明導電膜形成用組成物を得た。こ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／ｍｉ
ｎの引き上げ速度でディップコートした。その基板を６
０℃で８分間乾燥した後、酸素中において５００℃で１
時間焼成し、さらに、窒素中において５００℃で５時間
熱処理した。得られた膜の厚みは０．０６μｍであっ
た。EXAMPLES Examples of the present invention will be described in detail below. Example 1 In a 1 liter Erlenmeyer flask, 36 g of indium nitrate In (NO 3 ) 3 3H 2 O was weighed, and diethylene glycol HOCH 2 CH 2 OCH 2 CH 2 OH was added to 3 g.
2 g (molar ratio to indium nitrate: 3) was added, and mixed and dissolved at room temperature. 0 to 8.1 g of stannous oxalate SnC 2 O 4 and 65 g of acetone were added to the solution and refluxed. The solution after the reflux was cooled to around room temperature to obtain a composition for forming a transparent conductive film. This transparent conductive film-forming composition was coated with a SiO 2 -coated glass substrate at 60 cm / mi.
Dip coating was performed at a pulling rate of n. The board 6
After drying at 0 ° C for 8 minutes, it is dried in oxygen at 500 ° C for 1 minute.
It was fired for an hour and further heat-treated in nitrogen at 500 ° C. for 5 hours. The thickness of the obtained film was 0.06 μm.
【００１６】上記の透明導電膜形成用組成物中のスズと
インジウムの原子比と得られた膜のシート抵抗との関係
を図１に示す。図中ａは酸素中で焼成後、ｂは窒素中で
熱処理後、ｃは窒素中で熱処理してから３日後の特性を
示す。図１において、シート抵抗のｂとｃの差が小さ
く、かつ絶対値の小さいものほどよい。スズ塩を活剤と
した本実施例においては、原子比Ｓｎ／Ｉｎ＝０．１０
〜０．２０の範囲が特に好ましい。FIG. 1 shows the relationship between the atomic ratio of tin to indium in the composition for forming a transparent conductive film and the sheet resistance of the obtained film. In the figure, a shows the characteristics after baking in oxygen, b shows the heat treatment in nitrogen, and c shows the characteristics three days after the heat treatment in nitrogen. In FIG. 1, the smaller the difference between the sheet resistances b and c and the smaller the absolute value, the better. In this example using a tin salt as the activator, the atomic ratio Sn / In = 0.10.
The range of ˜0.20 is particularly preferred.
【００１７】［実施例２］ジエチレングリコールの量を
６４ｇ（硝酸インジウムに対するモル比６）、シュウ酸
第一スズの量を３ｇ（原子比Ｓｎ／Ｉｎ＝０．１５）と
する他は実施例１と同様にして透明導電膜を形成した。Example 2 As Example 1 except that the amount of diethylene glycol was 64 g (molar ratio to indium nitrate 6) and the amount of stannous oxalate was 3 g (atomic ratio Sn / In = 0.15). A transparent conductive film was formed in the same manner.
【００１８】［実施例３］ジエチレングリコールの代わ
りにトリエチレングリコールＨＯ（ＣＨ2）2Ｏ（Ｃ
Ｈ2）2Ｏ（ＣＨ2）2ＯＨを９０ｇ（硝酸インジウムに対
するモル比６）用いた他は実施例２と同様にして透明導
電膜を形成した。[Example 3] Triethylene glycol HO (CH 2 ) 2 O (C
A transparent conductive film was formed in the same manner as in Example 2 except that 90 g of H 2 ) 2 O (CH 2 ) 2 OH (molar ratio to indium nitrate was 6) was used.
【００１９】［実施例４］ジエチレングリコール６４ｇ
の代わりに、ジエチレングリコール２０ｇ（硝酸インジ
ウムに対するモル比２）とトリエチレングリコール１５
ｇ（硝酸インジウムに対するモル比１）を用いた他は実
施例２と同様にして透明導電膜を形成した。[Example 4] 64 g of diethylene glycol
Instead of 20 g diethylene glycol (molar ratio to indium nitrate 2) and triethylene glycol 15
A transparent conductive film was formed in the same manner as in Example 2 except that g (molar ratio to indium nitrate was 1) was used.
【００２０】［実施例５］アセトンの代わりに６５ｇの
メタノールを用いた他は実施例２と同様にして透明導電
膜を形成した。[Example 5] A transparent conductive film was formed in the same manner as in Example 2 except that 65 g of methanol was used instead of acetone.
【００２１】［実施例６］活剤として、さらにシュウ酸
マグネシウムを０．０３ｇ（原子比Ｍｇ／Ｉｎ＝０．０
０５）加えた他は実施例２と同様にして透明導電膜を形
成した。Example 6 As an activator, 0.03 g of magnesium oxalate (atomic ratio Mg / In = 0.0) was further added.
05) A transparent conductive film was formed in the same manner as in Example 2 except for the addition.
【００２２】［比較例１］１リットルの三角フラスコ
に、塩化インジウムＩｎＣｌ3・３Ｈ2Ｏを２８ｇ、塩化
第二スズＳｎＣｌ4・５Ｈ2Ｏを５．３ｇ（原子比Ｓｎ／
Ｉｎ＝０．１５）、さらにアセトンを６５ｇ加えて、攪
拌・混合し、透明導電膜形成用組成物を合成した。この
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、６０℃で５分間
乾燥した後、酸素中において５００℃で１時間焼成し、
さらに、窒素中において５００℃で５時間熱処理した。[0022] [Comparative Example 1] 1-liter Erlenmeyer flask, the indium chloride InCl 3 · 3H 2 O 28g, stannic SnCl 4 · 5H 2 O and 5.3g chloride (atomic ratio Sn /
In = 0.15), 65 g of acetone was further added, and the mixture was stirred and mixed to synthesize a composition for forming a transparent conductive film. This transparent conductive film-forming composition was dip-coated with a SiO 2 -coated glass substrate at a pulling rate of 60 cm / min. The substrate is left at room temperature for 5 minutes, dried at 60 ° C for 5 minutes, and then baked in oxygen at 500 ° C for 1 hour,
Furthermore, it heat-processed at 500 degreeC in nitrogen for 5 hours.
【００２３】［比較例２］１リットルの三角フラスコ
に、硝酸インジウム４５ｇ、アセチルアセトン５０ｇ、
塩化第二スズ５．３ｇ（原子比Ｓｎ／Ｉｎ＝０．１５）
およびアセトン６５ｇを加えて、攪拌・還流し、透明導
電膜形成用組成物を合成した。こ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／ｍｉ
ｎ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、６０℃で５分間乾燥した後、酸素中
において５００℃で１時間焼成し、さらに、窒素中にお
いて５００℃で５時間熱処理した。Comparative Example 2 In a 1-liter Erlenmeyer flask, 45 g of indium nitrate, 50 g of acetylacetone,
Stannic chloride 5.3 g (atomic ratio Sn / In = 0.15)
And 65 g of acetone were added, and the mixture was stirred and refluxed to synthesize a composition for forming a transparent conductive film. This transparent conductive film-forming composition was coated with a SiO 2 -coated glass substrate at 60 cm / mi.
Dip coating was performed at a pulling rate of n. The board 5
After left at room temperature for 5 minutes and dried at 60 ° C. for 5 minutes, it was baked in oxygen at 500 ° C. for 1 hour, and further heat-treated in nitrogen at 500 ° C. for 5 hours.
【００２４】以上の実施例２〜６および比較例１、２の
透明導電膜の特性を表１に示す。なお、シート抵抗は、
酸素中で焼成後の値、焼成後の窒素中での熱処理後の
値、窒素中で熱処理してから３日後の値である。また、
透過率は両面に透明導電膜がコートされた基板の３８０
〜７８０ｎｍでの平均透過率である。Table 1 shows the characteristics of the transparent conductive films of Examples 2 to 6 and Comparative Examples 1 and 2. The sheet resistance is
It is the value after firing in oxygen, the value after heat treatment in nitrogen after firing, and the value 3 days after heat treatment in nitrogen. Also,
The transmittance is 380 for a substrate coated with a transparent conductive film on both sides.
Average transmittance at ~ 780 nm.
【００２５】[0025]
【表１】 [Table 1]
【００２６】[0026]
【発明の効果】本発明によれば、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に得る
ことができ、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。According to the present invention, it is possible to easily and inexpensively obtain a transparent conductive film having excellent conductivity and transparency in the visible region, and to use it as a transparent electrode such as a display element or a heating resistor. It is suitable.
【図１】本発明の実施例により得られた透明導電膜の原
子比Ｓｎ／Ｉｎとシート抵抗の関係を示す図である。FIG. 1 is a diagram showing a relationship between an atomic ratio Sn / In and a sheet resistance of a transparent conductive film obtained according to an example of the present invention.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 吉田 昭彦 大阪府門真市大字門真1006番地 松下電器 産業株式会社内 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Akihiko Yoshida 1006 Kadoma, Kadoma City, Osaka Prefecture Matsushita Electric Industrial Co., Ltd.
Claims (5)
体および活剤を有機溶剤に溶解してなる透明導電膜形成
用組成物。1. A composition for forming a transparent conductive film obtained by dissolving indium nitrate, a polyhydric alcohol condensate, and an activator in an organic solvent.
グリコールおよびトリエチレングリコールよりなる群か
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。2. The composition for forming a transparent conductive film according to claim 1, wherein the polyhydric alcohol condensate is selected from the group consisting of diethylene glycol and triethylene glycol.
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 activator is a metal dicarboxylic acid salt.
体および活剤を有機溶剤に溶解して透明導電膜形成用組
成物を調製する工程、および前記組成物を基板に塗布
し、焼成して基板上に透明導電膜を生成させる工程を有
することを特徴とする透明導電膜の製造方法。4. A step of preparing a composition for forming a transparent conductive film by dissolving indium nitrate, a condensate of polyhydric alcohol, and an activator in an organic solvent, and applying the composition to a substrate and firing the substrate. A method for producing a transparent conductive film, comprising the step of forming a transparent conductive film on the top.
ジウムを多価アルコールの縮合体に溶解する工程、およ
び前記で得られた溶液に活剤と有機溶剤を加えて加熱す
る工程からなる請求項４記載の透明導電膜の製造方法。5. The step of preparing the composition comprises a step of dissolving indium nitrate in a polyhydric alcohol condensate, and a step of adding an activator and an organic solvent to the solution obtained above and heating the solution. Item 5. A method for producing a transparent conductive film according to item 4.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6105583A JPH07320541A (en) | 1994-05-19 | 1994-05-19 | Composition for forming transparent conductive film and method for producing transparent conductive film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6105583A JPH07320541A (en) | 1994-05-19 | 1994-05-19 | Composition for forming transparent conductive film and method for producing transparent conductive film |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH07320541A true JPH07320541A (en) | 1995-12-08 |
Family
ID=14411529
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6105583A Pending JPH07320541A (en) | 1994-05-19 | 1994-05-19 | Composition for forming transparent conductive film and method for producing transparent conductive film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH07320541A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2014120712A (en) * | 2012-12-19 | 2014-06-30 | Ricoh Co Ltd | Coating liquid for metal oxide film formation, metal oxide film, field effect transistor, and process of manufacturing field effect transistor |
| KR20140097475A (en) | 2011-11-30 | 2014-08-06 | 가부시키가이샤 리코 | Coating liquid for forming metal oxide thin film, metal oxide thin film, field-effect transistor, and method for manufacturing field-effect transistor |
| US9748097B2 (en) | 2013-03-29 | 2017-08-29 | Ricoh Company, Ltd. | Coating liquid for forming metal oxide film, metal oxide film, field-effect transistor, and method for producing field-effect transistor |
| KR20180067738A (en) | 2010-11-29 | 2018-06-20 | 가부시키가이샤 리코 | Coating liquid for forming metal oxide thin film, metal oxide thin film, field effect transistor, and method for producing the field effect transistor |
| US11908945B2 (en) | 2015-09-15 | 2024-02-20 | Ricoh Company, Ltd. | Coating liquid for forming n-type oxide semiconductor film, method for producing n-type oxide semiconductor film, and method for producing field-effect transistor |
-
1994
- 1994-05-19 JP JP6105583A patent/JPH07320541A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20180067738A (en) | 2010-11-29 | 2018-06-20 | 가부시키가이샤 리코 | Coating liquid for forming metal oxide thin film, metal oxide thin film, field effect transistor, and method for producing the field effect transistor |
| KR20140097475A (en) | 2011-11-30 | 2014-08-06 | 가부시키가이샤 리코 | Coating liquid for forming metal oxide thin film, metal oxide thin film, field-effect transistor, and method for manufacturing field-effect transistor |
| US9418842B2 (en) | 2011-11-30 | 2016-08-16 | Ricoh Company, Ltd. | Coating liquid for forming metal oxide thin film, metal oxide thin film, field-effect transistor, and method for manufacturing field-effect transistor |
| JP2014120712A (en) * | 2012-12-19 | 2014-06-30 | Ricoh Co Ltd | Coating liquid for metal oxide film formation, metal oxide film, field effect transistor, and process of manufacturing field effect transistor |
| US9748097B2 (en) | 2013-03-29 | 2017-08-29 | Ricoh Company, Ltd. | Coating liquid for forming metal oxide film, metal oxide film, field-effect transistor, and method for producing field-effect transistor |
| US11908945B2 (en) | 2015-09-15 | 2024-02-20 | Ricoh Company, Ltd. | Coating liquid for forming n-type oxide semiconductor film, method for producing n-type oxide semiconductor film, and method for producing field-effect transistor |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4268539A (en) | Liquid coating composition for forming transparent conductive films and a coating process for using said composition | |
| US5578248A (en) | Composition for use in a transparent and electrically conductive film and a method for making the film | |
| JPH07320541A (en) | Composition for forming transparent conductive film and method for producing transparent conductive film | |
| AU575648B2 (en) | Iridescence suppressing coating process | |
| JP2001035273A (en) | Adjusting method for sheet resistance value of transparent conductive film and forming method for the transparent conductive film | |
| JP3208794B2 (en) | Composition for forming transparent conductive film and method for forming transparent conductive film | |
| JPH07109119A (en) | Composition for forming metal oxide film, its production and formation of metal oxide film | |
| JP4522566B2 (en) | Method for adjusting sheet resistance value of transparent conductive film | |
| JP3049890B2 (en) | Method for forming transparent conductive film | |
| JP3091606B2 (en) | Method for producing composition for forming transparent conductive film and method for forming transparent conductive film | |
| JPH0696619A (en) | Composition for forming transparent conductive film and method for forming the same | |
| JP3144951B2 (en) | Method of manufacturing heat reflection window | |
| JPH07161235A (en) | Transparent conductive film and method for manufacturing the same | |
| JPH05116941A (en) | Production of electric conductive transparent film | |
| GB2428689A (en) | Process for preparing transparent conducting metal oxides | |
| JP3889221B2 (en) | Coating liquid for forming ITO transparent conductive film and method for forming transparent conductive film | |
| JP2708120B2 (en) | Method for producing coating liquid for transparent oxide thin film and substrate with transparent oxide thin film | |
| JPH05114314A (en) | Transparent conductive membrane moulding method | |
| JP4683525B2 (en) | Transparent conductive film and transparent conductive film forming material | |
| JPH07122359A (en) | Microwave oven window | |
| JPH01133961A (en) | Glass deposited with transparent thin oxide film and production thereof | |
| JP3984400B2 (en) | Transparent conductive film forming coating liquid, transparent conductive film and method for producing the same | |
| JP2004018913A (en) | Liquid for forming transparent conductive film and method for manufacturing substrate coated with transparent conductive film using the same | |
| JPH08339723A (en) | Method for producing composition for forming transparent conductive film | |
| JPH01264929A (en) | Production of transparent electroconductive zinc oxide film |