JPH10283847A - Transparent conductive film - Google Patents
Transparent conductive filmInfo
- Publication number
- JPH10283847A JPH10283847A JP8287597A JP8287597A JPH10283847A JP H10283847 A JPH10283847 A JP H10283847A JP 8287597 A JP8287597 A JP 8287597A JP 8287597 A JP8287597 A JP 8287597A JP H10283847 A JPH10283847 A JP H10283847A
- Authority
- JP
- Japan
- Prior art keywords
- transparent conductive
- conductive film
- tin oxide
- fine particles
- film
- 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.)
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- Conductive Materials (AREA)
- Non-Insulated Conductors (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、透明導電膜に関
し、より詳細には、太陽電池、液晶素子、その他電子デ
バイス全般に適用されるもので、塗布法により膜を形成
し得る当該透明導電膜に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a transparent conductive film, and more particularly to a transparent conductive film which can be applied to a solar cell, a liquid crystal element, and other electronic devices, and can form a film by a coating method. About.
【０００２】[0002]
【従来の技術】近年、太陽電池、液晶素子、その他電子
デバイス用の電極として、透明導電膜の必要性が高くな
ってきている。また、従来、光が関係する素子に用いる
透明導電性材料として、アンチモンドープ酸化錫、フッ
素ドープ酸化錫、アルミニウムドープ酸化亜鉛、ガリウ
ムドープ酸化亜鉛、酸化インジウム錫などが知られてい
る。そして、透明導電膜作製方法としてはスパッタリン
グ法、ＣＶＤ法、真空蒸着法、塗布法があるが、塗布法
以外の方法は設備コストが高く、量産性に欠ける。これ
に対し、塗布法は設備的に低コストであり、量産性にも
富むため、これまで盛んに研究され、検討されてきた。
具体的な方法としては、導電性微粒子をバインダ樹脂に
分散させた液を塗布する方法があり、また、ゾル−ゲル
法のように導電性材料の原料のゾルを塗布、乾燥レゲル
化する方法がある。2. Description of the Related Art In recent years, there has been an increasing need for transparent conductive films as electrodes for solar cells, liquid crystal elements, and other electronic devices. Conventionally, as a transparent conductive material used for an element involving light, antimony-doped tin oxide, fluorine-doped tin oxide, aluminum-doped zinc oxide, gallium-doped zinc oxide, indium tin oxide, and the like are known. As a method for producing a transparent conductive film, there are a sputtering method, a CVD method, a vacuum evaporation method, and a coating method. However, methods other than the coating method have high equipment costs and lack mass productivity. On the other hand, the coating method is inexpensive in terms of equipment and rich in mass productivity, and thus has been actively studied and studied.
As a specific method, there is a method of applying a liquid in which conductive fine particles are dispersed in a binder resin, and a method of applying a sol of a raw material of a conductive material, such as a sol-gel method, and drying and regelating. is there.
【０００３】[0003]
【発明が解決しようとする課題】導電性微粒子をバイン
ダ樹脂に分散させる例として、特開平５−５０６９号公
報、同５−１５１８２６、同６−７６６３６、同６−１
１９８１６、同６−１２５１０１、同７−２４２８４２
号公報が挙げられる。特開平６−１１９８１６号公報を
例に挙げると、導電性微粒子を酸化インジウム錫微粒子
としたものであるが、バインダ樹脂がシリカで絶縁性で
あるため、そこをキァリアが通りにくく、また、キァリ
アが消滅しやすいことで低抵抗化に限界がある。Examples of dispersing conductive fine particles in a binder resin are disclosed in JP-A-5-5069, JP-A-5-151826, JP-A-5-151826, JP-A-6-76636, and JP-A-6-76636.
19816, 6-125101, 7-242842
Publication. For example, Japanese Patent Application Laid-Open No. HEI 6-119816 discloses that the conductive fine particles are made of indium tin oxide fine particles. However, since the binder resin is silica and insulating, the carrier hardly passes therethrough. There is a limit in lowering resistance because it is easily extinguished.
【０００４】また、ゾル−ゲル法を用いる例としては、
特開平５−２８８３４号公報、同５−１１６９４１、同
６−９６６１９、同６−１５０７４１、同７−９４０４
４、同７−１８２９３９号公報が挙げられる。特開平５
−２８８３４号公報を例に挙げると、透明導電膜として
酸化インジウム錫ゾル−ゲル膜を用いているが、ゾル−
ゲル膜では塗膜にクラックや粒界が生じやすいため均一
な膜を形成するのが困難である。そのため、この方法に
も低抵抗化に限界がある。また、特開平５−３１４８２
０号公報、同７−２６２８４０ではバインダ樹脂として
導電性の酸化インジウム錫を用いているが、導電性微粒
子の粒径が大きく、膜が緻密でないため、現状では、こ
れらの塗布法においては１０-3Ωｃｍオーダーが限界で
あり、１０-4Ωｃｍ台の抵抗を実現することが不可能で
あった。[0004] Examples of using the sol-gel method include:
JP-A-5-28834, JP-A-5-11694, JP-A-6-96619, JP-A-6-150741, and JP-A-7-9404
4, No. 7-182939. JP 5
For example, JP-A-28834 uses an indium tin oxide sol-gel film as a transparent conductive film.
In the case of a gel film, it is difficult to form a uniform film because cracks and grain boundaries tend to occur in the coating film. Therefore, this method also has a limit in reducing the resistance. In addition, Japanese Patent Application Laid-Open No. 5-31482
0 JP, but using a conductive indium tin oxide as the 7-262840 In the binder resin, the particle size is large of the conductive fine particles, since the film is not dense, at present, in these coating methods 10 - The limit was on the order of 3 Ωcm, and it was impossible to realize a resistance of the order of 10 −4 Ωcm.
【０００５】本発明は、上述した従来技術における問題
点に鑑みてなされたもので、導電性及び光の透過性に優
れ、容易に作製でき、光素子の電気的接続手段として適
用し得る透明導電膜を提供することをその解決課題とす
る。SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned problems in the prior art, and has excellent conductivity and light transmission, can be easily manufactured, and can be used as a means for electrically connecting optical elements. The problem is to provide a membrane.
【０００６】[0006]
【課題を解決するための手段】請求項１の発明は、導電
性バインダの組成液中に分散させた導電性微粒子を含有
する導電性塗料を基体に塗布し、乾燥することにより光
透過性薄膜を形成してなる透明導電膜としたものであ
る。According to the first aspect of the present invention, a light-transmitting thin film is formed by applying a conductive paint containing conductive fine particles dispersed in a composition solution of a conductive binder to a substrate, followed by drying. Is formed as a transparent conductive film.
【０００７】請求項２の発明は、請求項１記載の透明導
電膜において、前記導電性微粒子の粒径が１０ｎｍ以下
であることを特徴としてなる透明導電膜としたものであ
る。According to a second aspect of the present invention, there is provided the transparent conductive film according to the first aspect, wherein the conductive fine particles have a particle size of 10 nm or less.
【０００８】請求項３の発明は、請求項１又は２記載の
透明導電膜において、前記導電性バインダの組成液がゾ
ル状を呈し、１０-2〜１０-4Ωｃｍの抵抗率を有するも
のであることを特徴としてなる透明導電膜としたもので
ある。According to a third aspect of the present invention, in the transparent conductive film according to the first or second aspect, the composition liquid of the conductive binder has a sol state and has a resistivity of 10 −2 to 10 −4 Ωcm. This is a transparent conductive film characterized by the following.
【０００９】請求項４の発明は、請求項１ないし３のい
ずれか記載の透明導電膜において、前記導電性バインダ
が酸化インジウム錫、アンチモンドープ酸化錫、フッ素
ドープ酸化錫、アルミニウムドープ酸化亜鉛あるいはガ
リウムドープ酸化亜鉛を含む組成であることを特徴とし
てなる透明導電膜としたものである。According to a fourth aspect of the present invention, in the transparent conductive film according to any one of the first to third aspects, the conductive binder is indium tin oxide, antimony-doped tin oxide, fluorine-doped tin oxide, aluminum-doped zinc oxide or gallium. This is a transparent conductive film characterized by having a composition containing doped zinc oxide.
【００１０】請求項５の発明は、請求項１ないし４のい
ずれか記載の透明導電膜において、前記導電性微粒子が
１０-3〜１０-4Ωｃｍの抵抗率を有するものであること
を特徴としてなる透明導電膜としたものである。A fifth aspect of the present invention is the transparent conductive film according to any one of the first to fourth aspects, wherein the conductive fine particles have a resistivity of 10 -3 to 10 -4 Ωcm. This is a transparent conductive film.
【００１１】請求項６の発明は、請求項１ないし５いず
れか記載の透明導電膜において、前記導電性微粒子が酸
化インジウム錫、アンチモンドープ酸化錫、フッ素ドー
プ酸化錫、アルミニウムドープ酸化亜鉛あるいはガリウ
ムドープ酸化亜鉛であることを特徴としてなる透明導電
膜としたものである。According to a sixth aspect of the present invention, in the transparent conductive film according to any one of the first to fifth aspects, the conductive fine particles are made of indium tin oxide, antimony-doped tin oxide, fluorine-doped tin oxide, aluminum-doped zinc oxide or gallium-doped. This is a transparent conductive film characterized by being zinc oxide.
【００１２】請求項７の発明は、請求項１ないし６いず
れか記載の透明導電膜において、前記透明導電膜が３〜
３０％のヘイズ率を有するものであることを特徴として
なる透明導電膜としたものである。According to a seventh aspect of the present invention, there is provided the transparent conductive film according to any one of the first to sixth aspects, wherein the transparent conductive film is 3 to
The transparent conductive film has a haze ratio of 30%.
【００１３】上記した課題解決手段では、クラックが少
なく、１０-4Ωｃｍオーダーの比抵抗を実現するための
バインダとしてかかる導電性バインダを用い、これに粒
径１０ｎｍ以下の導電性微粒子を分散させることにより
透明導電膜を得る。導電性の微粒子はクラック防止のた
めのフィラとしての効果も示す。In the above-mentioned means for solving the above problems, such a conductive binder is used as a binder for realizing a specific resistance of the order of 10 −4 Ωcm with few cracks, and conductive fine particles having a particle size of 10 nm or less are dispersed therein. To obtain a transparent conductive film. The conductive fine particles also have an effect as a filler for preventing cracks.
【００１４】酸化インジウム錫（以下「ＩＴＯ」と略記
する）を例として具体的に説明すると、導電性バインダ
の原料として、ＩＴＯゾル液を作製し、このゾルと粒径
１〜１０ｎｍのＩＴＯ超微粒子を混合し、塗布液とす
る。混合比は微粒子／ゾル液が９／１から１／１の間が
適当である。導電性微粒子および導電性バインダの材質
はＩＴＯに限定されず、アンチモンドープ酸化錫、フッ
素ドープ酸化錫、アルミニウムドープ酸化亜鉛、ガリウ
ムドープ酸化亜鉛を用いても良い。Specifically, indium tin oxide (hereinafter abbreviated as “ITO”) will be specifically described. An ITO sol solution is prepared as a raw material of a conductive binder, and this sol is mixed with ultrafine ITO particles having a particle size of 1 to 10 nm. Are mixed to form a coating solution. The mixing ratio of fine particles / sol solution is suitably between 9/1 and 1/1. The material of the conductive fine particles and the conductive binder is not limited to ITO, and antimony-doped tin oxide, fluorine-doped tin oxide, aluminum-doped zinc oxide, and gallium-doped zinc oxide may be used.
【００１５】得られた塗布液の塗布方法は、一般的によ
く知られた塗布方法、例えば、スピンコート法、ディッ
プコート法、エアナイフコート法、カーテンコート法、
ロールコート法、ワイヤーバーコード法、グラビアコー
ト法により塗布することが出来る。塗布基板としては、
ガラス、ポリエチレンテレフタレートフィルム（ＰＥ
Ｔ，ＰＥＮ等）、フッ素系フィルム（ＰＦＡ，ＦＥＰ
等）、ステンレス、透明セラミックス等が挙げられる。[0015] The coating method of the obtained coating solution is a well-known coating method such as a spin coating method, a dip coating method, an air knife coating method, a curtain coating method, and the like.
It can be applied by a roll coating method, a wire barcode method, or a gravure coating method. As a coating substrate,
Glass, polyethylene terephthalate film (PE
T, PEN, etc.), fluorinated films (PFA, FEP)
Etc.), stainless steel, transparent ceramics and the like.
【００１６】このように、導電性微粒子のバインダを導
電性のバインダとすることでキャリアが消滅しにくくな
り、キャリア移動度が向上する。また、導電性バインダ
自体、キャリアを多く保有しているのでキャリア濃度も
増加する。従って、低抵抗率を得ることが出来る。ま
た、微粒子に起因する表面凹凸もあり、１０〜３０％の
ヘイズ率があり、光散乱による光閉じ込め効果がある。
透過率は高く、光の吸収ロスも少ない。As described above, by making the binder of the conductive fine particles a conductive binder, carriers are less likely to disappear and carrier mobility is improved. In addition, since the conductive binder itself has many carriers, the carrier concentration also increases. Therefore, a low resistivity can be obtained. In addition, there are surface irregularities due to fine particles, a haze ratio of 10 to 30%, and an effect of confining light by light scattering.
High transmittance and low light absorption loss.
【００１７】[0017]
（実施例１）次のような組成で試薬を混合、撹拌し、Ｉ
ＴＯゾル液を得た。 酢酸（９９.９％、キシダ化学製） ２０ ｃｃ インジウム（III)アセチルアセトナート(キシダ化学製) ２.３ ｇ 塩化錫（IV)・ｎ水和物（塩化錫ｗｔ％＝７４％、 ｎ＝４〜７、キシダ化学製） ０.３ ｇ 硝酸（比重１.３８、キシダ化学製） ０.５ ｃｃ このようにして得られたゾル液とＩＴＯ超微粒子分散液
（平均粒径６ｎｍ、固形分濃度１０％）を超微粒子分散
液／ゾル液＝９／１の比で混合して塗布液を得た。この
ようにして得られた塗布液をスピンコート法により、２
００ｒｐｍ、９０ｓｅｃの条件で１０ｃｍ角のコーニン
グガラス上に塗布した。次に、これを４００℃で１時間
窒素雰囲気中で焼成を行った。得られた塗膜の膜厚を自
動エリプソメータで、比抵抗、キァリア濃度、キァリア
移動度をホール測定装置で、ヘイズ率をヘイズメータ
で、透過率を自記分光光度計で測定した。その結果を表
１に示す。表１に示すように、この実施例による透明導
電膜では、３.２×１０-4Ωｃｍという比抵抗が得られ
ており、１０-4Ωｃｍオーダーの膜が実現している。(Example 1) A reagent having the following composition was mixed and stirred, and
A TO sol solution was obtained. Acetic acid (99.9%, manufactured by Kishida Chemical) 20 cc indium (III) acetylacetonate (manufactured by Kishida Chemical) 2.3 g Tin (IV) chloride · n hydrate (tin chloride wt% = 74%, n = 4-7, manufactured by Kishida Chemical) 0.3 g Nitric acid (specific gravity: 1.38, manufactured by Kishida Chemical) 0.5 cc The sol solution thus obtained and an ultrafine particle dispersion of ITO (average particle size: 6 nm, solid content: (Concentration: 10%) at a ratio of ultrafine particle dispersion / sol liquid = 9/1 to obtain a coating liquid. The coating solution obtained in this manner was spin-coated to obtain 2
It was applied on a 10 cm square corning glass under the conditions of 00 rpm and 90 sec. Next, this was fired at 400 ° C. for 1 hour in a nitrogen atmosphere. The film thickness of the obtained coating film was measured with an automatic ellipsometer, the specific resistance, the carrier concentration, and the carrier mobility were measured with a Hall measuring device, the haze ratio was measured with a haze meter, and the transmittance was measured with a self-recording spectrophotometer. Table 1 shows the results. As shown in Table 1, in the transparent conductive film according to this example, a specific resistance of 3.2 × 10 −4 Ωcm was obtained, and a film on the order of 10 −4 Ωcm was realized.
【００１８】（実施例２）次のような組成で試薬を混
合、撹拌し、アルミニウムドープ酸化亜鉛ゾル液を得
た。 酢酸（９９.９％、キシダ化学製） ２０ ｃｃ 亜鉛アセチルアセトナート（キシダ化学製） ２.０ ｇ 塩化アルミニウム（III)（キシダ化学製） ０.２ ｇ 硝酸（比重１.３８、キシダ化学製） ０.５ ｃｃ このようにしてゾル液を得た。このゾル液以外は上記実
施例１と同様であり、導電性微粒子としてはＩＴＯ超微
粒子を用いた。この実施例による透明導電膜では、６.
７×１０-4Ωｃｍという比抵抗が得られており、１０-4
Ωｃｍオーダーの膜が実現している（表１，参照）。Example 2 A reagent having the following composition was mixed and stirred to obtain an aluminum-doped zinc oxide sol solution. Acetic acid (99.9%, manufactured by Kishida Chemical) 20 cc zinc acetylacetonate (manufactured by Kishida Chemical) 2.0 g Aluminum chloride (III) (manufactured by Kishida Chemical) 0.2 g Nitric acid (specific gravity 1.38, manufactured by Kishida Chemical) ) 0.5 cc In this way, a sol solution was obtained. Except for this sol solution, it was the same as in Example 1 above, and ITO ultrafine particles were used as the conductive fine particles. In the transparent conductive film according to this embodiment, 6.
7 × 10 -4 and the resistivity obtained that [Omega] cm, 10 -4
A film on the order of Ωcm has been realized (see Table 1).
【００１９】（実施例３）次のような組成で試薬を混
合、撹拌し、アンチモンドープ酸化錫ゾル液を得た。 酢酸（９９.９％、キシダ化学製） ２０ ｃｃ 錫アセチルアセトナート（キシダ化学製） ２.０ ｇ 塩化アンチモン（III)（キシダ化学製） ０.２５ｇ 硝酸（比重１.３８、キシダ化学製） ０.５ ｃｃ このようにしてゾル液を得た。このゾル液以外は実施例
１と同様であり、導電性微粒子としてはＩＴＯ超微粒子
を用いた。この実施例による透明導電膜では、５.５×
１０-4Ωｃｍという比抵抗が得られており、１０-4Ωｃ
ｍオーダーの膜が実現している（表１，参照）。Example 3 Reagents having the following composition were mixed and stirred to obtain an antimony-doped tin oxide sol solution. Acetic acid (99.9%, Kishida Chemical) 20 cc tin acetylacetonate (Kishida Chemical) 2.0 g Antimony (III) chloride (Kishida Chemical) 0.25 g Nitric acid (specific gravity 1.38, Kishida Chemical) 0.5 cc Thus, a sol solution was obtained. Except for this sol solution, it was the same as Example 1, and ITO ultrafine particles were used as the conductive fine particles. In the transparent conductive film according to this embodiment, 5.5 ×
A specific resistance of 10 -4 Ωcm has been obtained, and 10 -4 Ωc
An m-order film has been realized (see Table 1).
【００２０】（実施例４）実施例１と同じ組成で得られ
るゾル液とアンチモンドープ酸化錫微粒子分散液（平均
粒径８ｎｍ、固形分濃度１０％）を超微粒子分散液／ゾ
ル液＝９／１の比で混合して塗布液を得た。この塗布液
を得た後のプロセスは実施例１と同様に行われる。結果
として、９.８×１０-4Ωｃｍという比抵抗が得られて
おり、１０-4Ωｃｍオーダーの膜が実現している（表
１，参照）。(Example 4) A sol solution obtained with the same composition as in Example 1 and an antimony-doped tin oxide fine particle dispersion (average particle size 8 nm, solid content concentration 10%) were mixed with an ultrafine particle dispersion / sol solution = 9 / The mixture was mixed at a ratio of 1 to obtain a coating solution. The process after obtaining this coating liquid is performed in the same manner as in Example 1. As a result, a specific resistance of 9.8 × 10 −4 Ωcm was obtained, and a film on the order of 10 −4 Ωcm was realized (see Table 1).
【００２１】（比較例１）次のような組成で試薬を混
合、撹拌し、シリカゾル液を得た。 エタノール（キシダ化学製） １５.４ ｇ テトラエキシシラン（キシダ化学製） ３５.１ ｇ 蒸留水 ０.３５ ｇ 塩酸（３５.５％、キシダ化学製） ０.５ ｇ このようにして得られたゾル液と実施例１で用いたと同
じＩＴＯ超微粒子分散液を超微粒子分散液／ゾル液＝９
／１の比で混合して塗布液を得た。この塗布液を得た後
のプロセスは実施例１と同様に行われる。結果として、
得られる導電膜は、比抵抗値２.６×１０-1Ωｃｍであ
り、１０-4Ωｃｍオーダーの値が得られない（表１，参
照）。Comparative Example 1 A reagent having the following composition was mixed and stirred to obtain a silica sol solution. Ethanol (manufactured by Kishida Chemical) 15.4 g Tetraexisilane (manufactured by Kishida Chemical) 35.1 g Distilled water 0.35 g Hydrochloric acid (35.5%, manufactured by Kishida Chemical) 0.5 g obtained in this manner. The sol liquid and the same ITO ultrafine particle dispersion used in Example 1 were mixed with ultrafine particle dispersion / sol liquid = 9.
The mixture was mixed at a ratio of / 1 to obtain a coating solution. The process after obtaining this coating liquid is performed in the same manner as in Example 1. as a result,
The obtained conductive film has a specific resistance of 2.6 × 10 −1 Ωcm, and a value on the order of 10 −4 Ωcm cannot be obtained (see Table 1).
【００２２】（比較例２）実施例１で得られたゾル液を
単独で塗布液とした。得られた塗布液をスピンコート法
により、２００ｒｐｍ、９０ｓｅｃの条件で１０ｃｍ角
のコーニングガラス上に塗布した。この塗布液を得た後
のプロセスは実施例１と同様に行われる。結果として、
得られる導電膜は、比抵抗値９.３×１０-3Ωｃｍであ
り、１０-4Ωｃｍオーダーの値が得られない（表１，参
照）。Comparative Example 2 The sol obtained in Example 1 was used alone as a coating liquid. The obtained coating liquid was applied on a 10 cm square corning glass by spin coating at 200 rpm and 90 sec. The process after obtaining this coating liquid is performed in the same manner as in Example 1. as a result,
The obtained conductive film has a specific resistance of 9.3 × 10 −3 Ωcm, and a value on the order of 10 −4 Ωcm cannot be obtained (see Table 1).
【００２３】（比較例３）実施例１で得られたゾル液と
ＩＴＯ微粒子分散液（平均粒径２０ｎｍ、固形分濃度１
０％、三菱マテリアル製）を超微粒子分散液／ゾル液＝
９／１の比で混合して塗布液を得た。この塗布液を得た
後のプロセスは実施例１と同様に行われる。結果とし
て、得られる導電膜は、比抵抗値６.５×１０-3Ωｃｍ
であり、１０-4Ωｃｍオーダーの値が得られない（表
１，参照）。(Comparative Example 3) The sol liquid obtained in Example 1 and a dispersion liquid of ITO fine particles (average particle diameter: 20 nm, solid content concentration: 1)
0%, manufactured by Mitsubishi Materials Corporation)
The mixture was mixed at a ratio of 9/1 to obtain a coating solution. The process after obtaining this coating liquid is performed in the same manner as in Example 1. As a result, the resulting conductive film has a specific resistance value of 6.5 × 10 −3 Ωcm.
And a value on the order of 10 −4 Ωcm cannot be obtained (see Table 1).
【００２４】[0024]
【表１】 [Table 1]
【００２５】本発明の透明導電膜はいずれも１０-4Ωｃ
ｍオーダーの比抵抗を有しており、従来法の透明導電膜
と比較して明らかに低抵抗である。実施例１〜４と比較
例１の比較よりバインダ樹脂として、導電性ゾル−ゲル
膜を使用することは低抵抗化に効果があることがわか
る。比較例２よりゾル−ゲル膜単独では低抵抗化が不十
分であることがわかる。実施例１と比較例３の比較よ
り、微粒子の粒径を小さくすることで低抵抗化に大きな
効果がでることがわかった。Each of the transparent conductive films of the present invention is 10 -4 Ωc.
It has a specific resistance of the order of m, and is clearly lower than the conventional transparent conductive film. From the comparison between Examples 1 to 4 and Comparative Example 1, it can be seen that the use of a conductive sol-gel film as the binder resin is effective in lowering the resistance. Comparative Example 2 shows that the use of the sol-gel film alone is insufficient to reduce the resistance. From a comparison between Example 1 and Comparative Example 3, it was found that reducing the particle size of the fine particles had a significant effect on lowering the resistance.
【００２６】[0026]
請求項１，２に対応する効果：導電性バインダを用いる
ことでキャリアが消滅しにくくなり、キャリア移動度が
向上し、また、導電性バインダ自体、キャリアを多く保
有しているのでキャリア濃度も増加することから、低抵
抗率を得ることができる。また、導電性微粒子を粒径を
１０ｎｍ以下とし、その微粒子のバインダ樹脂を導電性
ゾル−ゲル膜とすることで、光の透過率が高く、光の吸
収ロスも少なく、かつ、微粒子に起因する表面凹凸もあ
り、光散乱による光閉じ込め効果をもつことになり、光
素子に適した導電膜が得られる。さらに、塗布という簡
単な方法で膜が形成されることから導電性，可視透過性
に優れた透明導電膜が低コストで容易に作製できること
になる。Effects corresponding to the first and second aspects: The use of the conductive binder makes it difficult for carriers to disappear, improves the carrier mobility, and increases the carrier concentration because the conductive binder itself has many carriers. Therefore, a low resistivity can be obtained. In addition, the conductive fine particles have a particle size of 10 nm or less, and the binder resin of the fine particles is a conductive sol-gel film, so that light transmittance is high, light absorption loss is small, and the fine particles are caused by the fine particles. There is also a surface unevenness, which has a light confinement effect by light scattering, and a conductive film suitable for an optical element can be obtained. Further, since a film is formed by a simple method of coating, a transparent conductive film having excellent conductivity and visible transmittance can be easily manufactured at low cost.
【００２７】請求項３，４に対応する効果：請求項１お
よび２の効果に加えて、導電性バインダの組成液として
１０-2〜１０-4Ωｃｍ抵抗率のものを用いることによ
り、導電性微粒子の特性を引き出すことを可能とする条
件付けをすることができ、かかる数値範囲を実現するた
めの組成物を具体的に提示することにより実施を可能と
する。Effects corresponding to the third and fourth aspects: In addition to the effects of the first and second aspects, the use of a conductive binder composition liquid having a resistivity of 10 −2 to 10 −4 Ωcm makes it possible to obtain conductive properties. Conditioning can be performed to enable the characteristics of the fine particles to be extracted, and the present invention can be implemented by specifically presenting a composition for achieving such a numerical range.
【００２８】請求項５，６に対応する効果：請求項１な
いし４の効果に加えて、粒径が１０ｎｍ以下の導電性微
粒子が持つ特性として実現可能な最も低い範囲の抵抗率
を限定するもので、優れた導電性をもつ膜が提供され、
かかる数値範囲を実現するための組成物を具体的に提示
することにより実施を可能とする。Effects corresponding to the fifth and sixth aspects: In addition to the effects of the first to fourth aspects, the present invention limits the lowest range of resistivity that can be realized as the characteristics of the conductive fine particles having a particle size of 10 nm or less. In, a film with excellent conductivity is provided,
Implementation is possible by specifically presenting a composition for realizing such a numerical range.
【００２９】請求項７に対応する効果：請求項１〜７の
効果に加えて、ヘイズ率が３〜１０％と低い場合には、
液晶素子、その他、電子デバイス用の電極として用い
る。また、微粒子を使用することによる光閉じ込め効果
により得られる高いヘイズ率１０〜３０％の場合に、太
陽電池として応用でき、太陽電池の変換効率向上に役立
つ。Effects corresponding to claim 7: In addition to the effects of claims 1 to 7, when the haze ratio is as low as 3 to 10%,
Used as electrodes for liquid crystal elements and other electronic devices. In addition, when the haze ratio is 10 to 30%, which is high due to the light confinement effect of using fine particles, it can be applied as a solar cell, which helps to improve the conversion efficiency of the solar cell.
Claims (7)
導電性微粒子を含有する導電性塗料を基体に塗布し、乾
燥することにより光透過性薄膜を形成してなる透明導電
膜。1. A transparent conductive film formed by applying a conductive paint containing conductive fine particles dispersed in a composition liquid of a conductive binder to a substrate, followed by drying to form a light-transmitting thin film.
記導電性微粒子の粒径が１０ｎｍ以下であることを特徴
としてなる透明導電膜。2. The transparent conductive film according to claim 1, wherein said conductive fine particles have a particle size of 10 nm or less.
て、前記導電性バインダの組成液がゾル状を呈し、１０
-2〜１０-4Ωｃｍの抵抗率を有するものであることを特
徴としてなる透明導電膜。3. The transparent conductive film according to claim 1, wherein the composition liquid of the conductive binder has a sol shape,
A transparent conductive film having a resistivity of -2 to 10 -4 Ωcm.
導電膜において、前記導電性バインダが酸化インジウム
錫、アンチモンドープ酸化錫、フッ素ドープ酸化錫、ア
ルミニウムドープ酸化亜鉛あるいはガリウムドープ酸化
亜鉛を含む組成であることを特徴としてなる透明導電
膜。4. The transparent conductive film according to claim 1, wherein the conductive binder contains indium tin oxide, antimony-doped tin oxide, fluorine-doped tin oxide, aluminum-doped zinc oxide, or gallium-doped zinc oxide. A transparent conductive film having a composition.
導電膜において、前記導電性微粒子が１０-3〜１０-4Ω
ｃｍの抵抗率を有するものであることを特徴としてなる
透明導電膜。5. The transparent conductive film according to claim 1, wherein the conductive fine particles are 10 -3 to 10 -4 Ω.
A transparent conductive film having a resistivity of about 0.5 cm.
電膜において、前記導電性微粒子が酸化インジウム錫、
アンチモンドープ酸化錫、フッ素ドープ酸化錫、アルミ
ニウムドープ酸化亜鉛あるいはガリウムドープ酸化亜鉛
であることを特徴としてなる透明導電膜。6. The transparent conductive film according to claim 1, wherein the conductive fine particles are indium tin oxide,
A transparent conductive film characterized by being antimony-doped tin oxide, fluorine-doped tin oxide, aluminum-doped zinc oxide or gallium-doped zinc oxide.
電膜において、前記透明導電膜が３〜３０％のヘイズ率
を有するものであることを特徴としてなる透明導電膜。7. The transparent conductive film according to claim 1, wherein said transparent conductive film has a haze ratio of 3 to 30%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8287597A JPH10283847A (en) | 1997-04-01 | 1997-04-01 | Transparent conductive film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8287597A JPH10283847A (en) | 1997-04-01 | 1997-04-01 | Transparent conductive film |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH10283847A true JPH10283847A (en) | 1998-10-23 |
Family
ID=13786473
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8287597A Pending JPH10283847A (en) | 1997-04-01 | 1997-04-01 | Transparent conductive film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH10283847A (en) |
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|---|---|---|---|---|
| JP2001332130A (en) * | 2000-05-19 | 2001-11-30 | Tdk Corp | Functional film |
| US6420647B1 (en) * | 1998-11-06 | 2002-07-16 | Pacific Solar Pty Limited | Texturing of glass by SiO2 film |
| US6759645B2 (en) | 2000-02-04 | 2004-07-06 | Kaneka Corporation | Hybrid thin-film photoelectric transducer and transparent laminate for the transducer |
| JP2004311704A (en) * | 2003-04-07 | 2004-11-04 | Kanegafuchi Chem Ind Co Ltd | Substrate for thin film photoelectric converter and thin film photoelectric converter using the same |
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1997
- 1997-04-01 JP JP8287597A patent/JPH10283847A/en active Pending
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6420647B1 (en) * | 1998-11-06 | 2002-07-16 | Pacific Solar Pty Limited | Texturing of glass by SiO2 film |
| US6759645B2 (en) | 2000-02-04 | 2004-07-06 | Kaneka Corporation | Hybrid thin-film photoelectric transducer and transparent laminate for the transducer |
| JP2001332130A (en) * | 2000-05-19 | 2001-11-30 | Tdk Corp | Functional film |
| JP2004311704A (en) * | 2003-04-07 | 2004-11-04 | Kanegafuchi Chem Ind Co Ltd | Substrate for thin film photoelectric converter and thin film photoelectric converter using the same |
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| JPWO2005050675A1 (en) * | 2003-11-18 | 2007-12-06 | 日本板硝子株式会社 | Transparent substrate with transparent conductive film, method for producing the same, and photoelectric conversion element including the substrate |
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| JP4542039B2 (en) * | 2003-11-18 | 2010-09-08 | 日本板硝子株式会社 | Transparent substrate with transparent conductive film, method for producing the same, and photoelectric conversion element including the substrate |
| JP2010262931A (en) * | 2003-11-18 | 2010-11-18 | Nippon Sheet Glass Co Ltd | Transparent base with transparent conductive film, method of manufacturing same, and photoelectric converter comprising such base |
| WO2005050675A1 (en) * | 2003-11-18 | 2005-06-02 | Nippon Sheet Glass Company, Limited | Transparent base with transparent conductive film, method for producing same, and photoelectric converter comprising such base |
| JP2009296000A (en) * | 2004-01-16 | 2009-12-17 | Semiconductor Energy Lab Co Ltd | Semiconductor device manufacturing method |
| US8293457B2 (en) | 2004-01-16 | 2012-10-23 | Semiconductor Energy Laboratory Co., Ltd. | Substrate having film pattern and manufacturing method of the same, manufacturing method of semiconductor device, liquid crystal television, and EL television |
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| JP2007280910A (en) * | 2006-04-03 | 2007-10-25 | Ind Technol Res Inst | Aluminum-added zinc oxide transparent conductive film and its manufacturing method containing metallic nano particles |
| JP2011119273A (en) * | 2006-04-03 | 2011-06-16 | Ind Technol Res Inst | Method of manufacturing aluminum-added zinc oxide transparent conductive film containing metal nanoparticle |
| JP2009266500A (en) * | 2008-04-23 | 2009-11-12 | Sumitomo Metal Mining Co Ltd | Transparent conductive film, transparent conductive substrate and device using the same, and method of manufacturing transparent conductive film |
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