JP4683525B2 - Transparent conductive film and transparent conductive film forming material - Google Patents
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本発明は、透明導電膜、及び透明導電膜形成材料に関し、より詳細には、インジウム化合物を含有する透明導電膜形成材料を用いて、化学的熱分解法により成膜した、Ｘ線回折パターンにおいて、（２２２）面に主配向を有する透明導電膜に関する。 The present invention relates to a transparent conductive film and a transparent conductive film forming material, and more specifically, in an X-ray diffraction pattern formed by a chemical pyrolysis method using a transparent conductive film forming material containing an indium compound. , (222) plane, a transparent conductive film having a main orientation.
酸化インジウムを主成分とする透明導電膜は、透明な導電性材料として有用であり、その優れた透明性と導電性を利用して、液晶ディスプレイ、エレクトロルミネッセンスディスプレイ、面発熱体、タッチパネル電極、太陽電池等に広く利用されている。 A transparent conductive film containing indium oxide as a main component is useful as a transparent conductive material. By utilizing its excellent transparency and conductivity, a liquid crystal display, an electroluminescence display, a surface heating element, a touch panel electrode, a solar Widely used for batteries.
透明導電膜は、このように広い分野で利用されるものであるため、使用目的によって種々のシート抵抗値、比抵抗値及び透明度を有するものが要求される。例えば、フラットパネルディスプレイ用の透明導電膜の場合、低抵抗かつ高透過率の膜であることが要求される。 Since the transparent conductive film is used in such a wide field, those having various sheet resistance values, specific resistance values, and transparency are required depending on the purpose of use. For example, in the case of a transparent conductive film for a flat panel display, it is required to be a film having low resistance and high transmittance.
上記のような所望の抵抗値を有する透明導電膜を形成する方法としては、例えば、スズがドープされた酸化インジウム膜（ＩＴＯ膜）を形成する場合に、パイロゾルプロセス法を用いると膜中のスズとインジウムの元素比がほぼ一定で、均一に分散した透明導電膜を得ることができることが知られている（特許文献１〜３）。 As a method for forming a transparent conductive film having a desired resistance value as described above, for example, when a tin-doped indium oxide film (ITO film) is formed, a pyrosol process method is used. It is known that a transparent conductive film in which the element ratio of tin and indium is substantially constant and uniformly dispersed can be obtained (Patent Documents 1 to 3).
しかしながら、これまで開示されているパイロゾルプロセス法により得られたＩＴＯ膜は、スパッタ法により得られたＩＴＯ膜に比べて、膜中元素の均一性には優れるものの、比抵抗値が劣るため、より導電性に優れた透明導電膜を得るためには劣っていた。また、パイロゾルプロセス法により成膜する場合は、成膜に長時間を要していた。本発明の課題は、透明性、膜中元素の均一性、低比抵抗、及び成膜性に優れた透明導電膜を提供することにある。 However, since the ITO film obtained by the pyrosol process method disclosed so far is superior in the uniformity of elements in the film as compared with the ITO film obtained by the sputtering method, the specific resistance value is inferior, It was inferior to obtain a transparent conductive film with more excellent conductivity. In addition, when forming a film by the pyrosol process, it takes a long time to form the film. An object of the present invention is to provide a transparent conductive film excellent in transparency, uniformity of elements in the film, low specific resistance, and film formability.
本発明者らは、化学的熱分解法により得られる透明導電膜の低比抵抗化、及び成膜速度の改善を目指して検討した結果、従来透明導電膜を形成する際に用いていた透明導電膜形成材料中の主成分であるトリス（アセチルアセトナート）インジウムの代わりに、トリス（２，６−ジメチル−３，５−ヘプタンジオネート）インジウム、又はトリス（ジピバロイルメタナート）インジウムを用いると、驚くべきことに、従来化学的熱分解法により得られていた透明導電膜とは結晶の配向性が異なる透明導電膜、すなわち、Ｘ線回折パターンにおいて、（４００）面ではなく、（２２２）面に主配向を有する透明導電膜が得られることを見い出し、本発明を完成するに至った。 As a result of studies aimed at lowering the specific resistance of a transparent conductive film obtained by a chemical pyrolysis method and improving the film formation rate, the present inventors have found that the transparent conductive film conventionally used for forming a transparent conductive film has been used. Instead of tris (acetylacetonate) indium as a main component in the film forming material, tris (2,6-dimethyl-3,5-heptanedionate) indium or tris (dipivaloylmethanato) indium is used. Surprisingly, when used, the transparent conductive film having a different crystal orientation from the transparent conductive film obtained by the conventional chemical pyrolysis method, that is, in the X-ray diffraction pattern, is not (400) plane, 222) It was found that a transparent conductive film having a main orientation on the surface was obtained, and the present invention was completed.
すなわち本発明は、
（１）インジウム化合物を含有する透明導電膜形成材料を用いて、化学的熱分解法により成膜した、Ｘ線回折パターンにおいて、（２２２）面に主配向を有することを特徴とする透明導電膜や、
（２）インジウム化合物が、式（Ｉ）
That is, the present invention
(1) using a transparent conductive film forming material containing an indium compound, was deposited by chemical pyrolysis method, the X-ray diffraction pattern, a transparent conductive film and having a main orientation to (222) plane Or
(2) The indium compound has the formula (I)
［式中、Ｒ1は、エチル基、イソプロピル基、又はｔ−ブチル基を表し、Ｒ2は、炭素数１〜１０のアルキル基、又はフェニル基を表す。］で表されるインジウム化合物であることを特徴とする（１）記載の透明導電膜や、
（３）式（Ｉ）で表されるインジウム化合物が、トリス（２，６−ジメチル−３，５−ヘプタンジオネート）インジウム、又はトリス（ジピバロイルメタナート）インジウムであることを特徴とする（２）記載の透明導電膜や、
（４）インジウム化合物を含有する透明導電膜形成材料が、さらにスズ化合物を含有する透明導電膜形成材料であることを特徴とする（１）〜（３）のいずれか記載の透明導電膜や、
（５）スズ化合物が、式（II）
[Wherein, R 1 represents an ethyl group, an isopropyl group, or a t-butyl group, and R 2 represents an alkyl group having 1 to 10 carbon atoms or a phenyl group. Characterized in that is an indium compound represented by (1) and a transparent conductive film according,
(3) The indium compound represented by the formula (I) is tris (2,6-dimethyl-3,5-heptanedionate) indium or tris (dipivaloylmethanate) indium. to (2) and a transparent conductive film according,
(4) forming a transparent conductive film material containing indium compound, and a transparent conductive film according to any one of features (1) to (3) that is a transparent conductive film forming material further contains a tin compound,
(5) The tin compound has the formula (II)
［式中、Ｒ3は、炭素数１〜１０のアルキル基を表し、Ｒ4は、炭素数１〜１０のアルキル基、又は炭素数１〜１０のアシル基を表す。］で表されるスズ化合物であることを特徴とする（４）記載の透明導電膜や、
（６）式（II）で表されるスズ化合物が、ジ−ｎ−ブチルスズジアセテートであることを特徴とする（５）記載の透明導電膜や、
（７）スズ化合物が、質量比で、インジウム化合物１に対して０．００１〜０．５含有されていることを特徴とする（４）〜（６）のいずれか記載の透明導電膜や、
（８）化学的熱分解法が、パイロゾルプロセス法であることを特徴とする（１）〜（７）いずれか記載の透明導電膜に関する。
[Wherein, R 3 represents an alkyl group having 1 to 10 carbon atoms, and R 4 represents an alkyl group having 1 to 10 carbon atoms or an acyl group having 1 to 10 carbon atoms. Characterized in that is a tin compound represented by (4) and a transparent conductive film according,
Tin compounds represented by (6) formula (II) is, and a transparent conductive film, wherein (5), wherein it is a di -n- butyl tin diacetate,
(7) a tin compound, the mass ratio, and a transparent conductive film according to any one of characterized in that it is 0.001 to 0.5 containing relative indium compound 1 (4) to (6),
(8) Chemical pyrogenic, characterized in that a pyro sol process method (1) to (7) about the transparent conductive film according to any one.
また、本発明は、
（９）インジウム化合物を含有し、化学的熱分解法により成膜した場合、Ｘ線回折パターンにおいて、（２２２）面に主配向を有する透明導電膜を形成することができることを特徴とする透明導電膜形成材料や、
（１０）インジウム化合物が、式（Ｉ）
The present invention also provides:
(9) A transparent conductive film containing an indium compound and capable of forming a transparent conductive film having a main orientation on the (222) plane in an X-ray diffraction pattern when formed by a chemical pyrolysis method and film-forming materials,
(10) The indium compound has the formula (I)
［式中、Ｒ1は、エチル基、イソプロピル基、又はｔ−ブチル基を表し、Ｒ2は、炭素数１〜１０のアルキル基、又はフェニル基を表す。］で表されるインジウム化合物を含有することを特徴とする（９）記載の透明導電膜形成材料や、
（１１）式（Ｉ）で表されるインジウム化合物が、トリス（２，６−ジメチル−３，５−ヘプタンジオネート）インジウム、又はトリス（ジピバロイルメタナート）インジウムであることを特徴とする（１０）記載の透明導電膜形成材料や、
（１２）透明導電膜形成材料が、さらにスズ化合物を含有する透明導電膜形成材料であることを特徴とする（９）〜（１１）のいずれか記載の透明導電膜形成材料や、
（１３）スズ化合物が、式（II）
[Wherein, R 1 represents an ethyl group, an isopropyl group, or a t-butyl group, and R 2 represents an alkyl group having 1 to 10 carbon atoms or a phenyl group. Characterized in that it contains an indium compound represented by (9) and a transparent conductive film formed materials according,
(11) The indium compound represented by the formula (I) is tris (2,6-dimethyl-3,5-heptanedionate) indium or tris (dipivaloylmethanato) indium. to (10) transparent conductive film forming materials described and,
(12) forming a transparent conductive film material, and a transparent conductive film formed materials according to any one of features (9) to (11) that is a transparent conductive film forming material further contains a tin compound,
(13) The tin compound has the formula (II)
［式中、Ｒ3は、炭素数１〜１０のアルキル基を表し、Ｒ4は、炭素数１〜１０のアルキル基、又は炭素数１〜１０のアシル基を表す。］で表されるスズ化合物であることを特徴とする（１２）記載の透明導電膜形成材料や、
（１４）式（II）で表されるスズ化合物が、ジ−ｎ−ブチルスズジアセテートであることを特徴とする（１３）記載の透明導電膜形成材料や、
（１５）スズ化合物が、質量比で、インジウム化合物１に対して０．００１〜０．５含有されていることを特徴とする（１２）〜（１４）のいずれか記載の透明導電膜形成材料や、
（１６）化学的熱分解法が、パイロゾルプロセス法であることを特徴とする（９）〜（１５）のいずれか記載の透明導電膜形成材料に関する。
[Wherein, R 3 represents an alkyl group having 1 to 10 carbon atoms, and R 4 represents an alkyl group having 1 to 10 carbon atoms or an acyl group having 1 to 10 carbon atoms. Characterized in that is a tin compound represented by (12) and a transparent conductive film formed materials according,
(14) a tin compound represented by the formula (II) is, and a transparent conductive film formed materials of which (13), wherein characterized in that the di -n- butyl tin diacetate,
(15) Tin compound, the mass ratio, characterized in that it is 0.001 to 0.5 containing relative indium compound 1 (12) transparent conductive film forming material according to any one of - (14) Fees ,
(16) Chemical pyrogenic, characterized in that a pyro sol process method (9) about the transparent conductive film forming materials according to any one of - (15).
本発明の化学的熱分解法により成膜した、Ｘ線回折パターンにおいて、（２２２）面に主配向を有する透明導電膜は、従来化学的熱分解法により得られていた、Ｘ線回折パターンにおいて、（４００）面に主配向を有する透明導電膜と比較して、低比抵抗であり、かつ結晶性に非常に優れているので、高導電率化及び成膜時間を大幅に短縮することができる優れた透明導電膜である。 In the X-ray diffraction pattern formed by the chemical pyrolysis method of the present invention, the transparent conductive film having the main orientation on the (222) plane is the same as the conventional X-ray diffraction pattern obtained by the chemical pyrolysis method. Compared with a transparent conductive film having a main orientation on the (400) plane, it has a low specific resistance and is very excellent in crystallinity, so that the increase in conductivity and the film formation time can be greatly shortened. It is an excellent transparent conductive film.
本発明の透明導電膜は、インジウム化合物を含有する透明導電膜形成材料を用いて、化学的熱分解法により成膜した透明導電膜であって、Ｘ線回折パターンにおいて、（２２２）面に主配向を有する透明導電膜であれば特に制限されるものではなく、また、本発明の透明導電膜形成材料としては、インジウム化合物を含有し、化学的熱分解法により成膜した場合、Ｘ線回折パターンにおいて、（２２２）面に主配向を有する透明導電膜を形成することができるものであればどのようなものでもよく、ここで、（２２２）面に主配向を有するとは、その他の配向、例えば（４００）、（２１１）、（４４０）等に配向を有してもよいが、θ／２θ法によるＸ線回折の一番強いピーク強度が（２２２）面にあることをいい、（２２２）／（４００）比が１．５以上であることが好ましい。 The transparent conductive film of the present invention is a transparent conductive film formed by a chemical pyrolysis method using a transparent conductive film forming material containing an indium compound, and is mainly formed on the (222) plane in the X-ray diffraction pattern. The transparent conductive film having an orientation is not particularly limited, and the transparent conductive film-forming material of the present invention contains an indium compound and is formed by a chemical pyrolysis method. Any pattern can be used as long as it can form a transparent conductive film having a main orientation on the (222) plane. Here, the main orientation on the (222) plane means any other orientation. For example, it may have an orientation at (400), (211), (440), etc., but it means that the strongest peak intensity of X-ray diffraction by the θ / 2θ method is on the (222) plane, 222) / (400) The ratio is preferably 1.5 or more.
上記インジウム化合物としては、インジウムを分子内に有する化合物であれば特に制限されないが、熱分解して酸化インジウムとなるものが好ましく、前記式（Ｉ）で表されるインジウム化合物であることがより好ましい。前記式（Ｉ）中、Ｒ1は、エチル基、イソプロピル基、又はｔ−ブチル基を表し、Ｒ2は、メチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、ｔ−ブチル基、ｎ−ペンチル基、ｎ−ヘキシル基等の炭素数１〜１０のアルキル基；又はフェニル基を表す。前記式（Ｉ）で表されるインジウム化合物のうち、特にトリス（２，６−ジメチル−３，５−ヘプタンジオネート）インジウム、又はトリス（ジピバロイルメタナート）インジウムが好ましい。 The indium compound is not particularly limited as long as it is a compound having indium in the molecule, but is preferably an indium compound that is thermally decomposed to become indium oxide, and more preferably the indium compound represented by the formula (I). . In the formula (I), R 1 represents an ethyl group, an isopropyl group, or a t-butyl group, and R 2 represents a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a t-butyl group, An alkyl group having 1 to 10 carbon atoms such as a butyl group, an n-pentyl group, and an n-hexyl group; or a phenyl group. Of the indium compounds represented by the formula (I), tris (2,6-dimethyl-3,5-heptanedionate) indium or tris (dipivaloylmethanato) indium is particularly preferable.
また、本発明の透明導電膜は、インジウム化合物を主成分として含有する透明導電膜であるが、化学的熱分解法により成膜した、Ｘ線回折パターンにおいて、（２２２）面に主配向を有する透明導電膜であれば、インジウム化合物の他に第２成分として、スズ化合物を含有したＩＴＯ膜、亜鉛化合物を含有したＩＺＯ膜等であってもよい。これらの中でも、成膜した際の透明導電膜の比抵抗値が低くなり、導電率が高い透明導電膜が得られる観点からスズ化合物を含有したＩＴＯ膜が好ましい。従って、本発明の透明導電膜形成材料は、インジウム化合物の他にスズ化合物を含有する透明導電膜形成材料であることが好ましい。 The transparent conductive film of the present invention is a transparent conductive film containing an indium compound as a main component, and has a main orientation on the (222) plane in an X-ray diffraction pattern formed by chemical pyrolysis. As long as it is a transparent conductive film, an ITO film containing a tin compound or an IZO film containing a zinc compound may be used as the second component in addition to the indium compound. Among these, an ITO film containing a tin compound is preferable from the viewpoint of obtaining a transparent conductive film having a low resistivity and a high conductivity when the film is formed. Therefore, the transparent conductive film forming material of the present invention is preferably a transparent conductive film forming material containing a tin compound in addition to the indium compound.
スズ化合物としては、特に制限はないが、熱分解して酸化第２スズとなるものが好ましく、例えば、前記式（II）で表されるスズ化合物、塩化第２スズ、ジメチルスズジクロライド、ジブチルスズジクロライド、テトラブチルスズ、スタニアスオクトエート（Ｓｎ（ＯＣＯＣ7Ｈ15）2）、ジブチルスズマレエート、ジブチルスズビスアセチルアセトナート、ジブチルスズジアセテート等を例示することができる。これらのうち、前記式（II）で表されるスズ化合物であるのが好ましい。式（II）中、Ｒ3は、メチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、ｔ−ブチル基、ｎ−ペンチル基、ｎ−ヘキシル基等の炭素数１〜１０のアルキル基を表し、Ｒ4は、メチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、ｔ−ブチル基、ｎ−ペンチル基、ｎ−ヘキシル基等の炭素数１〜１０のアルキル基；アセチル基、プロピオニル基等の炭素数１〜１０のアシル基を表す。前記式（II）で表されるスズ化合物のうち、特にジ−ｎ−ブチルスズジアセトナートであるのが好ましい。 Although there is no restriction | limiting in particular as a tin compound, The thing which thermally decomposes and becomes a stannic oxide is preferable, for example, the tin compound represented by the said Formula (II), stannic chloride, dimethyltin dichloride, dibutyltin dichloride , Tetrabutyltin, stannia octoate (Sn (OCOC 7 H 15 ) 2 ), dibutyltin maleate, dibutyltin bisacetylacetonate, dibutyltin diacetate, and the like. Of these, tin compounds represented by the formula (II) are preferable. In the formula (II), R 3 has 1 to 10 carbon atoms such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, t-butyl group, n-pentyl group, and n-hexyl group. R 4 is a C 1-10 carbon atom such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a t-butyl group, an n-pentyl group, or an n-hexyl group. An alkyl group of 1 to 10 carbon atoms such as an acetyl group and a propionyl group. Of the tin compounds represented by the formula (II), di-n-butyltin diacetate is particularly preferable.
また、透明導電膜形成材料中のインジウム化合物とスズ化合物の配合割合は、通常、スズ化合物が、質量比で、インジウム化合物１に対して０．００１〜０．５であり、好ましくは、０．０１〜０．４、より好ましくは、０．０２〜０．３の割合である。 Moreover, the compounding ratio of the indium compound and the tin compound in the transparent conductive film forming material is usually 0.001 to 0.5 with respect to the indium compound 1 in terms of the mass ratio of the tin compound, and is preferably 0.00. The ratio is from 01 to 0.4, and more preferably from 0.02 to 0.3.
また、インジウム化合物とスズ化合物とを含有する透明導電膜形成材料を用いる場合は、成膜した際の透明導電膜中のインジウムとスズが均一に拡散されているほうが、均一な導電性及び透明性を保有できる点で好ましい。このような透明導電膜を形成するためには、透明導電膜形成材料に含有されるインジウム化合物とスズ化合物の熱分解温度がより近い方が、両者が均一に拡散して均一な膜質を形成することができると考えられる。 In addition, when a transparent conductive film forming material containing an indium compound and a tin compound is used, it is more uniform conductivity and transparency when indium and tin in the transparent conductive film are uniformly diffused when the film is formed. Is preferable in that it can be retained. In order to form such a transparent conductive film, the closer the thermal decomposition temperatures of the indium compound and the tin compound contained in the transparent conductive film forming material, the more uniformly diffuses to form a uniform film quality. It is considered possible.
また、透明導電膜形成材料において、スズ化合物を含有する場合は、さらに第３成分として、Ｍｇ、Ｃａ、Ｓｒ、Ｂａ等の周期律表第２族元素、Ｓｃ、Ｙ等の第３族元素、Ｌａ、Ｃｅ、Ｎｄ、Ｓｍ、Ｇｄ等のランタノイド、Ｔｉ、Ｚｒ、Ｈｆ等の第４族元素、Ｖ、Ｎｂ、Ｔａ等の第５族元素、Ｃｒ、Ｍｏ、Ｗ等の第６族元素、Ｍｎ等の第７族元素、Ｃｏ等の第９族元素、Ｎｉ、Ｐｄ、Ｐｔ等の第１０族元素、Ｃｕ、Ａｇ等の第１１族元素、Ｚｎ、Ｃｄ等の第１２族元素、Ｂ、Ａｌ、Ｇａ等の第１３族元素、Ｓｉ、Ｇｅ、Ｐｂ等の第１４族元素、Ｐ、Ａｓ、Ｓｂ等の第１５族元素、Ｓｅ、Ｔｅ等の第１６族元素等からなる単体若しくはこれらの化合物を含有することも好ましい。これらの元素の添加割合は、インジウムに対して、０．０５〜２０原子％程度が好ましく、添加元素によって添加割合は異なり、目的とする抵抗値にあった元素及び添加量を適宜選定することができる。 Further, in the transparent conductive film forming material, when a tin compound is contained, as a third component, a periodic table group 2 element such as Mg, Ca, Sr, Ba, a group 3 element such as Sc, Y, Lanthanoids such as La, Ce, Nd, Sm and Gd, Group 4 elements such as Ti, Zr and Hf, Group 5 elements such as V, Nb and Ta, Group 6 elements such as Cr, Mo and W, Mn Group 9 elements such as Co, Group 9 elements such as Co, Group 10 elements such as Ni, Pd and Pt, Group 11 elements such as Cu and Ag, Group 12 elements such as Zn and Cd, B, Al , Ga, and other group 13 elements, Si, Ge, Pb and other group 14 elements, P, As, Sb and other group 15 elements, Se, Te and other group 16 elements, etc. It is also preferable to contain. The addition ratio of these elements is preferably about 0.05 to 20 atomic% with respect to indium. The addition ratio varies depending on the addition element, and the element and the addition amount that meet the target resistance value can be selected as appropriate. it can.
上記透明導電膜形成材料は、必要に応じて有機溶媒に溶解させた透明導電膜形成液として用いることもできる。かかる有機溶媒としては、アセチルアセトン、アセトン、メチルイソブチルケトン、ジエチルケトン、２，６−ジメチル−３，５−ヘプタンジオン、ジピバロイルメタン等のケトン系溶媒；メタノール、エタノール、プロパノール、イソプロパノール、ブタノール等のアルコール系溶媒；酢酸エチル、酢酸ブチル等のエステル系溶媒、メチルセルソルブ、テトラヒドロフラン等のエーテル系溶媒；ベンゼン、トルエン、キシレン等の芳香族炭化水素類；ヘキサン、ヘプタン、オクタン、シクロヘキサン等の脂肪族炭化水素類などを挙げることができる。 The said transparent conductive film formation material can also be used as a transparent conductive film formation liquid dissolved in the organic solvent as needed. Examples of the organic solvent include ketone solvents such as acetylacetone, acetone, methyl isobutyl ketone, diethyl ketone, 2,6-dimethyl-3,5-heptanedione, and dipivaloylmethane; methanol, ethanol, propanol, isopropanol, butanol Alcohol solvents such as ethyl acetate, ester solvents such as butyl acetate, ether solvents such as methyl cellosolve, tetrahydrofuran; aromatic hydrocarbons such as benzene, toluene, xylene; hexane, heptane, octane, cyclohexane, etc. Examples thereof include aliphatic hydrocarbons.
これらの有機溶媒の種類及び添加量は、透明導電膜のシート抵抗値の設定値等に依存し、透明導電膜の種類、透明導電膜の膜厚、用いる有機溶媒の種類、加熱温度、加熱時間等により適宜定めることができる。例えば、他の条件を同一にして、より熱分解しやすい有機溶媒を多量に添加することにより、シート抵抗値をより低くすることができる。以上のようにして、用いる有機溶媒の種類、添加量及び加熱温度を適宜選択・設定することにより、所望のシート抵抗値を有する透明導電膜を得ることができる。 The type and amount of these organic solvents depend on the set value of the sheet resistance value of the transparent conductive film, etc., and the type of transparent conductive film, the film thickness of the transparent conductive film, the type of organic solvent used, the heating temperature, and the heating time. Etc. can be determined as appropriate. For example, the sheet resistance value can be further reduced by adding a large amount of an organic solvent that is more easily pyrolyzed under the same conditions. As described above, a transparent conductive film having a desired sheet resistance value can be obtained by appropriately selecting and setting the type, addition amount, and heating temperature of the organic solvent to be used.
上記化学的熱分解法としては、透明導電膜形成材料に含有されるインジウム化合物等を、熱により分解させて基体又は中間膜上に堆積させる方法や、透明導電膜形成材料をコーティングした後、インジウム化合物等を熱により分解させて基体又は中間膜上に固定する方法を挙げることができ、例えば、スプレー法、ディップコーティング法、スピンコート法、ＬＢ法、ゾル−ゲル法、液相エピタキシー法、熱ＣＶＤ法、プラズマＣＶＤ法、ＭＯＣＶＤ法、パイロゾルプロセス法（超音波霧化による常圧ＣＶＤ法）、ＳＰＤ法、Ｃａｔ−ＣＶＤ法等のＣＶＤ法（chemical vapor deposition）等が挙げられ、これらの中でもパイロゾルプロセス法を用いることが特に好ましい。パイロゾルプロセス法を用いることにより、より均一な膜質を有する透明導電膜を製造することができる。 Examples of the chemical thermal decomposition method include a method in which an indium compound or the like contained in a transparent conductive film forming material is decomposed by heat and deposited on a substrate or an intermediate film, or after coating a transparent conductive film forming material, indium Examples thereof include a method of decomposing a compound or the like by heat and fixing it on a substrate or an intermediate film, for example, spray method, dip coating method, spin coating method, LB method, sol-gel method, liquid phase epitaxy method, heat CVD method, plasma CVD method, MOCVD method, pyrosol process method (atmospheric pressure CVD method by ultrasonic atomization), SPD method, Cat-CVD method and other CVD methods (chemical vapor deposition), etc. It is particularly preferred to use the pyrosol process method. By using the pyrosol process method, a transparent conductive film having a more uniform film quality can be produced.
本発明の透明導電膜は、通常、基体上に成膜するが、このような基体としては、シート状（基板）、ハニカム状、ファイバー状、ビーズ状、発泡状やそれらが集積したもの等であってもよく、透明導電膜形成材料の成分が熱分解を起こす温度で耐熱性を有するものであれば特に制限されるものではないが、例えば、ガラス基板、セラミックス基板、金属基板等を挙げることができる。これらのうち、本発明の透明導電膜を成膜する基体は、ガラス基板を用いるのが好ましい。ガラス基板としては、例えば、ケイ酸ガラス（石英ガラス）、ケイ酸アルカリガラス、ソーダ石灰ガラス、カリ石灰ガラス、鉛ガラス、バリウムガラス、ホウケイ酸ガラス等を挙げることができる。 The transparent conductive film of the present invention is usually formed on a substrate. Examples of such a substrate include a sheet (substrate), a honeycomb, a fiber, a bead, a foam, and an accumulation thereof. There is no particular limitation as long as the component of the transparent conductive film forming material has heat resistance at a temperature causing thermal decomposition, and examples thereof include a glass substrate, a ceramic substrate, and a metal substrate. Can do. Among these, it is preferable to use a glass substrate for the substrate on which the transparent conductive film of the present invention is formed. Examples of the glass substrate include silicate glass (quartz glass), alkali silicate glass, soda lime glass, potash lime glass, lead glass, barium glass, and borosilicate glass.
また、本発明の透明導電膜を基体上に成膜する際に、基体上に中間膜を設けて、中間膜上に本発明の透明導電膜を成膜してもよい。このような中間膜は、一層の膜であってもよく、二層以上の膜であってもよい。かかる中間膜としては、例えば、酸化シリコン膜、有機ポリシラン化合物から形成されるポリシラン膜、ＭｇＦ2膜、ＣａＦ2膜、ＳｉＯ2とＴｉＯ2の複合酸化物膜等を挙げることができる。これらの中間膜は、例えば、基板としてソーダーガラスを用いる場合のＮａイオンの拡散防止の為に形成される。また、透明導電膜と異なる屈折率、好ましくは低屈折率の下地膜を形成することによって、反射防止或いは透明性を向上させることもできる。これらの膜は、一般に知られている成膜方法、例えば、スパッタ法、ＣＶＤ法、スプレー法、ディップ法等により形成することができ、膜厚としては、特に制限されるものではないが、通常２０〜２００ｎｍ程度である。 Further, when the transparent conductive film of the present invention is formed on the substrate, an intermediate film may be provided on the substrate, and the transparent conductive film of the present invention may be formed on the intermediate film. Such an intermediate film may be a single-layer film or a film having two or more layers. Examples of the intermediate film include a silicon oxide film, a polysilane film formed from an organic polysilane compound, an MgF 2 film, a CaF 2 film, and a composite oxide film of SiO 2 and TiO 2 . These intermediate films are formed, for example, for preventing diffusion of Na ions when using soda glass as a substrate. Further, by forming a base film having a refractive index different from that of the transparent conductive film, preferably a low refractive index, antireflection or transparency can be improved. These films can be formed by generally known film formation methods such as sputtering, CVD, spraying, dipping, etc. The film thickness is not particularly limited, but is usually It is about 20 to 200 nm.
また、本発明の透明導電膜を成膜する際に、前記パイロゾルプロセス法を用いる場合には、インジウム化合物等を、有機溶媒に溶解させた透明導電膜形成液を超音波によるアトマイジング法を利用して、粒状の比較的そろった微小な小液滴からなるエアゾルにし、インジウム化合物等が、熱分解を起こして酸化インジウム等を形成し得る温度、例えば、３００〜８００℃の均一な温度に管理した加熱炉内の基体上に供給して、インジウム化合物等を、加熱炉内で気化させ気相状態から基体上で反応させて透明導電膜を形成する。 In addition, when using the pyrosol process method when forming the transparent conductive film of the present invention, an ultrasonic atomizing method is used to form a transparent conductive film forming solution in which an indium compound or the like is dissolved in an organic solvent. It is used to form an aerosol composed of small, relatively uniform droplets, and the indium compound or the like can be thermally decomposed to form indium oxide or the like, for example, a uniform temperature of 300 to 800 ° C. A transparent conductive film is formed by supplying an indium compound or the like to the substrate in the controlled heating furnace and allowing the indium compound or the like to vaporize in the heating furnace and react on the substrate from a gas phase state.
また、本発明の透明導電膜を還元的雰囲気下で処理することで、さらに低抵抗な透明導電膜を得ることができる。 Moreover, the transparent conductive film of further low resistance can be obtained by processing the transparent conductive film of the present invention in a reducing atmosphere.
以下、実施例により本発明をより具体的に説明するが、本発明の技術的範囲はこれらの例示に限定されるものではない。 EXAMPLES Hereinafter, although an Example demonstrates this invention more concretely, the technical scope of this invention is not limited to these illustrations.
［実施例１］
トリス（２，６−ジメチル−３，５−ヘプタンジオネート）インジウム（インジウム化合物）をトルエン（有機溶媒）にモル濃度で０．１ｍｏｌ／Ｌになるように溶解して透明溶液を得た。この溶液にＳｎ／Ｉｎ＝１２質量％となるようにスズ化合物としてジ−ｎ−ブチルスズジアセテートを加えたＩＴＯ膜形成液（透明導電膜形成液）を調製した。このＩＴＯ膜形成液を用いてパイロゾルプロセス法により、ＩＴＯ膜形成液の霧化により、ガラス基板上に５１５℃（成膜温度）で５分間成膜し、無色透明のＩＴＯ膜を有するＩＴＯ膜付ガラス基板（透明導電膜膜付基体）を得た。得られたＩＴＯ膜について、日本電子社製（ＪＤＸ−８０２０、Ｘ−ＲＡＹ ＤＩＦＦＲＡＣＴＯＭＥＴＥＲ）を用いて、θ／２θ法によりＸ線回折測定を行った。測定条件として、ターゲット：Ｃｕ、管電圧：４０ｋＶ、管電流：２０ｍＡで、ステップ角度：０．０２０°、測定時間：０．２０ｓｅｃとした。結果を図１に示す。図１から明らかなように、（２２２）面の配向を示す３０°付近に強いピークが観測された。また、得られた（２２２）面の回折強度は４５５、（４００）面の回折強度は検出されなかった。
[Example 1]
Tris (2,6-dimethyl-3,5-heptanedionate) indium (indium compound) was dissolved in toluene (organic solvent) so as to have a molar concentration of 0.1 mol / L to obtain a transparent solution. An ITO film forming liquid (transparent conductive film forming liquid) was prepared by adding di-n-butyltin diacetate as a tin compound so that Sn / In = 12% by mass in this solution. An ITO film having a colorless and transparent ITO film formed on a glass substrate at 515 ° C. (film formation temperature) for 5 minutes by atomization of the ITO film formation liquid by the pyrosol process method using this ITO film formation liquid An attached glass substrate (substrate with a transparent conductive film) was obtained. About the obtained ITO film | membrane, X-ray-diffraction measurement was performed by (theta) / 2 (theta) method using the JEOL company make (JDX-8020, X-RAY DIFFRACTOMETER). As measurement conditions, target: Cu, tube voltage: 40 kV, tube current: 20 mA, step angle: 0.020 °, measurement time: 0.20 sec. The results are shown in FIG. As is clear from FIG. 1, a strong peak was observed around 30 ° indicating the orientation of the (222) plane. Further, the diffraction intensity of the obtained (222) plane was 455, and the diffraction intensity of the (400) plane was not detected.
［実施例２］
実施例１で成膜温度を４８０℃に代えた以外は、実施例１と同様にしてＩＴＯ膜形成液（透明導電膜形成液）を調製した。その後、実施例１と同様にしてＩＴＯ膜を成膜し、得られたＩＴＯ膜について、θ／２θ法によりＸ線回折測定を行った。結果を図２に示す。図２から明らかなように、（２２２）面の配向を示す３５°付近に強いピークが観測された。また、得られた（２２２）面の回折強度は９０、（４００）面の回折強度は５８、（２２２）／（４００）面の回折強度比は１．５５であった。
[Example 2]
An ITO film forming liquid (transparent conductive film forming liquid) was prepared in the same manner as in Example 1 except that the film forming temperature was changed to 480 ° C. in Example 1. Thereafter, an ITO film was formed in the same manner as in Example 1, and the obtained ITO film was subjected to X-ray diffraction measurement by the θ / 2θ method. The results are shown in FIG. As is clear from FIG. 2, a strong peak was observed around 35 ° indicating the orientation of the (222) plane. The obtained (222) plane had a diffraction intensity of 90, the (400) plane had a diffraction intensity of 58, and the (222) / (400) plane had a diffraction intensity ratio of 1.55.
［実施例３］
実施例１でインジウム化合物としてトリス（ジピバロイルメタナート）インジウムに代えた以外は、実施例１と同様にしてＩＴＯ膜形成液（透明導電膜形成液）を調製した。その後、実施例１と同様にしてＩＴＯ膜を成膜し、得られたＩＴＯ膜について、θ／２θ法によりＸ線回折測定を行った。結果を図３に示す。図３から明らかなように、（２２２）面の配向を示す３５°付近に強いピークが観測された。また、得られた（２２２）面の回折強度は１５１、（４００）面の回折強度は３１、（２２２）／（４００）面の回折強度比は４．８７であった。
[Example 3]
An ITO film forming liquid (transparent conductive film forming liquid) was prepared in the same manner as in Example 1 except that tris (dipivaloylmethanato) indium was used as the indium compound in Example 1. Thereafter, an ITO film was formed in the same manner as in Example 1, and the obtained ITO film was subjected to X-ray diffraction measurement by the θ / 2θ method. The results are shown in FIG. As is clear from FIG. 3, a strong peak was observed around 35 ° indicating the orientation of the (222) plane. The obtained (222) plane had a diffraction intensity of 151, the (400) plane had a diffraction intensity of 31, and the (222) / (400) plane had a diffraction intensity ratio of 4.87.
［実施例４］
実施例２でインジウム化合物としてトリス（ジピバロイルメタナート）インジウムに代えた以外は、実施例２と同様にしてＩＴＯ膜形成液（透明導電膜形成液）を調製した。その後、実施例２と同様にしてＩＴＯ膜を成膜し、得られたＩＴＯ膜について、θ／２θ法によりＸ線回折測定を行った。結果を図４に示す。図４から明らかなように、（２２２）面の配向を示す３５°付近に強いピークが観測された。また、得られた（２２２）面の回折強度は１４３、（４００）面の回折強度は３１、（２２２）／（４００）面の回折強度比は４．６１であった。
[Example 4]
An ITO film forming liquid (transparent conductive film forming liquid) was prepared in the same manner as in Example 2 except that tris (dipivaloylmethanato) indium was used as the indium compound in Example 2. Thereafter, an ITO film was formed in the same manner as in Example 2, and the obtained ITO film was subjected to X-ray diffraction measurement by the θ / 2θ method. The results are shown in FIG. As is clear from FIG. 4, a strong peak was observed around 35 ° indicating the orientation of the (222) plane. The obtained (222) plane had a diffraction intensity of 143, the (400) plane had a diffraction intensity of 31, and the (222) / (400) plane had a diffraction intensity ratio of 4.61.
［比較例１］
実施例１でインジウム化合物としてトリス（アセチルアセトナート）インジウムに、有機溶媒としてアセチルアセトンに代えた以外は、実施例１と同様にしてＩＴＯ膜形成液（透明導電膜形成液）を調製した。その後、実施例１と同様にしてＩＴＯ膜を成膜し、得られたＩＴＯ膜について、θ／２θ法によりＸ線回折測定を行った。結果を図５に示す。図５から明らかなように、（４００）面の配向を示す３５°付近に強いピークが観測された。また、得られた（２２２）面の回折強度は３８、（４００）面の回折強度は８４、（２２２）／（４００）面の回折強度比は０．４５であった。
[Comparative Example 1]
An ITO film forming liquid (transparent conductive film forming liquid) was prepared in the same manner as in Example 1 except that tris (acetylacetonato) indium was used as the indium compound and acetylacetone was used as the organic solvent in Example 1. Thereafter, an ITO film was formed in the same manner as in Example 1, and the obtained ITO film was subjected to X-ray diffraction measurement by the θ / 2θ method. The results are shown in FIG. As is clear from FIG. 5, a strong peak was observed in the vicinity of 35 ° indicating the orientation of the (400) plane. The obtained (222) plane had a diffraction intensity of 38, the (400) plane had a diffraction intensity of 84, and the (222) / (400) plane had a diffraction intensity ratio of 0.45.
［比較例２］
比較例１で成膜温度を４８０℃に代えた以外は、比較例１と同様にしてＩＴＯ膜形成液（透明導電膜形成液）を調製した。その後、比較例１と同様にしてＩＴＯ膜を成膜し、得られたＩＴＯ膜について、θ／２θ法によりＸ線回折測定を行った。結果を図６に示す。図６から明らかなように、（４００）面の配向を示す３５°付近に強いピークが観測された。また、得られた（２２２）面の回折強度は検出されず、（４００）面の回折強度は３８であった。
[Comparative Example 2]
An ITO film forming liquid (transparent conductive film forming liquid) was prepared in the same manner as in Comparative Example 1, except that the film forming temperature was changed to 480 ° C. in Comparative Example 1. Thereafter, an ITO film was formed in the same manner as in Comparative Example 1, and X-ray diffraction measurement was performed on the obtained ITO film by the θ / 2θ method. The results are shown in FIG. As is clear from FIG. 6, a strong peak was observed around 35 ° indicating the orientation of the (400) plane. Further, the diffraction intensity of the obtained (222) plane was not detected, and the diffraction intensity of the (400) plane was 38.
［試験例１］
実施例１〜４及び比較例１、２に係るＩＴＯ膜付ガラス基板の比抵抗値をロレスタ（三菱化学社製）を用いて測定し、シート抵抗値を算出した。なお、シート抵抗値は、比抵抗／導電膜の膜厚で求められる値である。その結果を表１に示す。表１から明らかなように、成膜時間が同じ場合に、本発明の実施例１〜４の透明導電膜は、比較例１、２の透明導電膜よりもシート抵抗値及び抵抗値が低い透明導電膜であり、かつ膜厚も厚く成膜できることから成膜性に優れた透明導電膜である。
[Test Example 1]
The specific resistance value of the glass substrate with an ITO film according to Examples 1 to 4 and Comparative Examples 1 and 2 was measured using Loresta (manufactured by Mitsubishi Chemical Corporation), and the sheet resistance value was calculated. The sheet resistance value is a value obtained by the specific resistance / film thickness of the conductive film. The results are shown in Table 1. As is clear from Table 1, when the film formation times are the same, the transparent conductive films of Examples 1 to 4 of the present invention have a lower sheet resistance value and resistance value than the transparent conductive films of Comparative Examples 1 and 2. Since it is a conductive film and can be formed with a large film thickness, it is a transparent conductive film with excellent film forming properties.
Claims (6)
6. The transparent conductive film forming material according to claim 4 , wherein the chemical thermal decomposition method is a pyrosol process method.
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| CN101313371A (en) * | 2005-11-21 | 2008-11-26 | 出光兴产株式会社 | Transparent conductive film, substrate using same, electronic device, and liquid crystal display device |
| JP5817327B2 (en) * | 2010-09-29 | 2015-11-18 | 東ソー株式会社 | Oxide sintered body, method for producing the same, oxide transparent conductive film obtained using the same, and solar cell |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2000048726A (en) * | 1998-07-28 | 2000-02-18 | Central Glass Co Ltd | Glass substrate with transparent conductive membrane and manufacture thereof |
| JP2002045735A (en) * | 2000-08-04 | 2002-02-12 | National Institute Of Advanced Industrial & Technology | Method and apparatus for forming thin ultrafine- particle film |
| JP2002170430A (en) * | 2000-11-29 | 2002-06-14 | Asahi Glass Co Ltd | Base body with conductive film and its manufacturing method |
| JP2004022388A (en) * | 2002-06-18 | 2004-01-22 | Nippon Soda Co Ltd | Manufacturing method of transparent conductive film forming liquid and substrate with transparent conductive film using same |
| JP2004018913A (en) * | 2002-06-14 | 2004-01-22 | Nippon Soda Co Ltd | Liquid for forming transparent conductive film and method for manufacturing substrate coated with transparent conductive film using the same |
| JP2004026554A (en) * | 2002-06-25 | 2004-01-29 | Nippon Soda Co Ltd | Transparent conductive film-forming liquid and method for manufacturing substrate having transparent conductive film using the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2000048726A (en) * | 1998-07-28 | 2000-02-18 | Central Glass Co Ltd | Glass substrate with transparent conductive membrane and manufacture thereof |
| JP2002045735A (en) * | 2000-08-04 | 2002-02-12 | National Institute Of Advanced Industrial & Technology | Method and apparatus for forming thin ultrafine- particle film |
| JP2002170430A (en) * | 2000-11-29 | 2002-06-14 | Asahi Glass Co Ltd | Base body with conductive film and its manufacturing method |
| JP2004018913A (en) * | 2002-06-14 | 2004-01-22 | Nippon Soda Co Ltd | Liquid for forming transparent conductive film and method for manufacturing substrate coated with transparent conductive film using the same |
| JP2004022388A (en) * | 2002-06-18 | 2004-01-22 | Nippon Soda Co Ltd | Manufacturing method of transparent conductive film forming liquid and substrate with transparent conductive film using same |
| JP2004026554A (en) * | 2002-06-25 | 2004-01-29 | Nippon Soda Co Ltd | Transparent conductive film-forming liquid and method for manufacturing substrate having transparent conductive film using the same |
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