JP2009224152A - Transparent electrode, transparent conductive substrate, and transparent touch panel - Google Patents
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Abstract
Description
この発明は、透明電極、透明導電性基板および透明タッチパネルに関し、より詳しくは、膜厚が極めて薄く、しかも耐熱性に優れた透明電極、透明導電性基板および透明タッチパネルに関する。 The present invention relates to a transparent electrode, a transparent conductive substrate, and a transparent touch panel, and more particularly to a transparent electrode, a transparent conductive substrate, and a transparent touch panel that are extremely thin and have excellent heat resistance.
近年、パーソナルコンピュータ、ワードプロセッサ、電子手帳、携帯端末等においては、コンピュータ本体（主記憶装置）へデータ入力を行うための入力装置の１つとして、入力面に指やペン等によって単に荷重を加えるだけでデータ入力を行うことができる透明タッチパネル（タッチスクリーンを含む）が多用されるようになってきた。このタッチパネルには、抵抗膜式や静電容量式など種々の原理のものがある。そして、抵抗膜式のタッチパネルは、アナログ型とデジタル型とに大別されるが、入力位置の検出感度向上の要求に伴い、最近ではアナログ型の透明タッチパネルが採用されつつある。 In recent years, in personal computers, word processors, electronic notebooks, portable terminals, etc., as an input device for inputting data to the computer main body (main storage device), a load is simply applied to the input surface with a finger or a pen. Transparent touch panels (including touch screens) that can perform data input have been widely used. There are various types of touch panels such as a resistance film type and a capacitance type. Resistive touch panels are roughly classified into an analog type and a digital type. Recently, an analog type transparent touch panel is being adopted in accordance with a demand for improving detection sensitivity of an input position.
透明タッチパネルの電極として使用される透明導電膜は、一般にＡＴＯ（アンチモン含有酸化スズ）、ＦＴＯ（フッ素含有酸化スズ）、ＩＴＯ（スズ含有酸化インジウム）、ＩＴｉＯ（チタン含有酸化インジウム）、ＦＡＴＯ（フッ素及びアンチモン含有酸化スズ）などの金属酸化物が用いられている。とりわけ、抵抗膜式アナログタイプの透明タッチパネルの場合には、表面抵抗値は２００〜３０００Ω／□（オーム・パー・スクエアと読む）で、かつ、透明性が高く、着色の少ない透明電極が電極として求められている。表面抵抗が２００Ω／□未満であると、２枚の透明基板を透明導電膜側が対面するように配置されるようにしてタッチパネルを構成すると、対向する透明導電膜が接触（ＯＮ時）するときに流れる電流が大きくなり、消費電流が大きくなる。また、透明導電膜の表面抵抗が３０００Ω／□を超えると、接触時の電気導通が不安定になる。また、静電容量式タッチパネルの場合には、７０〜２００Ω／□の透明度の高い透明導電膜が電極として求められている。 Transparent conductive films used as electrodes for transparent touch panels are generally ATO (antimony-containing tin oxide), FTO (fluorine-containing tin oxide), ITO (tin-containing indium oxide), ITiO (titanium-containing indium oxide), FATO (fluorine and Metal oxides such as antimony-containing tin oxide) are used. In particular, in the case of a resistance film type analog type transparent touch panel, a surface resistance value is 200 to 3000 Ω / □ (read as ohm-per-square), and a transparent electrode with high transparency and little color is used as an electrode. It has been demanded. When the touch panel is configured such that the surface resistance is less than 200Ω / □ and the two transparent substrates are arranged so that the transparent conductive film side faces each other, the opposing transparent conductive film comes into contact (when ON). The flowing current increases and the current consumption increases. On the other hand, when the surface resistance of the transparent conductive film exceeds 3000 Ω / □, electrical conduction at the time of contact becomes unstable. In the case of a capacitive touch panel, a transparent conductive film having a high transparency of 70 to 200Ω / □ is required as an electrode.
抵抗膜式アナログタイプの透明タッチパネルは、一例として、表面に透明導電膜より構成される下部電極とドット状のスペーサとを設けたガラス板やフィルムなどの絶縁基板より構成される下部電極基板と、表面に透明導電膜より構成される上部電極を設けたフィルムなどの絶縁基板より構成される上部電極基板とを積層した構造となっており、入力面側から透明タッチパネルの表面の一部を押圧することにより、両電極を接触させ電気的に導通させて入力できるものである。
この透明導電膜は、通常、蒸着法、スパッタリング法などの物理的成膜法、またはＣＶＤ法などの化学的気相法により形成される。そして、これらの方法においては、透明導電膜の膜表面で観察される平面内の平均結晶粒径を制御することが可能である。たとえば、物理的成膜法の場合、一般的にＩＴＯやＩＴｉＯより構成される透明導電膜が主流であり、表面抵抗値としては、抵抗膜式タッチパネルの場合は２００〜３０００Ω／□で、液晶ディスプレイ用電極に比べてやや高めのものが求められる。しかし、ＩＴＯやＩＴｉＯは比抵抗が小さいため、膜厚を７〜５０ｎｍ程度の極薄膜で成膜して表面抵抗値を高める必要がある。
抵抗膜式のタッチパネルは、一般に、透明導電膜の薄膜が形成された透明基板からなる上部電極と、ガラスや樹脂基体に透明導電体を設けた下部電極とを、間隔をおいて配置した構造を有している。この抵抗膜式タッチパネルでは、入力に際して、上部電極の透明導電膜と下部電極の透明導電膜が接触した状態で、ペンなどを用いて表面をこするため、透明導電膜が基体から剥離してしまうことがある。透明導電膜が除去された部分は、上下の電極間の抵抗値が大きくなり、入力に支障を生ずるようになる。一般に、透明導電膜は、結晶膜の方が基体から剥離しにくく、耐久性に優れる。
As an example, a resistive film type analog type transparent touch panel has a lower electrode substrate constituted by an insulating substrate such as a glass plate or a film provided with a lower electrode constituted by a transparent conductive film and a dot-like spacer on the surface, It has a structure in which an upper electrode substrate composed of an insulating substrate such as a film provided with an upper electrode composed of a transparent conductive film is laminated on the surface, and a part of the surface of the transparent touch panel is pressed from the input surface side. Thus, both electrodes can be brought into contact with each other to be electrically conducted for input.
This transparent conductive film is usually formed by a physical film formation method such as vapor deposition or sputtering, or a chemical vapor phase method such as CVD. In these methods, it is possible to control the average crystal grain size in the plane observed on the surface of the transparent conductive film. For example, in the case of a physical film forming method, a transparent conductive film generally composed of ITO or ITiO is generally used, and the surface resistance value is 200 to 3000Ω / □ in the case of a resistive film type touch panel. Slightly higher than the electrode for use is required. However, since ITO and ITiO have a small specific resistance, it is necessary to increase the surface resistance value by forming the film with a very thin film having a thickness of about 7 to 50 nm.
In general, a resistive touch panel has a structure in which an upper electrode made of a transparent substrate on which a thin film of a transparent conductive film is formed and a lower electrode in which a transparent conductor is provided on a glass or resin substrate are arranged at intervals. Have. In this resistive touch panel, when the input is made, the transparent conductive film peels off from the substrate because the surface is rubbed with a pen or the like while the transparent conductive film of the upper electrode and the transparent conductive film of the lower electrode are in contact with each other. Sometimes. In the portion where the transparent conductive film has been removed, the resistance value between the upper and lower electrodes becomes large, resulting in hindrance to input. In general, a transparent conductive film is more difficult to peel from a substrate than a crystal film, and is excellent in durability.
透明タッチパネル用透明電極は、透明基板と、この一表面上に形成された透明導電膜とを有する。
例えば、ＩＴＯやＩＴｉＯ膜の透明導電膜をスパッタリング法により成膜するには、まず、洗浄工程において、水（純水）又はアルカリ水で透明基板を洗浄し、大気中で１２０℃以上の温度で１〜４時間乾燥する。そして、真空下、２００〜４００℃の温度においてＩＴＯやＩＴｉＯのスパッタリング成膜を行う。このような高温成膜を行うことで、基板に対する付着力が強くて耐久性に優れた結晶性の透明導電膜を得ることができる。この後、電極及びリード電極の接続部に銀ペーストを塗布し、１３０〜１７０℃の温度において硬化する。この際、形成した透明電極の耐熱性が充分でないと、表面抵抗値の変化が大きく、また、１５０〜２００℃の温度環境下で、透明電極の表面抵抗の変化が大きいと、高い耐熱性が要求される車載のカーナビ用タッチパネルの電極として使用できない。
The transparent electrode for a transparent touch panel has a transparent substrate and a transparent conductive film formed on the one surface.
For example, in order to form a transparent conductive film such as an ITO or ITiO film by a sputtering method, first, in a cleaning process, a transparent substrate is cleaned with water (pure water) or alkaline water, and at a temperature of 120 ° C. or higher in the atmosphere. Dry for 1-4 hours. Then, sputtering film formation of ITO or ITiO is performed at a temperature of 200 to 400 ° C. under vacuum. By performing such high-temperature film formation, a crystalline transparent conductive film having strong adhesion to the substrate and excellent durability can be obtained. Thereafter, a silver paste is applied to the connection portion between the electrode and the lead electrode, and cured at a temperature of 130 to 170 ° C. At this time, if the heat resistance of the formed transparent electrode is not sufficient, the change in the surface resistance value is large, and if the change in the surface resistance of the transparent electrode is large in a temperature environment of 150 to 200 ° C., the high heat resistance is high. It cannot be used as an electrode for the required on-vehicle car navigation touch panel.
耐熱性を改善することを目的として、これまでに数多くの研究が行われている。透明導電膜そのものの耐熱性を改善するものとして、特許文献１においては、ＺｎＯ透明導電膜中のＧａ濃度をＧａ／Ｚｎ原子比で０．５〜１２％に制御し、かつ膜の（００２）Ｘ線回折線の半値幅が０．６度以下になるように膜の結晶性を制御することが提案されている。これにより、比抵抗値がＩＴＯと同等に２×１０−４Ω・ｃｍと低く、さらに５００℃以上にて大気中で熱処理した後に導電性の劣化はなく、酸化性雰囲気での耐熱性にきわめて優れた膜が得られると記載されている。 Numerous studies have been conducted so far to improve heat resistance. As for improving the heat resistance of the transparent conductive film itself, in Patent Document 1, the Ga concentration in the ZnO transparent conductive film is controlled to 0.5 to 12% in terms of Ga / Zn atomic ratio, and (002) It has been proposed to control the crystallinity of the film so that the half width of the X-ray diffraction line is 0.6 degrees or less. As a result, the specific resistance value is as low as 2 × 10 −4 Ω · cm, which is equivalent to that of ITO. Furthermore, there is no deterioration in conductivity after heat treatment in air at 500 ° C. or higher, and extremely high heat resistance in an oxidizing atmosphere It is described that an excellent film can be obtained.
また、特許文献２には、インジウム、錫及、亜鉛及び酸素を含有し、Ｘ線回折（ＸＲＤ）によってビックスバイト構造化合物のピークのみが実質的に観測される、Ｉｎ２Ｏ３で表されるスパッタリングターゲットを用いて成膜した透明導電膜が提案されている。ここには、インジウム含有量を６０〜７５原子％の範囲内に削減しても、ＩＺＯ並みのエッチング加工性とＩＴＯ並みの膜性能を示し、さらに、インジウムが削減されていても導電性、エッチング性、耐熱性等に優れ、液晶ディスプレイに代表されるディスプレイやタッチパネル、太陽電池等各種の用途に適していること、成膜条件を調整してＴＦＴ（薄膜トランジスタ）に代表される透明酸化物半導体の成膜にも適用できることが記載されている。 Patent Document 2 discloses a sputtering target represented by In 2 O 3 that contains indium, tin, zinc, and oxygen, and in which only the peak of the bixbite structure compound is substantially observed by X-ray diffraction (XRD). A transparent conductive film formed by using the film has been proposed. Here, even if the indium content is reduced within the range of 60 to 75 atomic%, the etching processability similar to that of IZO and the film performance equivalent to that of ITO are exhibited. Excellent in heat resistance, heat resistance, etc., suitable for various applications such as liquid crystal displays, touch panels, solar cells, etc. It is described that it can also be applied to film formation.
さらに、透明導電膜を積層膜として耐熱性を改善しようとする試みも提案されている。特許文献３には、酸化インジウム、酸化スズ等の金属酸化物を主成分とした従来の透明導電膜上に、充分な耐食性を有しながら導電膜の電気的・光学的特性を低下させない保護膜として、ガリウムを含有する酸化亜鉛を主成分とした保護膜を形成した透明導電膜が開示されている。 Furthermore, an attempt to improve heat resistance using a transparent conductive film as a laminated film has also been proposed. Patent Document 3 discloses a protective film that does not deteriorate the electrical and optical characteristics of a conductive film while having sufficient corrosion resistance on a conventional transparent conductive film mainly composed of a metal oxide such as indium oxide or tin oxide. A transparent conductive film is disclosed in which a protective film mainly composed of zinc oxide containing gallium is formed.
また、ポリアリレート成形物を基材として用いてＩＴＯ膜を形成し透明導電性積層体とすると、熱処理、湿熱処理によって電気抵抗値が変化してしまう場合があるが、特許文献４には、透明な基体の少なくとも片面に、高いバリア性を有する、主として非晶質の酸化インジウムからなる層を高濃度酸素雰囲気下におけるスパッタリングにより中間層として形成し、該中間層上に主としてインジウムとスズからなる酸化物で構成される透明導電層を形成することが提案され、これにより、透明な基体としてポリアリレート等を用いても耐熱性、耐湿熱性に優れる透明導電性積層体が得られることが開示されている。 In addition, when an ITO film is formed using a polyarylate molded article as a base material to form a transparent conductive laminate, the electrical resistance value may change due to heat treatment and wet heat treatment. A layer mainly composed of amorphous indium oxide having a high barrier property is formed on at least one surface of a simple substrate as an intermediate layer by sputtering in a high-concentration oxygen atmosphere, and an oxide mainly composed of indium and tin is formed on the intermediate layer. It has been proposed to form a transparent conductive layer composed of a product, and it is disclosed that a transparent conductive laminate having excellent heat resistance and moist heat resistance can be obtained even when polyarylate or the like is used as a transparent substrate. Yes.
このように、耐熱性、耐湿熱性等に優れる透明導電膜、透明導電性積層体が提案されているが、いずれの透明導電膜も膜厚が７〜５０ｎｍ程度になると、１５０〜２００℃における大気中での耐熱性劣化が顕著となる。これは、膜厚が５０ｎｍ以下の極薄膜であるために、上記の環境下での膜表面の酸化及び膜表面からの酸素の拡散進入により電気特性を劣化させやすいからと考えられる。タッチパネル製造工程における加熱工程や、カーナビ用途の高い耐熱温度の要請に対して表面抵抗値が安定した透明電極はこれまで得られていなかった。
本発明の目的は、上記のような問題点に鑑み、膜厚が５０ｎｍ以下の極薄膜でも、１５０℃以上における大気中で耐熱性に優れた透明電極、透明導電性基板および透明タッチパネルを提供することにある。 In view of the above problems, an object of the present invention is to provide a transparent electrode, a transparent conductive substrate, and a transparent touch panel that are excellent in heat resistance in the air at 150 ° C. or higher even with an extremely thin film having a film thickness of 50 nm or less. There is.
本発明者らは、上記課題を解決するにあたり、鋭意研究を重ねた結果、基板上に酸化インジウムを主成分とする結晶性透明導電膜と、酸化インジウムを主成分とする非晶質性透明導電膜がそれぞれ特定の膜厚で順次形成された積層構造の透明電極とすることで、光学特性を損なうことなく透明導電膜としての耐熱性が改善され、さらに、透明導電膜が高温で作製された場合でも積層膜の特性に影響が出にくいものとなることを見出し、本発明を完成するに至った。 As a result of intensive studies in solving the above problems, the present inventors have found that a crystalline transparent conductive film mainly composed of indium oxide and an amorphous transparent conductive film mainly composed of indium oxide on the substrate. Heat resistance as a transparent conductive film was improved without impairing optical properties by forming a transparent electrode having a laminated structure in which films were sequentially formed with specific film thicknesses, and further, a transparent conductive film was produced at a high temperature. Even in this case, it was found that the characteristics of the laminated film are hardly affected, and the present invention has been completed.
すなわち、本発明の第１の発明によれば、基板（Ｃ）上に、酸化インジウムを主成分とする結晶性透明導電膜（Ａ）と酸化インジウムを主成分とする非晶質性透明導電膜（Ｂ）が順次形成された積層構造の透明電極であって、結晶性透明導電膜（Ａ）は膜厚が５〜４０ｎｍであり、非晶質透明導電膜（Ｂ）は膜厚が２〜１０ｎｍであり、表面抵抗が７０〜３０００Ω／□であることを特徴とする透明電極が提供される。 That is, according to the first invention of the present invention, on the substrate (C), the crystalline transparent conductive film (A) mainly composed of indium oxide and the amorphous transparent conductive film mainly composed of indium oxide. (B) is a transparent electrode having a laminated structure in which the crystalline transparent conductive film (A) has a film thickness of 5 to 40 nm, and the amorphous transparent conductive film (B) has a film thickness of 2 to 2. A transparent electrode having a thickness of 10 nm and a surface resistance of 70 to 3000 Ω / □ is provided.
また、本発明の第２の発明によれば、第１の発明において、結晶性透明導電膜（Ａ）が、スズ、又はチタンから選ばれる少なくとも１種の添加元素（Ｍｅ）を含む酸化インジウムであり、その含有量が総量としてＭｅ／Ｉｎ原子数比で０．０１〜０．１５であることを特徴とする透明電極が提供される。
また、本発明の第３の発明によれば、第１の発明において、非晶質透明導電膜（Ｂ）が、ガリウム、セリウム、シリコン、ゲルマニウム、タングステン、又は亜鉛から選ばれる少なくとも１種の添加元素（Ｍｅ）を含む酸化インジウムであり、その含有量が総量としてＭｅ２／Ｉｎ原子数比で０．０４〜０．８０であることを特徴とする透明電極が提供される。
また、本発明の第４の発明によれば、第３の発明において、非晶質透明導電膜（Ｂ）の結晶化温度が、２５０℃以上であることを特徴とする透明電極が提供される。
また、本発明の第５の発明によれば、第１の発明において、基板（Ｃ）が、ガラス板、プラスチック樹脂板、又は樹脂フィルムから選ばれるいずれかの透明基板であることを特徴とする透明電極が提供される。
また、本発明の第６の発明によれば、第１〜５のいずれかの発明において、スパッタリング法で、２００℃以上に加熱された基板（Ｃ）上に、結晶性透明導電膜（Ａ）と非晶質透明導電膜（Ｂ）が順次成膜されて得られる透明電極が提供される。
また、本発明の第７の発明によれば、第１の発明において、表面抵抗の変化率（Ｒ／Ｒ０、ここで、Ｒ：大気中において１５０℃以上の温度で１時間加熱する耐熱試験後の表面抵抗、Ｒ０：試験前の表面抵抗）が０．８０〜１．２０であることを特徴とする透明電極が提供される。
さらに、本発明の第８の発明によれば、第７の発明において、耐熱試験において、透明電極が、２００℃に加熱されることを特徴とする透明電極が提供される。
According to the second invention of the present invention, in the first invention, the crystalline transparent conductive film (A) is an indium oxide containing at least one additive element (Me) selected from tin or titanium. The transparent electrode is characterized in that the total content is 0.01 to 0.15 in terms of Me / In atomic ratio.
According to the third invention of the present invention, in the first invention, the amorphous transparent conductive film (B) is added with at least one selected from gallium, cerium, silicon, germanium, tungsten, or zinc. A transparent electrode is provided, which is indium oxide containing an element (Me) and has a total content of 0.04 to 0.80 in terms of Me 2 / In atomic ratio.
According to a fourth aspect of the present invention, there is provided the transparent electrode according to the third aspect, wherein the crystallization temperature of the amorphous transparent conductive film (B) is 250 ° C. or higher. .
According to a fifth aspect of the present invention, in the first aspect, the substrate (C) is any transparent substrate selected from a glass plate, a plastic resin plate, or a resin film. A transparent electrode is provided.
According to the sixth invention of the present invention, in any one of the first to fifth inventions, the crystalline transparent conductive film (A) on the substrate (C) heated to 200 ° C. or higher by the sputtering method. And an amorphous transparent conductive film (B) are sequentially formed to provide a transparent electrode.
According to the seventh invention of the present invention, in the first invention, the rate of change in surface resistance (R / R 0 , where R: heat resistance test for 1 hour at a temperature of 150 ° C. or higher in the atmosphere. A transparent electrode is provided in which the subsequent surface resistance, R 0 : surface resistance before test) is 0.80 to 1.20.
Furthermore, according to the eighth invention of the present invention, there is provided the transparent electrode according to the seventh invention, wherein the transparent electrode is heated to 200 ° C. in the heat resistance test.
一方、本発明の第９の発明によれば、第１〜８のいずれかの発明に係り、前記透明電極が、透明基板の表面に形成されてなる透明導電性基板が提供される。
また、本発明の第１０の発明によれば、第９の発明において、前記透明導電性基板を下部電極及び／又は上部電極として用いた透明タッチパネルが提供される。
さらに、本発明の第１１の発明によれば、第１０の発明において、下部電極と上部電極とがスペーサを介して向かい合って積層されていることを特徴とする透明タッチパネルが提供される。
On the other hand, according to the ninth invention of the present invention, there is provided a transparent conductive substrate according to any one of the first to eighth inventions, wherein the transparent electrode is formed on the surface of the transparent substrate.
According to a tenth aspect of the present invention, in the ninth aspect, there is provided a transparent touch panel using the transparent conductive substrate as a lower electrode and / or an upper electrode.
Furthermore, according to an eleventh aspect of the present invention, there is provided the transparent touch panel according to the tenth aspect, wherein the lower electrode and the upper electrode are laminated facing each other with a spacer interposed therebetween.
本発明の透明電極は、膜厚が５０ｎｍ以下という極薄膜であるにも係わらず、１５０℃以上の大気中での耐熱性に優れる。すなわち、電極及びリード電極を銀ペーストにて塗布し、１３０〜１７０℃の温度で硬化する際に、形成した透明電極の表面抵抗値の変化が極めて小さい。また、本発明の透明電極は、２００℃の大気中での耐熱性にも優れるため、車載のカーナビ用タッチパネルの電極として好適である。
よって、本発明の透明電極を用いた透明タッチパネルは優れた耐熱性を有しており、液晶表示装置、エレクトロルミネッセンス素子、プラズマディスプレイ素子、蛍光表示管、フィールドエミッションディスプレイなどのフラットディスプレイの表示画面に積層して入力装置として好適に使用でき、工業的に極めて有用である。
The transparent electrode of the present invention is excellent in heat resistance in the air at 150 ° C. or higher, despite being an extremely thin film having a thickness of 50 nm or less. That is, when the electrode and the lead electrode are applied with silver paste and cured at a temperature of 130 to 170 ° C., the change in the surface resistance value of the formed transparent electrode is extremely small. Moreover, since the transparent electrode of the present invention is excellent in heat resistance in the atmosphere at 200 ° C., it is suitable as an electrode for an in-vehicle car navigation touch panel.
Therefore, the transparent touch panel using the transparent electrode of the present invention has excellent heat resistance, and is used for a display screen of a flat display such as a liquid crystal display device, an electroluminescence element, a plasma display element, a fluorescent display tube, and a field emission display. It can be suitably used as an input device by being laminated, and is extremely useful industrially.
次に、本発明の特徴点を図面を参照しながら、詳しく説明する。 Next, features of the present invention will be described in detail with reference to the drawings.
１．透明電極
本発明の透明電極は、基板（Ｃ）上に、酸化インジウムを主成分とする結晶性透明導電膜（Ａ）と酸化インジウムを主成分とする非晶質性透明導電膜（Ｂ）が順次形成された積層構造の透明電極であって、結晶性透明導電膜（Ａ）は膜厚が５〜４０ｎｍであり、非晶質透明導電膜（Ｂ）は膜厚が２〜１０ｎｍであり、表面抵抗が７０〜３０００Ω／□であることを特徴とする。
1. Transparent electrode The transparent electrode of the present invention comprises a crystalline transparent conductive film (A) mainly composed of indium oxide and an amorphous transparent conductive film (B) mainly composed of indium oxide on a substrate (C). A transparent electrode having a laminated structure formed in sequence, the crystalline transparent conductive film (A) has a thickness of 5 to 40 nm, the amorphous transparent conductive film (B) has a thickness of 2 to 10 nm, The surface resistance is 70 to 3000 Ω / □.
（１）透明電極の構造
本発明の透明電極の構造を図１に示す。本発明の透明電極（４）は、基板（３）上に酸化インジウムを主成分とする結晶性透明導電膜（１）と酸化インジウムを主成分とする非晶質性透明導電膜（２）が順次形成され積層構造を呈している。
(1) Structure of transparent electrode The structure of the transparent electrode of this invention is shown in FIG. The transparent electrode (4) of the present invention comprises a crystalline transparent conductive film (1) mainly composed of indium oxide and an amorphous transparent conductive film (2) mainly composed of indium oxide on a substrate (3). It is formed sequentially and has a laminated structure.
図３は、本発明の透明電極の断面ＴＥＭ像を示したものである。図３にはガラス基板３の上に、結晶粒界７で確認される結晶性透明導電膜（Ｉｎ−Ｔｉ−Ｓｎ−Ｏ膜）１が形成されている。また膜１の上には、膜厚４ｎｍの膜２が形成されている。この膜には結晶粒界が存在せず、原子配列が規則的でないから非晶質性透明導電膜（Ｉｎ−Ｇａ−Ｏ膜）２である。なお、１ｎｍの領域に電子線を絞って局所領域での電子線回折測定を行うと、膜１は結晶膜に特有の回折スポットが観察され、膜２は非晶質膜に特有のハローパターンが観察される。 FIG. 3 shows a cross-sectional TEM image of the transparent electrode of the present invention. In FIG. 3, a crystalline transparent conductive film (In—Ti—Sn—O film) 1 confirmed at a crystal grain boundary 7 is formed on a glass substrate 3. On the film 1, a film 2 having a thickness of 4 nm is formed. This film is an amorphous transparent conductive film (In—Ga—O film) 2 because there is no crystal grain boundary and the atomic arrangement is not regular. When electron beam diffraction measurement is performed in a local region by focusing an electron beam on the 1 nm region, a diffraction spot peculiar to a crystalline film is observed in the film 1, and a halo pattern peculiar to an amorphous film is observed in the film 2. Observed.
本発明の透明電極は、結晶性透明導電膜（１）の表面に非晶質性透明導電膜（２）が積層された構造でなければならない。非晶質性透明導電膜（２）は、結晶性透明導電膜（１）の導電性を表面に伝達するだけでなく、大気中からの酸素の進入を阻止するためのガスバリア機能を有する。非晶質膜は、結晶膜と違って、粒界がないためガスの進入が極めて少ない。これにより、大気中で１５０〜２００℃の高温環境下でも、結晶性透明導電膜の酸化を阻止し、耐熱性を飛躍的に改善することができるのである。 The transparent electrode of the present invention must have a structure in which an amorphous transparent conductive film (2) is laminated on the surface of a crystalline transparent conductive film (1). The amorphous transparent conductive film (2) not only transmits the conductivity of the crystalline transparent conductive film (1) to the surface, but also has a gas barrier function for preventing oxygen from entering the atmosphere. Unlike a crystal film, an amorphous film has very little gas ingress because there is no grain boundary. Thereby, even in a high temperature environment of 150 to 200 ° C. in the atmosphere, the oxidation of the crystalline transparent conductive film can be prevented and the heat resistance can be dramatically improved.
本発明の透明電極は、表面抵抗が７０〜３０００Ω／□であることが必要である。この範囲を逸脱すると静電容量式タッチパネルもしくは抵抗式タッチパネルとして利用することができない。 The transparent electrode of the present invention needs to have a surface resistance of 70 to 3000 Ω / □. If it deviates from this range, it cannot be used as a capacitive touch panel or a resistive touch panel.
（２）結晶性透明導電膜（Ａ）
本発明の透明電極における結晶性透明導電膜は、酸化インジウムを主成分とし、これにスズ、チタンから選ばれる少なくとも１種を含むものがより好ましい。
(2) Crystalline transparent conductive film (A)
More preferably, the crystalline transparent conductive film in the transparent electrode of the present invention contains indium oxide as a main component and contains at least one selected from tin and titanium.
スズ、チタンから選ばれる少なくとも１種を含む酸化インジウム膜は、結晶性に優れており、膜厚が５〜４０ｎｍの極薄膜でもタッチパネルとして好適な表面抵抗値（７０〜３０００Ω／□）を実現することができる。スズ、チタンから選ばれる少なくとも１種の添加元素（Ｍｅ）は、総量として、Ｍｅ／Ｉｎ原子数比で０．０１〜０．１５であることが好ましい。
当然ながらスズとチタンを同時に含ませることでも同じ効果が得られるが、特にチタンを含んでスズが極力少ない酸化インジウム薄膜は結晶性に優れていて、基板に対する付着力も強く、耐久性に優れた電極を形成でき、また表面凹凸の大きな電極が形成されやすくタッチパネルの応答速度の向上につながるため好ましい。また、スズとチタン以外に、他の元素（例えば、亜鉛、マグネシウム、ガリウム、ゲルマニウム、シリコン、タングステン、モリブデン、セリウムなど）が、本発明の特性を損なわない程度に、微量に含まれていてもかまわない。
An indium oxide film containing at least one selected from tin and titanium has excellent crystallinity, and realizes a surface resistance value (70 to 3000 Ω / □) suitable as a touch panel even with an extremely thin film thickness of 5 to 40 nm. be able to. The total amount of at least one additive element (Me) selected from tin and titanium is preferably 0.01 to 0.15 in terms of the Me / In atomic ratio.
Of course, the same effect can be obtained by including both tin and titanium at the same time. However, the indium oxide thin film containing titanium and containing as little tin as possible has excellent crystallinity, strong adhesion to the substrate, and excellent durability. It is preferable because an electrode can be formed and an electrode with large surface irregularities is easily formed, leading to an improvement in the response speed of the touch panel. Further, in addition to tin and titanium, other elements (for example, zinc, magnesium, gallium, germanium, silicon, tungsten, molybdenum, cerium, etc.) may be contained in a trace amount to such an extent that the characteristics of the present invention are not impaired. It doesn't matter.
結晶性透明導電膜の膜厚は、５〜４０ｎｍである。５ｎｍ未満であると、特に、ガラスなどの膜とは異種組成の基板上に形成した場合に、膜が島状になってしまって安定した表面抵抗値を発揮しないため好ましくなく、４０ｎｍを超えると、その表面に覆う非晶質透明導電膜も含めた膜が厚くなりすぎてしまい、透過率が低下するからである。可視域の透過率が透明電極単体で９１％以上の優れた光透過性を達成するためには、結晶性透明導電膜と非晶質性透明導電膜の積層体の総膜厚が５０ｎｍ以下である必要がある。 The film thickness of the crystalline transparent conductive film is 5 to 40 nm. When the thickness is less than 5 nm, it is not preferable because the film becomes an island shape and does not exhibit a stable surface resistance particularly when formed on a substrate having a composition different from that of glass or the like. This is because the film including the amorphous transparent conductive film covering the surface becomes too thick and the transmittance decreases. In order to achieve an excellent light transmittance of 91% or more with a transparent electrode alone in the visible region, the total film thickness of the laminate of the crystalline transparent conductive film and the amorphous transparent conductive film is 50 nm or less. There must be.
（３）非晶質透明導電膜（Ｂ）
また、本発明の透明電極における非晶質透明導電膜は、酸化インジウムを主成分とし、これにガリウム、セリウム、シリコン、ゲルマニウム、タングステン、亜鉛から選ばれる少なくとも１種を含むものがより好ましい。
(3) Amorphous transparent conductive film (B)
The amorphous transparent conductive film in the transparent electrode of the present invention is more preferably one containing indium oxide as a main component and containing at least one selected from gallium, cerium, silicon, germanium, tungsten and zinc.
酸化インジウムにガリウム、セリウム、シリコン、ゲルマニウム、タングステン、亜鉛から選ばれる少なくとも１種を添加すると、結晶化温度が顕著に増大し、１５０〜２００℃の高温環境下でも結晶化が起きず、基板温度が２００〜２３０℃におけるスパッタリング成膜でも安定に非晶質膜を得ることができるから好都合である。
ガリウム、セリウム、シリコン、ゲルマニウム、タングステン、亜鉛から選ばれる少なくとも１種の添加元素（Ｍｅ）は、総量として、Ｍｅ／Ｉｎ原子数比で、０．０４〜０．８０が好ましい。０．０４未満であると、結晶化温度が低すぎて、非晶質性が安定して得られず、０．８０を超えると、非晶質膜の電気特性が絶縁性に近くなり、結晶性透明導電膜の導電性を表面に伝達することができないから好ましくない。
また上記の中でも、ガリウムを含む酸化インジウムは、特に耐熱性、ガスバリア性に優れているため最も好ましい。また、ガリウム、セリウム、シリコン、ゲルマニウム及び／又はタングステン以外に、他の元素（例えば、マグネシウム、カルシウム、スズ、チタン、モリブデンなど）が、本発明の特性を損なわない程度に、微量に含まれていてもかまわない。
When at least one selected from gallium, cerium, silicon, germanium, tungsten, and zinc is added to indium oxide, the crystallization temperature is remarkably increased, and crystallization does not occur even in a high temperature environment of 150 to 200 ° C., and the substrate temperature However, it is advantageous because an amorphous film can be stably obtained even by sputtering film formation at 200 to 230 ° C.
The total amount of at least one additive element (Me) selected from gallium, cerium, silicon, germanium, tungsten, and zinc is preferably 0.04 to 0.80 in terms of the Me / In atomic ratio. If it is less than 0.04, the crystallization temperature is too low and amorphousness cannot be stably obtained, and if it exceeds 0.80, the electrical properties of the amorphous film become close to insulating properties, It is not preferable because the conductivity of the conductive transparent conductive film cannot be transmitted to the surface.
Among these, indium oxide containing gallium is most preferable because it is particularly excellent in heat resistance and gas barrier properties. In addition to gallium, cerium, silicon, germanium, and / or tungsten, other elements (eg, magnesium, calcium, tin, titanium, molybdenum, etc.) are contained in a trace amount to such an extent that the characteristics of the present invention are not impaired. It doesn't matter.
なお、上記成膜条件でも所望の特性を得るためには、非晶質性透明導電膜（２）の結晶化温度は２５０℃以上であることが必要である。より好ましくは３５０℃以上であることが良い。これは、カーナビ用タッチパネルなどに要求される２００℃の耐熱性に対しても、表面の非晶質透明導電膜が結晶化しないために必要であるだけでなく、基板上に高い付着力の結晶性透明導電膜と非晶質透明導電膜を形成するためには、２００〜２３０℃に加熱した基板上にスパッタリング法で連続して透明導電膜を成膜することが非常に効果的であり、上記基板温度で結晶性透明導電膜を形成した後、時間をあまりあけずに引き続き、所望の非晶質透明導電膜を成膜するためには、上記結晶化温度を有する非晶質性透明導電膜であることが必要であり、その場合、上記のような製造工程においても利用することができ、非晶質膜として安定に維持することができるからである。
ガスバリア機能を発揮する非晶質膜には、一般に、ＳｉＯ２、ＳｉＯｘ、ＳｉＯＮ、ＳｉＮｘなどの薄膜が知られているが、これらは絶縁性であるため、透明導電膜の表面に覆うと、導電性を表面に伝達することができない。本発明では、ガスバリア性だけでなく、導電性も有しており、しかも、２５０℃以上、さらには３５０℃以上でも構造が安定で導電性が維持された非晶質透明導電膜で結晶性透明導電膜の表面上を覆うことが大きな特徴点である。
In order to obtain desired characteristics even under the above film forming conditions, the crystallization temperature of the amorphous transparent conductive film (2) needs to be 250 ° C. or higher. More preferably, it is 350 degreeC or more. This is not only necessary for the heat resistance of 200 ° C. required for touch panels for car navigation systems, etc., because the amorphous transparent conductive film on the surface does not crystallize, but also a crystal with high adhesion on the substrate. In order to form a conductive transparent conductive film and an amorphous transparent conductive film, it is very effective to continuously form a transparent conductive film by sputtering on a substrate heated to 200 to 230 ° C., After forming the crystalline transparent conductive film at the substrate temperature, the amorphous transparent conductive film having the crystallization temperature is used to form a desired amorphous transparent conductive film without taking much time. This is because the film needs to be a film, and in that case, it can be used in the manufacturing process as described above and can be stably maintained as an amorphous film.
In general, thin films such as SiO 2 , SiOx, SiON, and SiNx are known as amorphous films that exhibit a gas barrier function. However, since these are insulative, if they are covered on the surface of a transparent conductive film, they are electrically conductive. Sex cannot be transmitted to the surface. In the present invention, it has not only gas barrier properties but also conductivity, and is an amorphous transparent conductive film having a stable structure and maintaining conductivity even at 250 ° C. or higher, more preferably 350 ° C. or higher. A major feature is to cover the surface of the conductive film.
また、非晶質性透明導電膜の膜厚は、２〜１０ｎｍである。２ｎｍ未満であると、ガスバリア性に劣り、得られる透明電極の耐熱性が悪くなってしまうからである。また非晶質性透明導電膜の膜厚が２ｎｍ以上だとガスバリア性を発揮するが、１０ｎｍを超えると、透明電極の総膜厚が厚くなりすぎて透過率が低下するだけでなく、材料コストも増大するため好ましくない。よって、非晶質性透明導電膜の膜厚は２〜１０ｎｍが好適である。 The film thickness of the amorphous transparent conductive film is 2 to 10 nm. It is because it is inferior to gas barrier property as it is less than 2 nm, and the heat resistance of the transparent electrode obtained will worsen. Moreover, when the film thickness of the amorphous transparent conductive film is 2 nm or more, gas barrier properties are exhibited. However, when the film thickness exceeds 10 nm, the total film thickness of the transparent electrode becomes too thick and the transmittance decreases, and the material cost also increases. Is also undesirable because it increases. Therefore, the film thickness of the amorphous transparent conductive film is preferably 2 to 10 nm.
（４）基板（Ｃ）
基板は、ガラス板でもプラスチック樹脂板でも樹脂フィルムでもよい。また、ガラス板やプラスチック樹脂板や樹脂フィルムの表面に、フィルムからの金属イオンやガスの侵出と膜への進入に対してバリア性に優れた酸化シリコンなどの薄膜を形成したものでもかまわない。
(4) Substrate (C)
The substrate may be a glass plate, a plastic resin plate, or a resin film. In addition, a thin film such as silicon oxide having excellent barrier properties against the leaching of metal ions and gas from the film and the entering of the film may be formed on the surface of the glass plate, the plastic resin plate or the resin film. .
（５）成膜方法
本発明の透明電極は、２００℃以上の基板温度で、スパッタリング法により、結晶性透明導電膜と非晶質性透明導電膜が順次成膜されて製造されることが好ましい。
(5) Film formation method The transparent electrode of the present invention is preferably produced by sequentially forming a crystalline transparent conductive film and an amorphous transparent conductive film by a sputtering method at a substrate temperature of 200 ° C. or higher. .
スパッタリング法は、一般に、約１０Ｐａ以下のアルゴンガス圧下で、基板を陽極、ターゲットを陰極とし、これらの間にグロー放電を起こしてアルゴンプラズマを発生させる。このプラズマ中のアルゴン陽イオンを陰極のターゲットに衝突させてターゲット成分の粒子を弾き飛ばし、この粒子を基板上に堆積させて成膜するというものである。
スパッタリング法は、アルゴンプラズマの発生方法で分類され、高周波プラズマを用いるものは高周波スパッタリング法、直流プラズマを用いるものは直流スパッタリング法という。また、ターゲットの裏側にマグネットを配置してアルゴンプラズマをターゲット直上に集中させ、アルゴンイオンの衝突効率を上げて低ガス圧でも成膜可能としたものをマグネトロンスパッタリング法という。
In the sputtering method, generally, under an argon gas pressure of about 10 Pa or less, a substrate is used as an anode and a target is used as a cathode, and glow discharge is generated between them to generate argon plasma. Argon cations in the plasma collide with a cathode target to blow off target component particles, and deposit the particles on a substrate to form a film.
Sputtering methods are classified according to the method of generating argon plasma. Those using high-frequency plasma are called high-frequency sputtering methods, and those using DC plasma are called DC sputtering methods. In addition, a magnetron sputtering method is a method in which a magnet is disposed on the back side of a target so that argon plasma is concentrated directly on the target to increase the collision efficiency of argon ions so that a film can be formed even at a low gas pressure.
本発明の透明電極は、２００℃以上の基板温度で、好ましくは、２００〜３５０℃の基板温度で、スパッタリング法により、結晶性透明導電膜と非晶質性透明導電膜が順次成膜される。
ガラス板などの基板上に結晶性透明導電膜（１）を形成するのは、基板と膜との付着性を増強させるためである。一般に、基板にはガラス、もしくは、プラスチック樹脂板、樹脂フィルムなどが一般に用いられるが、透明導電膜とは組成や結晶構造が異なるため、化学的結合が乏しく、強い付着力を得ることが難しい。特に、樹脂の上に形成する場合は強い付着力を得ることが難しい。しかし、結晶性の透明導電膜を、２００℃以上の高温でスパッタリング成膜することで強靱な付着力を得ることができる。逆に、非晶質透明導電膜や、結晶と非晶質が混在した膜が形成されると、膜が基板から剥離しやすくなり、耐久性に劣る。
そのため大気中で１５０〜２００℃の高温環境下に結晶性透明導電膜のみがあると、大気中の酸素を膜が吸収して酸化し、顕著な導電性の変化が生じる。特に、膜厚が５〜４０ｎｍの薄い膜の場合は、膜の内部への酸素の拡散進入が容易であり、導電性の変化が著しい。
In the transparent electrode of the present invention, a crystalline transparent conductive film and an amorphous transparent conductive film are sequentially formed by sputtering at a substrate temperature of 200 ° C. or higher, preferably 200 to 350 ° C. .
The reason why the crystalline transparent conductive film (1) is formed on a substrate such as a glass plate is to enhance the adhesion between the substrate and the film. In general, glass, a plastic resin plate, a resin film, or the like is generally used for the substrate. However, since the composition and crystal structure are different from those of the transparent conductive film, the chemical bond is poor and it is difficult to obtain a strong adhesive force. In particular, when it is formed on a resin, it is difficult to obtain a strong adhesive force. However, a strong adhesion can be obtained by sputtering a crystalline transparent conductive film at a high temperature of 200 ° C. or higher. On the other hand, when an amorphous transparent conductive film or a film in which crystals and amorphous are mixed is formed, the film is easily peeled off from the substrate, resulting in poor durability.
Therefore, if there is only a crystalline transparent conductive film in a high temperature environment of 150 to 200 ° C. in the atmosphere, the film absorbs oxygen in the atmosphere and oxidizes, resulting in a significant change in conductivity. In particular, in the case of a thin film having a thickness of 5 to 40 nm, it is easy to diffuse and enter oxygen into the film, and the change in conductivity is remarkable.
基板温度が２００℃未満では、結晶性透明導電膜と基板との間の付着力が弱く、ペンなどで擦って使用したときの耐久性に劣る。また、５００℃を超えると、軟化点が低い樹脂板やフィルムを使用できないだけでなく、冷却時間が必要になり時間がかかって製造コストなどの問題が生じてしまう。このような製法で得られた透明電極は基板に対して高付着力を有するため、ペンなどで擦って使用したときの耐久性に優れる。 When the substrate temperature is less than 200 ° C., the adhesive force between the crystalline transparent conductive film and the substrate is weak, and the durability when used by rubbing with a pen or the like is poor. Further, when the temperature exceeds 500 ° C., not only a resin plate or film having a low softening point cannot be used, but a cooling time is required, which takes time and causes problems such as manufacturing costs. Since the transparent electrode obtained by such a manufacturing method has a high adhesion to the substrate, it has excellent durability when rubbed with a pen or the like.
成膜条件は、基板温度が重要であり、得られる膜の結晶性を考慮したうえでターゲットの種類（添加元素の含有量）を適切に選択し、酸素量、圧力、不活性ガス、投入電力量などを調整して行われる。
ターゲットとしては、粉末焼結法、即ち実質的にインジウム酸化物に添加元素となる金属元素の酸化物を所望の組成に配合し、加圧成形した後、１４００℃以上の温度で焼結する方法により製造された酸化インジウム系焼結体が使用される。この酸化インジウム系焼結体は、平面研削等により加工し、所定の寸法にしてから、バッキングプレートに貼り付けられている。
ターゲットの添加元素量は、成膜時に組成ズレがほとんど生じないと考えて良く、膜組成と同じものを選択する。本発明においては、基板上の結晶性透明導電膜には、結晶性を妨げる元素が含まれない方が好ましいため、ターゲットとしては、ガリウム、セリウム、シリコン、ゲルマニウム、タングステン、亜鉛を含まないものを用いることが望ましい。ガリウム、セリウム、シリコン、ゲルマニウム、タングステン、亜鉛から選ばれる少なくとも１種の添加元素（Ｍｅ）を含む場合は、その総量が、Ｍｅ／Ｉｎ原子数比で０．０２未満であるターゲットを用いることが、２００℃以上の高温基板で結晶膜を得るためには必要である。
酸素量、圧力、投入電力量は、成膜装置にも依存するので一概に規定できないが、ガス圧：０．１〜２．０Ｐａ、ガス種：アルゴンと酸素の混合ガスで酸素混合量は０．５〜１０％投入電力量：０．８〜３．５Ｗ／ｃｍ２とされる。
このような条件で、結晶性透明導電膜が５〜４０ｎｍの厚さになるまで成膜する。５ｎｍ未満であると、特に、ガラスなどの膜とは異種組成の基板上に形成した場合に、膜が島状になってしまって安定した表面抵抗値を発揮しないため好ましくなく、４０ｎｍを超えると、その表面に覆う非晶質透明導電膜も含めた膜が厚くなりすぎてしまい、透過率が低下する。可視域の透過率が透明電極単体で９１％以上の優れた光透過性を達成するためには、結晶性透明導電膜と非晶質性透明導電膜の積層体の総膜厚が５０ｎｍ以下である必要がある。
The substrate temperature is important for the film formation conditions, and the target type (additive element content) is selected appropriately in consideration of the crystallinity of the resulting film, and the oxygen content, pressure, inert gas, input power It is done by adjusting the amount.
As a target, a powder sintering method, that is, a method in which an oxide of a metal element that is substantially an additive element is added to indium oxide in a desired composition, pressure-molded, and then sintered at a temperature of 1400 ° C. or higher. The indium oxide-based sintered body produced by the above is used. The indium oxide-based sintered body is processed by surface grinding or the like to have a predetermined dimension, and is then attached to a backing plate.
The amount of the additive element of the target may be considered that composition deviation hardly occurs at the time of film formation, and the same amount as the film composition is selected. In the present invention, it is preferable that the crystalline transparent conductive film on the substrate does not contain an element that hinders crystallinity, so that the target does not contain gallium, cerium, silicon, germanium, tungsten, or zinc. It is desirable to use it. In the case where at least one additive element (Me) selected from gallium, cerium, silicon, germanium, tungsten, and zinc is included, a target whose total amount is less than 0.02 in terms of Me / In atomic ratio is used. In order to obtain a crystal film with a high temperature substrate of 200 ° C. or higher, it is necessary.
The oxygen amount, pressure, and input electric power amount also depend on the film forming apparatus and cannot be generally specified, but the gas pressure is 0.1 to 2.0 Pa, the gas type is a mixed gas of argon and oxygen, and the oxygen mixture amount is 0. .5 to 10% input power amount: 0.8 to 3.5 W / cm 2
Under such conditions, the film is formed until the crystalline transparent conductive film has a thickness of 5 to 40 nm. When the thickness is less than 5 nm, it is not preferable because the film becomes an island shape and does not exhibit a stable surface resistance particularly when formed on a substrate having a composition different from that of glass or the like. The film including the amorphous transparent conductive film covering the surface becomes too thick, and the transmittance decreases. In order to achieve an excellent light transmittance of 91% or more with a transparent electrode alone in the visible region, the total film thickness of the laminate of the crystalline transparent conductive film and the amorphous transparent conductive film is 50 nm or less. There must be.
その後、ターゲットを変えて、非晶質透明導電膜を成膜する。非晶質透明導電膜には、結晶性を妨げる元素を含む方が好ましいため、ターゲットとしては、ガリウム、セリウム、シリコン、ゲルマニウム、タングステン、亜鉛を含むものを用いることが望ましい。ガリウム、セリウム、シリコン、ゲルマニウム、タングステン、亜鉛から選ばれる少なくとも１種の添加元素（Ｍｅ）の総量は、Ｍｅ／Ｉｎ原子数比で０．０４以上であるターゲットを用いることが、２００℃以上の高温基板で非晶質膜が得られるためには必要である。ただし、添加元素（Ｍｅ）の総量が、Ｍｅ／Ｉｎ原子数比で０．８０を超えるターゲットを用いると、ターゲットとほぼ同じ組成である非晶質膜の電気特性が絶縁性に近くなり、結晶性透明導電膜の導電性を表面に伝達することができないから好ましくない。
なお、基板温度、酸素量、圧力、投入電力量は、上記範囲で変更しても良いが、本発明は、結晶性透明導電膜を成膜する条件と同じでもよい。このため、従来よりも操作が簡単で、生産性を高めることができ透明電極のコストを低減することも可能となる。
Thereafter, an amorphous transparent conductive film is formed by changing the target. Since it is preferable that the amorphous transparent conductive film contains an element that hinders crystallinity, it is preferable to use a target containing gallium, cerium, silicon, germanium, tungsten, or zinc. The total amount of at least one additive element (Me) selected from gallium, cerium, silicon, germanium, tungsten, and zinc is 200 ° C. or higher by using a target having a Me / In atomic ratio of 0.04 or more. It is necessary to obtain an amorphous film with a high temperature substrate. However, when a target having a total amount of additive element (Me) exceeding 0.80 in the Me / In atomic ratio is used, the electrical characteristics of the amorphous film having almost the same composition as the target become close to insulating, and the crystal It is not preferable because the conductivity of the conductive transparent conductive film cannot be transmitted to the surface.
The substrate temperature, oxygen amount, pressure, and input power amount may be changed within the above ranges, but the present invention may be the same as the conditions for forming the crystalline transparent conductive film. For this reason, operation is easier than before, productivity can be increased, and the cost of the transparent electrode can be reduced.
これにより得られる本発明の透明電極は、大気中において１５０℃以上の温度で１時間加熱する耐熱試験において、試験前（室温）の表面抵抗Ｒ０と試験後の表面抵抗Ｒとしたとき、その変化（Ｒ／Ｒ０）が０．８０〜１．２０である。このような優れた耐熱性を有しているため、電極及びリード電極の接続部に銀ペーストを塗布し、１５０℃の温度で硬化させる際に、透明電極の表面抵抗値の変化が極めて小さく、品質の安定したタッチパネルを製造することができる。本発明の透明電極は、大気中で２００℃にて１時間加熱する耐熱試験においても、試験前の表面抵抗Ｒ０と試験後の表面抵抗Ｒとしたとき、その変化（Ｒ／Ｒ０）が０．８０〜１．２０である。
従来の透明電極で上記と同様な耐熱試験を行い、表面抵抗Ｒの変化（Ｒ／Ｒ０）を測定すると、殆どのものが１．２０を超えることから、本発明の透明電極は、優れた耐熱性を有しているといえ、車載のカーナビ用タッチパネルの電極にも好適である。
The transparent electrode of the present invention thus obtained has a surface resistance R 0 before the test (room temperature) and a surface resistance R after the test in a heat resistance test that is heated in the atmosphere at a temperature of 150 ° C. or higher for 1 hour. The change (R / R 0 ) is 0.80 to 1.20. Because of having such excellent heat resistance, when the silver paste is applied to the connection portion of the electrode and the lead electrode and cured at a temperature of 150 ° C., the change in the surface resistance value of the transparent electrode is extremely small, A touch panel with stable quality can be manufactured. In the heat resistance test in which the transparent electrode of the present invention is heated in the atmosphere at 200 ° C. for 1 hour, when the surface resistance R 0 before the test and the surface resistance R after the test are taken, the change (R / R 0 ) 0.80 to 1.20.
When a heat resistance test similar to the above was performed on a conventional transparent electrode and the change in surface resistance R (R / R 0 ) was measured, most of them exceeded 1.20. Therefore, the transparent electrode of the present invention was excellent. Although it has heat resistance, it is also suitable for an electrode of a car navigation touch panel.
２．透明導電性基板
本発明の透明導電性基板は、上記透明電極が、透明基板の表面に形成されてなるものである。
2. Transparent conductive substrate The transparent conductive substrate of the present invention is such that the transparent electrode is formed on the surface of the transparent substrate.
本発明の透明導電性基板は、酸化インジウムを主成分とする結晶性透明導電膜と酸化インジウムを主成分とする非晶質性透明導電膜が順次形成された積層構造の透明電極を有する透明な基体である。前記のとおり、結晶性透明導電膜は膜厚が５〜４０ｎｍであり、非晶質性透明導電膜は膜厚が２〜１０ｎｍであり、表面抵抗が７０〜３０００Ω／□である。
透明な基体は、上記の製造工程においても変質しない耐熱性に優れた材質である必要があり、ガラスや２００℃以上の耐熱性を有する耐熱性樹脂板、耐熱性樹脂フィルムが適しており、具体的には、ポリイミド、アラミド、ポリフェニレンサルファド、ポリエーテルサルフォンなどが挙げられるが、これらに限定されない。樹脂板や樹脂フィルムは、その内部もしくは表面に酸化シリコンや酸化窒化シリコンや窒化シリコンなどの無機膜が形成されていてもかまわない。その厚さは、特に制限されないが、ガラスと耐熱性樹脂板では０．３〜３．２ｍｍ、耐熱性樹脂フィルムであれば、５０μｍ〜３．２ｍｍが適切である。
The transparent conductive substrate of the present invention has a transparent electrode having a laminated structure in which a crystalline transparent conductive film mainly composed of indium oxide and an amorphous transparent conductive film mainly composed of indium oxide are sequentially formed. It is a substrate. As described above, the crystalline transparent conductive film has a thickness of 5 to 40 nm, the amorphous transparent conductive film has a thickness of 2 to 10 nm, and the surface resistance is 70 to 3000 Ω / □.
The transparent substrate needs to be a material having excellent heat resistance that does not change even in the above manufacturing process, and glass, a heat resistant resin plate having a heat resistance of 200 ° C. or higher, and a heat resistant resin film are suitable. Specific examples include, but are not limited to, polyimide, aramid, polyphenylene sulfide, polyether sulfone, and the like. The resin plate or the resin film may have an inorganic film such as silicon oxide, silicon oxynitride, or silicon nitride formed inside or on the surface thereof. Although the thickness in particular is not restrict | limited, For glass and a heat resistant resin board, 0.3-3.2 mm is appropriate, and if it is a heat resistant resin film, 50 micrometers-3.2 mm are suitable.
３．透明タッチパネル
また、本発明の透明タッチパネルは、上記透明導電性基板を下部電極及び／又は上部電極として用いて得られ、図２のように下部電極と上部電極とがスペーサを介して向かい合って積層された構造である。上部電極または下部電極の基板は、ガラス、樹脂板、樹脂フィルムのいずれかでよいが、ガラス基板であれば、機械的強度があり、多くの用途に採用できる。本発明の透明タッチパネルでは、少なくとも一方の電極に、上記の耐熱性に優れた透明電極を用いていることから、車載のカーナビ用途にも好適に利用できるものである。
3. Transparent touch panel The transparent touch panel of the present invention is obtained by using the transparent conductive substrate as a lower electrode and / or an upper electrode, and the lower electrode and the upper electrode are laminated with a spacer therebetween as shown in FIG. Structure. The substrate of the upper electrode or the lower electrode may be glass, a resin plate, or a resin film, but if it is a glass substrate, it has mechanical strength and can be used for many applications. In the transparent touch panel of the present invention, since the transparent electrode having excellent heat resistance is used for at least one of the electrodes, it can be suitably used for in-vehicle car navigation applications.
アナログ式タッチパネルでは、図２に示すように、透明電極（４−１）が形成されたガラス製の基板（３−１）からなる上部電極（６）を用意し、透明電極（４−１）の形成面に、レジスト印刷して、エッチングし、銀インキ印刷と絶縁インキ印刷を行い、平行電極と引回し回路を形成する。その後、導電性ヒートシールインキで印刷し、両面テ−プを用いて貼り合わせ、打ち抜いて電極とする。また、ガラス製の基板（３−２）に透明導電膜（４−２）を設けた下部電極９を用意して、これも同様に平行電極と引回し回路を作製する。次に、両者の透明電極面が向かい合わせになるようにして、スペーサ（５、９）を配設して、間隔を空けて上下電極を貼り合わせる。スペーサとしては、例えば直径３〜１０μｍ程度の球状のガラスや硬質樹脂が好ましい。その使用量は、スペーサの種類やタッチパネルのタイプにもよるが、例えば５０〜３００個／ｍｍ２の密度で配設することが好ましい。また、上下電極の間隔は、タッチパネルのタイプにもよるが、例えば３〜２０μｍ空けることが好ましい。最後に、ヒートシール加工して、電気的に接続してタッチパネルとする。 In the analog touch panel, as shown in FIG. 2, an upper electrode (6) made of a glass substrate (3-1) on which a transparent electrode (4-1) is formed is prepared, and the transparent electrode (4-1) On the formation surface, resist printing, etching, silver ink printing and insulating ink printing are performed to form parallel electrodes and routing circuits. Then, it prints with electroconductive heat seal ink, it bonds together using a double-sided tape, and it punches out to make an electrode. Moreover, the lower electrode 9 which provided the transparent conductive film (4-2) on the glass-made board | substrate (3-2) is prepared, and a parallel electrode and a lead circuit are similarly produced for this. Next, spacers (5, 9) are disposed so that the transparent electrode surfaces of the two faces each other, and the upper and lower electrodes are bonded to each other with a space therebetween. As the spacer, for example, spherical glass or hard resin having a diameter of about 3 to 10 μm is preferable. The amount used depends on the type of the spacer and the type of the touch panel, but it is preferably disposed at a density of 50 to 300 / mm 2 , for example. Moreover, although the space | interval of an upper-and-lower electrode is based also on the type of a touch panel, it is preferable to leave 3-20 micrometers, for example. Finally, it is heat-sealed and electrically connected to form a touch panel.
本発明の透明タッチパネルは、ＬＣＤを直接貼りつけることが可能であり、これにより反射光が減少し、表示が見やすくなる。また、落下による割れを防止するために、構成部材である透明基板をより衝撃強度の高いガラスとしたり、特殊樹脂を用いたりすることもできる。本発明の透明タッチパネルは、これらの公知の構成のいずれを採ってもかまわない。
本発明の透明タッチパネルは、ＬＣＤや有機ＥＬなどの表示体に搭載されて使用される。ペンで入力した場合、透明タッチパネルを通して加わった力がＬＣＤなどの表示を滲ませることがあるので、透明タッチパネルはＬＣＤと空隙を設けて取り付けられるのが好ましい。
The transparent touch panel of the present invention can be directly attached to the LCD, which reduces reflected light and makes the display easier to see. Moreover, in order to prevent the crack by fall, the transparent substrate which is a structural member can be made into glass with higher impact strength, or special resin can also be used. The transparent touch panel of the present invention may adopt any of these known configurations.
The transparent touch panel of the present invention is used by being mounted on a display body such as an LCD or an organic EL. When the input is performed with a pen, the force applied through the transparent touch panel may blur the display of the LCD or the like. Therefore, the transparent touch panel is preferably attached with a gap from the LCD.
以下に、上記実施形態のより具体的な実施例を挙げ、その優れた作用効果を比較例と対比して示す。本発明は、これら実施例によって限定されるものではない。なお、積層体の透明電極の特性・性状は次のようにして測定し評価した。 Hereinafter, more specific examples of the above-described embodiment will be given, and the excellent operational effects will be shown in comparison with comparative examples. The present invention is not limited to these examples. The properties and properties of the transparent electrode of the laminate were measured and evaluated as follows.
＜透明電極各層の結晶性＞
積層体の透明電極層の結晶性は、ＦＩＢ加工により薄片化して、断面ＴＥＭ観察と電子線回折測定にて実施した。各層の膜厚も断面ＴＥＭ像から測定した。試料の第１層および第２層の断面ＴＥＭ観察を行い、結晶配列が観察されている層は結晶性と判断し、配列されていない層は非晶質と判断した。また、第１層および第２層に電子線回折を行い、回折斑点や回折リングが観察された層は結晶質と判断し、ハローパターンが観察された層は非晶質と判断した。
<Crystallinity of each layer of transparent electrode>
The crystallinity of the transparent electrode layer of the laminate was thinned by FIB processing and carried out by cross-sectional TEM observation and electron diffraction measurement. The film thickness of each layer was also measured from a cross-sectional TEM image. Cross-sectional TEM observation of the first layer and the second layer of the sample was performed, and the layer in which the crystal alignment was observed was determined to be crystalline, and the non-arranged layer was determined to be amorphous. Further, electron beam diffraction was performed on the first layer and the second layer, and the layer in which diffraction spots and diffraction rings were observed was judged to be crystalline, and the layer in which the halo pattern was observed was judged to be amorphous.
＜透明電極膜の特性評価＞
表面抵抗値は、抵抗率測定装置（三菱化学製Ｌｏｒｅｓｔａ―ＥＰ ＭＣＰ―Ｔ３６０）を用いて四端針法により測定した。
分光透過特性は、分光光度計（日本分光製、Ｖ−５７０）で測定した。基板のみの透過率（ＴＳ（％））と膜が付着した基板の透過率（ＴＳ＋Ｆ（％））を波長１ｎｍ毎に測定し、膜自体の透過率（ＴＦ（％）＝（ＴＳ＋Ｆ／ＴＳ）×１００）を算出し、可視域（波長４００〜８００ｎｍ）の平均透過率を算出した。
<Characteristic evaluation of transparent electrode film>
The surface resistance value was measured by a four-end needle method using a resistivity measuring device (Loresta-EP MCP-T360 manufactured by Mitsubishi Chemical Corporation).
Spectral transmission characteristics were measured with a spectrophotometer (manufactured by JASCO, V-570). The transmittance of only the substrate (T S (%)) and the transmittance of the substrate to which the film is attached (T S + F (%)) are measured every wavelength of 1 nm, and the transmittance of the film itself (T F (%) = (T S + F / T S ) × 100) and the average transmittance in the visible region (wavelength 400 to 800 nm) was calculated.
＜各層の膜の組成分析＞
合成石英基板に、第１層の薄膜のみを２μｍの膜厚だけ成膜した。その成膜条件は、透明電極の作製における結晶性透明導電膜の成膜条件と同じにした。この膜サンプルを用いて、ＩＣＰ発光分光分析法による組成を分析し、透明電極における第１層の薄膜の組成とした。第２層の薄膜の組成も同様の手順で決定した。また、この膜のＸ線回折測定を行い、下記の積層体を作製したときの各層の結晶性を予備的に解析した。
<Composition analysis of each layer film>
Only a thin film of the first layer was formed to a thickness of 2 μm on a synthetic quartz substrate. The film formation conditions were the same as the film formation conditions for the crystalline transparent conductive film in the production of the transparent electrode. Using this film sample, the composition by ICP emission spectroscopic analysis was analyzed to obtain the composition of the thin film of the first layer in the transparent electrode. The composition of the second layer thin film was determined in the same procedure. Moreover, the X-ray diffraction measurement of this film | membrane was performed, and the crystallinity of each layer when producing the following laminated body was analyzed preliminary.
（実施例１〜１４、比較例１〜６）
まず、下記の要領で薄膜作製用ターゲットを作製した。
＜第１層の薄膜作製用ターゲット＞
（１）Ｉｎ−Ｔｉ−Ｏ系透明導電膜作製用ターゲット
所定量の酸化インジウム粉末と酸化チタン粉末を様々な割合で混合し、その混合体を成形した後、加熱焼結して、チタンを含有する酸化インジウム焼結体を作製した。これらの焼結体を６インチΦ×５ｍｍｔに加工し、Ｉｎ系合金を用いて無酸素銅製のバッキングプレートに貼り合わせてスパッタリング用ターゲットとした。
（２）Ｉｎ−Ｓｎ−Ｏ系透明導電膜作製用ターゲット
所定量の酸化インジウム粉末と酸化スズ粉末を様々な割合で混合し、その混合体を成形した後、加熱焼結して、スズを含有する酸化インジウム焼結体を作製した。これらの焼結体を６インチΦ×５ｍｍｔに加工し、Ｉｎ系合金を用いて無酸素銅製のバッキングプレートに貼り合わせてスパッタリング用ターゲットとした。
（３）Ｉｎ−Ｔｉ−Ｓｎ−Ｏ系透明導電膜作製用ターゲット
所定量の酸化インジウム粉末と酸化チタン粉末と酸化スズ粉末を様々な割合で混合し、その混合体を成形した後、加熱焼結して、チタンとスズを含有する酸化インジウム焼結体を作製した。これらの焼結体を６インチΦ×５ｍｍｔに加工し、Ｉｎ系合金を用いて無酸素銅製のバッキングプレートに貼り合わせてスパッタリング用ターゲットとした。
＜第２層の薄膜作製用ターゲット＞
（４）Ｉｎ−Ｇａ−Ｏ系透明導電膜作製用ターゲット
所定量の酸化インジウム粉末と酸化ガリウム粉末を様々な割合で混合し、その混合体を成形した後、加熱焼結して、チタンを含有する酸化インジウム焼結体を作製した。これらの焼結体を６インチΦ×５ｍｍｔに加工し、Ｉｎ系合金を用いて無酸素銅製のバッキングプレートに貼り合わせてスパッタリング用ターゲットとした。
（５）Ｉｎ−Ｓｎ−Ｏ系透明導電膜作製用ターゲット
所定量の酸化インジウム粉末と酸化スズ粉末を様々な割合で混合し、その混合体を成形した後、加熱焼結して、スズを含有する酸化インジウム焼結体を作製した。これらの焼結体を６インチΦ×５ｍｍｔに加工し、Ｉｎ系合金を用いて無酸素銅製のバッキングプレートに貼り合わせてスパッタリング用ターゲットとした。これは前記（２）と同じものである。
（６）Ｉｎ−Ｇａ−Ｓｎ−Ｏ系透明導電膜作製用ターゲット
所定量の酸化インジウム粉末と酸化ガリウムと酸化スズ粉末を様々な割合で混合し、その混合体を成形した後、加熱焼結して、スズを含有する酸化インジウム焼結体を作製した。これらの焼結体を６インチΦ×５ｍｍｔに加工し、Ｉｎ系合金を用いて無酸素銅製のバッキングプレートに貼り合わせてスパッタリング用ターゲットとした。
(Examples 1-14, Comparative Examples 1-6)
First, a thin film production target was produced in the following manner.
<First Layer Thin Film Target>
(1) In-Ti-O-based transparent conductive film production target A predetermined amount of indium oxide powder and titanium oxide powder are mixed in various proportions, the mixture is molded, and then heated and sintered to contain titanium. An indium oxide sintered body was prepared. These sintered bodies were processed into 6 inches Φ × 5 mmt, and bonded to a backing plate made of oxygen-free copper using an In-based alloy to obtain a sputtering target.
(2) Target for preparing an In—Sn—O-based transparent conductive film A predetermined amount of indium oxide powder and tin oxide powder are mixed in various proportions, the mixture is molded, and then heated and sintered to contain tin. An indium oxide sintered body was prepared. These sintered bodies were processed into 6 inches Φ × 5 mmt, and bonded to a backing plate made of oxygen-free copper using an In-based alloy to obtain a sputtering target.
(3) In-Ti-Sn-O-based transparent conductive film preparation target A predetermined amount of indium oxide powder, titanium oxide powder, and tin oxide powder are mixed in various proportions, the mixture is molded, and then heated and sintered. Thus, an indium oxide sintered body containing titanium and tin was produced. These sintered bodies were processed into 6 inches Φ × 5 mmt, and bonded to a backing plate made of oxygen-free copper using an In-based alloy to obtain a sputtering target.
<Second-layer thin film target>
(4) In-Ga-O-based transparent conductive film production target A predetermined amount of indium oxide powder and gallium oxide powder are mixed in various proportions, and the mixture is molded, then heated and sintered to contain titanium. An indium oxide sintered body was prepared. These sintered bodies were processed into 6 inches Φ × 5 mmt, and bonded to a backing plate made of oxygen-free copper using an In-based alloy to obtain a sputtering target.
(5) In-Sn-O-based transparent conductive film production target A predetermined amount of indium oxide powder and tin oxide powder are mixed in various proportions, and the mixture is molded, then heated and sintered to contain tin. An indium oxide sintered body was prepared. These sintered bodies were processed into 6 inches Φ × 5 mmt, and bonded to a backing plate made of oxygen-free copper using an In-based alloy to obtain a sputtering target. This is the same as (2) above.
(6) In—Ga—Sn—O-based transparent conductive film production target A predetermined amount of indium oxide powder, gallium oxide and tin oxide powder are mixed in various proportions, the mixture is molded, and then heated and sintered. Thus, an indium oxide sintered body containing tin was produced. These sintered bodies were processed into 6 inches Φ × 5 mmt, and bonded to a backing plate made of oxygen-free copper using an In-based alloy to obtain a sputtering target.
＜透明電極の作製＞
次に、直流マグネトロンスパッタリング装置の２カ所の非磁性体ターゲット用カソードに、（１）〜（３）のなかの１つのターゲットと、（４）〜（６）のなかの１つのターゲットを取り付けた。
基板ホルダーには厚み１ｍｍのガラス基板を取り付けた。基板ホルダーは成膜真空槽内で移動することができ、各ターゲットの対向面に基板を配置させることができる。初めに第１層の薄膜作製用ターゲットの対向部分に基板を静止配置させて第１層の薄膜を成膜した後、その基板を第２層の薄膜作製用ターゲットの対向部分に静止配置させて第２層の薄膜を成膜し、透明電極を作製した。各ターゲットと基板との距離は５０〜８０ｍｍとした。
その後、実施例１〜１０及び比較例１〜４では、成膜真空槽内の基板ホルダーに固定したガラス基板を３００℃の温度に加熱し、成膜真空槽内の真空度が１×１０―４Ｐａ以下に達した時点で、純度９９．９９９９質量％のアルゴンガスを成膜真空槽に導入して、ガス圧０．３〜０．８Ｐａとし、酸素ガスを０．２５〜５％だけアルゴンガス中に混合させた。ターゲットと基板間に直流電力３５０Ｗを投入して直流プラズマを発生させ、スパッタリング成膜を行った。各ターゲットとも、ターゲット表面のクリーニングの為に２０分間のプリスパッタを行った後、所定の膜厚の第１層の薄膜と第２層の薄膜を順次成膜した。
一方、実施例１１〜１４及び比較例５〜６では、成膜真空槽内の基板ホルダーに固定したガラス基板を２００℃の温度に加熱した以外は、上記と同様に行った。
<Preparation of transparent electrode>
Next, one target from (1) to (3) and one target from (4) to (6) were attached to the two nonmagnetic target cathodes of the DC magnetron sputtering apparatus. .
A glass substrate having a thickness of 1 mm was attached to the substrate holder. The substrate holder can be moved in the deposition vacuum chamber, and the substrate can be disposed on the opposing surface of each target. First, the substrate is stationaryly arranged on the facing portion of the first layer thin film production target to form the first layer thin film, and then the substrate is statically arranged on the facing portion of the second layer thin film production target. A second layer thin film was formed to produce a transparent electrode. The distance between each target and the substrate was 50 to 80 mm.
Thereafter, in Examples 1 to 10 and Comparative Examples 1 to 4, the glass substrate fixed to the substrate holder in the film formation vacuum chamber was heated to a temperature of 300 ° C., and the degree of vacuum in the film formation vacuum chamber was 1 × 10 −. When the pressure reaches 4 Pa or less, argon gas having a purity of 99.9999% by mass is introduced into the film-formation vacuum chamber so that the gas pressure is 0.3 to 0.8 Pa and oxygen gas is argon by 0.25 to 5%. Mixed into gas. A direct current power of 350 W was applied between the target and the substrate to generate direct current plasma, and sputtering film formation was performed. Each target was pre-sputtered for 20 minutes to clean the target surface, and then a first layer thin film and a second layer thin film having a predetermined thickness were sequentially formed.
On the other hand, in Examples 11-14 and Comparative Examples 5-6, it carried out similarly to the above except having heated the glass substrate fixed to the substrate holder in the film-forming vacuum chamber to the temperature of 200 degreeC.
＜加熱試験＞
実施例１〜１０及び比較例１〜４では、作製した透明電極を２００℃に加熱した大気オーブンに入れて、１時間加熱した後、オーブンから取り出して室温まで冷却した。加熱試験前後の室温（２３℃）における透明電極の表面抵抗値は四探針法によって測定した。
また、実施例１１〜１４及び比較例５〜６では、作製した透明電極を、１５０℃に加熱した大気オーブンに入れて、１時間加熱した後、オーブンから取り出して室温（２３℃）まで冷却して表面抵抗値の測定を行った。
作製した透明電極の構成と、加熱試験の結果を表１に示す。
<Heating test>
In Examples 1 to 10 and Comparative Examples 1 to 4, the produced transparent electrode was put in an atmospheric oven heated to 200 ° C., heated for 1 hour, then taken out of the oven and cooled to room temperature. The surface resistance value of the transparent electrode at room temperature (23 ° C.) before and after the heating test was measured by the four probe method.
Moreover, in Examples 11-14 and Comparative Examples 5-6, the produced transparent electrode was put into the atmospheric oven heated at 150 degreeC, and after heating for 1 hour, it took out from oven and cooled to room temperature (23 degreeC). The surface resistance value was measured.
Table 1 shows the configuration of the produced transparent electrode and the results of the heating test.
＜評価＞
表１の実施例１〜１０、比較例１〜４は、３００℃にて成膜した透明電極であり、加熱試験は２００℃にて実施した結果である。図３に実施例１の透明電極の断面ＴＥＭ像を示す。図３には基板３（この場合、ガラス基板）の上に、結晶粒界７で確認される結晶性透明導電膜１（この場合、Ｉｎ−Ｔｉ−Ｓｎ−Ｏ膜）が形成されていることが確認された。また膜１の上には、膜厚４ｎｍの膜２が形成されているが、結晶粒界が存在しないこと、原子配列が規則的でないことから非晶質性透明導電膜２（この場合、Ｉｎ−Ｇａ−Ｏ膜）であることが確認できた。また１ｎｍの領域に電子線を絞って局所領域での電子線回折測定を行うと、膜１は回折スポットが観察されたことからも結晶膜であることが確認され、膜２はハローパターンが観察されたことから非晶質膜であることが確認された。実施例１以外の各透明電極（比較例も含む）についても同様のＴＥＭと電子線回折測定から各層の結晶性を評価し、その結果を表１に記した。表１から明らかなように、比較例１〜４の透明電極は、第２層の薄膜が結晶質であるが、大気中２００℃で１時間加熱する試験前後の表面抵抗値の変化（Ｒ／Ｒ０）は、０．８０〜１．２０の範囲を逸脱しており、このような透明電極は、耐熱性を要求される車載カーナビなどのタッチパネルの電極としては利用できない。
<Evaluation>
Examples 1 to 10 and Comparative Examples 1 to 4 in Table 1 are transparent electrodes formed at 300 ° C., and the heating test is the result of carrying out at 200 ° C. FIG. 3 shows a cross-sectional TEM image of the transparent electrode of Example 1. In FIG. 3, a crystalline transparent conductive film 1 (in this case, an In—Ti—Sn—O film) confirmed at a crystal grain boundary 7 is formed on a substrate 3 (in this case, a glass substrate). Was confirmed. On the film 1, a film 2 having a thickness of 4 nm is formed. However, since there is no crystal grain boundary and the atomic arrangement is not regular, the amorphous transparent conductive film 2 (in this case, In -Ga-O film). Further, when electron beam diffraction measurement is performed in a local region by narrowing the electron beam to the 1 nm region, it is confirmed that the film 1 is a crystal film because a diffraction spot is observed, and the film 2 has a halo pattern observed. As a result, it was confirmed to be an amorphous film. For each of the transparent electrodes other than Example 1 (including comparative examples), the crystallinity of each layer was evaluated from the same TEM and electron diffraction measurement, and the results are shown in Table 1. As is clear from Table 1, in the transparent electrodes of Comparative Examples 1 to 4, the second layer thin film was crystalline, but the change in the surface resistance value before and after the test heated at 200 ° C. for 1 hour in the atmosphere (R / R 0 ) deviates from the range of 0.80 to 1.20, and such a transparent electrode cannot be used as an electrode for a touch panel such as an in-vehicle car navigation system that requires heat resistance.
一方、実施例１〜１０の透明電極は、第２層の薄膜がＩｎ−Ｇａ−Ｏ系もしくはＩｎ−Ｇａ−Ｓｎ−Ｏ系透明導電膜であり、３００℃で成膜したにもかかわらず非晶質であるため、第１層の透明導電膜の表面に薄く（膜厚で２〜１０ｎｍ）覆うことで、第１層の膜の酸化に対するバリア性を発揮し、加熱試験前後の表面抵抗値の変化（Ｒ／Ｒ０）が０．８０〜１．２０の範囲内に極めて小さく抑制することができている。また、加熱試験前の透明電極自体の可視域の平均透過率が９１％以上であり透過性についても優れていた。よって、このような透明電極は、耐熱性を要求される車載カーナビなどのタッチパネルの電極として有効に利用できる。 On the other hand, in the transparent electrodes of Examples 1 to 10, the second layer thin film was an In—Ga—O-based or In—Ga—Sn—O-based transparent conductive film, and was not formed even though it was formed at 300 ° C. Since it is crystalline, it covers the surface of the transparent conductive film of the first layer thinly (2 to 10 nm in thickness), thereby exhibiting a barrier property against oxidation of the film of the first layer, and the surface resistance value before and after the heating test Change (R / R 0 ) can be suppressed to an extremely small range of 0.80 to 1.20. Moreover, the average transmittance | permeability of the visible region of the transparent electrode itself before a heat test was 91% or more, and the transparency was also excellent. Therefore, such a transparent electrode can be effectively used as an electrode for a touch panel such as an in-vehicle car navigation system that requires heat resistance.
なお、表１の実施例１１〜１４、比較例５〜６は、２００℃にて成膜した透明電極であり、１５０℃での加熱試験を実施している。実施例１１〜１４の透明電極は、１５０℃で１時間の加熱試験で表面抵抗値の変化（Ｒ／Ｒ０）が１．０５未満であり、変化が極めて小さい。また、２００℃での成膜のときは、第２層の薄膜が非晶質となるための組成範囲（Ｇａ／Ｉｎ）は３００℃での成膜の時と比べて広い。例えば、３００℃での成膜の比較例１では、Ｇａ／Ｉｎ＝０．０８０の組成の第２層が結晶質であったが、２００℃での成膜の実施例１３では、同じ組成でも非晶質となっており、バリア効果が見られている。一般に、膜中のＧａ量が多くなると結晶化温度が高くなり、Ｇａ／Ｉｎ＝０．０８０の膜は、結晶化温度が２００〜３００℃の間に存在すると推測できる。
比較例５〜６は、大気中１５０℃で１時間加熱試験する前後の表面抵抗値の変化（Ｒ／Ｒ０）は、０．８０〜１．２０の範囲を逸脱している。比較例５〜６のような透明電極は、タッチパネル製造時の、電極及びリード電極の接続部に銀ペーストを塗布して硬化する際の加熱工程（１５０℃）において、抵抗値の変化が顕著であるため、特性の均一な安定に製造することができない。
In addition, Examples 11 to 14 and Comparative Examples 5 to 6 in Table 1 are transparent electrodes formed at 200 ° C., and a heating test at 150 ° C. is performed. In the transparent electrodes of Examples 11 to 14, the change in surface resistance value (R / R 0 ) was less than 1.05 in a heating test at 150 ° C. for 1 hour, and the change was extremely small. When the film is formed at 200 ° C., the composition range (Ga / In) for making the second layer thin film amorphous is wider than that at the time of film formation at 300 ° C. For example, in Comparative Example 1 of film formation at 300 ° C., the second layer having a composition of Ga / In = 0.080 was crystalline, but in Example 13 of film formation at 200 ° C., the same composition was used. It is amorphous and has a barrier effect. In general, when the amount of Ga in the film increases, the crystallization temperature increases, and it can be assumed that a film with Ga / In = 0.080 exists between 200 and 300 ° C. in the crystallization temperature.
In Comparative Examples 5 to 6, the change in surface resistance value (R / R 0 ) before and after the heat test at 150 ° C. for 1 hour in the atmosphere deviates from the range of 0.80 to 1.20. In the transparent electrode as in Comparative Examples 5 to 6, in the heating process (150 ° C.) when the silver paste is applied to the connection portion of the electrode and the lead electrode and cured at the time of manufacturing the touch panel, the resistance value changes significantly. For this reason, it cannot be manufactured with uniform and stable characteristics.
（実施例１５〜１６、比較例７〜８）
第２層の薄膜としてＩｎ−Ｃｅ−Ｏ系、Ｉｎ−Ｃｅ−Ｓｎ−Ｏ系を選択した以外は実施例１３〜１４と同様の要領で透明電極を作製し評価した。ターゲットの作製は以下の要領で実施した。スパッタリングによる成膜時の基板温度は２００℃とした。
（７）Ｉｎ−Ｃｅ−Ｏ系透明導電膜作製用ターゲット
所定量の酸化インジウム粉末と酸化セリウム粉末を様々な割合で混合し、その混合体を成形した後、加熱焼結して、セリウムを含有する酸化インジウム焼結体を作製した。これらの焼結体を６インチΦ×５ｍｍｔに加工し、Ｉｎ系合金を用いて無酸素銅製のバッキングプレートに貼り合わせてスパッタリング用ターゲットとした。
（８）Ｉｎ−Ｃｅ−Ｓｎ−Ｏ系透明導電膜作製用ターゲット
所定量の酸化インジウム粉末と酸化セリウム粉末と酸化スズ粉末を様々な割合で混合し、その混合体を成形した後、加熱焼結して、セリウムとスズを含有する酸化インジウム焼結体を作製した。これらの焼結体を６インチΦ×５ｍｍｔに加工し、Ｉｎ系合金を用いて無酸素銅製のバッキングプレートに貼り合わせてスパッタリング用ターゲットとした。
評価結果を表２に示す。
(Examples 15-16, Comparative Examples 7-8)
A transparent electrode was prepared and evaluated in the same manner as in Examples 13 to 14 except that In—Ce—O and In—Ce—Sn—O were selected as the second layer thin film. The target was produced as follows. The substrate temperature during film formation by sputtering was 200 ° C.
(7) In-Ce-O-based transparent conductive film production target A predetermined amount of indium oxide powder and cerium oxide powder are mixed in various proportions, the mixture is molded, and then heated and sintered to contain cerium. An indium oxide sintered body was prepared. These sintered bodies were processed into 6 inches Φ × 5 mmt, and bonded to a backing plate made of oxygen-free copper using an In-based alloy to obtain a sputtering target.
(8) In-Ce-Sn-O-based transparent conductive film preparation target A predetermined amount of indium oxide powder, cerium oxide powder, and tin oxide powder are mixed in various proportions, the mixture is molded, and then heated and sintered. Thus, an indium oxide sintered body containing cerium and tin was produced. These sintered bodies were processed into 6 inches Φ × 5 mmt, and bonded to a backing plate made of oxygen-free copper using an In-based alloy to obtain a sputtering target.
The evaluation results are shown in Table 2.
比較例７〜８は、第２層のＩｎ−Ｃｅ−Ｏ（Ｉｎ−Ｃｅ−Ｓｎ−Ｏ）系薄膜が結晶質膜であるため、大気中１５０℃で１時間加熱する試験前後の表面抵抗値の変化（Ｒ／Ｒ０）は、０．８０〜１．２０の範囲を逸脱してしまった。比較例７〜８のような透明電極は、タッチパネル製造時の、電極及びリード電極の接続部に銀ペーストを塗布して硬化する際の加熱工程（１５０℃）において、抵抗値の変化が顕著であるため、特性の均一な安定に製造することができない。実施例１５〜１６は、第２層のＩｎ−Ｃｅ−Ｏ（Ｉｎ−Ｃｅ−Ｓｎ−Ｏ）系薄膜が非晶質膜で覆われているため、抵抗値変化はその範囲内におさまっている。また、加熱試験前の透明電極自体の可視域の平均透過率は９１％以上であり、透過性についても優れている。よって、実施例１５〜１６の透明電極は、耐熱性のタッチパネルの電極として有用である。 In Comparative Examples 7 to 8, since the In-Ce-O (In-Ce-Sn-O) thin film of the second layer is a crystalline film, the surface resistance values before and after the test heated at 150 ° C. for 1 hour in the atmosphere Change (R / R 0 ) deviated from the range of 0.80 to 1.20. In the transparent electrode as in Comparative Examples 7 to 8, the resistance value changes significantly in the heating step (150 ° C.) when the silver paste is applied to the connecting portion of the electrode and the lead electrode and cured when the touch panel is manufactured. For this reason, it cannot be manufactured with uniform and stable characteristics. In Examples 15 to 16, since the second-layer In—Ce—O (In—Ce—Sn—O) -based thin film is covered with an amorphous film, the change in resistance value is within that range. . Moreover, the average transmittance | permeability of the visible region of the transparent electrode itself before a heat test is 91% or more, and is excellent also about the transmittance | permeability. Therefore, the transparent electrode of Examples 15-16 is useful as an electrode of a heat resistant touch panel.
（実施例１７〜１８、比較例９〜１０）
第２層の薄膜としてＩｎ−Ｓｉ−Ｏ系、Ｉｎ−Ｓｉ−Ｓｎ−Ｏ系を選択した以外は実施例１３〜１４と同様の要領で透明電極を作製し評価した。ターゲットの作製は以下の要領で実施した。スパッタリングによる成膜時の基板温度は２００℃とした。
（９）Ｉｎ−Ｓｉ−Ｏ系透明導電膜作製用ターゲット
所定量の酸化インジウム粉末と酸化セリウム粉末を様々な割合で混合し、その混合体を成形した後、加熱焼結して、チタンを含有する酸化インジウム焼結体を作製した。これらの焼結体を６インチΦ×５ｍｍｔに加工し、Ｉｎ系合金を用いて無酸素銅製のバッキングプレートに貼り合わせてスパッタリング用ターゲットとした。
（１０）Ｉｎ−Ｓｉ−Ｓｎ−Ｏ系透明導電膜作製用ターゲット
所定量の酸化インジウム粉末と酸化セリウム粉末と酸化スズ粉末を様々な割合で混合し、その混合体を成形した後、加熱焼結して、チタンを含有する酸化インジウム焼結体を作製した。これらの焼結体を６インチΦ×５ｍｍｔに加工し、Ｉｎ系合金を用いて無酸素銅製のバッキングプレートに貼り合わせてスパッタリング用ターゲットとした。
評価結果を表３に示す。
(Examples 17-18, Comparative Examples 9-10)
A transparent electrode was prepared and evaluated in the same manner as in Examples 13 to 14 except that an In—Si—O system or an In—Si—Sn—O system was selected as the second layer thin film. The target was produced as follows. The substrate temperature during film formation by sputtering was 200 ° C.
(9) In-Si-O-based transparent conductive film production target A predetermined amount of indium oxide powder and cerium oxide powder are mixed in various proportions, the mixture is molded, and then heated and sintered to contain titanium. An indium oxide sintered body was prepared. These sintered bodies were processed into 6 inches Φ × 5 mmt, and bonded to a backing plate made of oxygen-free copper using an In-based alloy to obtain a sputtering target.
(10) In-Si-Sn-O-based transparent conductive film production target A predetermined amount of indium oxide powder, cerium oxide powder, and tin oxide powder are mixed in various proportions, the mixture is molded, and then heated and sintered. Thus, an indium oxide sintered body containing titanium was produced. These sintered bodies were processed into 6 inches Φ × 5 mmt, and bonded to a backing plate made of oxygen-free copper using an In-based alloy to obtain a sputtering target.
The evaluation results are shown in Table 3.
比較例９〜１０は、第２層のＩｎ−Ｓｉ−（Ｓｎ―）Ｏ系薄膜が結晶質膜であるため、大気中１５０℃で１時間の加熱試験前後の表面抵抗値の変化（Ｒ／Ｒ０）は、０．８０〜１．２０の範囲を逸脱してしまった。比較例９〜１０のような透明電極は、タッチパネル製造時の、電極及びリード電極を銀ペーストにて塗布して硬化する際の加熱工程（１５０℃）において、抵抗値の変化が顕著であるため、特性の均一な安定に製造することができない。一方、実施例１７〜１８は、第２層のＩｎ−Ｓｉ−（Ｓｎ―）Ｏ系薄膜が非晶質膜で覆われているため、抵抗値変化はその範囲内におさまっている。また加熱試験前の透明電極自体の可視域の平均透過率は９１％以上であり透過性についても優れている。よって実施例１７〜１８の透明電極は耐熱性が要求されるタッチパネルの電極として有用である。 In Comparative Examples 9 to 10, since the second layer In—Si— (Sn—) O-based thin film is a crystalline film, the change in the surface resistance value before and after the 1 hour heating test at 150 ° C. in the atmosphere (R / R 0 ) has deviated from the range of 0.80 to 1.20. The transparent electrodes as in Comparative Examples 9 to 10 have a remarkable change in resistance value in the heating step (150 ° C.) when the electrode and the lead electrode are applied with a silver paste and cured when the touch panel is manufactured. , It cannot be produced with uniform and stable characteristics. On the other hand, in Examples 17 to 18, since the second In-Si- (Sn-) O-based thin film is covered with an amorphous film, the change in resistance value is within that range. Moreover, the average transmittance | permeability of the visible region of the transparent electrode itself before a heat test is 91% or more, and is excellent also about the transmittance | permeability. Therefore, the transparent electrodes of Examples 17 to 18 are useful as electrodes for touch panels that require heat resistance.
（実施例１９〜２２、比較例１１〜１４）
第２層の薄膜として下記のＩｎ−Ｗ−Ｚｎ−Ｏ系、Ｉｎ−Ｚｎ−Ｏ系、Ｉｎ−Ｇｅ−Ｓｎ−Ｏ系、を選択した場合についても、実施例１３〜１４と同様の要領で実施した。表４、表５に示すように耐熱性試験の結果は同様であった。また、加熱試験前における実施例１９〜２２の透明電極自体の可視域の平均透過率は９１％以上であり透過性についても優れていた。
（１１）Ｉｎ−Ｗ−Ｚｎ−Ｏ系透明導電膜作製用ターゲット
所定量の酸化インジウム粉末と酸化タングステン粉末、酸化亜鉛粉末を様々な割合で混合し、その混合体を成形した後、加熱焼結して、タングステン、亜鉛を含有する酸化インジウム焼結体を作製した。これらの焼結体を６インチΦ×５ｍｍｔに加工し、Ｉｎ系合金を用いて無酸素銅製のバッキングプレートに貼り合わせてスパッタリング用ターゲットとした。
（１２）Ｉｎ−Ｚｎ−Ｏ系透明導電膜作製用ターゲット
所定量の酸化インジウム粉末と酸化亜鉛粉末を様々な割合で混合し、その混合体を成形した後、加熱焼結して、亜鉛を含有する酸化インジウム焼結体を作製した。これらの焼結体を６インチΦ×５ｍｍｔに加工し、Ｉｎ系合金を用いて無酸素銅製のバッキングプレートに貼り合わせてスパッタリング用ターゲットとした。
（１３）Ｉｎ−Ｇｅ−Ｓｎ−Ｏ系透明導電膜作製用ターゲット
所定量の酸化インジウム粉末と酸化ゲルマニウム、酸化スズ粉末を様々な割合で混合し、その混合体を成形した後、加熱焼結して、ゲルマニウム、スズを含有する酸化インジウム焼結体を作製した。これらの焼結体を６インチΦ×５ｍｍｔに加工し、Ｉｎ系合金を用いて無酸素銅製のバッキングプレートに貼り合わせてスパッタリング用ターゲットとした。
(Examples 19-22, Comparative Examples 11-14)
Even when the following In—W—Zn—O system, In—Zn—O system, and In—Ge—Sn—O system are selected as the second layer thin film, the same manner as in Examples 13 to 14 is used. Carried out. As shown in Tables 4 and 5, the results of the heat resistance test were the same. Moreover, the average transmittance | permeability of the visible region of the transparent electrode itself of Examples 19-22 before a heat test was 91% or more, and was excellent also about the transmittance | permeability.
(11) In-W-Zn-O-based transparent conductive film production target A predetermined amount of indium oxide powder, tungsten oxide powder, and zinc oxide powder are mixed in various proportions, the mixture is molded, and then heated and sintered. Thus, an indium oxide sintered body containing tungsten and zinc was produced. These sintered bodies were processed into 6 inches Φ × 5 mmt, and bonded to a backing plate made of oxygen-free copper using an In-based alloy to obtain a sputtering target.
(12) In-Zn-O-based transparent conductive film production target A predetermined amount of indium oxide powder and zinc oxide powder are mixed in various proportions, and the mixture is molded, then heated and sintered to contain zinc. An indium oxide sintered body was prepared. These sintered bodies were processed into 6 inches Φ × 5 mmt, and bonded to a backing plate made of oxygen-free copper using an In-based alloy to obtain a sputtering target.
(13) In-Ge-Sn-O-based transparent conductive film production target A predetermined amount of indium oxide powder, germanium oxide, and tin oxide powder are mixed in various proportions, and the mixture is molded, then heated and sintered. Thus, an indium oxide sintered body containing germanium and tin was produced. These sintered bodies were processed into 6 inches Φ × 5 mmt, and bonded to a backing plate made of oxygen-free copper using an In-based alloy to obtain a sputtering target.
（比較例１５〜２３）
実施例１〜７、実施例１３〜１４において、第２層を積層しない場合の透明電極の評価を同様に実施した。その結果を表６に示す。２００℃、１５０℃の何れの加熱試験においても、表面抵抗の変化は著しく、耐熱性に優れたタッチパネル用透明電極としては利用できない。
(Comparative Examples 15-23)
In Examples 1-7 and Examples 13-14, evaluation of the transparent electrode in the case where the second layer was not laminated was performed in the same manner. The results are shown in Table 6. In any of the heating tests at 200 ° C. and 150 ° C., the change in surface resistance is remarkable and cannot be used as a transparent electrode for a touch panel having excellent heat resistance.
（比較例２４〜２５）
実施例１５〜１６において、第１層を積層しない場合の透明電極の評価を同様に実施した。その結果を表７に示す。１５０℃の加熱試験においても、表面抵抗の変化は小さく、耐熱性に優れた透明電極であった。しかし、後述する比較例２９におけるタッチパネルを組み立て、耐熱性、耐湿性試験を行うと、膜剥がれが激しく、タッチパネル用透明電極としては利用できない。
(Comparative Examples 24-25)
In Examples 15 to 16, the transparent electrode was evaluated in the same manner when the first layer was not laminated. The results are shown in Table 7. Even in the heating test at 150 ° C., the change in surface resistance was small, and the transparent electrode was excellent in heat resistance. However, when a touch panel in Comparative Example 29 described later is assembled and a heat resistance and moisture resistance test is performed, film peeling off is severe and cannot be used as a transparent electrode for a touch panel.
（比較例２６〜２７）
実施例１〜２において、第１層の膜と第２層の膜を入れ替えた積層構造、すなわち、基板の上に非晶質透明導電膜を形成し、その上に結晶質透明導電膜を積層した構造の透明電極を作成した。作製条件は実施例１〜２と同じである。透明電極の構成と、実施例１〜２と同様の要領で加熱試験を行ったときの抵抗値変化を表８に記した。２００℃の加熱試験において、表面抵抗の変化は著しく、耐熱性に優れたタッチパネル用透明電極としては利用できないことがわかった。また、１５０℃の加熱試験においても、同様の結果であり抵抗値変化は大きかった。
(Comparative Examples 26-27)
In Examples 1 and 2, a laminated structure in which the first layer film and the second layer film are interchanged, that is, an amorphous transparent conductive film is formed on a substrate, and a crystalline transparent conductive film is stacked thereon. A transparent electrode having the above structure was prepared. The production conditions are the same as in Examples 1-2. Table 8 shows the structure of the transparent electrode and the change in resistance value when the heating test was performed in the same manner as in Examples 1 and 2. In the heating test at 200 ° C., the change in surface resistance was remarkable, and it was found that it could not be used as a transparent electrode for a touch panel having excellent heat resistance. In the heating test at 150 ° C., the same result was obtained, and the resistance value change was large.
（比較例２８）
実施例８において、第２層の非晶質透明導電膜の膜厚を２０ｎｍに変えた以外は、全く同様の積層構造の透明電極膜を作製した。実施例８と同様に加熱試験を行ったときの抵抗値変化は、実施例８と同様に小さく、耐熱性に優れた透明電極であったが、実施例８と同様の方法で加熱試験前に測定した透明電極自体の可視域の平均透過率は８８％であり、実施例と比べて透過性に劣っていた。よって、視認性を重要視するタッチパネル用透明電極としては利用できない。
(Comparative Example 28)
In Example 8, a transparent electrode film having the same laminated structure was produced except that the film thickness of the second layer of amorphous transparent conductive film was changed to 20 nm. The change in resistance value when the heating test was performed in the same manner as in Example 8 was a transparent electrode having a small and excellent heat resistance as in Example 8, but before the heating test in the same manner as in Example 8. The average transmittance in the visible region of the measured transparent electrode itself was 88%, which was inferior in permeability compared to the examples. Therefore, it cannot be used as a transparent electrode for a touch panel that places importance on visibility.
（実施例２３）
実施例１〜２２で得られた透明電極付ガラス基板を用いて、常法により、図２に示すようなアナログ式タッチパネルを作製した。
まず、実施例１〜２２の透明電極（４−１）が形成されたガラス製の基板（３−１）からなる上部電極（６）を用意し、透明電極（４−１）の形成面に、レジスト印刷して、エッチングし、銀インキ印刷と絶縁インキ印刷を行い、平行電極と引回し回路を形成した。その後、導電性ヒートシールインキで印刷し、両面テ−プを用いて貼り合わせ、打ち抜いて電極とした。ガラス製の基板（３−２）に透明導電膜（４−２）を設けた下部電極９も同様にして、平行電極と引回し回路を作製した。透明電極面を向かい合わせにして、直径７μｍの球状のスペーサ（５、９）を１００個／ｍｍ２の密度で配設して、間隔を７μｍ空けて上下電極を貼り合わせ、ヒートシール加工して、電気的に接続してタッチパネルを製造した。
タッチパネルの組み立てには、加熱工程を含むが、得られたタッチパネルの抵抗値分布（いわゆるリニアリティ）は良好であった。これは、耐熱性に優れる実施例１〜２２の透明導電膜の良好なリニアリティが維持されているためと考えられる。
作製したタッチパネルに対して、耐熱性試験（９０℃，２４ｈ）を行った後で、１ｍｍ２の面積に圧力１．９６Ｎ（２００ｇ）を加えて２秒間、タッチパネル表面を押す行為を５００回繰り返す試験（以下、押し試験という）を行った。試験前後のタッチパネルの表面の状態を目視及び顕微鏡により観察したところ、膜剥がれは全くなく、耐熱性に極めて優れていることがわかった。
また、耐湿性試験として、セルの電極間に、６０℃、９５％ＲＨの雰囲気下で、８Ｖの電位を２５０時間印加し、その後、正の電位を印加した側の透明導電膜について、シート抵抗値を測定し、初期シート抵抗値との比を算出し判定したところ、１．０２〜１．０５であり、変化が非常に小さく、高い可視光線透過率を維持しており、耐湿性はきわめて良好であった。
(Example 23)
Using the glass substrate with a transparent electrode obtained in Examples 1 to 22, an analog touch panel as shown in FIG. 2 was produced by a conventional method.
First, the upper electrode (6) which consists of the glass-made board | substrates (3-1) in which the transparent electrode (4-1) of Examples 1-22 was formed is prepared, and it forms in the formation surface of a transparent electrode (4-1). Then, resist printing, etching, silver ink printing and insulating ink printing were performed, and parallel electrodes and routing circuits were formed. Then, it printed with the electroconductive heat seal ink, bonded together using the double-sided tape, and was punched out, and it was set as the electrode. Similarly, the lower electrode 9 provided with the transparent conductive film (4-2) on the glass substrate (3-2) was also connected to the parallel electrode to produce a circuit. With the transparent electrode faces facing each other, spherical spacers (5, 9) with a diameter of 7 μm are arranged at a density of 100 pieces / mm 2 , the upper and lower electrodes are bonded together with a spacing of 7 μm, and heat sealing is performed. The touch panel was manufactured by electrical connection.
The assembly of the touch panel includes a heating step, but the resistance value distribution (so-called linearity) of the obtained touch panel was good. This is considered because the favorable linearity of the transparent conductive film of Examples 1-22 excellent in heat resistance is maintained.
A test that repeats the action of pressing the surface of the touch panel 500 times for 2 seconds after applying a pressure 1.96N (200 g) to an area of 1 mm 2 after performing a heat resistance test (90 ° C., 24 h) on the manufactured touch panel (Hereinafter referred to as a push test). When the surface state of the touch panel before and after the test was observed visually and with a microscope, it was found that there was no film peeling and the heat resistance was extremely excellent.
Further, as a moisture resistance test, a sheet resistance was applied to the transparent conductive film on the side to which a positive potential was applied after applying a potential of 8 V for 250 hours between the electrodes of the cell in an atmosphere of 60 ° C. and 95% RH. When the value was measured and the ratio with the initial sheet resistance value was calculated and judged, it was 1.02 to 1.05, the change was very small, high visible light transmittance was maintained, and the moisture resistance was extremely high. It was good.
（実施例２４）
上部電極に、市販されている透明導電膜付き樹脂フィルム（商品名：３００ＲＫ、東洋紡社製、フィルム材質：ＰＥＴ、透明導電膜：ＩＴＯ膜、厚さ１２５μｍ）を用いた以外は実施例２３と同様にパネル化したところ、実施例２３と同様に耐熱性、耐湿性は良好な結果を示した。
(Example 24)
The same as Example 23, except that a commercially available resin film with a transparent conductive film (trade name: 300RK, manufactured by Toyobo Co., Ltd., film material: PET, transparent conductive film: ITO film, thickness 125 μm) was used for the upper electrode. As a result, the heat resistance and moisture resistance were good as in Example 23.
（比較例２９）
実施例２３と同様に、比較例１〜２７の透明電極を形成したガラス製の基板を用いてタッチパネルを組み立て、耐熱性、耐湿性試験を実施した。
タッチパネルの耐熱性試験では、押し試験の後の目視及び顕微鏡による観察を行うと、膜剥がれが著しくて白濁するようすが観察され、透過率の低下が見られた。
よって、車載カーナビなどの耐熱性を要求する用途としてのタッチパネルとしては利用できない。
(Comparative Example 29)
In the same manner as in Example 23, a touch panel was assembled using the glass substrate on which the transparent electrodes of Comparative Examples 1 to 27 were formed, and heat resistance and moisture resistance tests were performed.
In the heat resistance test of the touch panel, when visual observation after the push test and observation with a microscope were performed, film peeling was observed to be noticeably clouded, and a decrease in transmittance was observed.
Therefore, it cannot be used as a touch panel as an application requiring heat resistance such as an in-vehicle car navigation system.
１ 結晶性透明導電膜
２ 非晶質透明導電膜
３ 基板
４ 透明電極
５ スペーサ
６ 上部電極
７ 結晶粒界
９ 下部電極
１０ ペン
DESCRIPTION OF SYMBOLS 1 Crystalline transparent conductive film 2 Amorphous transparent conductive film 3 Substrate 4 Transparent electrode 5 Spacer 6 Upper electrode 7 Grain boundary 9
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| JPWO2015115237A1 (en) * | 2014-01-28 | 2017-03-23 | 株式会社カネカ | Substrate with transparent electrode and manufacturing method thereof |
| TWI651208B (en) * | 2014-01-28 | 2019-02-21 | 日商鐘化股份有限公司 | Substrate with transparent electrode and method of manufacturing same |
| US10270010B2 (en) | 2014-01-28 | 2019-04-23 | Kaneka Corporation | Substrate with transparent electrode and method for producing same |
| CN106483721A (en) * | 2015-08-25 | 2017-03-08 | 群创光电股份有限公司 | Display device |
| CN113113430A (en) * | 2021-03-30 | 2021-07-13 | Tcl华星光电技术有限公司 | Array substrate, manufacturing method thereof and display panel |
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