JP3031224B2 - Transparent conductive film - Google Patents
Transparent conductive filmInfo
- Publication number
- JP3031224B2 JP3031224B2 JP7333224A JP33322495A JP3031224B2 JP 3031224 B2 JP3031224 B2 JP 3031224B2 JP 7333224 A JP7333224 A JP 7333224A JP 33322495 A JP33322495 A JP 33322495A JP 3031224 B2 JP3031224 B2 JP 3031224B2
- Authority
- JP
- Japan
- Prior art keywords
- oxide
- thin film
- conductive film
- silver
- transparent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Landscapes
- Liquid Crystal (AREA)
- Laminated Bodies (AREA)
- Physical Vapour Deposition (AREA)
- Gas-Filled Discharge Tubes (AREA)
- Non-Insulated Conductors (AREA)
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、液晶ディスプレ
イ、入出力装置、あるいはプラズマディスプレイ等の表
示装置の透明電極等に用いられる透明導電膜に係り、特
に、薄膜で導電性と可視光線透過率が高く、しかも保存
安定性に優れた透明導電膜の改良に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a transparent conductive film used for a transparent electrode of a display device such as a liquid crystal display, an input / output device, or a plasma display, and more particularly to a thin film having conductivity and visible light transmittance. The present invention relates to improvement of a transparent conductive film which is high and has excellent storage stability.
【０００２】[0002]
【従来の技術】ガラス、プラスチックフィルム等の基板
上に可視光線を透過する電極形状の透明導電膜が設けら
れた電極板は、液晶ディスプレイ等の各種表示装置の表
示用電極やこの表示装置の表示画面から直接入力する入
出力電極等に広く使用されている。2. Description of the Related Art An electrode plate provided with a transparent conductive film in the form of an electrode that transmits visible light on a substrate such as a glass or plastic film is used as a display electrode of various display devices such as a liquid crystal display and a display device of the display device. Widely used for input / output electrodes etc. that input directly from the screen.
【０００３】この透明導電膜としては、その高い導電性
に着目して、酸化インジウム中に酸化錫を添加したＩＴ
Ｏ薄膜が広く利用されており、その比抵抗はおよそ２．
４×１０-4Ω・cmで、透明電極として通常適用される２
４０ｎｍの膜厚の場合その面積抵抗はおよそ１０Ω／□
である。[0003] Focusing on the high conductivity of this transparent conductive film, IT in which tin oxide is added to indium oxide is used.
O thin films are widely used and have a specific resistance of about 2.
4 × 10 -4 Ω · cm, usually used as a transparent electrode 2
For a film thickness of 40 nm, the sheet resistance is about 10Ω / □.
It is.
【０００４】また、この他にも、酸化錫薄膜、この酸化
錫に酸化アンチモンを添加して構成される薄膜（ネサ
膜）、酸化亜鉛に酸化アルミニウムを添加して構成され
る薄膜等が知られているが、これらはいずれも上記ＩＴ
Ｏ薄膜よりその導電性が劣り、また、酸やアルカリ等に
対する耐薬品性あるいは耐水性等が不十分なため一般に
は普及していない。[0004] In addition, there are known tin oxide thin films, thin films formed by adding antimony oxide to tin oxide (Nesa films), thin films formed by adding aluminum oxide to zinc oxide, and the like. However, these are all IT
It is not widely used because it is inferior in conductivity to the O thin film and has insufficient chemical resistance or water resistance to acids and alkalis.
【０００５】一方、１９８２年日本で開催された第７回
ＩＣＶＭにおいて、熱線反射膜として銀薄膜の表裏面に
ＩＴＯ薄膜又は酸化インジウム薄膜（ＩＯ薄膜）を積層
させて構成される三層構造の透明導電膜が提案されてい
る。この三層構造の透明導電膜はおよそ５Ω／□程度の
低い面積抵抗率を有しており、その高い導電性を生かし
て上記透明電極への応用が期待された。On the other hand, at the 7th ICVM held in Japan in 1982, a three-layer transparent film constituted by laminating an ITO thin film or an indium oxide thin film (IO thin film) on the front and back surfaces of a silver thin film as a heat ray reflective film. Conductive films have been proposed. The transparent conductive film having the three-layer structure has a low sheet resistivity of about 5Ω / □, and is expected to be applied to the transparent electrode by utilizing its high conductivity.
【０００６】[0006]
【発明が解決しようとする課題】ところで、上記ディス
プレイ装置や入出力装置においては、近年、画素密度を
増大させて緻密な画面を表示することが求められ、これ
に伴って上記透明電極パターンの緻密化が要求されてお
り、例えば１００μｍ程度のピッチで上記透明電極の端
子部を構成することが要求されている。また、液晶ディ
スプレイ装置において基板に液晶駆動用ＩＣが直接接続
される方式（ＣＯＧ）においては、配線の引き回しが幅
２０〜５０μｍという細線となる部分があり、従来にな
い高度のエッチング加工適性と高い導電性（低い抵抗
率）が要求されている。In the above-mentioned display devices and input / output devices, it has recently been required to increase the pixel density and display a fine screen. For example, it is required that the terminal portions of the transparent electrode be formed at a pitch of about 100 μm. Further, in a system (COG) in which a liquid crystal driving IC is directly connected to a substrate in a liquid crystal display device, there is a portion where wiring is a thin line having a width of 20 to 50 μm, and a high degree of aptitude for etching processing, which has not been achieved in the past, is high. Conductivity (low resistivity) is required.
【０００７】また、その一方で表示画面の大型化も求め
られており、このような大画面について上述したような
緻密パターンの透明電極を形成し、しかも液晶に充分な
駆動電圧を印加できるようにするためには、上記透明電
極として５Ω／□以下という高い導電性を備えた透明導
電膜を適用する必要があった。また、これに加えて、Ｓ
ＴＮ液晶等を利用した単純マトリクス駆動方式の液晶表
示装置において１６階調以上の多階調表示を行う場合に
は３Ω／□以下という更に低い面積抵抗が要求されてい
る。On the other hand, there is also a demand for an increase in the size of a display screen. For such a large screen, a transparent electrode having a dense pattern as described above is formed so that a sufficient driving voltage can be applied to the liquid crystal. To do so, it was necessary to apply a transparent conductive film having a high conductivity of 5 Ω / □ or less as the transparent electrode. In addition, S
In a simple matrix drive type liquid crystal display device using a TN liquid crystal or the like, when a multi-gradation display of 16 gradations or more is performed, a lower sheet resistance of 3 Ω / □ or less is required.
【０００８】しかしながら、第７回ＩＣＶＭにおいて提
案された上記三層構造の透明導電膜においても、高々５
Ω／□程度の面積抵抗が得られるに過ぎず、十分な導電
性が確保できないという問題点があった。なお、銀薄膜
の厚さを１６〜１８ｎｍ程度に厚くすることによりその
面積抵抗率を約３Ω／□に低下させることは可能である
が、可視光線透過率（特に波長６１０ｎｍ程度の長波長
側の可視光線透過率）が７５％程度まで低下し、透明導
電膜としての機能が損なわれてしまう。However, the transparent conductive film having the three-layer structure proposed in the 7th ICVM also has at most 5
There is a problem that only a sheet resistance of about Ω / □ can be obtained, and sufficient conductivity cannot be secured. Although it is possible to reduce the sheet resistivity to about 3 Ω / □ by increasing the thickness of the silver thin film to about 16 to 18 nm, the visible light transmittance (particularly, the wavelength at the long wavelength side of about 610 nm). (Visible light transmittance) is reduced to about 75%, and the function as a transparent conductive film is impaired.
【０００９】更に、上記三層構造の透明導電膜において
は銀の薄膜が積層界面等から侵入した空気中の水分と化
合し易く、その表面に酸化物を生成してシミ状の欠陥を
生じ、例えば液晶表示装置の透明電極に適用した場合に
はその表示画面に表示欠陥等を生じ易いという問題点が
あった。Further, in the above-mentioned transparent conductive film having a three-layer structure, the silver thin film is apt to be combined with moisture in the air penetrating from a laminating interface or the like, and an oxide is generated on the surface to cause spot-like defects. For example, when applied to a transparent electrode of a liquid crystal display device, there is a problem that a display defect or the like easily occurs on a display screen thereof.
【００１０】本発明はこのような問題点に着目してなさ
れたもので、その課題とするところは、薄膜で導電性と
可視光線透過率が高く、しかも経時劣化がなく保存安定
性に優れた透明導電膜を提供することにある。The present invention has been made in view of such problems, and it is an object of the present invention to provide a thin film having high conductivity, high visible light transmittance, and excellent storage stability without deterioration over time. It is to provide a transparent conductive film.
【００１１】[0011]
【課題を解決するための手段】上述のような技術的課題
に鑑みて本発明者等が鋭意検討を重ねたところ、上記三
層構造の透明導電膜において、ＩＴＯ薄膜やＩＯ薄膜の
代わりに酸化インジウムと酸化セリウム等との混合酸化
物から成る透明酸化物を利用すると、その屈折率が増大
して光反射率を低下させると共に可視光線透過率を増大
させ、導電性に優れた膜厚の厚い銀薄膜を利用ししかも
可視光線透過率が高い透明導電膜が得られ、更にこの透
明導電膜は極めて高い耐湿性を有することを発見した。
本発明はこのような技術的発見に基づいてなされたもの
である。Means for Solving the Problems In view of the technical problems as described above, the present inventors have conducted intensive studies. As a result, in the above-mentioned transparent conductive film having a three-layer structure, oxidation was performed in place of the ITO thin film and the IO thin film. When a transparent oxide made of a mixed oxide of indium and cerium oxide is used, the refractive index increases, the light reflectance decreases, and the visible light transmittance increases. It has been found that a transparent conductive film using a silver thin film and having high visible light transmittance can be obtained, and that this transparent conductive film has extremely high moisture resistance.
The present invention has been made based on such technical findings.
【００１２】本発明者らは、５Ω／□以下の低抵抗と高
透過率をかねそなえる構成として、０．１〜３原子パー
セント（以下単にat％という）の銅を含有する銀系薄膜
を透明酸化物薄膜で挟持する構造の導電膜も提案してい
るが、この構成では耐湿性がやや不十分であった。例え
ば、耐湿性の加速試験として、６０℃，９０％湿度の高
温高湿環境下にて１at％銅を含有する銀系薄膜を挟持す
る構造の導電膜のパターンに微小なシミが発生してしま
う欠点があり、不十分であった。The present inventors have developed a silver-based thin film containing 0.1 to 3 atomic percent (hereinafter simply referred to as at%) of copper as a material having a low resistance of 5 Ω / □ or less and a high transmittance. A conductive film having a structure sandwiched by oxide thin films has also been proposed, but with this configuration, the moisture resistance was somewhat insufficient. For example, as an accelerated test for moisture resistance, a minute stain is generated in a conductive film pattern having a structure in which a silver-based thin film containing 1 at% copper is sandwiched in a high-temperature and high-humidity environment of 60 ° C. and 90% humidity. There were drawbacks and were inadequate.
【００１３】[0013]
【００１４】[0014]
【００１５】銀系薄膜において、金を少量含有する銀金
合金は、全率固溶（包晶）であり、完全に固溶し合い、
銀銅合金（共晶）のように銅の銀合金中での析出がみら
れないため、可視域でかなり良好な透過率をもってい
る。銀系薄膜を挟持する構成の導電膜を、ＳＴＮ液晶表
示装置のような、５Ω／□以下の低抵抗を要求する単純
マトリクス液晶表示装置に用いる場合は、銀合金中の金
の添加量を４at％以下に抑えないと５Ω／□以下の低抵
抗と、高透過率を両立しにくい。また、逆に銀系薄膜を
挟持する構成の導電膜の耐湿性向上への寄与は、０．１
at％の少量添加から効果がある。すなわち、請求項１に
かかる発明は、厚さ５〜２０ｎｍの銀系薄膜を透明参加
物薄膜にて挟持する３層構造の透明導電膜において、上
記透明参加物薄膜が、銀と固溶しやすい金属の酸化物で
ある酸化インジウムからなる第１の基材と、銀と固溶し
にくい金属の酸化物である酸化セリウム、酸化ジルコニ
ウム、酸化ハフニウムもしくは酸化タンタルから選択さ
れた少なくとも１種を含む第２の基材との混合酸化物で
あり、かつ銀系薄膜が少なくとも金を０．１〜４at％
（原子パーセント）含有する銀合金であることを特徴と
する透明導電膜である。 In the silver-based thin film, the silver-gold alloy containing a small amount of gold is completely solid-solubilized (peritectic) and completely solid-solved,
Since silver does not precipitate in a silver alloy like a silver-copper alloy (eutectic), it has a considerably good transmittance in the visible region. When a conductive film having a structure in which a silver-based thin film is sandwiched is used for a simple matrix liquid crystal display device requiring a low resistance of 5 Ω / □ or less, such as an STN liquid crystal display device, the amount of gold added to the silver alloy is 4 at. % Or less, it is difficult to achieve both low resistance of 5Ω / □ or less and high transmittance. Conversely, the contribution of the conductive film having the structure sandwiching the silver-based thin film to the improvement of the moisture resistance is 0.1%.
Effective from small addition of at%. That is, in the invention according to claim 1 , a silver thin film having a thickness of 5 to 20 nm is transparently joined.
In a three-layered transparent conductive film sandwiched between material thin films,
The transparent participant thin film is a metal oxide that easily dissolves with silver.
A first base material made of indium oxide and a solid solution with silver
Cerium oxide and zirconium oxide, which are difficult metal oxides
, Hafnium oxide or tantalum oxide
Mixed oxide with a second substrate containing at least one of
And the silver-based thin film contains at least 0.1 to 4 at% gold
(Atomic percent) containing silver alloy
Transparent conductive film.
【００１６】また、エッチング液を用いた透明導電膜の
パターニングを前提とする場合、金を２．５at％より多
く添加した銀系薄膜を挟持する構成の場合、エッチング
後の基板表面に金を中心とする残渣が残りやすいため、
さらに好ましくは、金の添加量を２．５at％以下にする
ことが良い。すなわち、請求項２に係る発明は、銀系薄
膜が金を０．１〜２．５at％含有する銀合金であること
を特徴とする。In the case where a transparent conductive film is patterned by using an etching solution, a silver-based thin film containing more than 2.5 at% of gold is sandwiched. Is likely to remain,
More preferably, the amount of gold added is set to 2.5 at% or less. That is, the invention according to claim 2 is characterized in that the silver-based thin film is a silver alloy containing 0.1 to 2.5 at% of gold.
【００１７】銀系薄膜を挟持する構成において、酸化イ
ンジウムに酸化セリウムを添加していくことは、透明導
電膜の耐湿性向上に効果があると同時に、酸化セリウム
等の銀と固溶しにくい金属の酸化物の添加量に応じて、
透明導電膜の透過率を改善せしめる効果がある。透明導
電膜の透過率は、銀系薄膜の膜厚を一定とすると、透明
酸化物薄膜の屈折率を高くすることで向上が見込める。
本発明者らは、種々の材料を検討した後、低抵抗化と、
高透過率、耐湿性およびエッチング加工性の全てを考慮
して、透明酸化物薄膜として酸化インジウムと酸化セリ
ウムの混合酸化物を見いだした。すなわち、請求項３に
係る発明は、第１の基材が、酸化インジウムであり、第
２の基材が、酸化セリウムであることを特徴とする。In a configuration in which a silver-based thin film is sandwiched, the addition of cerium oxide to indium oxide is effective in improving the moisture resistance of the transparent conductive film, and at the same time, a metal such as cerium oxide which is hardly dissolved in silver. Depending on the amount of oxide added,
This has the effect of improving the transmittance of the transparent conductive film. Assuming that the thickness of the silver-based thin film is constant, the transmittance of the transparent conductive film can be expected to be improved by increasing the refractive index of the transparent oxide thin film.
The present inventors, after examining various materials, low resistance,
A mixed oxide of indium oxide and cerium oxide was found as a transparent oxide thin film in consideration of all of high transmittance, moisture resistance and etching processability. That is, the invention according to claim 3 is characterized in that the first base material is indium oxide and the second base material is cerium oxide.
【００１８】透明酸化物薄膜として、その屈折率は、
２．０〜２．４程度の範囲内にあることが望ましい。屈
折率は、高い方が良いが、２．４を越えると透明酸化物
薄膜そのものからの反射が大きくなり、透明導電膜とし
て高透過率・低反射率を維持しにくくなる。逆に２．０
以下の屈折率では、たとえば１５ｎｍの膜厚で挿入され
た銀系薄膜による光の反射がおさえられなくなり、同様
に高透過率・低反射率が保てない。酸化インジウムと酸
化セリウムの混合酸化物での酸化セリウムの添加量を金
属元素換算にて（酸素元素を除いて換算した）１０〜８
０at％とすると、その屈折率は、およそ２．０〜２．４
の範囲となる。すなわち、請求項４に係る発明は、透明
酸化物薄膜が、酸化セリウムを金属元素換算にて１０〜
８０at％含有する酸化インジウムとの混合酸化物である
ことを特徴とする。As a transparent oxide thin film, its refractive index is
It is desirable to be within the range of about 2.0 to 2.4. The higher the refractive index, the better, but if it exceeds 2.4, the reflection from the transparent oxide thin film itself increases, and it becomes difficult to maintain high transmittance and low reflectance as a transparent conductive film. Conversely 2.0
At the following refractive index, reflection of light by a silver-based thin film inserted with a thickness of, for example, 15 nm cannot be suppressed, and similarly, high transmittance and low reflectance cannot be maintained. The addition amount of cerium oxide in the mixed oxide of indium oxide and cerium oxide was 10 to 8 in terms of metal element (converted excluding oxygen element).
Assuming 0 at%, the refractive index is approximately 2.0 to 2.4.
Range. That is, in the invention according to claim 4 , the transparent oxide thin film has a cerium oxide content of 10 to 10 in terms of a metal element.
It is a mixed oxide with indium oxide containing 80 at%.
【００１９】単純マトリクス型の液晶表示装置向け透明
電極のように、パターン形成を前提とする場合、細かい
パターンでのエッチング加工が必要である。本発明にお
いて、透明酸化物薄膜中の酸化セリウムを４０at％を越
えるレベルとすると、湿式エッチングによるパターン形
成がむつかしくなる。望ましくは、酸化セリウムの添加
量は、４０at％以下が良い。すなわち、請求項５に係る
発明は、透明酸化物薄膜が、酸化セリウムを金属元素換
算にて１０〜４０at％含有する酸化インジウムとの混合
酸化物であることを特徴とする。なお、酸化セリウムと
酸化インジウムとの混合酸化物をスパッタリング法にて
蒸着する際、原料材料であるスパッターターゲットの密
度や導電性、強度を向上させるため、異種の酸化物を少
量加えてターゲットとして形成することは可能である。When a pattern is to be formed, as in the case of a transparent electrode for a simple matrix type liquid crystal display device, etching with a fine pattern is required. In the present invention, if the cerium oxide content in the transparent oxide thin film exceeds 40 at%, pattern formation by wet etching becomes difficult. Desirably, the addition amount of cerium oxide is 40 at% or less. That is, the invention according to claim 5 is characterized in that the transparent oxide thin film is a mixed oxide with indium oxide containing 10 to 40 at% of cerium oxide in terms of a metal element. When a mixed oxide of cerium oxide and indium oxide is deposited by a sputtering method, a small amount of a different kind of oxide is added as a target to improve the density, conductivity, and strength of a sputter target as a raw material. It is possible to do.
【００２０】なお、上記銀系薄膜の膜厚が５ｎｍに満た
ない場合には透明導電膜の導電性が低く、また２０ｎｍ
を越える場合にはその光透過率が低くなり、いずれの場
合も上記透明導電膜に適さなくなる。When the thickness of the silver-based thin film is less than 5 nm, the conductivity of the transparent conductive film is low,
When the ratio exceeds the above, the light transmittance becomes low, and in any case, it is not suitable for the transparent conductive film.
【００２１】また、上記透明酸化物薄膜と銀系薄膜と
は、いずれも硝酸をエッチング液としたエッチング処理
によりパターニングすることができる。すなわち、基板
上に、透明酸化物薄膜、銀系薄膜及び透明酸化物薄膜の
三層を成膜して本発明に係る透明導電膜を成膜し、次に
表面に露出した透明酸化物薄膜上にレジスト膜をパター
ン状に形成した後、このレジスト膜から露出した部位を
硝酸系エッチング液によってエッチングすることによ
り、上記三層の薄膜が互いに位置整合したパターン形状
にパターニングすることが可能である。このエッチング
液としては、硝酸の他、塩酸や硫酸又は酢酸等の他種の
酸を硝酸に添加して成る酸等の硝酸系の混酸、あるいは
界面活性剤を若干量添加した硝酸が利用できる。Both the transparent oxide thin film and the silver-based thin film can be patterned by etching using nitric acid as an etchant. That is, a transparent oxide thin film, a silver-based thin film, and a transparent oxide thin film are formed on a substrate, and a transparent conductive film according to the present invention is formed. After a resist film is formed in a pattern, a portion exposed from the resist film is etched with a nitric acid-based etchant, whereby the three thin films can be patterned into a pattern shape that is aligned with each other. As the etchant, in addition to nitric acid, nitric acid-based mixed acid such as acid obtained by adding another kind of acid such as hydrochloric acid, sulfuric acid or acetic acid to nitric acid, or nitric acid to which a slight amount of a surfactant is added can be used.
【００２２】また、上記銀系薄膜と透明酸化物薄膜と
は、いずれも上述したスパッタリング法によって成膜で
きる他、真空蒸着法やイオンプレーティング法等の真空
成膜法によって成膜することが可能であるが、その生産
性の点からスパッタリング法が適している。そして、成
膜の際、成膜装置内部の酸素量を制御することにより上
記透明酸化物薄膜中の酸素元素含有量を調整してその屈
折率をコントロールすることができる。また、この際、
銀系薄膜の劣化を防止するため成膜装置内部の水分は少
ない方が好ましく、透明酸化物薄膜のエッチング適性を
確保するため１８０℃以下又は室温の基板温度で成膜す
ることが望ましい。そして、銀系薄膜と透明酸化物薄膜
の全体を１８０℃以下又は室温の基板温度で成膜した
後、これら三層膜全体を硝酸系エッチング液でエッチン
グ処理し、次に２００℃以上の温度でアニーリング処理
を施すことによりこれら三層膜全体の導電性を増大させ
ることが可能である。The silver-based thin film and the transparent oxide thin film can both be formed by the above-described sputtering method, and can also be formed by a vacuum film forming method such as a vacuum deposition method or an ion plating method. However, the sputtering method is suitable from the viewpoint of productivity. Then, at the time of film formation, by controlling the amount of oxygen inside the film forming apparatus, the oxygen element content in the transparent oxide thin film can be adjusted and the refractive index thereof can be controlled. At this time,
In order to prevent the deterioration of the silver-based thin film, it is preferable that the water content in the film forming apparatus is small. Then, after forming the entirety of the silver-based thin film and the transparent oxide thin film at a substrate temperature of 180 ° C. or lower or at room temperature, the entire three-layer film is etched with a nitric acid-based etchant, and then at a temperature of 200 ° C. or higher. By performing the annealing process, it is possible to increase the conductivity of the entire three-layer film.
【００２３】次に、本発明に係る透明導電膜を支持する
基板としては、例えば、ガラス、プラスチックボード、
プラスチックフィルム等が利用できる。また、本発明に
係る透明導電膜は、カラーフィルターを備えるかあるい
はこれを備えない液晶表示装置の透明電極として適用で
きる他、ＣＲＴのガラスのフェースプレートを基板とし
てその表示面に設けてもよい。また、本発明に係る透明
導電膜は、太陽電池素子の光入射側に配置される透明電
極として利用することも可能である。Next, as the substrate for supporting the transparent conductive film according to the present invention, for example, glass, plastic board,
Plastic films and the like can be used. Further, the transparent conductive film according to the present invention may be used as a transparent electrode of a liquid crystal display device with or without a color filter, or may be provided on a display surface of a CRT glass face plate as a substrate. Further, the transparent conductive film according to the present invention can be used as a transparent electrode disposed on the light incident side of a solar cell element.
【００２４】なお、本発明に係る透明導電膜上に保護層
を設けることも可能である。このような保護層として
は、例えば、透明合成樹脂やＳｉＯ2 等の透明無機薄膜
が適用できる。また、この保護層として低屈折率の樹脂
層や光散乱層を適用してＡＲ（反射防止）やＡＧ（アン
チ・グレアー）膜として利用することも可能である。Incidentally, a protective layer can be provided on the transparent conductive film according to the present invention. As such a protective layer, for example, a transparent synthetic resin or a transparent inorganic thin film such as SiO 2 can be applied. In addition, a resin layer having a low refractive index or a light scattering layer can be applied as the protective layer to be used as an AR (anti-reflection) or AG (anti-glare) film.
【００２５】ＡＧ膜上に低反射率のＥＭＩ（電磁波シー
ルド）兼用膜として積層することもできる。また、ＡＲ
の観点から、本発明に係る透明導電膜の上下層、いずれ
かの部位に屈折率の異なる透明薄膜を積層あるいは挿入
して、反射率や透過率の最適化を行なっても良い。A low reflection EMI (electromagnetic shield) film can also be laminated on the AG film. Also, AR
In view of the above, the reflectance and the transmittance may be optimized by laminating or inserting a transparent thin film having a different refractive index in any part of the upper and lower layers of the transparent conductive film according to the present invention.
【００２６】請求項１記載の発明に係る透明導電膜によ
れば、銀系薄膜は銀もしくは銀合金に金を含有するた
め、銀系薄膜を挟持する構造の導電膜の耐湿性を向上で
きる。さらに、銅を添加した銀合金による同様構成の導
電膜より光透過率の点でより良い導電膜が得られる。請
求項１、２記載の発明に係る透明導電膜によれば、金の
銀系薄膜への添加量を４ないし2.5at％以下におさえる
ため、低抵抗で高透過率の導電膜が、エッチング可能な
膜として提供できる。請求項３〜５記載の発明に係る透
明導電膜によれば、透明酸化物薄膜を高屈折率の透明酸
化物薄膜により高透過率・低反射率の導電膜が提供でき
る。加えて、酸化インジウムへ酸化セリウムを添加する
ことによりエッチング性を保持したまま、耐湿性に富む
導電膜が提供できる。According to the transparent conductive film of the first aspect of the present invention, since the silver-based thin film contains gold in silver or silver alloy, the moisture resistance of the conductive film having the structure sandwiching the silver-based thin film can be improved. Further, a conductive film having a better light transmittance can be obtained than a conductive film having the same configuration using a silver alloy to which copper is added. According to the transparent conductive film according to the invention of claim 1, wherein, in order to suppress for 4 to the amount of gold to the silver-based thin film of below 2.5 at%, the conductive film having a high transmittance at low resistance, can be etched It can be provided as a simple film. According to the transparent conductive film according to the third to fifth aspects of the present invention, it is possible to provide a transparent oxide thin film having a high transmittance and a low reflectance by using a transparent oxide thin film having a high refractive index. In addition, by adding cerium oxide to indium oxide, a conductive film with high moisture resistance can be provided while maintaining etching properties.
【００２７】[0027]
【発明の実施の形態】以下、図面を参照して本発明の実
施例について詳細に説明する。Embodiments of the present invention will be described below in detail with reference to the drawings.
【００２８】[0028]
＜実施例１＞この実施例に係る透明導電膜１は、図１に
示すように厚さ０．７ｍｍのガラス基板１０上に順次積
層された厚さ３３ｎｍの透明酸化物薄膜１１と、厚さ１
５ｎｍの銀系薄膜１２、及び、厚さ３４ｎｍの透明酸化
物薄膜１３とでその主要部が構成されている。なお、上
記透明酸化物薄膜１１，１３は、そのいずれもが酸化セ
リウムを酸素を除く金属元素換算で３０at％、酸化イン
ジウムの薄膜に加えた混合酸化物とした。また、銀系薄
膜１２は、銀に金を１．０at％添加した銀合金である。<Example 1> A transparent conductive thin film 11 according to this example includes a transparent oxide thin film 11 having a thickness of 33 nm sequentially laminated on a glass substrate 10 having a thickness of 0.7 mm as shown in FIG. 1
The main part is composed of a silver-based thin film 12 having a thickness of 5 nm and a transparent oxide thin film 13 having a thickness of 34 nm. Each of the transparent oxide thin films 11 and 13 was a mixed oxide in which cerium oxide was added to a thin film of indium oxide at 30 at% in terms of a metal element excluding oxygen. The silver-based thin film 12 is a silver alloy obtained by adding 1.0 at% of gold to silver.
【００２９】そして、この透明導電膜１は以下のような
方法で成膜されている。まず、ガラス基板１０の表面を
アルカリ系界面活性剤と水とで洗浄した後、真空槽内に
収容し、逆スパッタリングと呼ばれるプラズマ処理を施
してさらに洗浄した。The transparent conductive film 1 is formed by the following method. First, the surface of the glass substrate 10 was washed with an alkali-based surfactant and water, then housed in a vacuum chamber, and further washed by performing a plasma treatment called reverse sputtering.
【００３０】次に、ガラス基板１０を真空槽中から取り
出すことなく、このガラス基板１０を室温に維持した状
態で、スパッタリング法により透明酸化物薄膜１１、銀
薄膜１２及び透明酸化物薄膜１３を順次成膜した。Next, without removing the glass substrate 10 from the vacuum chamber, the transparent oxide thin film 11, the silver thin film 12, and the transparent oxide thin film 13 are sequentially formed by sputtering while keeping the glass substrate 10 at room temperature. A film was formed.
【００３１】次に、透明酸化物薄膜１３上に電極形状の
レジスト膜を形成し、このレジスト膜から露出した部位
を硝酸系エッチング液によりエッチングして上記三層の
薄膜を互いに位置整合させた状態で電極形状にパターニ
ングし、続いて、２２０℃、１時間のアニール処理を施
して上記透明導電膜１を形成した。こうして得られた透
明導電膜１の面積抵抗は約２．９Ω／□であった。ま
た、その可視光線透過率を実線にて図２に示す。このパ
ターン形成した透明導電膜１を６０℃、湿度９５％内に
５００時間保持した後、表面観察をしたが、何ら外観変
化を生じるものではなかった。なお、この混合酸化物に
よる透明導電膜の屈折率を測定したところ２．２４であ
った。Next, an electrode-shaped resist film is formed on the transparent oxide thin film 13, and the portions exposed from the resist film are etched with a nitric acid-based etchant so that the three thin films are aligned with each other. Then, annealing was performed at 220 ° C. for one hour to form the transparent conductive film 1. The sheet resistance of the transparent conductive film 1 thus obtained was about 2.9Ω / □. The visible light transmittance is shown in FIG. 2 by a solid line. After keeping the patterned transparent conductive film 1 at 60 ° C. and a humidity of 95% for 500 hours, the surface was observed, but no change in appearance was found. The refractive index of the transparent conductive film made of the mixed oxide was 2.24.
【００３２】＜比較例＞実施例１と同様に、ただし銀系
薄膜は銀に銅を１．０at％添加した銀合金とした構成に
て、膜厚および製法を同じくして透明導電膜を形成し
た。可視光線透過率を破線にて図２に併せ示した。実施
例１より若干透過率の点で下回った。さらに、比較例の
透明導電膜を６０℃、湿度９５％内に保管したところ１
９０時間後にシミが発生し不良となった。<Comparative Example> A transparent conductive film was formed in the same manner as in Example 1 except that the silver-based thin film was a silver alloy obtained by adding 1.0 at% of copper to silver, and the thickness and the manufacturing method were the same. did. The visible light transmittance is also shown in FIG. 2 by a broken line. The transmittance was slightly lower than that of Example 1. Further, when the transparent conductive film of Comparative Example was stored at 60 ° C. and 95% humidity,
After 90 hours, spots occurred and became defective.
【００３３】＜実施例２＞実施例１と同構成、同製法に
て、図１に示す透明導電膜１をガラス基板上に形成し
た。ただし、銀系薄膜１２の膜厚は１５ｎｍと同じであ
るが、銀系薄膜１２の銀合金の組成を０．１〜４at％と
した透明導電膜各々の面積抵抗値を表１に示す。なお、
面積抵抗値は２２０℃、１時間のアニール処理後に測定
した値である。Example 2 The transparent conductive film 1 shown in FIG. 1 was formed on a glass substrate by the same configuration and the same manufacturing method as in Example 1. However, the film resistance of the silver-based thin film 12 is the same as 15 nm, but the sheet resistance of each transparent conductive film in which the silver alloy composition of the silver-based thin film 12 is 0.1 to 4 at% is shown in Table 1. In addition,
The sheet resistance is a value measured after annealing at 220 ° C. for 1 hour.
【００３４】[0034]
【表１】 [Table 1]
【００３５】表１に示したように金を４at％添加した銀
合金による透明導電膜においても、４．９Ω／□という
極めて低い面積抵抗値を有している。２２０℃、１時間
のアニール処理後の各々の透明導電膜の光透過率は、５
４５ｎｍ（緑色）の波長にていずれも９０％以上であっ
た。６１０ｎｍ（赤色）の波長では、金を４at％添加し
たもので、８９％と光透過率が少し低下している。光透
過率の点からも４at％を越える金の添加は、あまり好ま
しいものではない。As shown in Table 1, even a transparent conductive film made of a silver alloy containing 4 at% of gold has an extremely low sheet resistance of 4.9 Ω / □. The light transmittance of each transparent conductive film after annealing at 220 ° C. for 1 hour is 5
All were 90% or more at a wavelength of 45 nm (green). At a wavelength of 610 nm (red), the light transmittance is slightly reduced to 89% when 4 at% is added to gold. From the viewpoint of light transmittance, addition of gold exceeding 4 at% is not very preferable.
【００３６】また、各々透明導電膜を６０℃、湿度９５
％の高温高湿下に保管し、２００時間後の外観変化を観
察したところ、いずれにもシミ発生なく良好であった。
また、５００時間同条件で保管した各々の透明導電膜の
外観をみたところ、０．４at％以上金を添加したものに
は外観変化がなかった。０．１at％、０．２at％のもの
には微小なシミが発生していた。いずれも銅を添加した
銀銅合金の比較例より良好であった。なお、金、銅いず
れも未添加の純銀による透明導電膜は、６０℃、湿度９
５％の高温高湿条件下では２４時間経過後には、大きな
シミが発生した。Each of the transparent conductive films was formed at 60 ° C. and 95% humidity.
% Under high temperature and high humidity, and the appearance change after 200 hours was observed.
In addition, when the appearance of each transparent conductive film stored under the same conditions for 500 hours was observed, there was no change in the appearance of those to which 0.4 at% or more of gold was added. Fine spots were generated in the samples of 0.1 at% and 0.2 at%. All were better than the silver-copper alloy to which copper was added in the comparative example. The transparent conductive film made of pure silver to which neither gold nor copper is added has a temperature of 60 ° C. and a humidity of 9 ° C.
Under the condition of high temperature and high humidity of 5%, a large stain occurred after 24 hours.
【００３７】[0037]
【発明の効果】本発明の透明導電膜によれば、銀系薄膜
を透明酸化物薄膜にて挟持する構造の導電膜であって、
銀系薄膜は銀もしくは銀合金に金を含有するため、耐湿
性が充分で高光透過率・低抵抗の透明導電膜が提供でき
ることとなった。According to the transparent conductive film of the present invention, there is provided a conductive film having a structure in which a silver-based thin film is sandwiched between transparent oxide thin films,
Since the silver-based thin film contains gold in silver or silver alloy, a transparent conductive film having sufficient moisture resistance, high light transmittance and low resistance can be provided.
【００３８】請求項１、２記載の発明に係る透明導電膜
によれば、金の銀系薄膜への添加量を４ないし2.5％以
下におさえるため、低抵抗で高透過率の導電膜が、湿式
エッチングにより精緻なパターン形成ができるという利
点がある。請求項３〜５記載の発明に係る透明導電膜に
よれば、透明酸化物膜膜を高屈折率・低反射率の導電膜
が提供できる。加えて、酸化インジウムへ酸化セリウム
を添加することによりエッチング性を保持したまま、耐
湿性に富む導電膜が提供できる。According to the transparent conductive film of the first and second aspects of the present invention, since the amount of gold added to the silver-based thin film is suppressed to 4 to 2.5% or less, the conductive film having low resistance and high transmittance can be obtained. There is an advantage that a fine pattern can be formed by wet etching. According to the transparent conductive film according to the third to fifth aspects of the present invention, a transparent oxide film having a high refractive index and a low reflectance can be provided. In addition, by adding cerium oxide to indium oxide, a conductive film with high moisture resistance can be provided while maintaining etching properties.
【００３９】[0039]
【図１】本発明の透明導電膜の一実施例を示す断面図で
ある。FIG. 1 is a sectional view showing one embodiment of a transparent conductive film of the present invention.
【図２】本発明の実施例１の透明導電膜の分光透過率と
比較例の導電膜の分光透過率を示すグラフ図である。FIG. 2 is a graph showing the spectral transmittance of a transparent conductive film of Example 1 of the present invention and the spectral transmittance of a conductive film of Comparative Example.
１ 透明導電膜 １０ ガラス基板 １１ 透明酸化物薄膜 １２ 銀薄膜 １３ 透明酸化物薄膜 DESCRIPTION OF SYMBOLS 1 Transparent conductive film 10 Glass substrate 11 Transparent oxide thin film 12 Silver thin film 13 Transparent oxide thin film
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ Ｈ０１Ｊ 11/02 Ｈ０１Ｊ 11/02 Ｂ (56)参考文献 特開 昭63−173395（ＪＰ，Ａ) 特開 平７−178863（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) C23C 14/00 - 14/58 B32B 7/02 104 B32B 9/00 ──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. 7 Identification symbol FI H01J 11/02 H01J 11/02 B (56) References JP-A-63-173395 (JP, A) JP-A-7-178863 ( JP, A) (58) Fields investigated (Int. Cl. 7 , DB name) C23C 14/00-14/58 B32B 7/02 104 B32B 9/00
Claims (5)
薄膜にて挟持する３層構造の透明導電膜において、上記
透明酸化物薄膜が、銀と固溶しやすい金属の酸化物であ
る酸化インジウムからなる第１の基材と、銀と固溶しに
くい金属の酸化物である酸化セリウム、酸化ジルコニウ
ム、酸化ハフニウムもしくは酸化タンタルから選択され
た少なくとも１種を含む第２の基材との混合酸化物であ
り、かつ銀系薄膜が少なくとも金を０．１〜４at％（原
子パーセント）含有する銀合金であることを特徴とする
透明導電膜。1. A 3-layer transparent conductive film structure for clamping the silver-based thin film having a thickness of 5~20nm of a transparent oxide thin, the transparent oxide thin film, an oxide of silver and easy solid solution metal Ah
Substrate made of indium oxide and cerium oxide and zirconium oxide, which are oxides of metals that are hardly dissolved in silver
Or hafnium oxide or tantalum oxide
A mixed oxide with a second base material containing at least one of the above, and the silver-based thin film contains at least 0.1 to 4 at% of gold (original material).
( Transparent conductive film).
有する銀合金であることを特徴とする請求項１記載の透2. The transparent alloy according to claim 1, wherein the silver alloy has
明導電膜。Light conductive film.
２の基材が、酸化セリウムであることを特徴とする請求2. The method according to claim 1, wherein the base material is cerium oxide.
項１〜２記載の透明導電膜。Item 3. The transparent conductive film according to Item 1 or 2.
素換算にて１０〜８０at％含有する酸化インジウムとのWith indium oxide containing 10 to 80 at% in elementary conversion
混合酸化物であることを特徴とする請求項１〜３記載のThe mixed oxide according to claim 1, wherein the mixed oxide is a mixed oxide.
透明導電膜。Transparent conductive film.
素換算にて１０〜４０at％含有する酸化インジウムとのWith indium oxide containing 10 to 40 at% in elementary conversion
混合酸化物であることを特徴とする請求項１〜４記載のThe mixed oxide according to claim 1, wherein the mixed oxide is a mixed oxide.
透明導電膜。Transparent conductive film.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7333224A JP3031224B2 (en) | 1995-12-21 | 1995-12-21 | Transparent conductive film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7333224A JP3031224B2 (en) | 1995-12-21 | 1995-12-21 | Transparent conductive film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH09176837A JPH09176837A (en) | 1997-07-08 |
| JP3031224B2 true JP3031224B2 (en) | 2000-04-10 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP7333224A Expired - Fee Related JP3031224B2 (en) | 1995-12-21 | 1995-12-21 | Transparent conductive film |
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| Country | Link |
|---|---|
| JP (1) | JP3031224B2 (en) |
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-
1995
- 1995-12-21 JP JP7333224A patent/JP3031224B2/en not_active Expired - Fee Related
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| KR102320414B1 (en) | 2020-03-25 | 2021-11-02 | 안승호 | Mole capture device buried underground |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH09176837A (en) | 1997-07-08 |
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