JPH0428114A - Transparent conductive layered product - Google Patents
Transparent conductive layered productInfo
- Publication number
- JPH0428114A JPH0428114A JP13498990A JP13498990A JPH0428114A JP H0428114 A JPH0428114 A JP H0428114A JP 13498990 A JP13498990 A JP 13498990A JP 13498990 A JP13498990 A JP 13498990A JP H0428114 A JPH0428114 A JP H0428114A
- Authority
- JP
- Japan
- Prior art keywords
- layer
- transparent conductive
- thin film
- transparent
- film layer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000010409 thin film Substances 0.000 claims abstract description 23
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 8
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052787 antimony Inorganic materials 0.000 claims abstract description 3
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910003437 indium oxide Inorganic materials 0.000 claims abstract description 3
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000000758 substrate Substances 0.000 claims description 11
- 150000004706 metal oxides Chemical class 0.000 claims description 6
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 3
- 229910001887 tin oxide Inorganic materials 0.000 claims description 2
- 230000007613 environmental effect Effects 0.000 abstract description 5
- 230000001590 oxidative effect Effects 0.000 abstract description 3
- 239000010410 layer Substances 0.000 description 55
- 238000000034 method Methods 0.000 description 13
- 239000010408 film Substances 0.000 description 11
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000007772 electrode material Substances 0.000 description 3
- 238000005401 electroluminescence Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000004973 liquid crystal related substance Substances 0.000 description 3
- 229920006254 polymer film Polymers 0.000 description 3
- 238000007740 vapor deposition Methods 0.000 description 3
- 229920002799 BoPET Polymers 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000004544 sputter deposition Methods 0.000 description 2
- 238000001771 vacuum deposition Methods 0.000 description 2
- BLBNEWYCYZMDEK-UHFFFAOYSA-N $l^{1}-indiganyloxyindium Chemical compound [In]O[In] BLBNEWYCYZMDEK-UHFFFAOYSA-N 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は基板上に透明な導電層を有する積層体に関し、
詳細には、基板上に形成した導電層が高い耐環境性を有
して安定であるので、透明タッチパネルや透明面状発熱
体として、あるいは液晶表示素子や分散型エレクトロル
ミネッセンスの電極材料等として有効に用いることので
きる透明導電積層体に関するものである。Detailed Description of the Invention (Industrial Application Field) The present invention relates to a laminate having a transparent conductive layer on a substrate,
Specifically, the conductive layer formed on the substrate has high environmental resistance and is stable, so it is effective as a transparent touch panel, a transparent sheet heating element, or as an electrode material for liquid crystal display elements and distributed electroluminescence. The present invention relates to a transparent conductive laminate that can be used for.
（従来の技術）
透明導電積層体は、透明タッチパネルや透明面状発熱体
として、あるいは液晶表示素子や分散型エレクトロルミ
ネッセンスの電極材料等として。(Prior Art) Transparent conductive laminates are used as transparent touch panels, transparent planar heating elements, or as electrode materials for liquid crystal display elements and distributed electroluminescence.
広い分野で数多く用いられている。It is widely used in a wide range of fields.
このような透明導電積層体は透明なガラス又は高分子フ
ィルム等の基板上に、主として、スパッタ法、蒸着法等
の真空成膜技術を用い、透明で導電性の金属または金属
酸化物系の薄膜層を形成したものである。一般に、高い
透明性と優れた導電性を有するという点で金属酸化物系
の薄膜層が用いられており、金属酸化物系の薄膜層とし
ては。Such transparent conductive laminates are made by depositing a transparent conductive metal or metal oxide thin film on a substrate such as transparent glass or polymer film using vacuum film forming techniques such as sputtering and vapor deposition. It is made up of layers. Generally, metal oxide thin film layers are used because they have high transparency and excellent conductivity.
酸化インヂウムに錫をドープした金属酸化物（ＩＴｏ）
よりなるものが用いられている。Metal oxide made by doping indium oxide with tin (ITo)
The following are used.
しかしながら、このＩＴＯは透明性と導電性には優れて
いるが、高温、多湿、酸化性の雰囲気等の厳しい環境条
件の下では安定性に劣っており。However, although this ITO has excellent transparency and conductivity, it has poor stability under severe environmental conditions such as high temperature, high humidity, and oxidizing atmosphere.
導電性が失われてしまうことが多かった。Conductivity was often lost.
また、ＩＴＯは安定性に欠けるという点で、透明導電積
層体を用いた最終製品を調製するまでの様々な工程中に
おいても、高温、高湿及び酸化性等の悪条件下の工程を
経ると、導電性等の特性に変化をきたしてしまうことも
あった。したがって透明導電積層体を用いた製品を製造
する場合には。In addition, ITO lacks stability, and even during various processes up to the preparation of final products using transparent conductive laminates, it is difficult to use ITO under adverse conditions such as high temperature, high humidity, and oxidation. In some cases, properties such as conductivity may change. Therefore, when manufacturing products using transparent conductive laminates.
好適な条件や適切な工程を正確に選んでやらねばならず
、多大の時間や労力を要した。This required a great deal of time and effort, as it required accurate selection of suitable conditions and processes.
（発明が解決しようとする課題）
このような状況に鑑み１本発明の課題は、厳しい環境条
件下においても安定な透明導電層を有している積層体の
提供にある。(Problems to be Solved by the Invention) In view of the above circumstances, an object of the present invention is to provide a laminate having a transparent conductive layer that is stable even under severe environmental conditions.
（課題を解決するための手段）
上記課題を解決すべく研究を重ねた結果、後述するよう
に透明導電層をＩＴＯ単独層ではなく１７０層の下に酸
化錫にアンチモンをドープした金属酸化物（ＡＴＯ）の
層を設けた積層構造にすると、上記課題を達成すること
ができるという知見を得１本発明に到達した。すなわち
本発明の要旨はつぎに述べるとおりである。(Means for Solving the Problems) As a result of repeated research to solve the above problems, as will be described later, the transparent conductive layer is not a single ITO layer, but a metal oxide (tin oxide doped with antimony) under the 170 layer. The present invention was achieved based on the knowledge that the above-mentioned problems can be achieved by using a laminated structure with a layer of ATO. That is, the gist of the present invention is as described below.
透明な基板上に、第一層としてＡＴＯよりなる透明で導
電性の薄膜層を形成させ、この薄膜層上に第二層として
ＩＴＯよりなる透明で導電性の薄膜層を形成させたもの
であることを特徴とする透明導電積層体。A transparent and conductive thin film layer made of ATO is formed as a first layer on a transparent substrate, and a transparent and conductive thin film layer made of ITO is formed as a second layer on this thin film layer. A transparent conductive laminate characterized by:
次に１本発明を詳述する。Next, one aspect of the present invention will be explained in detail.
本発明における透明な基板としてはガラス又は高分子フ
ィルムが用いられ１種類や形状はなんら限定されない。Glass or a polymer film is used as the transparent substrate in the present invention, and the type and shape are not limited at all.
これらの基板上に、まず第一層として透明で導電性のＡ
ＴＯの薄膜層を形成し、このＡＴＯの薄膜層上に第二層
として透明で導電性のＩＴＯの薄膜層を形成させる。Ｉ
ＴＯは酸化物系の透明な導電体の中では導電率が高いが
安定性に欠ける。On these substrates, a transparent and conductive A is first layered as a first layer.
A thin film layer of TO is formed, and a second transparent conductive thin film layer of ITO is formed on the thin film layer of ATO. I
Although TO has high conductivity among oxide-based transparent conductors, it lacks stability.
方ＡＴＯはＩＴＯに比べると安定性が高いが、導電率が
ＩＴＯの１０分の１程しかなく電気を通しにくい。その
ため、安定性の高い導電層を得ようとしてＡＴＯ単独で
導電層を形成させて、導電性のよい透明導電積層体を作
るには膜厚をかなり厚くしなくてはならないなどの問題
がある。そこで。On the other hand, ATO has higher stability than ITO, but its conductivity is only about one-tenth that of ITO, making it difficult to conduct electricity. Therefore, in order to form a conductive layer using ATO alone in order to obtain a highly stable conductive layer, there are problems such as the need to increase the film thickness considerably in order to produce a transparent conductive laminate with good conductivity. Therefore.
種々検討の結果、ＡＴＯ層の上に１７０層を積層すると
透明で導電性で安定性のよい積層体が得られた。そして
この積層体からは透明電極を効率よく作成することがで
きた。As a result of various studies, a transparent, conductive, and stable laminate was obtained by laminating 170 layers on the ATO layer. A transparent electrode could be efficiently produced from this laminate.
このとき、第一層のＡＴＯ層の膜厚は数１０〜数１００
人とするのが好ましく、第二層の１７０層の膜厚は数１
００〜数１０００人とするのが好ましい。そして、必要
に応じてその膜厚を変える。例えば。At this time, the thickness of the first ATO layer is several tens to several hundreds
It is preferable to use a human layer, and the thickness of the second layer of 170 is several 1.
It is preferable to set the number to 00 to several 1000 people. Then, the film thickness is changed as necessary. for example.
より抵抗値の小さな積層体が必要なときには、ＩＴＯの
膜厚を厚くすればよい。また１例えば、透明導電積層体
から透明電極を作成する場合、第一層のＡＴＯ層が数１
００Å以下であれば電極全体としての導電性にはほとん
ど影響しない。また、第一層のＡＴＯ層が第二層の１７
０層よりも薄ければ透明電極全体としての導電性にも影
響しない。If a laminate with a lower resistance value is required, the ITO film can be made thicker. For example, when creating a transparent electrode from a transparent conductive laminate, the first ATO layer is
If the thickness is 00 Å or less, the conductivity of the electrode as a whole is hardly affected. In addition, the first layer ATO layer is the second layer 17
If it is thinner than 0 layer, it will not affect the conductivity of the transparent electrode as a whole.
したがって、第二層の１７０層の膜厚を第一層のＡＴＯ
層の膜厚よりも厚く数１００〜数１０００人とすること
が好ましい。Therefore, the thickness of the second layer is 170 layers compared to the first layer ATO.
It is preferable that the number of layers is thicker than the thickness of the layer, and the number of layers is several hundred to several thousand.
薄膜の形成方法としてはスパッタ法、蒸着法等様々な成
膜方法があるが、特にその成膜方法を限定するものでな
い。There are various methods for forming a thin film, such as sputtering and vapor deposition, but the method is not particularly limited.
一般に、酸化物系の透明な導電薄膜層を、スＲ１１，タ
法、蒸着法等の真空成膜技術を用いて作成する場合、成
膜時の基板の温度は高い方が得られる導電薄膜層の安定
性はよい。しかし、ＰＥＴフィルム等の高分子フィルム
を基板として用いるどきは、高分子の特性上余り高温に
することはできない。その点１本発明による積層体構造
のものは。In general, when creating an oxide-based transparent conductive thin film layer using a vacuum film formation technique such as the SR11 method, the TA method, or the vapor deposition method, the conductive thin film layer obtained is generally obtained by increasing the temperature of the substrate during film formation. The stability of is good. However, when using a polymer film such as PET film as a substrate, the temperature cannot be raised too high due to the characteristics of the polymer. Point 1: The laminate structure according to the present invention.
かなり低い温度で導電薄膜層を形成しても安定な導電層
を得ることができ、この導電薄膜層を有する積層体を用
いて最終製品を製造する工程においても導電薄膜層が安
定であるので厳しい環境下での経時変化が少ない。Even if the conductive thin film layer is formed at a fairly low temperature, a stable conductive layer can be obtained, and even in the process of manufacturing final products using a laminate having this conductive thin film layer, the conductive thin film layer is stable, so it is difficult to obtain a stable conductive layer. There is little change over time in the environment.
（実施例） 以下１本発明を実施例にて具体的に説明する。(Example) The present invention will be specifically explained below using examples.
厚さ１２５μｍのＰＥＴフィルム上に９反応性真空蒸着
法により、ＡＴＯ層を膜厚が５０．１００．１５０゜２
００人になるように形成した。この際９組成比が５ｎ０
２： ５ｂ２０３＝９０：１０ （重量比）である焼結
ターゲットを用い、成膜の条件は、基板温度１００度、
成膜速度７人／ｓｅｃとし、 Ａｒガス、０．ガスの導
入量はそれぞれ２０ｓｃｃｍ、 １５ｓｃｃｍ、 ＲＦ
出力は８０Ｗとした。また、真空度は４ Ｘ １０−’
Ｔｏｒｒとしたた。続いてＡＴＯ層上に、前記と同様に
して反応性真空蒸着法により、ＩＴＯ層を膜厚が３００
人となるように形成した。この際９組成比がＩｎ２Ｏ。An ATO layer with a film thickness of 50.100.150°2 was deposited on a 125 μm thick PET film by 9-reactive vacuum deposition method.
It was formed to have 00 people. At this time, the composition ratio of 9 is 5n0
A sintered target with a weight ratio of 2:5b203=90:10 was used, and the conditions for film formation were a substrate temperature of 100 degrees,
The film formation rate was 7 people/sec, Ar gas, 0. The amount of gas introduced is 20 sccm, 15 sccm, and RF.
The output was 80W. Also, the degree of vacuum is 4 x 10-'
It was Torr. Subsequently, an ITO layer was formed on the ATO layer to a thickness of 300 mm using the same reactive vacuum deposition method as described above.
He was formed to become a man. At this time, the composition ratio of 9 is In2O.
：ＳｎＯ□＝９５：５（重量比）である焼結ターゲット
を用い、成膜条件は、基板温度１００度、成膜速度１０
人／ｓｅｃとし、Ａｒガス、０２ガスの導入量はそれぞ
れ２０ｓｃｃｍ、 １５ｓｃｃｍ、 ＲＦ出力は８０
Ｗとした。また、真空度は４ Ｘ １０−’Ｔｏｒｒと
した。なお。:SnO□=95:5 (weight ratio) using a sintered target, the film forming conditions were a substrate temperature of 100 degrees, a film forming rate of 10
person/sec, the amounts of Ar gas and 02 gas introduced are 20 sccm and 15 sccm, respectively, and the RF output is 80 sccm.
It was set as W. Further, the degree of vacuum was set to 4×10-'Torr. In addition.
ＡＴＯ層を形成せず、ＩＴＯ層のみのものを比較例とし
た。A comparative example was one in which no ATO layer was formed and only an ITO layer was formed.
作製したそれぞれの透明導電積層体の特性について１次
に述べるようにして評価した。The characteristics of each of the produced transparent conductive laminates were evaluated as described below.
得られた各積層体について９日立製作所製Ｕ−３４００
分光計にて５５０層ｍの波長の平行光線透過率を測定し
た。この結果を第１表に示す。9 for each laminate obtained U-3400 manufactured by Hitachi, Ltd.
Parallel light transmittance at a wavelength of 550 layer m was measured using a spectrometer. The results are shown in Table 1.
また、各積層体を、−辺５ｃｍに切取り、それぞれ５点
用意し、それぞれ１点につき５つの点で表面抵抗値を、
共和理研製に一７０５ＲＤ四探針表面抵抗測定器により
測定した。ＡＴＯ層の膜厚と表面抵抗値（平均値）の関
係を第１表に示す。In addition, each laminate was cut to 5 cm on the negative side, 5 points were prepared for each, and the surface resistance value was calculated at 5 points for each point.
It was measured using a 1705RD four-probe surface resistance meter manufactured by Kyowa Riken. Table 1 shows the relationship between the thickness of the ATO layer and the surface resistance value (average value).
その後、６０℃、９５％ＲＨに調節したヤマ）ＩＨ−４
２Ｈ恒温恒湿槽内で５００時間保持した後１表面抵抗値
を前記と同様にして測定し、恒温恒湿槽に入れる前の表
面抵抗値と比較した。入れる前の値をＲ６，取り出した
後の値をＲ１とし、Ｒ，／Ｒ８Ｏ値を求め、その結果を
第１表に示す。After that, IH-4 was adjusted to 60℃ and 95%RH.
After being held in a 2H constant temperature and humidity chamber for 500 hours, the surface resistance value was measured in the same manner as described above, and compared with the surface resistance value before being placed in the constant temperature and humidity chamber. The value before input is R6, and the value after extraction is R1, and the R,/R8O value is determined, and the results are shown in Table 1.
また、別に各積層体をそれぞれ５点ずつ用意し。In addition, 5 pieces of each laminate were prepared separately.
上記の方法で表面抵抗値を測定し、これを３Ｎの塩酸に
５分間漬けた後取り出し、水で洗浄、乾燥し２表面抵抗
値を測定し、５点のうち表面抵抗値の変化率が１０％以
内のものの数を数えた。この結果を第１表に示す。Measure the surface resistance value using the above method, soak it in 3N hydrochloric acid for 5 minutes, take it out, wash it with water, dry it, measure the surface resistance value, and out of 5 points, the rate of change in surface resistance value is 10. The number of items within % was counted. The results are shown in Table 1.
第１表から明らかなように本発明の透明導電積層体は、
導電層がＩＴＯ単独層よりなるもの（比較例）に比べて
高温、高湿及び酸化性環境下における安定性に優れてい
る。As is clear from Table 1, the transparent conductive laminate of the present invention is
The conductive layer is superior in stability under high temperature, high humidity, and oxidizing environments compared to a conductive layer consisting of a single layer of ITO (comparative example).
第１表
（第二層の１７０層の膜厚は３００人とした）（発明の
効果）
以上のように構成されているので９本発明の透明導電積
層体は、高温、多湿、酸化性等の悪い環境下において安
定である。したがって、透明タッチパネル、透明面状発
熱体として、あるいは液晶表示素子や分散型エレクトロ
ルミネッセンスの電極材料等と有効に利用できる。Table 1 (The thickness of the second layer of 170 layers was 300 layers.) (Effects of the invention) Since it is constructed as described above, 9 the transparent conductive laminate of the present invention is susceptible to high temperatures, high humidity, oxidation, etc. Stable under adverse environmental conditions. Therefore, it can be effectively used as a transparent touch panel, a transparent sheet heating element, or as an electrode material for liquid crystal display elements and distributed electroluminescence.
特許出願人 ユニチカ株式会社Patent applicant: Unitika Co., Ltd.
Claims (1)
ンをドープした金属酸化物よりなる透明で導電性の薄膜
層を形成させ、この薄膜層上に第二層として酸化インヂ
ウムに錫をドープした金属酸化物よりなる透明で導電性
の薄膜層を形成させたものであることを特徴とする透明
導電積層体。(1) On a transparent substrate, a transparent and conductive thin film layer made of a metal oxide in which tin oxide is doped with antimony is formed as a first layer, and on this thin film layer, a second layer is formed in which indium oxide is doped with tin. A transparent conductive laminate comprising a transparent conductive thin film layer made of a doped metal oxide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13498990A JPH0428114A (en) | 1990-05-23 | 1990-05-23 | Transparent conductive layered product |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13498990A JPH0428114A (en) | 1990-05-23 | 1990-05-23 | Transparent conductive layered product |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0428114A true JPH0428114A (en) | 1992-01-30 |
Family
ID=15141333
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP13498990A Pending JPH0428114A (en) | 1990-05-23 | 1990-05-23 | Transparent conductive layered product |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0428114A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH043492U (en) * | 1990-04-25 | 1992-01-13 | ||
| FR2844136A1 (en) * | 2002-09-03 | 2004-03-05 | Corning Inc | MATERIAL FOR USE IN THE MANUFACTURE OF LIGHT DISPLAY DEVICES, PARTICULARLY ORGANIC LIGHT EMITTING DIODES |
| CN109501396A (en) * | 2017-09-14 | 2019-03-22 | 东莞市荣腾纳米科技有限公司 | A kind of leaded light thermal isolation film and preparation method thereof |
-
1990
- 1990-05-23 JP JP13498990A patent/JPH0428114A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH043492U (en) * | 1990-04-25 | 1992-01-13 | ||
| FR2844136A1 (en) * | 2002-09-03 | 2004-03-05 | Corning Inc | MATERIAL FOR USE IN THE MANUFACTURE OF LIGHT DISPLAY DEVICES, PARTICULARLY ORGANIC LIGHT EMITTING DIODES |
| US7161171B2 (en) | 2002-09-03 | 2007-01-09 | Corning Incorporated | Material for use in the manufacturing of luminous display devices |
| CN109501396A (en) * | 2017-09-14 | 2019-03-22 | 东莞市荣腾纳米科技有限公司 | A kind of leaded light thermal isolation film and preparation method thereof |
| CN109501396B (en) * | 2017-09-14 | 2021-06-22 | 东莞市荣腾纳米科技有限公司 | Light guide and heat insulation film and preparation method thereof |
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