JPS62227082A - Formation of electrically conductive transparent film - Google Patents
Formation of electrically conductive transparent filmInfo
- Publication number
- JPS62227082A JPS62227082A JP7044486A JP7044486A JPS62227082A JP S62227082 A JPS62227082 A JP S62227082A JP 7044486 A JP7044486 A JP 7044486A JP 7044486 A JP7044486 A JP 7044486A JP S62227082 A JPS62227082 A JP S62227082A
- Authority
- JP
- Japan
- Prior art keywords
- film
- sputtering
- layer
- transparent
- low resistance
- 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.)
- Granted
Links
- 230000015572 biosynthetic process Effects 0.000 title description 3
- 238000004544 sputter deposition Methods 0.000 claims abstract description 27
- 239000007789 gas Substances 0.000 claims abstract description 24
- 239000000758 substrate Substances 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 18
- 229910003437 indium oxide Inorganic materials 0.000 claims abstract description 14
- 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 14
- 239000011261 inert gas Substances 0.000 claims abstract description 14
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910001887 tin oxide Inorganic materials 0.000 claims abstract description 13
- 239000001257 hydrogen Substances 0.000 claims abstract description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000002834 transmittance Methods 0.000 claims description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 13
- 239000001301 oxygen Substances 0.000 abstract description 13
- 229910052760 oxygen Inorganic materials 0.000 abstract description 13
- 239000008246 gaseous mixture Substances 0.000 abstract 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 26
- 238000010438 heat treatment Methods 0.000 description 17
- 229910052786 argon Inorganic materials 0.000 description 13
- 239000011521 glass Substances 0.000 description 9
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 229910001882 dioxygen Inorganic materials 0.000 description 7
- 239000004973 liquid crystal related substance Substances 0.000 description 7
- 238000010304 firing Methods 0.000 description 5
- 229910001128 Sn alloy Inorganic materials 0.000 description 4
- 238000000151 deposition Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229910000846 In alloy Inorganic materials 0.000 description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 3
- 238000001755 magnetron sputter deposition Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 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
- 238000000059 patterning Methods 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910001120 nichrome Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000005546 reactive sputtering Methods 0.000 description 1
- 239000005361 soda-lime glass Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- -1 tin oxide Chemical compound 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】
（１） 産業上の利用分野
本発明は基板上に透明導電膜を形成する方法、特に透明
基板上に透明導電膜を形成した液晶表示素子の透明電極
に好適な透明導電膜を形成する方法に関する。DETAILED DESCRIPTION OF THE INVENTION (1) Industrial Application Field The present invention relates to a method for forming a transparent conductive film on a substrate, particularly a method for forming a transparent conductive film on a transparent substrate suitable for a transparent electrode of a liquid crystal display element. The present invention relates to a method of forming a conductive film.
（２）従来の技術
従来、液晶表示素子の透明電極基板は透明基板上に非晶
質構造の低級酸化物からなる酸化錫を含む酸化インジウ
ム膜を付着し、電極のパタニング加工後、液晶表示素子
の液晶配向膜の硬化工程中の熱処理と同時に電極の透明
化および低抵抗化を行っていた。(2) Conventional technology Conventionally, a transparent electrode substrate for a liquid crystal display element is made by depositing an indium oxide film containing tin oxide made of a lower oxide with an amorphous structure on a transparent substrate, and after patterning the electrode, the liquid crystal display element At the same time as the heat treatment during the curing process of the liquid crystal alignment film, the electrodes were made transparent and lower in resistance.
例えば、非晶質構造の低級酸化物からなる酸化錫を含む
酸化インジウム膜はインジウムと錫の合金よりなるター
ゲットを陰極として酸素を含むアルゴン等の不活性ガス
中で放電を生じさせてスパッタリングすることにより、
＠極上に置がれた基板上に酸化錫を含む酸化インジウム
膜を付着され１その後の液晶表示素子の製造工程中の熱
処理により該膜の光透過率の向上と抵抗の安定化をさせ
ていた。For example, an indium oxide film containing tin oxide, which is a lower oxide with an amorphous structure, can be sputtered by generating a discharge in an inert gas such as argon containing oxygen using a target made of an alloy of indium and tin as a cathode. According to
An indium oxide film containing tin oxide was deposited on the substrate placed on top of the substrate, and heat treatment during the subsequent manufacturing process of liquid crystal display elements improved the light transmittance and stabilized the resistance of the film. .
（３）発明が解決しようとする問題点
しかしながら前記方法で、膜厚が７０００１以上の厚い
膜を基板に付着しようとするとインジウムと錫の合金の
ターゲット表面が初期の状態から変化し、同じ膵質の酸
化錫を含む酸化インジウム膜 −を形成することが困難
であった。またインジウムと錫の合金ターゲットを過度
に酸素不足の雰囲気でスパッタリングして形成できる酸
化錫を含む酸化インジウム膜は熱処理工程で膜面上にイ
ンジウムが凝集し、粒状の欠点があられれ、一方インジ
ウムと錫の合金ターゲットを過剰の酸素を含む雰囲気で
形成できる酸化錫を含む酸化インジウム膜はターゲット
の酸化が促進され、異常放電により被膜に粒状の欠点が
生じる。(3) Problems to be Solved by the Invention However, when using the above method to attach a thick film of 70001 or more to a substrate, the target surface of the indium and tin alloy changes from its initial state, and the same pancreatic It was difficult to form an indium oxide film containing tin oxide. In addition, indium oxide films containing tin oxide, which can be formed by sputtering an alloy target of indium and tin in an excessively oxygen-deficient atmosphere, tend to aggregate on the film surface during the heat treatment process, resulting in grainy defects. In an indium oxide film containing tin oxide, which can be formed using a tin alloy target in an atmosphere containing excess oxygen, oxidation of the target is promoted, and granular defects occur in the film due to abnormal discharge.
また、酸化錫な含む酸化インジウムの導電膜は酸素をよ
り多く含む場合には、被膜形成後の熱処理により透明化
はするが、抵抗が上昇する欠点があり、一方酸化不足の
場合には低抵抗化することができるが、完・全に透明化
することが困難であるという欠点を有する。In addition, if a conductive film made of indium oxide, such as tin oxide, contains a large amount of oxygen, it can be made transparent by heat treatment after film formation, but it has the disadvantage of increasing resistance, whereas if it is insufficiently oxidized, it will have low resistance. However, it has the disadvantage that it is difficult to make it completely transparent.
しかも、インジウムと錫の合金をターゲットとした反応
性スパッタリング法では適度の酸化度を有する被膜を再
現よく形成することは困難である。Moreover, it is difficult to reproducibly form a film having an appropriate degree of oxidation using a reactive sputtering method using an alloy of indium and tin as a target.
（４）間頴点を解決するための手段
本発明は前記欠点を解決するためになされたものであっ
て、本発明は酸化錫を含む酸化インジウム焼結体からな
るターゲットを用いてスパッタリングすることにより、
基板上に透明導電膜を形成する方法であって、該基板を
７００”Ｃ以下とし、減圧された不活性ガスまたは不活
性ガスと水素との混合ガス中でスパッタリングすること
により、低抵抗化石を基板上に形成し、その後減圧され
た不活性ガスと酸素との混合ガス中でスパッタリングし
て該低抵抗化層上に透明化層を積層し、該低抵抗化層と
透明化層との積層膜を焼成することにより、該積層膜の
抵抗を減少し、且つ光透過率を増加することを特徴とす
る透明導電膜の形成方法である。(4) Means for Solving the Solving Point The present invention has been made to solve the above-mentioned drawbacks. According to
A method of forming a transparent conductive film on a substrate, in which the substrate is heated to 700"C or less and sputtered in a reduced pressure inert gas or a mixed gas of inert gas and hydrogen, thereby forming a low-resistance fossil film. Formed on a substrate, then sputtered in a reduced pressure mixed gas of inert gas and oxygen to laminate a transparent layer on the low resistance layer, and laminated the low resistance layer and the transparent layer. This method of forming a transparent conductive film is characterized in that the resistance of the laminated film is reduced and the light transmittance is increased by firing the film.
本発明はターゲットとして高純度の酸化インジウムの粉
末と６で化銅の粉末とを混合して、所定形・状に加圧成
形後高温で焼成したものを用いる。このターゲットの酸
化錫の含有量は被膜の比抵抗が大にならないように、３
重量％〜ｌ！；重量％にされる。The present invention uses as a target a mixture of high-purity indium oxide powder and copper oxide powder, which is pressure-molded into a predetermined shape and shape, and then fired at a high temperature. The content of tin oxide in this target is set to 3.
Weight%~l! ; Expressed as % by weight.
本発明は通常マグネトロンスパッタ法が用いられ、スパ
ッタリング時の真空度は最初にｊＸｌｏ−５’１’ｏｒ
ｒ以下にし、その彼放電ガスを導入してｌ×／ ０−３
Ｔｏｒｒ以下にし、その後放電ガスを導入して／Ｘｌ０
−３Ｔｏｒｒ 〜７Ｘ１０−３Ｔｏｒｒ、特に２Ｘ１０
−３ＴＯｒｒ−≠Ｘ ／ ０−３Ｔｏｒｒの範囲にする
ことが好ましい。In the present invention, a magnetron sputtering method is usually used, and the degree of vacuum during sputtering is initially jXlo-5'1'or
r or less, and then introduce discharge gas to l×/0-3
Torr or less, then introduce discharge gas to /Xl0
-3Torr ~7X10-3Torr, especially 2X10
It is preferable to set the range to -3Torr-≠X/0-3Torr.
本発明は、低抵抗層がアルゴンガスあるいはアルゴンと
水素との混合ガスをスパッタリングガスとして前記所定
圧になるように真空容器内に導入し、スパッタリングす
ることにより形成し、引続きスパッタリングを中止する
ことなく、アルゴンガスあるいはアルゴンと水素との混
合ガスをアルゴンと酸素の混合ガスに切替え、前記所定
圧を保ちつつ透明化層を形成する。透明化層を形成する
ときの酸素の導入量は被膜の透明化作用が少なくならな
いように体積比で０．７％以上にする必要があり、また
被膜の抵抗値を低くおさえるためにはψ％以下にする必
要がある。一般に酸素の導入量は被膜の熱処理温度をＪ
ｊ Ｏ’Ｃと高くする場合には少なくシ、被膜の熱処
理温度を比較的低くする場合には多くする。真空度が２
×１０−３〜弘Ｘ／にｌ−３Ｔｏｒｒでマグネトロンス
パッタリングをする場合には酸素の導入量を体積比で０
．３〜２．０％の範囲にすることが好ましい。In the present invention, the low resistance layer is formed by introducing argon gas or a mixed gas of argon and hydrogen as a sputtering gas into a vacuum container so that the predetermined pressure is reached, and performing sputtering, without continuing sputtering. Then, the argon gas or the mixed gas of argon and hydrogen is changed to the mixed gas of argon and oxygen, and a transparent layer is formed while maintaining the predetermined pressure. The amount of oxygen introduced when forming the transparent layer needs to be at least 0.7% by volume so as not to reduce the transparency effect of the film, and in order to keep the resistance value of the film low, ψ% It is necessary to do the following. Generally, the amount of oxygen introduced is J
If the heat treatment temperature of the film is to be relatively low, the amount should be increased. Vacuum degree is 2
When performing magnetron sputtering at 10-3 to 10-3 Torr, the volume ratio of oxygen introduced is 0.
．． It is preferably in the range of 3 to 2.0%.
本発明は前記積層膜の膜厚は１０００Ａ以上にして電極
の抵抗値を小さくすることが好ましく、その場合前記透
明化層は後工程の熱処理温度により、前記積層膜の全膜
厚の／／２以下の値を選ぶことができる。In the present invention, it is preferable that the thickness of the laminated film is 1000A or more to reduce the resistance value of the electrode. You can choose from the following values:
すなわち、被膜を２００℃−２！；Ｏ′Ｃの比較的低温
で熱処理する場合には透明化層は前記積層膜の／／２の
厚みに近づけ、３００”Ｃ〜３ｊＯ℃の比較的高温で熱
処理する場合には透明化層は比較的薄い膜厚に設定され
る。この熱処理はポリイミドやポリアミド系の液晶配向
剤の硬化の際に行なわれ、その硬化の際に加えられる温
度に依存し、その温度によって透明化層の厚みを決める
ことができる。In other words, the coating was heated to 200℃-2! ; When heat-treated at a relatively low temperature of O'C, the transparent layer approaches the thickness of //2 of the laminated film, and when heat-treated at a relatively high temperature of 300"C to 3JOC, the transparent layer becomes The film thickness is set to be relatively thin.This heat treatment is performed when curing polyimide or polyamide-based liquid crystal alignment agents, and depends on the temperature applied during curing, and the thickness of the transparent layer is determined by that temperature. You can decide.
（５）作用
本発明によれば、基板を１００℃以下に保って、スパッ
タリングにより被膜を付着するものであるから、被膜の
構造が非晶質マトリックスを主とする結晶化が進んでい
ない構造となり、極めて稀薄な塩酸で微細な電極のパタ
ニング加工をすることができるうえ、被膜を熱処理する
ことにより、その抵抗を減少し、且つ光透過率を増加す
ることができる。(5) Effects According to the present invention, since the film is deposited by sputtering while keeping the substrate at 100°C or lower, the structure of the film is a structure consisting mainly of an amorphous matrix with no progress in crystallization. , it is possible to perform fine patterning of electrodes using extremely dilute hydrochloric acid, and by heat-treating the film, its resistance can be reduced and its light transmittance can be increased.
また、本発明はターゲットに酸化インジウム焼結体を用
い、減圧された、不活性ガスまたは不活性ガスと水素と
の混合ガス中でスパッタリングし、その後減圧された不
活性ガスと酸素との混合ガス中でスパッタリングするこ
とにより、被膜を形成するものであるから、最初のスパ
ッタリングでは不活性ガスイオンのボンバードにより酸
素と低級酸化物に解離し１．基板に酸素不足の組成の被
膜になり、これが熱処理により低抵抗層を形成でき、そ
して粒状異物のない被膜を再現よく形成できる。Further, the present invention uses an indium oxide sintered body as a target, sputters in a reduced pressure in an inert gas or a mixed gas of an inert gas and hydrogen, and then sputters in a reduced pressure mixed gas of an inert gas and oxygen. Since the film is formed by sputtering in the atmosphere, the first sputtering dissociates into oxygen and lower oxides due to bombardment of inert gas ions.1. A film with an oxygen-deficient composition is formed on the substrate, and this can be heat-treated to form a low-resistance layer, and a film free of particulate foreign matter can be formed with good reproducibility.
（６）実施例 以下に本発明の実施例について詳述する。(6) Examples Examples of the present invention will be described in detail below.
実施例１
酸化錫を含む酸化インジウムの半透明導電膜をソーダ石
灰ガラス板上に被覆するに当り、ガラス板（寸法／ ０
０ｍｍ×／ ００＋ｔｔａ×９ｍ ）を中性洗剤で洗浄
し水洗後７レオン蒸気により乾燥した。このガラス板を
マグネトロンスパッタ装置のスパッタ室に、ガラス板と
ターゲットの距離が７９ｍｍとなるように金属製支持具
で対向するように固定した。前記のターゲットは酸化錫
５．７重量％を含む酸化インジウム焼結体を銅製の水冷
プレートにメタルボンドにより貼付けたものとした。ス
パッタ装置内をｊＸ ／ ０−”ｒｏｒｒまで排気した
後、該スパッタ装置内に３．０ｘ１０−３ＴＯｒｒ に
圧力を絣持するようにスパッタガスを導入した。導入ガ
スは低抵抗化層を堆積する場合は、アルゴンガスのみと
し透明化層を堆積するときはアルゴンガスに加えて酸素
ガスを導入した。アルゴンガスの導入量はｒｏｓｃａｕ
とし、酸素ガスの導入量はＯＪ ＳＣｊＣＭとした。透
明化層を被着するときはスパッタリングを中断すること
なくスパッタリングの途中より酸素ガスを導入した。Example 1 In coating a soda lime glass plate with a translucent conductive film of indium oxide containing tin oxide, the glass plate (dimensions/0
0mm×/00+tta×9m) was washed with a neutral detergent, washed with water, and dried with 7 Leon steam. This glass plate was fixed in a sputtering chamber of a magnetron sputtering device so that the glass plate and the target were facing each other with a distance of 79 mm using metal supports. The target was an indium oxide sintered body containing 5.7% by weight of tin oxide attached to a copper water-cooled plate by metal bonding. After evacuating the inside of the sputtering apparatus to jX/0-''rorr, sputtering gas was introduced into the sputtering apparatus so as to maintain a pressure of 3.0x10-3 TOrr.The introduced gas was used when depositing a low-resistance layer. used only argon gas and introduced oxygen gas in addition to argon gas when depositing the transparent layer.The amount of argon gas introduced was
The amount of oxygen gas introduced was OJ SCjCM. When depositing the transparent layer, oxygen gas was introduced during the sputtering without interrupting the sputtering.
堆積する低抵抗化層と透明化層との膜厚比に応じて、酸
素ガスの導入を開始する時間を変化させた。The time to start introducing oxygen gas was varied depending on the thickness ratio of the deposited low resistance layer and transparent layer.
ガラス板はとくに加熱せず、直流電源からターゲットに
供給するスパッタ電流を一アンペアとし、あらかじめ予
備テストにより求めた膜厚とスパッタ時間の関係からス
パッタ時間を定め、膜厚が約１０００ｋになるようにス
パッタ時間を定めた。本発明に係る積層構造とした実施
例のサンプル／。The glass plate was not heated in particular, the sputtering current supplied to the target from the DC power source was 1 ampere, and the sputtering time was determined based on the relationship between the film thickness and sputtering time determined in advance by a preliminary test, so that the film thickness was approximately 1000K. The sputtering time was determined. Example sample/with a laminated structure according to the present invention.
２．３．及びｌを得た。得られた膜は、熱処理前の抵抗
、透過率および２！；Ｏ”Ｃ，，３００′Ｃ，３！；０
℃の３水阜の温度で３０分間大気中で焼成した後の抵抗
、波長ｊｊＯｎｍの光透過率、および段差触針計で膜厚
を測定した。また熱処理前の瞑のエツチング性をＯ０ｊ
規定の濃度で≠ｊ℃に加温した０、２規定の塩酸水溶液
に５分間浸漬し、膜が除去できるかどうかをも調べた。2.3. and l were obtained. The obtained film showed resistance, transmittance and 2! before heat treatment. ;O"C,,300'C,3!;0
After firing in the air for 30 minutes at a temperature of 3 degrees Celsius, the resistance, light transmittance at a wavelength of jj Onm, and film thickness were measured using a step stylus meter. In addition, the etching properties of the mesh before heat treatment are O0j.
It was also investigated whether the film could be removed by immersing it in a 0 or 2N aqueous hydrochloric acid solution at a specified concentration and heated to ≠j°C for 5 minutes.
以上の結果を第１表にまとめて示す。The above results are summarized in Table 1.
次に比較例としてスパッタ装置内のガスをアルゴンガス
のみ、またアルゴンガスに酸素ガスを加えた混合ガスの
みとして、その他のスパッタリング条件は実施例と同一
として、夫々比較サンプル！、及び６を得て、実施例と
同様の処理を行い、これらの特性を第１表に示した。Next, as a comparative example, the gas in the sputtering apparatus was only argon gas, or only a mixed gas of argon gas and oxygen gas, and other sputtering conditions were the same as in the example. , and 6 were obtained and treated in the same manner as in Examples, and their properties are shown in Table 1.
第１表から明らかなように比較サンプルＳは光透過率が
低く、透明性に問題があり、比較サンプル６は、光透過
性は良好であるが、面積抵抗は熱処理により高くなる。As is clear from Table 1, comparative sample S has a low light transmittance and a problem with transparency, and comparative sample 6 has good light transmittance, but its sheet resistance increases due to heat treatment.
しかしながら、本発明に係るサンプル／〜ｌはサンプル
弘の面積抵抗が多少高いことを除き、光透過率が高く、
面積抵抗が低い。However, the samples/~l according to the present invention have high light transmittance, except that the sheet resistance of Sample Hiro is somewhat high;
Low sheet resistance.
本発明に係るサンプル／−１の膜は熱処理前に於いて、
０．２規定の稀塩酸の水溶液に！分間浸ｆｆＪしたとこ
ろ膜はいずれのサンプルについても完全に消失除去でき
た。The film of sample/-1 according to the present invention had the following properties before heat treatment:
For an aqueous solution of 0.2N dilute hydrochloric acid! When immersed in ffJ for a minute, the membrane completely disappeared and was removed for all samples.
実施例２
全膜厚が／！；００Ａおよび３２００ｋ になるように
した以外は、実施例／と同様に透明化層と低抵抗化層の
積居膜からなる本発明に係るサンプル７゜ざ、９．１０
と透明化層のみからなる比較サンプルｌ／、低抵抗
化層からのみなる比較サンプル／２を作成し、これらの
膜の特性を第２表に示す。Example 2 Total film thickness is /! ;00A and 3200k, sample 7 according to the present invention consisting of a laminated film of a transparent layer and a low resistance layer was prepared in the same manner as in Example 9.10.
A comparative sample 1/2 consisting only of a transparent layer and a comparative sample 2 consisting only a low resistance layer were prepared, and the characteristics of these films are shown in Table 2.
本発明に係るサンプル７、ｒ、９．１０は熱処理前では
Ｘ線回折測定の結果、非晶質相が主体である構造を示し
、厚膜であるにもかかわらず実施例／と同様０．２規定
の塩酸水溶液で３分以内に完全に膜は消失した。２ｊＯ
°Ｃ，３００℃，３！；Ｏ℃で３０分間焼成することに
よりいずれの温度でも、面積抵抗が７３〜３０９７口の
低抵抗膜となっていると同時に、！ｊＯ℃の低温の焼成
においても波長！； 、！；ｐ ｎｍの光でざ０％以上
の高透過率を有し実用可能な膜特性が得られていること
が分る。本発明に係る膜はサンプル１０に示されるよう
に３２００１の厚膜に於いてもその効果を発揮できるこ
とが第２表より証明される。As a result of X-ray diffraction measurement, samples 7, r, and 9.10 according to the present invention showed a structure mainly composed of an amorphous phase before heat treatment, and although they were thick films, they had a 0.0. The film completely disappeared within 3 minutes with a 2N aqueous hydrochloric acid solution. 2jO
°C, 300℃, 3! By firing at 0°C for 30 minutes, the film has a low resistance film with a sheet resistance of 73 to 3097 at any temperature. Wavelength even when firing at a low temperature of 0°C! ;、! It can be seen that the film has a high transmittance of 0% or more for p nm light, and has practical film characteristics. Table 2 proves that the film according to the present invention can exhibit its effects even in a thick film of 32001 as shown in Sample 10.
比較例のサン、プル／／は厚膜であるにもかかわらず高
抵抗となる。一方低抵抗化層のみからなるサンプル／２
は３５０℃の高温の熱処理においても１０％以上の高透
過率にならず、透明電極膜として良好な特性をもってい
ないことが分る。Comparative example sample PULL// has high resistance even though it is a thick film. On the other hand, sample/2 consisting only of a low resistance layer
It can be seen that even after heat treatment at a high temperature of 350° C., the film did not have a high transmittance of 10% or more, and did not have good characteristics as a transparent electrode film.
実施例３
全体の膜厚を／３００Ａとし、透明化層を約／／３にな
るように実施例１と同じように酸素ガスをアルゴンに添
加して膜を作成した。このときガラス板の背面にあるニ
クロムヒーターによりガラスを加熱してサンプル／４’
、 ／！； 、 ／４をまた加熱せずにサンプル／３
を得た。得られたサンプル７３〜／６の膜特性を第３表
に示す。Example 3 A film was prepared by adding oxygen gas to argon in the same manner as in Example 1 so that the total film thickness was /300A and the transparent layer was about /3. At this time, the glass was heated with a nichrome heater on the back of the glass plate, and the sample/4'
, /! ; , sample /3 without heating /4 again
I got it. Table 3 shows the film characteristics of the obtained samples 73-/6.
被膜形成中のガラス温度が室温、７０”Ｃ、１０Ｏ′Ｃ
の本発明に係るサンプル１３．／ψ、ｌｊでは、２５０
°Ｃ、３００℃、３５０℃のいずれの温度で熱処理して
も抵抗が処理前より低下し波長ｊｊ（７ｎｍの光でｇｏ
％以上の高透過率を有する。またサンプル／３ 、 ／
’７ 。Glass temperature during film formation is room temperature, 70"C, 10O'C
Sample 13 according to the present invention. /ψ, lj, 250
℃, 300℃, and 350℃, the resistance is lower than before the treatment and the wavelength jj (7 nm light)
% or more. Also sample /3, /
'7.
１５共実施例１と同様膜の除去が可能であった。As in Example 1, the film could be removed in both cases.
ガラスの温度が１５０°Ｃの比較のサンプル１６では２
ｊＯ〜３！；Ｏ”Ｃのいずれの焼成温度に於いても面積
抵抗が上昇してしまい低抵抗化の特性は得られなかった
。また比較サンプル／６は熱処理前の膜に於いてすでに
結晶化が進み実施例／と同じエツチング条件では、膜は
除去不可能であった。2 for comparative sample 16 where the glass temperature is 150°C.
jO~3! ; At any firing temperature of O"C, the sheet resistance increased and the characteristic of lowering the resistance could not be obtained. Also, in comparison sample 6, crystallization had already progressed in the film before heat treatment. The film could not be removed under the same etching conditions as in Example/.
以上は本発明の実施例を示したものであるが、本発明の
特許請求の範囲内において変形できる。Although the embodiments of the present invention have been described above, modifications can be made within the scope of the claims of the present invention.
すなわち、本発明は透明化層の形成を行うに当り、酸素
ガス量は透明化層形成の過程で一定の濃度に保ってもよ
いし、また徐々に増やしてもよいし、更にまた間歇的に
加えてもよい。That is, in forming the transparent layer of the present invention, the amount of oxygen gas may be maintained at a constant concentration during the process of forming the transparent layer, may be increased gradually, or may be increased intermittently. May be added.
また、本発明はプラズマを発生する電源として実施例に
おいては直流電源を用いたが高周波電源を用いることも
できる。Further, in the present invention, a DC power source is used in the embodiment as a power source for generating plasma, but a high frequency power source may also be used.
更にまた、積層膜の熱処理は実施例では大気中で行った
が、窒素やアルゴンのような不活性ガス雰囲気中、ある
いは真空中でも行うことができる。Furthermore, although the heat treatment of the laminated film was performed in the atmosphere in the examples, it can also be performed in an inert gas atmosphere such as nitrogen or argon, or in a vacuum.
更にまた、透明導電膜を形成する基板としては可視域で
透明な基板又はフィルムが利用でき、ガラス板のセラミ
ックスの他、ポリイミド、ポリアミド、シリコーン等の
有機物も用いることができる。Furthermore, as the substrate on which the transparent conductive film is formed, a substrate or film that is transparent in the visible range can be used, and in addition to ceramics such as glass plates, organic materials such as polyimide, polyamide, and silicone can also be used.
（７）発明の効果
以上から明らかなように、本発明は光透過率が高く、且
つ面積抵抗が高い透明導電膜を形成でき、しかも、膜厚
が３０００１以上の膜厚になっても光透過率を大にする
ことができ、透明な低抵抗の導電膜を形成できる。(7) Effects of the Invention As is clear from the above, the present invention can form a transparent conductive film with high light transmittance and high sheet resistance, and moreover, even when the film thickness is 30001 or more, light transmission is possible. It is possible to increase the conductive film and form a transparent conductive film with low resistance.
また、本発明は基板の温度が１００℃以下に保たれてい
るので熱処理前には被膜が非晶質であるので、極めて稀
薄な塩酸（例えば０．／〜／８０規定）でレジストでき
、微細な電極のパタニングをすることができる。In addition, in the present invention, since the temperature of the substrate is kept below 100°C, the film is amorphous before heat treatment, so it can be resisted with extremely dilute hydrochloric acid (e.g. 0./~/80 normal) and fine It is possible to pattern electrodes in various ways.
更にまた、本発明に係る透明導電膜を液晶表示素子の透
明？ＩＩＥｌ＋に用いる場合には配向膜の硬化処理と同
峙に透明化と低抵抗化の熱処理を行うことができる。し
たがって、本発明に係る透明導電膜は低抵抗化層と透明
化層と膜厚比率を配向膜の硬化処理湿度及び時間とを考
慮の上、決めることができる。Furthermore, the transparent conductive film according to the present invention may be used as a transparent conductive film for liquid crystal display devices. When used in IIEl+, heat treatment for making the alignment film transparent and reducing resistance can be performed at the same time as the hardening treatment for the alignment film. Therefore, in the transparent conductive film according to the present invention, the thickness ratio of the low resistance layer to the transparent layer can be determined in consideration of the humidity and time of the curing process of the alignment film.
Claims (3)
ゲットを用いてスパッタリングすることにより、基板上
に透明導電膜を形成する方法であって、該基板を１００
℃以下とし、減圧された、不活性ガスまたは不活性ガス
と水素との混合ガス中でスパッタリングすることにより
、低抵抗化層を基板上に形成し、その後減圧された不活
性ガスと酸素との混合ガス中でスパッタリングして該低
抵抗化層上に透明化層を積層し、該低抵抗化層と透明化
層との積層膜を熱処理することにより、該積層膜の抵抗
を減少し、且つ光透過率を増加することを特徴とする透
明導電膜の形成方法。(1) A method of forming a transparent conductive film on a substrate by sputtering using a target made of an indium oxide sintered body containing tin oxide, the method comprising:
A low-resistance layer is formed on the substrate by sputtering in an inert gas or a mixed gas of an inert gas and hydrogen under reduced pressure at temperatures below A transparent layer is laminated on the low-resistance layer by sputtering in a mixed gas, and the laminated film of the low-resistance layer and the transparent layer is heat-treated to reduce the resistance of the laminated film, and A method for forming a transparent conductive film characterized by increasing light transmittance.
の範囲第１項に記載の透明導電膜の形成方法。(2) The method for forming a transparent conductive film according to claim 1, wherein the laminated film has a thickness of 1000 Å or more.
る特許請求の範囲第１項又は第２項に記載の透明導電膜
の形成方法。(3) The method for forming a transparent conductive film according to claim 1 or 2, wherein the transparent layer has a thickness of 1/2 or less of the total thickness of the laminated film.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7044486A JPH0723532B2 (en) | 1986-03-28 | 1986-03-28 | Method for forming transparent conductive film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7044486A JPH0723532B2 (en) | 1986-03-28 | 1986-03-28 | Method for forming transparent conductive film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62227082A true JPS62227082A (en) | 1987-10-06 |
| JPH0723532B2 JPH0723532B2 (en) | 1995-03-15 |
Family
ID=13431670
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP7044486A Expired - Lifetime JPH0723532B2 (en) | 1986-03-28 | 1986-03-28 | Method for forming transparent conductive film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0723532B2 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0254755A (en) * | 1988-08-19 | 1990-02-23 | Ulvac Corp | Manufacture of transparent conductive film |
| JPH02163363A (en) * | 1988-03-09 | 1990-06-22 | Ulvac Corp | Production of transparent conductive film |
| JPH0364450A (en) * | 1989-07-31 | 1991-03-19 | Kyocera Corp | Formation of transparent conductive film |
| WO2008133285A1 (en) * | 2007-04-24 | 2008-11-06 | Asahi Glass Company, Limited | Substrate with film, substrate with transparent conductive film, and light-emitting device |
| WO2008143232A1 (en) * | 2007-05-22 | 2008-11-27 | Nippon Electric Glass Co., Ltd. | Transparent electrode |
-
1986
- 1986-03-28 JP JP7044486A patent/JPH0723532B2/en not_active Expired - Lifetime
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02163363A (en) * | 1988-03-09 | 1990-06-22 | Ulvac Corp | Production of transparent conductive film |
| JPH0254755A (en) * | 1988-08-19 | 1990-02-23 | Ulvac Corp | Manufacture of transparent conductive film |
| JPH0364450A (en) * | 1989-07-31 | 1991-03-19 | Kyocera Corp | Formation of transparent conductive film |
| WO2008133285A1 (en) * | 2007-04-24 | 2008-11-06 | Asahi Glass Company, Limited | Substrate with film, substrate with transparent conductive film, and light-emitting device |
| JPWO2008133285A1 (en) * | 2007-04-24 | 2010-07-29 | 旭硝子株式会社 | Substrate with film, substrate with transparent conductive film, and light emitting device |
| JP5093231B2 (en) * | 2007-04-24 | 2012-12-12 | 旭硝子株式会社 | Substrate with film, substrate with transparent conductive film, and light emitting device |
| WO2008143232A1 (en) * | 2007-05-22 | 2008-11-27 | Nippon Electric Glass Co., Ltd. | Transparent electrode |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0723532B2 (en) | 1995-03-15 |
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