JPS58209009A - Method of forming transparent conductive film - Google Patents
Method of forming transparent conductive filmInfo
- Publication number
- JPS58209009A JPS58209009A JP57089677A JP8967782A JPS58209009A JP S58209009 A JPS58209009 A JP S58209009A JP 57089677 A JP57089677 A JP 57089677A JP 8967782 A JP8967782 A JP 8967782A JP S58209009 A JPS58209009 A JP S58209009A
- Authority
- JP
- Japan
- Prior art keywords
- transparent conductive
- conductive film
- film
- forming
- 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.)
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- Manufacturing Of Electric Cables (AREA)
Abstract
(57)【要約】本公報は電子出願前の出願データであるた
め要約のデータは記録されません。(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.
Description
【発明の詳細な説明】
本発明は酸化インジウムを主成分とするターゲットを用
いたスパッタリング法により、１００℃以下で低抵抗か
つ膜表面凹凸が平滑な膜が得られる透明導電膜の形成方
法に関するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for forming a transparent conductive film that can obtain a film with low resistance and smooth film surface irregularities at 100° C. or lower by a sputtering method using a target containing indium oxide as a main component. It is.
一般に、酸化インジウムを主成分とするターゲット材料
をスパッタリング法によｐ透光性基板上に被着させて透
明導電膜を形成する方法は、液晶表示素子用電極や撮像
管光電変換面用電極等の形成として工業化されている。In general, a method of forming a transparent conductive film by depositing a target material containing indium oxide as a main component on a p-transparent substrate by sputtering is used for forming electrodes for liquid crystal display elements, electrodes for photoelectric conversion surfaces of image pickup tubes, etc. It has been industrialized as the formation of
これらの用途、特に有機樹脂材料を用いた色分解フィル
タ内蔵形の撮像管分野においては、色分解フィルタの耐
熱温度（約１３０℃）以下で透明導電膜を形成すること
が必要であり、続いて透明導電膜上に形成される光電変
換膜は透明導電膜側からの正孔注入、々らびいわゆる阻
止型構造にすると撮像管の暗電流が抑制されて、高感度
で、かつ焼付、残像の少ない高画質の映像が得られるこ
とが知られている。For these applications, especially in the field of image pickup tubes with built-in color separation filters using organic resin materials, it is necessary to form a transparent conductive film at a temperature below the heat resistance temperature of the color separation filter (approximately 130°C). The photoelectric conversion film formed on the transparent conductive film prevents hole injection from the transparent conductive film side, and if it has a so-called blocking type structure, the dark current of the image pickup tube is suppressed, resulting in high sensitivity and prevention of burn-in and afterimages. It is known that high-quality images can be obtained with little effort.
ｐ型の電気伝導性を示す光電変換膜を用いる阻止型撮像
管ターゲット、特に、透光性基板上にもうけられた透明
導電膜、ないしはその上に積層されたｎ型半導体薄層と
セレンを主体とするｐ型光電変換層との間に形成される
整流性接触を逆バイアスにして用いる阻止型撮像管ター
ゲット（例えば特公簀昭５２−３００９１ ）において
、良好な撮像特性を得るためにに、基盤となる透明導電
膜の表面粒状炭が平滑であることが要求される。A blocking type image pickup tube target using a photoelectric conversion film exhibiting p-type electrical conductivity, especially a transparent conductive film formed on a transparent substrate, or an n-type semiconductor thin layer laminated thereon and selenium. In order to obtain good imaging characteristics in a blocking type image pickup tube target (for example, Japanese Patent Publication No. 52-30091) in which the rectifying contact formed between the p-type photoelectric conversion layer and the p-type photoelectric conversion layer is reverse biased, It is required that the surface granular carbon of the transparent conductive film serving as the base is smooth.
有機樹脂材料による色分解フィルタを内蔵しない撮像管
用透光性ガラス基板上に透明導電膜を形成する場合には
、（１） Ｓ ｎ Ｃｔ４溶液をスプレー法により３０
０〜５００℃に加熱した基板上に吹付ける方法、（２）
Ｂ ｎ Ｃｔ４溶液を不活性なガスを用いて蒸気状態
にし、酸素もしくは水蒸気と反応させ、３００〜５００
℃に加熱した基板上に気相成長法（ＣＶＤ法）により形
成する方法、（３）インジウムもしくは酸化インジウム
を酸素雰囲気中で真空蒸着および電子ビーム蒸着し、酸
化雰囲気中１６０〜３００℃で加熱処理する方法、（４
）金属インジウムまたは酸化インジウムを生成分とする
ターゲットを用い、酸化雰囲気もしくは不活性雰囲気中
で２００〜３００℃に加熱した基板上に被膜を形成する
、もしくは膜形成後加熱処理を行う方法、等が行われて
いる。When forming a transparent conductive film on a transparent glass substrate for an image pickup tube that does not have a built-in color separation filter made of an organic resin material, (1) Spray a S n Ct4 solution at 30%
Method of spraying onto a substrate heated to 0 to 500°C, (2)
The B n Ct4 solution is made into a vapor state using an inert gas, and reacted with oxygen or water vapor to give 300 to 500
(3) Indium or indium oxide is vacuum evaporated and electron beam evaporated in an oxygen atmosphere, and then heat-treated at 160 to 300°C in an oxidizing atmosphere. How to do (4
) A method in which a film is formed on a substrate heated to 200 to 300°C in an oxidizing atmosphere or an inert atmosphere using a target containing metallic indium or indium oxide, or a method in which a heat treatment is performed after the film is formed. It is being done.
上記の方法の内、（］）〜（３）の形成膜光面の凹凸は
粗く１、形成後膜表面を研摩やドライエツチング等の処
理を行い表面を平滑にする方法が採用されている。また
、（４）は（１）〜（３）に比較すると膜表面は平滑で
ある。し７か１７．１３０℃以下で形成するには上記（
１）〜（４）のいずれの場合も適さない。Among the above methods, methods (1) to (3) are employed in which the formed film has rough unevenness on the optical surface, and the film surface is smoothed by polishing, dry etching, etc. after formation. Moreover, the film surface of (4) is smoother than that of (1) to (3). 7 or 17.For formation at 130℃ or below, the above (
None of cases 1) to (4) are suitable.
本発明の目的は、酸化インジウムを主成分とするターゲ
ットを用い、スパッタリング法により、１３０℃以下で
膜表面凹凸が平滑で緻密、かつ、低抵抗、高透過率の透
明導電膜形成方法を提供することにある。An object of the present invention is to provide a method for forming a transparent conductive film with smooth and dense film surface irregularities, low resistance, and high transmittance at 130° C. or lower by sputtering using a target containing indium oxide as a main component. There is a particular thing.
酸化インジウムを主成分とするターゲットを用−轡不活
性ガれしくに不活性ガ３と酸素混合ガ３−
ス雰囲気中でスパッタリング法により透明導電膜を形成
する方法は液晶表示素子用や画像表示素子用の透明電極
形成として一般に適用されている。A method of forming a transparent conductive film by a sputtering method in an atmosphere using a target containing indium oxide as a main component - an inert gas and a mixed gas of inert gas and oxygen - is suitable for use in liquid crystal display devices and image displays. It is generally applied to form transparent electrodes for devices.
このとき低抵抗の膜を得るためにはスパッタ時の被膜形
成用基板ガラスを加熱すれば容易に低抵抗膜が得られる
。また、高透過率の膜を形成するには、不活性ガス中に
微量の酸素を導入し、例えばアルゴン（Ａｒ）に酸素を
０．５〜２％混合した雰囲気中でスパッタリングさせれ
ば膜厚５００Ａで透過率９０％以上の腹を形成すること
が出来る。At this time, in order to obtain a low-resistance film, a low-resistance film can be easily obtained by heating the substrate glass for film formation during sputtering. In addition, in order to form a film with high transmittance, it is possible to introduce a small amount of oxygen into an inert gas and perform sputtering in an atmosphere containing, for example, 0.5 to 2% oxygen mixed with argon (Ar). An antinode with a transmittance of 90% or more can be formed at 500A.
しか（７、有機樹脂材料で形成され次色分解フィルタを
内蔵した撮像管用ストライプフィルタ面板ガラス上にネ
サ膜を形成するには、フィルタ耐熱温度１３０℃以下で
低抵抗、高透過率の膜を形成しなけねげならない。また
発明者の実検結果によれば、基板を加熱しないで雰囲気
ガスに酸素を導入すれば膜の抵抗は酸素の濃度増加に伴
い増加する傾向があり低抵抗の膜は得られない。また雰
囲気ガスにＡｒのみを用い、基板を加熱し危いで低抵抗
膜を形成するには、スパッタ時のＡｒガス圧力４−
を減少されれば良いことが解かった。第１図にアルゴン
圧力と透明導電膜の抵抗値の関係を示す。However, in order to form a Nesa film on the face plate glass of a striped filter for image pickup tubes made of organic resin material and containing a built-in next color separation filter, it is necessary to form a film with low resistance and high transmittance at a filter heat resistance temperature of 130°C or less. Furthermore, according to the inventor's actual test results, if oxygen is introduced into the atmospheric gas without heating the substrate, the resistance of the film tends to increase as the concentration of oxygen increases, making it difficult to obtain a film with low resistance. In addition, it was found that in order to form a low-resistance film using only Ar as the atmospheric gas and heating the substrate, which is dangerous, it is sufficient to reduce the Ar gas pressure during sputtering. Fig. 1 shows the relationship between argon pressure and the resistance value of the transparent conductive film.
アルゴン圧力を増すと抵抗値は４ｆ）口する。しかも、
アルゴン圧力が６ ｘ １０ Ｉｔ Ｔｏｒｒ以上では
形成膜表面の電子顕微鏡写真によると表面状態は粗く、
６Ｘ１０’以下では表面凹凸は平滑となることが解った
。［２かし、スパッタ中のガス圧力は他制限に低く出来
るものではなく ８ ｘ １０ ’Ｔｏｒｒ以下ではグ
ロー放電が起らなくなりスパッタは停止してしまう。結
局基板の加熱なしでガス圧力６×１０ ” 〜８Ｘ
１０ ’ Ｔｏｒｒ をスパッタ雰囲気アルゴンガスと
して導入すれば、低抵抗でかつ表面の平滑な透明導電膜
が得られる。また透過率も９０係以上のものが得られる
ことが解った。ガラス基板上にＡｒ圧Ｉ Ｘ １０
”Ｔｏｒｒ 、 ３ ｘ １０ ”Ｔｏｒｒ、６Ｘ１
０ Ｔｏｒｒ、 ｌＸｌ０ Ｔｏｒｒ で形成した
膜に各々１μｍ厚のセレン膜を形成し、第２図に示した
方法により１基板側から光を入れないときターゲット電
圧ＶＴ とその時に流れる膜の電流（暗電流）との関係
、すなわちセレン膜に対するネサ膜のブロッキング特性
を第３図に示Ｌ７た。When the argon pressure is increased, the resistance value increases to 4f). Moreover,
When the argon pressure is 6 x 10 It Torr or higher, electron micrographs of the surface of the formed film show that the surface condition is rough;
It was found that the surface unevenness becomes smooth when the size is 6×10' or less. [2 However, the gas pressure during sputtering cannot be lowered to any other limit; if it is less than 8 x 10' Torr, no glow discharge will occur and sputtering will stop. After all, the gas pressure is 6×10”~8× without heating the substrate.
If argon gas of 10' Torr is introduced into the sputtering atmosphere, a transparent conductive film with low resistance and a smooth surface can be obtained. It was also found that a transmittance of 90 coefficient or higher can be obtained. Ar pressure I x 10 on glass substrate
”Torr, 3 x 10”Torr, 6X1
A selenium film with a thickness of 1 μm is formed on each of the films formed at 0 Torr and 1 ), that is, the blocking characteristics of the Nesa film with respect to the selenium film, are shown in FIG. 3.
ロッキング特性がすぐれていることが解かる。It can be seen that the locking characteristics are excellent.
なお、第２図において、１は基板ガラス、２は透明導電
膜、３は厚さ１μｍのセレン膜、４は電子銃カソード、
５は電子ビーム、６は電流計、γは電圧計である。また
、第３図において、イ、０、ハ、二はそれぞれＡｒ圧力
がｌ Ｘ １０ Ｔｏｒｒ。In addition, in FIG. 2, 1 is a substrate glass, 2 is a transparent conductive film, 3 is a selenium film with a thickness of 1 μm, 4 is an electron gun cathode,
5 is an electron beam, 6 is an ammeter, and γ is a voltmeter. In addition, in FIG. 3, the Ar pressures at A, 0, C, and 2 are l x 10 Torr, respectively.
３Ｘ１０ Ｔｏｒｒ、’６Ｘ１０ Ｔｏｒｒ、ｌ
Ｘ１０ ”Ｔｏｒｒ の特性である。3X10 Torr, '6X10 Torr, l
This is a characteristic of X10” Torr.
以下、本発明の一実施例を説明する。An embodiment of the present invention will be described below.
酸化インジウムを９５重量％、酸化錫を５重量％含む焼
結体ターゲットを用い、Ａｒ圧力３Ｘ１０ ”Ｔｏｒ
ｒとし、 膜形成温度７０℃で有機樹脂材料を用いた色
分解ストライプフィルタ内蔵のガラス基板上に５００Ｘ
厚、１００Ω／口、９０％透過率で表面の平滑な透明導
電膜を形成し、その上に Ｓｅ −Ａｓ −Ｔｅ から
なる非晶質光導電膜を蒸着形成して撮像ターゲットとし
、電子銃部を封着した撮像管を作成した。この結果、暗
電流の少ない極めて高画質の撮像管が得られた。Using a sintered target containing 95% by weight of indium oxide and 5% by weight of tin oxide, Ar pressure was set at 3×10” Tor.
500X on a glass substrate with a built-in color separation stripe filter using an organic resin material at a film formation temperature of 70°C.
A transparent conductive film with a smooth surface was formed with a thickness of 100 Ω/hole and a transmittance of 90%, and an amorphous photoconductive film made of Se-As-Te was deposited thereon to serve as an imaging target. An image pickup tube sealed with As a result, an extremely high-quality image pickup tube with low dark current was obtained.
このように本発明によれば、低温でかつ低抵抗、高透過
率であるとともに表面が平滑な透明導電膜が、スパッタ
中のＡｒガス雰囲気の制御のみで簡単に得られ、従来の
様に研磨やドライエツチング等の工程を追加する必要な
しに、暗電流の極めて少ない撮像管を得ることができる
というすぐれた効果がある。As described above, according to the present invention, a transparent conductive film having a low temperature, low resistance, high transmittance, and a smooth surface can be easily obtained by simply controlling the Ar gas atmosphere during sputtering, and it can be easily obtained by simply controlling the Ar gas atmosphere during sputtering. An excellent effect is that an image pickup tube with extremely low dark current can be obtained without the need for additional processes such as etching and dry etching.
なお本発明による透明導電膜とセレンを生体とする電荷
阻止形光導電層との間に、従来から知られているｎ型半
導体薄層、例えばＣｅ０ｚ（％願昭５０−１１９６３３
号）を導入すれば効果はさらに犬となる。Furthermore, between the transparent conductive film according to the present invention and the charge-blocking photoconductive layer made of selenium, a conventionally known n-type semiconductor thin layer, for example, Ce0z
The effect will be even more pronounced if we introduce the issue.
本発明による透明導電膜は、以−ヒ説明した撮像管ター
ゲット電極と１７て有用であるのみならず、当然の仁と
なから電子写真、太陽電池５画像表示累子等の透明電極
として適用できると七は云うまでもない１．The transparent conductive film according to the present invention is not only useful as the image pickup tube target electrode described below, but also can be applied as a transparent electrode for electrophotography, solar cell image display devices, etc. Needless to say, 7 is 1.
第１図はスパッタ雰囲気中のＡｒガス圧力と抵抗値の関
係図、第２図は本発明によって形成した膜の評価方法の
説明図、第３図は本発明によるＡｒ圧力とブロッキング
特性の関係図である。
１・・・・基板ガラス、２・・・・透明導電膜、３・・
・・セレン膜、４・・・・電子銃カソード、５・・・・
電子ビーム、６・・・・電流計、７・・・パ電圧１ｔ−
１−６
第１図
７１レプ゛ン斥六 （Ｔｏｒｒ）
第２図Figure 1 is a diagram showing the relationship between Ar gas pressure in the sputtering atmosphere and resistance value, Figure 2 is an explanatory diagram of the evaluation method for a film formed according to the present invention, and Figure 3 is a diagram showing the relationship between Ar pressure and blocking characteristics according to the present invention. It is. 1...Substrate glass, 2...Transparent conductive film, 3...
... Selenium film, 4... Electron gun cathode, 5...
Electron beam, 6... Ammeter, 7... Power voltage 1t-
1-6 Figure 1 71 Repun Torroku (Torr) Figure 2
Claims (1)
料を用い、不活性ガス雰囲気中でスパッタリングさせて
所定の基板上に透明導電膜を被着形成させる透明導電膜
の形成方法において、膜形成時の基板温度を１００℃以
下とし、かつ前記雰囲気ガスにアルゴンを用い、ガス圧
力を５Ｘ１０’〜６×ＩＯ”Ｔｏｒｒ とし、被着形
成した膜表面の凹凸を１００Ｘ以下にすることを特徴と
する透明導電膜の形成方法。 ２゜基板に、有機染色材料を用いた撮像管用色分解スト
ライプフィルタを内蔵した透光性ガラス薄板または透光
性有機樹脂板を用いたことを特徴とする特許請求の範囲
第１項記載の透明導電膜の形成方法。 ３、透光性基板上または有機染色材料を用いた撮像管用
色分解ストライプフィルタを内蔵した透光性薄板ガラス
上に、少なくとも透明導電膜と電荷阻止形光導電膜を有
する撮像管ターゲットにおいて、該透明導電膜を特許請
求の範囲第１項記載によって形成することを特徴とする
透明導電膜の形成方法。[Claims] 1. Formation of a transparent conductive film using a sintered target material containing indium oxide as a main component and depositing the transparent conductive film on a predetermined substrate by sputtering in an inert gas atmosphere. In the method, the substrate temperature during film formation is 100°C or less, argon is used as the atmospheric gas, the gas pressure is 5X10' to 6XIO'' Torr, and the unevenness of the deposited film surface is 100X or less. A method for forming a transparent conductive film characterized by using a transparent glass thin plate or a transparent organic resin plate having a built-in color-separating stripe filter for an image pickup tube using an organic dyeing material as a 2° substrate. 3. A method for forming a transparent conductive film according to claim 1. 3. A method for forming a transparent conductive film according to claim 1. A method for forming a transparent conductive film in an image pickup tube target having a transparent conductive film and a charge-blocking photoconductive film, the transparent conductive film being formed as described in claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57089677A JPS58209009A (en) | 1982-05-28 | 1982-05-28 | Method of forming transparent conductive film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57089677A JPS58209009A (en) | 1982-05-28 | 1982-05-28 | Method of forming transparent conductive film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS58209009A true JPS58209009A (en) | 1983-12-05 |
| JPH0370327B2 JPH0370327B2 (en) | 1991-11-07 |
Family
ID=13977379
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP57089677A Granted JPS58209009A (en) | 1982-05-28 | 1982-05-28 | Method of forming transparent conductive film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS58209009A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS593814A (en) * | 1982-06-30 | 1984-01-10 | 株式会社東芝 | Method of producing transparent conductive film |
| JPS6139321A (en) * | 1984-07-30 | 1986-02-25 | 株式会社半導体エネルギー研究所 | Method of producing tin oxide conductive film |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5469183A (en) * | 1977-11-15 | 1979-06-02 | Asahi Glass Co Ltd | Preparation of transparent, electrically-conductive plastic |
| JPS54127598A (en) * | 1978-03-27 | 1979-10-03 | Sharp Corp | Process for fabricating transparent conductive film |
-
1982
- 1982-05-28 JP JP57089677A patent/JPS58209009A/en active Granted
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5469183A (en) * | 1977-11-15 | 1979-06-02 | Asahi Glass Co Ltd | Preparation of transparent, electrically-conductive plastic |
| JPS54127598A (en) * | 1978-03-27 | 1979-10-03 | Sharp Corp | Process for fabricating transparent conductive film |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS593814A (en) * | 1982-06-30 | 1984-01-10 | 株式会社東芝 | Method of producing transparent conductive film |
| JPS6139321A (en) * | 1984-07-30 | 1986-02-25 | 株式会社半導体エネルギー研究所 | Method of producing tin oxide conductive film |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0370327B2 (en) | 1991-11-07 |
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