JP2718046B2 - Transparent conductive film - Google Patents
Transparent conductive filmInfo
- Publication number
- JP2718046B2 JP2718046B2 JP63015806A JP1580688A JP2718046B2 JP 2718046 B2 JP2718046 B2 JP 2718046B2 JP 63015806 A JP63015806 A JP 63015806A JP 1580688 A JP1580688 A JP 1580688A JP 2718046 B2 JP2718046 B2 JP 2718046B2
- Authority
- JP
- Japan
- Prior art keywords
- transparent conductive
- conductive film
- film
- zinc oxide
- glass substrate
- 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
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
Description
【発明の詳細な説明】 ［産業上の利用分野］ 本発明は、低抵抗で、高透過率を有する透明導電膜
で、太陽電池、表示素子用の透明導電基板の透明導電膜
として有用な透明導電膜に関するものである。The present invention relates to a transparent conductive film having a low resistance and a high transmittance, which is useful as a transparent conductive film for a transparent conductive substrate for a solar cell or a display element. It relates to a conductive film.
［従来の技術］ 一般に、透明導電膜は、太陽電池用基板、液晶・電場
発光素子等の表示素子用電極等に広く使用されている。
透明導電膜としては低抵抗で、可視光において透明であ
ることが必要であり、かかる条件を満たす透明導電膜の
材料としては、酸化錫、酸化インジウム、酸化亜鉛等が
知られている。現在は錫をドープした導電性酸化インジ
ウム膜やフッ素やアンチモンをドープした導電性酸化錫
膜が高性能の膜が得られることから最も広く利用されて
いるが、原料のインジウムが高価であるため比較的低価
格で成膜可能な酸化亜鉛膜が上記の導電性酸化インジウ
ム膜等の代替材料として注目され、近年活発な研究が行
われている。[Related Art] In general, a transparent conductive film is widely used for a substrate for a solar cell, an electrode for a display element such as a liquid crystal / electroluminescent element, and the like.
The transparent conductive film needs to have low resistance and be transparent to visible light, and tin oxide, indium oxide, zinc oxide, and the like are known as materials for the transparent conductive film satisfying such conditions. At present, tin-doped conductive indium oxide films and fluorine and antimony-doped conductive tin oxide films are most widely used because high-performance films can be obtained, but the indium used as the raw material is expensive. A zinc oxide film which can be formed at a relatively low price has been attracting attention as an alternative material to the above-mentioned conductive indium oxide film and the like, and active research has been conducted in recent years.
従来、酸化亜鉛はＮ型の半導体でありながら電導性に
は乏しいとされていた。近年、膜中にアルミニウム、イ
ンジウム、ガリウム等の３価の金属を活剤として導入す
ると低抵抗化に効果的であることが見出され、比抵抗ｐ
が10-4Ω・cm台の低抵抗膜も作成されている。（例え
ば、T.Minami et.al.,Jpn.J,Appl.Phys.Part2,23（198
4）p280;S.Major,A.Banerjee et.al.,Thin Solid Films
Vol.125（1985）p179参照）。Conventionally, zinc oxide has been considered to be poor in conductivity even though it is an N-type semiconductor. In recent years, it has been found that introducing a trivalent metal such as aluminum, indium, or gallium into a film as an activator is effective for lowering the resistance.
However, low resistance films of the order of 10 −4 Ω · cm have been created. (For example, T. Minami et.al., Jpn.J, Appl.Phys.Part2, 23 (198
4) p280; S. Major, A. Banerjee et.al., Thin Solid Films
Vol.125 (1985) p179).
しかしながら、安定で蒸気圧が高い３価の金属の化合
物が得にくいため常圧下で成膜する場合、スプレー法よ
りも成膜の制御性が高く、排ガス量の少ない常圧CVD法
によって上記３価の金属をドープした低抵抗酸化亜鉛膜
を成膜するのは困難であるという問題点を有している。
又、入手可能な上記３価の金属化合物の出発原料は爆発
等の危険があり取扱いが困難であるという欠点もあっ
た。However, it is difficult to obtain a trivalent metal compound that is stable and has a high vapor pressure. Therefore, when forming a film under normal pressure, the controllability of film formation is higher than that of the spray method, and the above-mentioned trivalent metal is formed by the normal pressure CVD method with a small exhaust gas amount. However, it is difficult to form a low-resistance zinc oxide film doped with a metal.
In addition, the available starting materials of the above-mentioned trivalent metal compound have a drawback that they are difficult to handle because of the danger of explosion.
［発明が解決しようとする課題］ 本発明は前述の問題点を解決し、かつ低抵抗を維持し
た透明導電膜を提供することを目的とする。[Problems to be Solved by the Invention] An object of the present invention is to solve the above-mentioned problems and to provide a transparent conductive film which maintains low resistance.
［課題を解決するための手段］ 本発明は、前述の課題を解決すべくなされたものであ
り、酸化亜鉛を主成分とする透明導電膜であって、該透
明導電膜は常圧CVD法により成膜され、酸化亜鉛に対し
３〜10wt％の弗素を含むことを特徴とする透明導電膜で
ある。Means for Solving the Problems The present invention has been made to solve the above-mentioned problems, and is a transparent conductive film containing zinc oxide as a main component, wherein the transparent conductive film is formed by a normal pressure CVD method. A transparent conductive film which is formed and contains 3 to 10% by weight of fluorine based on zinc oxide.
以下、本発明を更に詳細に説明する。 Hereinafter, the present invention will be described in more detail.
本発明における酸化亜鉛を主成分とする透明導電膜
は、透過率をさほど低下させることなく比抵抗を低下さ
せる為に、弗素が酸化亜鉛に対し0.05〜30wt％、好まし
くは３〜10wt％含有された弗素ドープ酸化亜鉛導電膜で
ある。The transparent conductive film containing zinc oxide as a main component in the present invention contains 0.05 to 30% by weight, preferably 3 to 10% by weight of fluorine based on zinc oxide in order to lower the specific resistance without significantly lowering the transmittance. A fluorine-doped zinc oxide conductive film.
かかる弗素ドープ酸化亜鉛導電膜は生産性，成膜時に
おける制御性が高い常圧CVD法により成膜する。かかる
透明導電膜は、得ようとする抵抗値、光学的特性などに
よってその膜厚が決定されるが、通常は５Å〜２μｍ程
度の範囲である。Such a fluorine-doped zinc oxide conductive film is formed by a normal pressure CVD method having high productivity and high controllability during film formation. The thickness of such a transparent conductive film is determined by the resistance value, optical characteristics, and the like to be obtained, but is usually in the range of about 5 to 2 μm.
本発明の弗素ドープ酸化亜鉛透明導電膜を形成する基
体としては、透明性、耐久性、光学的特性、電気的物性
等の点から、ソーダライムシリケートガラス板、アルミ
ノシリケートガラス板、硼珪酸塩ガラス板、リチウムア
ルミノシリケートガラス板などのアルカリ含有ガラス
板、低アルカリ含有ガラス板、あるいは無アルカリガラ
ス板、石英ガラス板などが好ましいが、場合によっては
透明性プラスチック板、あるいは透明性プラスチックフ
ィルムを使用することもできる。Substrates for forming the fluorine-doped zinc oxide transparent conductive film of the present invention include soda lime silicate glass plate, aluminosilicate glass plate, and borosilicate glass in terms of transparency, durability, optical characteristics, electrical properties, and the like. Plate, an alkali-containing glass plate such as a lithium aluminosilicate glass plate, a low alkali-containing glass plate, or a non-alkali glass plate, a quartz glass plate or the like is preferable, but in some cases, a transparent plastic plate or a transparent plastic film is used. You can also.
なお、ソーダライムシリケートガラス板などのアルカ
リ含有ガラス板、低アルカリ含有ガラス板を本発明の透
明導電膜を形成する基板として用いる場合には、該アル
カリ含有ガラス板の表面のアルカリ成分が透明導電膜に
溶出してヘイズ（曇り）が発生しない様に、上記アルカ
リ含有ガラス板の透明導電膜形成面側に、SiO2,Al2O3,Z
rO2などの酸化物を主体とするアルカリバリヤー膜を形
成しておくのが好ましい。When an alkali-containing glass plate such as a soda lime silicate glass plate or a low alkali-containing glass plate is used as a substrate on which the transparent conductive film of the present invention is formed, the alkali component on the surface of the alkali-containing glass plate is changed to a transparent conductive film. SiO 2 , Al 2 O 3 , Z
It is preferable to form an alkali barrier film mainly containing an oxide such as rO 2 .
又、酸化亜鉛膜は水素プラズマの還元力に対して強い
耐性を有しているので、本発明の透明導電膜をガラス基
板上に形成した透明導電基板を用いて太陽電池を作成す
る場合、大変有利である。すなわち、酸化亜鉛膜つきガ
ラス基板を基板温度300℃に上げ高周波出力100mW/cm2程
度の水素プラズマ中に５分間曝したところ電導性、透過
率とも全く変化を示さず、又酸化亜鉛の膜厚が全く減少
しなかったことから、太陽電池のａ−si層を形成する時
に通常用いられるプラズマCVD法によっても、本発明の
透明導電膜は全く劣化せず、酸化錫や酸化インジウムを
主成分とする透明導電膜など水素プラズマ耐性の低い透
明導電膜と比べ大変有利である。又、上記酸化錫や酸化
インジウムなどを主成分とする水素プラズマ耐性の低い
透明導電膜の上に水素プラズマ耐性を向上させるための
保護膜としてａ−Si層を形成する前に本発明の透明導電
膜を形成することもできる。この場合、本発明の透明導
電膜は低抵抗であり、かつ透明性も高いので、太陽電池
用の透明導電基板としての性能を損なうこともない。こ
のように保護膜として本発明の透明導電膜を形成する最
の膜厚は、下地となる酸化錫、酸化インジウムなどを主
成分とする透明導電膜の水素プラズマ耐性を向上させる
という点だけを考えればバルクに近い特性が得られる程
度の薄い膜厚で十分であるが、膜厚が薄くなるにしたが
いその構造に不均一を生じやすく、水素プラズマ耐性の
面で特性が劣る傾向が生じるので、かかる不均一が生じ
ないためには膜厚５Å以上、好ましくは15〜2000Å程度
であることが望ましい。Further, since the zinc oxide film has a strong resistance to the reducing power of hydrogen plasma, it is very difficult to produce a solar cell using a transparent conductive substrate in which the transparent conductive film of the present invention is formed on a glass substrate. It is advantageous. That is, when a glass substrate with a zinc oxide film was heated to a substrate temperature of 300 ° C. and exposed to a hydrogen plasma having a high-frequency output of about 100 mW / cm 2 for 5 minutes, neither the conductivity nor the transmittance showed any change. Did not decrease at all, the transparent conductive film of the present invention did not deteriorate at all even by the plasma CVD method usually used when forming an a-si layer of a solar cell, and mainly composed of tin oxide or indium oxide. This is very advantageous as compared with a transparent conductive film having low hydrogen plasma resistance such as a transparent conductive film. Before forming an a-Si layer as a protective film for improving hydrogen plasma resistance on a transparent conductive film having low hydrogen plasma resistance containing tin oxide or indium oxide as a main component, the transparent conductive film of the present invention is formed. A film can also be formed. In this case, the transparent conductive film of the present invention has low resistance and high transparency, and thus does not impair the performance as a transparent conductive substrate for a solar cell. As described above, the most preferable thickness for forming the transparent conductive film of the present invention as a protective film is considered only to improve the hydrogen plasma resistance of the transparent conductive film mainly containing tin oxide, indium oxide, or the like as a base. If the film thickness is small enough to obtain characteristics close to bulk, it is sufficient.However, as the film thickness becomes thinner, the structure tends to become non-uniform, and the characteristics tend to be inferior in terms of hydrogen plasma resistance. In order to prevent non-uniformity from occurring, it is desirable that the film thickness is 5 mm or more, preferably about 15 to 2000 mm.
［実施例］ 以下、本発明の実施例を説明する。[Example] Hereinafter, an example of the present invention will be described.
比較例１ アルカリバイヤー膜としてCVD法により形成されたSiO
2膜（膜厚約1000Å）を表面に持つソーダライムシリケ
ートガラス板（5cm×5cm×1mm）を十分に洗浄し、次い
でこのガラス基板を常圧CVD装置に入れた。Comparative Example 1 SiO formed by CVD as an alkaline buyer film
A soda lime silicate glass plate (5 cm × 5 cm × 1 mm) having two films (thickness: about 1000 mm) on the surface was sufficiently washed, and then the glass substrate was put into a normal pressure CVD apparatus.
ガラス基板を550℃に加熱した後、このガラス基板表
面に亜鉛アセチルアセトン錯塩の蒸気（１×10-3mol/
分）と弗素添加原料としてフロン22（ジフロロクロロメ
タン）（0.05／分）を含むN2ガス（2.5／分）を吹
き付け、約500Å／分で膜中に0.1wt％の弗素を含む酸化
亜鉛からなる透明導電膜（膜厚3000Å）を形成した。か
かる透明導電膜の表面抵抗、比抵抗、透過率（以後膜特
性と記す）は表１に示す通りであった。After heating the glass substrate to 550 ° C., a vapor of zinc acetylacetone complex (1 × 10 −3 mol /
Min) and blowing N 2 gas (2.5 / min) containing Freon 22 as fluorine-doped material (difluoromethylthio chloromethane) (0.05 / min), zinc oxide containing a 0.1 wt% fluorine in the film of about 500 Å / min A transparent conductive film (thickness: 3000 Å) was formed. The surface resistance, specific resistance, and transmittance (hereinafter referred to as film characteristics) of the transparent conductive film were as shown in Table 1.
実施例１ 比較例１と同様のガラス基板を充分に洗浄し、次いで
常圧CVD装置に入れた。ガラス基板を550℃に加熱した
後、このガラス基板表面に亜鉛アセチルアセトン錯塩の
蒸気（１×10-3mol/分）と弗素添加原料としてフロン22
（ジフロロクロロメタン）（0.2／分）を含むN2ガス
（2.5／分）を吹き付け、約500Å／分で膜中に5wt％
の弗素を含む酸化亜鉛からなる透明導電膜（膜厚3000
Å）を形成した。かかる透明導電膜の膜特性は表１に示
す通りであった。Example 1 The same glass substrate as in Comparative Example 1 was sufficiently washed, and then placed in a normal pressure CVD apparatus. After the glass substrate was heated to 550 ° C., the vapor of zinc acetylacetone complex salt (1 × 10 −3 mol / min) and Freon 22
(Difluoromethylthio chloromethane) blowing (0.2 / min) N 2 gas containing (2.5 / min), 5 wt% in the film of about 500 Å / min
Transparent conductive film made of zinc oxide containing fluorine
Å) formed. The film characteristics of the transparent conductive film were as shown in Table 1.
比較例２ 比較例１と同様のガラス基板を充分に洗浄し、次いで
常圧CVD装置に入れた。ガラス基板を550℃に加熱した
後、このガラス基板表面に亜鉛アセチルアセトン錯塩の
蒸気（１×10-3mol/分）と弗素添加原料としてフロン13
B1（トリフロロブロモメタン）（0.05／分）を含むN2
ガス（2.5／分）を吹き付け、約500Å／分で膜中に0.
1wt％の弗素を含む酸化亜鉛からなる透明導電膜（膜厚3
000Å）を形成した。かかる透明導電膜の膜特性は表１
に示す通りであった。Comparative Example 2 The same glass substrate as in Comparative Example 1 was sufficiently washed, and then placed in a normal pressure CVD apparatus. After the glass substrate was heated to 550 ° C., a vapor of zinc acetylacetone complex (1 × 10 −3 mol / min) and chlorofluorocarbon 13 as a fluorine-added raw material were applied to the surface of the glass substrate.
B1 N 2 containing (trifluoromethyl bromo methane) (0.05 / min)
Gas (2.5 / min) is blown at about 500Å / min.
Transparent conductive film made of zinc oxide containing 1 wt% fluorine (thickness 3
000Å). Table 1 shows the film properties of such a transparent conductive film.
As shown in FIG.
実施例２ 比較例１と同様のガラス基板を充分に洗浄し、次いで
常圧CVD装置に入れた。ガラス基板を550℃に加熱した
後、このガラス基板表面に亜鉛アセチルアセトン錯塩の
蒸気（１×10-3mol/分）と弗素添加原料としてフロン13
B1（トリフロロブロモメタン）（0.2／分）を含むN2
ガス（2.5／分）を吹き付け、約500Å／分で膜中に5w
t％の弗素を含む酸化亜鉛からなる透明導電膜（膜厚300
0Å）を形成した。かかる透明導電膜の膜特性は表１に
示す通りであった。Example 2 The same glass substrate as in Comparative Example 1 was sufficiently washed, and then placed in a normal pressure CVD apparatus. After the glass substrate was heated to 550 ° C., a vapor of zinc acetylacetone complex (1 × 10 −3 mol / min) and chlorofluorocarbon 13 as a fluorine-added raw material were applied to the surface of the glass substrate.
B1 N 2 containing (trifluoromethyl bromo methane) (0.2 / min)
Gas (2.5 / min) is blown, and 5w
Transparent conductive film made of zinc oxide containing t% fluorine (thickness 300
0Å). The film characteristics of the transparent conductive film were as shown in Table 1.
比較例３ 比較例１と同様のガラス基板を充分に洗浄し、次いで
常圧CVD装置に入れた。ガラス基板を550℃に加熱した
後、このガラス基板表面に亜鉛アセチルアセトン錯塩の
蒸気（１×10-3mol/分）と弗素添加原料として弗酸（0.
04／分）を含むN2ガス（2.5／分）を吹き付け、約5
00Å／分で膜中に0.1wt％の弗素を含む酸化亜鉛からな
る透明導電膜（膜厚3000Å）を形成した。かかる透明導
電膜の膜特性は表１に示す通りであった。Comparative Example 3 The same glass substrate as in Comparative Example 1 was sufficiently washed, and then placed in a normal pressure CVD apparatus. After heating the glass substrate to 550 ° C., a vapor of zinc acetylacetone complex (1 × 10 −3 mol / min) and hydrofluoric acid (0.
N 2 blowing gas (2.5 / min) containing 04 / min), about 5
A transparent conductive film (thickness: 3000 Å) made of zinc oxide containing 0.1 wt% of fluorine in the film was formed at 00 Å / min. The film characteristics of the transparent conductive film were as shown in Table 1.
実施例３ 比較例１と同様のガラス基板を充分に洗浄し、次いで
常圧CVD装置に入れた。ガラス基板を550℃に加熱した
後、このガラス基板表面に亜鉛アセチルアセトン錯塩の
蒸気（１×10-3mol/分）と弗素添加原料として弗酸（0.
2／分）を含むN2ガス（2.5／分）を吹き付け、約50
0Å／分で膜中に5wt％の弗素を含む酸化亜鉛からなる透
明導電膜（膜厚3000Å）を形成した。かかる透明導電膜
の膜特性は表１に示す通りであった。Example 3 The same glass substrate as in Comparative Example 1 was sufficiently washed, and then placed in a normal pressure CVD apparatus. After heating the glass substrate to 550 ° C., a vapor of zinc acetylacetone complex (1 × 10 −3 mol / min) and hydrofluoric acid (0.
2 / min) and N 2 gas (2.5 / min)
At 0 ° / min, a transparent conductive film (thickness 3000 °) made of zinc oxide containing 5 wt% of fluorine in the film was formed. The film characteristics of the transparent conductive film were as shown in Table 1.
比較例４ 比較例１と同様のガラス基板を充分に洗浄し、次いで
常圧CVD装置に入れた。ガラス基板を550℃に加熱した
後、このガラス基板表面に亜鉛アセチルアセトン錯塩の
蒸気（１×10-3mol/分）を含むN2ガス（2.5／分）と
弗素添加原料としてトリフロロ酢酸を（0.02／分）吹
き付け、約500Å／分で膜中に0.1wt％の弗素を含む酸化
亜鉛からなる透明導電膜（膜厚3000Å）を形成した。か
かる透明導電膜の膜特性は表１に示す通りであった。Comparative Example 4 The same glass substrate as in Comparative Example 1 was sufficiently washed, and then placed in a normal pressure CVD apparatus. After the glass substrate was heated to 550 ° C., N 2 gas (2.5 / min) containing zinc acetylacetone complex salt vapor (1 × 10 −3 mol / min) and trifluoroacetic acid (0.02 / Minute) to form a transparent conductive film (thickness 3000 °) made of zinc oxide containing 0.1 wt% of fluorine in the film at about 500 ° / minute. The film characteristics of the transparent conductive film were as shown in Table 1.
実施例４ 比較例１と同様のガラス基板を充分に洗浄し、次いで
常圧CVD装置に入れた。ガラス基板を550℃に加熱した
後、このガラス基板表面に亜鉛アセチルアセトン錯塩の
蒸気（１×10-3mol/分）を含むN2ガス（2.5／分）と
弗素添加原料としてトリフロロ酢酸を（0.2／分）吹
き付け、約500Å／分で膜中に5wt％の弗素を含む酸化亜
鉛からなる透明導電膜（膜厚3000Å）を形成した。かか
る透明導電膜の膜特性は表１に示す通りであった。Example 4 The same glass substrate as in Comparative Example 1 was sufficiently washed, and then placed in a normal pressure CVD apparatus. After the glass substrate was heated to 550 ° C., N 2 gas (2.5 / min) containing the vapor of zinc acetylacetone complex salt (1 × 10 −3 mol / min) and trifluoroacetic acid (0.2%) were added to the surface of the glass substrate. / Min) to form a transparent conductive film (thickness: 3000 か ら) made of zinc oxide containing 5 wt% of fluorine in the film at about 500 Å / min. The film characteristics of the transparent conductive film were as shown in Table 1.
比較例５ 比較例１と同様のガラス基板を充分に洗浄し、次いで
常圧CVD装置に入れた。ガラス基板を550℃に加熱した
後、このガラス基板表面に亜鉛アセチルアセトン錯塩の
蒸気（１×10-3mol/分）を含むN2ガス（2.5／分）を
吹き付け、約500Å／分で弗素を含まない酸化亜鉛から
なる透明導電膜（膜厚3000Å）を形成した。かかる透明
導電膜の膜特性は表１に示す通りであった。Comparative Example 5 The same glass substrate as in Comparative Example 1 was sufficiently washed, and then placed in a normal pressure CVD apparatus. After heating the glass substrate to 550 ° C., N 2 gas (2.5 / min) containing the vapor of zinc acetylacetone complex (1 × 10 −3 mol / min) is blown onto the surface of the glass substrate, and fluorine is applied at about 500 ° / min. A transparent conductive film (thickness: 3000 mm) made of zinc oxide not containing was formed. The film characteristics of the transparent conductive film were as shown in Table 1.
実施例５ アルカリバリヤー膜としてCVD法により形成されたSiO
2膜（膜厚3000Å）を表面に持つシリカ・アルカリバリ
ヤー膜付ソーダ・ライム・シリケートガラス基板（板厚
2.0mm）を充分に洗浄し、次いでこのガラス基板をCVD装
置に入れた。ガラス基板を550℃に加熱した後、このガ
ラス基板表面に四塩化錫１×10-2／分を１として水蒸
気（10）、メチルアルコール（0.5）およびフッ酸（0.
5）を含む窒素ガス（250）を吹き付け、約5000Å／分で
膜中に1.0wt％の窒素を含む酸化錫からなる透明導電膜
（膜厚7000Å）を形成した。次いで、実施例２と同様に
して亜鉛アセチルアセトン錯塩の蒸気（１×10-3mol/
分）と弗素添加原料としてフロン13B1（トリフロロブロ
モメタン）（0.2／分）を含むN2ガス（2.5／分）を
吹き付け、約500Å／分で弗素を含む酸化亜鉛からなる
透明導電膜を形成した。かかるフッ素のドープされた酸
化亜鉛と膜厚は100Åであった。このようにして得られ
た透明導電膜は比抵抗4.0×10-4Ω・cm、透過率80％
で、オーバーコートしなかったものとほとんど変化なか
った。 Example 5 SiO formed by CVD as an alkali barrier film
Soda lime silicate glass substrate (plate thickness) with silica / alkali barrier film with 2 films (thickness 3000mm) on the surface
2.0 mm) was sufficiently washed, and then the glass substrate was put into a CVD apparatus. After heating the glass substrate to 550 ° C., water vapor (10) as one of the 1 × 10 -2 / min tin tetrachloride on the glass substrate surface, methyl alcohol (0.5) and hydrofluoric acid (0.
Nitrogen gas (250) containing 5) was sprayed to form a transparent conductive film (7000 膜厚 thick) made of tin oxide containing 1.0 wt% of nitrogen in the film at about 5000 Å / min. Then, in the same manner as in Example 2, the vapor of zinc acetylacetone complex salt (1 × 10 −3 mol /
Min) and N blowing 2 gas (2.5 / min) containing chlorofluorocarbon 13B1 as fluorine-doped material (trifluoromethyl bromo methane) (0.2 / min), forming a transparent conductive film made of zinc oxide containing fluorine of about 500 Å / min did. The thickness of the fluorine-doped zinc oxide was 100 °. The transparent conductive film thus obtained has a specific resistance of 4.0 × 10 −4 Ω · cm and a transmittance of 80%.
And there was almost no change from the one without overcoating.
これらの透明導電膜基板上に通常のａ−Si製造用プラ
ズマCVD装置を使用し、同装置のチャンバー内を油拡散
ポンプによって１×10-5Torr程度にまで排気した後、Si
H4ガスと1000ppmに水素で希釈されたB2H6ガスを体積化
1:10でチャンバー内へ導入しRF出力100nw/cm2と、基板
温度300℃でＰ型ａ−Si膜を形成した後ヒドラジン−水
和物を使用して同ａ−Si膜をエッチングして透明導電膜
能の比抵抗、透過率を測定した。その結果、何もオバー
コートしない膜では比抵抗が1.6倍に、透過率が0.9倍に
変化していたのに対し、本実施例のフッ素のドープされ
た酸化亜鉛の保護膜をオーバコートした膜では比抵抗、
透過率ともに全く変化していなかった。Using a conventional plasma CVD apparatus for producing a-Si on these transparent conductive film substrates, the chamber of the apparatus was evacuated to about 1 × 10 −5 Torr by an oil diffusion pump,
Volumeizing H 4 gas and B 2 H 6 gas diluted with hydrogen to 1000 ppm
After introducing a p-type a-Si film at 1:10 into the chamber and RF output of 100 nw / cm 2 and a substrate temperature of 300 ° C., the same a-Si film was etched using hydrazine hydrate. The specific resistance and transmittance of the transparent conductive film were measured. As a result, in the film without any overcoat, the specific resistance was changed to 1.6 times and the transmittance was changed to 0.9 times, whereas the film overcoated with the protective film of fluorine-doped zinc oxide of the present example. Then the specific resistance,
The transmittance was not changed at all.
［発明の効果］ 本発明によれば、酸化亜鉛透明導電膜の透過率をさほ
ど下げることなく電気抵抗を低下させることができ、
又、これを安価に製造することが可能となる。このた
め、特に表示素子や太陽電池入の基板として用途に広く
利用することができる。[Effects of the Invention] According to the present invention, the electrical resistance can be reduced without significantly lowering the transmittance of the zinc oxide transparent conductive film,
Further, it can be manufactured at low cost. Therefore, it can be widely used especially as a display element or a substrate for a solar cell.
又、本発明によれば、弗素を添加する方法が制限され
ない。Further, according to the present invention, the method of adding fluorine is not limited.
さらに、本発明の透明導電膜は高い水素プラズマ耐性
を有しているので、水素プラズマ耐性の低い膜にオーバ
ーコートとして用いることもできる。特にａ−Si太陽電
池を製造する際に、ａ−Si膜作成時における透明導電膜
の劣化を大幅に防ぐことができる。Further, since the transparent conductive film of the present invention has high hydrogen plasma resistance, it can be used as an overcoat on a film having low hydrogen plasma resistance. In particular, when an a-Si solar cell is manufactured, the deterioration of the transparent conductive film when the a-Si film is formed can be largely prevented.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｇ０２Ｆ 1/1343 Ｇ０２Ｆ 1/1343 Ｈ０１Ｌ 31/04 Ｈ０１Ｌ 31/04 Ｌ ──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. 6 Identification code Agency reference number FI Technical indication G02F 1/1343 G02F 1/1343 H01L 31/04 H01L 31/04 L
Claims (1)
て、該透明導電膜は常圧CVD法により成膜され、酸化亜
鉛に対し３〜10wt％の弗素を含むことを特徴とする透明
導電膜。1. A transparent conductive film containing zinc oxide as a main component, wherein the transparent conductive film is formed by a normal pressure CVD method and contains 3 to 10% by weight of fluorine based on zinc oxide. Transparent conductive film.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63015806A JP2718046B2 (en) | 1988-01-28 | 1988-01-28 | Transparent conductive film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63015806A JP2718046B2 (en) | 1988-01-28 | 1988-01-28 | Transparent conductive film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01194208A JPH01194208A (en) | 1989-08-04 |
| JP2718046B2 true JP2718046B2 (en) | 1998-02-25 |
Family
ID=11899085
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63015806A Expired - Fee Related JP2718046B2 (en) | 1988-01-28 | 1988-01-28 | Transparent conductive film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2718046B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001073160A1 (en) * | 2000-03-27 | 2001-10-04 | Tohoku Techno Arch Co., Ltd. | Method for preparing zinc oxide semi-conductor material |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01249634A (en) * | 1988-03-30 | 1989-10-04 | Nippon Sheet Glass Co Ltd | Conductive glass and production thereof |
| US4990286A (en) * | 1989-03-17 | 1991-02-05 | President And Fellows Of Harvard College | Zinc oxyfluoride transparent conductor |
| JP2539294B2 (en) * | 1991-01-18 | 1996-10-02 | 本荘ケミカル株式会社 | Method for producing translucent conductive zinc oxide film |
| JP2713847B2 (en) * | 1992-12-28 | 1998-02-16 | キヤノン株式会社 | Thin film solar cell |
| US5316697A (en) * | 1993-03-24 | 1994-05-31 | Kerr-Mcgee Corporation | Conductive, particulate, fluorine-doped zinc oxide |
| JP2858444B2 (en) * | 1993-10-18 | 1999-02-17 | キヤノン株式会社 | Photovoltaic device and method of manufacturing the same |
| JP3660372B2 (en) * | 1994-06-29 | 2005-06-15 | セイコーインスツル株式会社 | Method for producing transparent conductive thin film |
| JPH09260695A (en) * | 1996-03-19 | 1997-10-03 | Canon Inc | Manufacture of photovoltaic device array |
| US5849108A (en) * | 1996-04-26 | 1998-12-15 | Canon Kabushiki Kaisha | Photovoltaic element with zno layer having increasing fluorine content in layer thickness direction |
| EP2059488A1 (en) * | 2006-08-29 | 2009-05-20 | Pilkington Group Limited | Method of making a low-resistivity, doped zinc oxide coated glass article and the coated glass article made thereby |
| CN106784089B (en) * | 2016-12-21 | 2018-05-01 | 蚌埠玻璃工业设计研究院 | A kind of preparation method of self-trapping smooth zno-based transparent conducting glass |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59149607A (en) * | 1983-02-15 | 1984-08-27 | 松下電器産業株式会社 | Transparent electrode |
| JPS6280918A (en) * | 1985-10-03 | 1987-04-14 | 住友電気工業株式会社 | Manufacturing transparent conductive film |
-
1988
- 1988-01-28 JP JP63015806A patent/JP2718046B2/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001073160A1 (en) * | 2000-03-27 | 2001-10-04 | Tohoku Techno Arch Co., Ltd. | Method for preparing zinc oxide semi-conductor material |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH01194208A (en) | 1989-08-04 |
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