JPH0323627B2 - - Google Patents
Info
- Publication number
- JPH0323627B2 JPH0323627B2 JP11754184A JP11754184A JPH0323627B2 JP H0323627 B2 JPH0323627 B2 JP H0323627B2 JP 11754184 A JP11754184 A JP 11754184A JP 11754184 A JP11754184 A JP 11754184A JP H0323627 B2 JPH0323627 B2 JP H0323627B2
- Authority
- JP
- Japan
- Prior art keywords
- tin oxide
- conductive film
- film
- fluorine
- 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
Links
- 229910052731 fluorine Inorganic materials 0.000 claims description 31
- 239000011737 fluorine Substances 0.000 claims description 30
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 30
- 229910001887 tin oxide Inorganic materials 0.000 claims description 30
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 29
- 239000000758 substrate Substances 0.000 claims description 18
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 229910001128 Sn alloy Inorganic materials 0.000 claims description 6
- 239000007858 starting material Substances 0.000 claims description 6
- 238000004544 sputter deposition Methods 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- ANOBYBYXJXCGBS-UHFFFAOYSA-L stannous fluoride Chemical compound F[Sn]F ANOBYBYXJXCGBS-UHFFFAOYSA-L 0.000 claims description 4
- 239000011521 glass Substances 0.000 claims description 3
- YUOWTJMRMWQJDA-UHFFFAOYSA-J tin(iv) fluoride Chemical compound [F-].[F-].[F-].[F-].[Sn+4] YUOWTJMRMWQJDA-UHFFFAOYSA-J 0.000 claims description 3
- 239000000919 ceramic Substances 0.000 claims description 2
- 239000012528 membrane Substances 0.000 claims description 2
- 230000002441 reversible effect Effects 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims 1
- 239000010408 film Substances 0.000 description 39
- 238000010438 heat treatment Methods 0.000 description 6
- 229910006404 SnO 2 Inorganic materials 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 238000002834 transmittance Methods 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000005229 chemical vapour deposition Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 229910052718 tin Inorganic materials 0.000 description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000002985 plastic film Substances 0.000 description 2
- 229920006255 plastic film Polymers 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 229960002799 stannous fluoride Drugs 0.000 description 2
- 238000001771 vacuum deposition Methods 0.000 description 2
- 229910008449 SnF 2 Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical compound [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000013077 target material Substances 0.000 description 1
- 230000008685 targeting Effects 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/08—Oxides
- C23C14/086—Oxides of zinc, germanium, cadmium, indium, tin, thallium or bismuth
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Physical Vapour Deposition (AREA)
- Non-Insulated Conductors (AREA)
- Manufacturing Of Electric Cables (AREA)
Description
【発明の詳細な説明】
『産業上の利用分野』
本発明は太陽電池、液晶表示パネル等に用いら
れる酸化スズ導電膜の作製方法に関するものであ
る。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a method for producing a tin oxide conductive film used for solar cells, liquid crystal display panels, etc.
『従来の技術』
透明導電膜にはAu等の金属薄物を用いるもの
と、SnO2、In2O3等の金属酸化物を用いるものと
がある。金属薄膜はその高い導電性の為低抵抗の
膜を作りやすい反面、可視域での吸収が大きい為
高透過率が得にくく、かつ膜の強度が劣るという
欠点を持つている、一方金属酸化物は適度の導電
性と高透過率そのうえ優れた膜強度をもつている
ので幅広く応用されている。``Prior Art'' Transparent conductive films include those that use thin metals such as Au, and those that use metal oxides such as SnO 2 and In 2 O 3 . Metal thin films have high conductivity, which makes it easy to create low-resistance films, but they have the drawbacks of high absorption in the visible range, making it difficult to obtain high transmittance, and poor film strength.Metal oxides, on the other hand, It is widely used because it has moderate conductivity, high transmittance, and excellent film strength.
現在一般に知られている金属酸化物はネサ膜と
呼ばれるSnO2膜、In2O3膜、ITO膜等でこれらの
うちIn2O3膜、ITO膜は比抵抗が10-4Ωcm程、
SnO2膜が10-3Ωcm程の膜質の物が得られている。 Currently, commonly known metal oxides include SnO 2 film called Nesa film, In 2 O 3 film, ITO film, etc. Among these, In 2 O 3 film and ITO film have a specific resistance of about 10 -4 Ωcm.
A SnO 2 film with a quality of about 10 -3 Ωcm was obtained.
『発明が解決しようとする問題点』
これらのうちSnO2膜は古くからスプレー法、
CVD法、真空蒸着法等により作製されていたが、
比抵抗が10-3Ωcmが限度で低い抵抗のものが得ら
れないという欠点があつた。``Problems to be solved by the invention'' Among these, SnO 2 film has been produced by spraying method,
It was manufactured using CVD method, vacuum evaporation method, etc.
The drawback was that the specific resistance was limited to 10 -3 Ωcm, making it impossible to obtain a low resistance product.
これを解決するためにスプレー法やCVD法に
おいて原料溶液または原料ガス中にフツ素を含む
物質（例えばNH4F、CF4）を添加してフツ素入
のSnO膜が作製されたがこれらの方法では基板を
400〜500℃という高温にしなければならずかかる
温度では基板が変形してしまうという欠点があつ
た。 To solve this problem, a fluorine-containing SnO film was fabricated by adding fluorine-containing substances (e.g. NH4F, CF4) to the raw material solution or raw material gas using the spray method or CVD method. of
The drawback was that it had to be heated to a high temperature of 400 to 500°C, and the substrate deformed at such temperatures.
さらにフツ素を添加するために膜作製に必要の
ない元素（例えばＮ、Ｃ、Ｈ）が膜中に入つてし
まい良好な膜質の酸化スズ導電膜が得られなかつ
たさらに、真空蒸着法によつてフツ素入の酸化ス
ズ導電膜を形成しようとした場合フツ素、スズフ
ツ化物とスズ、スズ酸化物との蒸気圧の違いによ
つて膜中に均一にフツ素を導入することはできな
かつた。 Furthermore, due to the addition of fluorine, elements not necessary for film fabrication (e.g. N, C, H) entered the film, making it impossible to obtain a tin oxide conductive film of good quality. When attempting to form a fluorine-containing tin oxide conductive film, it was not possible to uniformly introduce fluorine into the film due to the difference in vapor pressure between fluorine and tin fluoride and tin and tin oxide. .
『発明の目的』
本発明は従来より信頼性が高く、しかも低い比
抵抗を有する酸化スズ導電膜を低温プロセスにお
いて作製する方法を発明することを目的とする。[Object of the Invention] An object of the present invention is to invent a method for producing a tin oxide conductive film having higher reliability and lower specific resistance than conventional methods in a low-temperature process.
『発明の構成』
本発明は、20wt％以下の濃度のフツ素元素を
含むスズ合金またはスズ酸化物を出発材料とし
て、スパツタリング法により基板上に酸化導電膜
を形成することを特徴とする酸化導電膜の作製方
法である。"Structure of the Invention" The present invention is an oxidized conductive film characterized in that an oxidized conductive film is formed on a substrate by a sputtering method using a tin alloy or tin oxide containing a fluorine element at a concentration of 20 wt% or less as a starting material. This is a method for producing a membrane.
この際の出発材料であるフツソ元素を含んだス
ズ合金またはスズ酸化物は、該スズ合金またはス
ズ酸化物にフツ化第一スズ（SnF2）またはフツ
化第二スズ（SnF4）等を添加することにより作
製することができる。 The starting material in this case, which is a tin alloy or tin oxide containing a fluorine element, is prepared by adding stannous fluoride (SnF 2 ) or stannic fluoride (SnF 4 ) to the tin alloy or tin oxide. It can be produced by
また酸化導電膜が形成される基板としては、ガ
ラス、セラミツク、金属、またはフイルム等の可
逆性基盤を用いることができる。 Further, as the substrate on which the oxidized conductive film is formed, a reversible substrate such as glass, ceramic, metal, or film can be used.
本発明により作製された酸化スズ導電膜中には
不純物としてフツ素元素を含み加熱する必要なく
低抵抗の酸化スズ導電膜が得られるものである。 The tin oxide conductive film produced according to the present invention contains fluorine element as an impurity, and a low resistance tin oxide conductive film can be obtained without the need for heating.
一般にフツ素を入れることによつて酸化スズ導
電膜の比抵抗を低くすることができる。第１図は
本発明の実施例において得られた酸化スズ導電膜
の比抵抗と出発材料であるターゲツト中のフツ素
の含有量（wt％）の関係を示したものである。 Generally, the specific resistance of a tin oxide conductive film can be lowered by adding fluorine. FIG. 1 shows the relationship between the specific resistance of the tin oxide conductive film obtained in the example of the present invention and the fluorine content (wt%) in the starting material target.
第１図によればターゲツト中のフツ素の含有量
（wt％）が20wt％以下であれば含有量0wt％の場
合に比較して比抵抗が低くなつていることがわか
る。 According to FIG. 1, it can be seen that when the content (wt%) of fluorine in the target is 20 wt% or less, the specific resistance is lower than when the content is 0 wt%.
しかし本発明のようにフツ素を含んだターゲツ
トを作製した場合、ターゲツト中のフツ素のwt
％が20％を越えるとターゲツトの材質がもろくな
るとういう問題が生じる。この結果ターゲツトが
すぐにへつてしまいほとんど被膜形成できない状
態が生じてしまう。これは、ターゲツトがスズ酸
化物を主体とするものであつてもスズ合金を主体
とするものであつても同様に現れる現象であつ
た。 However, when a target containing fluorine is prepared as in the present invention, the wt of fluorine in the target is
If the percentage exceeds 20%, a problem arises in that the target material becomes brittle. As a result, the target quickly wears out, resulting in a state in which almost no film can be formed. This phenomenon occurs regardless of whether the target is primarily a tin oxide or a tin alloy.
本発明において、フツ素元素のwt％を20wt％
以下と限定したのは上記の実験事実に基づくもの
である。 In the present invention, the wt% of fluorine element is 20wt%
The following limitations are based on the above experimental facts.
『作用』
フツ素元素をふくむ酸化スズ導電膜中において
一部の酸素とフツ素が置換されてドナーレベルを
形成する為導電性は向上するものと考えられる。[Effect] It is thought that conductivity is improved because part of the oxygen in the tin oxide conductive film containing the fluorine element is substituted with fluorine to form a donor level.
以下に実施例により本発明を説明する。 The present invention will be explained below with reference to Examples.
実施例 １
基板としては厚さ２mmのガラス基板を用いて、
DCスパツタリング法によりフツ化第１スズをふ
くむ酸化スズをターゲツトとして酸化スズ導電膜
を作製した。これはターゲツトにフツ化第１スズ
を添加させることによりフツ素を含むスズ酸化物
を得るものである。Example 1 A glass substrate with a thickness of 2 mm was used as the substrate.
A tin oxide conductive film was prepared using a DC sputtering method using tin oxide containing stannous fluoride as a target. In this method, a tin oxide containing fluorine is obtained by adding stannous fluoride to a target.
●ターゲツト SnF2 5.0wt％ SnO2 95.0wt％ ●ガス アルゴン 100％ ●圧力 ３×10-3Torr ●基板加熱 なし 得られた膜の物性は次の通りであつた。●Target SnF 2 5.0wt% SnO 2 95.0wt% ●Gas Argon 100% ●Pressure 3×10 -3 Torr ●Substrate heating None The physical properties of the obtained film were as follows.
●膜厚 1000Å
●比抵抗 １×10-4Ωcm
●透過率 85％
第１図に実施例において得られた酸化スズ酸化
物の比抵抗値とターゲツト中のフツ素含有量
（wt％）を関係をしめす。● Film thickness 1000Å ● Specific resistance 1×10 -4 Ωcm ● Transmittance 85% Figure 1 shows the relationship between the specific resistance value of tin oxide obtained in the example and the fluorine content (wt%) in the target. Shows.
実施例 ２
基板として厚さ100μｍのプラスチツクフイル
ムを用いてDCスパツタリング法によりフツ素元
素を含むスズ合金をターゲツトとして酸化スズ導
電膜を作製した。以下にその作製条件をしめす。Example 2 A tin oxide conductive film was prepared by DC sputtering using a 100 μm thick plastic film as a substrate, targeting a tin alloy containing fluorine element. The manufacturing conditions are shown below.
●ターゲツト フツ素 5.0wt％ スズ 95.0wt％ ●ガス アルゴン、酸素 ●圧力 ３×10-3Torr ●酸素分圧 ４×10-5Torr ●基板加熱 なし 得られたまくの物性は次の通りであつた。●Target Fluorine 5.0wt% Tin 95.0wt% ●Gas Argon, Oxygen ●Pressure 3×10 -3 Torr ●Oxygen partial pressure 4×10 -5 Torr ●Substrate heating None The physical properties of the obtained cloud are as follows. Ta.
●膜厚 1000Å
●比抵抗 ５×10-4Ωcm
●透過率 85％
比抵抗値とターゲツト中のフツ素含有量（wt
％）の関係は、実施例１と同様な結果、すなわち
第１図に示すスパツタリングによつて得られた酸
化スズ導電膜の比抵抗値とターゲツト中のフツ素
含有量（wt％）の関係が得られた。●Film thickness 1000Å ●Resistivity 5×10 -4 Ωcm ●Transmittance 85% Specific resistance value and fluorine content in target (wt
%) is the same result as in Example 1, that is, the relationship between the specific resistance value of the tin oxide conductive film obtained by sputtering and the fluorine content (wt%) in the target as shown in FIG. Obtained.
『発明の効果』
本発明により作製された酸化スズ導電膜は第１
図に示されるように、その比抵抗率をフツ素を含
まない出発材料（ターゲツト）によつて作製した
場合に比べ低くすることができた。"Effects of the Invention" The tin oxide conductive film produced by the present invention is the first
As shown in the figure, the specific resistivity could be lowered compared to the case of fabrication using a starting material (target) that does not contain fluorine.
特にターゲツト中のフツ素の量が約17wt％で
あれば、従来のものより約１桁以上低い比抵抗を
簡単に得ることができるようになつた。また従来
のフツ素入酸化スズ導電膜を作製するのに用いら
れたスプレー法、CVD法、真空蒸着法は、基板
加熱を必要としていたため基板の変形、基板から
の不純物の熱拡散等の問題があつたが本発明は基
板加熱を必要としないためそれらの問題は全くお
こらない、また原料中にはSn、Ｏ、Ｆのみを含
むので、ターゲツトの純度を良くするだけで簡単
に膜中の不純物が極力少なくすることができる。 In particular, when the amount of fluorine in the target is about 17 wt%, it has become possible to easily obtain a resistivity that is about one order of magnitude lower than that of the conventional method. In addition, the spray method, CVD method, and vacuum evaporation method used to produce conventional fluorine-containing tin oxide conductive films require substrate heating, which causes problems such as deformation of the substrate and thermal diffusion of impurities from the substrate. However, since the present invention does not require substrate heating, these problems do not occur at all, and since the raw materials only contain Sn, O, and F, it is easy to improve the purity of the target. Impurities can be reduced as much as possible.
さらに加熱する必要がないためプラスチツクフ
イルム等の耐熱性の低い基板の上等にもフツ素入
の酸化スズ導電膜を形成することができるという
大きな特徴を有する。 Furthermore, since there is no need for heating, a significant feature is that a fluorine-containing tin oxide conductive film can be formed on a substrate with low heat resistance such as a plastic film.
第１図は比抵抗値とターゲツト中のフツ素含有
量（wt％）の関係をしめす。
Figure 1 shows the relationship between the specific resistance value and the fluorine content (wt%) in the target.
Claims (1)
合金またはスズ酸化物を出発材料として、スパツ
タリング法により基板上に酸化スズ導電膜を形成
することを特徴とする酸化スズ導電膜の作製方
法。 ２ 特許請求の範囲第１項における前記出発材料
であるフツソ元素を含んだスズ酸化物は、該スズ
酸化物にフツ化第一スズ（SnF2）またはフツ化
第二スズ（SnF4）が添加されていることを特徴
とする酸化スズ導電膜の作製方法。 ３ 特許請求の範囲第１項における酸化導電膜が
形成される基板としては、ガラス、セラミツク、
金属、またはフイルム等の可逆性基板であること
を特徴とする酸化スズ導電膜の作製方法。[Claims] 1. A tin oxide conductive film characterized in that a tin oxide conductive film is formed on a substrate by a sputtering method using a tin alloy or tin oxide containing a fluorine element at a concentration of 20 wt% or less as a starting material. Membrane preparation method. 2. The starting material in claim 1, which is a tin oxide containing a fluorine element, is obtained by adding stannous fluoride (SnF 2 ) or stannic fluoride (SnF 4 ) to the tin oxide. A method for producing a tin oxide conductive film, characterized in that: 3. The substrate on which the oxidized conductive film in claim 1 is formed may be glass, ceramic,
A method for producing a tin oxide conductive film, characterized in that the substrate is a reversible substrate such as metal or film.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11754184A JPS60262962A (en) | 1984-06-08 | 1984-06-08 | Manufacture of electrically conductive tin oxide film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11754184A JPS60262962A (en) | 1984-06-08 | 1984-06-08 | Manufacture of electrically conductive tin oxide film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS60262962A JPS60262962A (en) | 1985-12-26 |
| JPH0323627B2 true JPH0323627B2 (en) | 1991-03-29 |
Family
ID=14714347
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11754184A Granted JPS60262962A (en) | 1984-06-08 | 1984-06-08 | Manufacture of electrically conductive tin oxide film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS60262962A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102839348B (en) * | 2012-09-27 | 2014-08-06 | 攀枝花学院 | Method for preparing fluorine-doped tin oxide thin film |
-
1984
- 1984-06-08 JP JP11754184A patent/JPS60262962A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS60262962A (en) | 1985-12-26 |
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