JPH0626185B2 - Method for producing hydrogenated amorphous silicon / carbon film - Google Patents
Method for producing hydrogenated amorphous silicon / carbon filmInfo
- Publication number
- JPH0626185B2 JPH0626185B2 JP61101163A JP10116386A JPH0626185B2 JP H0626185 B2 JPH0626185 B2 JP H0626185B2 JP 61101163 A JP61101163 A JP 61101163A JP 10116386 A JP10116386 A JP 10116386A JP H0626185 B2 JPH0626185 B2 JP H0626185B2
- Authority
- JP
- Japan
- Prior art keywords
- amorphous silicon
- hydrogenated amorphous
- carbon
- carbon film
- 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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims description 18
- 229910021417 amorphous silicon Inorganic materials 0.000 title claims description 16
- 229910003481 amorphous carbon Inorganic materials 0.000 title claims description 14
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- 239000000126 substance Substances 0.000 claims description 14
- 239000000758 substrate Substances 0.000 claims description 13
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 7
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 claims description 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 5
- 229910052710 silicon Inorganic materials 0.000 claims description 5
- 238000000151 deposition Methods 0.000 claims description 3
- PZPGRFITIJYNEJ-UHFFFAOYSA-N disilane Chemical compound [SiH3][SiH3] PZPGRFITIJYNEJ-UHFFFAOYSA-N 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 150000004756 silanes Chemical class 0.000 claims description 3
- VEDJZFSRVVQBIL-UHFFFAOYSA-N trisilane Chemical compound [SiH3][SiH2][SiH3] VEDJZFSRVVQBIL-UHFFFAOYSA-N 0.000 claims description 3
- YXHKONLOYHBTNS-UHFFFAOYSA-N Diazomethane Chemical compound C=[N+]=[N-] YXHKONLOYHBTNS-UHFFFAOYSA-N 0.000 description 7
- 229910052799 carbon Inorganic materials 0.000 description 7
- 238000005229 chemical vapour deposition Methods 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 5
- 238000006303 photolysis reaction Methods 0.000 description 4
- 150000001721 carbon Chemical group 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 230000015843 photosynthesis, light reaction Effects 0.000 description 3
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 238000005268 plasma chemical vapour deposition Methods 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- CCGKOQOJPYTBIH-UHFFFAOYSA-N ethenone Chemical compound C=C=O CCGKOQOJPYTBIH-UHFFFAOYSA-N 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
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
Landscapes
- Photovoltaic Devices (AREA)
Description
【発明の詳細な説明】 （産業上の利用分野） この発明は、水素化非晶質シリコン・炭素膜の製造方法
に関する。詳しく言えば、水素化非晶質シリコン・炭素
を基体の表面上に堆積させて、その膜を形成する方法に
関する。かかる水素化非晶質シリコン炭素膜は、光学的
バンドギヤツプが比較的大きいという特性を有し、従つ
てこれを板状の透明基体の表面上に形成したものは、例
えば太陽電池の窓材に適する。The present invention relates to a method for producing a hydrogenated amorphous silicon / carbon film. More specifically, it relates to a method of depositing hydrogenated amorphous silicon / carbon on the surface of a substrate to form a film thereof. Such a hydrogenated amorphous silicon carbon film has a characteristic that the optical band gap is relatively large, and accordingly, the film formed on the surface of a plate-shaped transparent substrate is suitable for, for example, a window material of a solar cell. .
（従来の技術） 従来、水素化非晶質シリコン・炭素膜を基体の表面上に
形成するには、分子内にシリコン原子を有する基体状物
質（例えば、モノシラン、ジシラン、トリシラン、弗化
シラン）と分子内に炭素原子を有する気体状物質（例え
ばメタン、エチレン、アセチレン、プロパンなど）の混
合物を、真空容器内の基体上に供給すると共にプラズマ
分解または光分解させて、これら分解反応で生成された
水素化非晶質シリコン・炭素を基体の表面上に堆積させ
るプラズマCVD（化学気相成長）法または光CVD法が採用
された。(Prior Art) Conventionally, in order to form a hydrogenated amorphous silicon / carbon film on the surface of a substrate, a substrate-like substance having a silicon atom in the molecule (for example, monosilane, disilane, trisilane, fluorinated silane). And a gaseous substance having a carbon atom in the molecule (for example, methane, ethylene, acetylene, propane, etc.) is supplied onto the substrate in the vacuum container and plasma-decomposed or photo-decomposed to generate these decomposition reactions. A plasma CVD (chemical vapor deposition) method or an optical CVD method for depositing hydrogenated amorphous silicon / carbon on the surface of the substrate was adopted.
（発明が解決しようとする問題点） 上述したようにプラズマCVD法または光CVD法では、水素
化非晶質シリコン・炭素に含有される炭素の生成源とし
て、分子内に炭素原子を有する気体状物質が使用されて
いるが、かかる気体状物質の分子は、炭素原子が水素や
弗素と形成する結合がシリコンのそれと比べて強いた
め、炭素を含む気体状物質は一般に極めて安定であり、
従つてプラズマまたは光による分解効率が低く、故に、
水素化非晶質シリコン・炭素膜の生成速度が遅いばかり
でなく、かかる膜において三次元ネツトワーク構造の発
達が十分でない上に、膜中に炭素が十分取込まれずに、
膜質が粗悪になる。(Problems to be Solved by the Invention) As described above, in the plasma CVD method or the photo CVD method, a gaseous state having carbon atoms in its molecule is used as a generation source of carbon contained in hydrogenated amorphous silicon / carbon. Although substances are used, the molecules of such gaseous substances generally have extremely stable bonds formed by carbon atoms with hydrogen and fluorine as compared with those of silicon, so gaseous substances containing carbon are generally extremely stable,
Therefore, the decomposition efficiency by plasma or light is low, and therefore
Not only is the rate of formation of hydrogenated amorphous silicon / carbon film slow, but the development of the three-dimensional network structure is not sufficient in such a film, and carbon is not sufficiently incorporated into the film.
The film quality becomes poor.
この発明は、従来の水素化非晶質シリコン・炭素膜の製
造方法の上述したような欠点を除去することを、主な課
題とする。The main object of the present invention is to eliminate the above-mentioned drawbacks of the conventional method for producing a hydrogenated amorphous silicon / carbon film.
（問題点を解決するための手段） この課題を解決するため、この発明によれば、プラズマ
を利用する技術において、従来使用された分子内に炭素
原子を有する気体状物質の代りに、気体状メチレンが使
用される。(Means for Solving the Problems) In order to solve this problem, according to the present invention, in the technique of utilizing plasma, a gaseous substance having a carbon atom in the molecule, which is conventionally used, is replaced by a gaseous substance. Methylene is used.
（作 用） 周知のように、メチレンはCH2のように二価の炭素原子
を含む不安定中間体であるから、メチレンを使用すれ
ば、プラズマ反応による効率が高くなる。(Operation) As is well known, methylene is an unstable intermediate containing a divalent carbon atom such as CH 2. Therefore, the use of methylene increases the efficiency of plasma reaction.
（実施例） 以下、図面を参照しながら、この発明による水素化非晶
質シリコン・炭素膜の製造方法の実施例について説明す
る。(Example) Hereinafter, an example of a method for producing a hydrogenated amorphous silicon / carbon film according to the present invention will be described with reference to the drawings.
第１図に示されるCVD装置は、真空容器１０を有し、こ
の真空容器１０は、排気口１１、第１送入口１２および
第２送入口１３を備える。排気口１１は、排気弁（図示
なし）を介して、真空排気装置（図示なし）に連結さ
れ、第１送入口１２は、第１送入弁（図示なし）を介し
て、モノシラン源（図示なし）に連結される。第２送入
口１３は、第２送入弁（図示なし）を介して、ジアゾメ
タン源（図示なし）に連結され、第２送入口１３とこれ
に連結された第２送入弁との間の気体通路１４は、この
気体通路１４を通過する気体に紫外線を照射するための
紫外光源１５を備える。The CVD apparatus shown in FIG. 1 has a vacuum container 10, which is provided with an exhaust port 11, a first inlet 12 and a second inlet 13. The exhaust port 11 is connected to a vacuum exhaust device (not shown) via an exhaust valve (not shown), and the first inlet 12 is connected to a monosilane source (not shown) via a first inlet valve (not shown). None). The second inlet port 13 is connected to a diazomethane source (not shown) via a second inlet valve (not shown), and between the second inlet port 13 and the second inlet valve connected thereto. The gas passage 14 includes an ultraviolet light source 15 for irradiating the gas passing through the gas passage 14 with ultraviolet rays.
真空容器１０の中には、板状の基体１６を水平に載置支
持するための支持機構１７、支持機構17で支持された基
体１６を加熱するための加熱機構１８、および支持機構
１７で支持された基体１６の上方に位置する高周波印加
電極１９が配置される。加熱機構１８は加熱電源２０に
接続され、高周波印加電極１９は、マツチング回路２１
を介して、高周波電源２２に接続される。In the vacuum container 10, a supporting mechanism 17 for horizontally mounting and supporting the plate-shaped substrate 16, a heating mechanism 18 for heating the substrate 16 supported by the supporting mechanism 17, and a supporting mechanism 17 are used. The high frequency applying electrode 19 located above the formed base 16 is arranged. The heating mechanism 18 is connected to the heating power source 20, and the high frequency applying electrode 19 is connected to the matching circuit 21.
Is connected to the high frequency power supply 22 via.
かかる第１図図示のCVD装置において、支持機構１７の
上に、例えば厚さ０．２cm×幅１０cm×長さ１０cmの石
英ガラスまたは硬質ガラスからなる透明の板状基体１６
を載置したのちに、真空容器１０の内部空間２３が、排
気口１１に連結された真空排気装置の運転によつて、１
０-7〜１０-9トールのような真空まで排気される。かか
る排気が完了したのちに、加熱機構１８の付勢によつ
て、基体１６が室温〜４００℃の温度まで加熱される。
次いで、紫外光源１５（これから放射される光の波長は
100〜300nm、電力は５〜100Ｗ）が点灯され、高周波電
極１９に、（接地されている支持機構１７に対して）５
０Ｖ〜１kV、毎秒400kサイクル〜13.56Ｍサイクルで最
大出力100Ｗ〜５ｋＷの高周波が印加される。これに続
いて、第１送入口１２に連結されるモノシラン源から、
モノシランが毎分１０〜2000sccmの割合で内部空間２３
内に送入され、また気体通路１４を介して第２送入口１
３に連結されるジアゾメタン源から、ジアゾメタン１０
〜2000sccmの割合で気体通路１４に送入される。In the CVD apparatus shown in FIG. 1, a transparent plate-shaped substrate 16 made of, for example, quartz glass or hard glass having a thickness of 0.2 cm, a width of 10 cm and a length of 10 cm is provided on a support mechanism 17.
After mounting, the internal space 23 of the vacuum container 10 is operated by the operation of the vacuum exhaust device connected to the exhaust port 11,
It is evacuated to a vacuum such as 0 -7 to 10 -9 Torr. After the exhaust is completed, the base 16 is heated to a temperature of room temperature to 400 ° C. by the urging of the heating mechanism 18.
Next, the ultraviolet light source 15 (wavelength of light emitted from this is
100 to 300 nm, power 5 to 100 W) is turned on, and the high frequency electrode 19 is turned on (to the grounded support mechanism 17).
A high frequency with a maximum output of 100 W to 5 kW is applied at 0 V to 1 kV and 400 k cycles to 13.56 M cycles per second. Following this, from a monosilane source connected to the first inlet 12,
Monosilane is contained in the internal space 23 at a rate of 10 to 2000 sccm per minute.
And the second inlet 1 through the gas passage 14.
From the diazomethane source connected to 3, diazomethane 10
It is fed into the gas passage 14 at a rate of ˜2000 sccm.
このようにすると、気体通路１４に送入されたジアゾメ
タンは、紫外光源１５からの紫外線の照射を受けて光分
解し、この光分解によつて生成されたCH2が、第２送入
口１３を通つて内部空間２３に流入する。このCH2は、
第１送入口１２を通つて内部空間２２に流入するモノシ
ランと共に、内部空間２２の中の0.01〜10トールの雰囲
気を構成し、基体１６の上に供給される。内部空間２２
がかかる雰囲気であつて、高周波電極19に前述した高周
波が印加されているので、高周波電極１９と支持機構１
７との間に、グロー放電が生起し、プラズマが発生す
る。このプラズマの作用で、ジアゾメタンとCH2の混合
物が反応し、水素化非晶質シリコン・炭素が基体１６の
表面上に堆積し、水素化非晶質シリコン・炭素の膜が形
成される。この膜の形成速度は、上述した作業条件で、
毎分０．５〜５nmの程度である。By doing so, the diazomethane fed into the gas passage 14 is photolyzed by the irradiation of ultraviolet rays from the ultraviolet light source 15, and CH 2 generated by this photolysis is fed into the second inlet 13. It passes through and flows into the internal space 23. This CH 2 is
With the monosilane flowing into the internal space 22 through the first inlet 12, an atmosphere of 0.01 to 10 Torr in the internal space 22 is formed and supplied onto the substrate 16. Interior space 22
In such an atmosphere where the high frequency is applied to the high frequency electrode 19, the high frequency electrode 19 and the support mechanism 1
A glow discharge is generated between the two, and plasma is generated. By the action of this plasma, the mixture of diazomethane and CH 2 reacts, hydrogenated amorphous silicon / carbon is deposited on the surface of the substrate 16, and a film of hydrogenated amorphous silicon / carbon is formed. The rate of formation of this film is
It is on the order of 0.5 to 5 nm per minute.
また、上述の実施例でCH2の生成にジアゾメタン（CH
2N2）の光分解が使用されているが、ジアゾメタン以外
の例えばケテン（C2H2O）の光分解によつて、CH2を生成
するようにしてもよい。さらに、分子内にシリコン原子
を有する気体状物質としてモノシラン（SiH4）を挙げた
が、かかる気体状物質として、ジシラン（Si2H6）、ト
リシラン（Si3H8）、弗化シラン（SiFXH4-X、ｘ＝１、
２、３、４）なども採用できる。Further, diazomethane to generate the CH 2 in the above-described embodiment (CH
Although photolysis of 2 N 2 ) is used, CH 2 may be produced by photolysis of, for example, ketene (C 2 H 2 O) other than diazomethane. Furthermore, although monosilane (SiH 4 ) was mentioned as a gaseous substance having a silicon atom in the molecule, disilane (Si 2 H 6 ), trisilane (Si 3 H 8 ), fluorinated silane (SiF 4 ) was used as such a gaseous substance. X H 4-X , x = 1,
2, 3, 4) can also be adopted.
（発明の効果） この発明の水素化非晶質シリコン・炭素膜の製造方法
は、二価の炭素原子を含む不安定中間体であるメチレン
のプラズマ反応を利用するので、水素化非晶質シリコン
・炭素膜の生成速度が早く、この膜において三次元ネツ
トワーク構造が十分に発達し、よつて良好な膜質のもの
が得られる。(Effect of the Invention) Since the method for producing a hydrogenated amorphous silicon / carbon film of the present invention utilizes the plasma reaction of methylene, which is an unstable intermediate containing divalent carbon atoms, hydrogenated amorphous silicon -The carbon film is produced at a high rate, and the three-dimensional network structure is sufficiently developed in this film, so that a film having good film quality can be obtained.
第１図は、この発明を実施するためのCVD装置の図解図
である。図面において、１０は真空容器、１１は真空排
気装置に連結する排気口、１２は分子内にシリコン原子
を有する気体状物質の源に連結する第１送入口、１３は
光分解によつてメチレンを生成する物質の源とこの源か
らの物質を光分解する手段とに連結する第２送入口、１
６は基体、１９は前記気体状物質とメチレンの混合物の
プラズマ反応に必要なプラズマの発生に使用される高周
波電極を示す。FIG. 1 is a schematic view of a CVD apparatus for carrying out the present invention. In the drawing, 10 is a vacuum container, 11 is an exhaust port connected to a vacuum exhaust device, 12 is a first inlet port connected to a source of a gaseous substance having a silicon atom in the molecule, and 13 is a photo-decomposition for methylene A second inlet connecting the source of the substance produced and the means for photolyzing the substance from this source, 1
Reference numeral 6 denotes a substrate, and 19 denotes a high-frequency electrode used for generating plasma necessary for plasma reaction of the mixture of the gaseous substance and methylene.
Claims (1)
化シランから選ばれた分子内にシリコン原子を有する気
体状物質と気体状メチレンとの混合物を、基体上に供給
すると共にプラズマ中で反応させて、水素化非晶質シリ
コン・炭素を基体の表面上に堆積させることを特徴とす
る水素化非晶質シリコン・炭素膜の製造方法。1. A mixture of a gaseous substance having a silicon atom in a molecule selected from monosilane, disilane, trisilane and fluorinated silane and gaseous methylene is supplied onto a substrate and reacted in plasma, A method for producing a hydrogenated amorphous silicon / carbon film, which comprises depositing hydrogenated amorphous silicon / carbon on the surface of a substrate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61101163A JPH0626185B2 (en) | 1986-05-02 | 1986-05-02 | Method for producing hydrogenated amorphous silicon / carbon film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61101163A JPH0626185B2 (en) | 1986-05-02 | 1986-05-02 | Method for producing hydrogenated amorphous silicon / carbon film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63260015A JPS63260015A (en) | 1988-10-27 |
| JPH0626185B2 true JPH0626185B2 (en) | 1994-04-06 |
Family
ID=14293370
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61101163A Expired - Fee Related JPH0626185B2 (en) | 1986-05-02 | 1986-05-02 | Method for producing hydrogenated amorphous silicon / carbon film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0626185B2 (en) |
-
1986
- 1986-05-02 JP JP61101163A patent/JPH0626185B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPS63260015A (en) | 1988-10-27 |
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