JPH0626184B2 - Method for producing hydrogenated amorphous silicon / carbon film - Google Patents
Method for producing hydrogenated amorphous silicon / carbon filmInfo
- Publication number
- JPH0626184B2 JPH0626184B2 JP9687286A JP9687286A JPH0626184B2 JP H0626184 B2 JPH0626184 B2 JP H0626184B2 JP 9687286 A JP9687286 A JP 9687286A JP 9687286 A JP9687286 A JP 9687286A JP H0626184 B2 JPH0626184 B2 JP H0626184B2
- Authority
- JP
- Japan
- Prior art keywords
- amorphous silicon
- hydrogenated amorphous
- substrate
- carbon
- carbon film
- 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
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title description 16
- 229910003481 amorphous carbon Inorganic materials 0.000 title description 12
- 229910021417 amorphous silicon Inorganic materials 0.000 title description 12
- 239000000758 substrate Substances 0.000 claims description 16
- 239000000126 substance Substances 0.000 claims description 13
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 8
- 229910052710 silicon Inorganic materials 0.000 claims description 8
- PZPGRFITIJYNEJ-UHFFFAOYSA-N disilane Chemical compound [SiH3][SiH3] PZPGRFITIJYNEJ-UHFFFAOYSA-N 0.000 claims description 7
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 claims description 6
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 3
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 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
- 239000000203 mixture Substances 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- 238000006303 photolysis reaction Methods 0.000 description 7
- YXHKONLOYHBTNS-UHFFFAOYSA-N Diazomethane Chemical compound C=[N+]=[N-] YXHKONLOYHBTNS-UHFFFAOYSA-N 0.000 description 6
- 238000005229 chemical vapour deposition Methods 0.000 description 6
- 230000015843 photosynthesis, light reaction Effects 0.000 description 6
- 230000005284 excitation Effects 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 150000001721 carbon Chemical group 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000005268 plasma chemical vapour deposition Methods 0.000 description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 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
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001723 carbon free-radicals Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000000151 deposition 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
- 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
- 230000003287 optical effect Effects 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
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（水素を含む
シリコンおよび炭素の混非晶）の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。Description: TECHNICAL FIELD The present invention relates to a method for producing a film of hydrogenated amorphous silicon / carbon (a mixed amorphous of hydrogen-containing silicon and carbon). 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. Therefore, the hydrogenated amorphous silicon / carbon film formed on the surface of a plate-shaped transparent substrate is used as, for example, a window material of a solar cell. Suitable.
（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、エタン、プロパン）
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、これら分解反応を経て水
素化非晶質シリコン・炭素を基体の表面上に沈積させる
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 its molecule (eg, monosilane, disilane, trisilane, fluorinated silane). And gaseous substances with carbon atoms in the molecule (eg methane, ethylene, acetylene, ethane, propane)
Is supplied to the substrate in a vacuum vessel and plasma-decomposed or photo-decomposed, and hydrogenated amorphous silicon / carbon is deposited on the surface of the substrate through these decomposition reactions. Plasma CVD (chemical vapor deposition) ) Method or photo CVD method was adopted.
（発明が解決しようとする問題点） 上述したようなプラズマ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、炭素原子が他の原
子と作る結合エネルギが、シリコンにおけるそれと比べ
て大きいため、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、膜の中に炭素が十分
に取込まれず、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的なネ
ツトワーク構造の発達が十分でなく膜質が粗悪になる。(Problems to be Solved by the Invention) In the plasma CVD method or the photo-CVD method as described above, 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 are extremely stable because the binding energy created by carbon atoms with other atoms is higher than that in silicon, and therefore the decomposition efficiency by plasma or light is high. Low, therefore, not enough carbon is incorporated into the film, not only the hydrogenated amorphous silicon / carbon film formation rate is slow, but also the three-dimensional network structure is not sufficiently developed in such a 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、光分解を
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 photolysis, a gas substance is used instead of the gaseous substance having a carbon atom in the molecule, which has been conventionally used. Methylene chloride 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、光による分解効率が高くなる。(Function) As is well known, methylene is an unstable intermediate containing a divalent carbon atom like CH 2. Therefore, the use of methylene increases the efficiency of decomposition by light.
（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、分子内にシリコンを含む気体（例えばジシラン）の
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 port 12 is made of silicon in the molecule via a first inlet valve (not shown). Is connected to a source (not shown) of a gas (eg disilane) containing The second inlet 13 is the second
A gas passage 14 connected to a diazomethane source (not shown) via a delivery valve (not shown) and between the second inlet 13 and the second inlet valve connected thereto is the gas passage 14 An ultraviolet light source 15 is provided for irradiating the gas passing therethrough 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の上方に位置する励起紫外線光源１９が配
置される。符号２０および２１は、紫外光源１５および
励起紫外線光源１９にそれぞれ接続された電源を示す。In the vacuum container 10, a heating mechanism 18 for heating the substrate 16 supported by a supporting mechanism 17 for horizontally mounting and supporting the plate-shaped substrate 16 and a substrate 16 supported by the supporting mechanism 17. Excited ultraviolet light source 19 is disposed above. Reference numerals 20 and 21 denote power sources connected to the ultraviolet light source 15 and the excitation ultraviolet light source 19, respectively.
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２２が、排気口１１に連結された真空排気装置の運
転によつて、10-5〜 10-7 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、励起紫外光源１９（これから放射
される光の波長は７０〜３００ｎｍ）および紫外光源１
５（これから放射される波長は２００〜３００ｎｍ）が
点灯され、これに続いて、第１送入口１２に連結される
ジシラン源から、ジシランが毎分１０〜１００sccmの割
合で内部空間22に送入され、また気体通路１４を介して
第２送入口１３に連結されるジアゾメタン源から、ジア
ゾメタンが毎分１０〜１００sccmの割合で気体通路１４
に送入される。In the CVD apparatus shown in FIG. 1, after the transparent plate-shaped substrate 16 made of, for example, quartz glass or hard glass is placed on the support mechanism 17, the internal space 22 of the vacuum container 10 is changed to the exhaust port 11 By the operation of the vacuum evacuation device connected to, a vacuum such as 10 −5 to 10 −7 Torr is exhausted. After such exhaust is completed, the heating mechanism 18
The substrate 16 is heated to a temperature of room temperature to 400 ° C. Next, the excitation ultraviolet light source 19 (wavelength of light emitted from this is 70 to 300 nm) and the ultraviolet light source 1
5 (wavelength emitted from 200 to 300 nm) is turned on, and subsequently, disilane is fed into the internal space 22 at a rate of 10 to 100 sccm from the disilane source connected to the first inlet 12. The diazomethane source is connected to the second inlet 13 via the gas passage 14, and the diazomethane is supplied at a rate of 10 to 100 sccm per minute.
Sent to.
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２２に流入する。このCH2は、
第１送入口１２を通つて内部空間２２に流入するジシラ
ンと共に、基体１６上に供給され、かつ励起紫外線光源
１９からの光の照射によつて光分解する。この光分解に
よつて、シリコンおよび炭素ラジカルが生成され、これ
らが基体１６の表面上に堆積して、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０．１〜５ｎｍの程度である。By doing so, the diazomethane fed into the gas passage 14 is photolyzed by receiving the irradiation of ultraviolet rays from the ultraviolet light source 15, and CH 2 produced by this photolysis passes through the second inlet 13. It passes through and flows into the internal space 22. This CH 2 is
It is supplied onto the substrate 16 together with disilane flowing into the internal space 22 through the first inlet 12, and is photolyzed by irradiation with light from the excitation ultraviolet light source 19. This photolysis produces silicon and carbon radicals, which are deposited on the surface of the substrate 16 to form a hydrogenated amorphous silicon-carbon film. The film forming rate is about 0.1 to 5 nm per minute under the above-mentioned working conditions.
上述した実施例で、CH2の生成にジアゾメタン（CH2N2）
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。また、分子内にシリコン原子を有する
気体状物質としてジシラン（Si2H6）を採用する例を挙
げたが、かかる気体状物質として、モノシラン（Si
Hs）、トリシラン（Si3H8）、弗化シラン（Si FXH4-X、x
＝1,2,3,4）なども採用できる。さらに、励起紫外線光
源１９に、エキシマレーザー等の紫外線レーザーも採用
できる。In the embodiments described above, diazomethane to generate the CH 2 (CH 2 N 2)
However, CH 2 may be generated by photolysis of ketene (C 2 H 2 O) other than diazomethane, for example. In addition, an example of adopting disilane (Si 2 H 6 ) as a gaseous substance having a silicon atom in the molecule was given. As such a gaseous substance, monosilane (Si 2
H s ), trisilane (Si 3 H 8 ), fluorinated silane (Si F X H 4-X , x
= 1,2,3,4) can also be adopted. Further, an ultraviolet laser such as an excimer laser can be adopted as the excitation ultraviolet light source 19.
（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
の光分解を利用するので、水素化非晶質シリコン・炭素
膜の生成速度が早く、この膜の中で三次元的ネツトワー
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。(Effects of the Invention) The method for producing a hydrogenated amorphous silicon / carbon film of the present invention utilizes photolysis of methylene, which is an unstable intermediate containing a divalent carbon atom. -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、この発明の製造方法を実施するための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、１６は基
体、１９は前記気体状物質とメチレンの混合物の光分解
のための励起紫外線光源を示す。FIG. 1 is a schematic view of a CVD apparatus for carrying out the manufacturing method of 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 to be produced and a means for photolyzing the substance from this source, 16 a substrate, and 19 an excited UV light source for the photolysis 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
し、紫外線ランプもしくは紫外線レーザーを照射して、
基体表面上で光分解反応を起させ、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 irradiated with an ultraviolet lamp or an ultraviolet laser. do it,
A method for producing a hydrogenated amorphous silicon-carbon film, which comprises causing a photolytic reaction on the surface of the substrate to deposit hydrogenated amorphous silicon-carbon on the surface of the substrate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9687286A JPH0626184B2 (en) | 1986-04-28 | 1986-04-28 | Method for producing hydrogenated amorphous silicon / carbon film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9687286A JPH0626184B2 (en) | 1986-04-28 | 1986-04-28 | Method for producing hydrogenated amorphous silicon / carbon film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62254420A JPS62254420A (en) | 1987-11-06 |
| JPH0626184B2 true JPH0626184B2 (en) | 1994-04-06 |
Family
ID=14176519
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP9687286A Expired - Fee Related JPH0626184B2 (en) | 1986-04-28 | 1986-04-28 | Method for producing hydrogenated amorphous silicon / carbon film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0626184B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN118610398B (en) * | 2024-05-22 | 2025-06-06 | 浙江格源新材料科技有限公司 | A silicon-carbon negative electrode prepared by photolysis of silane and a preparation method thereof |
-
1986
- 1986-04-28 JP JP9687286A patent/JPH0626184B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPS62254420A (en) | 1987-11-06 |
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