JPS63241970A - Manufacture of optoelectric transducer - Google Patents
Manufacture of optoelectric transducerInfo
- Publication number
- JPS63241970A JPS63241970A JP62074292A JP7429287A JPS63241970A JP S63241970 A JPS63241970 A JP S63241970A JP 62074292 A JP62074292 A JP 62074292A JP 7429287 A JP7429287 A JP 7429287A JP S63241970 A JPS63241970 A JP S63241970A
- Authority
- JP
- Japan
- Prior art keywords
- thin film
- gas
- film
- photoelectric conversion
- impurity
- 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.)
- Pending
Links
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- 239000010409 thin film Substances 0.000 claims abstract description 56
- 238000000034 method Methods 0.000 claims abstract description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 10
- 150000001875 compounds Chemical class 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims description 28
- 239000000758 substrate Substances 0.000 claims description 22
- 229910000077 silane Inorganic materials 0.000 abstract description 11
- 239000012535 impurity Substances 0.000 abstract description 9
- -1 silane compound Chemical class 0.000 abstract description 8
- 230000006866 deterioration Effects 0.000 abstract description 3
- 238000005229 chemical vapour deposition Methods 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 abstract 2
- 230000002542 deteriorative effect Effects 0.000 abstract 1
- 238000007599 discharging Methods 0.000 abstract 1
- 230000003287 optical effect Effects 0.000 abstract 1
- 239000000126 substance Substances 0.000 abstract 1
- 239000010408 film Substances 0.000 description 34
- 239000007789 gas Substances 0.000 description 22
- 230000015572 biosynthetic process Effects 0.000 description 14
- 238000005268 plasma chemical vapour deposition Methods 0.000 description 12
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 5
- 239000003085 diluting agent Substances 0.000 description 5
- PZPGRFITIJYNEJ-UHFFFAOYSA-N disilane Chemical compound [SiH3][SiH3] PZPGRFITIJYNEJ-UHFFFAOYSA-N 0.000 description 5
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 5
- 230000003247 decreasing effect Effects 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 229910021417 amorphous silicon Inorganic materials 0.000 description 3
- 239000007772 electrode material Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 150000001343 alkyl silanes Chemical class 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- UBHZUDXTHNMNLD-UHFFFAOYSA-N dimethylsilane Chemical compound C[SiH2]C UBHZUDXTHNMNLD-UHFFFAOYSA-N 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- AQRLNPVMDITEJU-UHFFFAOYSA-N triethylsilane Chemical compound CC[SiH](CC)CC AQRLNPVMDITEJU-UHFFFAOYSA-N 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
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- UCXUKTLCVSGCNR-UHFFFAOYSA-N diethylsilane Chemical compound CC[SiH2]CC UCXUKTLCVSGCNR-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- KCWYOFZQRFCIIE-UHFFFAOYSA-N ethylsilane Chemical compound CC[SiH3] KCWYOFZQRFCIIE-UHFFFAOYSA-N 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- UIUXUFNYAYAMOE-UHFFFAOYSA-N methylsilane Chemical compound [SiH3]C UIUXUFNYAYAMOE-UHFFFAOYSA-N 0.000 description 1
- 229910001120 nichrome Inorganic materials 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 150000003376 silicon Chemical class 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- VCZQFJFZMMALHB-UHFFFAOYSA-N tetraethylsilane Chemical compound CC[Si](CC)(CC)CC VCZQFJFZMMALHB-UHFFFAOYSA-N 0.000 description 1
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 239000012780 transparent material Substances 0.000 description 1
- PQDJYEQOELDLCP-UHFFFAOYSA-N trimethylsilane Chemical compound C[SiH](C)C PQDJYEQOELDLCP-UHFFFAOYSA-N 0.000 description 1
- VEDJZFSRVVQBIL-UHFFFAOYSA-N trisilane Chemical compound [SiH3][SiH2][SiH3] VEDJZFSRVVQBIL-UHFFFAOYSA-N 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 238000001771 vacuum deposition Methods 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
Abstract
Description
【発明の詳細な説明】
［技術分野］
本発明は非晶質シリコン（以下ａ−５ｉ：Ｈとも略称す
る）光電変換素子に関し、特に優れた光電特性を安定し
て有する光電変換素子に関する。DETAILED DESCRIPTION OF THE INVENTION [Technical Field] The present invention relates to an amorphous silicon (hereinafter also abbreviated as a-5i:H) photoelectric conversion element, and particularly to a photoelectric conversion element that stably has excellent photoelectric properties.
［従来技術およびその問題点］
光電変換素子特に非晶質シリコン太陽電池の高効率化が
検討され、その中でも、第一の導電性薄膜と光活性層で
ある実質的に真性の薄膜との界面の制御が重要であるこ
とが指摘され、実際に第一の導電性薄膜の形成用ガスで
あるジポランやメタンやアセチレンの流量制御を行い界
面層を形成し光電特性の向上することが報告されている
。（例えば ケ、ニス、リム他「ア ノーベル ストラ
クチュア、ハイ コンバージョン エフイタエンシーｐ
−３ｉＣ／ダレイデイドρ−３ｔＣ／１−５ｉ／ｎ−５
ｉ／メタルサブストレイト−タイプ アモルファス シ
リコンソーラー セル」ジャーナル オブ アプライド
フィジックス（Ｋ、Ｓ、Ｌｉｍ他、ｒＡ Ｎｏｖｅｌｓ
ｔｒｕｃｔｕｒｅｌｈｉｇｈ ｃｏｎｖｅｒｓｉｏｎ
ｅｆｆｉｃｉｅｎｃｙ ｐ−３ｉＣ／ｇｒａｄｅｄ ｐ
−３ｉＣ／１−３ｔ／ｎ−５ｔ／ｍｅｔａｌ ｓｕｂｓ
ｔｒａｔｅ−ｔｙｐｅａｍｏｒｐｈｏｕｓ ５ｉｌｉｃ
ｏｎ ５ｏｌａｒ ｃｅｌｌ Ｊ ）５６（２）、第５
３８頁〜第５４２頁）しかしながら、上記のような検討
は光ＣＶＤやモノシランを用いたプラズマＣＶＤで０．
１〜１．ＯＡ／ｓ程度の比較的低い成膜速度で行われた
ものであり、高次シランのプラズマＣＶＤ法による高速
成膜条件においては、本界面層の制御は更に検討する必
要があることがわかった。[Prior art and its problems] Improvements in the efficiency of photoelectric conversion elements, particularly amorphous silicon solar cells, have been studied, and among them, the interface between the first conductive thin film and the substantially intrinsic thin film that is the photoactive layer has been studied. In fact, it has been reported that controlling the flow rate of diporane, methane, and acetylene, which are the gases used to form the first conductive thin film, forms an interfacial layer and improves the photoelectric properties. There is. (For example, Ke, Nis, Lim et al. ``A Nobel Structure, High Conversion Efficiency P
-3iC/Daleidade ρ-3tC/1-5i/n-5
i/Metal Substrate-Type Amorphous Silicon Solar Cell” Journal of Applied Physics (K, S, Lim et al., rA Novels
structure high conversion
efficiency p-3iC/graded p
-3iC/1-3t/n-5t/metal subs
rate-type amorphous 5ilic
on 5olar cell J) 56(2), No. 5
(pages 38 to 542) However, the above studies have shown that photo-CVD or plasma CVD using monosilane is not suitable for 0.
1-1. This was done at a relatively low deposition rate of about OA/s, and it was found that it is necessary to further investigate the control of this interface layer under high-speed deposition conditions using high-order silane plasma CVD method. .
［発明の目的］
本発明の目的は高次シランのプラズマＣｖＤ法による高
速成膜条件においても接合界面における特性劣化を起こ
すことがない、高光電変換効率の光電変換素子を再現性
良く製造する方法を提供することである。[Objective of the Invention] The object of the present invention is to provide a method for manufacturing a photoelectric conversion element with high photoelectric conversion efficiency with good reproducibility, which does not cause characteristic deterioration at the bonding interface even under high-speed film formation conditions using high-order silane plasma CVD method. The goal is to provide the following.
［発明の開示］
本発明光電変換素子の製造方法は上記問題点を解決すべ
く鋭意検討した結果到達したもので、その要旨とすると
ころは、基体上に、第一の電極、第一の導電性薄膜、よ
り薄い第一の実質的に真性の薄膜、より厚い第二の実質
的に真性の薄膜、第二の導電性薄膜、第二の電極の順に
形成せしめる方法であって、該第−の導電性薄膜を形成
した後、該第−の導電性を賦与する不純物の供給を停止
し、炭素含有化合物ガスの流量を第一の導電性薄膜から
、より厚い第二の実質的に真性の薄膜に向かって階段状
に変化させて、咳より薄い第一の実質的に真性の薄膜を
形成することを特徴とする光電変換素子の製造方法を要
旨とするものである。[Disclosure of the Invention] The method for manufacturing a photoelectric conversion element of the present invention was arrived at as a result of intensive studies to solve the above problems, and its gist is that a first electrode, a first conductive a conductive thin film, a thinner first substantially intrinsic thin film, a thicker second substantially intrinsic thin film, a second conductive thin film, and a second electrode, the method comprising: After forming the conductive thin film, the supply of the second conductivity-imparting impurity is stopped, and the flow rate of the carbon-containing compound gas is reduced from the first conductive thin film to the thicker second substantially intrinsic film. The gist of the present invention is a method for manufacturing a photoelectric conversion element, which is characterized by forming a first substantially intrinsic thin film thinner than a thin film by changing the thickness stepwise toward the thin film.
本発明の方法により製造される素子を、第１図に示した
模式図を参照しながらより具体的に定義すれば、基体上
に形成せしめられた第一の電極上に、第一の導電性薄膜
が形成されており、該第−の導電性薄膜上に、より薄い
第一の実質的に真性の薄膜が形成されており、咳より薄
い第一の実質的に真性の薄膜上に、より厚い第二の実質
的に真性の薄膜が形成されており、咳より厚い第二の実
質的に真性の薄膜上に、第二の導電性薄膜が形成されて
おり、さらに該第二の導電性薄膜上に、第二の電極が順
次形成せしめられた光電変換素子である。If the device manufactured by the method of the present invention is defined more specifically with reference to the schematic diagram shown in FIG. a thinner first substantially intrinsic thin film is formed on the first conductive thin film; a thinner first substantially intrinsic thin film is formed on the thinner first substantially intrinsic thin film; a thick second substantially intrinsic thin film is formed, a second electrically conductive thin film is formed on the thicker second substantially intrinsic thin film; This is a photoelectric conversion element in which second electrodes are sequentially formed on a thin film.
以下、本発明の詳細な説明する。The present invention will be explained in detail below.
本発明において、第一の導電性薄膜と第二の導電性薄膜
とは、互に異なる導電型を有するものである０例えば、
第一の導電型をｐ型とすれば、第二の導電型はｎ型にな
る。In the present invention, the first conductive thin film and the second conductive thin film have different conductivity types, for example,
If the first conductivity type is p-type, the second conductivity type is n-type.
以下、第一の導電型をｐ型とした場合について説明する
が、その逆の場合もありえることは云うまでもない。The case where the first conductivity type is p-type will be described below, but it goes without saying that the opposite case is also possible.
第一の導電性薄膜つまりｐ膜は、高次シラン化合物、第
一の導電型を与える不純物ガス、希釈ガスおよび炭素含
有化合物ガス等の混合ガスをグロー放電または、光ＣＶ
Ｄにより形成される。The first conductive thin film, that is, the p-film, is formed by using a glow discharge or a photoCV method to conduct a mixed gas such as a higher-order silane compound, an impurity gas giving the first conductivity type, a diluent gas, and a carbon-containing compound gas.
Formed by D.
本発明において高次シラン化合物としては、一般式 ５
１ｎＨｚ＋＋＊ｚ（特にｎ＝２および３）で表わされる
水素化シリコンが好ましいものとして挙げられる。ここ
でｎ＝２および３はそれぞれ具体的にジシラン（ＳｉＪ
ａ）およびトリシラン（ＳｉＪｓ）に対応する。また、
炭素含有化合物ガスとしては、メタン、エタン、プロパ
ン等の飽和炭化水素；エチレン、アセチレン等の不飽和
炭化水素；モノメチルシラン、ジメチルシラン、トリメ
チルシラン、テトラメチルシラン、モノエチルシラン、
ジエチルシラン、トリエチルシラン、テトラエチルシラ
ン等のアルキルシランが好適に用いられる。これらの中
でも、アルキルシラン、アセチレンを用いることが光電
変換素子の特性向上のために好ましい。In the present invention, the higher order silane compound has the general formula 5
Hydrogenated silicon of 1 nHz++*z (in particular n=2 and 3) is preferred. Here, n=2 and 3 are specifically disilane (SiJ
a) and trisilane (SiJs). Also,
Carbon-containing compound gases include saturated hydrocarbons such as methane, ethane, and propane; unsaturated hydrocarbons such as ethylene and acetylene; monomethylsilane, dimethylsilane, trimethylsilane, tetramethylsilane, monoethylsilane,
Alkylsilanes such as diethylsilane, triethylsilane, and tetraethylsilane are preferably used. Among these, it is preferable to use alkylsilane and acetylene in order to improve the characteristics of the photoelectric conversion element.
さらに、ｐ型の導電性を賦与するガスとしては、ジボラ
ン、希釈ガスとしては、水素が好ましい。Furthermore, diborane is preferable as the gas imparting p-type conductivity, and hydrogen is preferable as the diluent gas.
本発明において、ｐ膜の厚みは通常約５０〜５００Ａ程
度であるが、その形成温度および形成圧力は、通常それ
ぞれ１００〜３００°Ｃおよび０．０３〜０．５Ｔｏｒ
ｒである。In the present invention, the thickness of the p-film is usually about 50 to 500A, and the formation temperature and pressure are usually 100 to 300°C and 0.03 to 0.5 Torr, respectively.
It is r.
本発明の最も特徴とするところは、第一の導電性薄膜上
に、少なくとも、より薄い第一の実質的に真性の薄膜を
形成する製造方法にあるが、その製造方法は、第一の導
電性薄膜を上述したように、高次シラン化合物、炭素含
有化合物ガス、第一の導電性を賦与する不純物ガスおよ
び希釈ガスなどの混合ガスをグロー放電法、または、光
ＣＶＤ法により分解し形成した後、不純物の供給の停止
および炭素含有化合物ガスを階段状に漸減していき、そ
の他の条件は同一として薄膜の形成を続行することであ
る。好ましくは、該より薄い第一の実質的に真性の薄膜
は非晶質（アモルファス） （ａ−５ｔ：Ｈまたはａ−
ＳｉＣ：Ｈ）であり、膜厚が２５Ａ以上の膜であること
である。膜厚が２５Ａ未満であると、接合界面における
特性の劣化を抑えることばできず、本発明の目的を達成
することは出来ない。The most characteristic feature of the present invention is a manufacturing method for forming at least a thinner first substantially intrinsic thin film on a first conductive thin film. As described above, the thin film was formed by decomposing a mixed gas such as a higher-order silane compound, a carbon-containing compound gas, an impurity gas that imparts the first conductivity, and a diluent gas by a glow discharge method or a photo-CVD method. After that, the supply of impurities is stopped and the carbon-containing compound gas is gradually reduced in a stepwise manner, and the thin film formation is continued under the same conditions. Preferably, the thinner first substantially intrinsic film is amorphous (a-5t:H or a-
SiC:H) and has a film thickness of 25A or more. If the film thickness is less than 25A, deterioration of the characteristics at the bonding interface cannot be suppressed, and the object of the present invention cannot be achieved.
なお、膜厚の上限は数千Ａ以内の範囲であれば特に臨界
的に限定されるものではないが、高ｈ５００八程度で充
分である。そして、特性および上記実用上の観点から、
プラズマＣＶＤにより形成された、５０乃至３００Ａの
範囲の厚みを有する非晶質薄膜が特に好ましい。Note that the upper limit of the film thickness is not particularly critically limited as long as it is within several thousand amps, but a high h of about 5008 is sufficient. From the characteristics and the above practical point of view,
Particularly preferred are amorphous thin films formed by plasma CVD and having a thickness in the range of 50 to 300 Å.
本発明において、特に重要な点は、不純物の供給の停止
および炭素含有化合物ガスを単に漸減しするのではなく
、「階段上に」漸減する点にあるのである０通常の当業
者の常識に従えば、漸減する場合は、出来るだけスムー
スにするのが好ましいると推察するので自然であり、こ
れを直線的もしくはカーブに従って、漸減せしめると云
う手段を採用するであろう。しかして、驚くべきことに
本発明者らは、これを「階段上に」に漸減した場合、決
して当業者に予測出来ない、特異的な変換効率の向上が
もたらされることを見出し本発明に到達したのである。In the present invention, what is particularly important is that the supply of impurities is stopped and that the carbon-containing compound gas is not simply gradually reduced, but is gradually reduced "in steps". For example, in the case of a gradual decrease, it is natural to assume that it is preferable to do it as smoothly as possible, and one would probably adopt a method of gradually decreasing the decrease linearly or following a curve. Surprisingly, however, the present inventors have found that when this is gradually reduced in a "stepwise" manner, a specific improvement in conversion efficiency that could never be predicted by those skilled in the art is brought about, and the present invention has been achieved. That's what I did.
本発明において、該階段の段数は２以上５０以内が好ま
しい。In the present invention, the number of steps of the stairs is preferably 2 or more and 50 or less.
なお、該薄膜が形成される時の基体の温度は、２００〜
４００°Ｃの範囲で行うが、好ましくは、本発明者らが
すでに提案しているように、第一の導電性薄膜の形成温
度≦該薄膜の形成温度≦より厚い第二の実質的に真性の
薄膜の形成温度の範囲で行うのが良い、また、雰囲気圧
力については０．０１〜１０Ｔｏｒｒの範囲で充分であ
る。Note that the temperature of the substrate when the thin film is formed is between 200 and 200℃.
400°C, but preferably, as already proposed by the present inventors, the formation temperature of the first conductive thin film ≦ the formation temperature of the thin film ≦ the thicker second substantially intrinsic It is preferable to carry out the thin film formation temperature within the range of 0.01 to 10 Torr for the atmospheric pressure.
また、本発明においては、少なくとも、より厚い実質的
に真性の薄膜は高次シランのプラズマＣＶＤによって行
われるが、その他の薄膜は膜厚も、それほど厚くないた
め、光ＣＶＤ法により形成されることも勿論好ましい実
施の態様である。Further, in the present invention, at least the thicker substantially intrinsic thin film is formed by plasma CVD of high-order silane, but other thin films are not so thick and therefore may be formed by photo-CVD. Of course, this is also a preferred embodiment.
本発明においては、より厚い実質的に真性の薄膜（以下
ｉ膜と略称する）は、上記したごとく高次シラン化合物
のプラズマＣＶＤ法により形成される。特に、該ｉ膜を
高速で形成するためには、本発明者らが既に提案してい
るように、ジシランを用い、かつ闇値以上の放電エネル
ギーの供給下に該プラズマＣＶＤが行われることが望ま
しい、より具体的には、本発明者らが特開昭５８−１７
２６号公報に開示している如くである。In the present invention, the thicker substantially intrinsic thin film (hereinafter abbreviated as i-film) is formed by the plasma CVD method using a higher-order silane compound as described above. In particular, in order to form the i-film at high speed, the plasma CVD may be performed using disilane and supplying discharge energy higher than the dark value, as already proposed by the present inventors. Desirably, more specifically, the inventors of the present invention
This is as disclosed in Publication No. 26.
ｉ膜の厚みは通常的２０００ Ａ〜１μ程度であるが、
その形成温度および形成圧力は、通常それぞれ２００〜
４００°ＣおよびＯ１旧〜１０Ｔｏｒｒの範囲で充分で
あり、水素やヘリウム等の希釈ガスにより希釈して使用
することもまた、光電変換素子の高性能化のために好ま
しいことである。The thickness of the i-film is typically about 2000A to 1μ, but
The forming temperature and forming pressure are usually 200~200°C each.
A temperature of 400° C. and O1 to 10 Torr is sufficient, and it is also preferable to use it diluted with a diluent gas such as hydrogen or helium in order to improve the performance of the photoelectric conversion element.
第二の導電性薄膜の形成条件については本発明に対し本
質的に臨界的な条件ではなく、したがって特に限定する
ものではないが、念のため以下好ましい実施の条件につ
いて説明する。Although the conditions for forming the second conductive thin film are not essentially critical to the present invention and are therefore not particularly limited, preferred conditions for implementation will be described below just in case.
第二の導電性薄膜つまりｎ膜は、シラン化合物、第二の
導電型を与える不純物ガスおよび希釈ガスをプラズマＣ
ＶＤで形成される。従って、シラン化合物としてはモノ
シランおよびジシランのいずれもが有効に用いられる。The second conductive thin film, that is, the n-film, is formed using a plasma C.
Formed by VD. Therefore, both monosilane and disilane can be effectively used as the silane compound.
ｎ型の導電性を賦与するガスとしては、ホスフィン、希
釈ガスとしては、水素が好ましい。なお、ｎ膜は微結晶
化させ、導電度を向上させることが好ましいため、水素
とシラン化合物の流量比が重要である。The gas imparting n-type conductivity is preferably phosphine, and the diluent gas is preferably hydrogen. Note that since it is preferable that the n film be microcrystalized to improve its conductivity, the flow rate ratio of hydrogen and silane compound is important.
ｎ膜の厚みは通常約１００〜８００Ａ程度であるが、そ
の形成温度および形成圧力は、通常それぞれ１００〜４
００°Ｃおよび０．０１〜１０Ｔｏｒｒ好ましくは０．
０５〜３Ｔｏｒｒである。なお、好ましい水素、シラン
化合物流量比は、５〜１００程度である。The thickness of the n film is usually about 100 to 800 A, but the forming temperature and forming pressure are usually about 100 to 4 A, respectively.
00°C and 0.01-10 Torr, preferably 0.00°C and 0.01-10 Torr.
05 to 3 Torr. Note that the preferred flow ratio of hydrogen and silane compound is about 5 to 100.
［発明を実施するための好ましい形態］本発明を実施す
るためには、プラズマＣＶＤが継続して実施できる成膜
装置が好適に用いられる。[Preferred form for carrying out the invention] In order to carry out the invention, a film forming apparatus capable of continuously carrying out plasma CVD is suitably used.
すなわち、基体導入手段、基体加熱手段、基体保持手段
、ガス導入手段、真空排気手段、プラズマ放電電極およ
びプラズマ放電電源の各手段を少なくとも基本的に具備
した成膜装置であり、好ましくは、これらの装置は、基
体移送手段を介して互に連結されており、かつ必要に応
じてゲート弁等で仕切られていることが好ましい。第２
図にはこのような、本発明を実施するに適した成膜装置
の例が模式的に示されている。That is, it is a film forming apparatus that is at least basically equipped with each of the following means: a substrate introduction means, a substrate heating means, a substrate holding means, a gas introduction means, a vacuum evacuation means, a plasma discharge electrode, and a plasma discharge power supply. Preferably, the apparatuses are connected to each other via a substrate transfer means, and are separated by a gate valve or the like as necessary. Second
The figure schematically shows an example of such a film forming apparatus suitable for carrying out the present invention.
まず、上記のごときプラズマＣＶＤ装置に第一の電極が
設けられた基体を設置し、前述したような条件でｐ膜（
第一の導電性薄膜）、より薄い第一の実質的に真性の薄
膜を２段から５０段の範囲で階段状に形成する。First, a substrate provided with a first electrode is installed in the plasma CVD apparatus as described above, and a p-film (
(first conductive thin film), a thinner first substantially intrinsic thin film is formed in a stepwise manner ranging from 2 steps to 50 steps.
つぎにこの薄膜を形成した基体は、基体移送手段により
、ｉ膜（より厚い第二の実質的に真性の薄膜）形成のた
めのプラズマＣＶＤ装置に移送される。ｉ膜形成室にお
いてｉ膜を形成した後、さらに基体移送手段により、ｎ
膜形成室に移送される、ｎ膜を形成した後、基体移送手
段により第二の電極形成装置に移送され、かくして第二
の電極が形成された後で光電変換素子として形成装置外
に取り出される。Next, the substrate on which this thin film has been formed is transferred by a substrate transfer means to a plasma CVD apparatus for forming an i-film (a thicker second substantially intrinsic thin film). After forming the i-film in the i-film formation chamber, the n
Transferred to the film forming chamber, after forming the n-film, transferred to the second electrode forming apparatus by the substrate transfer means, thus forming the second electrode, and then taken out of the forming apparatus as a photoelectric conversion element. .
勿論、上記の実施態様は、第一の電極を分割しておいて
複数の光電変換素子、たとえば太陽電池を形成し、第二
の電極でこれらを直列接続した形で得る集積型太陽電池
の形成においても有用である。Of course, the above embodiments are not limited to forming an integrated solar cell in which the first electrode is divided to form a plurality of photoelectric conversion elements, such as solar cells, and these are connected in series using the second electrode. It is also useful in
本発明で用いる基体や電極の材料については特に制限さ
れず、従来用いられている物質が有効に用いられている
。The materials for the substrate and electrodes used in the present invention are not particularly limited, and conventionally used materials can be effectively used.
たとえば、基体としては絶縁性または導電性、透明、不
透明のいずれかの性質を有するものでもよい、基本的に
はガラス、アルミナ、シリコン、ステンレススチイール
、アルミニウム、モリブデン、耐熱性高分子等の物質で
形成されるフィルムあるいは板状の材料を有効に用いる
ことができる、電極材料としては、光入射側にはもちろ
ん透明あるいは透明性の材料を用いなければならないが
、これ以外の実質的な制限はない、アルミニウム、モリ
ブデン、ニクロム、ＩＴＯ、酸化錫、ステンレススチイ
ール等の薄膜または薄板が電極材料として有効に用いら
れる。For example, the substrate may be insulating or conductive, transparent, or opaque, and is basically a material such as glass, alumina, silicon, stainless steel, aluminum, molybdenum, and heat-resistant polymers. As the electrode material, a transparent or transparent material must of course be used on the light incident side, but there are no other practical limitations. However, thin films or thin plates of aluminum, molybdenum, nichrome, ITO, tin oxide, stainless steel, etc. can be effectively used as electrode materials.
以下、実施例により、本発明の実施の態様をさらに具体
的に説明する。Hereinafter, embodiments of the present invention will be explained in more detail with reference to Examples.
［実施例］
成膜装置として、第２図に模式的に示したものを使用し
た。基体装入室１で真空加熱された基体６は、Ｐ膜形成
室２に移送された。ｐ膜は、原料ガスの流量比が、ジボ
ラン／ジシラン−３／１００、アセチレン／ジシラン−
１７１０、形成温度２５０°Ｃ１圧力０．Ｉ Ｔｏｒｒ
の条件の光ＣＶＤ法により、約１０ＯＡの厚みに形成さ
れた。ついで、ジボランの供給を停止して、アセチレン
／ジシランの比１／２Ｏ−４（比較例）、または、核化
が１７１０から０へと６段で階段状に減少させ（実施例
）、基体温度３００°Ｃで第一の実質的に真性の薄膜を
１５ＯＡ形成した。[Example] The film forming apparatus schematically shown in FIG. 2 was used. The substrate 6 heated in vacuum in the substrate loading chamber 1 was transferred to the P film forming chamber 2. The p-film has a raw material gas flow ratio of diborane/disilane-3/100 and acetylene/disilane-3/100.
1710, forming temperature 250°C1 pressure 0. I Torr
It was formed to a thickness of about 10 OA by photo-CVD under the following conditions. Then, the supply of diborane was stopped, and the acetylene/disilane ratio was reduced to 1/2O-4 (comparative example), or the nucleation was decreased stepwise from 1710 to 0 in 6 steps (example), and the substrate temperature was decreased. A first substantially intrinsic thin film was formed at 15 OA at 300°C.
ついで、ゲート弁１９を解放し、基体移送手段１６によ
り、該基体をｉ膜形成室３に移送した。ｉ膜形成室では
形成温度３００°Ｃ１圧力０．０５ Ｔｏｒｒで放電エ
ネルギーの閾値以上の条件において、ジシランのプラズ
マＣＶＤによりｉ膜が形成された。次に、ｎ膜形成室４
に移送され、モノシランと水素希釈ホスフィンとから微
結晶化ｎ膜がプラズマＣＶＤにより形成された。原料ガ
ス流量比は、ホスフィン／モノシラン＝２／１００ 、
モノシラン／水素＝ １／４０であった。ついで電極形
成室５へ移送され、真空蒸着により、アルミラム電極が
形成された。Then, the gate valve 19 was opened, and the substrate was transferred to the i-film forming chamber 3 by the substrate transfer means 16. In the i-film formation chamber, the i-film was formed by plasma CVD of disilane under conditions of a formation temperature of 300° C., a pressure of 0.05 Torr, and a discharge energy equal to or higher than the threshold value. Next, the n-film formation chamber 4
A microcrystallized n film was formed from monosilane and hydrogen-diluted phosphine by plasma CVD. The raw material gas flow rate ratio is phosphine/monosilane = 2/100,
Monosilane/hydrogen = 1/40. Then, it was transferred to the electrode forming chamber 5, and an aluminum ram electrode was formed by vacuum deposition.
かくして得られた光発電変換素子の光電変換特性がＡＭ
Ｉ 、１００ｍＷ／ｃｍ”の光を照射しつつ計測された
。結果を第１表に示した。The photoelectric conversion characteristics of the photovoltaic conversion element thus obtained are AM
The results are shown in Table 1.
第１表 より薄い第一の実質的に真性の薄膜の形成条件
と光電変換素子特性
この表かられかるように、ジメチルシランの流量を階段
状に減少させた場合、当業者の予測に反した著しい光電
変換効率の改善がもたらされていることがわかる。その
結果として、光電変換効率が１１χを越える優れた光電
変換素子が得られている。Table 1 Conditions for forming thinner first substantially intrinsic thin film and characteristics of photoelectric conversion element As can be seen from this table, when the flow rate of dimethylsilane was decreased in a stepwise manner, contrary to the predictions of those skilled in the art, It can be seen that a significant improvement in photoelectric conversion efficiency has been brought about. As a result, an excellent photoelectric conversion element with a photoelectric conversion efficiency exceeding 11χ has been obtained.
［発明の効果］
以上のごとく、本発明の光電変換素子の製造法の実施に
よって、上記実施例に示すような特性値が大幅の改善が
見られた。その結果として、光電変換効率が極めて優れ
た光電変換素子の提供が可能となり、その産業上の利用
可能性は極めて大きいと云わねばならない。[Effects of the Invention] As described above, by implementing the method for manufacturing a photoelectric conversion element of the present invention, a significant improvement in the characteristic values as shown in the above examples was observed. As a result, it has become possible to provide a photoelectric conversion element with extremely excellent photoelectric conversion efficiency, and it must be said that its industrial applicability is extremely large.
第１図は本発明より得られる光電変換素子の構成の一例
を示す断面模式図である。
第２図は本発明の素子を形成するために好ましい装置の
一例を示す模式図である０図において、■・・・・・・
基体装入室、２・・・・・・ｐ膜形成室、３・・・・・
・ｉ膜形成室、４・・・・・・ｎ膜形成室、５・・・・
・・第二電極形成室兼基体取り出し室、６・・・・・・
基体、９・・・・・・放電電力印加電極、１０・・・・
・・設置電極、１１・・・・・・基体加熱ヒーター、１
２・・・・・・電極材料加熱ヒーター、１３・・・・・
・金属マスク、１４および２０・・・・・・真空排気ラ
イン、１５・・・・・・原料ガス導入ライン、１６・・
・・・・基体移送手段、１７・・・・・・絶縁性物質、
１８・・・・・・放電電力印加電源、１９・・・・・・
ゲート弁
特許出願人 三井東圧化学株式会社
手続補正書（方式）
昭和６２年７月７日
特許庁長官 小 川 邦 夫 殿
１、事件の表示
昭和６２年特許願第７４２９２ 号
２、発明の名称
光電変換素子の製造方法
３、補正をする者
事件との関係 特許出願人
住所 東京都千代田区霞が関三丁目２番５号名称（３１
２） 三井東圧化学株式会社４、補正命令の日付
昭和６２年６月３０日（発送）
５、補正の対象FIG. 1 is a schematic cross-sectional view showing an example of the structure of a photoelectric conversion element obtained by the present invention. FIG. 2 is a schematic diagram showing an example of a preferable apparatus for forming the element of the present invention.
Substrate charging chamber, 2...P film formation chamber, 3...
・I film formation chamber, 4...N film formation chamber, 5...
・・Second electrode formation chamber/substrate removal chamber, 6...
Substrate, 9...Discharge power application electrode, 10...
... Installation electrode, 11 ... Substrate heating heater, 1
2...Electrode material heating heater, 13...
・Metal mask, 14 and 20... Vacuum exhaust line, 15... Raw material gas introduction line, 16...
... Substrate transfer means, 17 ... Insulating material,
18...Discharge power application power supply, 19...
Gate valve patent applicant Mitsui Toatsu Kagaku Co., Ltd. Procedural amendment (method) July 7, 1985 Director General of the Patent Office Kunio Ogawa 1, Indication of the case 1988 Patent Application No. 74292 2, Title of the invention Manufacturing method for photoelectric conversion elements 3, relationship with the amended person case Patent applicant address 3-2-5 Kasumigaseki, Chiyoda-ku, Tokyo Name (31
2) Mitsui Toatsu Chemical Co., Ltd. 4. Date of amendment order: June 30, 1985 (shipped) 5. Subject of amendment
Claims (1)
薄い第一の実質的に真性の薄膜、より厚い第二の実質的
に真性の薄膜、第二の導電性薄膜、第二の電極の順に形
成せしめられた光電変換素子の製法において、炭素含有
化合物ガスの流量を第一の導電性薄膜から、より厚い第
二の実質的に真性の薄膜に向かって、階段状に減らして
、より薄い第一の実質的に真性の薄膜を形成することを
特徴とする光電変換素子の製法。(1) on a substrate, a first electrode, a first conductive thin film, a thinner first substantially intrinsic thin film, a thicker second substantially intrinsic thin film, a second conductive thin film; In a method for manufacturing a photoelectric conversion element in which a second electrode is formed in this order, the flow rate of a carbon-containing compound gas is stepped from a first conductive thin film toward a thicker second substantially intrinsic thin film. A method for manufacturing a photoelectric conversion element, characterized in that a first substantially intrinsic thin film is formed by reducing the thickness of the thin film.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62074292A JPS63241970A (en) | 1987-03-30 | 1987-03-30 | Manufacture of optoelectric transducer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62074292A JPS63241970A (en) | 1987-03-30 | 1987-03-30 | Manufacture of optoelectric transducer |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63241970A true JPS63241970A (en) | 1988-10-07 |
Family
ID=13542917
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62074292A Pending JPS63241970A (en) | 1987-03-30 | 1987-03-30 | Manufacture of optoelectric transducer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63241970A (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60192374A (en) * | 1984-03-13 | 1985-09-30 | Sanyo Electric Co Ltd | Manufacture of photovoltaic device |
| JPS60258975A (en) * | 1984-06-05 | 1985-12-20 | Sanyo Electric Co Ltd | Photovoltaic device |
| JPS61184816A (en) * | 1985-02-12 | 1986-08-18 | Canon Inc | Formation of deposited film |
| JPS6216514A (en) * | 1985-07-15 | 1987-01-24 | Mitsui Toatsu Chem Inc | Manufacture of photoelectric conversion element |
-
1987
- 1987-03-30 JP JP62074292A patent/JPS63241970A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60192374A (en) * | 1984-03-13 | 1985-09-30 | Sanyo Electric Co Ltd | Manufacture of photovoltaic device |
| JPS60258975A (en) * | 1984-06-05 | 1985-12-20 | Sanyo Electric Co Ltd | Photovoltaic device |
| JPS61184816A (en) * | 1985-02-12 | 1986-08-18 | Canon Inc | Formation of deposited film |
| JPS6216514A (en) * | 1985-07-15 | 1987-01-24 | Mitsui Toatsu Chem Inc | Manufacture of photoelectric conversion element |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP2951146B2 (en) | Photovoltaic devices | |
| AU746388B2 (en) | Apparatus and method for forming a deposited film by means of plasma CVD | |
| JPS63241970A (en) | Manufacture of optoelectric transducer | |
| JP3181121B2 (en) | Deposition film formation method | |
| JPS63220579A (en) | Manufacture of photoelectric conversion element | |
| JP2659369B2 (en) | Photoelectric conversion element | |
| JPH07183550A (en) | Amorphous photoelectric conversion device | |
| JPH0691010B2 (en) | Amorphous thin film manufacturing method | |
| JPH0714075B2 (en) | Method for manufacturing photoelectric conversion element | |
| Itozaki et al. | Amorphous Silicon-Germanium Deposited by Photo-CVD | |
| JPH0276266A (en) | Photoelectric conversion element | |
| JPH0554692B2 (en) | ||
| JPS63220581A (en) | Manufacture of photoelectric conversion element | |
| JPH0815220B2 (en) | Method for manufacturing photoelectric conversion element | |
| JP2575397B2 (en) | Method for manufacturing photoelectric conversion element | |
| JPH04286167A (en) | Photosensor | |
| JP2688221B2 (en) | Amorphous solar cell | |
| JP3069714B2 (en) | Hydrogenated amorphous silicon film deposition system | |
| JPH0714072B2 (en) | Method for manufacturing photoelectric conversion element | |
| JPH08181079A (en) | Forming method of amorphous semiconductor thin film | |
| JP3046644B2 (en) | Method for manufacturing photovoltaic element | |
| JPH06275538A (en) | Formation of amorphous silicon alloy film | |
| JPH0653532A (en) | Photoelectric conversion element | |
| JPH0815219B2 (en) | Method for manufacturing photoelectric conversion element | |
| JPH0653533A (en) | Amorphous solar cell |