JPH0815219B2 - Method for manufacturing photoelectric conversion element - Google Patents
Method for manufacturing photoelectric conversion elementInfo
- Publication number
- JPH0815219B2 JPH0815219B2 JP62053054A JP5305487A JPH0815219B2 JP H0815219 B2 JPH0815219 B2 JP H0815219B2 JP 62053054 A JP62053054 A JP 62053054A JP 5305487 A JP5305487 A JP 5305487A JP H0815219 B2 JPH0815219 B2 JP H0815219B2
- Authority
- JP
- Japan
- Prior art keywords
- thin film
- amorphous silicon
- photoelectric conversion
- conversion element
- substantially intrinsic
- 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
- 238000006243 chemical reaction Methods 0.000 title claims description 25
- 238000000034 method Methods 0.000 title claims description 18
- 238000004519 manufacturing process Methods 0.000 title claims description 10
- 239000010409 thin film Substances 0.000 claims description 47
- 229910021417 amorphous silicon Inorganic materials 0.000 claims description 26
- 239000000758 substrate Substances 0.000 claims description 21
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 17
- 238000000354 decomposition reaction Methods 0.000 claims description 13
- 229910000077 silane Inorganic materials 0.000 claims description 12
- 239000010408 film Substances 0.000 description 14
- 239000007789 gas Substances 0.000 description 10
- 210000004027 cell Anatomy 0.000 description 6
- PZPGRFITIJYNEJ-UHFFFAOYSA-N disilane Chemical compound [SiH3][SiH3] PZPGRFITIJYNEJ-UHFFFAOYSA-N 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000007772 electrode material Substances 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000006303 photolysis reaction Methods 0.000 description 3
- 230000015843 photosynthesis, light reaction Effects 0.000 description 3
- 238000005268 plasma chemical vapour deposition Methods 0.000 description 3
- -1 silane compound Chemical class 0.000 description 3
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 238000003780 insertion Methods 0.000 description 2
- 230000037431 insertion Effects 0.000 description 2
- 229910021424 microcrystalline silicon Inorganic materials 0.000 description 2
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000126 substance Substances 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
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-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
- RBFQJDQYXXHULB-UHFFFAOYSA-N arsane Chemical compound [AsH3] RBFQJDQYXXHULB-UHFFFAOYSA-N 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 150000001722 carbon compounds Chemical class 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910001120 nichrome Inorganic materials 0.000 description 1
- 210000004180 plasmocyte Anatomy 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002952 polymeric resin Substances 0.000 description 1
- 229910002059 quaternary alloy Inorganic materials 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 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
- 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
- 238000007740 vapor 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
Landscapes
- Photovoltaic Devices (AREA)
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−Si:Hとも略す
る）光電変換素子の製造方法に関するものであり、特に
優れた光電特性を安定して有する光電変換素子の製造方
法に関する。TECHNICAL FIELD The present invention relates to a method for manufacturing an amorphous silicon (hereinafter abbreviated as a-Si: H) photoelectric conversion element, and particularly excellent photoelectric characteristics are stably obtained. The present invention relates to a method for manufacturing the photoelectric conversion element included.
［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、ある程度の成果が得られつつある。変換効
率の向上には、光入射側の導電性薄膜が、モノシラン、
メタンおよびジボランの混合ガスのグロー放電分解によ
り形成された非晶質シリコンカ−バイドやｐ型あるいは
ｎ型の微結晶シリコンの採用、また、超薄膜を繰返し積
層した超格子構造も採用され、変換効率の光効率化の検
討が為されている。また別の方法として、非晶質シリコ
ンを堆積させる基体を表面凹凸の大きな透明導電性薄膜
が形成されたガラス基板や、下地基板（たとえば、セラ
ミックス基板、ステンレスや高分子樹脂などの可撓性基
板）に表面凹凸を持たせたものが用いられ、変換効率の
向上を図り、成果をあげている。[Prior art and its problems] Higher efficiency of a photoelectric conversion element, particularly an amorphous silicon solar cell has been studied, and some results have been obtained. In order to improve the conversion efficiency, the conductive thin film on the light incident side should be monosilane,
Amorphous silicon carbide formed by glow discharge decomposition of a mixed gas of methane and diborane and p-type or n-type microcrystalline silicon are adopted, and a superlattice structure in which ultrathin films are repeatedly laminated is also adopted, and conversion efficiency is improved. Is being studied to improve light efficiency. As another method, a substrate on which amorphous silicon is deposited is a glass substrate on which a transparent conductive thin film having large surface irregularities is formed, or a base substrate (for example, a ceramic substrate, a flexible substrate such as stainless steel or polymer resin). ) With uneven surface is used to improve the conversion efficiency and achieve results.
さらに、ｐ型とｎ型の半導体薄膜の特性改善を目的と
し、プラズマ分解プロセスに代えて光分解プロセスによ
り、薄膜を堆積させ、特性を改善することも試みられて
いる。Furthermore, for the purpose of improving the characteristics of the p-type and n-type semiconductor thin films, it has been attempted to improve the characteristics by depositing a thin film by a photolysis process instead of the plasma decomposition process.
以上の研究においては、ある点に関して非常に効果的
で、例えば変換効率を著しく改善させたものもあるが、
いずれも一長一短があり、たとえば、光分解プロセスを
用いた場合、曲線因子の改善は得られたが、堆積速度が
プラズマ・プロセスに比較して非常に小さいため、太陽
電池の製造において、全プロセスをプラズマ・プロセス
に代えるには、光分解プロセスは十分なプロセスとは言
えない。また微結晶層が導電性薄膜に適用されている
が、太陽電池の構造の違いにより、下地層へのプラズマ
損傷が問題となり、適用できない場合がある。In the above research, some of them are very effective in some respects, for example, they have significantly improved the conversion efficiency.
Both have merits and demerits. For example, when the photolysis process was used, the fill factor was improved, but the deposition rate was much smaller than that of the plasma process, so that the whole process was not performed in the production of solar cells. The photolysis process is not a sufficient process to replace the plasma process. Further, the microcrystalline layer is applied to the conductive thin film, but due to the difference in the structure of the solar cell, plasma damage to the underlayer becomes a problem, and it may not be applicable.
さらに、最近、太陽電池特性の向上のために、短絡光
電流、曲線因子、開放端電圧総ての因子が改善されると
して、導電性薄膜層と真性薄膜層の界面に緩衝層を導入
する提案が多くされている。これは、例えば、透明導電
性薄膜が形成されているガラス基板上に、第一の導電性
薄膜としてｐ型非晶質シリコンカ−バイド（以下ｐ層と
略す）、真性薄膜として非晶質シリコン（以下ｉ層と略
す）、第二の導電性薄膜としてｎ型非晶質シリコン（以
下ｎ層と略す）、最後にアルミニウムを取出し電極とす
る太陽電池構造において、ｐ層とｉ層の界面において、
格子定数の違いや、電気的不一致を避けるために、緩衝
層（界面層）として少量の炭素原子が添加された層を導
入するものであって、各研究機関において、種々の検討
が行われている。かかる緩衝層導入の成果は、徐々に挙
げられており、特に開放端電圧の向上には効果的である
結果が得られている。Furthermore, recently, in order to improve the solar cell characteristics, it is proposed that a buffer layer be introduced at the interface between the conductive thin film layer and the intrinsic thin film layer, assuming that all of the short-circuit photocurrent, fill factor, and open-circuit voltage are improved. Has been a lot. This is, for example, on a glass substrate on which a transparent conductive thin film is formed, a p-type amorphous silicon carbide (hereinafter abbreviated as p layer) as a first conductive thin film, and an amorphous silicon (as an intrinsic thin film). (Hereinafter abbreviated as i layer), n-type amorphous silicon (hereinafter abbreviated as n layer) as the second conductive thin film, and finally, in a solar cell structure in which aluminum is used as an extraction electrode, at the interface between the p layer and the i layer,
In order to avoid differences in lattice constants and electrical inconsistencies, a layer containing a small amount of carbon atoms is introduced as a buffer layer (interface layer), and various studies have been conducted at each research institute. There is. The results of introducing such a buffer layer have been gradually raised, and particularly effective results have been obtained in improving the open circuit voltage.
しかしながら、該技術に関してもいくつかの問題があ
る。すなわち、緩衝層には、シリコン原子に極微量の炭
素原子と硼素原子が同時あるいは単独で任意に添加され
ているが、ｐ層とｉ層の特性に依存した不純物原子添加
量の非常に精緻な制御が必要であり、また、この緩衝層
は、結合水素原子を含め四元系であるために、さらに制
御が複雑、困難である。さらに、本緩衝層が抵抗層とし
て影響するために、結果的には、曲線因子を十分には向
上できないと云う問題がある。また、この緩衝層に用い
た炭素原子や硼素原子が、真性薄膜層のｉ層に不純物と
して混入し、太陽電池特性を低下させる問題もあった。However, there are also some problems with this technique. That is, although a very small amount of carbon atoms and boron atoms are arbitrarily or simultaneously added to silicon atoms in the buffer layer, the amount of impurity atoms added depends on the characteristics of the p layer and the i layer. Control is required, and this buffer layer is a quaternary system including bonded hydrogen atoms, and therefore control is more complicated and difficult. Further, since the buffer layer affects the resistance layer, there is a problem that the fill factor cannot be sufficiently improved. Further, there is also a problem that carbon atoms and boron atoms used in this buffer layer are mixed as impurities in the i layer of the intrinsic thin film layer to deteriorate the solar cell characteristics.
［発明の目的］ しかして、本発明の目的は、開放端電圧を著しく向上
させ、かつ短絡光電流と曲線因子を同時に改善させた高
光電変換効率の光電変換素子の製造方法を提供すること
である。[Object of the Invention] Accordingly, an object of the present invention is to provide a method of manufacturing a photoelectric conversion element having a high photoelectric conversion efficiency in which the open-circuit voltage is significantly improved, and the short-circuit photocurrent and the fill factor are simultaneously improved. is there.
［発明の開示］ 本発明者らは、上記点に鑑み鋭意検討した結果、これ
らの問題は、第一の導電性薄膜と実質的に真性な薄膜の
間に形成する薄膜層である緩衝層に不純物を導入するこ
とに本質的な問題があることを見出し、本発明を完成し
た。DISCLOSURE OF THE INVENTION As a result of intensive studies in view of the above points, the present inventors have found that these problems are caused by a buffer layer which is a thin film layer formed between a first conductive thin film and a substantially intrinsic thin film. The present invention has been completed by finding that there is an essential problem in introducing impurities.
すなわち、本発明は、 基体上に、まず第一の電極、次いでｐ型の非晶質シリ
コン系薄膜、その次により薄い第一の実質的に真性の非
晶質シリコン薄膜、さらにその次により厚い第二の実質
的に真性の非晶質シリコン薄膜、引き続いてｎ型の非晶
質シリコン系薄膜、最後に第二の電極の順に形成せしめ
る光電変換素子の製造方法において、前記より薄い第一
の実質的に真性の非晶質シリコン薄膜は、一般式Sin H
2n+2（ｎは２以上の整数）で表わされる高次シランのプ
ラズマ分解により形成し、前記より厚い第二の実質的に
真性の非晶質シリコン薄膜はモノシランのプラズマ分解
により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。That is, the present invention provides that on a substrate, first a first electrode, then a p-type amorphous silicon based thin film, then a thinner first substantially intrinsic amorphous silicon thin film, and then a thicker one. In a method of manufacturing a photoelectric conversion element, in which a second substantially intrinsic amorphous silicon thin film, an n-type amorphous silicon thin film, and finally a second electrode are formed in this order, A substantially intrinsic amorphous silicon thin film has the general formula Si n H
2n + 2 (n is an integer of 2 or more) is formed by plasma decomposition of a higher order silane, and the thicker second substantially intrinsic amorphous silicon thin film is formed by plasma decomposition of monosilane. The gist is a method for manufacturing a photoelectric conversion element having the characteristics.
以下、本発明を詳細に説明する。 Hereinafter, the present invention will be described in detail.
本発明における、より薄い第一の実質的に真性の薄膜
とは、一般式SinH2n+2（ここでｎは、２以上の整数）で
表わされる高次シランのプラズマ分解により形成された
非晶質シリコンである。該薄膜層の厚みは、10〜5000Å
であり、本発明の目的を十分に発揮し、高変換効率を得
るためには、50〜5000Åが好ましく、さらには50〜500
Åがより好ましく、50〜200Åが最も好ましい。In the present invention, the thinner first substantially intrinsic thin film is formed by plasma decomposition of a higher-order silane represented by the general formula Si n H 2n + 2 (where n is an integer of 2 or more). It is amorphous silicon. The thickness of the thin film layer is 10 ~ 5000Å
Therefore, in order to fully exert the object of the present invention and obtain high conversion efficiency, 50 to 5000 Å is preferable, and further 50 to 500
Å is more preferable, and 50 to 200 Å is most preferable.
本発明における高次シランとは、上記したごとく一般
式SinH2n+2で表わされるものであって、式中ｎは２以上
の整数である。具体的には、ジシラン、トリシラン、テ
トラシランなどが好ましいものとして挙げられるが、取
扱上、気体であるジシランが特に好ましい。The high-order silane in the present invention is represented by the general formula Si n H 2n + 2 as described above, and n is an integer of 2 or more. Specifically, disilane, trisilane, tetrasilane and the like are mentioned as preferable ones, but gas is particularly preferable in terms of handling.
本発明においては、かかる高次シランのプラズマ分解
法により、該真性の薄膜を形成する。In the present invention, the intrinsic thin film is formed by the plasma decomposition method of the higher order silane.
該薄膜形成時の基板温度は、50〜300℃であり、反応
圧力は、0.01〜10.0Torr、高次シラン流量は、１〜100c
c/min、プラズマ発生のための高周波電力密度は、0.002
〜1.0W/cm2（高周波電力を高周波電極面積にて除した
値）である。なお、ヘリウム、アルゴンなどの不活性ガ
スや水素ガスを同時に添加しても構わない。また、これ
らのガスにより稀釈された高次シランを用いても構わな
い。The substrate temperature during the thin film formation is 50 to 300 ° C., the reaction pressure is 0.01 to 10.0 Torr, and the high order silane flow rate is 1 to 100 c.
c / min, high frequency power density for plasma generation is 0.002
1.01.0 W / cm 2 (value obtained by dividing high-frequency power by high-frequency electrode area). Note that an inert gas such as helium or argon or a hydrogen gas may be added at the same time. Further, higher order silane diluted with these gases may be used.
本発明においては、より厚い第二の実質的に真性の薄
膜は、モノシランのプラズマ分解により形成された、結
合水素を含んだ非晶質シリコンである。In the present invention, the thicker second substantially intrinsic thin film is amorphous silicon containing bound hydrogen formed by plasma decomposition of monosilane.
その膜厚は、0.3〜10μであり、変換効率の点から、
0.5〜0.8μが特に好ましい。The film thickness is 0.3 to 10μ, and from the viewpoint of conversion efficiency,
0.5 to 0.8 μ is particularly preferable.
該薄膜形成時の基板温度は、50〜350℃であり、好ま
しくは、100〜350℃である。モノシランガスは、ヘリウ
ム、アルゴンなどの不活性ガスや水素ガスにより稀釈さ
れたもの、なんら稀釈されていないもののいずれでも構
わない。純モノシラン換算で、流量は、１〜100cc/min
である。反応圧力は、0.01〜10Torrであり、プラズマ発
生のための高周波電力は、0.001〜1.0W/cm2の範囲であ
る。The substrate temperature at the time of forming the thin film is 50 to 350 ° C, preferably 100 to 350 ° C. The monosilane gas may be diluted with an inert gas such as helium or argon or hydrogen gas, or may not be diluted at all. Flow rate is 1 to 100cc / min in terms of pure monosilane
Is. The reaction pressure is 0.01 to 10 Torr, and the high frequency power for plasma generation is 0.001 to 1.0 W / cm 2 .
本発明においては、第一の電極上の第一の導電性薄膜
は、具体的には、ｐ型非晶質シリコン系薄膜であり、シ
ラン化合物SinH2n+2（ｎは１以上の自然数）とジボラン
B2H6の混合ガスのプラズマ分解によるｐ型非晶質シリコ
ン、あるいは、シラン化合物、ジボランおよび炭素化合
物（たとえばメタン、エタンの飽和炭化水素、アセチレ
ン、エチレンなどの不飽和系炭化水素、あるいはモノメ
チルシランなどの有機シラン化合物）のプラズマ分解に
より形成されたｐ型非晶質シリコンカ−バイドが好まし
い。In the present invention, the first conductive thin film on the first electrode is specifically a p-type amorphous silicon-based thin film, and the silane compound Si n H 2n + 2 (n is a natural number of 1 or more). ) And diborane
P-type amorphous silicon produced by plasma decomposition of a mixed gas of B 2 H 6 , or silane compounds, diborane and carbon compounds (for example, saturated hydrocarbons of methane and ethane, unsaturated hydrocarbons such as acetylene and ethylene, or monomethyl P-type amorphous silicon carbide formed by plasma decomposition of (organic silane compound such as silane) is preferable.
一方、第二の導電性薄膜は、具体的には、ｎ型非晶質
シリコン系薄膜であり、上記シラン化合物とフォスフィ
ンPH3あるいはアルシンAsH3の混合ガスのプラズマ分解
によるｎ型非晶質シリコンあるいは、ｎ型微結晶シリコ
ンが好ましい。On the other hand, the second conductive thin film is specifically an n-type amorphous silicon-based thin film, which is formed by plasma decomposition of a mixed gas of the above silane compound and phosphine PH 3 or arsine AsH 3. Alternatively, n-type microcrystalline silicon is preferable.
本発明で用いられる基体や電極材料については、とく
に制限されず、従来用いられている物質および材料が有
効に用いられる。The substrate and electrode material used in the present invention are not particularly limited, and conventionally used substances and materials can be effectively used.
たとえば、基板としては絶縁性又は導電性、透明又は
不透明に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、ステンレススティ
ール、アルミニウム、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基体として有効に用い
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光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、酸化インジウム錫、酸化錫、ス
テンレススティール等の薄膜又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 either insulating or conductive, transparent or opaque. Basically, a film or plate-like material formed of a substance such as glass, alumina, silicon, stainless steel, aluminum, and heat resistant polymer can be effectively used as the substrate. As the electrode material, of course, a transparent or translucent material must be used on the light incident side, but there is no other practical limitation. aluminum,
A thin film or a thin plate of molybdenum, nichrome, indium tin oxide, tin oxide, stainless steel, or the like is effectively used as an electrode material.
以下、実施例により本発明に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 described more specifically with reference to examples.
［実施例］ 太陽電池作製装置として、第１図に模式的に示したプ
ラズマCVD装置を用いた。Example As a solar cell manufacturing apparatus, a plasma CVD apparatus schematically shown in FIG. 1 was used.
基体挿入室１にて真空排気しながら加熱された基体10
は、ｐ層形成室２に移動させられ、ｐ膜が形成される。
ｐ膜は、原料ガスの流量比がジボラン／ジシラン＝2/10
0、アセチレン／ジシラン＝1/10,ジシラン／水素＝1/2
0、で形成温度100〜300℃、圧力0.05〜1.0Torrでグロー
放電により、約150Åの厚みに形成された。ｐ膜形成
後、原料ガス導入を停止し、10-6Torr以下まで真空排気
し、第一に実質的に真性の薄膜形成室３に移し、ついで
ジシランを導入し、圧力0.05〜1.0Torrで、流量１〜50c
c/min、形成温度100〜300℃で、同じくグロー放電によ
り、第一の実質的に真性の薄膜を第１表に示す形成条件
にて形成した。ついで、基体移送手段20により、該基体
をｉ膜形成室４に移送した。ｉ膜形成室では、形成温度
100〜400℃、圧力0.03〜5Torr、モノシラン流量１〜100
cc/minでグロー放電により、ｉ膜、すなわち第二の実質
的に真性の薄膜を約8000Å形成した。次にｎ膜形成室５
に移送され、モノシランと水素稀釈フォスフィンとか
ら、微結晶化ｎ膜がプラズマCVDにより、形成された。
次いで、電極形成室６へ移送され、真空蒸着により、ア
ルミニウム電極が形成された。Substrate 10 heated while being evacuated in substrate insertion chamber 1
Is moved to the p-layer formation chamber 2 to form a p-film.
The p film has a source gas flow ratio of diborane / disilane = 2/10
0, acetylene / disilane = 1/10, disilane / hydrogen = 1/2
It was formed to a thickness of about 150Å by glow discharge at a forming temperature of 100 to 300 ° C and a pressure of 0.05 to 1.0 Torr at 0. After forming the p-film, the introduction of the raw material gas is stopped, the gas is evacuated to 10 -6 Torr or less, first moved to the substantially intrinsic thin film forming chamber 3, then disilane is introduced, and the pressure is 0.05 to 1.0 Torr. Flow rate 1-50c
A first substantially intrinsic thin film was formed under the forming conditions shown in Table 1 by the same glow discharge at c / min and a forming temperature of 100 to 300 ° C. Then, the substrate was transferred to the i-film forming chamber 4 by the substrate transfer means 20. In the i-film formation chamber, the formation temperature
100-400 ℃, pressure 0.03-5 Torr, monosilane flow 1-100
A glow discharge at cc / min formed an i-film, a second substantially intrinsic thin film, about 8000 liters. Next, n film forming chamber 5
Then, a microcrystallized n film was formed by plasma CVD from monosilane and hydrogen diluted phosphine.
Then, it was transferred to the electrode forming chamber 6 and an aluminum electrode was formed by vacuum vapor deposition.
このようにして得られた光電変換素子の光電変換が、
AM1、100mW/cm2の光照射下で計測された。結果を第１表
に実施例１〜５として示した。The photoelectric conversion of the photoelectric conversion element thus obtained is
It was measured under the light irradiation of AM1 and 100 mW / cm 2 . The results are shown in Table 1 as Examples 1-5.
第１表には、また比較例のための例として、より薄い
第一の実質的に真性の薄膜を全く形成しない例（比較例
１）および該薄膜が4000Åと厚い場合（比較例２）もま
た示されている。 Table 1 also shows, as an example for a comparative example, an example in which a thinner first substantially intrinsic thin film is not formed at all (Comparative Example 1) and the thin film is as thick as 4000Å (Comparative Example 2). Also shown.
比較例と比べれば、明らかなように本発明の実施例に
おいては、開放端電圧（Voc）と短絡光電流（Jsc）に著
しい改善が認められ、また曲線因子（FF）についても、
低下することなく、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が得られることが明らかであ
る。As is apparent from the comparison with the comparative example, in the example of the present invention, a remarkable improvement was observed in the open-circuit voltage (Voc) and the short-circuit photocurrent (Jsc), and the fill factor (FF) was also improved.
It is apparent that as a result, a photoelectric conversion element having extremely excellent photoelectric conversion efficiency can be obtained.
［発明の効果］ 以上のごとく、本発明の方法、すなわちプラズマCVD
法により、形成された第一の導電性薄膜と第二に実質的
に真性の薄膜との間に、特定の厚みをもった第一の実質
的に真性の薄膜を、高次シランのプラズマ分解により、
形成し、介在させることにより、光電変換素子を作製す
れば、上記実施例の如く、開放端電圧と短絡光電流等の
特性値が著しく改善され、光電変換効率が極めて優れた
光電変換素子が提供されるのである。本発明の産業上の
利用可能性は極めて大きいと言わねばならない。[Effect of the Invention] As described above, the method of the present invention, that is, plasma CVD
The first substantially intrinsic thin film having a specific thickness is formed between the first conductive thin film and the second substantially intrinsic thin film formed by the method by plasma decomposition of higher silane. Due to
If a photoelectric conversion element is manufactured by forming and interposing the photoelectric conversion element, characteristic values such as an open-circuit voltage and a short-circuit photocurrent are remarkably improved, and a photoelectric conversion element having extremely excellent photoelectric conversion efficiency is provided, as in the above-mentioned embodiment. Is done. It must be said that the industrial applicability of the present invention is extremely high.
第１図は、本発明の製造方法を実施するために好ましい
装置の一例を示す模式図である。図において、１……基
体挿入および予備加熱室、２……ｐ膜形成室、３……第
一の実質的に真性の薄膜形成室、４……ｉ膜形成室、５
……ｎ膜形成室、６……第二電極形成室および基体取出
し室、10……基体、11……ヒーター内蔵加熱板、12……
高周波印加電極、20……原料ガス導入ライン、21……真
空排気ライン、22……高周波電源、30……基体移送手
段、31……仕切弁、32……絶縁物質、40……第二電極材
料加熱ヒーター、41……第二電極用マスクを示す。FIG. 1 is a schematic diagram showing an example of a preferable apparatus for carrying out the manufacturing method of the present invention. In the figure, 1 ... Substrate insertion and preheating chamber, 2 ... P film forming chamber, 3 ... First substantially intrinsic thin film forming chamber, 4 ... i film forming chamber, 5 ...
... n film forming chamber, 6 ... second electrode forming chamber and substrate take-out chamber, 10 ... substrate, 11 ... heating plate with built-in heater, 12 ...
High frequency applying electrode, 20 ... Raw material gas introduction line, 21 ... Vacuum exhaust line, 22 ... High frequency power supply, 30 ... Substrate transfer means, 31 ... Gate valve, 32 ... Insulating material, 40 ... Second electrode Material heating heater, 41 ... Shows a mask for the second electrode.
Claims (1)
非晶質シリコン系薄膜、その次により薄い第一の実質的
に真性の非晶質シリコン薄膜、さらにその次により厚い
第二の実質的に真性の非晶質シリコン薄膜、引き続いて
ｎ型の非晶質シリコン系薄膜、最後に第二の電極の順に
形成せしめる光電変換素子の製造方法において、前記よ
り薄い第一の実質的に真性の非晶質シリコン薄膜は、一
般式Sin H2n+2（ｎは２以上の整数）で表わされる高次
シランのプラズマ分解により形成し、前記より厚い第二
の実質的に真性の非晶質シリコン薄膜のモノシランのプ
ラズマ分解により形成することを特徴とする光電変換素
子の製造方法。1. A first electrode, then a p-type amorphous silicon-based thin film, then a thinner first substantially intrinsic amorphous silicon thin film, and then a thicker first electrode on a substrate. A second substantially intrinsic amorphous silicon thin film, an n-type amorphous silicon-based thin film, and finally a second electrode in this order. A substantially intrinsic amorphous silicon thin film is formed by plasma decomposition of a higher-order silane represented by the general formula Si n H 2n + 2 (n is an integer of 2 or more), and the thicker second substantially intrinsic A method for manufacturing a photoelectric conversion element, which comprises forming the amorphous silicon thin film by plasma decomposition of monosilane.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62053054A JPH0815219B2 (en) | 1987-03-10 | 1987-03-10 | Method for manufacturing photoelectric conversion element |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62053054A JPH0815219B2 (en) | 1987-03-10 | 1987-03-10 | Method for manufacturing photoelectric conversion element |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63220577A JPS63220577A (en) | 1988-09-13 |
| JPH0815219B2 true JPH0815219B2 (en) | 1996-02-14 |
Family
ID=12932143
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62053054A Expired - Fee Related JPH0815219B2 (en) | 1987-03-10 | 1987-03-10 | Method for manufacturing photoelectric conversion element |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0815219B2 (en) |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6074584A (en) * | 1983-09-30 | 1985-04-26 | Komatsu Ltd | Method for manufacturing amorphous silicon solar cells |
| JPS60192374A (en) * | 1984-03-13 | 1985-09-30 | Sanyo Electric Co Ltd | Manufacture of photovoltaic device |
| JPS61160979A (en) * | 1985-01-08 | 1986-07-21 | Sharp Corp | Manufacture of amorphous solar cell |
-
1987
- 1987-03-10 JP JP62053054A patent/JPH0815219B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPS63220577A (en) | 1988-09-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US5151255A (en) | Method for forming window material for solar cells and method for producing amorphous silicon solar cell | |
| JPH07130661A (en) | Method for producing amorphous silicon oxide thin film | |
| JPH0815220B2 (en) | Method for manufacturing photoelectric conversion element | |
| JPH0815219B2 (en) | Method for manufacturing photoelectric conversion element | |
| JP2575397B2 (en) | Method for manufacturing photoelectric conversion element | |
| JPH0719906B2 (en) | Method for manufacturing semiconductor device | |
| JP2659369B2 (en) | Photoelectric conversion element | |
| JP2688219B2 (en) | Photoelectric conversion element | |
| JP3201540B2 (en) | Solar cell and method of manufacturing the same | |
| JP3040247B2 (en) | Manufacturing method of silicon thin film | |
| JPH07183550A (en) | Amorphous photoelectric conversion element | |
| JPH0612835B2 (en) | Manufacturing method of photoelectric conversion element | |
| JPH0563223A (en) | Non-single crystal tandem solar cell manufacturing method and manufacturing apparatus used therefor | |
| JPH0714075B2 (en) | Method for manufacturing photoelectric conversion element | |
| JPH04192373A (en) | photovoltaic element | |
| Itozaki et al. | Amorphous Silicon-Germanium Deposited by Photo-CVD | |
| JPS59165468A (en) | Manufacturing method of window frame material for solar cells | |
| JP2688220B2 (en) | Amorphous solar cell | |
| JPH0815221B2 (en) | Method for manufacturing photoelectric conversion element | |
| JPH08181079A (en) | Method for forming amorphous semiconductor thin film | |
| JP2728874B2 (en) | Semiconductor device manufacturing method | |
| JPH0516655B2 (en) | ||
| JPH0519833B2 (en) | ||
| JPH0714074B2 (en) | Method for manufacturing photoelectric conversion element | |
| JPH0815222B2 (en) | Method for manufacturing photoelectric conversion element |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |