JPH0523024B2 - - Google Patents
Info
- Publication number
- JPH0523024B2 JPH0523024B2 JP60051514A JP5151485A JPH0523024B2 JP H0523024 B2 JPH0523024 B2 JP H0523024B2 JP 60051514 A JP60051514 A JP 60051514A JP 5151485 A JP5151485 A JP 5151485A JP H0523024 B2 JPH0523024 B2 JP H0523024B2
- Authority
- JP
- Japan
- Prior art keywords
- silicon semiconductor
- electrode
- light
- film
- thiophene
- 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 - Lifetime
Links
- 239000004065 semiconductor Substances 0.000 claims description 34
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 27
- 229910052710 silicon Inorganic materials 0.000 claims description 27
- 239000010703 silicon Substances 0.000 claims description 27
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Divinylene sulfide Natural products C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims description 9
- 229930192474 thiophene Natural products 0.000 claims description 8
- 229920000642 polymer Polymers 0.000 claims description 6
- 125000001931 aliphatic group Chemical group 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 12
- QENGPZGAWFQWCZ-UHFFFAOYSA-N 3-Methylthiophene Chemical compound CC=1C=CSC=1 QENGPZGAWFQWCZ-UHFFFAOYSA-N 0.000 description 10
- -1 aliphatic thiophene derivative Chemical class 0.000 description 9
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 8
- 239000010408 film Substances 0.000 description 7
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- 239000010409 thin film Substances 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 229910052736 halogen Inorganic materials 0.000 description 4
- 150000002367 halogens Chemical class 0.000 description 4
- 229910052697 platinum Inorganic materials 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 230000000379 polymerizing effect Effects 0.000 description 3
- 239000003115 supporting electrolyte Substances 0.000 description 3
- YNJQKNVVBBIPBA-UHFFFAOYSA-M tetrabutylazanium;trifluoromethanesulfonate Chemical compound [O-]S(=O)(=O)C(F)(F)F.CCCC[N+](CCCC)(CCCC)CCCC YNJQKNVVBBIPBA-UHFFFAOYSA-M 0.000 description 3
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000001678 irradiating effect Effects 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- 229920006254 polymer film Polymers 0.000 description 2
- 239000005297 pyrex Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- KWMRVTDUWMBHRV-UHFFFAOYSA-N 3,4-diethylthiophene Chemical compound CCC1=CSC=C1CC KWMRVTDUWMBHRV-UHFFFAOYSA-N 0.000 description 1
- GPSFYJDZKSRMKZ-UHFFFAOYSA-N 3,4-dimethylthiophene Chemical compound CC1=CSC=C1C GPSFYJDZKSRMKZ-UHFFFAOYSA-N 0.000 description 1
- FPFSGDXIBUDDKZ-UHFFFAOYSA-N 3-decyl-2-hydroxycyclopent-2-en-1-one Chemical compound CCCCCCCCCCC1=C(O)C(=O)CC1 FPFSGDXIBUDDKZ-UHFFFAOYSA-N 0.000 description 1
- SLDBAXYJAIRQMX-UHFFFAOYSA-N 3-ethylthiophene Chemical compound CCC=1C=CSC=1 SLDBAXYJAIRQMX-UHFFFAOYSA-N 0.000 description 1
- QZNFRMXKQCIPQY-UHFFFAOYSA-N 3-propylthiophene Chemical compound CCCC=1C=CSC=1 QZNFRMXKQCIPQY-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 229910021417 amorphous silicon Inorganic materials 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- GTKRFUAGOKINCA-UHFFFAOYSA-M chlorosilver;silver Chemical compound [Ag].[Ag]Cl GTKRFUAGOKINCA-UHFFFAOYSA-M 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 230000015843 photosynthesis, light reaction Effects 0.000 description 1
- 229920000128 polypyrrole Polymers 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/20—Light-sensitive devices
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
- C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
- C08G61/123—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds
- C08G61/126—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds with a five-membered ring containing one sulfur atom in the ring
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/50—Processes
- C25B1/55—Photoelectrolysis
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M14/00—Electrochemical current or voltage generators not provided for in groups H01M6/00 - H01M12/00; Manufacture thereof
- H01M14/005—Photoelectrochemical storage cells
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
-
- 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
- Y02E10/546—Polycrystalline silicon PV cells
-
- 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
- Y02E10/548—Amorphous silicon PV cells
-
- 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
- Y02E10/549—Organic PV cells
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
- Y02P20/133—Renewable energy sources, e.g. sunlight
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Electrochemistry (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Power Engineering (AREA)
- Health & Medical Sciences (AREA)
- Metallurgy (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Materials Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Inorganic Chemistry (AREA)
- Photovoltaic Devices (AREA)
- Hybrid Cells (AREA)
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
Description
【発明の詳細な説明】
(a) 技術分野の説明
本発明は、エネルギー利用技術に関するもので
あり、詳しく言えば、光エネルギーを電気エネル
ギーなどに変換する湿式光電池に用いられる被覆
シリコン半導体電極の製造方法に関するものであ
る。[Detailed Description of the Invention] (a) Description of the Technical Field The present invention relates to energy utilization technology, and more specifically, to the production of coated silicon semiconductor electrodes used in wet photovoltaic cells that convert light energy into electrical energy, etc. It is about the method.
(b) 従来技術の説明
半導体電極を用いた湿式光電池は、光エネルギ
ーを電気エネルギーに変換するためのものとし
て、また、水の光分解による水素の製造など、す
なわち化学エネルギーへの変換のためのものとし
て注目されている。しかし、半導体電極を電解質
溶液に浸漬するために、半導体が電解質溶液に溶
解したり、酸化されたりして、電極の寿命の短縮
や性能の急速な低下を招く場合が多いという欠点
をもつている。特に、シリコン半導体を動作電極
として、光照射して電気エネルギーへの変換を行
つた場合には、数秒間で電極表面にSiO2の膜が
生成し、急激な性能の劣化が起こる。これらの問
題点を解決するため、従来から半導体電極表面を
金などの貴金属の薄膜で被覆する方法（例えば、
Y.Nakato，K.Abe，H.Tsubomura，Ber.
Bunsenges.Phys.Chem，80，1002（1976））や、
ポリピロールなどの導電性高分子の薄膜で被覆す
る方法（例えば、R.Noufi，D.Tench，L.F.
Warren，J.Electrochem.Soc.128，2596（1981））
が試みられているが、均一な厚さの膜を生成する
ことが困難であつたり、また被覆電極を長時間使
用した場合には、被覆の剥離などが起こり、十分
な解決を見るには至つていないのが現状である。(b) Description of the prior art Wet photovoltaic cells using semiconductor electrodes are used for converting light energy into electrical energy, and also for producing hydrogen by photolysis of water, that is, for converting it into chemical energy. It is attracting attention as a thing. However, since the semiconductor electrode is immersed in the electrolyte solution, the semiconductor often dissolves in the electrolyte solution or becomes oxidized, resulting in shortened electrode life and rapid deterioration of performance. . In particular, when a silicon semiconductor is used as a working electrode and light is irradiated to convert it into electrical energy, a SiO 2 film is formed on the electrode surface within a few seconds, resulting in rapid performance deterioration. To solve these problems, a conventional method has been to coat the surface of a semiconductor electrode with a thin film of a noble metal such as gold (for example,
Y. Nakato, K. Abe, H. Tsubomura, Ber.
Bunsenges.Phys.Chem, 80 , 1002 (1976)) and
A method of coating with a thin film of conductive polymer such as polypyrrole (for example, R. Noufi, D. Tench, LF
Warren, J.Electrochem.Soc. 128 , 2596 (1981))
However, it is difficult to produce a film with a uniform thickness, and if a coated electrode is used for a long time, the coating may peel off, so it is difficult to find a satisfactory solution. The current situation is that this is not the case.
(c) 発明の目的
本発明は上記の点に鑑み、長時間の使用におい
ても安定な性能をもつた被覆シリコン半導体電極
を製造することを目的とする。(c) Object of the Invention In view of the above points, the object of the present invention is to manufacture a coated silicon semiconductor electrode that has stable performance even during long-term use.
(d) 発明の構成
この目的は本発明によれば、シリコン半導体の
表面において、チオフエンの脂肪族誘導体を光照
射と同時に電解重合して、その重合体の膜を生成
することによつて達成される。(d) Structure of the Invention According to the present invention, this object is achieved by electrolytically polymerizing an aliphatic derivative of thiophene on the surface of a silicon semiconductor simultaneously with light irradiation to produce a film of the polymer. Ru.
まず、シリコン半導体としては、単結晶または
多結晶または無定形のシリコンにリン、アンチモ
ンなどをドープして半導体をもたせたものが用い
られる。 First, as the silicon semiconductor, single crystal, polycrystal, or amorphous silicon is doped with phosphorus, antimony, etc. to provide a semiconductor.
チオフエンの脂肪族誘導体としては、チオフエ
ン、３−メチルチオフエン、３−エチルチオフエ
ン、３−プロピルチオフエン、３，４−ジメチル
チオフエン、３，４−ジエチルチオフエンなどを
用いることができる。 As aliphatic derivatives of thiophene, thiophene, 3-methylthiophene, 3-ethylthiophene, 3-propylthiophene, 3,4-dimethylthiophene, 3,4-diethylthiophene, etc. can be used.
次に、シリコン半導体の表面において、チオフ
エン脂肪族誘導体を電解重合して、その重合体の
膜を生成させるには、まず精製したアセトニトリ
ルなどの溶媒にチオフエンの脂肪族誘導体を溶解
し、さらに支持電解質として、トリフルオロメタ
ンスルホン酸テトラブチルアンモニウムなどを添
加した溶液を調製する。これにフツ化水素酸で表
面をエツチングしたシリコン半導体電極と白金な
どの対極を入れ、ハロゲンランプなどの光源から
の光をシリコン半導体表面に照射すると同時に、
シリコン半導体に正の電圧を加えて、その表面に
おいて電解重合させるのである。ここにおいて、
単にシリコン半導体表面に光を照射する操作、又
は、単にシリコン半導体に正の電圧を加えて、そ
の表面において電解重合させる操作では、シリコ
ン半導体表面を被覆する均一な厚さのチオフエン
の脂肪族誘導体の重合体膜を形成することはでき
ず、光照射と同時に電解重合することによつて、
はじめて均一な膜が得られるのである。 Next, in order to electrolytically polymerize a thiophene aliphatic derivative on the surface of a silicon semiconductor to form a film of the polymer, the aliphatic thiophene derivative is first dissolved in a solvent such as purified acetonitrile, and then a supporting electrolyte is added. A solution is prepared by adding tetrabutylammonium trifluoromethanesulfonate. A silicon semiconductor electrode whose surface has been etched with hydrofluoric acid and a counter electrode such as platinum are placed in this, and at the same time the silicon semiconductor surface is irradiated with light from a light source such as a halogen lamp.
A positive voltage is applied to a silicon semiconductor to cause electrolytic polymerization on its surface. put it here,
In the operation of simply irradiating the silicon semiconductor surface with light, or simply applying a positive voltage to the silicon semiconductor and electrolytically polymerizing it on the surface, a uniform thickness of aliphatic derivative of thiophene is coated on the silicon semiconductor surface. It is not possible to form a polymer film, but by electrolytically polymerizing at the same time as light irradiation,
Only then can a uniform film be obtained.
ここで用いる光源としては、ハロゲンランプ、
タングステンランプ、キセノンランプ、水銀灯な
どのほか、太陽光でもよい。 The light source used here is a halogen lamp,
In addition to tungsten lamps, xenon lamps, mercury lamps, etc., sunlight may also be used.
また、支持電解質としては、上記トリフルオロ
メタンスルホン酸テトラブチルアンモニウムのほ
か、テトラフルオロホウ酸テトラブチルアンモニ
ウム、ヘキサフルオロリン酸テトラブチルアンモ
ンニウムなどが用いられる。 Further, as the supporting electrolyte, in addition to the above-mentioned tetrabutylammonium trifluoromethanesulfonate, tetrafluoroborate tetrabutylammonium, hexafluorophosphate tetrabutylammonium, etc. are used.
溶媒としては、アセトニトリルのほか、ニトロ
ベンゼン、ニトロメタンなどでもよい。 In addition to acetonitrile, nitrobenzene, nitromethane, etc. may be used as the solvent.
このように光照射を伴う電解重合によりシリコ
ンの表面に生成したチオフエン化合物ポリマーの
膜は支持電解質として用いた化合物の成分イオン
（例えばトリフルオロメタンスルホン酸イオン）
を含むため、高度の導電性を有する。また、通
常、半導体の表面に電解重合により、均一な膜を
形成することは、半導体の溶解、酸化などが起こ
るため困難であるが、本発明の方法によれば、容
易に均一な薄膜が得られる。一般にシリコン半導
体はきわめて酸化されやすく、湿式光電池の動作
電極として電解質中で用い、光照射した場合には
数秒間以内に光電流が極度に減衰することが知ら
れているが、本発明の方法によりシリコン半導体
表面に形成された均一な膜は、長時間にわたつて
保護効果を示し、電極の性能は安定であつた。
（参考例参照）
(e) 発明の実施例
以下、本発明の代表的な実施例を示す。 In this way, the thiophene compound polymer film produced on the surface of silicon by electrolytic polymerization accompanied by light irradiation contains component ions of the compound used as the supporting electrolyte (e.g. trifluoromethanesulfonate ion).
It has a high degree of conductivity. Furthermore, it is normally difficult to form a uniform film on the surface of a semiconductor by electrolytic polymerization because the semiconductor dissolves, oxidizes, etc. However, according to the method of the present invention, a uniform thin film can be easily obtained. It will be done. In general, silicon semiconductors are extremely susceptible to oxidation, and when used in an electrolyte as a working electrode in a wet photovoltaic cell and irradiated with light, it is known that the photocurrent is extremely attenuated within a few seconds. The uniform film formed on the silicon semiconductor surface exhibited a protective effect over a long period of time, and the electrode performance was stable.
(See Reference Examples) (e) Examples of the Invention Typical examples of the present invention will be shown below.
実施例 １
精製した３−メチルチオフエン2.5gとトリフル
オロメタンスルホン酸テトラブチルアンモニウム
0.5gを精製したアセトニトリル29mlに溶解し、パ
イレツクス・ガラス製容器に入れ、これに白金電
極とフツ化水素酸であらかじめエツチングしたｎ
型単結晶シリコン半導体電極を浸漬し、アルゴン
ガスを６分間吹込んだ。このガラス製容器の外部
からシリコン半導体電極の表面にハロゲンランプ
の光を33.2mW／cm2の強度で照射すると同時に、
3.2ボルトの電圧をシリコン半導体電極に印加し
て、４分間電解重合したところ、シリコン半導体
の表面にトリフルオロメタンスルホン酸イオンを
含んだ３−メチルチオフエン・ポリマーの薄い膜
が生成した。なお、電解重合の際の電流はシリコ
ン半導体表面１cm2当り2.4〜0.83mAであつた。Example 1 2.5 g of purified 3-methylthiophene and tetrabutylammonium trifluoromethanesulfonate
Dissolve 0.5 g in 29 ml of purified acetonitrile and place in a Pyrex glass container, to which a platinum electrode and an etched nanotube pre-etched with hydrofluoric acid are added.
A type single-crystal silicon semiconductor electrode was immersed, and argon gas was blown in for 6 minutes. At the same time, the surface of the silicon semiconductor electrode is irradiated with light from a halogen lamp at an intensity of 33.2 mW/cm 2 from the outside of this glass container.
When a voltage of 3.2 volts was applied to the silicon semiconductor electrode and electrolytic polymerization was performed for 4 minutes, a thin film of 3-methylthiophene polymer containing trifluoromethanesulfonate ions was formed on the surface of the silicon semiconductor. The current during electrolytic polymerization was 2.4 to 0.83 mA per cm 2 of the silicon semiconductor surface.
実施例 ２
精製した３−メチルチオフエン2.5gとテトラフ
ルオロホウ酸テトラブチルアンモニウム0.42gを
精製したアセトニトリル29mlに溶解し、パイレツ
クス・ガラス製容器に入れ、これに白金電極とフ
ツ化水素酸であらかじめエツチングしたｎ型単結
晶シリコン半導体電極を浸漬し、アルゴンガスを
６分間吹込んだ。これに実施例１と同様の方法
で、112mW／cm2の強度で光照射すると同時に、
3.8ボルトの電圧をシリコン半導体に印加して、
１分間電解重合したところ、シリコン半導体の表
面にテトラフルオロホウ酸イオンを含んだ３−メ
チルチオフエン・ポリマーの薄い膜が生成した。
電解重合の際の電流はシリコン半導体表面１cm2当
り5.2〜3.3mAであつた。Example 2 2.5 g of purified 3-methylthiophene and 0.42 g of tetrabutylammonium tetrafluoroborate were dissolved in 29 ml of purified acetonitrile, placed in a Pyrex glass container, and etched in advance with a platinum electrode and hydrofluoric acid. The n-type single-crystal silicon semiconductor electrode thus prepared was immersed, and argon gas was blown therein for 6 minutes. This was irradiated with light at an intensity of 112 mW/cm 2 in the same manner as in Example 1, and at the same time,
By applying a voltage of 3.8 volts to a silicon semiconductor,
When electropolymerized for 1 minute, a thin film of 3-methylthiophene polymer containing tetrafluoroborate ions was formed on the surface of the silicon semiconductor.
The current during electrolytic polymerization was 5.2 to 3.3 mA per cm 2 of the silicon semiconductor surface.
参考例 １
光照射用の窓をもつガラス製容器に硫酸ナトリ
ウム、硫酸第１鉄、硫酸第２鉄アンモニウムそれ
ぞれ0.1モル／、硫酸0.12モル／を含む水溶
液（PH1.0）を入れ、これに実施例１で得られた
被覆シリコン半導体電極、銀−塩化銀比較電極及
び白金の対極を浸漬し、ハロゲンランプの光を
33.2mW／cm2の強度で照射して、光電流を測定し
た。照射開始後１時間における光電流の減衰率は
8.6％であつた。なお被覆しないシリコン電極の
光電流の減衰率は１分間でほぼ100％であつた。Reference example 1 An aqueous solution (PH 1.0) containing 0.1 mol/each of sodium sulfate, ferrous sulfate, and ferric ammonium sulfate and 0.12 mol/of sulfuric acid was placed in a glass container with a window for light irradiation. The coated silicon semiconductor electrode obtained in Example 1, the silver-silver chloride comparison electrode, and the platinum counter electrode were immersed and exposed to light from a halogen lamp.
The photocurrent was measured by irradiating with an intensity of 33.2 mW/cm 2 . The decay rate of photocurrent for 1 hour after the start of irradiation is
It was 8.6%. Note that the photocurrent attenuation rate of the uncoated silicon electrode was approximately 100% in 1 minute.
(f) 発明の効果
本発明による被覆シリコン半導体電極は湿式光
電池の動作電極として用いる場合、電解質水溶液
中においても安定で良好な性能を有し、また接着
性の良いチオフエン化合物ポリマーを被覆したも
のであるため、被膜の剥離が起こらず、長時間の
使用に耐えることができる。これを用いて湿式光
電池を組立てれば、太陽エネルギーを電気エネル
ギーなどに変換して利用することが可能である。(f) Effects of the invention When the coated silicon semiconductor electrode of the present invention is used as a working electrode of a wet photovoltaic cell, it is stable and has good performance even in an electrolyte aqueous solution, and is coated with a thiophene compound polymer that has good adhesive properties. Because of this, the coating does not peel off and can withstand long-term use. If a wet photovoltaic cell is assembled using this, solar energy can be converted into electrical energy and used.
Claims (1)
の脂肪族誘導体を光照射と同時に電解重合して、
その重合体の膜を生成させることを特徴とする被
覆シリコン半導体電極の製造方法。1 On the surface of a silicon semiconductor, an aliphatic derivative of thiophene is electrolytically polymerized simultaneously with light irradiation,
A method for producing a coated silicon semiconductor electrode, comprising producing a film of the polymer.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60051514A JPS61211964A (en) | 1985-03-14 | 1985-03-14 | Manufacture of coated silicon semiconductor electrode |
| US06/838,822 US4647348A (en) | 1985-03-14 | 1986-03-12 | Method for production of film-coated silicon semiconductor electrode |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60051514A JPS61211964A (en) | 1985-03-14 | 1985-03-14 | Manufacture of coated silicon semiconductor electrode |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61211964A JPS61211964A (en) | 1986-09-20 |
| JPH0523024B2 true JPH0523024B2 (en) | 1993-03-31 |
Family
ID=12889112
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60051514A Granted JPS61211964A (en) | 1985-03-14 | 1985-03-14 | Manufacture of coated silicon semiconductor electrode |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS61211964A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02292872A (en) * | 1989-05-02 | 1990-12-04 | Agency Of Ind Science & Technol | Manufacture of stabilized semiconductor electrode |
-
1985
- 1985-03-14 JP JP60051514A patent/JPS61211964A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS61211964A (en) | 1986-09-20 |
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