JPS61278174A - Manufacture of photoelectric conversion device - Google Patents
Manufacture of photoelectric conversion deviceInfo
- Publication number
- JPS61278174A JPS61278174A JP60120196A JP12019685A JPS61278174A JP S61278174 A JPS61278174 A JP S61278174A JP 60120196 A JP60120196 A JP 60120196A JP 12019685 A JP12019685 A JP 12019685A JP S61278174 A JPS61278174 A JP S61278174A
- Authority
- JP
- Japan
- Prior art keywords
- type
- polyacetylene
- photoelectric conversion
- type polymer
- polymer semiconductor
- 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
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
- 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
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、Ｐ型、 Ｋｌ型半導体とも高分子化合物から
なるｐ −１１へテロ接合型光電変換素子を製造する方
法に関するものである。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a method for manufacturing a p-11 heterojunction photoelectric conversion element made of a polymer compound for both P-type and Kl-type semiconductors.
近年、高分子化合物に電気的機能を付与し、光電変換素
子、ダイオード、トランジスタ、光センサー等のデバイ
スに利用しようとする試みが行なわれている。In recent years, attempts have been made to impart electrical functions to polymer compounds and use them in devices such as photoelectric conversion elements, diodes, transistors, and optical sensors.
その中でも、太陽電池へ応用することができる光電変換
素子に関しては、ポリアセチレン、ポリピロール、ポリ
チェニレンな、どの導電性高分子を使用したｐ−■墓へ
テロ接合型光電変換素子が報告されている。Among them, with respect to photoelectric conversion elements that can be applied to solar cells, p-type heterojunction type photoelectric conversion elements using conductive polymers such as polyacetylene, polypyrrole, and polythenylene have been reported.
例えば、Ｐ型、！１型型半体ともポリアセチレンを使用
したものあるいは本発明者らが先に提案したＩｆ型ポリ
アセチレンとポリピロール系化合物またはポリチェニレ
ン系化合物の一方または双方から成るｐ型高分子半導体
とｆＣＣ分会たもの（特願昭５９−２４７０８４号）な
どが挙げられる。このような高分子化合物を使用した光
電変換素子は。For example, type P! The type 1 halves both use polyacetylene, or the p-type polymer semiconductor consisting of If-type polyacetylene and one or both of polypyrrole-based compound or polythenylene-based compound and fCC branch (specially proposed by the present inventors). (No. 59-247084). Photoelectric conversion elements using such polymer compounds.
従来のシリコン等の無機化合物を使用した素子に比べて
、軽量性、柔軟性に優れており、しかも大面積化が可能
である。Compared to conventional devices using inorganic compounds such as silicon, they are lighter and more flexible, and can be made larger in area.
このｐ型、 １Ｌ型型半体とも高分子化合物よりなる光
電変換素子は、一般にｐ型高分子半導体とｎ型高分子半
導体とを接合して、＃造されている。Both the p-type and 1L-type halves are made of a polymer compound, and the photoelectric conversion element is generally manufactured by bonding a p-type polymer semiconductor and an n-type polymer semiconductor.
ｐ型とｎ型の高分子半導体の接合としては、（４）プレ
ス等により圧着、接着する方法、 （Ａ） ｐ型高分子
−半導体上でチーグラ型触媒を用いてポリアセチレン金
重合させて、その後練ポリアセチレンをｒＩ型に機能化
させる方法、 （ｃ） １に型高分子半導体上にｐ型高
分子半導体を直接電解重合させる方法などが考えられて
いる（０ 、に、Ｏｈｉ４ｎｇら、Ａｐｐｌ・ｐｈｙｓ
、 Ｌｅｔｔｅｒ 、３３（ＩＬ １８ 、１９７８
、特開昭５５−１３０１６０．１５０１６１．１５８８
７０．１３８８７ｉ、１５８８７９．１４６９８２゜１
５４７８Ｑ号公報）。The p-type and n-type polymer semiconductors can be joined by (4) pressure bonding and adhesion using a press, etc., (A) polyacetylene gold polymerization using a Ziegler catalyst on the p-type polymer-semiconductor, and then A method of functionalizing refined polyacetylene into rI type, and (c) a method of directly electrolytically polymerizing a p-type polymer semiconductor on a 1-type polymer semiconductor are being considered.
, Letter, 33 (IL 18, 1978
, JP-A-55-130160.150161.1588
70.13887i, 158879.146982゜1
5478Q Publication).
しかしながら、上記の（ａ）方法では２両高分子半導体
を完全に接触させることはできず、接合力は低く、更に
接触を編めるために圧力を加えると。However, in the above method (a), it is not possible to bring the two polymer semiconductors into complete contact, and the bonding force is low, and if pressure is applied to further form the contact.
素子自体の破壊をまねいてしまう。また（ｂ）方法では
、ｐ型高分子半導体に触媒を塗布するため、ｐ型半導体
の劣化をまねき、しかも残存触媒により光！変換効率が
低下してしまう、、 （Ｃ）方法においては、ｐ型高分
子半導体の電解重合時に正極としてＩｌ型高分子半導体
を使用するため、このｎ型半導体の劣化が滅しく、光電
変換効率が低下してしまう。This may lead to destruction of the element itself. In addition, in method (b), since a catalyst is applied to the p-type polymer semiconductor, it causes deterioration of the p-type semiconductor, and furthermore, the remaining catalyst causes a loss of light! In method (C), since an Il-type polymer semiconductor is used as a positive electrode during electrolytic polymerization of a p-type polymer semiconductor, the deterioration of this n-type semiconductor is unlikely, and the photoelectric conversion efficiency is reduced. will decrease.
上記のように従来の方法では、Ｐ型半導体とｎ型半導体
との不完全な接合あるいは半導体基材の劣化などの問題
があり、光ｗＬ斐換効率の高い素子を得ることはできな
い。As described above, in the conventional method, there are problems such as incomplete bonding between the P-type semiconductor and the n-type semiconductor or deterioration of the semiconductor substrate, and it is not possible to obtain an element with high light wL exchange efficiency.
本発明は、上記従来の問題点を解消し、ｐ型とｌＩ型と
の接合力が極めて強く、かつ光電変換効率の高いｐ型・
ｎ型へテロ接合型光電変換素子を製造する方法を提供し
ようとするものである。The present invention solves the above-mentioned conventional problems, and provides an extremely strong bonding force between p-type and II-type, as well as a high photoelectric conversion efficiency.
The present invention aims to provide a method for manufacturing an n-type heterojunction photoelectric conversion element.
本発明は、ｐｍ高分子半導体とポリアセチレンから成る
Ｉｔ型高分子半導体とのｐ−ｎｇ会の光電変換素子を製
造する方法でおって、！１１型高子半導体の基材を有機
溶媒で膨潤させると共にｐ型高分子半導体と接触させて
、しかる後練基材を乾燥することによりｐ型高分子半導
体と上記基材とを接合させることを特徴とするものであ
る。The present invention is a method for manufacturing a p-ng photoelectric conversion element of a pm polymer semiconductor and an It type polymer semiconductor made of polyacetylene, comprising: The base material of the 11-type polymer semiconductor is swollen with an organic solvent and brought into contact with the p-type polymer semiconductor, and the p-type polymer semiconductor and the base material are bonded by drying the post-mixed base material. This is a characteristic feature.
なお９本発明にかかる１１型高分子半導体の基材は、ｐ
型高分子半導体に接触させる前にｘｉ ｍに機能化させ
てもよく、またｐ型高分子半導体と接触あるいは乾燥さ
せた後１１ｍに機能化させてもよい。9 The base material of the 11-type polymer semiconductor according to the present invention is p
The xi m may be functionalized before contacting with the p-type polymer semiconductor, or the 11 m may be functionalized after contacting or drying with the p-type polymer semiconductor.
本発明において、ｐ型高分子半導体はｎ ｍ高分子半導
体と対になり、ｐ型・ｎ型へテロ接合の光電変換素子を
形成するものである。In the present invention, a p-type polymer semiconductor is paired with an nm polymer semiconductor to form a p-type/n-type heterojunction photoelectric conversion element.
該ｐ型高分子半導体を構成する高分子化合物としては、
ポリピロール系化合物、ポリチェニレン系化合物、ポリ
７ラン系化合物、ポリアニリン系化合物、ポリアズレン
系化合物等が挙げられる。As the polymer compound constituting the p-type polymer semiconductor,
Examples include polypyrrole compounds, polythenylene compounds, poly7rane compounds, polyaniline compounds, and polyazulene compounds.
例えば、上記ポリピロール系化合物とはポリピロー／ｖ
、ポリーＮ−メチルビロール、ポリーＮ−二千ルビロー
ル等であり、ポリチェニレン系化合物とはボリチェニＶ
７．ポリー６−メチｌレチェニレン、ボＵ−３、４−ツ
メチルチェニレン等であり、ポリ７ラン未化合物とはポ
リフラン等であり。For example, the polypyrrole compound mentioned above is polypyrrole/v
, poly-N-methylpyrrol, poly-N-2,000-ruvirol, etc., and polythenylene-based compounds include polythenylene V
7. These include poly-6-methyl-rechenylene, bo-U-3,4-methyl-chenylene, etc., and the poly-7-ran uncompounds include polyfuran and the like.
ポリアニリン系化合物とはポリアニリン、ポリー〇−ヨ
ード７ニリン、ポリー〇−ブロモアニリン等であり、ポ
リアズレン系化廿物とはポリアズレン、 １１−ブチル
アズレン、アミノアズレン等である。しかして、これら
高分子化合物は１種または２種以上を使用する。なお２
種以上の高分子化合物を使用する場合には、その混合重
会体でも共重合体でも使用することができる。The polyaniline compounds include polyaniline, poly(0-iodo-7-niline), poly(0-bromoaniline), and the like, and the polyazulene compounds include polyazulene, 11-butylazulene, aminoazulene, and the like. Therefore, one type or two or more types of these polymer compounds are used. Note 2
When using more than one type of polymer compound, a mixed polymer or copolymer thereof can be used.
上記高分子化合物をｐ型に機能化させる方法としては、
該高分子化合物の電解置台と同時にドーピング剤がドー
ピングされることを利用するのがよい。As a method for functionalizing the above-mentioned polymer compound into p-type,
It is preferable to utilize the fact that the doping agent is doped at the same time as the electrolytic stand for the polymer compound.
この方法は、上記高分子化合物の単量体とドーピング剤
とをｆ４解させた電解液中に正電極及び負電極を浸漬し
て、該電解液に直流電流を通電することにより正電極上
に高分子化合物が析出するもの、である。該高分子化合
物は電解液中のドーピング剤をとり込みＰ型に機能化し
ている。この正電極に酸化インジウム、酸化スズ等の透
明材料を使用すると光電変換素子の電極としてそのまま
使用することができる。また２通常する直流電流は。In this method, a positive electrode and a negative electrode are immersed in an electrolytic solution in which a monomer of the polymer compound and a doping agent have been dissolved in F4, and a direct current is passed through the electrolytic solution, so that a direct current is applied to the positive electrode. This is one in which a polymer compound precipitates. The polymer compound takes in the doping agent in the electrolyte and is functionalized into a P-type. If a transparent material such as indium oxide or tin oxide is used for this positive electrode, it can be used as it is as an electrode of a photoelectric conversion element. Also, the direct current that normally occurs is 2.
その電流密度が正電極単位面積当り１〜１０ ｒｎＡ／
ｌ噛の範囲内が望ましい。The current density is 1 to 10 rnA/per unit area of the positive electrode.
It is desirable that it be within the range of 1 bit.
また、上記高分子化合物をＰ型に機能化させるドーピン
グ剤としては、過塩素酸塩、四フッ化ホウ酸塩、六７ツ
化リン酸塩等がある。例えば、過塩素酸塩は、過塩素酸
銀、過塩素酸ナトＩＪウム。Doping agents for functionalizing the above-mentioned polymer compound into P-type include perchlorates, tetrafluoroborates, hexagonal phosphates, and the like. For example, perchlorates include silver perchlorate and sodium perchlorate.
過塩素酸テトラメチルアンモニウム等が挙ケラれ。Examples include tetramethylammonium perchlorate.
四７ツ化ホウ酸朧は、四フッ化ホウ酸ナトリウム。Tetrafluoroboric acid oboro is sodium tetrafluoroborate.
四７ツ化ホウ酸テトラメチルアンモニウム、四フッ化ホ
ウ酸テトラブチルアンモニウム等が挙ケラれ、六７ツ化
リン酸塩は、六７ツ化リン酸ナトリウム、六フッ化りｙ
ｄテトラメチ／レアンモニウム。Examples include tetramethylammonium tetrafluoroborate, tetrabutylammonium tetrafluoroborate, etc., and hexafluoride phosphates include sodium hexafluoride phosphate, sodium hexafluoride phosphate, etc.
dTetramethy/leammonium.
六７ツ化リン酸テトラブチルアンモニウム等が挙げられ
る。しかして、これらドーピング剤は１種または２種以
上を使用する。Examples thereof include tetrabutylammonium hexagonal phosphate. Therefore, these doping agents may be used alone or in combination of two or more.
上記ドーピング剤のドーピング量は、前記高分子化合物
１モルに対して０．０１〜Ｃ１，５七〜の範囲内が望ま
しい、該ドーピング量がａ、０１モル未満の場合、高分
子化合物がｐ型に機能しがたく、他方、α３モＡ／を越
える場合、ドーピング量に見合うだけの比抵抗の低下が
凭られない１．なｐ、比抵抗に換算した場合、ｐ型高分
子半導体が１０〜１０婁Ω・備の範囲内となるようにド
ーピングするのがよい。The doping amount of the doping agent is preferably within the range of 0.01 to C1,57 to 1 mole of the polymer compound.If the doping amount is less than a,01 mole, the polymer compound is of p-type. On the other hand, if α3moA/ is exceeded, the specific resistance cannot be reduced by an amount commensurate with the amount of doping.1. It is preferable to dope the p-type polymer semiconductor so that the p-type polymer semiconductor has a specific resistance of 10 to 10 ohms.
また、該ｐ型高分子半導体の形状としては、板状または
膜状で使用するのが操作の容易性より望ましい。その場
合の厚さは、１０１〜Ｉ Ｑ ｐｉｎの範囲内が望まし
い。その厚さが１０１μＩｎ未満ではｐ型ドーピング剤
とｆｌ型ドーピング剤との拡散により絶縁相が形成され
、高分子化合物がｐ型に機能しにくくなり、しかも収り
扱いが困難である。Further, as for the shape of the p-type polymer semiconductor, it is preferable to use it in the form of a plate or a film for ease of operation. In that case, the thickness is preferably within the range of 101 to IQ pin. If the thickness is less than 101 μIn, an insulating phase is formed due to diffusion of the p-type doping agent and the fl-type doping agent, making it difficult for the polymer compound to function as a p-type, and moreover, it is difficult to accommodate and handle it.
他方、厚さが１０μｆｉｌを越える場合には、照射光を
ｐ調高分子半導体から入射させる際に光の吸収が大きく
なり、接合界面まで光が透過せず、光起電力が得られな
いおそれがある。更に優れた光電変換素子は０．１〜１
１．５μｒｎの厚さの範囲内で得られる。On the other hand, if the thickness exceeds 10 μfil, the absorption of light will be large when the irradiation light is incident from the p-tone polymer semiconductor, and there is a risk that the light will not be transmitted to the bonding interface and no photovoltaic force will be obtained. be. Even better photoelectric conversion elements are 0.1 to 1
Obtained within a thickness range of 1.5 μrn.
Ｔｌ型高分子半導体は上記ｐ型高分千半４体と対になる
ものである。The Tl-type polymer semiconductor is a pair of the above-mentioned p-type polymer semiconductor.
該Ｔｌ型高分子半導体を構成する高分子化合物としては
、ポリアセチレンを用いるｕ譲ボ＋ｓアｔチレンはシス
体でもトランス体でもどちらでも使用することができる
。As the polymer compound constituting the Tl-type polymer semiconductor, polyacetylene can be used in either the cis form or the trans form of u-containing polyester + s-atylene.
本発明において２口型高分子半導体の基材であるポリア
セチレンをまずｆ磯溶謀で膨潤させると共に前記ｐ調高
分子半導体と接触させる。In the present invention, polyacetylene, which is the base material of the two-port polymer semiconductor, is first swollen by f-isomerization and brought into contact with the p-tone polymer semiconductor.
上ｈＥ 有ｔＪｍ 溶には、ペンタン２ヘキサン、ベン
ゼン、トルエン等の無極性有秦溶諜、アセトン、アセト
ニトリル、ジメチルホルムアミド等の極性有’１ｋｔＢ
謀のいずれも使用することができ、それら有機溶媒のう
ちの１撫または２種以上を使用する。For the upper hE and tJm solutions, nonpolar solvents such as pentane, hexane, benzene, and toluene, and polar solvents such as acetone, acetonitrile, and dimethylformamide are used.
Any of these organic solvents may be used, and one or more of these organic solvents may be used.
しかし、望ましくは、非プロトン性の有機溶媒であるの
がよい。これはポリアセチレンはプロトンにより還元さ
れ、π共役型の２重結合構造が破壊され、かつｎ型ドナ
ーのドーピング剤が電子受容型のプロトンにより破壊さ
れるおそれがあるためである。更に理想的には、ポリア
セチレンの気液界面合成の際に使用したベキサンあるい
はヘキサンと相溶性のめるトルエンを使用するのがよい
。However, it is preferable to use an aprotic organic solvent. This is because polyacetylene is reduced by protons, the π-conjugated double bond structure is destroyed, and the n-type donor doping agent is likely to be destroyed by electron-accepting protons. More ideally, toluene, which is compatible with bexane or hexane used in the gas-liquid interfacial synthesis of polyacetylene, is preferably used.
また、ポリアセチレンとｐ調高分子半導体とを接触させ
る方法としては、ｐ型高分子半導体上にポリアセチレン
をしわがよらないように、しかもｐ型高分子半導体とポ
リアセチレンとの間に気体や異物が混入しないように均
一に接触させるだけでよい。したがって、ｐ型高分子半
導体とポリアセチレンとを加圧する必要はない。In addition, as a method for bringing polyacetylene into contact with a p-type polymer semiconductor, it is necessary to avoid wrinkles of the polyacetylene on the p-type polymer semiconductor, and to prevent gases or foreign substances from entering between the p-type polymer semiconductor and the polyacetylene. All you need to do is to make sure that they are in even contact. Therefore, there is no need to pressurize the p-type polymer semiconductor and polyacetylene.
なお９通常はポリアセチレンを前記有機溶媒で膨潤させ
た後、該ポリアセチレンをｐ型高分子半接触体を浸漬さ
せてポリアセチレンを膨潤させてもよいｕ更に有機溶媒
中でポリアセチレンとＰ機高分子半導体とを接触させる
こともできる。この場合、ｐ型窩分子半導体も有機溶媒
で膨潤する。9 Usually, after the polyacetylene is swollen in the organic solvent, the polyacetylene may be immersed in a p-type polymer semi-contact member to swell the polyacetylene. It is also possible to contact the In this case, the p-type cavity molecular semiconductor also swells with the organic solvent.
その後、上記有機溶媒で膨潤したポリアセチレンとｐ型
窩分子半導体との板触体のポリアセチレンを乾燥させる
。なお、前記のようにＰ機高分子半導体も膨潤している
場合は、該ｐ型窩分子半導体も乾燥させる。Thereafter, the polyacetylene swollen with the organic solvent and the p-type cavity molecule semiconductor are dried. Note that if the P-type polymer semiconductor is also swollen as described above, the p-type polymer semiconductor is also dried.
この乾燥により、高分子中に含浸している有機溶媒を蒸
発除去する。乾燥条件は、有機溶媒がほぼ完全に除去さ
れる範囲であり、その方法としては、自然乾燥あるいは
有機溶媒の蒸発速度を高めるために加熱乾燥により行な
う。なお、加熱乾燥の場合、加熱温度は２００°Ｃ以下
とするのが望ましい。２００°Ｃより高温であると、Ｐ
型、ｎ型の高分子半導体が劣化するおそれがある。This drying evaporates and removes the organic solvent impregnated into the polymer. The drying conditions are such that the organic solvent is almost completely removed, and the method is natural drying or heating drying to increase the evaporation rate of the organic solvent. In addition, in the case of heat drying, the heating temperature is preferably 200°C or less. If the temperature is higher than 200°C, P
There is a risk that the type and n-type polymer semiconductors may deteriorate.
！！型高分子半導体の基材であるポリアセチレンをＩＩ
型に機能化させるのは、ポリアセチレントＰ型高分子半
導体とを接触させる前でもよく、接触または乾燥後でも
よい。なお、接触した後にｎ型に暗能化させる場合には
、ポリアセチレンのみに！ｉｉ機能化処理を施す。! ! Polyacetylene, which is the base material of type polymer semiconductor, is
The mold may be functionalized before contacting with the polyacetylene P-type polymer semiconductor, or after contacting or drying. In addition, if you want to darken to n-type after contact, use only polyacetylene! ii) Perform functionalization treatment.
このポリアセチレンをＸｌ型に機能化させる方法として
は、ナトリウム−ナフタレンｉ体のＴＨＦ溶液に浸漬す
る方法、有機アミン化合物と金属アミドとの混会物をド
ーピング剤として、その炭化水素溶液を利用する方ｆ−
Ａ（特願昭５８−１８９６５８号、５９−６９００号、
５９−４２２７３号による。）、６るいはテトラメチル
アンモニウム塩、デトラエチルアンモニウム塩等のドー
ピング剤を電気的にドーピングする方法等が挙げられる
。Methods for functionalizing this polyacetylene into the Xl type include a method of immersing it in a THF solution of sodium-naphthalene i-form, and a method of using a mixture of an organic amine compound and a metal amide as a doping agent and a hydrocarbon solution thereof. f-
A (Patent Application No. 58-189658, No. 59-6900,
According to No. 59-42273. ), a method of electrically doping with a doping agent such as hexafluoride, tetramethylammonium salt, detraethylammonium salt, and the like.
該ポリアセチレンにドーピング剤をドーピングする量は
、ポリアセチレン１モルに対シて０．０１〜０．３モル
の範囲内が望ましい。該ドーピング量がＱ、０１モル未
満の場合、ポリアセチレンが１１５に機能しがたく、他
方、α３モルを越える場合。The amount of doping agent doped into the polyacetylene is preferably within the range of 0.01 to 0.3 mol per 1 mol of polyacetylene. When the doping amount is less than 1 mole of Q, polyacetylene has difficulty functioning as 115, while on the other hand, when it exceeds 3 moles of α.
ドーピングしただけの比抵抗の低下が見られない。No decrease in resistivity was observed due to doping.
なお、比抵抗に換算した場ｔｋ 、 ｎ型のポリアセチ
レンが１０−３〜１０１Ω・備の範囲内になるようにド
ーピングするのがよい。Note that it is preferable to dope the n-type polyacetylene so that the specific resistance, tk, falls within the range of 10<-3> to 10<1>[Omega].
また、ポリアセチレンの形状としては、膨潤時に膜状ま
たは板状で使用するのが操作の容易性より望ましい。こ
の膨潤時に膜状または・板状とした場合のその厚さとし
ては［Ｌ１μｍ〜１０ｆｌの範囲内が望ましい。その厚
さが［Ｌ１μｍ未満では、有機Ｉ＠謀を蒸発させた際に
、乾燥による収縮でポリアセチレンが破れるおそれがあ
り、しかも取り扱いが困難である。他方、厚さが１０ｍ
を越える場分、高分子化会物の利点である柔軟性が低下
するおそれがある。更に優れた光電変換機能は１μｒｎ
〜１ｆｌの厚さの範囲内で得られる。Further, as for the shape of the polyacetylene, it is preferable to use it in the form of a film or a plate during swelling for ease of operation. When it is formed into a membrane or plate shape during this swelling, its thickness is preferably in the range of 1 μm to 10 fl. If the thickness is less than 1 μm, there is a risk that the polyacetylene will be torn due to shrinkage due to drying when the organic I@plot is evaporated, and it will be difficult to handle. On the other hand, the thickness is 10m
If the amount exceeds this, there is a risk that the flexibility, which is an advantage of polymerized compounds, may be reduced. Even better photoelectric conversion function is 1μrn
Obtained within a thickness range of ~1 fl.
本発明により製造された光電変換素子は、金。The photoelectric conversion element manufactured according to the present invention is made of gold.
銀、銅、白金等の電極をそれぞれ１１型高分子半導体、
Ｐ型高分子半導体に接続し、光を照射して。Electrodes of silver, copper, platinum, etc. are each made of 11-type polymer semiconductor,
Connect it to a P-type polymer semiconductor and irradiate it with light.
使用される。この光照射により、 ｔｉ型嵩高分子半導
体ｐ型筒分子半導体との界面で電子の模勧が生じ、起電
力が発生する。used. By this light irradiation, electrons are stimulated at the interface between the Ti-type bulky polymer semiconductor and the P-type cylindrical molecule semiconductor, and an electromotive force is generated.
なお、この光電変換素子への光照射は、ｐ型高分子半導
体側から行なうのが、起電力が大きい。Note that the electromotive force is large when the photoelectric conversion element is irradiated with light from the p-type polymer semiconductor side.
そのため、ｐ型窩分子半導体は、照射光の透過率の大な
るもの全使用するのがよい。Therefore, it is preferable to use all p-type cavity molecular semiconductors that have a high transmittance to irradiated light.
本発明によれば、Ｐ型半導体とＩＩ ｍ半導体との接合
が強固な光電変換素子を簡便に製造することができる。According to the present invention, a photoelectric conversion element with a strong junction between a P-type semiconductor and a IIm semiconductor can be easily manufactured.
また本発明では、Ｐ型半導体と■１型型半体との接合に
際して、従来のごとき圧着等による外力を加えないため
、厚さが極めて薄く、シかも材料劣化の少ない光電変換
素子をｔＭ造することができる。In addition, in the present invention, when joining the P-type semiconductor and the 1-type half body, no external force is applied by crimping or the like as in conventional methods, so the photoelectric conversion element is extremely thin and has less material deterioration due to tM manufacturing. can do.
七のため、製造された光電変換素子の抵抗は低い。7, the resistance of the manufactured photoelectric conversion element is low.
従って２本発明では、充電変換効率の高い素子を製造す
ることができる。Therefore, in the present invention, an element with high charge conversion efficiency can be manufactured.
〔実施例〕 以下９本発明の詳細な説明する。〔Example〕 Hereinafter, nine aspects of the present invention will be described in detail.
実施例１゜
第１図及び第２図に示すような本実施例にががる光電変
換素子を形成した。なお、第１図は光電変換素子の斜視
図、第２図は第１図のｎ−ｍに沿う断面図である。Example 1 A photoelectric conversion element according to this example as shown in FIGS. 1 and 2 was formed. Note that FIG. 1 is a perspective view of the photoelectric conversion element, and FIG. 2 is a sectional view taken along line nm in FIG. 1.
まず、以丁のようにｗｔ解重合を利用してＰ型高分子半
導体を形成した。First, a P-type polymer semiconductor was formed using wt depolymerization as described in Itcho.
ピロール単量体とドーピング剤としての四７．：。47. Pyrrole monomer and as a doping agent. :.
化ホウ酸テトラブチルアンモニウムとをアセトニトリル
に溶解した溶液に正及び負電極を浸漬し。The positive and negative electrodes were immersed in a solution of tetrabutylammonium borate dissolved in acetonitrile.
該膜・負電極間に正電極単位面積当りａ ｒｎＡ ／
ｄの直流電流を約７秒間流した。なお正電極は導電性ネ
サガラス（Ｉｎ！０１ ） 、負ＴｊＬ極はステンレス
板を用いた。これにより正電極のネサガラス上に膜厚ｏ
、 ｏ ｓ ｐｒｎ 、長さ２０Ｍ１１Ｘ幅２０Ｍ１の
ポリピロール膜を析出させた。、該ポリピロール膜は比
抵抗が１０・口のｐｍ半導体であった。ｐ型ポリビロー
ＩＬ／膜は、電極に析出したままで光電変換素子に供し
た。Between the membrane and the negative electrode, a rnA / per unit area of the positive electrode
A direct current of d was applied for about 7 seconds. Note that conductive Nesa glass (In!01) was used for the positive electrode, and a stainless steel plate was used for the negative TjL electrode. This results in a film thickness of o on the Nesa glass of the positive electrode.
, o sprn , a polypyrrole film having a length of 20M11 and a width of 20M1 was deposited. The polypyrrole film was a pm semiconductor with a specific resistance of 10. The p-type polybillow IL/film was applied to the photoelectric conversion element while being deposited on the electrode.
次に以下のようにｎ型高分子半導体を形成した。Next, an n-type polymer semiconductor was formed as follows.
チーグラ型触媒を用いて合成し、ヘキサンで触媒を取り
除き精製して、ポリアセチレン膜を形成したＵ線膜はヘ
キサンで膨潤していた。The U-ray membrane, which was synthesized using a Ziegler type catalyst and purified by removing the catalyst with hexane to form a polyacetylene membrane, swelled with hexane.
次に２−アミノエチルアミノメチルトリメチｌレジラン
とリチウムアミドとを入れたトルエン溶液を６０分加熱
還流し、該溶液に上記膨潤ポリアセチレン膜を浸漬し、
膨潤１１型ボリアｔチレン膜を得た。該ｎ型ポリアセチ
レン膜はヘキサンとトルエンとで膨潤していた。なお該
ｎ＠ポリアセチレンは乾燥状態では膜厚が２０μｍであ
り、比抵抗が１０’Ω・αであった。Next, a toluene solution containing 2-aminoethylaminomethyltrimethyl resinane and lithium amide was heated to reflux for 60 minutes, and the swollen polyacetylene membrane was immersed in the solution.
A swollen type 11 boria t-tyrene membrane was obtained. The n-type polyacetylene film was swollen with hexane and toluene. Note that the n@polyacetylene had a film thickness of 20 μm in a dry state and a specific resistance of 10′Ω·α.
この膨潤したＩｌ型ポリアセチレン膜を前記電極に析出
した状態のｐ型ポリピロール膜上に被覆するように接触
させ、その後ｎ型ポリアセチレン膜を３０°Ｃで１２０
分間乾燥させて、ヘキサンとトルエンを除去した。これ
によりｎｍポリアセチレン膜とＰ型ポリピロール膜とが
密着してなる光電変換素子を製造した。This swollen Il-type polyacetylene film was brought into contact with the p-type polypyrrole film deposited on the electrode so as to cover it, and then the n-type polyacetylene film was heated at 30°C for 120°C.
The hexane and toluene were removed by drying for a minute. In this way, a photoelectric conversion element was manufactured in which the nm polyacetylene film and the P-type polypyrrole film were in close contact with each other.
該光電変換素子１は、第１図及び第２図に示すように、
ｎ型ポリアセチレン膜２とＰ′型ポリピロール膜５とが
接合されてなるものでおり、該ｐｍポリピロール膜３ｔ
ｉｔ解重合時の正電極として快用した導電性ネサガヲス
４１表面に析出させた状態で接合されてなる。The photoelectric conversion element 1, as shown in FIGS. 1 and 2,
It is formed by joining an n-type polyacetylene film 2 and a P'-type polypyrrole film 5, and the pm polypyrrole film 3t
It is bonded in a deposited state on the surface of conductive Nesagawasu 41, which was commonly used as a positive electrode during IT depolymerization.
この光電変換素子１のｎ型ポリアセチレン２の上部に銀
ペースト４２を取り付は電極とし、２ｍポリピロール３
ｉｆｉの４イ性ネサガヲス４１をその対電極とした。史
に上記両電極に鋼線４６をそれぞれ取り付けた。なおｇ
４１１Ｌ性ネサガラス４１には銀ペースト４４を介して
銅線４６を取り付けた。A silver paste 42 is attached to the top of the n-type polyacetylene 2 of this photoelectric conversion element 1 as an electrode, and a 2m polypyrrole 3
Ifi 4-type Nesagawosu 41 was used as the counter electrode. A steel wire 46 was attached to each of the above electrodes. Nao g
A copper wire 46 was attached to the 411L Nesa glass 41 via a silver paste 44.
この両ｗｔ極を電圧計及び電流計（図示せず）に接続し
、光電変換素子のｐ型ポリピロール膜面より白色光（ｓ
ｏｏｗ）を入射し、その時の開放電圧と短絡電流を測定
した。Both wt poles are connected to a voltmeter and an ammeter (not shown), and white light (s) is applied from the p-type polypyrrole film surface of the photoelectric conversion element.
oow), and the open circuit voltage and short circuit current at that time were measured.
その結果、開放電圧４ ＋ｎＶ 、短絡電流５ ×１０
’μＡでめった。As a result, open circuit voltage 4 + nV, short circuit current 5 × 10
'It was rare with μA.
また比較のため、Ｐ型ポリビロー／１／膜と！電型ポリ
アセチレン膜とを圧着により接合した比較用光電変換素
子を製造した。なお、ｐ型ポリピロール膜Ｊｔｌｌポリ
アセチＶン膜とも上記と同様に形成しｌｌ１ｍポリアセ
チレン膜はＰａポリピロール膜との接合前に乾燥しであ
る。またｐ型と！ｌ型の半導体の振盆は電解重什時の正
を極の表面土に析出させた状態のｐ型ポリピロール腺と
ｎ型ポリアセチレン膜とを接触するように配置し、２Ｋ
ｑ／／−１１の圧力でＰ型とｎ型との高分子半導体全圧
省して行なった。Also, for comparison, with P-type polybillow/1/membrane! A comparison photoelectric conversion element was manufactured by bonding an electro-type polyacetylene film by pressure bonding. The p-type polypyrrole film and the Jtll polyacetylene film were formed in the same manner as described above, and the ll1m polyacetylene film was dried before being bonded to the Pa polypyrrole film. With p-type again! The L-type semiconductor shaking tray is arranged so that the p-type polypyrrole gland in which the positive energy during electrolysis is deposited on the surface soil of the electrode is in contact with the n-type polyacetylene film, and the 2K
The test was carried out at a pressure of q//-11 while omitting the total pressure of the P-type and n-type polymer semiconductors.
この比較用光電変換素子について、上記と同様にして開
放電圧と短絡電流を測定した。Regarding this comparative photoelectric conversion element, the open circuit voltage and short circuit current were measured in the same manner as above.
その結果、開放電圧はα３ ｓｎ’Ｖ 、短絡電流は１
．７×１０″１μＡでおった。As a result, the open circuit voltage is α3 sn'V and the short circuit current is 1
．． 7×10″ and 1 μA.
このことにより１本発明によれば光電変換効率の良好な
充電変換素子を製造できることがわかる。This shows that according to the present invention, a charge conversion element with good photoelectric conversion efficiency can be manufactured.
実施例２
本実施例では、 Ｅｌ型高分子半導体の基材であるポリ
アセチレンとｐ型高分子半導体とを接触させた後にポリ
アセチレンをＩｆ型にＳ態化させた例を示す。Example 2 This example shows an example in which polyacetylene, which is a base material of an El-type polymer semiconductor, is brought into contact with a p-type polymer semiconductor, and then the polyacetylene is converted into an If-type S state.
チーグラ型触媒を用いて合成し、ヘキサンで触媒を収り
除き精製した膨潤ポリアセチレン膜を１１型に機能化さ
せずに実施例１と同様にして、膨潤ポリアセチレン膜（
乾燥時の膜厚２０μ皇口）とｐ型ポリピロール膜（電解
重合時の！極上に析出させた状態のもので、膜厚α０５
μｍ）とを接触させた。その後膨潤ポリアセチレン膜を
乾燥させて。A swollen polyacetylene membrane synthesized using a Ziegler type catalyst and purified by removing the catalyst with hexane was prepared in the same manner as in Example 1 without functionalizing it to type 11.
The film thickness when dry is 20 μm) and the p-type polypyrrole film (during electrolytic polymerization! The film thickness is α05).
μm) were brought into contact with each other. Then dry the swollen polyacetylene membrane.
ヘキサンを蒸発除去した。そして、２−アミンエチルア
ミノメチルトリメチルシランとリチウムアミドとをトル
エンに入れた溶液を５０分間加熱還流し、該溶液に上記
接合体を浸漬した。これによりポリアセチレン膜をｎ型
に機能化させ、その後接合体を乾燥させ、トルエンを除
去してｌｎｍポリアセチレン膜とｐ型ポリピロール膜と
が接合してなる光電変換素子を形成した。Hexane was removed by evaporation. Then, a solution of 2-amineethylaminomethyltrimethylsilane and lithium amide in toluene was heated under reflux for 50 minutes, and the above bonded body was immersed in the solution. This functionalized the polyacetylene film into n-type, and then dried the bonded body and removed toluene to form a photoelectric conversion element in which the lnm polyacetylene film and the p-type polypyrrole film were bonded.
この光電変換素子について、実施例１と同様にして白色
光を入射し、電圧と電流を測定した。その結果、電圧は
３ ｍＶ 、電流は５ Ｘ １０＝μＡであった。White light was applied to this photoelectric conversion element in the same manner as in Example 1, and the voltage and current were measured. As a result, the voltage was 3 mV and the current was 5×10=μA.
実施例五
本実施例では、実施例１におけるｐ型ポリビロー〜に代
えてＰ型ポリチェニレンを使用した例を示す。Example 5 This example shows an example in which p-type polythenylene was used in place of the p-type polybillow in Example 1.
Ｐ５ポリチェニレンの合成は、チェニレン単量体とドー
ピング剤としての過塩素酸テトラエチルアンモニウムと
を溶解したニトロベンゼン溶液ヲ使用して、正電極単位
面積当り ５ ｎ１ＩＡ／ｄの直流−流を約１０秒間流
し、それ以外は実施例１と同様な条件で電解重合を行な
った。欠に実施例１と同様にしこの正電極上に析出させ
た状態のｐ型ポリチェ： Ｖ ７膜（膜Ｌ’ｓ （，１
ｐｍ 、長さ２０ＨＸ幅２０書、比抵抗１Ω・ｃｒｌｌ
）と膨潤！ｌ型ポリアセチレン膜と接触させ、該Ｉｔ型
ポリアセチレン膜を乾燥して、光電変換素子を製造した
。P5 polythenylene was synthesized by using a nitrobenzene solution in which theningylene monomer and tetraethylammonium perchlorate as a doping agent were dissolved, and flowing a direct current of 5 nlIA/d per unit area of the positive electrode for about 10 seconds. Electrolytic polymerization was carried out under the same conditions as in Example 1 except for the above. The p-type polycheon film deposited on the positive electrode as in Example 1: V7 film (film L's (,1
pm, length 20H x width 20 lines, specific resistance 1Ω・crll
) and swelling! It was brought into contact with an I-type polyacetylene film, and the It-type polyacetylene film was dried to produce a photoelectric conversion element.
この光電変換素子について、実施例１と同様にして白色
光を入射し、電圧と電流を測定した。その結果、電圧は
４ｍＶ、電流は４ Ｘ １０’μＡであった。White light was applied to this photoelectric conversion element in the same manner as in Example 1, and the voltage and current were measured. As a result, the voltage was 4 mV and the current was 4 x 10'μA.
実施例４゜
実施例５と同様なＰ型ポリチェニレン膜を使用した以外
は、５ｊ！施例２と同様にしてｐ型ポリチェニレン膜と
ｎ型ポリアセチレン膜とが接合してなる光電変換素子を
製造した。Example 4゜5j! except that the same P-type polythenylene film as in Example 5 was used. A photoelectric conversion element in which a p-type polythenylene film and an n-type polyacetylene film were bonded was manufactured in the same manner as in Example 2.
この光電変換素子について、実施例１と同様にして白色
光を入射し、を圧と電流を測定した。その結果、電圧は
４ ｒｎＶ ＋ 電流は４ Ｘ １０４μＡでめった。White light was applied to this photoelectric conversion element in the same manner as in Example 1, and the pressure and current were measured. As a result, the voltage was 4 rnV + and the current was 4 x 104 μA.
第１図は実施例１における本発明にがかる光電変換素子
の斜視図、第２図は第１図のＩｔ−ＩＩに沿う断面図で
ある。1 is a perspective view of a photoelectric conversion element according to the present invention in Example 1, and FIG. 2 is a sectional view taken along It-II in FIG. 1.
Claims (3)
高分子半導体とのｐ−ｎ接合の光電変換素子を製造する
方法であって、ｎ型高分子半導体の基材を有機溶媒で膨
潤させると共にｐ型高分子半導体と接触させて、しかる
後該基材を乾燥することによりｐ型高分子半導体と上記
基材とを接合させることを特徴とする光電変換素子の製
造方法。(1) A method for manufacturing a p-n junction photoelectric conversion element between a P-type polymer semiconductor and an n-type polymer semiconductor made of polyacetylene, the method comprising: swelling the base material of the n-type polymer semiconductor with an organic solvent; A method for manufacturing a photoelectric conversion element, which comprises bonding the p-type polymer semiconductor and the base material by bringing the base material into contact with the p-type polymer semiconductor and then drying the base material.
、ポリチェニレン系化合物、ポリフラン系化合物、ポリ
アニリン系化合物、ポリアズレン系化合物のうちの１種
または２種以上からなる特許請求の範囲第（１）項記載
の光電変換素子の製造方法。(2) The p-type polymer semiconductor comprises one or more of polypyrrole-based compounds, polythenylene-based compounds, polyfuran-based compounds, polyaniline-based compounds, and polyazulene-based compounds, as claimed in claim (1). A method for manufacturing the photoelectric conversion element described above.
、トルエン、アセトン、アセトニトリル、ジメチルホル
ムアミドのうちの１種または２種以上である特許請求の
範囲第（１）項記載の光電変換素子の製造方法。(3) The method for producing a photoelectric conversion element according to claim (1), wherein the organic solvent is one or more of pentane, hexane, benzene, toluene, acetone, acetonitrile, and dimethylformamide. .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60120196A JPS61278174A (en) | 1985-06-03 | 1985-06-03 | Manufacture of photoelectric conversion device |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60120196A JPS61278174A (en) | 1985-06-03 | 1985-06-03 | Manufacture of photoelectric conversion device |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS61278174A true JPS61278174A (en) | 1986-12-09 |
Family
ID=14780285
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60120196A Pending JPS61278174A (en) | 1985-06-03 | 1985-06-03 | Manufacture of photoelectric conversion device |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS61278174A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011029651A (en) * | 2001-10-10 | 2011-02-10 | Merck Patent Gmbh | Combined etching and doping substance |
| JP2011096914A (en) * | 2009-10-30 | 2011-05-12 | Mitsubishi Chemicals Corp | Solar cell and method of manufacturing the same |
-
1985
- 1985-06-03 JP JP60120196A patent/JPS61278174A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011029651A (en) * | 2001-10-10 | 2011-02-10 | Merck Patent Gmbh | Combined etching and doping substance |
| JP2011096914A (en) * | 2009-10-30 | 2011-05-12 | Mitsubishi Chemicals Corp | Solar cell and method of manufacturing the same |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Saito et al. | Application of poly (3, 4-ethylenedioxythiophene) to counter electrode in dye-sensitized solar cells | |
| JP4043135B2 (en) | Functional element and multi-component multi-phase polymer molding | |
| Killian et al. | Polypyrrole composite electrodes in an all‐polymer battery system | |
| Saito et al. | Solid state dye sensitized solar cells using in situ polymerized PEDOTs as hole conductor | |
| US6300015B1 (en) | Proton conductive polymer battery and method of forming the same | |
| KR100882503B1 (en) | Highly Efficient Counter Electrodes for Dye-sensitized Solar Cells and Method for Manufacturing Thereof | |
| US7248461B2 (en) | Conducting polymer composite and solid electrolytic capacitor using the same | |
| KR19990067043A (en) | Electrochemical cell with symmetrical inorganic electrode | |
| Chakraborty et al. | Co-assembled conductive hydrogel of N-fluorenylmethoxycarbonyl phenylalanine with polyaniline | |
| US6482299B1 (en) | Polymer gel electrode | |
| WO1998026463A1 (en) | Polymer electrolyte and an electrochemical cell containing the electrolyte | |
| IMOTO et al. | Activated carbon counter electrode for dye-sensitized solar cell | |
| Li et al. | Dual conductivity of ionic polyacetylene by the metathesis cyclopolymerization of dendronized triazolium-functionalized 1, 6-heptadiyne | |
| KR102413065B1 (en) | Dye-sensitized solar cell comprising hydrogel electrolyte and method for manufacturing the same | |
| JPS61278174A (en) | Manufacture of photoelectric conversion device | |
| Kim et al. | Liquid crystals embedded in polymeric electrolytes for quasi‐solid state dye‐sensitized solar cell applications | |
| CN110534345B (en) | Counter electrode of dye-sensitized solar cell and preparation method and application thereof | |
| JPH0378978A (en) | Manufacture of photo-electrochemical cell | |
| GB2571770A (en) | Battery, electrode and method | |
| Kim et al. | Impedance spectroscopy on dye-sensitized solar cells with a poly (ethylenedioxythiophene): poly (styrenesulfonate) counter electrolyte | |
| JPS618854A (en) | Cell and its manufacturing method | |
| JPS61125090A (en) | Photoelectric conversion element | |
| JPS618855A (en) | Cell and its manufacture | |
| US20200411847A1 (en) | Polymer battery formed from freestanding electrode films | |
| JPS63205063A (en) | Manufacture of battery |