JP3618009B2 - Superconducting composite and its manufacturing method - Google Patents
Superconducting composite and its manufacturing method Download PDFInfo
- Publication number
- JP3618009B2 JP3618009B2 JP06920295A JP6920295A JP3618009B2 JP 3618009 B2 JP3618009 B2 JP 3618009B2 JP 06920295 A JP06920295 A JP 06920295A JP 6920295 A JP6920295 A JP 6920295A JP 3618009 B2 JP3618009 B2 JP 3618009B2
- Authority
- JP
- Japan
- Prior art keywords
- conductive polymer
- fullerene
- doped
- alkaline earth
- superconducting
- 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
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
- Y02E40/00—Technologies for an efficient electrical power generation, transmission or distribution
- Y02E40/60—Superconducting electric elements or equipment; Power systems integrating superconducting elements or equipment
Landscapes
- Carbon And Carbon Compounds (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
- Superconductors And Manufacturing Methods Therefor (AREA)
Description
【０００１】
【産業上の利用分野】
本発明は導体、電気機器、エレクトロニクス素子、センサー等に有用な超伝導複合体に関する。
【０００２】
【従来の技術】
現在、画期的な性能、機能を有する導体及び様々な電気機器、エレクトロニクス素子用として超伝導材料の利用が進められつつあるが、主としてＮｂＴｉ、Ｎｂ３ Ｇｅを始めとする無機金属系超伝導体及び遷移金属酸化物を始めとするセラミック超伝導体等が利用されようとしている。これら無機系材料からなる超伝導体は転移温度が比較的低いという問題以外に可撓性に劣るという課題が残っている。
また、近年有機系超伝導体として電荷移動錯体型物質及びＣ６０等のフラーレンの蒸着膜や結晶等の超伝導体が見出されて注目されている。特に、Ｃ６０にアルカリ金属、アルカリ土類金属をドーピングした超伝導体は有機系超伝導体の中では比較的高い超伝導転移温度を有しているが、やはり、可撓性に劣り、取り扱いが容易でないという課題を残している。従って、実用材料としては、まだ利用できるとは云い難い。
以上述べた様に、特にＣ６０にアルカリ金属、アルカリ土類金属をドーピングした超伝導体等は蒸着膜又は単結晶として用いられるので、脆く、可撓性もなく、非常に取り扱いにくい。
【０００３】
【発明が解決しようとする課題】
本発明は、超伝導材料に可撓性を付与し、取り扱いを容易とし、加工性、成型性も付与し、更に新たな性能、機能をも持たせた超伝導複合体を提供するものである。
【０００４】
【課題を解決するための手段】
本発明者等は、上記の課題を解決するため、導電性高分子と呼ばれる共役系の発達した高分子と複数の種類のドーパントとを複合化することにより、以下の検討や考察を通じて、導電性高分子と複数のドーパントとを含む超伝導複合体であり、しかも可撓性、機械的強度、加工性及び成型性に優れた超伝導複合体を見出すに至った。
【０００５】
すなわち本発明は次に記す発明である。
〔１〕導電性高分子と複数の種類のドーパントとを含む超伝導複合体。
〔２〕複数の種類のドーパントのそれぞれがそれ自体では超伝導性を示さないドーパントであることを特徴とする〔１〕記載の超伝導複合体。
〔３〕複数の種類のドーパントがフラーレンとアルカリ金属及び／又はアルカリ土類金属であることを特徴とする〔１〕または〔２〕記載の超伝導複合体。
〔４〕フラーレンがドーピングされてなる導電性高分子にアルカリ金属及び／又はアルカリ土類金属をドーピングすることを特徴とする〔３〕記載の超伝導複合体の製造方法。
〔５〕アルカリ金属及び／又はアルカリ土類金属をドーピングしたフラーレンを導電性高分子にドーピングすることを特徴とする〔３〕記載の超伝導複合体の製造方法。
〔６〕フラーレンがＣ６０又はＣ６０誘導体であることを特徴とする〔３〕記載の超伝導複合体。
〔７〕フラーレンがＣ６０又はＣ６０誘導体であることを特徴とする〔４〕または〔５〕記載の超伝導複合体の製造方法。
【０００６】
以下、本発明の導電性高分子と複数のドーパントとを主要構成成分とする超伝導複合体について詳細に説明する。
本発明の超伝導複合体においては、導電性高分子が該超伝導複合体の主要な構成成分となるため、可撓性、機械的強度、加工性、成型性を該超伝導複合体に付与することが可能となり、また、この導電性高分子が不安定なドーパントであっても、それを保護する役目を果たし、更に、複数のドーパントを複合化することで、単一のドーパントでは超伝導体とならない場合であっても導電性高分子とドーパント間、さらには異なるドーパント間の電子的相互作用の結果、超伝導性を発現するに至る。しかも、このような相互作用が母体の導電性高分子中で生ずることから、例えドーパント間の相互作用で生ずる超伝導性が耐環境性という面から不安定な系であっても、安定に複合体が形成されることになる。
さらに、このドーパントは必ずしも分子又は原子単独でドーピングされる必要はなく、クラスターを形成してもよい。その結果、クラスター間又はドーパント分子間、ドーパント分子−ドーパント原子間の相互作用に導電性高分子の電子状態が関与することによって、新規な超伝導特性を付与することが可能となる。
【０００７】
本発明に用いられる導電性高分子は、共役系の発達した主鎖を有する高分子であり、多量に存在するπ電子が高い導電性を与えるものである。一般的には０．５〜３．５電子ボルト（ｅＶ）程度の禁止帯幅を有し、絶縁体又は半導体的性質を示すが、ドーピングによって絶縁体−金属転移を生じ、高ドーピング状態では金属的性質を示すものが好適に利用できる。
このような導電性の変化は導電性高分子とドーピングされたドーパントの間に特徴的な電子的相互作用が生じるためである。ここで、導電性高分子と電子的な相互作用を示す分子や原子をドーパントと称する。即ち、導電性高分子は様々なドーパントがドーピングできるというところに最も大きな特色の一つがある。
【０００８】
本発明に用いることのできる導電性高分子としては、ポリアセチレン、ポリ−ｐ−フェニレン、ポリチオフェン、ポリピロール、ポリ−ｐ−フェニレンビニレンを始めとする共役系の発達した主鎖構造を有する多くの種類の高分子及びそれらの誘導体があるが、本発明は何ら特定の構造の導電性高分子に限定されるものではない。導電性高分子の例としては多くの成書に示されている〔例えば吉野勝美編著「導電性高分子の基礎と応用」（株）アイピーシー、１９８８〕。
【０００９】
これら導電性高分子の中で、成型性や加工性の観点から、可溶性中間体を経て得られるものやそれ自体が可溶性であるものが好ましい。具体的な例として、可溶性中間体を経て得られるものでは、ポリアセチレン、ポリ−ｐ−フェニレン、ポリ−ｐ−フェニレンビニレン及びそれらの誘導体が例示される。
また、それ自体が可溶性であるものではポリ−ｐ−フェニレン、ポリチオフェン、ポリピロールやポリ−ｐ−フェニレンビニレンに少なくとも一つの置換基が置換したものが例示される。置換基としては炭素数１から２２までのアルキル基、アルコキシ基、アルキルチオ基、アリール基、アルキルアリール基、またはアルコキシアリール基が例示され、好ましくは炭素数４以上２２以下の基が例示される。
置換基の置換位置としては芳香環や複素環を構成する炭素原子であり主鎖の結合位置にない炭素原子上、また、ポリピロールでは複素環を構成する窒素原子上、又はポリ−ｐ−フェニレンビニレンではビニレン基の炭素原子上である。置換基の数については導電性高分子の溶解性が良好ならば特に制限はないが、通常、少なくとも一つあればよい。
【００１０】
また、ドーパントとしてもドーピングの結果、導電性高分子と複数の種類のドーパントを含む複合体が超伝導性を示しさえすれば、何ら特定の分子、原子等に限定されるものではない。例えば、本発明に有効なドーパントとして、（１）フラーレンと（２）アルカリ金属及び／又はアルカリ土類金属が例示される。
まず、フラーレンについて説明すれば、フラーレンは炭素原子のみからなる分子であり、Ｃ６０では６０個の炭素がサッカーボール状に結合している（例えば谷垣勝己ら著 「フラーレン」、産業図書、平成４年）。
本発明に用いられるフラーレンは、Ｎａｔｕｒｅ ３４７巻、３５４ページ（１９９０年）に開示された方法などで得られる。例えば、黒鉛電極を用い、１〜１００ｍｍＨｇのヘリウム雰囲気でアーク放電し、得られた煤から溶媒抽出し、カラム分離精製することにより得られる。フラーレンのうちで、Ｃ６０、Ｃ７０又はその誘導体が好ましく、Ｃ６０又はその誘導体が特に好ましい。
【００１１】
このＣ６０等のフラーレンはそれ単独では超伝導性を示さないが、Ｋ、Ｒｂ等のアルカリ金属又はアルカリ土類金属のドーピングにより超伝導性を示すことが知られている。しかし、アルカリ金属やアルカリ土類金属単独での超伝導性は知られていない。
また、アルカリ金属やアルカリ土類金属は導電性高分子のドーパントとして作用することが知られている。一方、従来ドーパントに対するホストと考えられていたＣ６０が逆に導電性高分子に対するドーパントとして利用できることが見出された〔例えば、吉野勝美、炭素１６０巻（１９９３）、２９０頁〕。
【００１２】
本発明でフラーレンと組み合わせて用いるドーパントとしては、アルカリ金属、アルカリ土類金属が例示される。これらの金属は単独でもよいが、複数の金属を組み合わせて用いてもよい。
【００１３】
本発明の導電性高分子と複数の種類のドーパントとを含む超伝導複合体で用いるドーパントの量としては、超伝導の転移温度や臨界電流密度等により変化するが、一般的には、ドーパント総量は複合体の８０モル％以下１モル％以上であり、好ましくは、５０モル％以下２モル％以上である。ドーパント間での量は超伝導の発現性で適宜決めればよい。
【００１４】
導電性高分子にフラーレンをドーピングし、更にそれにアルカリ金属及び／又はアルカリ土類金属をドーピングすることにより超伝導性が発現する。その場合、アルカリ金属やアルカリ土類金属等はフラーレンにドーピングされているだけでなく、導電性高分子にもドーピングされ、フラーレン及びアルカリ金属やアルカリ土類金属等のドーピング量によっては超伝導クラスターがジョゼフソン結合した特性を有する特徴的な超伝導体複合体が得られる。
【００１５】
ドーパントの一つがフラーレンの場合の導電性高分子と複数の種類のドーパントの超伝導複合体の製造方法としては、導電性高分子にフラーレンをドーピングしたものに、アルカリ金属及び／又はアルカリ土類金属をドーピングする方法や、フラーレンにアルカリ金属又はアルカリ土類金属をドーピングしたのち、導電性高分子にドーピングする方法が挙げられる。
【００１６】
ドーピング方法としては、公知の方法で得ることができるが、化学ドーピング、電解ドーピング、光ドーピング、イオンインプランテーション等の手法が開示される。さらに、可溶性中間体法で得られる導電性高分子や可溶性導電性高分子の場合には、溶液中で導電性高分子とドーパントとを混合することで、又は可溶性中間体では中間体とドーパントを混合し、さらに導電性高分子に変換することで、導電性高分子−ドーパント複合体を作成することもできる。
【００１７】
【実施例】
以下、実施例をもって本発明の詳細な例を示すが、本発明は何ら本実施例に限定されるものではない。
実施例１
特開平１−７９２１７号公報の実施例６で、２，５−ジヘプチル−ｐ−キシリレンジブロミドの代わりに２，５−ジヘプチルオキシ−ｐ−キシリレンジブロミドを用いて、導電性高分子の一つであるポリ（２、５−ジヘプチルオキシ−ｐ−フェニレンビニレン）（以下、ＨＯ−ＰＰＶと記すことがある。）を合成した。フラーレンの一つとして、Ｃ６０はグラファイト電極を用いてアーク放電法により作製したものを用いた〔サイエンスラボラトリー（株）から購入〕。
【００１８】
１０ｃｃのトルエンに３３０ｍｇのＨＯ−ＰＰＶを溶かした溶液と２０ｃｃのトルエンに３．６ｍｇのＣ６０を溶かした溶液とを混合した後、キャスティングし、ＨＯ−ＰＰＶにＣ６０を５モル％ドーピングしたフレキシブルなフィルムを作製した。比較のためにＣ６０をドーピングしていないＨＯ−ＰＰＶフィルムも作製した。
このフィルムに２ゾーン温度法によりカリウム（Ｋ）をドーピングした。即ち、パイレックス管中にフィルムとカリウム金属を真空封入し、フィルムを２４０℃、カリウムを２２０℃に保ち、４８時間保持し、フィルムへのカリウムドーピングを行なった。得られた二重ドーピングフィルムのＬＦＳ（低周波マイクロ波吸収）及びＳＱＵＩＤの測定を行なった。
【００１９】
その結果、１７Ｋで超伝導転移が生ずることを見出した。
なお、Ｃ６０をあらかじめドーピングしていないフィルムにカリウムドーピングしても超伝導性は発現しなかった。
【００２０】
実施例２
３−ヘキシルチオフェンを塩化第二鉄を用いて重合した導電性高分子であるポリ（３−ヘキシルチオフェン）を１６６ｍｇ取り、１０ｃｃのトルエンに溶かした。また、Ｃ６０ ３．６ｍｇを２０ｃｃのトルエンに溶かし、これらの溶液を混合し、５モル％ドーピングしたフレキシブルな複合フィルムを作製した。実施例１と同様に真空中でポリ（３―ヘキシルチオフェン）−Ｃ６０複合フィルムを１３０℃、カリウムを１２０℃に保ってドーピングした。フィルムのＬＦＳ及びＳＱＵＩＤによる測定を行ない超伝導転移温度が１６Ｋであることを確認した。
【００２１】
【発明の効果】
本発明の導電性高分子と複数の種類のドーパントを含む超伝導複合体は導電性高分子が有する可撓性、成型性、加工性と同様の特性を有している。また、導電性高分子により、環境に対して安定化された超伝導性を示す。
このように、本発明の超伝導複合体は可撓性、成型性、加工性に優れ、容易に作成でき、しかも安定であるので、高性能、高機能な導体、電気機器、エレクトロニクス素子、センサー等に好ましく使用できる。[0001]
[Industrial application fields]
The present invention relates to a superconducting composite useful for conductors, electrical equipment, electronic elements, sensors and the like.
[0002]
[Prior art]
Currently, the use of superconducting materials for conductors with epoch-making performance and functions, as well as various electrical devices and electronics elements is being promoted, but mainly inorganic metal superconductors including NbTi and Nb 3 Ge Ceramic superconductors such as transition metal oxides are being used. Superconductors made of these inorganic materials have a problem that they are inferior in flexibility in addition to the problem that the transition temperature is relatively low.
Further, attention has been paid in recent years organic been found superconductor deposited film or crystal like fullerene such as a charge transfer complex-type materials and C 60 as a superconductor. In particular, alkali metal C 60, superconductor doped with alkaline earth metals have a relatively high superconducting transition temperature in organic superconductors, but also inferior in flexibility, handling The problem remains that is not easy. Therefore, it cannot be said that it can still be used as a practical material.
As mentioned above, in particular alkali metal C 60, since the superconductor or the like doped with an alkaline earth metal is used as a vapor deposition film or single crystal, fragile, flexible without any, very difficult to handle.
[0003]
[Problems to be solved by the invention]
The present invention provides a superconducting composite that imparts flexibility to a superconducting material, facilitates handling, imparts processability and moldability, and has new performance and functions. .
[0004]
[Means for Solving the Problems]
In order to solve the above-mentioned problems, the present inventors have synthesized a conductive polymer called a conductive polymer with a plurality of types of dopants and a plurality of types of dopants. The present inventors have found a superconducting composite containing a polymer and a plurality of dopants and having excellent flexibility, mechanical strength, workability and moldability.
[0005]
That is, the present invention is the invention described below.
[1] A superconducting composite containing a conductive polymer and a plurality of types of dopants.
[2] The superconducting composite according to [1], wherein each of the plurality of types of dopants is a dopant that does not exhibit superconductivity by itself.
[3] The superconducting composite according to [1] or [2], wherein the plurality of types of dopants are fullerene, an alkali metal and / or an alkaline earth metal.
[4] The method for producing a superconducting composite according to [3], wherein the conductive polymer doped with fullerene is doped with an alkali metal and / or an alkaline earth metal.
[5] The method for producing a superconducting composite according to [3], wherein the conductive polymer is doped with fullerene doped with an alkali metal and / or an alkaline earth metal.
[6] fullerene characterized in that it is a C 60 or C 60 derivative (3) superconductor composite according.
[7] fullerene characterized in that it is a C 60 or C 60 derivative [4] or [5] the production method of the superconducting composite according.
[0006]
Hereinafter, the superconducting composite having the conductive polymer of the present invention and a plurality of dopants as main components will be described in detail.
In the superconducting composite of the present invention, since a conductive polymer is a main constituent of the superconducting composite, flexibility, mechanical strength, workability, and moldability are imparted to the superconducting composite. In addition, even if this conductive polymer is an unstable dopant, it serves to protect it. Furthermore, by combining multiple dopants, superconductivity can be achieved with a single dopant. Even if it is not a body, superconductivity is exhibited as a result of electronic interaction between the conductive polymer and the dopant, and also between different dopants. Moreover, since such interaction occurs in the base conductive polymer, even if the superconductivity generated by the interaction between dopants is unstable in terms of environmental resistance, it can be stably combined. The body will be formed.
Furthermore, this dopant need not necessarily be doped with molecules or atoms alone, but may form clusters. As a result, new superconducting properties can be imparted by the electronic state of the conductive polymer participating in the interaction between clusters, between dopant molecules, and between dopant molecules and dopant atoms.
[0007]
The conductive polymer used in the present invention is a polymer having a main chain in which a conjugated system is developed, and a large amount of π electrons give high conductivity. In general, it has a forbidden band width of about 0.5 to 3.5 electron volts (eV) and exhibits an insulator or semiconductor property. However, an insulator-metal transition is caused by doping, and in a highly doped state, it is a metal. Can be suitably used.
This change in conductivity is due to a characteristic electronic interaction between the conductive polymer and the doped dopant. Here, a molecule or an atom that exhibits an electronic interaction with the conductive polymer is referred to as a dopant. That is, the conductive polymer has one of the biggest features in that various dopants can be doped.
[0008]
As the conductive polymer that can be used in the present invention, many kinds of main chain structures having a conjugated system such as polyacetylene, poly-p-phenylene, polythiophene, polypyrrole, and poly-p-phenylenevinylene are developed. Although there are polymers and derivatives thereof, the present invention is not limited to conductive polymers having any specific structure. Examples of conductive polymers are shown in many books (for example, edited by Katsumi Yoshino, “Basics and Applications of Conductive Polymers”, IPC, 1988).
[0009]
Among these conductive polymers, from the viewpoint of moldability and processability, those obtained through a soluble intermediate and those which are themselves soluble are preferred. As a specific example, what is obtained through a soluble intermediate is exemplified by polyacetylene, poly-p-phenylene, poly-p-phenylene vinylene, and derivatives thereof.
Examples of those that are themselves soluble include poly-p-phenylene, polythiophene, polypyrrole, and poly-p-phenylene vinylene substituted with at least one substituent. Examples of the substituent include an alkyl group having 1 to 22 carbon atoms, an alkoxy group, an alkylthio group, an aryl group, an alkylaryl group, and an alkoxyaryl group, preferably a group having 4 to 22 carbon atoms.
The substitution position of the substituent is a carbon atom constituting an aromatic ring or a heterocyclic ring and not on the bonding position of the main chain, and in the case of polypyrrole, a nitrogen atom constituting a heterocyclic ring or poly-p-phenylene vinylene Then, it is on the carbon atom of the vinylene group. The number of substituents is not particularly limited as long as the solubility of the conductive polymer is good, but usually at least one is sufficient.
[0010]
Further, as a dopant, as a result of doping, as long as a composite containing a conductive polymer and a plurality of types of dopants exhibits superconductivity, it is not limited to any particular molecule or atom. For example, (1) fullerene and (2) alkali metal and / or alkaline earth metal are exemplified as a dopant effective in the present invention.
First, fullerenes will be explained. Fullerenes are molecules consisting of only carbon atoms, and in C60 , 60 carbons are bonded in a soccer ball shape (for example, “Fullerene” written by Katsumi Tanigaki et al. Year).
The fullerene used in the present invention can be obtained by the method disclosed in Nature 347, page 354 (1990). For example, it can be obtained by arc discharge using a graphite electrode in a helium atmosphere of 1 to 100 mmHg, solvent extraction from the obtained soot, and column separation and purification. Among the fullerenes, C 60 , C 70 or a derivative thereof is preferable, and C 60 or a derivative thereof is particularly preferable.
[0011]
Show no fullerene superconductivity by itself in the C 60, etc., it is known to exhibit superconductivity K, doping of alkali metals or alkaline earth metals Rb like. However, the superconductivity of alkali metal or alkaline earth metal alone is not known.
In addition, alkali metals and alkaline earth metals are known to act as dopants for conductive polymers. On the other hand, C 60 was thought to host for the conventional dopant was found to be utilized as a dopant for the conductive polymer in the opposite [e.g., Katsumi Yoshino, carbon 160 vol (1993), 290 pp.].
[0012]
Examples of the dopant used in combination with fullerene in the present invention include alkali metals and alkaline earth metals. These metals may be used alone or in combination of a plurality of metals.
[0013]
The amount of dopant used in the superconducting composite containing the conductive polymer of the present invention and a plurality of types of dopants varies depending on the superconducting transition temperature, critical current density, etc. Is 80 mol% or less and 1 mol% or more of the composite, preferably 50 mol% or less and 2 mol% or more. What is necessary is just to determine the quantity between dopants suitably with the expression of superconductivity.
[0014]
Superconductivity is exhibited by doping the conductive polymer with fullerene and further doping it with an alkali metal and / or an alkaline earth metal. In that case, alkali metal or alkaline earth metal is not only doped in fullerene, but also in conductive polymer, and depending on the doping amount of fullerene and alkali metal or alkaline earth metal, superconducting clusters may be formed. A characteristic superconductor complex with Josephson-bonded properties is obtained.
[0015]
As a method for producing a superconducting composite of a conductive polymer and a plurality of types of dopants when one of the dopants is fullerene, an alkali metal and / or alkaline earth metal is added to the conductive polymer doped with fullerene. And a method of doping a fullerene with an alkali metal or an alkaline earth metal and then doping a conductive polymer.
[0016]
As a doping method, a known method can be used, but methods such as chemical doping, electrolytic doping, optical doping, and ion implantation are disclosed. Furthermore, in the case of a conductive polymer or a soluble conductive polymer obtained by the soluble intermediate method, the conductive polymer and the dopant are mixed in a solution, or in the soluble intermediate, the intermediate and the dopant are mixed. A conductive polymer-dopant complex can also be prepared by mixing and further converting to a conductive polymer.
[0017]
【Example】
Hereinafter, although a detailed example of the present invention is shown with an example, the present invention is not limited to this example at all.
Example 1
In Example 6 of Japanese Patent Application Laid-Open No. 1-79217, by using 2,5-diheptyloxy-p-xylylene dibromide instead of 2,5-diheptyl-p-xylylene dibromide, Poly (2,5-diheptyloxy-p-phenylene vinylene) (hereinafter sometimes referred to as HO-PPV) was synthesized. One of the fullerene, C 60 is [purchased from Science Laboratory (Ltd.) using a disk produced by an arc discharge method using a graphite electrode.
[0018]
A solution in which 330 mg of HO-PPV is dissolved in 10 cc of toluene and a solution of 3.6 mg of C 60 in 20 cc of toluene are mixed, cast, and HO-PPV is doped with 5 mol% of C 60 The film was made. HO-PPV film which is not doped with C 60 for comparison were also prepared.
This film was doped with potassium (K) by the two-zone temperature method. That is, the film and potassium metal were vacuum-sealed in a Pyrex tube, the film was kept at 240 ° C. and potassium was kept at 220 ° C., and held for 48 hours to perform potassium doping on the film. The resulting double doping film was measured for LFS (low frequency microwave absorption) and SQUID.
[0019]
As a result, it was found that a superconducting transition occurs at 17K.
Note that did not express superconductivity by potassium doping film without previously doped with C 60.
[0020]
Example 2
166 mg of poly (3-hexylthiophene), which is a conductive polymer obtained by polymerizing 3-hexylthiophene with ferric chloride, was taken and dissolved in 10 cc of toluene. Further, 3.6 mg of C 60 was dissolved in 20 cc of toluene, and these solutions were mixed to prepare a flexible composite film doped with 5 mol%. In the same manner as in Example 1, the poly (3-hexylthiophene) -C 60 composite film was doped at 130 ° C. and potassium at 120 ° C. in a vacuum. The film was measured by LFS and SQUID, and it was confirmed that the superconducting transition temperature was 16K.
[0021]
【The invention's effect】
The superconducting composite containing the conductive polymer of the present invention and a plurality of types of dopants has the same characteristics as the flexibility, moldability and processability of the conductive polymer. Moreover, the superconductivity stabilized with respect to the environment by a conductive polymer is shown.
As described above, the superconducting composite of the present invention is excellent in flexibility, moldability and processability, can be easily produced, and is stable, so that it has high performance, high performance conductors, electrical equipment, electronics elements, sensors. Etc. can be preferably used.
Claims (7)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP06920295A JP3618009B2 (en) | 1995-03-28 | 1995-03-28 | Superconducting composite and its manufacturing method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP06920295A JP3618009B2 (en) | 1995-03-28 | 1995-03-28 | Superconducting composite and its manufacturing method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH08264038A JPH08264038A (en) | 1996-10-11 |
| JP3618009B2 true JP3618009B2 (en) | 2005-02-09 |
Family
ID=13395914
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP06920295A Expired - Fee Related JP3618009B2 (en) | 1995-03-28 | 1995-03-28 | Superconducting composite and its manufacturing method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3618009B2 (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8394330B1 (en) * | 1998-10-02 | 2013-03-12 | The California Institute Of Technology | Conductive organic sensors, arrays and methods of use |
| DE60026309T2 (en) | 1999-05-10 | 2006-12-14 | California Institute Of Technology, Pasadena | USE OF A SPATIAL-TIME REACTION BEHAVIOR IN SENSOR ARRAYS FOR THE DETECTION OF ANALYTES IN FLUIDS |
| JP2002193606A (en) | 2000-12-22 | 2002-07-10 | Nec Corp | Superconducting material and method of manufacturing it |
| JP5476660B2 (en) * | 2006-09-26 | 2014-04-23 | 住友化学株式会社 | Organic photoelectric conversion device and polymer useful for production thereof |
| US20100084000A1 (en) * | 2006-09-26 | 2010-04-08 | Sumitomo Chemical Company, Limited | Organic photoelectric conversion device and polymer useful for producing the same |
-
1995
- 1995-03-28 JP JP06920295A patent/JP3618009B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH08264038A (en) | 1996-10-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Yang et al. | Recent developments in flexible thermoelectric devices | |
| Sainz et al. | A soluble and highly functional polyaniline–carbon nanotube composite | |
| Dubey et al. | Conducting polymers: efficient thermoelectric materials | |
| Chen et al. | Flexible and transparent supercapacitor based on In2O3 nanowire/carbon nanotube heterogeneous films | |
| Dai et al. | Doping of conducting polymers by sulfonated fullerene derivatives and dendrimers | |
| JP6699039B2 (en) | Thermoelectric conversion material and thermoelectric conversion element | |
| Huang et al. | Highly conducting organic–inorganic hybrid copper sulfides CuxC6S6 (x= 4 or 5.5): ligand‐based oxidation‐induced chemical and electronic structure modulation | |
| Kobayashi et al. | Ring-expanded porphyrins as an approach towards highly conductive molecular semiconductors | |
| JP2002507822A (en) | Electroluminescent element, method of manufacturing the same, and information display screen using electroluminescent element | |
| Zhong et al. | Interface investigation of the alcohol-/water-soluble conjugated polymer PFN as cathode interfacial layer in organic solar cells | |
| Cheetham et al. | Chemical synthesis and materials discovery | |
| JP3618009B2 (en) | Superconducting composite and its manufacturing method | |
| Faruk et al. | Recent advances in PEDOT: PSS integrated graphene and MXene-based composites for electrochemical supercapacitor applications | |
| US20070295395A1 (en) | Photovoltaic Device With Trimetaspheres | |
| Prassides et al. | Fullerene physics | |
| Kim et al. | Rhenium oxide as an efficient p-dopant to overcome S-shaped current density-voltage curves in organic photovoltaics with a deep highest occupied molecular orbital level donor layer | |
| Ramamurthy et al. | Mechanical and electrical properties of solution-processed polyaniline/multiwalled carbon nanotube composite films | |
| Wang et al. | Polymer-assisted deposition of SrTiO3 film as cathode buffer layer in inverted polymer solar cells | |
| Susumu et al. | Theoretical approach to the design of supramolecular conjugated porphyrin polymersElectronic supplementary information (ESI) available: Figs. A–I (see text for details). See http://www. rsc. org/suppdata/jm/b1/b102614n | |
| Chang et al. | Blending platinum nanoparticles into poly (3-hexylthiophene):[6, 6]-phenyl-C61-butyric acid methyl ester enhances the efficiency of polymer solar cells | |
| Benedek et al. | Prediction of new sp 2 and sp 2/sp 3 hollow carbon crystals | |
| Ramamurthy et al. | Integration and distribution of carbon nanotubes in solution-processed polyaniline/carbon nanotube composites | |
| Chun et al. | Enhancement of organic light-emitting diodes efficiency using carbon nanotube doped hole-injection layer on the Al-doped ZnO anode | |
| Saito | Organic superconducting solids | |
| Li et al. | Bilayer memory device based on a conjugated copolymer and a carbon nanotube/polyaniline composite |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20031126 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20040106 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20040302 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20040615 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20040810 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20041102 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20041108 |
|
| R150 | Certificate of patent or registration of utility model |
Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20071119 Year of fee payment: 3 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20081119 Year of fee payment: 4 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20081119 Year of fee payment: 4 |
|
| RD04 | Notification of resignation of power of attorney |
Free format text: JAPANESE INTERMEDIATE CODE: R3D04 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20081119 Year of fee payment: 4 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20091119 Year of fee payment: 5 |
|
| LAPS | Cancellation because of no payment of annual fees |