JPH034407A - Organic conductor - Google Patents

Organic conductor

Info

Publication number
JPH034407A
JPH034407A JP1137913A JP13791389A JPH034407A JP H034407 A JPH034407 A JP H034407A JP 1137913 A JP1137913 A JP 1137913A JP 13791389 A JP13791389 A JP 13791389A JP H034407 A JPH034407 A JP H034407A
Authority
JP
Japan
Prior art keywords
ttf
atoms
bedt
organic conductor
formula
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
Application number
JP1137913A
Other languages
Japanese (ja)
Inventor
Yoshinobu Ueha
上羽　良信
Yuka Sakata
阪田　由加
Takayuki Mishima
隆之 三島
Hiroyuki Kusuhara
楠原　博行
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sumitomo Electric Industries Ltd
Original Assignee
Sumitomo Electric Industries Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Sumitomo Electric Industries Ltd filed Critical Sumitomo Electric Industries Ltd
Priority to JP1137913A priority Critical patent/JPH034407A/en
Publication of JPH034407A publication Critical patent/JPH034407A/en
Pending legal-status Critical Current

Links

Classifications

    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/09—Use of materials for the conductive, e.g. metallic pattern
    • 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

  • Nitrogen And Oxygen Or Sulfur-Condensed Heterocyclic Ring Systems (AREA)
  • Superconductors And Manufacturing Methods Therefor (AREA)

Abstract

PURPOSE:To obtain a high critical temperature or a high conductivity by substituting one or more of S atoms of BEDT-TTF by O, Se or Te, and using a specific anion. CONSTITUTION:In a bisetylenedithiotetrathiofullbalen(BEDT-TTF) organic conductor shown in Formula I, X represents an anion shown in Formula II and one or more of S atoms in BEDT-TTF in Formula I is/are substituted by an atom(s) of O, Se or Te. In Formula II, M represents Ni, Cu, Pd, Ag, Pt, Au, Cd or Hg while Y represents O, S, Se or Te. Therefore, a high critical temperature or a high conductivity can be obtained.

Description

【発明の詳細な説明】 〈産業上の利用分野〉 本発明は、超電導性を示す高い臨界温度または高い電導
度を有する有機電導体に関する。DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to an organic conductor having a high critical temperature or high conductivity exhibiting superconductivity.

〈従来の技術〉 従来より、超電導または高い電導度を有する有機電導体
としては、 ＴＴＦ−ＴＣＮＱ　（テトラチアフルバレン−テトラシ
アノキノジメタン）、 （ＴＭＴＳＦ）２　Ｘ’　　（ＴＭＴＳＦ　：テトラメ
チルテトラセレノフルバレン、ＸＩ：Ｃ１０４ＰＦ６−
などの陰イオン）、 （ＢＥＤＦ−ＴＴＦ）ｚ　Ｘ２　（ＢＥＤＦ−ＴＴＦ：
ビスエチレンジチアテトラチアフルバレン、Ｘ２　：Ｒ
ｅ０ａ−，１３−、Ｃｕ　（ＮＣＳ）２などの陰イオン
）、 （ＤＭＥＴ）２　Ｘ３　（ＤＭＥＴ　：ジメチルエチレ
ンジチアジセレノジチアフルバレン、Ｘ３　：陰イオン
）、 （ＭＤＴ）２　Ｘ’　　（ＭＤＴ　：メチレンジチアジ
テトラチアフルバレン、Ｘ４．陰イオン）など電荷移動
錯体系有機電導体が知られている。<Prior art> Conventionally, as organic conductors having superconductivity or high conductivity, TTF-TCNQ (tetrathiafulvalene-tetracyanoquinodimethane), (TMTSF)2X' (TMTSF: tetramethyltetraselenofluor Ballen, XI:C104PF6-
anions such as), (BEDF-TTF)z X2 (BEDF-TTF:
Bisethylene dithiatetrathiafulvalene, X2:R
e0a-, 13-, anion such as Cu (NCS)2), (DMET)2 Charge transfer complex organic conductors such as dithiaditetrathiafulvalene (X4. anion) are known.

〈発明が解決しようとする課題〉 これらの電荷移動錯体系有機電導体は、室温での電気伝
導度がせいぜい１０２〜１０’Ｓ／ａｍであり、必ずし
も電導体として十分な電気伝導度、例えば１０４〜ＩＱ
５ｓ／ｃ−程度の電気伝導度を有するものは得られてい
ない。<Problems to be Solved by the Invention> These charge transfer complex organic conductors have an electrical conductivity of at most 102 to 10'S/am at room temperature, and do not necessarily have sufficient electrical conductivity as an electrical conductor, for example 104 ~IQ
No material having an electrical conductivity of about 5 s/c has been obtained.

また、上記有機電導体のうちのあるものは、常圧または
加圧下の低温で超電導を示すことが知られているが、こ
れらの有機電導体の超電導転移温度、すなわち臨界温度
Ｔｃは最も高いものでも１１〜１２Ｋにすぎない。Furthermore, it is known that some of the above organic conductors exhibit superconductivity at low temperatures under normal pressure or pressurization, but the superconducting transition temperature, that is, the critical temperature Tc, of these organic conductors is the highest. But it's only 11-12K.

本発明は以上の事情に鑑みてなされたものでありで、−
その目的とするところは、高い臨界温度Ｔｃまたは高い
電導性を有する有機電導体を提供することを目的とする
。The present invention has been made in view of the above circumstances, and -
The aim is to provide an organic conductor having a high critical temperature Tc or high conductivity.

く課題を解決するための手段〉 本発明の有機電導体は、一般式（１）：（式中、Ｘは陰
イオンである）で表されるビスエチレンジチアテトラチ
アフルバレン（以下、ＢＥＤＴ−ＴＴＦという）系の有
機電導体において、前記Ｘが一般式（２Ｊ： Ｍ　（ＹＣＮ）　２　　　　　　　（２）（式中、Ｍは
Ｎｉ、Ｃｕ、Ｐｄ、Ａｇ、Ｐｔ、Ａｕ、ＣｄまたはＨｇ
を示す原子であり、Ｙは０゜Ｓ、ＳｅまたはＴｅを示す
原子である）で表される陰イオンであり、かつ前記一般
式（１）におけるＢＥＤＴ−ＴＴＦが有するＳ原子の１
または２以上をＯ，ＳｅまたはＴｅの原子で置換したも
のである。Means for Solving the Problems> The organic conductor of the present invention is a bisethylene dithiatetrathiafulvalene (hereinafter referred to as BEDT- (referred to as TTF), the X has the general formula (2J: M (YCN) 2 (2) (where M is Ni, Cu, Pd, Ag, Pt, Au, Cd or Hg).
and Y is an atom representing 0°S, Se or Te), and 1 of the S atoms of BEDT-TTF in the general formula (1).
Or two or more atoms are substituted with O, Se or Te atoms.

ＢＥＤＴ−ＴＴＦ系有機電導体しては、前述のように種
々のものが従来より知られているが、このうち（ＢＥＤ
Ｔ−ＴＴＦ）２　Ｃｕ　（ＮＣＳ）ｚは現在最も臨界温
度Ｔｃの高い有機超電導体として知られている。本発明
はかかるＢＥＤＴ−ＴＴＦ系有機電導体のうち、少なく
ともＢＥＤＴ−ＴＴＦ部分）のＳ原子の１または２以上
をＯ，ＳｅまたはＴｅの原子で置換したものである。Various types of BEDT-TTF organic conductors have been known as mentioned above, but among them (BED
T-TTF)2Cu(NCS)z is currently known as an organic superconductor with the highest critical temperature Tc. The present invention relates to a BEDT-TTF organic conductor in which one or more of the S atoms in at least the BEDT-TTF portion are replaced with O, Se, or Te atoms.

Ｓ原子を０原子で置換することにより、分子量を１原子
あたり１６減少させることができる。従来の（ＢＥＤＴ
−ＴＴＦ）２　Ｃｕ　（ＮＣＳ）ｚでは１８個のＳ原子
を含んでいることから、分子量の減少は最大２８８とな
る。By replacing the S atoms with 0 atoms, the molecular weight can be reduced by 16 per atom. Conventional (BEDT)
-TTF)2Cu(NCS)z contains 18 S atoms, so the maximum molecular weight decrease is 288.

ＢＣＳ理論では、臨界温度Ｔｃは質量数の二乗機に反比
例するので、Ｓ原子を０原子に置換することにより、臨
界温度Ｔｃが上昇することが期待される。In the BCS theory, since the critical temperature Tc is inversely proportional to the square of the mass number, it is expected that the critical temperature Tc will increase by replacing S atoms with 0 atoms.

（以下余白） 一方、本発明者らはさらに研究を重ねた結果、式： で表されるＢＥＤＴ−ＴＴＦの８個の水素原子をＤ原子
に置換すると、（ＢＥＤＴ−ＴＴＦ）　２　Ｃｕ　（Ｎ
　Ｃ５）２の臨界温度Ｔｃは約ＩＫ上昇するという結果
が得られた。この結果は、従来のＢＣ３理論では説明で
きない。かかる知見に基づき、本発明者らは、ＢＥＤＴ
−ＴＴＦ系有機電導体に含まれるＳ原子の一部または全
部をＯ，Ｓｅ、Ｔｅ原子で置換すると、臨界温度Ｔｃが
上昇するはずであるという予測の下に実験を行い、本発
明を完成するに到った。ちなみに、例えばＳ原子をＳｅ
原子で置換すると１原子あたり４６．９だけ分子量が増
加し、全部置換では分子量の増加は８４４となり、未置
換の分子量に対して１．８９倍となる。(Left below) On the other hand, as a result of further research, the present inventors found that when the 8 hydrogen atoms of BEDT-TTF represented by the formula are replaced with D atoms, (BEDT-TTF) 2 Cu (N
The result was obtained that the critical temperature Tc of C5)2 increased by about IK. This result cannot be explained by the conventional BC3 theory. Based on this knowledge, the present inventors developed BEDT
- Conducted experiments based on the prediction that the critical temperature Tc should increase when some or all of the S atoms contained in a TTF-based organic conductor are replaced with O, Se, or Te atoms, and completed the present invention. reached. By the way, for example, the S atom is Se
When an atom is substituted, the molecular weight increases by 46.9 per atom, and when all the atoms are replaced, the molecular weight increases by 844, which is 1.89 times the molecular weight without substitution.

本発明におけるＢＥＤＴ−ＴＴＦ部分における８個のＳ
原子のうち、置換されるＳ原子の数や置換位置は特に制
限されるものではなく、１〜８個のＳ原子のうち全部ま
たは一部を置換することができる。8 S in the BEDT-TTF part in the present invention
Among the atoms, the number of S atoms to be substituted and the substitution positions are not particularly limited, and all or part of 1 to 8 S atoms can be substituted.

また、一般式２）で示される陰イオン Ｍ（ＹＣＮ）２−は次式により生成される。In addition, an anion represented by general formula 2) M(YCN)2- is generated by the following equation.

Ｍ−ＹＣＮ＋に−ＹＣＮ →　Ｍ　（ＹＣＮ）２−　十Ｋ” （式中、Ｍ、Ｙは前記と同じである） 本発明の有機電導体を得るには、Ｓ原子の一部または全
部が置換された前記ＢＥＤＴ−ＴＴＦとＭ−ＹＣＮとに
−ＹＣＮと溶媒とを結晶育成セルに仕込み、このセル内
に取り付けた電極間に直流電流を流し、電気化学的に酸
化・還元を行わせて合成と結晶生長とを行わせる、いわ
ゆる電解法が好適に採用される。-YCN to M-YCN+ -YCN → M (YCN)2- 10K" (in the formula, M and Y are the same as above) In order to obtain the organic conductor of the present invention, some or all of the S atoms are substituted. The above-mentioned BEDT-TTF and M-YCN are charged with -YCN and a solvent in a crystal growth cell, and a direct current is passed between the electrodes installed in this cell to perform electrochemical oxidation and reduction to synthesize them. A so-called electrolytic method in which crystal growth and crystal growth are performed is preferably employed.

前記溶媒としては、例えば１，１．２−トリクロロエタ
ン、テトラヒドロフラン、１．２−ジクロロエタン、ジ
クロロメタン、クロロベンゼン、フルオロベンゼン、ア
ニソール、アセトニトリル、ベンゾニトリルなどがあげ
られる。また、これらの溶媒にメタノール、エタノール
、プロパツール、ｎ−ブタノール、ペンタノールなどを
添加するのが、有機電導体の結晶生長速度や結晶のサイ
ズを増大させるうえで好ましい。Examples of the solvent include 1,1,2-trichloroethane, tetrahydrofuran, 1,2-dichloroethane, dichloromethane, chlorobenzene, fluorobenzene, anisole, acetonitrile, and benzonitrile. Further, it is preferable to add methanol, ethanol, propatool, n-butanol, pentanol, etc. to these solvents in order to increase the crystal growth rate and crystal size of the organic conductor.

次に実施例をあげて本発明の有機電導体を説明する。Next, the organic conductor of the present invention will be explained with reference to Examples.

〈実施例〉 実施例１ ビスエチレンジセレナテトラチアフルバレン（ＢＥＤＳ
ｅ−ＴＴＦ）　　３０ｍｇ、　　Ｃｕ５ＣＮ７０膳ｇ、
ＫＳＣＮ１２６ｍｇおよび１８−クラウン−６−エーテ
ル２１０５ｇを、窒素ガス置換を行った結晶成長セルに
加え、続いて溶媒として精製１，１゜２−トリクロロエ
タンおよびエタノール（１，１゜２−トリクロロエタン
に対して２重量％）を注射器で注入し、窒素ガス雰囲気
下でかつ遮光した状態で一夜攪拌した。ついで、不溶分
を沈降させたのち、外径１■の白金電極を取り付けた。<Example> Example 1 Bisethylene diselena tetrathiafulvalene (BEDS
e-TTF) 30mg, Cu5CN70g,
126 mg of KSCN and 2105 g of 18-crown-6-ether were added to a crystal growth cell purged with nitrogen gas, followed by purified 1,1° 2-trichloroethane and ethanol (1,1° 2-trichloroethane vs. % by weight) was injected with a syringe and stirred overnight under a nitrogen gas atmosphere and shielded from light. Then, after settling the insoluble matter, a platinum electrode with an outer diameter of 1 cm was attached.

次に、結晶成長セルを２０．０±０．２℃に保持した恒
温槽に入れ、温度を安定させた後、０．５０±０．０２
μＡの直流電流を白金電極間に流し、有機電導体の合成
・結晶成長を開始させた。Next, the crystal growth cell was placed in a constant temperature bath maintained at 20.0±0.2℃, and after stabilizing the temperature, 0.50±0.02℃
A direct current of μA was passed between the platinum electrodes to start the synthesis and crystal growth of the organic conductor.

その結果、約１カ月後に正電極上に黒色板状の結晶が多
数得られた。この結晶を取り出し、メタノールで洗浄し
、乾燥後、４端子法により室温での電導度を測定したと
ころ、約１０Ｏ３／ａｍであった。As a result, many black plate-like crystals were obtained on the positive electrode after about one month. The crystals were taken out, washed with methanol, dried, and then measured for electrical conductivity at room temperature using a four-terminal method, which was approximately 10 O3/am.

実施例２ 前記ＢＥＤＳｅ−ＴＴＦに代えてビスエチレンジオキシ
テトラチアフルバレン（ＢＥＤＯ−ＴＴＦ）を用いたほ
かは実施例１と同様にして有８１電導体の合成・結晶成
長を行わせた。Example 2 A 81 conductor was synthesized and crystal grown in the same manner as in Example 1, except that bisethylenedioxytetrathiafulvalene (BEDO-TTF) was used in place of the BEDSe-TTF.

その結果、約１．５力月後に正電極上に黒色板状の結晶
が多数得られた。この結晶を取り出し、メタノールで洗
浄し、乾燥後、４端子法により室温での電導度を測定し
たところ、約１〜１０Ｓ／ｃ■であり、室温付近での電
導度の温度依存性は金属・的であった。As a result, many black plate-like crystals were obtained on the positive electrode after about 1.5 months. This crystal was taken out, washed with methanol, and after drying, the electrical conductivity at room temperature was measured using the 4-terminal method. It was a target.

〈発明の効果〉 本発明の有機電導体は、ＢＥＤＴ−ＴＴＦ系有ａｌ電導
体ノウち、ＢＥＤＴ−ＴＴＦＩＩＢ分（７）Ｓ原子の１
または２以上を０．ＳｅまたはＴｅの原子で置換し、か
つ一般式（２）　： ％式％ （式中、ＭおよびＹは前記と同じであるンで表される陰
イオンＸを用いたため、高い臨界温度Ｔｃあるいは高い
電導度を発揮するほか、幅広い電導度（半導体的から金
属的まで）を発揮する。<Effects of the Invention> The organic conductor of the present invention is a BEDT-TTF based aluminum conductor, and has a BEDT-TTFIIB content (7) of 1 S atom.
Or 2 or more to 0. Substituted with a Se or Te atom, and general formula (2): % formula % (wherein M and Y are the same as above). In addition to exhibiting electrical conductivity, it also exhibits a wide range of electrical conductivity (from semiconducting to metallic).

従って、本発明の有機電導体は、各種配線、線材、プリ
ント回路、センサ、素子、シールド材料、反射材料、光
導電材料、磁性材料などへの応用に好適である。Therefore, the organic conductor of the present invention is suitable for application to various wirings, wires, printed circuits, sensors, elements, shielding materials, reflective materials, photoconductive materials, magnetic materials, and the like.

Claims (1)

【特許請求の範囲】 １、一般式（１）： ▲数式、化学式、表等があります▼ （式中、Ｘは陰イオンである）で表されるビスエチレン
ジチアテトラチアフルバレン（ＢＥＤＴ−ＴＴＦ）系の
有機電導体において、 前記Ｘが一般式（２）： Ｍ（ＹＣＮ）＿２（２） （式中、ＭはＮｉ、Ｃｕ、Ｐｄ、Ａｇ、Ｐｔ、Ａｕ、Ｃ
ｄまたはＨｇを示す原子であり、ＹはＯ、Ｓ、Ｓｅまた
はＴｅを示す原子である）で表される陰イオンであり、 かつ前記一般式（１）におけるビスエチレンジＴＴＦ）
が有するＳ原子の１または２以上をＯ、ＳｅまたはＴｅ
の原子で置換したものであることを特徴とする有機電導
体。[Claims] 1. General formula (1): ▲There are mathematical formulas, chemical formulas, tables, etc.▼ Bisethylene dithiatetrathiafulvalene (BEDT-TTF) represented by (wherein, X is an anion) ) system organic conductor, wherein the X has the general formula (2): M(YCN)_2(2) (wherein, M is Ni, Cu, Pd, Ag, Pt, Au, C
d or Hg, and Y is an atom representing O, S, Se, or Te), and bisethylene di-TTF in the general formula (1) above)
One or more of the S atoms possessed by O, Se or Te
An organic conductor characterized by being substituted with atoms of
JP1137913A 1989-05-31 1989-05-31 Organic conductor Pending JPH034407A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP1137913A JPH034407A (en) 1989-05-31 1989-05-31 Organic conductor

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP1137913A JPH034407A (en) 1989-05-31 1989-05-31 Organic conductor

Publications (1)

Publication Number Publication Date
JPH034407A true JPH034407A (en) 1991-01-10

Family

ID=15209611

Family Applications (1)

Application Number Title Priority Date Filing Date
JP1137913A Pending JPH034407A (en) 1989-05-31 1989-05-31 Organic conductor

Country Status (1)

Country Link
JP (1) JPH034407A (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006022194A1 (en) * 2004-08-23 2006-03-02 Semiconductor Energy Laboratory Co., Ltd. Electron injecting composition, and light emitting element and light emitting device using the electron injecting composition

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006022194A1 (en) * 2004-08-23 2006-03-02 Semiconductor Energy Laboratory Co., Ltd. Electron injecting composition, and light emitting element and light emitting device using the electron injecting composition

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