JPS61163659A - Manufacture of mis diode - Google Patents
Manufacture of mis diodeInfo
- Publication number
- JPS61163659A JPS61163659A JP60003601A JP360185A JPS61163659A JP S61163659 A JPS61163659 A JP S61163659A JP 60003601 A JP60003601 A JP 60003601A JP 360185 A JP360185 A JP 360185A JP S61163659 A JPS61163659 A JP S61163659A
- Authority
- JP
- Japan
- Prior art keywords
- layer
- electrode
- type
- electron
- diode
- 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
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 23
- 150000002894 organic compounds Chemical class 0.000 claims abstract description 13
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 8
- 150000001422 N-substituted pyrroles Chemical class 0.000 claims abstract description 3
- 229920001577 copolymer Polymers 0.000 claims abstract description 3
- 229920000547 conjugated polymer Polymers 0.000 claims description 25
- 239000004065 semiconductor Substances 0.000 claims description 16
- 229910052751 metal Inorganic materials 0.000 claims description 13
- 239000002184 metal Substances 0.000 claims description 13
- 229920000767 polyaniline Polymers 0.000 claims description 2
- 229920000323 polyazulene Polymers 0.000 claims description 2
- 229920000123 polythiophene Polymers 0.000 claims description 2
- 229920000414 polyfuran Polymers 0.000 claims 1
- 229920000128 polypyrrole Polymers 0.000 claims 1
- 229920002717 polyvinylpyridine Polymers 0.000 claims 1
- 150000003233 pyrroles Chemical class 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 abstract description 12
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 abstract description 9
- 238000006243 chemical reaction Methods 0.000 abstract description 6
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 abstract description 4
- 239000011521 glass Substances 0.000 abstract description 4
- 239000003115 supporting electrolyte Substances 0.000 abstract description 4
- PCCVSPMFGIFTHU-UHFFFAOYSA-N tetracyanoquinodimethane Chemical compound N#CC(C#N)=C1C=CC(=C(C#N)C#N)C=C1 PCCVSPMFGIFTHU-UHFFFAOYSA-N 0.000 abstract description 4
- 230000008021 deposition Effects 0.000 abstract description 3
- 150000001450 anions Chemical class 0.000 abstract description 2
- 150000001768 cations Chemical class 0.000 abstract description 2
- 239000000178 monomer Substances 0.000 abstract description 2
- 239000002052 molecular layer Substances 0.000 abstract 2
- 230000000052 comparative effect Effects 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- -1 poly7rane Polymers 0.000 description 8
- 239000010931 gold Substances 0.000 description 7
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 7
- 238000000151 deposition Methods 0.000 description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- 238000001704 evaporation Methods 0.000 description 4
- 229920000620 organic polymer Polymers 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 238000007740 vapor deposition Methods 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 3
- 229910052737 gold Inorganic materials 0.000 description 3
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 239000002019 doping agent Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical class OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- BBEAQIROQSPTKN-UHFFFAOYSA-N pyrene Chemical compound C1=CC=C2C=CC3=CC=CC4=CC=C1C2=C43 BBEAQIROQSPTKN-UHFFFAOYSA-N 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 125000005207 tetraalkylammonium group Chemical group 0.000 description 2
- 238000007738 vacuum evaporation Methods 0.000 description 2
- OXHNLMTVIGZXSG-UHFFFAOYSA-N 1-Methylpyrrole Chemical compound CN1C=CC=C1 OXHNLMTVIGZXSG-UHFFFAOYSA-N 0.000 description 1
- JEGZRTMZYUDVBF-UHFFFAOYSA-N Benz[a]acridine Chemical compound C1=CC=C2C3=CC4=CC=CC=C4N=C3C=CC2=C1 JEGZRTMZYUDVBF-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229910000807 Ga alloy Inorganic materials 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- 208000037062 Polyps Diseases 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- UATJOMSPNYCXIX-UHFFFAOYSA-N Trinitrobenzene Chemical compound [O-][N+](=O)C1=CC([N+]([O-])=O)=CC([N+]([O-])=O)=C1 UATJOMSPNYCXIX-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- SCIYPPJMKCXIGM-UHFFFAOYSA-N ethane-1,1,1,2-tetracarbonitrile Chemical compound N#CCC(C#N)(C#N)C#N SCIYPPJMKCXIGM-UHFFFAOYSA-N 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- GVEPBJHOBDJJJI-UHFFFAOYSA-N fluoranthrene Natural products C1=CC(C2=CC=CC=C22)=C3C2=CC=CC3=C1 GVEPBJHOBDJJJI-UHFFFAOYSA-N 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- DZVCFNFOPIZQKX-LTHRDKTGSA-M merocyanine Chemical compound [Na+].O=C1N(CCCC)C(=O)N(CCCC)C(=O)C1=C\C=C\C=C/1N(CCCS([O-])(=O)=O)C2=CC=CC=C2O\1 DZVCFNFOPIZQKX-LTHRDKTGSA-M 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920003227 poly(N-vinyl carbazole) Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000000807 solvent casting Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- UGNWTBMOAKPKBL-UHFFFAOYSA-N tetrachloro-1,4-benzoquinone Chemical compound ClC1=C(Cl)C(=O)C(Cl)=C(Cl)C1=O UGNWTBMOAKPKBL-UHFFFAOYSA-N 0.000 description 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N tetrahydrofuran Substances C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-M toluene-4-sulfonate Chemical class CC1=CC=C(S([O-])(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-M 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 238000001947 vapour-phase growth Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/10—Organic polymers or oligomers
- H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K10/00—Organic devices specially adapted for rectifying, amplifying, oscillating or switching; Organic capacitors or resistors having a potential-jump barrier or a surface barrier
Abstract
Description
【発明の詳細な説明】
この発明は、有機系材料を用いた新規なＭＩＳダイオー
ドの製造方法に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel method for manufacturing MIS diodes using organic materials.
第Ｓ図は一般的なＭＩＳダイオードの断面図であり、図
において、ｌｉｔ 、 ＋６１はリード線、（２１は電
極となる金属層、（３）は絶縁層、（４）は半導体層、
＋５１電極となる導電層であり、金員−絶縁物−半導体
（Ｍ工８）の順く構成されたもので、従来より第６図に
示す８１−８１０−金属構造のもの、即ちＭＯ８ダイオ
ードが実用化されている。Figure S is a cross-sectional view of a general MIS diode, and in the figure, lit, +61 is a lead wire, (21 is a metal layer that becomes an electrode, (3) is an insulating layer, (4) is a semiconductor layer,
It is a conductive layer that becomes the +51 electrode, and is composed of metal, insulator, and semiconductor (M-8) in this order. Conventionally, the 81-810-metal structure shown in Fig. 6, that is, the MO8 diode, is It has been put into practical use.
図において、ｆ７１ｒ１８１ ＯＮｉ％ １８１はＳｉ
層である。In the figure, f71r181 ONi% 181 is Si
It is a layer.
以前より８１０．−８１構造に帰因する劣化が起ると言
われていたが、現在ではこの問題の解明が進み、理想に
近いＭＯＢＱ造が作られるようＫなり、実用性も高まっ
てきている。これ等の製法としては、８１の気相成長の
方法に酸素、又ｔ−ｔｅ素を含むＣＯ４，ＨＩＯなどの
ガスを導入しＢｉ 上に８１０．を成長させる方法、お
よびＢ１Ｂａと０．を反応させてｓｔｏｗ、を製膜する
方法などがあるー有機ＮＩＢダイオードも最近作られる
ようになったが、これ等は有機半導体の上に絶縁性の有
機高分子を来着法、およびプラズマ重合法などにより２
Ｏ−１０ｏｆ程度の層を堆積し、その上に金属電極をつ
けたものである。また、無機半導体の上に上記の方法で
有機高分子を堆積させ７’ｔＭＩＳダイオードも知られ
ている。810 from before. It was said that deterioration occurred due to the -81 structure, but now this problem has been solved, MOBQ structures close to the ideal have been created, and their practicality is increasing. The manufacturing method for these is to introduce gas such as CO4, HIO, etc. containing oxygen or t-te element into the vapor phase growth method of 810. and how to grow B1Ba and 0. Organic NIB diodes have also recently been produced, but these methods involve depositing an insulating organic polymer onto an organic semiconductor, and plasma heavy deposition. 2 due to legality etc.
A layer of approximately O-10of is deposited, and a metal electrode is attached on top of it. Furthermore, a 7'tMIS diode is also known in which an organic polymer is deposited on an inorganic semiconductor using the above method.
しかし、従来の蒸着法、プラズマ重合法による絶縁性有
機高分子層の超薄膜の堆積は、ピンホールが出来易い、
層の構造に再現性が無い。However, the deposition of ultra-thin insulating organic polymer layers using conventional vapor deposition methods and plasma polymerization methods is prone to pinholes.
Layer structure is not reproducible.
層厚のコントロールが困難である、装置が高価格である
、操作が惟しくコストが高いなどの欠点を持ち、Ｍ工Ｓ
ダイオードの絶縁性有機高分子層を堆積さ−せるには不
適当な方法であった。M-S
This method was unsuitable for depositing insulating organic polymer layers for diodes.
この発明は上記のような問題点を解消するためになされ
たもので、容易に、高性能でかつ性能の安定し７？−Ｍ
ＩＳダイオードの製造方法を得ることを目的とする。This invention was made to solve the above-mentioned problems, and it can easily achieve high performance and stable performance. -M
The purpose of this invention is to obtain a method for manufacturing an IS diode.
この発明に係るＭＩＳダイオードの製造方法は、電極と
なる導電層、電解重合法により形成されたπ−共役系高
分子からなる半導体層、電子受容性基および電子供与性
基の少なくとも一方を有する絶縁性有機化合物層、並び
に電極となる金属層を積層するものである。The method for manufacturing an MIS diode according to the present invention includes a conductive layer serving as an electrode, a semiconductor layer made of a π-conjugated polymer formed by electrolytic polymerization, and an insulating layer having at least one of an electron-accepting group and an electron-donating group. This method consists of stacking a chemical organic compound layer and a metal layer that becomes an electrode.
この発明は、後述するように、Ｓ層のπ−共役系高分子
中のドーパントがＩｉ％の電子受容性基あるいは電子供
与性基と接掴することにより相互作用して仏教すること
を利用したものである。これにより、Ｓ層と１層の界面
に多数存在してい次キャリアのトラップレベルが均一化
され、ブた１屑中にドーパントが侵入することにより、
一種の電荷移動型錯体を部分的に形成し、見かけのトン
ネル長さが実際の絶縁層の厚さよりも短いものとなる傾
向が出現する・従って例えばこの発明の方法で製造され
たＭＩＳダイオードでは、１層の厚さが前記した従来の
方法で製造され＋Ｍ工Ｓダイオードの２Ｏ−１００７Ｆ
よりも厚りもの、例えばｔｏｏ〜８０００Ａ’となり、
ピンホールレスの膜を容易に作ることができる。This invention utilizes the fact that the dopant in the π-conjugated polymer of the S layer interacts with the electron-accepting group or electron-donating group of Ii%, as will be described later. It is something. As a result, the trap level of the secondary carriers present in large numbers at the interface between the S layer and the first layer is made uniform, and the dopant penetrates into the dust of the first layer.
A kind of charge transfer type complex is partially formed, and the apparent tunnel length tends to be shorter than the actual thickness of the insulating layer. Therefore, for example, in the MIS diode manufactured by the method of the present invention, The thickness of one layer is 2O-1007F of the +M S diode manufactured by the conventional method described above.
Thicker than, for example, too~8000A',
Pinhole-free membranes can be easily created.
この発明に係わ４る電極となる導電層に用いる導電材料
としては、一般的に電極に用いる、例えば金および白金
等の金属およびカーボン等があり、単独および各種基板
と共に用いる＠この発明に係６る半導体層に用いる１［
解重合法により形成されるπ−共役系高分子としては例
えばピロールとＮ−ｆｉ置換ピロール共重合体、ビロー
ルのホモポリマー、Ｎ−置換ピロールのホモポリマー、
ポリチェニレン、ポリアニリン、ポリ７ラン、ポリアズ
レン、ポリビニルヒリジン、およびポリチオフェン、な
どの内少なくとも一種が好ましく用いられる。The conductive material used for the conductive layer that becomes the electrode according to the present invention includes metals such as gold and platinum, carbon, etc., which are generally used for electrodes, and can be used alone or with various substrates@according to the present invention. 1[
Examples of π-conjugated polymers formed by the depolymerization method include pyrrole and N-fi substituted pyrrole copolymers, virol homopolymers, N-substituted pyrrole homopolymers,
At least one of polythenylene, polyaniline, poly7rane, polyazulene, polyvinylhyridine, polythiophene, and the like is preferably used.
例えば上記π−共役系高分子の半導体層を電極となる導
電層に設けるには、上記π−共役系などの対極との間に
電流を通じて電解重合法により作用電極上に所望のπ−
共役系高分子層を析出させ、析出したπ−共役系高分子
層をよく洗滌した後、窒素雰囲気中で乾燥するという方
法を用いる・この場合、析出したπ−共役系高分子層は
反応時に支持電解質のアニオンがドーピングされｐ型半
導体となる。一方、このｐ型半導体を脱Ｖ−プし、さら
にカチオンをドープすることにより、ｎ型半導体とする
ことができる。ここで、有機溶媒としては、支持電解質
および上記モノマーを溶解させるものならよく、例、ｔ
ハフセトニトリル、ニトロメンセ゛ン、ニトロメタン
、Ｎ、Ｎ−ジメチルホルムアミド（ＤＭＰ ）、ジメチ
ルスルホキシド（ＤＭ８０）、ジクロロメタン、５テト
ラヒドロフラン、エチルアルコールおよびメチルアルコ
ール等の極性溶媒が単独又は８種以上の混合溶液として
用いられる。支持電解質としては酸化電位および還元電
位が高く、電解重合にそれ１青が酸化又は還元反応を受
けず、かつ溶媒中に溶解させることによって溶液に電導
性を付与することのできる物質であり、例えば、過塩素
酸テトラアルキルアンモニクム塩、テトラアルキルアン
モニウム、テトラフルオロポレート塩、テトラアルキル
アンモニウム、ヘキサフルオロホスフェート塩、テ）ラ
アルキルアンモニクム、パラトルエンスルホネート塩お
よび水酸化ナトリウム等が用いられるが、勿論２種以上
を併用しても構わない。For example, in order to provide a semiconductor layer of the above-mentioned π-conjugated polymer on a conductive layer serving as an electrode, a desired π-
A method is used in which a conjugated polymer layer is deposited, the deposited π-conjugated polymer layer is thoroughly washed, and then dried in a nitrogen atmosphere.In this case, the deposited π-conjugated polymer layer is removed during the reaction. The supporting electrolyte is doped with anions to become a p-type semiconductor. On the other hand, by de-V-doping this p-type semiconductor and further doping it with cations, it can be made into an n-type semiconductor. Here, the organic solvent may be any organic solvent as long as it can dissolve the supporting electrolyte and the above monomer, for example, t
Polar solvents such as hafcetonitrile, nitromethane, nitromethane, N,N-dimethylformamide (DMP), dimethyl sulfoxide (DM80), dichloromethane, 5-tetrahydrofuran, ethyl alcohol, and methyl alcohol are used alone or in a mixed solution of eight or more. The supporting electrolyte is a substance that has a high oxidation potential and reduction potential, does not undergo oxidation or reduction reactions during electrolytic polymerization, and can impart conductivity to a solution by dissolving it in a solvent. For example, , tetraalkylammonicum perchlorate salt, tetraalkylammonium, tetrafluoroporate salt, tetraalkylammonium, hexafluorophosphate salt, tetraalkylammonicum, paratoluenesulfonate salt, sodium hydroxide, etc. are used, but, of course, Two or more types may be used in combination.
この発明に係わる電子受容性基および電子供与性基の少
なくとも一方を有する絶縁性有機化合物は、単体では絶
縁性であるが電荷移動錯体を形成すると半導性になるも
のである。The insulating organic compound having at least one of an electron-accepting group and an electron-donating group according to the present invention is insulating when alone, but becomes semiconducting when a charge transfer complex is formed.
かかる電子受容性基を有する化合物としては、；のＪえ
ばテトラシアノキノジメタン（ＴＣＮＱ、）、テトラシ
アノエタンｒＴＯＮ］！り、ｐ−クロラニｌし、ｐ−ブ
ロマニル、ｐ−１オダニル、ｐ−７０ラニル、ジシアノ
ジクロロキノン、ジシアノシフ。Examples of compounds having such an electron-accepting group include tetracyanoquinodimethane (TCNQ), tetracyanoethane rTON]! p-chloranil, p-bromanyl, p-1 odanyl, p-70ranyl, dicyanodichloroquinone, dicyanosif.
ロモキノン、トリニトロベンセ゛ン、ピレン、アントラ
セン、ペンアントラセン、ベンズアクリジンなどの化合
物や、これらの誘導体、あるいは分子末端にこれらの基
を有する化合物が挙げられる。Examples include compounds such as lomoquinone, trinitrobenzene, pyrene, anthracene, penanthracene, and benzacridine, derivatives thereof, and compounds having these groups at the molecular terminals.
また電子供与性基を有する化合物として汀、アニリン、
ジメチルアニリン、ジアミノベンセ°ン、Ｎ 、 Ｎ’
−置換ジアミノベンゼンなどやこれらの誘導体の芳香族
アミン類、モノ、ジ、トリ、テトラ置換アンモニクム塩
類、訃よびこれらの化合物にＯ１８，８１３ｙｉ、子を
含有した化合物、あるいは分子末端にこれらの基を有す
る化合物が挙げられる。なお、こねら化合物の詳細につ
ｈては、例えば’ Ｏｒｇａｎｉｃ ８ｅｍｉｃｏｎ
−４ｕｃｔｉｎｇ ｐｏｌｙｍｅｒｓ“Ｊ、 Ｉ！ｉ、
Ｋａｌ；Ｏｎ著などに示されている。In addition, as compounds having an electron-donating group, sulfur, aniline,
Dimethylaniline, diaminobenzene, N, N'
- Aromatic amines such as substituted diaminobenzenes and their derivatives, mono-, di-, tri-, and tetra-substituted ammonicum salts, and compounds containing O18,813yi and children in these compounds, or having these groups at the end of the molecule Examples include compounds. In addition, for details of the compound, see, for example, 'Organic 8emicon
-4ucting polymers “J, I!i,
It is shown in books such as those written by Kal;On.
また、−分子内に電子受容性基と電子供与性基の両方を
有する化合物、例えば分子内電荷移動型と呼ばれるよう
な化合物や両者を混合したものも場合に゛よっては好ま
しく用いられる。In some cases, compounds having both an electron-accepting group and an electron-donating group in the molecule, such as a compound called an intramolecular charge transfer type, or a mixture of both may be preferably used.
なお、前記π−共役系高分子にアクセプターがＦ−プさ
れているＣｐ型半導体）場合には、絶縁性有機化合物が
電子供与・性基を何し、ドナーがドープされている。（
ｎ型半導体）場合には、電子受容性基を有していること
が必要である。また、これら絶縁性有機化合物層げ、溶
媒キャスト法等の通常の塗布法、真空蒸着法、プラズマ
重合法あるいは電解重合法などにより形成される。In the case of a Cp type semiconductor in which an acceptor is F-doped in the π-conjugated polymer, an insulating organic compound acts as an electron donating group and is doped with a donor. (
n-type semiconductor), it is necessary to have an electron-accepting group. Further, it can be formed by layering these insulating organic compounds, by a conventional coating method such as a solvent casting method, by a vacuum evaporation method, by a plasma polymerization method, by an electrolytic polymerization method, or the like.
この発明に保わる電極となる金属層の金属としては、半
導体層がｐ型の場合は、例えばインジクム（Ｉｎ）、ガ
リウム（Ｇ ａ ）、インジクムーガリクム合金、アル
ミニクム（ムｔ ） 、ｆｌ （Ａｇ）、スズ（８ｎ）
およびゲルマニウム（Ｇｅ ）などの仕事関数の小さい
金属が、ｎ型の場合には、例えば金（Ａｕ）、白金（ｐ
ｔ）および鋼（Ｃｕ）などの仕事関数の大きい金属が用
いられ、蒸着、スパッタリング、ＣＶＤ成長およびメッ
キなどの方法で被着させる。When the semiconductor layer is p-type, the metal of the metal layer serving as the electrode according to the present invention includes, for example, indicum (In), gallium (G a ), indicum-moo-gallium alloy, aluminum (Mt ), and fl. (Ag), tin (8n)
When the metal with a small work function such as germanium (Ge) is n-type, for example, gold (Au), platinum (p
High work function metals such as t) and steel (Cu) are used and are deposited by methods such as evaporation, sputtering, CVD growth and plating.
以下、仁の発明の実施例について具体的に説明するが、
この発明は、これらに限定されるものではない。Examples of Jin's invention will be described in detail below.
This invention is not limited to these.
実施例１
３、 ｌ ｃＩＩＸ ？ ５１１１のガラス基板上に真
′４！蒸着法によって厚さ１ｏ００ｊｆ’のクロム層を
設け、更にこの上に金（Ａｕ）層をｇｏｏｏｆの厚さに
真空蒸着法によって設けたもの全作用電極とした（有効
作用電極面積は９ ｃｍ ｘ ８．５ ａｍ ）。Example 1 3, lcIIX? True '4 on the 5111 glass substrate! A chromium layer with a thickness of 1000jf' was formed by vapor deposition, and on top of this a gold (Au) layer was formed to a thickness of gooof by vacuum evaporation to form the entire working electrode (the effective working electrode area was 9 cm x 8 cm). .5 am).
ｔｏｏｍｚのアセトニトリル中にＮ−メチルピロール（
０−８ｇ ） 、テトラエチルアンモニクムパークロレ
イトＣｏ、’Ｉｇ）ｔ−溶解させた液を反応溶液とした
。N-methylpyrrole (
0-8g), tetraethylammonicum perchlorate Co,'Ig)t-The dissolved solution was used as a reaction solution.
対極として白金（ｐｔ）電極を、参照電極としてａｃｚ
ｃ飽和カロメル電極）を使用し、反応溶液中に作用電極
と共に浸し、窒素ガス雰囲気下で作用電極ｉｌ！＃Ｊ極
として対極との間に一定電流（０，１５ｍＡ）？：９０
分間流し、作用゛電極上にπ−共役系高分子層約＋ｏｏ
ｏｆの厚さに析出させ、アセトニトリルで洗浄後、窒素
ガス雰囲気下で乾燥し、π−共役系高分子試料（Ｉ）を
得た。A platinum (pt) electrode was used as a counter electrode, and an acz electrode was used as a reference electrode.
Using a saturated calomel electrode), immerse it together with the working electrode in the reaction solution, and place the working electrode il! under a nitrogen gas atmosphere! # Constant current (0.15mA) between the J electrode and the opposite electrode? :90
π-conjugated polymer layer on the working electrode for about +oo minutes.
After washing with acetonitrile and drying in a nitrogen gas atmosphere, a π-conjugated polymer sample (I) was obtained.
次に、π−共役系高分子試料（Ｉ）の上に、絶縁性有機
化合物としてポリビニルカルバゾールを＊Ｏｔｌの厚さ
に真空加熱蒸着法により設けた。Next, polyvinylcarbazole was provided as an insulating organic compound on the π-conjugated polymer sample (I) to a thickness of *Otl by vacuum heating evaporation.
この際の蒸着条件は、圧力１． ＯＸ １０ Ｔｏｒ
ｒ％加熱温度６ｓｏ℃、ポリｐ−７エ＝ｔｚｙｌ 、
３ 、４−オキサジアゾニルの仕込み量０．１ｇ、π−
共役系扁分子試料（Ｉ）と加熱源との距離１ｏｃｇ
である。このようにしてπ−共役系高分子試料（１１）
を得る。The vapor deposition conditions at this time were pressure 1. OX10 Tor
r% heating temperature 6so℃, polyp-7e=tzyl,
3, Amount of 4-oxadiazonyl charged: 0.1 g, π-
Distance between conjugated thin molecule sample (I) and heating source: 1 ocg
It is. In this way, the π-conjugated polymer sample (11)
get.
さらに、π−共役系高分子試料（ＩＩ）の上に真空蒸着
法によりインジウム（Ｉｎ）層を約ａｏｏｏ ７Ｐの厚
さで設けること罠より得られたＭＩＤダイオードＩＭ工
Ｓダイオ−Ｆ試料（Ｉ）とする。Furthermore, an indium (In) layer was formed on the π-conjugated polymer sample (II) by vacuum evaporation to a thickness of approximately 7P. ).
実施例Ｂ
実施例１で得られたπ−共役系高分子試料（Ｉ）を用い
て、この上に、加熱温度２８０℃とした以外は実施例１
と同様の方法で、メロシアニン系色素ＮＫ−１１０４５
（日本感光色素社製） ｔ’ １０００ｊの厚さに設け
、さらに実施例１こ同様にＩｎ層を設けることによって
ＭＩ８ダイオード試料（［［）を得た。Example B Example 1 was applied except that the π-conjugated polymer sample (I) obtained in Example 1 was used and the heating temperature was 280°C.
In the same manner as above, merocyanine dye NK-11045
(manufactured by Nippon Kanko Shiki Co., Ltd.) A MI8 diode sample ([[) was obtained by providing a thickness of t' 1000j and further providing an In layer in the same manner as in Example 1.
実施例８
実施例１と同様の方法でπ−共役系高分子層を約４００
ｏｊＰの厚さに析出させた後、作用ｔｔ！ｉｉと対極
を短絡し１ｇｏ分間ホールドした後、洗浄、乾燥し、８
０℃で８時間空気中で加熱処理を行つ次。しかる後にこ
の試料をトリエチルアミン蒸気中に３０分間さらし、π
−共役系高分子試料（ｎ）を得た。Example 8 Approximately 400 π-conjugated polymer layers were formed in the same manner as in Example 1.
After depositing to the thickness of ojP, the action tt! After short-circuiting ii and the counter electrode and holding for 1 minute, wash and dry.
Next, perform heat treatment in air for 8 hours at 0 °C. The sample was then exposed to triethylamine vapor for 30 minutes and π
- A conjugated polymer sample (n) was obtained.
次に、π−共役系高分子試料（ｎ）の上に、絶縁性有機
化合物として、テトラシアノキノジメタン（ＴＯＮＱ）
溶液を厚さ１００Ｇ７’になるようにスピナーで塗
布し、実施例１と同様にＩｎ層を設けることによってＭ
工８ダイオード試料（２））を得た。Next, tetracyanoquinodimethane (TONQ) was added as an insulating organic compound on the π-conjugated polymer sample (n).
M
A diode sample (2)) was obtained.
比較例１
実施例１で得られたπ−共役系高分子試料（夏）ノ上に
工ｎ／ｍヲ約ａｏｏｏ７Ｐの厚さで設けることによって
得られた有機ショットキーダイオードを比較試料（Ｉ）
とする。Comparative Example 1 Comparative sample (I) was an organic Schottky diode obtained by disposing an organic Schottky diode with a thickness of about 7 P in n/m on the π-conjugated polymer sample (Summer) obtained in Example 1.
shall be.
比較例２
実施例１で得られたπ−共役系高分子試料（１）の上に
ポリエチレン（ｐＩｌり層を真空加熱蒸着法を用いて１
ＧＯＡ’の厚さになる様に設けた。この際の蒸着条件は
、圧力１． ＯＸ １０ ＴＯｒｒ、加熱温度２５０
℃、Ｐｉｌ＋の仕込み量０．０５ｇ、π−共役系高分子
試料（Ｉｌと加熱源との距離７ａである。この様罠して
得られた試料をπ−共役系高分子試料（マ）とする。Comparative Example 2 A polyethylene (pIl layer) was deposited on the π-conjugated polymer sample (1) obtained in Example 1 using a vacuum heating evaporation method.
It was provided so as to have the thickness of GOA'. The vapor deposition conditions at this time were pressure 1. OX 10 Torr, heating temperature 250
°C, the amount of Pil+ charged is 0.05 g, the π-conjugated polymer sample (distance between Il and the heating source is 7a), and the sample obtained by trapping in this way is called the π-conjugated polymer sample (Ma). do.
さらに、π−共役系高分子試料（マ）の上ＫＩｎ層を約
５ｏｏｏ７′の厚さで設けることによって得られたＭＩ
Ｂダイオードを比較試料（ＩＮ）とする。Furthermore, the MI obtained by providing a KIn layer on the π-conjugated polymer sample (Ma) with a thickness of about 5007'
The B diode is used as a comparison sample (IN).
第１図にＭ工Ｓダイオード試料（１）な−し試料（叫の
、第３図に比較試料（夏）の、第３図に比較試料（ｒｌ
）の断面図を示す。Figure 1 shows the M-S diode sample (1) without sample (sold out), Figure 3 shows the comparative sample (summer), and Figure 3 shows the comparative sample (rl
) is shown.
図において（９）、（ＩＩＦｉリード線、（１０１＃：
を工ｎ電極、（１１）は絶縁性有機化合物層、 （１２
１はボｌｌＮ−メチルビロール膜、（Ｉ４はＡｕ電極、
（ＩＦＡはガラス基板、鐸けｐＦＸ蒸着膜である。In the figure (9), (IIFi lead wire, (101#:
(11) is an insulating organic compound layer, (12
1 is a bollN-methylvirol film, (I4 is an Au electrode,
(IFA is a glass substrate and a pFX deposited film.
変化を示すＩ−マ特性図である妙
図中、（財）、四は比較試料（１）および比較試料（Ｉ
ｍ）の特性、彌〜（至）は各々ＭＩＥＩダイオード試料
（夏）〜試料（Ｉｌｌ）の特性である。なお、正電圧側
か順方向、負電圧側が逆方向である。これによると、こ
の発明の実施例により得られたＶ工Ｓダイオードは、良
好な整流特性が観測され、しかもＰ！、線層の層厚が厚
いにもかかわらず順方向で大きな電流が得られ、製造時
の層厚制御により所望の特性のＭ工Ｓダイオードを得る
ことができることが解る。The I-ma characteristic diagram showing the changes in Myozuchu (Taiwan), 4 shows the comparative sample (1) and the comparative sample (I
The characteristics of m) and 匌 (to) are the characteristics of the MIEI diode sample (summer) to sample (Ill), respectively. Note that the positive voltage side is the forward direction, and the negative voltage side is the reverse direction. According to this, the V-type S diode obtained according to the embodiment of the present invention was observed to have good rectification characteristics, and moreover, P! It can be seen that a large current can be obtained in the forward direction despite the thick line layer, and that an M-S diode with desired characteristics can be obtained by controlling the layer thickness during manufacturing.
以上のように、この発明によれば、電極となる導電層、
電解本合法により形成されたπ−共役系高分子からなる
半導体層、電子受容性基および電子供与性基の少なくと
も一方を有する絶縁性有機化合物層、並びに電極となる
金属層を積層するので、容易に、高性能でかつ性能の安
定したＭＩＳダイオードの製造方法を得ることができる
。As described above, according to the present invention, a conductive layer serving as an electrode,
A semiconductor layer made of a π-conjugated polymer formed by an electrolytic method, an insulating organic compound layer having at least one of an electron-accepting group and an electron-donating group, and a metal layer serving as an electrode can be laminated easily. Furthermore, a method for manufacturing an MIS diode with high performance and stable performance can be obtained.
、なお、絶縁性有機化合物層ｔ−蒸発法でｔｂ成すれば
、層厚制御も容易であり、例えば光センサや光電変換素
子など種々の部品の製造に有用である。Note that if the insulating organic compound layer tb is formed by the t-evaporation method, the layer thickness can be easily controlled, and it is useful for manufacturing various parts such as optical sensors and photoelectric conversion elements, for example.
第１図はこの発明の一実施例による方法で製造されたＭ
工Ｓダイオードを示す断面図、第８図は一般的な有機シ
ョットキーダイオードを示す断面図、第８図は従来の一
般的な有機Ｍ工Ｓダイオードを示す断面図、第４図はこ
の発明の一実施例によるＭＩＳダイオード、一般的な有
機ショットキーグイオーＦ、および従来の一般的な有機
Ｍ工Ｓダイオードを比較するための電流（Ｉ）−電圧（
マ）特性図、第５図は一般的なＭ工８ダイオードを示す
断面図、第６図は従来のＭＯＳダイオードを示す断面図
である。
図において、（１）、（６）、（９：、Ｑ３１はリード
線、（２１は電極となる金属層、（３；は絶縁層、（４
１は半導体層、＋５１ Ｆｉ電極となる導電ｉ’Ｒｓ
（７１［８１０１層、（８）はＳ１層、ｆｌｏｌ ｒｉ
Ｉｎ層、（ＩＩ） ［絶縁性有機化合物層、＋１２）は
ポリＮ−メチルピロール膜、０４はＡｕ電極、−はガラ
ス基板、（２１はＰＥ蒸着膜、（財）、（至）は−それ
ぞれ比較試料（Ｉ）および（■）の特性、四〜ｆ２１は
それぞれこの発明の一実施例により得られたＷＥＢダイ
オード試料（Ｉ）〜−）の特性である。
なお、各図中同一符号は１ｉ５１−また＃−を相当部分
？示すものとする。FIG. 1 shows an M manufactured by a method according to an embodiment of the present invention.
8 is a cross-sectional view showing a general organic Schottky diode. FIG. 8 is a cross-sectional view showing a conventional general organic M-S diode. FIG. Current (I) - Voltage (
Fig. 5 is a sectional view showing a general M8 diode, and Fig. 6 is a sectional view showing a conventional MOS diode. In the figure, (1), (6), (9:, Q31 is a lead wire, (21 is a metal layer that becomes an electrode, (3; is an insulating layer, (4;
1 is a semiconductor layer, +51 is a conductive i'Rs that becomes a Fi electrode.
(71 [8101 layer, (8) is S1 layer, flol ri
In layer, (II) [Insulating organic compound layer, +12] is polyN-methylpyrrole film, 04 is Au electrode, - is glass substrate, (21 is PE vapor deposited film, (goods), (to) - respectively The characteristics of comparative samples (I) and (■), and 4 to f21 are the characteristics of WEB diode samples (I) to -) obtained in accordance with an embodiment of the present invention, respectively. In addition, the same symbols in each figure are 1i51- and #- are the corresponding parts? shall be indicated.
Claims (2)
層、および電極となる金属層を積層するＭＩＳダイオー
ドの製造方法において、上記半導体層が電解重合法によ
り形成されたπ−共役系高分子からなり、上記絶縁性有
機化合物が電子受容性基および電子供与性基の少なくと
も一方を有することを特徴とするＭＩＳダイオードの製
造方法。(1) In a method for manufacturing an MIS diode in which a conductive layer, a semiconductor layer, an insulating organic compound layer, and a metal layer as an electrode are laminated, the semiconductor layer is a π-conjugated polymer formed by electrolytic polymerization. A method for manufacturing an MIS diode, characterized in that the insulating organic compound has at least one of an electron-accepting group and an electron-donating group.
置換ピロール、ピロールとＮ−置換ピロールの共重合体
、ポリチエニレン、ポリアニリン、ポリフラン、ポリア
ズレン、ポリビニルピリジンおよびポリチオフェンの内
の少くとも一種である特許請求の範囲第１項記載のＭＩ
Ｓダイオードの製造方法。(2) The π-conjugated polymer is polypyrrole, poly-N-
MI according to claim 1, which is at least one of substituted pyrrole, copolymer of pyrrole and N-substituted pyrrole, polythienylene, polyaniline, polyfuran, polyazulene, polyvinylpyridine, and polythiophene.
Method of manufacturing S diode.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60003601A JPS61163659A (en) | 1985-01-12 | 1985-01-12 | Manufacture of mis diode |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60003601A JPS61163659A (en) | 1985-01-12 | 1985-01-12 | Manufacture of mis diode |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS61163659A true JPS61163659A (en) | 1986-07-24 |
Family
ID=11562004
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60003601A Pending JPS61163659A (en) | 1985-01-12 | 1985-01-12 | Manufacture of mis diode |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS61163659A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01294856A (en) * | 1988-05-20 | 1989-11-28 | Nippon Telegr & Teleph Corp <Ntt> | Manufacture of organic functional film and itself |
| EP0449226A1 (en) * | 1990-03-27 | 1991-10-02 | Seiko Epson Corporation | Non-linear resistor switching element, active matrix liquid crystal panel using the same, and method for manufacturing the non-linear resistor switching element |
| US5140398A (en) * | 1986-12-24 | 1992-08-18 | Canon Kabushiki Kaisha | Switching device |
| US5175114A (en) * | 1989-01-13 | 1992-12-29 | Seiko Epson Corporation | Method for production of a bidirectional nonlinear resistor, active matrix liquid crystal panel using bidirectional nonlinear resistor |
| US5294560A (en) * | 1989-01-13 | 1994-03-15 | Seiko Epson Corporation | Bidirectional nonlinear resistor, active matrix liquid crystal panel using bidirectional nonlinear resistor, and method for production thereof |
| US5485294A (en) * | 1987-12-18 | 1996-01-16 | Seiko Epson Corporation | Process for producing MIM elements by electrolytic polymerization |
| FR2821575A1 (en) * | 2001-03-02 | 2002-09-06 | Commissariat Energie Atomique | METHOD FOR LOCALIZED ORGANIC GRAFTING WITHOUT MASK ON CONDUCTIVE OR SEMICONDUCTOR PROPERTIES OF COMPOSITE SURFACES |
-
1985
- 1985-01-12 JP JP60003601A patent/JPS61163659A/en active Pending
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5140398A (en) * | 1986-12-24 | 1992-08-18 | Canon Kabushiki Kaisha | Switching device |
| US5485294A (en) * | 1987-12-18 | 1996-01-16 | Seiko Epson Corporation | Process for producing MIM elements by electrolytic polymerization |
| JPH01294856A (en) * | 1988-05-20 | 1989-11-28 | Nippon Telegr & Teleph Corp <Ntt> | Manufacture of organic functional film and itself |
| US5175114A (en) * | 1989-01-13 | 1992-12-29 | Seiko Epson Corporation | Method for production of a bidirectional nonlinear resistor, active matrix liquid crystal panel using bidirectional nonlinear resistor |
| US5294560A (en) * | 1989-01-13 | 1994-03-15 | Seiko Epson Corporation | Bidirectional nonlinear resistor, active matrix liquid crystal panel using bidirectional nonlinear resistor, and method for production thereof |
| EP0449226A1 (en) * | 1990-03-27 | 1991-10-02 | Seiko Epson Corporation | Non-linear resistor switching element, active matrix liquid crystal panel using the same, and method for manufacturing the non-linear resistor switching element |
| FR2821575A1 (en) * | 2001-03-02 | 2002-09-06 | Commissariat Energie Atomique | METHOD FOR LOCALIZED ORGANIC GRAFTING WITHOUT MASK ON CONDUCTIVE OR SEMICONDUCTOR PROPERTIES OF COMPOSITE SURFACES |
| WO2002070148A1 (en) * | 2001-03-02 | 2002-09-12 | Commissariat A L'energie Atomique | Method for mask-free localised organic grafting on conductive or semiconductive portions of composite surfaces |
| JP2004524149A (en) * | 2001-03-02 | 2004-08-12 | コミツサリア タ レネルジー アトミーク | Method for mask-free local grafting of organics onto conductive or semiconductive parts of composite surfaces |
| AU2002241072B2 (en) * | 2001-03-02 | 2007-02-01 | Commissariat A L'energie Atomique | Method for mask-free localised organic grafting on conductive or semiconductive portions of composite surfaces |
| KR101017493B1 (en) | 2001-03-02 | 2011-02-25 | 꼼미사리아 아 레네르지 아또미끄 에 오 에네르지 알떼르나띠브스 | Method for mask-free localised organic grafting on conductive or semiconductive portions of composite surfaces |
| JP4667715B2 (en) * | 2001-03-02 | 2011-04-13 | コミッサリア ア レネルジー アトミーク エ オ ゼネルジ ザルタナテイヴ | Method for locally grafting organic matter mask-free onto conductive or semiconductive portions of a composite surface |
| US8394460B2 (en) | 2001-03-02 | 2013-03-12 | Commissariat A L'energie Atomique | Method for mask-free localized organic grafting on conductive or semiconductive portions of composite surfaces |
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