JP5667558B2 - Organic switching element and manufacturing method thereof - Google Patents
Organic switching element and manufacturing method thereof Download PDFInfo
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- JP5667558B2 JP5667558B2 JP2011501677A JP2011501677A JP5667558B2 JP 5667558 B2 JP5667558 B2 JP 5667558B2 JP 2011501677 A JP2011501677 A JP 2011501677A JP 2011501677 A JP2011501677 A JP 2011501677A JP 5667558 B2 JP5667558 B2 JP 5667558B2
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- formula
- metal fine
- switching element
- carbon atoms
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- 238000004519 manufacturing process Methods 0.000 title claims description 4
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- 229910052751 metal Inorganic materials 0.000 claims description 66
- 239000002184 metal Substances 0.000 claims description 66
- 229920000587 hyperbranched polymer Polymers 0.000 claims description 34
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 29
- 238000000034 method Methods 0.000 claims description 26
- 125000004432 carbon atom Chemical group C* 0.000 claims description 25
- 239000002270 dispersing agent Substances 0.000 claims description 25
- 239000010409 thin film Substances 0.000 claims description 24
- 229910052757 nitrogen Inorganic materials 0.000 claims description 22
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 19
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 19
- 229920000642 polymer Polymers 0.000 claims description 17
- 125000005843 halogen group Chemical group 0.000 claims description 14
- 239000002245 particle Substances 0.000 claims description 14
- 125000002947 alkylene group Chemical group 0.000 claims description 12
- 229910052697 platinum Inorganic materials 0.000 claims description 11
- 125000000217 alkyl group Chemical group 0.000 claims description 10
- 125000004122 cyclic group Chemical group 0.000 claims description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 10
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 9
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- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 8
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- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 5
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- 229940100684 pentylamine Drugs 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
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- 239000004065 semiconductor Substances 0.000 description 4
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- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-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
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 3
- 229910006404 SnO 2 Inorganic materials 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000005227 gel permeation chromatography Methods 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 239000012212 insulator Substances 0.000 description 3
- 229910052741 iridium Inorganic materials 0.000 description 3
- 239000011572 manganese Substances 0.000 description 3
- 229910052750 molybdenum Inorganic materials 0.000 description 3
- XTAZYLNFDRKIHJ-UHFFFAOYSA-N n,n-dioctyloctan-1-amine Chemical group CCCCCCCCN(CCCCCCCC)CCCCCCCC XTAZYLNFDRKIHJ-UHFFFAOYSA-N 0.000 description 3
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- 239000011701 zinc Substances 0.000 description 3
- KHUFHLFHOQVFGB-UHFFFAOYSA-N 1-aminoanthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2N KHUFHLFHOQVFGB-UHFFFAOYSA-N 0.000 description 2
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- LEWZOBYWGWKNCK-UHFFFAOYSA-N 2,3-dihydro-1h-inden-5-amine Chemical compound NC1=CC=C2CCCC2=C1 LEWZOBYWGWKNCK-UHFFFAOYSA-N 0.000 description 1
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- JBIJLHTVPXGSAM-UHFFFAOYSA-N 2-naphthylamine Chemical compound C1=CC=CC2=CC(N)=CC=C21 JBIJLHTVPXGSAM-UHFFFAOYSA-N 0.000 description 1
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
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- DTVYNUOOZIKEEX-UHFFFAOYSA-N 5-aminoisoquinoline Chemical compound N1=CC=C2C(N)=CC=CC2=C1 DTVYNUOOZIKEEX-UHFFFAOYSA-N 0.000 description 1
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- 230000002194 synthesizing effect Effects 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- AOCSUUGBCMTKJH-UHFFFAOYSA-N tert-butyl n-(2-aminoethyl)carbamate Chemical compound CC(C)(C)OC(=O)NCCN AOCSUUGBCMTKJH-UHFFFAOYSA-N 0.000 description 1
- POHWAQLZBIMPRN-UHFFFAOYSA-N tert-butyl n-(3-aminopropyl)carbamate Chemical compound CC(C)(C)OC(=O)NCCCN POHWAQLZBIMPRN-UHFFFAOYSA-N 0.000 description 1
- ZFQWJXFJJZUVPI-UHFFFAOYSA-N tert-butyl n-(4-aminobutyl)carbamate Chemical compound CC(C)(C)OC(=O)NCCCCN ZFQWJXFJJZUVPI-UHFFFAOYSA-N 0.000 description 1
- YBRBMKDOPFTVDT-UHFFFAOYSA-N tert-butylamine Chemical compound CC(C)(C)N YBRBMKDOPFTVDT-UHFFFAOYSA-N 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 229910052716 thallium Inorganic materials 0.000 description 1
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- DANYXEHCMQHDNX-UHFFFAOYSA-K trichloroiridium Chemical compound Cl[Ir](Cl)Cl DANYXEHCMQHDNX-UHFFFAOYSA-K 0.000 description 1
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N70/00—Solid-state devices having no potential barriers, and specially adapted for rectifying, amplifying, oscillating or switching
- H10N70/20—Multistable switching devices, e.g. memristors
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- 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
- H10K85/141—Organic polymers or oligomers comprising aliphatic or olefinic chains, e.g. poly N-vinylcarbazol, PVC or PTFE
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N70/00—Solid-state devices having no potential barriers, and specially adapted for rectifying, amplifying, oscillating or switching
- H10N70/011—Manufacture or treatment of multistable switching devices
- H10N70/021—Formation of switching materials, e.g. deposition of layers
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N70/00—Solid-state devices having no potential barriers, and specially adapted for rectifying, amplifying, oscillating or switching
- H10N70/801—Constructional details of multistable switching devices
- H10N70/821—Device geometry
- H10N70/826—Device geometry adapted for essentially vertical current flow, e.g. sandwich or pillar type devices
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N70/00—Solid-state devices having no potential barriers, and specially adapted for rectifying, amplifying, oscillating or switching
- H10N70/801—Constructional details of multistable switching devices
- H10N70/881—Switching materials
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- 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 potential barriers
- H10K10/50—Bistable switching devices
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- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Semiconductor Memories (AREA)
- Conductive Materials (AREA)
Description
本発明は、有機メモリ素子などへの応用が期待される、2つの電極間に有機双安定性材料を挟み込んだスイッチング素子に関する。 The present invention relates to a switching element in which an organic bistable material is sandwiched between two electrodes, which is expected to be applied to an organic memory element or the like.
従来の半導体材料に対して、低コスト、高い柔軟性などの特性を有する有機電子材料の開発は目覚しい進展をみせている。特に、材料に電圧を印加していくと、ある電圧以上で急激に回路の電流が増加してスイッチング現象が観測される有機双安定材料は、高密度な有機メモリ素子などへの適用を検討されている。 Compared to conventional semiconductor materials, organic electronic materials having characteristics such as low cost and high flexibility have made remarkable progress. In particular, when a voltage is applied to a material, an organic bistable material whose switching current is observed due to a sudden increase in circuit current above a certain voltage is being considered for application to high-density organic memory devices. ing.
このような素子の動作機構は二つの抵抗状態での可逆的なスイッチングによってなされる。例えば、Yang Yangらは、アミノイミダゾールジカーボニトリル(AIDCN)、ヒドロキシキノリンアルミニウム(Alq)などの有機半導体やポリスチレン、PMMA等の有機絶縁体中に、アルミニウム、銅、銀、金、ニッケル、マグネシウム、インジウム、カルシウム、リチウム等の高導電率材料を薄膜形成、もしくは微粒子として分散させることにより、電圧印加によって高抵抗状態と低抵抗状態の双安定性を得ることができ、電圧をゼロにしても情報が保持される不揮発性メモリであることを示した(特許文献1、2、非特許文献1参照)。 The operation mechanism of such an element is achieved by reversible switching between two resistance states. For example, Yang Yang et al. In aluminum, copper, silver, gold, nickel, magnesium, organic semiconductors such as aminoimidazole dicarbonitrile (AIDCN), hydroxyquinoline aluminum (Alq), and organic insulators such as polystyrene and PMMA, High-conductivity materials such as indium, calcium, and lithium can be formed into thin films or dispersed as fine particles to obtain bistability in a high resistance state and a low resistance state by applying a voltage. Is a non-volatile memory (see Patent Documents 1 and 2 and Non-Patent Document 1).
また、特許文献3には、一つの分子内に電子供与性の官能基と電子受容性の官能基とを有する有機双安定材料層中に、導電性微粒子として平均粒径5nm以下の白金又はロジウム微粒子が分散したスイッチング素子が記載されている。そしてこれにより、粒径にばらつきの少ない微粒子を膜厚の薄い微粒子分散層中に均一に分散することができるので、安定した特性のスイッチング素子が得られることが記載される。 Patent Document 3 discloses platinum or rhodium having an average particle size of 5 nm or less as conductive fine particles in an organic bistable material layer having an electron-donating functional group and an electron-accepting functional group in one molecule. A switching element in which fine particles are dispersed is described. It is described that fine particles with little variation in particle size can be uniformly dispersed in a fine particle dispersion layer having a small film thickness, and a switching element with stable characteristics can be obtained.
しかしながら、金属微粒子を分散させた有機双安定材料において、その素子特性の安定化は重要な課題として残されている。これは、金属微粒子の粒径が多分散であり、粒子へ注入される電荷が一定とはならずばらつきが生ずるためである。この課題は、有機半導体又は有機絶縁体中への分散性が高い、粒径が均一な金属微粒子を開発することにより達せられるものと考えられる。これに対し、上記特許文献1、2及び非特許文献1に記載の技術は、有機半導体又は有機絶縁体における金属微粒子の分散剤について具体的に提案していない。また、従来の素子は、高抵抗状態(ON状態)及び低抵抗状態(OFF状態)における電流値が比較的低く、情報としての読み取りが困難であるという問題があった。 However, in organic bistable materials in which metal fine particles are dispersed, stabilization of device characteristics remains an important issue. This is because the particle size of the metal fine particles is polydispersed, and the electric charge injected into the particles is not constant and varies. This problem is considered to be achieved by developing metal fine particles having high dispersibility in an organic semiconductor or an organic insulator and having a uniform particle size. On the other hand, the techniques described in Patent Documents 1 and 2 and Non-Patent Document 1 do not specifically propose a dispersant for metal fine particles in an organic semiconductor or an organic insulator. Further, the conventional element has a problem that current values in a high resistance state (ON state) and a low resistance state (OFF state) are relatively low, and reading as information is difficult.
本発明者らは、上記の課題を解決するために鋭意検討した結果、アンモニウム基を含有する金属微粒子分散剤を採用したことにより、粒子径が小さく、ばらつきが極めて少ない金属微粒子を得ることができた。また、この金属微粒子を使用した双安定性材料を用いることによって、十分に高いON/OFF比が安定的に得られ、ON状態及びOFF状態の電流値を従来の素子よりも高めることに成功した。 As a result of intensive investigations to solve the above-mentioned problems, the present inventors have been able to obtain metal fine particles having a small particle diameter and very little variation by adopting a metal fine particle dispersant containing an ammonium group. It was. Moreover, by using a bistable material using the metal fine particles, a sufficiently high ON / OFF ratio was stably obtained, and the current values in the ON state and the OFF state were successfully increased as compared with the conventional device. .
即ち、本発明は、第1観点として、金属微粒子を含有する有機薄膜を2つの電極で挟んだ構造を有し、印加される電圧に対して2種類の安定な抵抗値を持つ電流双安定性を示すスイッチング素子において、前記金属微粒子が、アンモニウム基を含有し重量平均分子量
が500ないし5,000,000である高分子からなる金属微粒子分散剤によって前記有機薄膜中に分散されていることを特徴とするスイッチング素子、
第2観点として、前記金属微粒子の金属種が、金、銀、白金及び銅よりなる群より選択される少なくとも1種である第1観点に記載のスイッチング素子、
第3観点として、前記金属微粒子分散剤が、アルキルアンモニウム基を含有する第1観点に記載のスイッチング素子、
第4観点として、前記金属微粒子分散剤が式(1):
R1は水素原子又はメチル基を表し、
R2、R3及びR4は、それぞれ独立して、水素原子、炭素原子数1ないし20の直鎖状、枝分かれ状又は環状のアルキル基、炭素原子数6ないし20のアリールアルキル基又は−(CH2CH2O)m−R5(式中、R5は水素原子又はメチル基を表し、mは2ないし100の任意の整数を表す。)を表すか、R2、R3及びR4が互いに直鎖状、枝分かれ状又は環状のアルキレン基で結合し、それらと結合する窒素原子と共に環を形成してもよく(該アルキル基及びアリールアルキル基はアルコキシ基、ヒドロキシル基、アンモニウム基、カルボキシル基又はシアノ基で置換されていてもよい)、
X−は陰イオンを表し、
A1は式(2)又は式(3):
Y1、Y2、Y3又はY4は、それぞれ独立して、水素原子、炭素原子数1ないし20のアルキル基、炭素原子数1ないし20のアルコキシ基、ニトロ基、ヒドロキシル基、アミ
ノ基、カルボキシル基又はシアノ基を表す。)で表される構造を表し、
nは繰り返し単位構造の数であって2ないし100,000の整数を表す。]で表される高分岐高分子化合物である第1観点に記載のスイッチング素子、
第5観点として、前記金属微粒子の平均粒径が1nm以上500nm以下である第1観点に記載のスイッチング素子、
第6観点として、前記有機薄膜を形成するマトリックス高分子が、ポリスチレン、ポリメタクリル酸メチル、又はハイパーブランチポリマーである第1観点に記載のスイッチング素子、
第7観点として、前記ハイパーブランチポリマーが、式(4)で表されるものである、第6観点に記載のスイッチング素子、
第8観点として、前記ハイパーブランチポリマーは、式中のA 2 が、式(7)又は式(8)で表されるものである、第7観点に記載のスイッチング素子、
第9観点として、基板上に電極を形成する工程、該電極上に金属微粒子を含有する有機薄膜を形成する工程、及び、該有機薄膜上に電極を形成する工程を含むことを特徴とする第1観点に記載のスイッチング素子の製造方法、
である。
That is, as a first aspect, the present invention has a structure in which an organic thin film containing metal fine particles is sandwiched between two electrodes, and has two types of stable resistance values with respect to an applied voltage. In the switching element, the metal fine particles are dispersed in the organic thin film by a metal fine particle dispersant made of a polymer containing an ammonium group and having a weight average molecular weight of 500 to 5,000,000. A switching element,
As a second aspect, the switching element according to the first aspect, wherein the metal species of the metal fine particles is at least one selected from the group consisting of gold, silver, platinum, and copper,
As a third aspect, the switching element according to the first aspect, in which the metal fine particle dispersant contains an alkyl ammonium group,
As a fourth aspect, the metal fine particle dispersant is represented by the formula (1):
R 1 represents a hydrogen atom or a methyl group,
R 2 , R 3 and R 4 are each independently a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, an arylalkyl group having 6 to 20 carbon atoms or — ( CH 2 CH 2 O) m —R 5 (wherein R 5 represents a hydrogen atom or a methyl group, m represents an arbitrary integer of 2 to 100), or R 2 , R 3 and R 4. May be bonded to each other by a linear, branched or cyclic alkylene group, and may form a ring together with the nitrogen atom bonded thereto (the alkyl group and the arylalkyl group are an alkoxy group, a hydroxyl group, an ammonium group, a carboxyl group) Group or a cyano group).
X − represents an anion,
A 1 represents formula (2) or formula (3):
Y 1 , Y 2 , Y 3 or Y 4 each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a nitro group, a hydroxyl group, an amino group, Represents a carboxyl group or a cyano group. )
n is the number of repeating unit structures and represents an integer of 2 to 100,000. The switching element according to the first aspect, which is a hyperbranched polymer compound represented by:
As a fifth aspect, the switching element according to the first aspect, wherein the metal fine particles have an average particle size of 1 nm or more and 500 nm or less,
As a sixth aspect, the switching polymer according to the first aspect, wherein the matrix polymer that forms the organic thin film is polystyrene, polymethyl methacrylate, or a hyperbranched polymer,
As a seventh aspect, the hyperbranched polymer is represented by the formula (4), the switching element according to the sixth aspect,
As an eighth aspect, the hyperbranched polymer is a switching element according to the seventh aspect, in which A 2 in the formula is represented by the formula (7) or the formula (8):
A ninth aspect includes a step of forming an electrode on a substrate, a step of forming an organic thin film containing metal fine particles on the electrode, and a step of forming an electrode on the organic thin film. A method for manufacturing a switching element according to one aspect,
It is.
微粒子分散型の有機メモリ素子において、アンモニウム基を有する高分子により分散された金属微粒子を採用したことにより、粒子径が小さく、ばらつきが極めて少ない金属微粒子を得ることができた。この金属微粒子は分散性が高く、粒子へ注入される電荷が一定となるため、この金属微粒子を使用した双安定性材料を用いることによって、ON状態及びOFF状態の電流値を従来の素子よりも高めることに成功した。 In the fine particle-dispersed organic memory element, metal fine particles dispersed by a polymer having an ammonium group were employed, whereby metal fine particles having a small particle diameter and extremely small variation could be obtained. Since this metal fine particle has high dispersibility and the electric charge injected into the particle becomes constant, by using a bistable material using this metal fine particle, the current value in the ON state and the OFF state can be made higher than that of the conventional device. Succeeded in raising.
以下、本発明を実施するための詳細を説明する。
図1に本発明のスイッチング素子1の実施形態を示す模式図を挙げる。スイッチング素子1は、基板上に第一電極2、有機薄膜3、第二電極4を積層した構造となっており、第一電極2及び第二電極4は、電気結線5及び6によってそれぞれ、電子制御ユニット7に接続されている。このうち、有機薄膜3は、金属微粒子8がマトリックス9中に分散して形成されている。
第一電極及び第二電極の形成方法としては、真空蒸着法、スパッタ法、塗布法、インクジェット法、印刷法、ゾルゲル法等が挙げることができ、更にそのパターニング方法としては、フォトリソグラフィー法、インクジェット法、スクリーン印刷、オフセット印刷、凸版印刷等の印刷法、マイクロコンタクトプリンティング法、シャドーマスクを用いた蒸着法及びこれらの手法を複数組み合わせた方法が挙げることができる。
また有機薄膜は、蒸着法、スピンコート法、ディップ法などから適宜選択して積層される。Details for carrying out the present invention will be described below.
FIG. 1 is a schematic diagram showing an embodiment of the switching element 1 of the present invention. The switching element 1 has a structure in which a first electrode 2, an organic thin film 3, and a second electrode 4 are stacked on a substrate. The first electrode 2 and the second electrode 4 are electronically connected by electrical connections 5 and 6, respectively. It is connected to the control unit 7. Among these, the organic thin film 3 is formed by dispersing metal fine particles 8 in a matrix 9.
Examples of the method for forming the first electrode and the second electrode include a vacuum deposition method, a sputtering method, a coating method, an ink jet method, a printing method, a sol-gel method, and the patterning method includes a photolithography method and an ink jet method. And printing methods such as screen printing, offset printing and letterpress printing, microcontact printing methods, vapor deposition methods using shadow masks, and methods combining a plurality of these methods.
The organic thin film is laminated by appropriately selecting from an evaporation method, a spin coating method, a dip method and the like.
第一電極及び第二電極材料としては、Au、Pt、Ag、Al、Cu、Rh、Ir、In、Ni、Pd、As、Se、Te、Mo、W、Mg、Zn等の金属、Mg/Cu、Mg/Ag、Mg/Al、Mg/In等の合金、SnO2、InO2、ZnO、InO2・SnO2(ITO)、Sb2O5・SnO2(ATO)等の金属酸化物、導電性ポリアニリン、導電性ポリピロール、導電性ポリチオフェン等の導電性高分子、カーボン等が挙げられる。As the first electrode and the second electrode material, metals such as Au, Pt, Ag, Al, Cu, Rh, Ir, In, Ni, Pd, As, Se, Te, Mo, W, Mg, Zn, Mg / Alloys such as Cu, Mg / Ag, Mg / Al, Mg / In, metal oxides such as SnO 2 , InO 2 , ZnO, InO 2 .SnO 2 (ITO), Sb 2 O 5 .SnO 2 (ATO), conductivity Examples thereof include conductive polymers such as polyaniline, conductive polypyrrole, and conductive polythiophene, and carbon.
有機薄膜に用いられる微粒子としては、有機化合物によって分散安定化されており、平均粒径が1ないし500nm、好ましくは1ないし100nm、より好ましくは、1ないし10nmのものが使用できる。また、金属微粒子の金属種としてはAu、Pt、Ag、Al、Cu、Rh、Ir、In、Ni、Pd、As、Se、Te、Mo、W、Mg、Zn等が挙げられ、好ましくはAu、Ag、Pt及Cuが挙げられる。 The fine particles used in the organic thin film can be dispersed and stabilized with an organic compound and have an average particle size of 1 to 500 nm, preferably 1 to 100 nm, more preferably 1 to 10 nm. Examples of the metal species of the metal fine particles include Au, Pt, Ag, Al, Cu, Rh, Ir, In, Ni, Pd, As, Se, Te, Mo, W, Mg, Zn, and preferably Au. , Ag, Pt and Cu.
有機薄膜のマトリックスとしては、ポリスチレン、ポリエステル類、ポリビニルアルコール、ポリカーボネート、ポリアクリル酸メチル等のポリアクリル酸類、ポリメタクリル酸メチル等のポリメタクリル酸類、ポリオレフィン類、ポリアミド類、ポリイミド類、ポリウレタン類、ポリアセタール類、ポリシリコーン類、ポリビニルピリジン等の材料が適用可能であり、好ましくは、ポリスチレン及びポリメタクリル酸メチルが挙げられる。 The matrix of the organic thin film includes polystyrene, polyesters, polyvinyl alcohol, polycarbonate, polyacrylic acids such as polymethyl acrylate, polymethacrylic acids such as polymethyl methacrylate, polyolefins, polyamides, polyimides, polyurethanes, and polyacetals. Materials such as styrene, poly-silicone, and polyvinyl pyridine are applicable, and polystyrene and polymethyl methacrylate are preferable.
有機薄膜をスピンコート法やディップ法などで塗布する場合は、トルエン、キシレン、ジクロロベンゼン等の芳香族系溶媒、メチルエチルケトン、シクロヘキサノン等のケトン系溶媒、テトラヒドロフラン等のエーテル系溶媒から選択して用いられる。 When an organic thin film is applied by a spin coating method or a dip method, an aromatic solvent such as toluene, xylene or dichlorobenzene, a ketone solvent such as methyl ethyl ketone or cyclohexanone, or an ether solvent such as tetrahydrofuran is used. .
本発明においては、アンモニウム基を有する高分子からなる金属微粒子分散剤が使用される。この金属微粒子分散剤の含有により、平均粒径が10nm以下、例えばおよそ3.5nmの金属微粒子に対しての分散状態を作り出すことができる。
なお、金属微粒子分散剤は、ゲル浸透クロマトグラフィーによるポリスチレン換算で測定される重量平均分子量Mwが500ないし5,000,000の範囲のものが使用される。該範囲以外のものであると、金属微粒子の分散性が十分ではない。好ましくは、金属微粒子分散剤は1,000ないし1,000,000の重量平均分子量を有し、より好ましくは2,000ないし500,000であり、特に好ましくは3,000ないし200,000である。また、金属微粒子分散剤の分散度Mw(重量平均分子量)/Mn(数平均分子量)としては1.0ないし7.0であり、好ましくは1.1ないし6.0であり、より好ましくは1.2ないし5.0である。In the present invention, a metal fine particle dispersant made of a polymer having an ammonium group is used. By containing this metal fine particle dispersant, it is possible to create a dispersion state for metal fine particles having an average particle size of 10 nm or less, for example, about 3.5 nm.
In addition, as the metal fine particle dispersant, those having a weight average molecular weight Mw measured in terms of polystyrene by gel permeation chromatography in the range of 500 to 5,000,000 are used. If it is outside this range, the dispersibility of the metal fine particles is not sufficient. Preferably, the metal fine particle dispersant has a weight average molecular weight of 1,000 to 1,000,000, more preferably 2,000 to 500,000, and particularly preferably 3,000 to 200,000. . Further, the dispersity Mw (weight average molecular weight) / Mn (number average molecular weight) of the metal fine particle dispersant is 1.0 to 7.0, preferably 1.1 to 6.0, more preferably 1. .2 to 5.0.
本発明に使用される金属微粒子分散剤は、アンモニウム基を有する高分岐高分子化合物からなり、該高分岐高分子化合物としては、例えば、式(1)
式(1)中、R1は水素原子又はメチル基を表す。また、式(1)中、R2、R3及びR4は、それぞれ独立して、水素原子、炭素原子数1ないし20の直鎖状、枝分かれ状又は環状のアルキル基、炭素原子数6ないし20のアリールアルキル基又は−(CH2CH2O)m−R5(式中、R5は水素原子又はメチル基を表し、mは2ないし100の任意の整数を表す。)を表す。該アルキル基及びアリールアルキル基はアルコキシ基、ヒドロキシル基、アンモニウム基、カルボキシル基又はシアノ基で置換されていてもよい。また、R2、R3及びR4が互いに直鎖状、枝分かれ状又は環状のアルキレン基で結合し、それらと結合する窒素原子と共に環を形成してもよい。また、式(1)中、X−は陰イオンを表し、X−として好ましいのはハロゲン原子、PF6 −、BF4 −又はパーフルオロアルカンスルホナートである。また、式(1)中、A1は式(2)又は式(3):
R 2 、R 3 及びR 4 で表される炭素原子数1ないし20の直鎖状のアルキル基としては、メチル基、エチル基、n−プロピル基、n−ブチル基、n−ペンチル基、n−ヘキシル基、n−ヘプチル基、n−オクチル基、n−ノニル基、n−デシル基、n−ウンデシル基、n−ドデシル基、n−トリデシル基、n−テトラデシル基、n−ペンタデシル基、n−ヘキサデシル基、n−ヘプタデシル基、n−オクタデシル基、n−ノナデシル基、n−エイコシル基等が挙げられる。枝分かれ状のアルキル基としては、イソプロピル基、イソブチル基、sec−ブチル基、tert−ブチル基等が挙げられる。環状のアルキル基としては、シクロペンチル環、シクロヘキシル環構造を有する基等が挙げられる。炭素原子数7ないし20のアリールアルキル基としては、ベンジル基、フェネチル基等が挙げられる。
R 2 、R 3 及びR 4 で表されるアルキレン基としては、メチレン基、エチレン基、ノルマルプロピレン基、ノルマルブチレン基、ノルマルヘキシレン基等の直鎖状アルキレン基等が挙げられる。枝分かれ状アルキレン基としては、イソプロピレン基、イソブチレン基、2−メチルプロピレン基等が挙げられる。環状のアルキレン基としては、炭素原子数3ないし30の単環式、多環式、架橋環式の環状構造の脂環式脂肪族基が挙げられる。具体的には、炭素原子数4以上のモノシクロ、ビシクロ、トリシクロ、テトラシクロ、ペンタシクロ構造等を有する基を挙げることができる。
さらに、式(1)で表される構造でR 2 、R 3 及びR 4 が互いに結合し、それらと結合する窒素原子と共に形成する環としては、ピリジン環、ピリミジン環、ピラジン環、キノリン環、ピピリジル環等が挙げられる。
The metal fine particle dispersant used in the present invention comprises a hyperbranched polymer compound having an ammonium group. Examples of the hyperbranched polymer compound include those represented by the formula (1)
In formula (1), R 1 represents a hydrogen atom or a methyl group. In formula (1), R 2 , R 3 and R 4 each independently represent a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, or 6 to 6 carbon atoms. 20 arylalkyl groups or — (CH 2 CH 2 O) m —R 5 (wherein R 5 represents a hydrogen atom or a methyl group, and m represents an arbitrary integer of 2 to 100). The alkyl group and arylalkyl group may be substituted with an alkoxy group, a hydroxyl group, an ammonium group, a carboxyl group, or a cyano group. R 2 , R 3 and R 4 may be bonded to each other by a linear, branched or cyclic alkylene group, and may form a ring together with the nitrogen atom bonded to them. In formula (1), X − represents an anion, and X − is preferably a halogen atom, PF 6 − , BF 4 — or perfluoroalkanesulfonate. Further, in the formula (1), A 1 has the formula (2) or Formula (3):
Examples of the linear alkyl group having 1 to 20 carbon atoms represented by R 2 , R 3 and R 4 include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, n -Hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n -A hexadecyl group, n-heptadecyl group, n-octadecyl group, n-nonadecyl group, n-eicosyl group, etc. are mentioned. Examples of the branched alkyl group include isopropyl group, isobutyl group, sec-butyl group, tert-butyl group and the like. Examples of the cyclic alkyl group include a cyclopentyl ring and a group having a cyclohexyl ring structure. Examples of the arylalkyl group having 7 to 20 carbon atoms include benzyl group and phenethyl group.
Examples of the alkylene group represented by R 2 , R 3 and R 4 include linear alkylene groups such as a methylene group, an ethylene group, a normal propylene group, a normal butylene group and a normal hexylene group. Examples of the branched alkylene group include an isopropylene group, an isobutylene group, and a 2-methylpropylene group. Examples of the cyclic alkylene group include alicyclic aliphatic groups having a monocyclic, polycyclic or bridged cyclic structure having 3 to 30 carbon atoms. Specific examples include groups having a monocyclo, bicyclo, tricyclo, tetracyclo, or pentacyclo structure having 4 or more carbon atoms.
Furthermore, R 2 , R 3 and R 4 are bonded to each other in the structure represented by the formula (1), and the ring formed together with the nitrogen atom bonded thereto includes a pyridine ring, a pyrimidine ring, a pyrazine ring, a quinoline ring, Examples include a piperidyl ring.
次に、分子末端にアミノ基を有する高分岐高分子化合物の製造法について説明する。
分子末端にアンモニウム基を有する高分岐高分子化合物は、例えば、分子末端にハロゲン原子を有する高分岐高分子化合物にアミン化合物を反応させることによって得ることができる。
なお、分子末端にハロゲン原子を有する高分岐高分子化合物は、国際公開第2008/029688号パンフレットの記載に従い合成することができる。Next, a method for producing a hyperbranched polymer compound having an amino group at the molecular end will be described.
A hyperbranched polymer compound having an ammonium group at the molecular end can be obtained, for example, by reacting an amine compound with a hyperbranched polymer compound having a halogen atom at the molecular end.
The hyperbranched polymer compound having a halogen atom at the molecular end can be synthesized according to the description in International Publication No. 2008/029688 pamphlet.
本反応で使用できるアミン化合物は、第一級アミンとしてN−メチルアミン、N−エチルアミン、N−n−プロピルアミン、N−イソプロピルアミン、N−n−ブチルアミン、N−n−イソブチルアミン、N−sec−ブチルアミン、N−tert−ブチルアミン、N−n−ペンチルアミン、N−n−ヘキシルアミン、N−n−ヘプチルアミン、N−n−オクチルアミン、N−n−ノニルアミン、N−n−デシルアミン、N−n−ウンデシルアミン、N−n−ドデシルミアン、N−n−トリデシルアミン、N−n−テトラデシルアミン、N−n−ペンタデシルアミン、N−n−ヘキサデシルアミン、N−n−ヘプタデシルアミン、N−n−オクタデシルアミン、N−n−ノナデシルアミン、N−n−エイコシルアミン等の脂肪族アミン、N−シクロペンチルアミン、N−シクロヘキシルアミン等の脂環式アミン、アニリン、p−n−ブチルアニリン、p−t−ブチルアニリン、p−n−オクチルアニリン、p−n−デシルアニリン、p−n−ドデシルアニリン、p−n−テトラデシルアニリン等のアニリン、N−ベンジルアミン、N−(2−フェニルエチル)アミン等のアルキルフェノール、1−ナフチルアミン、2−ナフチルアミン等のナフチルアミン、1−アミノアントラセン、2−アミノアントラセン等のアミノアントラセン、1−アミノアントラキノン等のアミノアントラキノン、4−アミノビフェニル、2−アミノビフェニル等のアミノビフェニル、2−アミノフルオレンアミノフルオレン、1−アミノ−9−フルオレノン、4−アミノ−9−フルオレノン等のアミノフルオレノン、5−アミノインダン等のアミノインダン、5−アミノイソキノリン等のアミノイソキノリン、9−アミノフェナントレン等のアミノフェナントレン等の芳香族アミンが挙げられる。更に、N−(tert−ブトキシカルボニル)−1,2−エチレンジアミン、N−(tert−ブトキシカルボニル)−1,3−プロピレンジアミン、N−(tert−ブトキシカルボニル)−1,4−ブチレンンジアミン、N−(tert−ブトキシカルボニル)−1,5−ペンタメチレンジアミン、N−(tert−ブトキシカルボニル)−1,6−ヘキサメチレンジアミン、N−(2−ヒドロキシエチル)アミン、N−(3−ヒドロキシプロピル)アミン、N−(2−メトキシエチル)アミン、N−(2−エトキシエチル)アミン等のアミン化合物が挙げられる。 The amine compounds that can be used in this reaction are, as primary amines, N-methylamine, N-ethylamine, Nn-propylamine, N-isopropylamine, Nn-butylamine, Nn-isobutylamine, N- sec-butylamine, N-tert-butylamine, Nn-pentylamine, Nn-hexylamine, Nn-heptylamine, Nn-octylamine, Nn-nonylamine, Nn-decylamine, Nn-undecylamine, Nn-dodecylmian, Nn-tridecylamine, Nn-tetradecylamine, Nn-pentadecylamine, Nn-hexadecylamine, Nn -Aliphatic amines such as heptadecylamine, Nn-octadecylamine, Nn-nonadecylamine, Nn-eicosylamine, N- Cyclopentylamine, cycloaliphatic amines such as N-cyclohexylamine, aniline, pn-butylaniline, pt-butylaniline, pn-octylaniline, pn-decylaniline, pn-dodecyl Aniline, aniline such as pn-tetradecylaniline, alkylphenols such as N-benzylamine and N- (2-phenylethyl) amine, naphthylamines such as 1-naphthylamine and 2-naphthylamine, 1-aminoanthracene, 2-amino Aminoanthracene such as anthracene, aminoanthraquinone such as 1-aminoanthraquinone, aminobiphenyl such as 4-aminobiphenyl, 2-aminobiphenyl, 2-aminofluoreneaminofluorene, 1-amino-9-fluorenone, 4-amino-9- Amino acids such as fluorenone Orenon, 5-aminoindane such aminoindan, 5-amino-isoquinoline, such as amino isoquinoline, aromatic amines such as amino-phenanthrene such 9-amino-phenanthrene and the like. Furthermore, N- (tert-butoxycarbonyl) -1,2-ethylenediamine, N- (tert-butoxycarbonyl) -1,3-propylenediamine, N- (tert-butoxycarbonyl) -1,4-butylenediamine, N- (tert-butoxycarbonyl) -1,5-pentamethylenediamine, N- (tert-butoxycarbonyl) -1,6-hexamethylenediamine, N- (2-hydroxyethyl) amine, N- (3-hydroxy And an amine compound such as N- (2-methoxyethyl) amine, N- (2-methoxyethyl) amine, and the like.
第二級アミンとしては、N,N−ジメチルアミン、N,N−ジエチルアミン、N,N−ジ−n−プロピルアミン、N,N−ジ−イソプロピルアミン、N,N−ジ−n−ブチルアミン、N,N−n−イソブチルアミン、N,N−ジ−sec−ブチルアミン、N,N−n−ペンチルアミン、N−メチル−N−エチルアミン、N−メチル−N−n−プロピルアミン、N−メチル−N−n−ブチルアミン、N−メチル−N−n−ペンチルアミン、N−エチル−N−イソプロピルアミン、N−エチル−N−n−ブチルアミン、N−エチル−N−n−ペンチルアミン、N−メチル−N−n−オクチルアミン、N−メチル−N−n−デシルアミン、N−メチル−N−n−ドデシルアミン、N−メチル−N−n−テトラデシルアミン、N−メチル−N−n−ヘキサデシルアミン、N−メチル−N−n−オクタデシルアミン、N−エチル−N−イソプロピルアミン、N−エチル−N−オクチルアミン、N,N−ジ−n−ヘキシルアミン、N,N−ジオクチルアミン、N,N−ジドデシルアミン、N,N−ジヘキサデシルアミン、N,N−ジオクタデシルアミン等の脂肪族アミン、N,N−ジシクロヘキシルアミン等の脂環式アミン、N,N−ジフェニルアミン、N,N−ジベンジルアミン等の芳香族アミン、フタルイミド、ピロール、ピペリジン、ピペラジン、イミダゾール等の窒素含有複素環式化合物が挙げられる。更に、N,N−ジ(2−ヒドロキシエチル)アミン、N,N−ジ(3−ヒドロキシプロピル)アミン、N,N−ジ(エトキシエチル)アミン、N,N−ジ(プロポキシエチル)アミン等が挙げられる。 Secondary amines include N, N-dimethylamine, N, N-diethylamine, N, N-di-n-propylamine, N, N-di-isopropylamine, N, N-di-n-butylamine, N, Nn-isobutylamine, N, N-di-sec-butylamine, N, Nn-pentylamine, N-methyl-N-ethylamine, N-methyl-Nn-propylamine, N-methyl -Nn-butylamine, N-methyl-Nn-pentylamine, N-ethyl-N-isopropylamine, N-ethyl-Nn-butylamine, N-ethyl-Nn-pentylamine, N- Methyl-Nn-octylamine, N-methyl-Nn-decylamine, N-methyl-Nn-dodecylamine, N-methyl-Nn-tetradecylamine, N-methyl-Nn- F Sadecylamine, N-methyl-Nn-octadecylamine, N-ethyl-N-isopropylamine, N-ethyl-N-octylamine, N, N-di-n-hexylamine, N, N-dioctylamine, N , N-didodecylamine, N, N-dihexadecylamine, aliphatic amines such as N, N-dioctadecylamine, alicyclic amines such as N, N-dicyclohexylamine, N, N-diphenylamine, N, Examples thereof include aromatic amines such as N-dibenzylamine, and nitrogen-containing heterocyclic compounds such as phthalimide, pyrrole, piperidine, piperazine and imidazole. Further, N, N-di (2-hydroxyethyl) amine, N, N-di (3-hydroxypropyl) amine, N, N-di (ethoxyethyl) amine, N, N-di (propoxyethyl) amine, etc. Is mentioned.
第三級アミンとしては、トリメチルアミン、トリエチルアミン、トリプロピルアミン、トリブチルアミン、トリペンチルアミン、N,N−ジメチル−N−オクチルアミン、N,N−ジエチル−N−n−デシルアミン、N,N−ジメチル−N−n−ドデシルアミン、N,N−ジメチル−N−n−テトラデシルアミン、N,N−ジメチル−N−n−ヘキサデシルアミン、N,N−ジメチル−N−n−オクタデシルアミン、N,N−ジメチル−N−n−エイコシルアミン、N,N−ジメチル−N−n−ドデシルアミン等の脂肪族アミン、ピリジン、ピラジン、ピリミジン、キノリン、1−メチルイミダゾール、4,4’−ピピリジル、4−メチル4,4’−ピピリジル等の窒素含有複素環式化合物が挙げられる。 Tertiary amines include trimethylamine, triethylamine, tripropylamine, tributylamine, tripentylamine, N, N-dimethyl-N-octylamine, N, N-diethyl-Nn-decylamine, N, N-dimethyl. -Nn-dodecylamine, N, N-dimethyl-Nn-tetradecylamine, N, N-dimethyl-Nn-hexadecylamine, N, N-dimethyl-Nn-octadecylamine, N , N-dimethyl-Nn-eicosylamine, aliphatic amines such as N, N-dimethyl-Nn-dodecylamine, pyridine, pyrazine, pyrimidine, quinoline, 1-methylimidazole, 4,4′-pipyridyl And nitrogen-containing heterocyclic compounds such as 4-methyl 4,4′-pipyridyl.
これらの反応で使用できるアミン化合物の使用量は、分子末端にハロゲン原子を有する高分岐高分子化合物中のハロゲン原子の1モル当量に対して0.1ないし20倍モル当量、好ましくは0.5ないし10倍モル当量、より好ましくは1ないし5倍モル当量であればよい。反応の条件としては、反応時間は0.01ないし100時間、反応温度は0ないし300℃から、適宜選択される。好ましくは反応時間が0.1ないし10時間で、反応温度が20ないし150℃である。 The amount of the amine compound that can be used in these reactions is 0.1 to 20 times the molar equivalent, preferably 0.5 to the molar equivalent of the halogen atom in the hyperbranched polymer compound having a halogen atom at the molecular end. It may be 10 to 10 molar equivalents, more preferably 1 to 5 molar equivalents. The reaction conditions are appropriately selected from a reaction time of 0.01 to 100 hours and a reaction temperature of 0 to 300 ° C. The reaction time is preferably 0.1 to 10 hours and the reaction temperature is 20 to 150 ° C.
分子末端のハロゲン原子とアミン化合物との反応は、水又は有機溶媒溶液中で、塩基の存在下又は非存在下で行なうことができる。使用する溶媒は、ハロゲン原子を有する高分岐高分子化合物とアミン化合物を溶解可能なものが好ましい。さらに、ハロゲン原子を有する高分岐高分子化合物とアミン化合物を溶解可能であるが、分子末端にアンモニウム基を有する高分岐高分子化合物を溶解しない溶媒であれば、単離が容易となりさらに好適である。
有機溶媒としては、本反応の進行を著しく阻害しないものであれば良く、水及び酢酸等の有機酸系溶媒、ベンゼン、トルエン、キシレン、エチルベンゼン、1,2−ジクロロベンゼン等の芳香族炭化水素類、テトラヒドロフラン、ジエチルエーテル等のエーテル系化合物、アセトン、メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノン等のケトン系化合物、クロロホルム、ジクロロメタン、1,2−ジクロロエタン、ノルマルヘプタン、ノルマルヘキサン、シクロヘキサン、ジメチルホルムアミド、ジメチルアセトアミド、N−メチルピロリドン等の脂肪族炭化水素類等が使用できる。これらの溶媒は一種を用いてもよいし、二種以上を混合して用いてもよい。また、使用量は、ハロゲン原子を分子末端に有する高分岐高分子化合物の質量に対して0.2ないし1,000倍質量、好ましくは1ないし500倍質量、より好ましくは5ないし100倍質量、最も好ましくは10ないし50倍質量の有機溶媒を使用することが好ましい。また、この反応では反応開始前には反応系内の酸素を十分に除去する必要があり、窒素、アルゴン等の不活性気体で系内を置換するとよい。反応条件としては、反応時間0.01ないし100時間、反応温度0ないし200℃から、適宜選択される。好ましくは反応時間が0.1ないし5時間で、反応温度が20ないし150℃である。The reaction between the halogen atom at the molecular end and the amine compound can be carried out in water or an organic solvent solution in the presence or absence of a base. The solvent to be used is preferably a solvent capable of dissolving the hyperbranched polymer compound having a halogen atom and the amine compound. Further, a highly branched polymer compound having a halogen atom and an amine compound can be dissolved, but a solvent that does not dissolve a highly branched polymer compound having an ammonium group at the molecular end is more preferable because it can be easily isolated. .
The organic solvent may be any organic solvent that does not significantly inhibit the progress of this reaction, such as water and acetic acid, and aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, and 1,2-dichlorobenzene. Ether compounds such as tetrahydrofuran, diethyl ether, ketone compounds such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, chloroform, dichloromethane, 1,2-dichloroethane, normal heptane, normal hexane, cyclohexane, dimethylformamide, dimethylacetamide, Aliphatic hydrocarbons such as N-methylpyrrolidone can be used. These solvents may be used alone or in combination of two or more. The amount used is 0.2 to 1,000 times, preferably 1 to 500 times, more preferably 5 to 100 times the mass of the hyperbranched polymer having a halogen atom at the molecular end. Most preferably, an organic solvent having a mass of 10 to 50 times is used. In this reaction, it is necessary to sufficiently remove oxygen in the reaction system before the start of the reaction, and the inside of the system may be replaced with an inert gas such as nitrogen or argon. The reaction conditions are appropriately selected from a reaction time of 0.01 to 100 hours and a reaction temperature of 0 to 200 ° C. Preferably, the reaction time is 0.1 to 5 hours and the reaction temperature is 20 to 150 ° C.
好適な塩基としては一般に、アルカリ金属水酸化物及びアルカリ土類金属水酸化物、アルカリ金属酸化物及びアルカリ土類金属酸化物、アルカリ金属水素化物及びアルカリ土類金属水素化物、アルカリ金属アミド、アルカリ金属炭酸塩及びアルカリ土類金属炭酸塩(例えば炭酸リチウム、炭酸カリウム、炭酸カルシウム)、アルカリ金属重炭酸塩(例えば重炭酸ナトリウム)等の無機化合物、並びにアルカリ金属アルキル、アルキルマグネシウムハロゲン化物、アルカリ金属アルコキシド、アルカリ土類金属アルコキシド、ジメトキシマグネシウム等の有機金属化合物が使用される。特に好ましいのは、炭酸カリウム及び炭酸ナトリウムである。また、塩基の使用量は、分子末端にハロゲン原子を有する高分岐高分子化合物の質量に対して0.2ないし10倍等量、好ましくは0.5ないし10等量、最も好ましくは1ないし5等量であることが好ましい。 Suitable bases generally include alkali metal hydroxides and alkaline earth metal hydroxides, alkali metal oxides and alkaline earth metal oxides, alkali metal hydrides and alkaline earth metal hydrides, alkali metal amides, alkalis Inorganic compounds such as metal carbonates and alkaline earth metal carbonates (eg lithium carbonate, potassium carbonate, calcium carbonate), alkali metal bicarbonates (eg sodium bicarbonate), and alkali metal alkyls, alkylmagnesium halides, alkali metals Organometallic compounds such as alkoxides, alkaline earth metal alkoxides, and dimethoxymagnesium are used. Particularly preferred are potassium carbonate and sodium carbonate. The amount of the base used is 0.2 to 10 times equivalent, preferably 0.5 to 10 equivalents, most preferably 1 to 5 times the mass of the hyperbranched polymer compound having a halogen atom at the molecular end. Equal amounts are preferred.
塩基の存在下で、第三級アミンを用いた場合は式(1)で表される高分岐高分子化合物を得ることができる。
塩基の非存在下で、第一級アミン又は第二級アミン化合物と分子末端にハロゲン原子を有する高分岐高分子化合物と反応させて分子末端にアミン末端を有する高分岐高分子化合物を得る際、それぞれに対応する高分岐高分子化合物の末端第二級アミン及び第三級アミンがプロトン化されたアンモニウム基末端の高分岐高分子化合物が得られる。
また、塩基を用いて反応を行った場合においても、有機溶媒中で塩酸、臭化水素、ヨウ化水素等の酸の水溶液と混合することにより、対応する高分岐高分子化合物の末端第二級アミン及び第三級アミンがプロトン化されたアンモニウム基末端の高分岐高分子化合物が得られる。When a tertiary amine is used in the presence of a base, a highly branched polymer compound represented by the formula (1) can be obtained.
In the absence of a base, when a primary amine or secondary amine compound is reacted with a hyperbranched polymer compound having a halogen atom at the molecular end to obtain a hyperbranched polymer compound having an amine end at the molecular end, A hyperbranched polymer compound having an ammonium group terminal obtained by protonating the terminal secondary amine and tertiary amine of the hyperbranched polymer compound corresponding to each is obtained.
In addition, even when the reaction is performed using a base, by mixing with an aqueous solution of an acid such as hydrochloric acid, hydrogen bromide, or hydrogen iodide in an organic solvent, the terminal secondary of the corresponding highly branched polymer compound is obtained. A highly branched polymer compound having an ammonium group terminal and protonated amine and tertiary amine is obtained.
本発明に使用される金属微粒子としては特に限定されず、スカンジウム、チタン、バナジウム、クロム、マンガン、鉄、コバルト、ニッケル、銅、亜鉛、ガリウム、ゲルマニウム、イットリウム、ジルコニウム、ニオブ、モリブデン、ルテニウム、ロジウム、パラジウム、銀、カドミウム、インジウム、スズ、アンチモン、ハフニウム、タンタル、タングステン、レニウム、オスミウム、イリジウム、白金、金、水銀、タリウム、鉛及びビスマスが挙げられ、これらの金属の1種類でもよいし二種以上の合金でも構わない。好ましくは、金、銀、白金及び銅等を挙げることができる。 The metal fine particles used in the present invention are not particularly limited, and scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, gallium, germanium, yttrium, zirconium, niobium, molybdenum, ruthenium, rhodium. Palladium, silver, cadmium, indium, tin, antimony, hafnium, tantalum, tungsten, rhenium, osmium, iridium, platinum, gold, mercury, thallium, lead, and bismuth. One of these metals may be used. More than one kind of alloy may be used. Preferably, gold, silver, platinum, copper, etc. can be mentioned.
本発明のスイッチング素子は例えば、マトリックス及び金属微粒子分散剤で処理された金属微粒子からなる溶液を電極層の上面に塗布し、そしてアニーリングして有機薄膜を作成し、さらにその上に電極層を蒸着することによって、作製され得る。 In the switching element of the present invention, for example, a solution composed of metal fine particles treated with a matrix and a metal fine particle dispersant is applied to the upper surface of the electrode layer, and annealed to form an organic thin film, and the electrode layer is further deposited thereon. Can be made.
金属微粒子分散剤で処理された金属微粒子の溶液は、金属微粒子分散剤と金属塩を混合し、得られた混合物に還元剤を添加し、金属イオンを還元することによって得られる。
金属塩としては、塩化金酸、硝酸銀、硫酸銅、硝酸銅、塩化第一白金、Pt(dba)2[dba=ジベンジリデンアセトン]、Pt(cod)2[cod=1,5−シクロオクタジエン]、PtMe2(cod)、塩化パラジウム、酢酸パラジウム、硝酸パラジウム、Pd(dba)2、塩化ロジウム、酢酸ロジウム、塩化ルテニウム、酢酸ルテニウム、Ru(cod)(cot)[cot=シクロオクタトリエン]、塩化イリジウム、酢酸イリジウム、Ni(cod)2等が挙げられる。また還元剤としては例えば、水素化ホウ素ナトリウム等のアルカリ金属水素化ホウ素塩、ヒドラジン化合物、クエン酸又はその塩、コハク酸又はその塩、アスコルビン酸又はその塩等を使用することができる。金属微粒子分散剤の添加量は、上記金属イオン100重量部に対して50ないし2000重量部が好ましい。50重量部未満であると、上記金属微粒子の分散性が不充分であり、2000重量部を超えると、有機物含有量が多くなり、物性等に不具合が生じやすくなる。より好ましくは、100ないし1000重量部である。The solution of the metal fine particles treated with the metal fine particle dispersant is obtained by mixing the metal fine particle dispersant and the metal salt, adding a reducing agent to the obtained mixture, and reducing metal ions.
Examples of the metal salt include chloroauric acid, silver nitrate, copper sulfate, copper nitrate, platinum chloride, Pt (dba) 2 [dba = dibenzylideneacetone], Pt (cod) 2 [cod = 1,5-cyclooctadiene. ], PtMe 2 (cod), palladium chloride, palladium acetate, palladium nitrate, Pd (dba) 2 , rhodium chloride, rhodium acetate, ruthenium chloride, ruthenium acetate, Ru (cod) (cot) [cot = cyclooctatriene], Examples thereof include iridium chloride, iridium acetate, Ni (cod) 2 and the like. Moreover, as a reducing agent, alkali metal borohydride salts, such as sodium borohydride, a hydrazine compound, a citric acid or its salt, a succinic acid or its salt, ascorbic acid or its salt etc. can be used, for example. The addition amount of the metal fine particle dispersant is preferably 50 to 2000 parts by weight with respect to 100 parts by weight of the metal ions. When the amount is less than 50 parts by weight, the dispersibility of the metal fine particles is insufficient, and when the amount exceeds 2000 parts by weight, the organic matter content increases, and problems such as physical properties tend to occur. More preferably, it is 100 to 1000 parts by weight.
また、金属微粒子分散剤で処理された金属微粒子の溶液は、低級アンモニウム配位子によりある程度安定化した金属微粒子を合成した後に高分岐高分子化合物により配位子を交換する方法や、アンモニウム基を有する高分岐高分子化合物の溶液中で、金属イオンを直接還元する方法によっても得られる。アミン系分散剤(アンモニウム配位子)以外にホスフィン系分散剤(ホスフィン配位子)を用いることによっても、あらかじめ金属微粒子をある程度安定化することができる。 In addition, the solution of the metal fine particles treated with the metal fine particle dispersant is prepared by synthesizing metal fine particles stabilized to some extent with a lower ammonium ligand and then exchanging the ligand with a highly branched polymer compound. It can also be obtained by a method in which a metal ion is directly reduced in a solution of a highly branched polymer compound. By using a phosphine dispersant (phosphine ligand) in addition to the amine dispersant (ammonium ligand), the metal fine particles can be stabilized to some extent in advance.
配位子交換法の合成方法として、原料となる低級アンモニウム配位子によりある程度安定化した金属微粒子は、Jounal of Organometallic Chemistry 1996 520 143−162等に記載の方法で合成することができる。得られた金属微粒子の反応混合溶液に、アンモニウム基を有する高分岐高分子化合物を溶解し、室温又は加熱攪拌することにより目的とする金属微粒子複合体を得ることができる。
使用する溶媒としては、金属微粒子と金属微粒子分散剤を必要濃度以上に溶解できる溶媒であれば特に限定はしないが、具体的には、エタノール、プロパノール等のアルコール系溶媒、塩化メチレン、クロロホルム等のハロゲン化炭化水素、テトラヒドロフラン、2−メチルテトラヒドロフラン、テトラヒドロピラン等の環状エーテル及びアセトニトリル、ブチロニトリル等のニトリル系溶媒等並びにこれらの溶媒の混合液が挙げられ、好ましくは、テトラヒドロフランが挙げられる。
金属微粒子と金属微粒子分散剤を混合する温度は、通常0℃ないし溶媒の沸点の範囲を使用することができ、好ましくは、室温ないし60℃の範囲である。As a synthesis method of the ligand exchange method, metal fine particles stabilized to some extent by a lower ammonium ligand as a raw material can be synthesized by a method described in Journal of Organometallic Chemistry 1996 520 143-162. A target metal fine particle composite can be obtained by dissolving a hyperbranched polymer compound having an ammonium group in the obtained reaction mixture solution of metal fine particles and stirring at room temperature or with heating.
The solvent to be used is not particularly limited as long as it is a solvent capable of dissolving the metal fine particles and the metal fine particle dispersant at a required concentration or more, and specifically, alcohol solvents such as ethanol and propanol, methylene chloride, chloroform and the like. Examples thereof include cyclic ethers such as halogenated hydrocarbons, tetrahydrofuran, 2-methyltetrahydrofuran, and tetrahydropyran, nitrile solvents such as acetonitrile and butyronitrile, and a mixture of these solvents. Tetrahydrofuran is preferable.
The temperature at which the metal fine particles and the metal fine particle dispersant are mixed usually ranges from 0 ° C. to the boiling point of the solvent, preferably from room temperature to 60 ° C.
直接還元方法としては、金属イオンとアンモニウム基を有する高分岐高分子化合物を溶媒に溶解し、水素ガス雰囲気下で反応させることにより、目的とする金属微粒子複合体を得ることができる。
使用する溶媒としては、金属イオンと分散剤を必要濃度以上溶解できる溶媒であれば特に限定はしないが、具体的には、エタノール、プロパノール等のアルコール系溶媒、塩化メチレン、クロロホルム等のハロゲン化炭化水素、テトラヒドロフラン、2−メチルテトラヒドロフラン、テトラヒドロピラン等の環状エーテル及びアセトニトリル、ブチロニトリル等のニトリル系溶媒等並びにこれらの溶媒の混合液が挙げられ、好ましくは、テトラヒドロフランが挙げられる。
金属イオンと分散剤を混合する温度は、通常0℃〜溶媒の沸点の範囲を使用することができ、好ましくは、室温である。As a direct reduction method, a target metal fine particle composite can be obtained by dissolving a hyperbranched polymer compound having a metal ion and an ammonium group in a solvent and reacting in a hydrogen gas atmosphere.
The solvent to be used is not particularly limited as long as it can dissolve metal ions and a dispersant at a concentration higher than the required concentration. Specifically, alcohol solvents such as ethanol and propanol, and halogenated carbonization such as methylene chloride and chloroform. Examples thereof include cyclic ethers such as hydrogen, tetrahydrofuran, 2-methyltetrahydrofuran and tetrahydropyran, and nitrile solvents such as acetonitrile and butyronitrile, and a mixture of these solvents, preferably tetrahydrofuran.
The temperature at which the metal ions and the dispersant are mixed can usually be in the range of 0 ° C. to the boiling point of the solvent, and is preferably room temperature.
以下に実施例を掲げて本発明をさらに詳しく説明するが、本発明はこれら実施例のみに限定されるものではない。
なお、式中の略語「Et」はエチル基を表す。Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to these examples.
The abbreviation “Et” in the formula represents an ethyl group.
合成例1
<ジチオカルバメート基を分子末端に有するスチレン系ハイパーブランチポリマー(HPS)の合成>
<Synthesis of Styrenic Hyperbranched Polymer (HPS) Having Dithiocarbamate Group at Molecular End>
合成例2
<ハロゲン原子を分子末端に有するスチレン系ハイパーブランチポリマー(HPS−Br)の合成>
飽和食塩水及び20質量%チオ硫酸ナトリウムを加えて、有機相を洗浄した。この溶液をメタノール500gに滴下して再沈を行った。得られた黄色粉末を再度クロロホルム40gに溶解し、500gのメタノールに滴下し、再沈を行い、得られた無色粉末を乾燥して、ジチオカルバメート基を分子末端に有するハイパーブランチポリマーのジチオカルバメート基部分が臭素原子に置換されたハイパーブランチポリマー4.6gを得た。ゲル浸透クロマトグラフィーによるポリスチレン換算で測定される重量平均分子量Mwは6,600、分散度Mw/Mnは2.2であった。元素分析の結果は、炭素50.2質量%、水素3.8質量%、窒素1.0質量%未満及び臭素33.2質量%であった。1H−NMRスペクトルより得られたハイパーブランチポリマーは上記式(10)で表される構造を有する。Synthesis example 2
<Synthesis of styrene-based hyperbranched polymer (HPS-Br) having a halogen atom at the molecular end>
Saturated brine and 20% by weight sodium thiosulfate were added to wash the organic phase. This solution was dropped into 500 g of methanol to perform reprecipitation. The obtained yellow powder was again dissolved in 40 g of chloroform, dropped into 500 g of methanol, reprecipitated, the resulting colorless powder was dried, and a dithiocarbamate group of a hyperbranched polymer having a dithiocarbamate group at the molecular end. The hyperbranched polymer 4.6g by which the part was substituted by the bromine atom was obtained. The weight average molecular weight Mw measured by gel permeation chromatography in terms of polystyrene was 6,600, and the degree of dispersion Mw / Mn was 2.2. The results of elemental analysis were 50.2 mass% carbon, 3.8 mass% hydrogen, less than 1.0 mass% nitrogen, and 33.2 mass% bromine. The hyperbranched polymer obtained from the 1 H-NMR spectrum has a structure represented by the above formula (10).
合成例3
<トリオクチルアンモニウム基を分子末端に有するスチレン系ハイパーブランチポリマー(HPS−N(Octyl)3Br)の合成>
<Synthesis of Styrenic Hyperbranched Polymer (HPS-N (Octyl) 3 Br) Having Trioctylammonium Group at Molecular Terminal>
合成例4
<トリオクチルアンモニウム基を分子末端に有するスチレン系ハイパーブランチポリマーに分散された白金微粒子の合成(HPS−N(Octyl)3−Pt)>
HPS−N(Octyl)3Br(27.8mg、0.05mmol)とPt(dba)2 [dba=ジベンジリデンアセトン](65.2mg、0.1mmL)を、20mLの二つ口フラスコに入れ、窒素置換し、THF5mLを加えた。系中を水素置換した後、室温で一晩攪拌した。反応溶液にアルゴンで脱気した水2mLを加え再沈精製を行い、濾過、減圧乾燥し、[HPS−N(Octyl)3Br]Pt粒子複合体の黒色沈殿物60mgを得た。ICP−MASSによりPt含有量は10質量%であった。また、得られた黒色沈殿物をTEM観察した画像を図2に示す。TEM観察により、粒子径は2nmであった。Synthesis example 4
<Synthesis of platinum fine particles dispersed in a styrene-based hyperbranched polymer having a trioctylammonium group at the molecular end (HPS-N (Octyl) 3 -Pt)>
HPS-N (Octyl) 3 Br (27.8 mg, 0.05 mmol) and Pt (dba) 2 [dba = dibenzylideneacetone] (65.2 mg, 0.1 mmL) were placed in a 20 mL two-necked flask, The atmosphere was replaced with nitrogen, and 5 mL of THF was added. After purging the system with hydrogen, the mixture was stirred overnight at room temperature. 2 mL of water degassed with argon was added to the reaction solution for purification by reprecipitation, followed by filtration and drying under reduced pressure to obtain 60 mg of a black precipitate of [HPS-N (Octyl) 3 Br] Pt particle complex. The Pt content was 10% by mass by ICP-MASS. Moreover, the image which observed the obtained black deposit by TEM is shown in FIG. The particle diameter was 2 nm by TEM observation.
実施例1
図1に示すようなスイッチング素子を作成した。まず、あらかじめ洗浄されたガラス基板の上面にアルミニウム(Al)を80nmの厚さで真空蒸着しAl電極層2を作成した。次に、マトリックスとして前記式(9)で示されるハイパーブランチポリマー(HPS)、金属微粒子として合成例4で得られた白金微粒子(HPS−N(Octyl)3−Pt)からなる有機薄膜を作成した。有機薄膜3は、まずオルト−ジクロロベンゼン中に、HPS、HPS(octyl)Pt及び8ヒドロキシキノリン(8HQ)を、重量比が60:20:20となるよう溶解して溶液を調製し、この溶液をAl電極層4の上面にスピンコートし、150℃で30分アニーリングを行うことにより作成した。有機薄膜3の膜厚は90nmであった。有機薄膜3の上面に、Al電極層4を蒸着させた。Al電極層4の膜厚は80nmであった。有機薄膜3上下のAl電極4は、水晶振動子膜厚計で膜厚を観測しながら約1×10-6Torrの真空下において蒸着した。Example 1
A switching element as shown in FIG. 1 was prepared. First, aluminum (Al) was vacuum-deposited with a thickness of 80 nm on the upper surface of a glass substrate that had been cleaned in advance, to produce an Al electrode layer 2. Next, an organic thin film made of the hyperbranched polymer (HPS) represented by the formula (9) as a matrix and platinum fine particles (HPS-N (Octyl) 3 -Pt) obtained in Synthesis Example 4 as metal fine particles was prepared. . The organic thin film 3 is prepared by dissolving HPS, HPS (octyl) Pt, and 8 hydroxyquinoline (8HQ) in ortho-dichlorobenzene so that the weight ratio is 60:20:20. Was spin-coated on the upper surface of the Al electrode layer 4 and annealed at 150 ° C. for 30 minutes. The film thickness of the organic thin film 3 was 90 nm. An Al electrode layer 4 was deposited on the upper surface of the organic thin film 3. The film thickness of the Al electrode layer 4 was 80 nm. The Al electrodes 4 above and below the organic thin film 3 were deposited under a vacuum of about 1 × 10 −6 Torr while observing the film thickness with a quartz oscillator film thickness meter.
この素子の電流密度対電圧(J−V)特性を図3に示す。曲線10(破線)は0Vからバイアス電圧を上昇させる場合であり、曲線11(実線)は0Vまで電圧を降下させる場合を示している。
アンモニウム基末端を有するハイパーブランチポリマー(HPS−N(Octyl)3−Pt)を分散剤とした白金微粒子を用いることにより、ON状態及びOFF状態の電流
値が高く、ON/OFF比も十分な良好なデバイスを作製することに成功した。FIG. 3 shows the current density vs. voltage (J-V) characteristics of this element. A curve 10 (broken line) indicates a case where the bias voltage is increased from 0V, and a curve 11 (solid line) indicates a case where the voltage is decreased to 0V.
By using platinum fine particles with a hyperbranched polymer (HPS-N (Octyl) 3 -Pt) having an ammonium group terminal as a dispersant, the current value in the ON state and the OFF state is high, and the ON / OFF ratio is sufficiently good. Succeeded in fabricating a simple device.
1 スイッチング素子 2 第一電極 3 有機薄膜 4 第二電極 5,6 電気結線 7 電子制御ユニット 8 金属微粒子 9 マトリックス 10 低抵抗状態(OFF状態)のバイアス電圧上昇過程を示す曲線 11 高抵抗状態(ON状態)のバイアス電圧降下過程を示す曲線 DESCRIPTION OF SYMBOLS 1 Switching element 2 1st electrode 3 Organic thin film 4 2nd electrode 5,6 Electrical connection 7 Electronic control unit 8 Metal fine particle 9 Matrix 10 Curve which shows the bias voltage rise process of a low resistance state (OFF state) 11 High resistance state (ON Curve) showing the bias voltage drop process
Claims (7)
前記金属微粒子が、アンモニウム基を含有し重量平均分子量が500ないし5,000,000である高分子からなる金属微粒子分散剤によって前記有機薄膜中に分散されており、かつ、
前記金属微粒子分散剤が式(1):
R 1 は水素原子又はメチル基を表し、
R 2 、R 3 及びR 4 は、それぞれ独立して、水素原子、炭素原子数1ないし20の直鎖状、枝分かれ状又は環状のアルキル基、炭素原子数6ないし20のアリールアルキル基又は−(CH 2 CH 2 O) m −R 5 (式中、R 5 は水素原子又はメチル基を表し、mは2ないし100の任意の整数を表す。)を表すか、
R 2 、R 3 及びR 4 が互いに直鎖状、枝分かれ状又は環状のアルキレン基で結合し、それ
らと結合する窒素原子と共に環を形成してもよく(該アルキル基及びアリールアルキル基はアルコキシ基、ヒドロキシル基、アンモニウム基、カルボキシル基又はシアノ基で置換されていてもよい)、
X − は陰イオンを表し、
A 1 は式(2)又は式(3):
Y 1 、Y 2 、Y 3 又はY 4 は、それぞれ独立して、水素原子、炭素原子数1ないし20のアルキル基、炭素原子数1ないし20のアルコキシ基、ニトロ基、ヒドロキシル基、アミノ基、カルボキシル基又はシアノ基を表す。)で表される構造を表し、
nは繰り返し単位構造の数であって2ないし100,000の整数を表す。]で表される高分岐高分子化合物であることを特徴とするスイッチング素子。 In a switching element having a structure in which an organic thin film containing metal fine particles is sandwiched between two electrodes and having two types of stable resistance values with respect to an applied voltage,
Wherein the metal fine particles, Ri Contact are dispersed in the organic thin film by the metal fine particle dispersant comprising a polymer is 5,000,000 to the 500 weight average molecular weight and containing ammonium groups, and
The metal fine particle dispersant is represented by the formula (1):
R 1 represents a hydrogen atom or a methyl group,
R 2 , R 3 and R 4 are each independently a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, an arylalkyl group having 6 to 20 carbon atoms or — ( during CH 2 CH 2 O) m -R 5 ( wherein, either R 5 represents a hydrogen atom or a methyl group, m represents represents.) any integer from 2 to 100,
R 2 , R 3 and R 4 are bonded to each other by a linear, branched or cyclic alkylene group,
May form a ring together with the nitrogen atom bonded thereto (the alkyl group and arylalkyl group may be substituted with an alkoxy group, a hydroxyl group, an ammonium group, a carboxyl group or a cyano group),
X − represents an anion,
A 1 represents formula (2) or formula (3):
Y 1 , Y 2 , Y 3 or Y 4 each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a nitro group, a hydroxyl group, an amino group, Represents a carboxyl group or a cyano group. )
n is the number of repeating unit structures and represents an integer of 2 to 100,000. ] The switching element characterized by the above-mentioned.
X 1 、X 2 、X 3 及びX 4 は、それぞれ独立して、水素原子、炭素原子数1ないし20のアルキル基、炭素原子数1ないし20のアルコキシ基、ハロゲン原子、ニトロ基、ヒドロキシル基、アミノ基、カルボキシル基又はシアノ基を表す。)で表される基を表し、
nは繰り返し単位構造の数であって2ないし100,000の整数を表す。] The switching element according to claim 4 , wherein the hyperbranched polymer is represented by Formula (4).
X 1 , X 2 , X 3 and X 4 are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a halogen atom, a nitro group, a hydroxyl group, Represents an amino group, a carboxyl group or a cyano group. ) Represents a group represented by
n is the number of repeating unit structures and represents an integer of 2 to 100,000. ]
The method according to claim 1, comprising a step of forming an electrode on the substrate, a step of forming an organic thin film containing metal fine particles on the electrode, and a step of forming an electrode on the organic thin film. A method for manufacturing a switching element.
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