JPH07116503A - Method for bridge-building semiconductor superfine particle and semiconductor superfine particle bridge-built material - Google Patents
Method for bridge-building semiconductor superfine particle and semiconductor superfine particle bridge-built materialInfo
- Publication number
- JPH07116503A JPH07116503A JP5268625A JP26862593A JPH07116503A JP H07116503 A JPH07116503 A JP H07116503A JP 5268625 A JP5268625 A JP 5268625A JP 26862593 A JP26862593 A JP 26862593A JP H07116503 A JPH07116503 A JP H07116503A
- Authority
- JP
- Japan
- Prior art keywords
- semiconductor
- particles
- ultrafine particles
- particle
- unsatd
- 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.)
- Granted
Links
- 239000004065 semiconductor Substances 0.000 title claims abstract description 116
- 239000000463 material Substances 0.000 title claims abstract description 58
- 239000002245 particle Substances 0.000 title claims abstract description 46
- 238000000034 method Methods 0.000 title description 49
- 150000001875 compounds Chemical class 0.000 claims abstract description 38
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 8
- 239000011882 ultra-fine particle Substances 0.000 claims description 154
- 238000004132 cross linking Methods 0.000 claims description 33
- 238000004519 manufacturing process Methods 0.000 claims description 24
- 239000002131 composite material Substances 0.000 claims description 7
- 239000011243 crosslinked material Substances 0.000 claims description 6
- 238000012986 modification Methods 0.000 claims description 4
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- 229920000642 polymer Polymers 0.000 abstract description 17
- 238000009826 distribution Methods 0.000 abstract description 9
- 238000010438 heat treatment Methods 0.000 abstract description 5
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- 238000006243 chemical reaction Methods 0.000 description 23
- 239000011163 secondary particle Substances 0.000 description 19
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 16
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 12
- 230000003287 optical effect Effects 0.000 description 11
- 229910052980 cadmium sulfide Inorganic materials 0.000 description 10
- 239000007789 gas Substances 0.000 description 10
- 239000002904 solvent Substances 0.000 description 10
- 239000007787 solid Substances 0.000 description 9
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 description 8
- 239000010419 fine particle Substances 0.000 description 8
- -1 for example Substances 0.000 description 8
- 239000007791 liquid phase Substances 0.000 description 8
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2,2'-azo-bis-isobutyronitrile Substances N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 7
- 230000005540 biological transmission Effects 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 6
- 238000001704 evaporation Methods 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 239000010409 thin film Substances 0.000 description 6
- UHYPYGJEEGLRJD-UHFFFAOYSA-N cadmium(2+);selenium(2-) Chemical compound [Se-2].[Cd+2] UHYPYGJEEGLRJD-UHFFFAOYSA-N 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 230000008020 evaporation Effects 0.000 description 5
- 150000002736 metal compounds Chemical class 0.000 description 5
- 239000012071 phase Substances 0.000 description 5
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 5
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
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- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 230000002194 synthesizing effect Effects 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
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- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-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
- 238000010521 absorption reaction Methods 0.000 description 3
- 238000000862 absorption spectrum Methods 0.000 description 3
- 150000004703 alkoxides Chemical class 0.000 description 3
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 3
- FRLJSGOEGLARCA-UHFFFAOYSA-N cadmium sulfide Chemical class [S-2].[Cd+2] FRLJSGOEGLARCA-UHFFFAOYSA-N 0.000 description 3
- 239000002537 cosmetic Substances 0.000 description 3
- 229910001873 dinitrogen Inorganic materials 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 3
- 229910010272 inorganic material Inorganic materials 0.000 description 3
- 229910052753 mercury Inorganic materials 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
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- 230000005855 radiation Effects 0.000 description 3
- 229910052724 xenon Inorganic materials 0.000 description 3
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 3
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- 229910004613 CdTe Inorganic materials 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 229910020366 ClO 4 Inorganic materials 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000003905 agrochemical Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 239000003125 aqueous solvent Substances 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N argon Substances [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 230000005587 bubbling Effects 0.000 description 2
- PQJZOTJHMRJOEM-UHFFFAOYSA-L cadmium(2+);diperchlorate;hexahydrate Chemical compound O.O.O.O.O.O.[Cd+2].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O PQJZOTJHMRJOEM-UHFFFAOYSA-L 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- 238000000366 colloid method Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000003618 dip coating Methods 0.000 description 2
- 238000001312 dry etching Methods 0.000 description 2
- 239000012776 electronic material Substances 0.000 description 2
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- 229910021480 group 4 element Inorganic materials 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 239000011147 inorganic material Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000012567 medical material Substances 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910001960 metal nitrate Inorganic materials 0.000 description 2
- 238000006011 modification reaction Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical class OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000011164 primary particle Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 238000007650 screen-printing Methods 0.000 description 2
- SBIBMFFZSBJNJF-UHFFFAOYSA-N selenium;zinc Chemical compound [Se]=[Zn] SBIBMFFZSBJNJF-UHFFFAOYSA-N 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 238000004528 spin coating Methods 0.000 description 2
- 230000000087 stabilizing effect Effects 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- QPQKUYVSJWQSDY-UHFFFAOYSA-N 4-phenyldiazenylaniline Chemical compound C1=CC(N)=CC=C1N=NC1=CC=CC=C1 QPQKUYVSJWQSDY-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- 229910001218 Gallium arsenide Inorganic materials 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000004931 aggregating effect Effects 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 150000004770 chalcogenides Chemical class 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 230000001112 coagulating effect Effects 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
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- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- PXJJSXABGXMUSU-UHFFFAOYSA-N disulfur dichloride Chemical compound ClSSCl PXJJSXABGXMUSU-UHFFFAOYSA-N 0.000 description 1
- 150000004662 dithiols Chemical class 0.000 description 1
- 238000002296 dynamic light scattering Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 239000012992 electron transfer agent Substances 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Chemical compound CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 238000007429 general method Methods 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
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- WPYVAWXEWQSOGY-UHFFFAOYSA-N indium antimonide Chemical compound [Sb]#[In] WPYVAWXEWQSOGY-UHFFFAOYSA-N 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000010365 information processing Effects 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 238000001182 laser chemical vapour deposition Methods 0.000 description 1
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- 239000000696 magnetic material Substances 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
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- 238000005259 measurement Methods 0.000 description 1
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- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- DCUFMVPCXCSVNP-UHFFFAOYSA-N methacrylic anhydride Chemical compound CC(=C)C(=O)OC(=O)C(C)=C DCUFMVPCXCSVNP-UHFFFAOYSA-N 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 238000001225 nuclear magnetic resonance method Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000001782 photodegradation Methods 0.000 description 1
- 238000005268 plasma chemical vapour deposition Methods 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920001483 poly(ethyl methacrylate) polymer Polymers 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 239000005373 porous glass Substances 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
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- 239000012495 reaction gas Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229920013730 reactive polymer Polymers 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000001226 reprecipitation Methods 0.000 description 1
- SPVXKVOXSXTJOY-UHFFFAOYSA-N selane Chemical compound [SeH2] SPVXKVOXSXTJOY-UHFFFAOYSA-N 0.000 description 1
- 229910000058 selane Inorganic materials 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- FKIZDWBGWFWWOV-UHFFFAOYSA-N trimethyl(trimethylsilylselanyl)silane Chemical compound C[Si](C)(C)[Se][Si](C)(C)C FKIZDWBGWFWWOV-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
- Y02B10/00—Integration of renewable energy sources in buildings
- Y02B10/10—Photovoltaic [PV]
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
Landscapes
- Light Receiving Elements (AREA)
- Physical Or Chemical Processes And Apparatus (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、光学材料、特に、光
−光変換素子や光−電子変換素子などに用いられる非線
形光電子材料や超格子素子などの電子材料や発光材料、
センサー材料などとして利用される通信、情報処理分
野、 磁気記録や光記録などの材料として利用される大容量
記録関連分野、 光反応性や触媒反応性材料として利用される医薬や農
薬分野、触媒関連分野、 無機材料原料や塗料・コーティング材料として利用さ
れる成形品、表面加工関連分野、および ＵＶ吸収剤などに利用される化粧品分野に好適に使用
される、半導体超微粒子に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an optical material, particularly an electronic material such as a non-linear optoelectronic material or a superlattice element used in a light-to-light conversion element or a light-to-electron conversion element, or a light-emitting material,
Communications and information processing fields used as sensor materials, mass storage related fields used as materials for magnetic recording and optical recording, pharmaceutical and agrochemical fields used as photoreactive and catalytic reactive materials, and catalyst related fields The present invention relates to semiconductor ultrafine particles, which are preferably used in the field, molded products used as raw materials for inorganic materials, paints and coating materials, surface processing related fields, and cosmetics fields used for UV absorbers and the like.
【０００２】[0002]
（半導体超微粒子の一般的特性）半導体は電子部品材
料、光電子材料、医用材料、触媒材料、センサー材料な
ど薄膜や粒子などの形態で、産業上の幅広い分野で用い
られていることはいうまでもない。一方、超微粒子と呼
ばれている１００ｎｍ以下の粒径の小さな粒子が、その
特異的な性質から、電子部品材料、光電子材料、医用材
料、触媒材料、センサー材料、塗料・コーティング材
料、化粧品など広い分野での応用が図られている。(General characteristics of semiconductor ultrafine particles) It goes without saying that semiconductors are used in a wide range of industrial fields in the form of thin films and particles such as electronic component materials, optoelectronic materials, medical materials, catalyst materials, and sensor materials. Absent. On the other hand, small particles with a particle size of 100 nm or less, called ultrafine particles, are widely used for electronic parts materials, optoelectronic materials, medical materials, catalyst materials, sensor materials, paints / coating materials, cosmetics due to their unique properties. It is being applied in the field.
【０００３】ごく小さな粒子である超微粒子の利点とし
ては、さまざまな媒体や溶媒に容易に分散したり、均一
に混合できる点などがあげられるが、さらには、構成原
子や分子が界面に存在する割合が多くなるため、表面原
子や表面分子層の特性が現れ、特異的な反応性の出現が
期待されている。また、半導体超微粒子や金属超微粒子
などでは、超微粒子であるため電子や正孔の動ける空間
が制約されることによって、バルク体や、マイクロメー
トル程度の粒子径の微粒子ではみられない挙動が出現
し、応用が図られている。なかでも、小さな結晶空間に
起因する電子的な特異性を利用した非線形光学特性の出
現が期待されている。このような閉じ込め効果による量
子化特性が出現する小さな結晶空間の形態には、薄膜状
や、棒状、ディスク状などの形態があるが、超微粒子の
場合にはこれらの形態に比べて性能出現の等方性に優れ
る点がある。The advantages of ultra-fine particles, which are extremely small particles, are that they can be easily dispersed in various media and solvents, and that they can be uniformly mixed. Furthermore, constituent atoms and molecules are present at the interface. Since the ratio becomes large, the characteristics of surface atoms and surface molecular layers appear, and it is expected that specific reactivity appears. In addition, since ultrafine particles such as semiconductor ultrafine particles and metal ultrafine particles are restricted to a space in which electrons and holes can move because of being ultrafine particles, a behavior that cannot be seen in a bulk body or fine particles with a particle diameter of about a micrometer appears. However, it is being applied. Above all, it is expected that nonlinear optical characteristics that utilize electronic singularity due to a small crystal space will appear. The morphology of the small crystal space in which the quantization characteristic due to the confinement effect appears is a thin film shape, a rod shape, a disk shape, or the like. It has excellent isotropy.
【０００４】（半導体超微粒子の製造方法）半導体超微
粒子の一般的な製造方法としては、機械的な粉砕による
製造方法や、熱やプラズマなどを用いる蒸発を利用した
気相での製造方法や、沈澱や加水分解などを利用した液
相での製造方法などが知られている。これらの製造方法
は、例えば、「微粒子ハンドブック」（神保元二ら編
集、朝倉書店、１９９１年）に記載されている。また、
発明者らは特開平０４−１８９８０１において、溶液中
に電子伝達剤と不飽和結合を有する単量体を共存させ、
光を照射しながら粒子径分布の制御された半導体超微粒
子を製造する方法を提案している。(Method for producing semiconductor ultrafine particles) As a general method for producing semiconductor ultrafine particles, there are a production method by mechanical pulverization, a vapor phase production method utilizing evaporation using heat or plasma, A liquid phase production method utilizing precipitation or hydrolysis is known. These manufacturing methods are described in, for example, "Particle Handbook" (edited by Genji Jimbo et al., Asakura Shoten, 1991). Also,
The inventors of the present invention, in JP-A-04-189801, make an electron transfer agent and a monomer having an unsaturated bond coexist in a solution,
A method for producing semiconductor ultrafine particles whose particle size distribution is controlled while irradiating light is proposed.
【０００５】（超微粒子を修飾する従来の技術）超微粒
子を他の材料と複合化したり、表面修飾して付加機能を
持たせたり、安定化させる技術がいくつか知られてい
る。例えば、従来からの超微粒子利用の際の大きな課題
のひとつは、超微粒子の凝集・凝結などを防ぎ、安定化
させることにあった。半導体超微粒子に関しては、例え
ば、セレン化カドミウム超微粒子表面をフェニル基でお
おい、これを安定化させた例が米国化学会誌（J. Am. C
hem. Soc. 1988, 110, 3046）に記載されている。(Conventional Techniques for Modifying Ultrafine Particles) There are known some techniques in which ultrafine particles are compounded with other materials or surface modified to have an additional function or to be stabilized. For example, one of the major problems in the conventional use of ultrafine particles has been to prevent the ultrafine particles from aggregating and coagulating and stabilizing them. Regarding semiconductor ultrafine particles, for example, the surface of the cadmium selenide ultrafine particles is covered with a phenyl group to stabilize the ultrafine particles. An example of stabilizing the ultrafine particles is J. Am. C.
hem. Soc. 1988, 110, 3046).
【０００６】また、超微粒子の組織された複合体として
は、例えば、金やアルミニウム表面上に２官能基を有す
るアルカンチオールの単分子層を形成し、硫化カドミウ
ム超微粒子層を形成した例が米国化学会誌（J. Am. Che
m. Soc. 1992, 114, 5221-5230）に記載されている。こ
れらの例での、超微粒子の複合化技術は、超微粒子の表
面修飾や超微粒子を固定するといった発想から検討され
てきているが、この発想は、従来のマイクロメートルサ
イズの粒子などでの複合化技術の延長であり、これを越
えるものではなかった。As an organized composite of ultrafine particles, for example, an example in which a monomolecular layer of alkanethiol having a bifunctional group is formed on the surface of gold or aluminum to form an ultrafine particle layer of cadmium sulfide is described in the US. Chemistry Journal (J. Am. Che
m. Soc. 1992, 114, 5221-5230). The ultrafine particle composite technology in these examples has been studied from the idea of surface modification of ultrafine particles and fixation of ultrafine particles. This idea is based on the conventional composite method using micrometer-sized particles. It was an extension of the technology for conversion, and it did not exceed this.
【０００７】一方、超微粒子同士の複合体としては、例
えば、有機化合物と無機化合物を結合させ、中間的な性
質の材料をつくることを目的に、反応性ミクロゲル（既
架橋型反応性ポリマーラテックス）とテトラエトキシシ
ランの結合複合化の報告が高分子学会予稿集、３８巻７
号、２３１９−２３２１頁になされている。しかしなが
ら、有機微粒子と無機微粒子を結合させ、混溶した材料
を形成させようとする試みであり、材料形成の前駆体と
しての利用形態である従来の粒子の概念を越えるもので
はなかった。On the other hand, as a composite of ultrafine particles, for example, a reactive microgel (pre-crosslinked reactive polymer latex) for the purpose of binding an organic compound and an inorganic compound to form a material having an intermediate property. A report on the binding and complexing of tetraethoxysilane and tetraethoxysilane is published in the Proceedings of the Polymer Society of Japan, 38, 7
No., pp. 2319-2321. However, this is an attempt to combine organic fine particles and inorganic fine particles to form a mixed material, which does not exceed the concept of conventional particles that are used as a precursor for material formation.
【０００８】（超微粒子分散技術）また、一方におい
て、産業的な利用上での超微粒子材料を形成する超微粒
子の分散技術は重要である。例えば、先に引用した「微
粒子ハンドブック」（神保元二ら編集、朝倉書店、１９
９１年）３４０頁に分散技術についての記載がある。こ
こでは、分散剤と呼ばれる添加物を加えたり、微粒子の
表面処理を行う方法などが知られているものの、超微粒
子と超微粒子を架橋することによって超微粒子の分散材
料を製造する技術は知られていない。すなわち、従来の
分散技術は、超微粒子間の空間距離を制御するような精
密なものではなく、粒子を溶媒などの「媒体中に分散す
る」技術以外の何物ものでもなかった。(Ultrafine Particle Dispersion Technology) On the other hand, an ultrafine particle dispersion technology for forming an ultrafine particle material for industrial use is important. For example, the “Particle Handbook” cited above (edited by Genji Jimbo et al., Asakura Shoten, 19
1991) Page 340 describes dispersion technology. Here, although a method of adding an additive called a dispersant or a method of performing surface treatment of fine particles is known, a technique for producing a dispersion material of ultrafine particles by crosslinking ultrafine particles is known. Not not. That is, the conventional dispersion technique is not a precise technique for controlling the spatial distance between ultrafine particles, and is nothing but a technique for "dispersing particles in a medium" such as a solvent.
【０００９】超微粒子を架橋するという点から、微粒子
と他の化合物、例えば微粒子と樹脂との架橋材料に関し
て、例をあげてみれば、プラスチック下地用の耐摩耗性
コーティング剤としてのポリシロキサン−シリカハイブ
リッド樹脂の記載がある（ACS Symp Ser NO.287, 129-1
34, 1985）。これは酸性シリカゲルの存在下で、アルキ
ルトリアルコキシシランの加水分解によって製造される
シリコーン樹脂マトリックスの内部で、シリカ微粒子が
化学的に結合したものである。しかしながら、この例に
おいても、粒子を「媒体中に分散する」という技術の範
疇でしかない。半導体超微粒子の電子的、光学的な特異
性を、効率よく発揮させたり、反応効率を向上させるた
めには、超微粒子を高濃度に分散すること、なかでも粒
径分布のそろった超微粒子を高濃度に分散させる技術が
期待されている。また超粒子間距離を制御できることも
求められている。すなわち、超微粒子の特性を生かした
高い機能を有する材料開発には、ナノメートルサイズで
の高度な分散技術が期待されているのである。From the point of cross-linking ultra fine particles, for example, a cross-linking material of fine particles and other compounds, for example, fine particles and resin, polysiloxane-silica as an abrasion resistant coating agent for plastic substrates is given. There is a description of hybrid resin (ACS Symp Ser NO.287, 129-1
34, 1985). This is one in which silica fine particles are chemically bonded inside a silicone resin matrix produced by hydrolysis of alkyltrialkoxysilane in the presence of acidic silica gel. However, even in this example, it is only in the category of the technique of "dispersing particles in a medium". In order to efficiently exhibit the electronic and optical peculiarities of semiconductor ultrafine particles and to improve the reaction efficiency, it is necessary to disperse the ultrafine particles in a high concentration, and especially to use ultrafine particles with a uniform particle size distribution. A technique for dispersing in high concentration is expected. It is also required to be able to control the distance between superparticles. That is, in order to develop a material having a high function that makes use of the characteristics of ultrafine particles, a high-level dispersion technology in the nanometer size is expected.
【００１０】[0010]
【発明が解決しようとする課題】本発明は、粒子径分布
のそろった半導体超微粒子が高濃度で分散し、半導体超
微粒子間の距離が制御可能な、新規な半導体超微粒子分
散体の製造方法と該半導体超微粒子分散体を得ようとす
るものである。DISCLOSURE OF THE INVENTION The present invention provides a method for producing a novel semiconductor ultrafine particle dispersion in which semiconductor ultrafine particles having a uniform particle size distribution are dispersed at a high concentration and the distance between the semiconductor ultrafine particles can be controlled. And to obtain the semiconductor ultrafine particle dispersion.
【００１１】[0011]
【課題を解決するための手段】本発明者らは、超微粒子
複合体の開発を鋭意進めたところ、全く新しい超微粒子
物質を発見し、これを創出した。すなわち、半導体超微
粒子が互いに架橋した超微粒子の集合体から主としてな
る、分子鎖と超微粒子から構成される新規な超微粒子分
散( 架橋 )材料を提供する。[Means for Solving the Problems] The inventors of the present invention have earnestly proceeded with the development of an ultrafine particle composite body, and have discovered and created a completely new ultrafine particle substance. That is, the present invention provides a novel ultrafine particle dispersion (crosslinking) material mainly composed of an aggregate of ultrafine particles in which semiconductor ultrafine particles are crosslinked with each other and composed of molecular chains and ultrafine particles.
【００１２】すなわち、本発明の特徴とするところは、
複数の不飽和基を有する化合物とともに、半導体超微粒
子に光を照射し、該半導体超微粒子に不飽和基を有する
分子鎖を修飾した後、この不飽和基が修飾された半導体
超微粒子同士を架橋させることを特徴とする、半導体超
微粒子架橋材料を製造する方法であり、また、複数の不
飽和基を有する化合物とともに、半導体超微粒子を製造
しながら、該生成する半導体超微粒子に光を照射し、該
生成される半導体超微粒子に不飽和基を有する分子鎖を
修飾した後、この不飽和基が修飾された半導体超微粒子
同士を架橋させることを特徴とする、半導体超微粒子架
橋材料を製造する方法であり、また、不飽和基を有する
分子鎖が修飾された半導体超微粒子同士を架橋させる手
段として架橋剤を用いる、これら半導体超微粒子架橋材
料を製造する方法でありまた、例えばこれらの方法によ
り製造しうる、半導体超微粒子が互いに架橋した超微粒
子の複合体から主としてなることを特徴とする半導体超
微粒子架橋材料であり、また、これらの半導体超微粒子
架橋材料が媒体中に分散されている半導体超微粒子架橋
材料、である。That is, the feature of the present invention is that
A semiconductor ultrafine particle is irradiated with light together with a compound having a plurality of unsaturated groups to modify the molecular chain having an unsaturated group in the semiconductor ultrafine particle, and then the semiconductor ultrafine particles modified with the unsaturated group are cross-linked. The method for producing a semiconductor ultrafine particle cross-linking material, characterized in that, while producing a semiconductor ultrafine particles together with a compound having a plurality of unsaturated groups, the semiconductor ultrafine particles to be generated is irradiated with light. A method for producing a semiconductor ultrafine particle cross-linking material, characterized in that the generated ultrafine semiconductor particles are modified with a molecular chain having an unsaturated group and then the semiconductor ultrafine particles modified with the unsaturated group are crosslinked with each other. Method, and a method for producing these semiconductor ultrafine particle crosslinked materials, wherein a crosslinking agent is used as a means for crosslinking semiconductor ultrafine particles modified with a molecular chain having an unsaturated group Also, for example, a semiconductor ultrafine particle crosslinked material, which can be produced by these methods, characterized in that the semiconductor ultrafine particles are mainly composed of a composite of ultrafine particles crosslinked with each other, and these semiconductor ultrafine particle crosslinked materials are also A semiconductor ultrafine particle cross-linking material dispersed in a medium.
【００１３】（発明の概念） （典型例）本発明を明快に説明するために、本発明であ
る半導体超微粒子架橋材料の製造方法を図によって示
す。まず、複数の不飽和基を有する化合物存在下におい
て、半導体超微粒子に光を照射し、該半導体超微粒子に
不飽和基を有する分子鎖を修飾する。これを図１に示
す。(Concept of the Invention) (Typical Example) In order to clearly explain the present invention, a method for producing a semiconductor ultrafine particle cross-linking material of the present invention is shown in the drawings. First, semiconductor ultrafine particles are irradiated with light in the presence of a compound having a plurality of unsaturated groups to modify the semiconductor ultrafine particles with a molecular chain having an unsaturated group. This is shown in FIG.
【００１４】図１は、多数の複数の不飽和基を有する化
合物存在下のなかで、半導体超微粒子に光を照射してい
る様子をモデル化して表している。黒い部分が不飽和基
を表している。中心の内核の部分が半導体超微粒子を表
し、これに光を照射すると表面部分で複数の不飽和基を
有する化合物と電子のやりとりが生じ、複数の不飽和基
を有する化合物から、部分的にまたは半導体超微粒子表
面全体に、分子鎖からなる表面修飾層が外殻として形成
される。FIG. 1 shows a model of a state in which semiconductor ultrafine particles are irradiated with light in the presence of a compound having a large number of plural unsaturated groups. The black part represents the unsaturated group. The central inner core portion represents semiconductor ultrafine particles, and when irradiated with light, electrons exchange with the compound having a plurality of unsaturated groups at the surface portion, and from the compound having a plurality of unsaturated groups, partially or A surface modification layer composed of molecular chains is formed as an outer shell on the entire surface of the semiconductor ultrafine particles.
【００１５】この高分子からなると考えられる外殻に
は、未反応の不飽和基が残留し、本発明では、これを
「不飽和基を有する分子鎖が修飾された状態」という。
この不飽和基を有する分子鎖が修飾された半導体超微粒
子をつくる方法として、半導体超微粒子を製造・成長さ
せながら行う方法もある。この場合、粒子径分布を制御
できる利点がある。An unreacted unsaturated group remains in the outer shell which is considered to be composed of this polymer, and in the present invention, this is referred to as "a state in which the molecular chain having an unsaturated group is modified".
As a method of producing semiconductor ultrafine particles having a modified molecular chain having an unsaturated group, there is also a method of producing and growing the semiconductor ultrafine particles. In this case, there is an advantage that the particle size distribution can be controlled.
【００１６】次に、この不飽和基が修飾された半導体超
微粒子同士を架橋させて半導体超微粒子架橋材料を製造
する。これを図２に表す。図２においては、図１で表し
た方法によって製造された、不飽和基が修飾された半導
体超微粒子同士を直接、または複数の不飽和基を有する
化合物存在下において、架橋剤の添加や加熱、または放
射線の照射などによって、不飽和基が修飾された半導体
超微粒子同士が架橋し、半導体超微粒子架橋体が製造さ
れる様子を表している。図２では１次粒子の場合を表し
ているが、構成単位となる半導体超微粒子が２次粒子で
あってもよいことはいうまでもない。すなわち、本発明
では、超微粒子を固定したり、修飾したりするという従
来の粒子加工としての考え方を越え、超微粒子架橋体と
して、超微粒子と分子鎖からなるナノメートルサイズの
新規物質を提供するものである。以下、さらに詳細に本
発明内容について記述する。Next, the semiconductor ultrafine particles modified with the unsaturated group are crosslinked to produce a semiconductor ultrafine particle crosslinked material. This is shown in FIG. In FIG. 2, the semiconductor ultrafine particles modified with unsaturated groups, which are produced by the method shown in FIG. 1, are directly added to each other or in the presence of a compound having a plurality of unsaturated groups. Alternatively, it shows a state in which semiconductor ultrafine particles modified with unsaturated groups are crosslinked with each other by irradiation of radiation to produce a crosslinked semiconductor ultrafine particles. Although FIG. 2 shows the case of primary particles, it goes without saying that the semiconductor ultrafine particles serving as the constitutional unit may be secondary particles. That is, the present invention provides a novel nanometer-sized substance composed of ultrafine particles and molecular chains, as a crosslinked ultrafine particle, overcoming the conventional idea of particle processing of fixing or modifying ultrafine particles. It is a thing. Hereinafter, the content of the present invention will be described in more detail.
【００１７】（超微粒子およびその測定方法）ここで言
うところの超微粒子とは、１００ナノメートル以下、好
ましくは２０ナノメートル以下、さらに好ましくは１０
ナノメートル以下の平均直径の粒子をいう。このような
ごく小さな粒子である超微粒子の粒径や組成を測る手段
としては、一般的に知られている方法、例えば、透過型
電子顕微鏡による観察や解析、粉末Ｘ線回析、光吸収ス
ペクトル測定などを用いることができる。特に、半導体
超微粒子の光吸収スペクトルを測定することにより、簡
便にその粒径分布の情報を得ることができる。すなわ
ち、粒子が小さくなるにしたがって、半導体空間内の電
子や正孔が閉じ込められ、量子箱的な現象が起こるため
に、粒子径が小さいほど光吸収末端が短波長側へ移動す
ることや、電子準位間の分裂が大きくなって光吸収ピー
クが出現することから、粒子径や粒子径分布を推定でき
るのである。(Ultrafine Particles and Measuring Method Thereof) The ultrafine particles mentioned here are 100 nanometers or less, preferably 20 nanometers or less, and more preferably 10 nanometers or less.
It refers to particles having an average diameter of nanometers or less. As a means for measuring the particle size and composition of ultrafine particles that are such extremely small particles, there are commonly known methods such as observation and analysis by a transmission electron microscope, powder X-ray diffraction, and optical absorption spectrum. Measurement or the like can be used. In particular, by measuring the light absorption spectrum of the semiconductor ultrafine particles, information on the particle size distribution can be easily obtained. That is, as the particles become smaller, electrons and holes in the semiconductor space are confined, and a quantum box-like phenomenon occurs.Therefore, the smaller the particle size, the more the light absorption terminal moves to the shorter wavelength side. Since the splitting between levels becomes large and a light absorption peak appears, the particle size and particle size distribution can be estimated.
【００１８】（半導体）本発明でいう超微粒子に用いら
れる半導体とは、シリコン、ゲルマニウムなどのIV族元
素、あるいはＴｉＯ2やＺｎＯなどの酸化物半導体や、
ＧａＡｓやＩｎＰ、ＩｎＳｂなどのIII −Ｖ族化合物半
導体、またはＣｄＳ、ＣｄＳｅ、ＺｎＳｅやＣｄＴｅな
どのII−VI族化合物半導体、さらにはＣｕＣｌ、ＣｕＢ
ｒなどのＩ−VII 族化合物半導体などをいう。(Semiconductor) The semiconductor used for the ultrafine particles in the present invention means a group IV element such as silicon or germanium, or an oxide semiconductor such as TiO 2 or ZnO,
III-V group compound semiconductors such as GaAs, InP and InSb, II-VI group compound semiconductors such as CdS, CdSe, ZnSe and CdTe, and further CuCl and CuB.
It means a group I-VII compound semiconductor such as r.
【００１９】（半導体微粒子の製造方法）半導体超粒子
は、一般に知られた、気相での製造方法や液相での製造
方法、また気相や液相を含む固体中での製造方法によっ
てあらかじめ製造されたり、これらの製造方法と組み合
わせて、製造しながら複数の不飽和基を有する化合物を
修飾することができる。例えば、気相においては、ガス
中蒸着法やレーザー蒸発法などの蒸発凝縮法、プラズマ
ＣＶＤ法、レーザーＣＶＤ法などのＣＶＤ法など、ま
た、液相では共沈法や金属アルコキシド法、保護コロイ
ド法などを用いて、半導体超微粒子を製造することがで
きる。反応を制御しやすい点や量産性の観点から、共沈
法や金属アルコキシド法、保護コロイド法、オルガノゾ
ル法などの液相中での製造方法を好ましい例としてあげ
ることができる。(Manufacturing Method of Semiconductor Fine Particles) Semiconductor superparticles can be prepared in advance by a generally known manufacturing method in a gas phase or a liquid phase, or in a solid containing a gas phase or a liquid phase. It can be produced or combined with these production methods to modify a compound having a plurality of unsaturated groups during production. For example, in the gas phase, evaporation condensation methods such as vapor deposition method and laser evaporation method, CVD methods such as plasma CVD method and laser CVD method, and in the liquid phase, coprecipitation method, metal alkoxide method, protective colloid method, etc. Etc. can be used to produce semiconductor ultrafine particles. From the viewpoints of easy control of reaction and mass productivity, production methods in a liquid phase such as a coprecipitation method, a metal alkoxide method, a protective colloid method, and an organosol method can be mentioned as preferable examples.
【００２０】（複数の不飽和基を有する化合物）本発明
でいう複数の不飽和基を有する化合物とは、化合物分子
内に複数の不飽和基を有するものであればよい。すなわ
ち、２重結合または３重結合を複数個有するものであれ
ばよく、より具体的な例としては、例えば、ジビニルベ
ンゼンやエチレンジメタクリレート、無水メタクリル
酸、ジアリールフタレートなどのジビニルあるいはジア
リル類や、トリビニルあるいはトリアリル類、さらには
複数のビニル基やアリル基を有するオリゴマーやポリマ
ーであってもよい。(Compound having a plurality of unsaturated groups) The compound having a plurality of unsaturated groups in the present invention may be any compound having a plurality of unsaturated groups in the compound molecule. That is, any compound having a plurality of double bonds or triple bonds may be used, and more specific examples include, for example, divinyl or diallyls such as divinylbenzene, ethylene dimethacrylate, methacrylic anhydride, and diaryl phthalate, It may be trivinyl or triallyl, or an oligomer or polymer having a plurality of vinyl groups or allyl groups.
【００２１】（半導体超微粒子の修飾方法）本発明で
は、まず、製造した半導体超微粒子または製造中の半導
体超微粒子に光を照射し、複数の不飽和基を有する化合
物を半導体表面に修飾する。複数の不飽和基を有する化
合物は、半導体超微粒子とともに溶液または気相中で拡
散、吸着が可能な状態で存在すればよい。照射する光
は、半導体超微粒子の種類、大きさによって、半導体超
微粒子が光を吸収できる波長領域が異なるため、これに
あわせて照射する光の波長を選択する。水銀灯やキセノ
ン灯、ハロゲンランプやこれに光学フィルターを組み合
わせて使用することができる。またレーザーを光源とし
て用いることもできる。(Method for Modifying Semiconductor Ultrafine Particles) In the present invention, first, the manufactured semiconductor ultrafine particles or the semiconductor ultrafine particles being manufactured are irradiated with light to modify the surface of the semiconductor with a compound having a plurality of unsaturated groups. The compound having a plurality of unsaturated groups may be present together with the semiconductor ultrafine particles in a state capable of being diffused and adsorbed in a solution or a gas phase. The wavelength of light to be irradiated is different depending on the type and size of the semiconductor ultrafine particles, and therefore the wavelength of the light to be irradiated is selected accordingly. A mercury lamp, a xenon lamp, a halogen lamp, or an optical filter can be used in combination. Also, a laser can be used as a light source.
【００２２】（半導体超微粒子の架橋方法）本発明で
は、複数の不飽和基を有する化合物を光照射によって修
飾された半導体超微粒子同士を架橋させ、半導体超微粒
子架橋体とする。架橋の方法としては、通常の加熱や高
周波加熱などの加熱、放射線や電子線の照射、架橋剤の
添加が好ましい方法としてあげることができる。本発明
における架橋剤としては、通常高分子の架橋反応に用い
られる化合物を好適に用いることができる。より具体的
には、いおうや塩化いおう、ジチオールなどのいおう化
合物、過酸化ベンゾイル、アミノアゾベンゼン、α,
α’−アゾビスイソブチロニトリルなどのラジカル発生
剤、キノンやポリニトロベンゼンなどの共鳴構造を持つ
酸化性物質をあげることができる。(Crosslinking Method of Semiconductor Ultrafine Particles) In the present invention, the semiconductor ultrafine particles are crosslinked with each other by modifying the compound having a plurality of unsaturated groups by light irradiation to obtain a crosslinked semiconductor ultrafine particles. As a method of crosslinking, heating such as normal heating or high frequency heating, irradiation of radiation or electron beam, and addition of a crosslinking agent can be mentioned as preferable methods. As the cross-linking agent in the present invention, compounds usually used in cross-linking reaction of polymers can be preferably used. More specifically, sulfur compounds such as sulfur and sulfur chloride, dithiols, benzoyl peroxide, aminoazobenzene, α,
Examples thereof include radical generators such as α'-azobisisobutyronitrile, and oxidizing substances having a resonance structure such as quinone and polynitrobenzene.
【００２３】（半導体超微粒子架橋材料の測定方法）超
微粒子架橋材料の測定方法としては、赤外吸収スペクト
ルや核磁気共鳴法、元素分析、質量分析、Ｘ線回折、電
子顕微鏡による観察などやクラマトグラフや遠心分離法
などの分離法との組合せなど、通常知られている方法で
これを観察することができる。(Measurement method of semiconductor ultrafine particle cross-linking material) Ultra fine particle cross-linking material can be measured by infrared absorption spectrum, nuclear magnetic resonance method, elemental analysis, mass spectrometry, X-ray diffraction, observation by electron microscope, or Kramato. This can be observed by a commonly known method such as a combination with a separation method such as a graph or a centrifugation method.
【００２４】（具体的な超微粒子を有する分子・構造体
の製造例）半導体超微粒子架橋材料のより具体的な製造
方法として、例えば、溶液中での製造方法の例を以下に
あげる。まず、溶媒中に半導体原料を溶解させる。使用
される溶媒は、水あるいは非水溶媒、好ましくは比較的
極性の大きな非水溶媒、具体的には、例えば、アセト
ン、アセトニトリル、ベンゾニトリル、ジメチルホルム
アミド、ジメチルスルフォキシド、クロロホルム、メタ
ノール、エタノール、ジオキサン、テトラヒドロフラ
ン、メチルエチルケトンなど、或はこれらを含有する混
合溶媒が用いられる。(Production Example of Specific Molecule / Structure Having Ultrafine Particles) As a more specific production method of the semiconductor ultrafine particle cross-linking material, an example of a production method in a solution will be given below. First, the semiconductor raw material is dissolved in a solvent. The solvent used is water or a non-aqueous solvent, preferably a relatively polar non-aqueous solvent, specifically, for example, acetone, acetonitrile, benzonitrile, dimethylformamide, dimethylsulfoxide, chloroform, methanol, ethanol. , Dioxane, tetrahydrofuran, methyl ethyl ketone, etc., or a mixed solvent containing these is used.
【００２５】半導体原料としては、このような液相中で
の半導体超微粒子合成においては、用いる溶媒に可溶な
金属化合物を用いる。これらの金属化合物は、好ましく
は１モル／リットル以下、より好ましくは１０ー6〜１０
ー1モル／リットルの程度の濃度の溶液にすることが望ま
しい。As the semiconductor raw material, a metal compound soluble in the solvent used in the synthesis of semiconductor ultrafine particles in such a liquid phase is used. These metal compounds are preferably 1 mol / liter or less, more preferably 10 −6 to 10
-It is desirable that the solution has a concentration of about 1 mol / liter.
【００２６】共存させる複数の不飽和基を有する化合物
の濃度としては、使用する金属化合物の０．０００１か
ら１００倍のモル濃度が好ましく用いられる。これらの
複数の不飽和基を有する化合物はあらかじめ混合させて
おいても、反応中に徐々に加えてもよく、また、加える
複数の不飽和基を有する化合物の種類を反応の進行とと
もに順次かえてもよい。また、あらかじめ複数の不飽和
基を有する化合物を共存させずに、半導体超微粒子を合
成した後に、光照射しながら複数の不飽和基を有する化
合物を共存させ、半導体超微粒子の修飾を行ってもよい
ことはいうまでもない。The concentration of the compound having a plurality of unsaturated groups to coexist is preferably 0.0001 to 100 times the molar concentration of the metal compound used. These compounds having a plurality of unsaturated groups may be mixed in advance, or may be gradually added during the reaction, and the kind of the compound having a plurality of unsaturated groups to be added may be sequentially changed as the reaction progresses. Good. In addition, after synthesizing the semiconductor ultrafine particles without preexisting the compound having a plurality of unsaturated groups, the compound having a plurality of unsaturated groups is allowed to coexist while being irradiated with light to modify the semiconductor ultrafine particles. It goes without saying that it is good.
【００２７】使用する金属化合物としては、例えば、酢
酸塩などの有機酸塩類、金属の硝酸塩類、過塩素酸塩
類、アルコキシド類、アセチルアセロナート類、ハロゲ
ン化物類などが用いられる。好ましくは、金属ハロゲン
化物類、金属硝酸塩類、金属過塩素酸類、金属酢酸塩類
が用いられる。これらは結晶水を含むものであってもよ
い。Examples of the metal compound to be used include organic acid salts such as acetate, metal nitrates, perchlorates, alkoxides, acetylaceronates, halides and the like. Preferably, metal halides, metal nitrates, metal perchlorates, and metal acetates are used. These may contain water of crystallization.
【００２８】金属種としては、III −Ｖ族化合物半導体
を生成するＡｌ、Ｇａ、ＩｎなどのIII 族元素、II−VI
族化合物半導体を生成するＺｎ、Ｃｄ、ＨｇなどのII族
元素、Ｉ−VI、Ｉ−VII 族化合物半導体を生成するＣｕ
などのＩ族元素、IV−VI族化合物半導体を生成するＰ
ｂ、Ｔｉ、ＳｎなどのIV族元素などが例としてあげられ
る。As the metal species, a group III element such as Al, Ga, or In which forms a group III-V compound semiconductor, II-VI.
Group II elements such as Zn, Cd, and Hg that produce group compound semiconductors, and Cu that produce group I-VI and group I-VII compound semiconductors
Group I element such as P, which produces a IV-VI group compound semiconductor
Examples include group IV elements such as b, Ti, and Sn.
【００２９】半導体に金属化合物を用いた場合、例え
ば、ＣｄＳ、ＣｄＳｅ、ＺｎＳｅやＣｄＴｅなどのII−
VI族化合物半導体超微粒子を製造する場合を例にあげる
と、硫化水素ガスやセレン化水素ガスなどの水素化物
や、ビストリメチルシリルイオウなどの有機カルコゲン
化物などの適当なカルコゲン化剤を、原料溶液に加える
ことによって、半導体超粒子を生成、成長させ、これを
得ることができる。これらの試薬はヘリウムや窒素など
の不活性ガスや溶媒によって希釈し、半導体粒子の生成
反応を制御することができる。反応ガス濃度としては、
体積で１００％〜０．０００１％の濃度が好ましく、流
量としては反応を定常的に進ませるに十分な量であれば
よい。反応溶液が１００ｍｌ以下の場合は、通常１ｍｌ
／分から５００ｍｌ／分の流量で好ましく、半導体超微
粒子の製造反応を行うことができる。When a metal compound is used for the semiconductor, for example, II-such as CdS, CdSe, ZnSe and CdTe.
Taking the case of producing Group VI compound semiconductor ultrafine particles as an example, hydrides such as hydrogen sulfide gas and hydrogen selenide gas, and suitable chalcogenizing agents such as organic chalcogenides such as bistrimethylsilylsulfur are used as raw material solutions. By adding, semiconductor superparticles can be generated and grown, and this can be obtained. These reagents can be diluted with an inert gas such as helium or nitrogen or a solvent to control the reaction for producing semiconductor particles. As the reaction gas concentration,
The concentration is preferably 100% to 0.0001%, and the flow rate may be an amount sufficient to allow the reaction to proceed steadily. If the reaction solution is 100 ml or less, usually 1 ml
A flow rate of from 1 / min to 500 ml / min is preferable, and the reaction for producing ultrafine semiconductor particles can be carried out.
【００３０】照射する光の光源としては、半導体粒子を
励起できるものであればよいが、粒径制御された複合粒
子を得るために、好ましくは、半導体粒子の吸収端付近
を単色光、もしくは特定波長より長波長の光を照射する
ことが望ましい。このような光源としては、キセノン
灯、水銀灯、タングステン灯およびこれにに波長カット
フィルターをかけたもの、アルゴンイオンレーザーや色
素レーザーなどのレーザー光源などがあげられる。The light source for irradiating light may be any one capable of exciting semiconductor particles, but in order to obtain composite particles having a controlled particle size, preferably, the vicinity of the absorption edge of the semiconductor particles is monochromatic light or a specific color. It is desirable to irradiate light with a wavelength longer than the wavelength. Examples of such a light source include a xenon lamp, a mercury lamp, a tungsten lamp, a lamp obtained by applying a wavelength cut filter thereto, and a laser light source such as an argon ion laser or a dye laser.
【００３１】照射する光の強度は、半導体粒子の生成反
応と競争して、修飾反応ができるように、より強い方が
好ましいが、あまりに光強度が強いと光劣化等の他の光
反応を引き起こすことがあるので、好ましくは０．００
２Ｗ／ｃｍ2〜１Ｗ／ｃｍ2程度であることが望ましい。
また、照射する光の波長は対象とする半導体の種類、制
御しようとする粒子径によって、任意に設定することが
できる。しかし、当然のことながら選択される光の波長
は、半導体のバルクの吸収波長よりも短くなければなら
ない。好ましくは半導体のバルクの吸収末端より２００
ｎｍ以内の短波長の光を照射する。The intensity of the irradiation light is preferably higher so that the modification reaction can be carried out by competing with the generation reaction of semiconductor particles, but if the light intensity is too high, other photoreactions such as photodegradation are caused. Therefore, 0.00 is preferable.
2W / cm 2 is desirably to 1 W / cm 2 approximately.
Further, the wavelength of the light to be irradiated can be arbitrarily set depending on the type of the target semiconductor and the particle size to be controlled. However, it should be appreciated that the wavelength of light selected must be shorter than the absorption wavelength of the bulk of the semiconductor. Preferably 200 from the absorption end of the bulk of the semiconductor
Irradiate light with a short wavelength within nm.
【００３２】照射する光は、反応溶液全体に照射される
ことが望ましい。また、反応が進んで半導体超微粒子が
生成された場合に、生成された半導体超微粒子が光を吸
収するので、最終生成溶液の光学濃度が吸光度で３以下
にするよう、あらかじめ原料濃度を調整したり、光照射
する反応器の光学距離を調整しておくと好適に反応をお
こなうことができる。修飾反応は、光吸収や粒径分布の
準弾性光散乱による観察などの方法によって、その進行
を観測することができる。The irradiation light is preferably applied to the entire reaction solution. Further, when the reaction progresses to generate semiconductor ultrafine particles, the generated semiconductor ultrafine particles absorb light. Therefore, the raw material concentration is adjusted in advance so that the optical density of the final solution is 3 or less in terms of absorbance. Alternatively, the reaction can be suitably performed by adjusting the optical distance of the reactor for light irradiation. The progress of the modification reaction can be observed by methods such as light absorption and observation of particle size distribution by quasi-elastic light scattering.
【００３３】次に、このようにして製造された複数の不
飽和基を有する化合物で修飾された半導体超微粒子を用
いて、架橋反応を行い、半導体超微粒子架橋材料とす
る。架橋の方法としては、加熱や放射線の照射、架橋剤
の添加などがあるが、架橋剤を用いる場合について例を
あげる。複数の不飽和基を有する化合物で修飾された半
導体超微粒子溶液に、架橋剤を半導体超微粒子の原料化
合物に対して、好ましくは０．０００１〜１モル比量加
え、必要に応じて加熱・還流させたり、光照射を行う。
このとき、架橋反応の進行の程度により、超微粒子架橋
物が懸濁したり、析出する。Next, the semiconductor ultrafine particles thus modified with the compound having a plurality of unsaturated groups are subjected to a crosslinking reaction to obtain a semiconductor ultrafine particle crosslinking material. Examples of the crosslinking method include heating, irradiation with radiation, and addition of a crosslinking agent. An example of using a crosslinking agent will be given. To the semiconductor ultrafine particle solution modified with a compound having a plurality of unsaturated groups, a crosslinking agent is preferably added in an amount of 0.0001 to 1 molar ratio with respect to the raw material compound of the semiconductor ultrafine particles, and heated / refluxed as necessary. Or light irradiation.
At this time, depending on the degree of progress of the crosslinking reaction, the ultrafine particle crosslinked product is suspended or precipitated.
【００３４】このようにして得られた溶液や沈澱物から
ゲルクロマトグラフなどのクロマトグラフや遠心分離
法、再結晶法、再沈澱法などの通常の分離精製法によ
り、それぞれの構造物を分離してもよく、また、溶媒を
エバポレーションや減圧蒸留などの方法により除去して
そのまま材料として用いてもよい。また、得られた溶液
にポリマー成分を溶解して、所望の分散材料を形成して
もよい。Each structure is separated from the thus obtained solution or precipitate by a chromatographic method such as a gel chromatograph or a usual separation and purification method such as a centrifugation method, a recrystallization method or a reprecipitation method. Alternatively, the solvent may be removed by a method such as evaporation or vacuum distillation and used as it is as a material. Further, the polymer component may be dissolved in the obtained solution to form a desired dispersion material.
【００３５】（利用の形態）本発明にかかる新規な超微
粒子架橋材料は、そのまま材料として使用することがで
きる。得られた超微粒子を有する分子または構造体は、
薄膜やこれらの多層膜、ブロック、レンズ、ファイバー
や導波路などの形態で用いられる。すなわち、適当にカ
ットしたり、圧縮や延伸をしたり、溶融させたり、また
溶液の状態でスクリーン印刷やディップコーティング、
スピンコーティングなどの方法や射出成形などの成形方
法により所望の形態に成形することができる。また、成
形した薄膜などを、ドライエッチングなど一般に知られ
た方法で、さらに加工して所望の形態の素子にすること
もできる。(Form of Utilization) The novel ultrafine particle cross-linking material according to the present invention can be used as it is as a material. The molecule or structure having the obtained ultrafine particles,
It is used in the form of thin films, multilayer films of these, blocks, lenses, fibers, waveguides, and the like. That is, properly cut, compressed or stretched, melted, screen printing or dip coating in solution,
It can be molded into a desired shape by a method such as spin coating or a molding method such as injection molding. Further, the formed thin film or the like can be further processed by a generally known method such as dry etching to form an element having a desired shape.
【００３６】（分散体）製造した超微粒子架橋材料は、
適当な媒体中に分散して、分散体として使用することも
できる。超微粒子を有する分子または構造体を真空中や
気相中に分散したり、液相中に分散したままでも、分散
空間を通過する光によって、光学材料や光電子材料とす
ることができるが、実用性の観点から固体の媒体中に分
散することが好ましい。また、分散した溶液状態のコー
ティング液などの形態で、種々の用途に提供することも
できる。固体中に超微粒子を有する分子または構造体を
分散する場合の媒体としては、ガラスなどの無機媒体や
ポリマーなどの有機媒体材料を好適に用いることができ
る。この分散体は、薄膜やこれらの多層膜、ブロック、
レンズ、ファイバーや導波路などの形態で用いられる。(Dispersion) The manufactured ultrafine particle cross-linking material is
It can also be used as a dispersion by dispersing in a suitable medium. Molecules or structures containing ultrafine particles can be made into optical materials and optoelectronic materials by light passing through the dispersion space even if they are dispersed in vacuum or in the gas phase, or even in the liquid phase. From the viewpoint of properties, it is preferable to disperse it in a solid medium. Further, it can be provided for various uses in the form of a coating solution in a dispersed solution state. An inorganic medium such as glass or an organic medium material such as a polymer can be preferably used as a medium for dispersing molecules or structures having ultrafine particles in a solid. This dispersion consists of thin films, multilayers of these, blocks,
Used in the form of lenses, fibers and waveguides.
【００３７】（超微粒子を有する分子または構造体の分
散体の製造方法）超微粒子架橋材料の分散体を形成する
方法としては、例えば、ガラスなどの無機媒体は、Ｓｉ
Ｏの酸素中蒸発によるＳｉＯ2媒体の形成や製造した超
微粒子を有する分子または構造体分散液の多孔質ガラス
への含浸、ゾル−ゲル法によるガラス媒体の形成などの
方法をとることができる。ポリマーなどの有機媒体を形
成する方法としては、粉末で取り出した超微粒子を有す
る分子または構造体を、ポリマー成分と混合する方法
や、液相中で製造した超微粒子を有する分子または構造
体分散液にポリマー成分を加え、これを重合反応などに
より硬化させたり、溶媒の除去によって固体媒体を形成
する方法をとることができる。これらの分散材料はさら
に圧縮したり、溶融させたり、また溶液の状態でスクリ
ーン印刷やディップコーティング、スピンコーティング
などの方法や射出成形などの成形方法により所望の形態
に成形することもできる。また、形成した半導体超微粒
子の分散薄膜などを、ドライエッチングなど一般に知ら
れた方法で、さらに加工して所望の形態の素子にするこ
ともできる。以下、実施例により本発明の実施の態様の
一例を説明する。(Method for Producing Dispersion of Molecules or Structures Having Ultrafine Particles) As a method for forming a dispersion of the ultrafine particle cross-linking material, for example, an inorganic medium such as glass is Si.
Methods such as formation of a SiO 2 medium by evaporation of O in oxygen, impregnation of the produced molecule or structure dispersion liquid having ultrafine particles into a porous glass, and formation of a glass medium by a sol-gel method can be used. As a method for forming an organic medium such as a polymer, a method of mixing a molecule or structure having ultrafine particles taken out in powder with a polymer component, or a molecule or structure dispersion liquid having ultrafine particles produced in a liquid phase It is possible to employ a method in which a polymer component is added to and cured by a polymerization reaction or the like, or a solid medium is formed by removing the solvent. These dispersion materials can be further compressed, melted, or formed into a desired form by a method such as screen printing, dip coating, spin coating, or a forming method such as injection molding in a solution state. Further, the formed dispersed thin film of semiconductor ultrafine particles can be further processed by a generally known method such as dry etching to obtain an element having a desired shape. Hereinafter, an example of an embodiment of the present invention will be described with reference to examples.
【００３８】分散材料の媒体としてポリマーを用いる場
合は、素子の用途に応じてポリマーを選択すればよく、
特に制限はないが、具体的な好ましい例としては、ポリ
メチルメタクリレート、ポリエチルメタクリレート、ポ
リ（２−ヒドロキシエチル）メタクリレート、ポリカー
ボネート、ポリスチレン、ポリエステル、ポリエチレン
テレフタレート、ポリ塩化ビニル、ポリエーテルスルホ
ン、ポリアクリロニトリル、塩化ビニルと酢酸ビニルの
共重合ポリマー、スチレンとアクリロニトリルの共重合
ポリマー、またはこれらの混合物などが挙げられる。ま
た、光硬化樹脂や熱硬化樹脂を用いることもできる。他
の成分として、界面活性剤などを混合してもよい。When a polymer is used as the medium of the dispersion material, the polymer may be selected according to the application of the device,
Although not particularly limited, specific preferable examples include polymethylmethacrylate, polyethylmethacrylate, poly (2-hydroxyethyl) methacrylate, polycarbonate, polystyrene, polyester, polyethyleneterephthalate, polyvinyl chloride, polyethersulfone, polyacrylonitrile. , A copolymer of vinyl chloride and vinyl acetate, a copolymer of styrene and acrylonitrile, or a mixture thereof. Further, a photocurable resin or a thermosetting resin can also be used. As another component, a surfactant or the like may be mixed.
【００３９】[0039]
【実施例】以下、本発明を実施例に基づき、更に詳細に
述べる。 実施例１ 過塩素酸カドミウム六水和物（Ｃｄ（ＣｌＯ4 ）2 ・６
Ｈ2Ｏ）を２．０×１０ー3ｍｏｌ／ｌ、ジビニルベンゼ
ンを８．０×１０ー2ｍｏｌ／ｌの濃度に溶かしたアセト
ニトリル溶液４５ｍｌを太鼓形枝付き石英セルに入れ、
マグネットスターラーで撹拌をおこないながら、アルゴ
ンイオンレーザーの波長４５７．９ｎｍ、光強度０．０
２０Ｗ／ｃｍ2の光を照射する。この溶液中に、０．０
２体積％のヘリウム希釈の硫化水素ガスを２７０ｍｌ／
ｍｉｎの供給速度で導入し、４０分間反応を行った。反
応後、窒素をガス導入管から系内に流し、残留硫化水素
ガスを除いた。反応操作は全てドラフト中で行った。こ
のようにして得られた溶液はうすい黄色透明であった。
以上の操作から表面がジビニルベンゼンの重合体で修飾
され、未反応のビニル基が残留している修飾された硫化
カドミウムのコロイド溶液を合成した。EXAMPLES The present invention will be described in more detail based on the following examples. Example 1 cadmium perchlorate hexahydrate (Cd (ClO 4) 2 · 6
H 2 O) was dissolved in a concentration of 2.0 × 10 −3 mol / l and divinylbenzene in a concentration of 8.0 × 10 −2 mol / l, and 45 ml of an acetonitrile solution was placed in a drum cell having a drum-shaped branch.
While stirring with a magnetic stirrer, argon ion laser wavelength 457.9 nm, light intensity 0.0
Irradiate with 20 W / cm 2 . In this solution, 0.0
270 ml of hydrogen sulfide gas diluted with 2% by volume of helium
It was introduced at a supply rate of min and reacted for 40 minutes. After the reaction, nitrogen was flown into the system through a gas introduction pipe to remove residual hydrogen sulfide gas. All reaction operations were carried out in a draft. The solution thus obtained was light yellow and transparent.
From the above operation, a modified cadmium sulfide colloidal solution in which the surface was modified with a polymer of divinylbenzene and unreacted vinyl groups remained was synthesized.
【００４０】次に、この合成したコロイド溶液をそのま
ま冷却管をつけた１００ｍｌの三ッ口フラスコに移し、
窒素ガスを２０分間バブリング下の後、これにα、α’
−アゾビスイソブチロニトリルを０．０６５ｇ加え、５
５℃で５時間加熱した。この結果、濁った黄色の溶液が
得られた。得られた溶液からの固形物を、透過型電子顕
微鏡で観察したところ、数１０個の２次粒子からなる集
合体群が多く観察された。すなわち、ひとつの硫化カド
ミウム超微粒子の直径は約２ｎｍであり、これらが集合
して２０ｎｍ程度の２次粒子を形成し、これを単位とし
て、２次粒子端と２次粒子端の間隔が約２５ｎｍでほぼ
均一な分散体であった。Next, the synthesized colloidal solution was transferred as it was to a 100 ml three-necked flask equipped with a cooling tube,
After bubbling nitrogen gas for 20 minutes, α, α '
-Add 0.065 g of azobisisobutyronitrile and add 5
Heated at 5 ° C. for 5 hours. This resulted in a cloudy yellow solution. When the solid matter from the obtained solution was observed with a transmission electron microscope, many aggregate groups composed of several tens of secondary particles were observed. That is, one cadmium sulfide ultrafine particle has a diameter of about 2 nm, and these aggregate to form a secondary particle of about 20 nm. With this as a unit, the interval between the secondary particle end and the secondary particle end is about 25 nm. The dispersion was almost uniform.
【００４１】比較のため、ジビニルベンゼンの重合体で
修飾された硫化カドミウム超微粒子溶液からの固形物を
透過型電子顕微鏡で観察したところ、ひとつの硫化カド
ミウム超微粒子の直径が約２ｎｍのものが集合した２０
ｎｍ程度の２次粒子は観察されたが、ばらばらに存在
し、数１０個の集合体群は観察されなかった。したがっ
て、高密度かつ超微粒子間隔が制御された超微粒子架橋
体が形成されていることが確認された。For comparison, when a solid substance from the cadmium sulfide ultrafine particle solution modified with a polymer of divinylbenzene was observed with a transmission electron microscope, one cadmium sulfide ultrafine particle having a diameter of about 2 nm was aggregated. Done 20
Although secondary particles having a size of about nm were observed, they were scattered and several tens of aggregates were not observed. Therefore, it was confirmed that a crosslinked ultrafine particle having a high density and a controlled ultrafine particle spacing was formed.
【００４２】実施例２ 実施例１よりも架橋反応時間を、α、α’−アゾビスイ
ソブチロニトリルを加えた後、５５℃で２０時間と長く
する以外は、実施例１と同じ条件で硫化カドミウム超微
粒子架橋体の製造をおこなった。この結果、一部沈澱を
含む濁った黄色の溶液が得られた。Example 2 Under the same conditions as in Example 1, except that the crosslinking reaction time was increased to 20 hours at 55 ° C. after the addition of α, α′-azobisisobutyronitrile as compared with Example 1. Cadmium sulfide ultrafine particle crosslinked product was manufactured. This resulted in a cloudy yellow solution with some precipitate.
【００４３】得られた溶液からの固形物を、透過型電子
顕微鏡で観察したところ、８０から数１００個の２次粒
子からなる集合体群が多く観察された。ひとつの硫化カ
ドミウム超微粒子の直径や、２次粒子の大きさ、２次粒
子端と２次粒子端の間隔は実施例１とほぼ同じであっ
た。したがって、架橋反応の進行にしたがって、大きさ
な超微粒子架橋体が形成されていることがわかる。When the solid matter from the obtained solution was observed with a transmission electron microscope, many aggregate groups consisting of 80 to several 100 secondary particles were observed. The diameter of one cadmium sulfide ultrafine particle, the size of the secondary particle, and the distance between the secondary particle end and the secondary particle end were almost the same as in Example 1. Therefore, it can be seen that as the cross-linking reaction proceeds, the ultrafine particle cross-linked body having a size is formed.
【００４４】実施例３ 実施例１と同じように、表面がジビニルベンゼンの重合
体で修飾され、未反応のビニル基が残留している修飾さ
れた硫化カドミウムのコロイド溶液を合成した後、さら
にジビニルベンゼンを２．０×１０ー1ｍｏｌ／ｌの濃度
に溶かしたアセトニトリル溶液３ｍｌを加え、実施例１
と同じ条件で架橋反応を行った。Example 3 As in Example 1, after synthesizing a modified cadmium sulfide colloidal solution in which the surface was modified with a polymer of divinylbenzene and unreacted vinyl groups remained, divinyl divinyl was further added. Example 1 was added with 3 ml of an acetonitrile solution in which benzene was dissolved at a concentration of 2.0 × 10 -1 mol / l.
The crosslinking reaction was carried out under the same conditions.
【００４５】得られた溶液からの固形物を、透過型電子
顕微鏡で観察したところ、ひとつの硫化カドミウム超微
粒子の直径や、２次粒子の大きさは、実施例１とほぼ同
じであったが、２次粒子端と２次粒子端の間隔は約３０
ｎｍと少し広くなっていることがわかった。したがっ
て、架橋反応のしかたによって、超微粒子の間隔が制御
可能であることがわかる。When the solid matter from the obtained solution was observed by a transmission electron microscope, the diameter of one of the cadmium sulfide ultrafine particles and the size of the secondary particles were almost the same as in Example 1. The distance between the secondary particle edge and the secondary particle edge is about 30.
It was found to be a little wider than nm. Therefore, it is understood that the distance between the ultrafine particles can be controlled by the way of the crosslinking reaction.
【００４６】実施例４ 過塩素酸カドミウム六水和物（Ｃｄ（ＣｌＯ4 ）2 ・６
Ｈ2Ｏ）を２．０×１０ー3ｍｏｌ／ｌ、ポリビニルピロ
リドン（平均分子量４万）を０．０１ｇ／ｌの濃度に溶
かしたアセトニトリル溶液４５ｍｌを太鼓形枝付き石英
セルに入れ、マグネットスターラーで撹拌をおこないな
がら、０℃にてビス（トリメチルシリルセレナイド）
（（（ＣＨ3 ）3 Ｓｉ）2 Ｓｅ）の２．０×１０ー2ｍｏ
ｌ／ｌのアセトニトリル溶液４５ｍｌを、窒素雰囲気
下、２０分かけてゆっくり滴下する。このようにして、
セレン化カドミウム超微粒子を合成した後、ジビニルベ
ンゼンを８．０×１０ー2ｍｏｌ／ｌの濃度になるまで加
え、よく撹拌する。この後、５００Ｗキセノンランプ光
を２時間直接照射した。このようにして得られた溶液は
うすいやや赤みがかった黄色透明であった。以上の操作
から表面がジビニルベンゼンの重合体で修飾され、未反
応のビニル基が残留している修飾されたセレン化カドミ
ウムのコロイド溶液を合成した。[0046] Example 4 cadmium perchlorate hexahydrate (Cd (ClO 4) 2 · 6
H 2 O) was added at a concentration of 2.0 × 10 −3 mol / l and polyvinylpyrrolidone (average molecular weight 40,000) at a concentration of 0.01 g / l. Bis (trimethylsilyl selenide) at 0 ° C with stirring.
(((CH 3 ) 3 Si) 2 Se) 2.0 × 10 −2 mo
45 ml of a 1 / l acetonitrile solution is slowly added dropwise over 20 minutes under a nitrogen atmosphere. In this way
After synthesizing the cadmium selenide ultrafine particles, divinylbenzene is added to a concentration of 8.0 × 10 −2 mol / l and well stirred. After this, 500 W xenon lamp light was directly irradiated for 2 hours. The solution thus obtained was light reddish yellow transparent. From the above operation, a colloidal solution of modified cadmium selenide whose surface was modified with a polymer of divinylbenzene and unreacted vinyl groups remained was synthesized.
【００４７】次に、この合成したコロイド溶液をそのま
ま冷却管をつけた１００ｍｌの三ッ口フラスコに移し、
窒素ガスを２０分間バブリング下の後、これにα、α’
−アゾビスイソブチロニトリルを０．０６５ｇ加え、５
５℃で５時間加熱した。この結果、濁った赤黄色の溶液
が得られた。得られた溶液からの固形物を、透過型電子
顕微鏡で観察したところ、数１０から１００個程度の２
次粒子からなる集合体群が多く観察された。１次粒子お
よび２次粒子の粒子径は分布が広いが、おおむね１０ｎ
ｍ程度の２次粒子を形成し、これを単位として、２次粒
子端と２次粒子端の間隔が約１５ｎｍから２０ｎｍの分
散体であった。したがって、半導体超微粒子を製造した
後に表面修飾を行っても、高密度かつ超微粒子間隔が制
御された超微粒子架橋体が形成されていることがわか
る。Next, this synthesized colloidal solution was transferred as it was to a 100 ml three-necked flask equipped with a cooling tube,
After bubbling nitrogen gas for 20 minutes, α, α '
-Add 0.065 g of azobisisobutyronitrile and add 5
Heated at 5 ° C. for 5 hours. This resulted in a cloudy red-yellow solution. Observation of the solid matter from the obtained solution with a transmission electron microscope revealed that several 10 to 100
Many aggregates composed of secondary particles were observed. The particle size of primary particles and secondary particles has a wide distribution, but is roughly 10n.
A secondary particle having a size of about m was formed, and with this as a unit, the distance between the secondary particle ends was about 15 nm to 20 nm, and the dispersion was a dispersion. Therefore, it is understood that even if the surface modification is performed after the production of the semiconductor ultrafine particles, a crosslinked ultrafine particle having a high density and controlled ultrafine particle spacing is formed.
【００４８】実施例５ 実施例１と同じように、表面がジビニルベンゼンの重合
体で修飾され、未反応のビニル基が残留している修飾さ
れた硫化カドミウムのコロイド溶液を合成した後、さら
にスチレンを１ｍｌ加え、冷却管をつけた１００ｍｌの
三ッ口フラスコに移し、窒素ガスを２０分間バブリング
下の後、これにα、α’−アゾビスイソブチロニトリル
を０．０６５ｇ加え、５５℃で５時間加熱した。この結
果、濁った黄色の溶液が得られた。この溶液から、エバ
ポレーションによって、溶媒を除去し、黄色の粉末を得
た。Example 5 As in Example 1, after synthesizing a colloidal solution of modified cadmium sulfide whose surface was modified with a polymer of divinylbenzene and unreacted vinyl groups remained, styrene was further added. 1 ml was added, the mixture was transferred to a 100 ml three-necked flask equipped with a condenser, nitrogen gas was bubbled for 20 minutes, and then 0.065 g of α, α′-azobisisobutyronitrile was added thereto, and at 55 ° C. Heated for 5 hours. This resulted in a cloudy yellow solution. The solvent was removed from this solution by evaporation to give a yellow powder.
【００４９】これに３ｍｌのアニリンを加えて溶解さ
せ、直径１ｃｍのシャーレにいれ、減圧乾燥させて溶媒
を飛ばしたところ、透明なフィルムを得た。このフィル
ムはアセトセトニトリルに再溶解せず、溶媒和できない
大きな構造体として生成していることが示された。この
フィルムの断面を切り出し、透過型電子顕微鏡で観察し
たところ、２次粒子端と２次粒子端の間隔がおおむね２
８ｎｍの分散していることが観察された。したがって、
超微粒子が架橋することによって、分散状態が制御され
た高密度硫化カドミウム超微粒子分散体が構築できたこ
とがわかる。To this, 3 ml of aniline was added and dissolved, placed in a petri dish having a diameter of 1 cm, dried under reduced pressure to remove the solvent, and a transparent film was obtained. It was shown that this film did not redissolve in acetocetonitrile and formed as a large unsolvable structure. When a cross section of this film was cut out and observed with a transmission electron microscope, the distance between the secondary particle ends and the secondary particle ends was roughly 2
It was observed to have a dispersion of 8 nm. Therefore,
It can be seen that, by crosslinking the ultrafine particles, a high density cadmium sulfide ultrafine particle dispersion having a controlled dispersion state was constructed.
【００５０】[0050]
【発明の効果】本発明によって、新規な超微粒子架橋材
料を提供する。この材料は、ナノメートルサイズで超微
粒子が高密度に分散した超微粒子分散体として提供さ
れ、光学材料、非線形光学材料、超格子素子などの電子
材料やセンサー材料、磁気材料、医薬、農薬、触媒材
料、無機材料、塗料・コーティング材料、化粧品材料へ
の利用が可能である。According to the present invention, a novel ultrafine particle cross-linking material is provided. This material is provided as an ultrafine particle dispersion in which ultrafine particles of nanometer size are dispersed at a high density, and is used as an optical material, nonlinear optical material, electronic material such as superlattice element, sensor material, magnetic material, pharmaceutical, agricultural chemical, catalyst. It can be used for materials, inorganic materials, paint / coating materials, and cosmetic materials.
【図１】超微粒子を複数の不飽和基を有する化合物で修
飾する方法の説明図FIG. 1 is an explanatory view of a method of modifying ultrafine particles with a compound having a plurality of unsaturated groups.
【図２】本発明の超微粒子架橋体の生成のモデル説明図FIG. 2 is an explanatory diagram of a model for forming a crosslinked ultrafine particle of the present invention.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 林 豊治 神奈川県横浜市栄区笠間町1190番地 三井 東圧化学株式会社内 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Toyoji Hayashi Mitsui Toatsu Chemical Co., Ltd. 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa
Claims (5)
に、半導体超微粒子に光を照射し、該半導体超微粒子に
不飽和基を有する分子鎖を修飾した後、この不飽和基が
修飾された半導体超微粒子同士を架橋させることを特徴
とする、半導体超微粒子架橋材料を製造する方法。1. A semiconductor ultrafine particle is irradiated with light together with a compound having a plurality of unsaturated groups to modify the molecular chain having an unsaturated group in the semiconductor ultrafine particle, and then the semiconductor having the unsaturated group modified. A method for producing a semiconductor ultrafine particle crosslinkable material, which comprises crosslinking ultrafine particles with each other.
に、半導体超微粒子を製造しながら、該生成する半導体
超微粒子に光を照射し、該生成される半導体超微粒子に
不飽和基を有する分子鎖を修飾した後、この不飽和基が
修飾された半導体超微粒子同士を架橋させることを特徴
とする、半導体超微粒子架橋材料を製造する方法。2. A molecular chain having an unsaturated group in the produced semiconductor ultrafine particles by irradiating the produced semiconductor ultrafine particles with light while producing the semiconductor ultrafine particles together with a compound having a plurality of unsaturated groups. The method for producing a semiconductor ultrafine particle cross-linking material, comprising cross-linking the semiconductor ultrafine particles modified with the unsaturated group after the modification.
導体超微粒子同士を架橋させる手段として架橋剤を用い
る、請求項１または請求項２記載の半導体超微粒子架橋
材料を製造する方法。3. The method for producing a crosslinked semiconductor ultrafine particle material according to claim 1, wherein a crosslinking agent is used as a means for crosslinking the ultrafine semiconductor particles modified with a molecular chain having an unsaturated group.
子の複合体から主としてなることを特徴とする半導体超
微粒子架橋材料。4. A semiconductor ultrafine particle cross-linking material, wherein the semiconductor ultrafine particles are mainly composed of a composite of ultrafine particles crosslinked with each other.
されている請求項４記載の半導体超微粒子架橋材料。5. The semiconductor ultrafine particle crosslinked material according to claim 4, wherein the semiconductor ultrafine particle crosslinked material is dispersed in a medium.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26862593A JP3363544B2 (en) | 1993-10-27 | 1993-10-27 | Method for crosslinking semiconductor ultrafine particles and semiconductor ultrafine particle crosslinked material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26862593A JP3363544B2 (en) | 1993-10-27 | 1993-10-27 | Method for crosslinking semiconductor ultrafine particles and semiconductor ultrafine particle crosslinked material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH07116503A true JPH07116503A (en) | 1995-05-09 |
| JP3363544B2 JP3363544B2 (en) | 2003-01-08 |
Family
ID=17461151
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP26862593A Expired - Lifetime JP3363544B2 (en) | 1993-10-27 | 1993-10-27 | Method for crosslinking semiconductor ultrafine particles and semiconductor ultrafine particle crosslinked material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3363544B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004006292A2 (en) * | 2001-06-15 | 2004-01-15 | University Of Massachusetts | Photovoltaic cell |
| US6949400B2 (en) * | 2002-01-25 | 2005-09-27 | Konarka Technologies, Inc. | Ultrasonic slitting of photovoltaic cells and modules |
| US7094441B2 (en) * | 2002-01-25 | 2006-08-22 | Konarka Technologies, Inc. | Low temperature interconnection of nanoparticles |
-
1993
- 1993-10-27 JP JP26862593A patent/JP3363544B2/en not_active Expired - Lifetime
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004006292A2 (en) * | 2001-06-15 | 2004-01-15 | University Of Massachusetts | Photovoltaic cell |
| WO2004006292A3 (en) * | 2001-06-15 | 2004-04-29 | Univ Massachusetts | Photovoltaic cell |
| US7323635B2 (en) | 2001-06-15 | 2008-01-29 | University Of Massachusetts | Photovoltaic cell |
| US6949400B2 (en) * | 2002-01-25 | 2005-09-27 | Konarka Technologies, Inc. | Ultrasonic slitting of photovoltaic cells and modules |
| US7094441B2 (en) * | 2002-01-25 | 2006-08-22 | Konarka Technologies, Inc. | Low temperature interconnection of nanoparticles |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3363544B2 (en) | 2003-01-08 |
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