JP2011184273A - Organic solvent dispersion in which flaky perovskite oxide particle is blended and method for producing the same, and perovskite oxide thin film using the organic solvent dispersion and method for producing the same - Google Patents
Organic solvent dispersion in which flaky perovskite oxide particle is blended and method for producing the same, and perovskite oxide thin film using the organic solvent dispersion and method for producing the same Download PDFInfo
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- JP2011184273A JP2011184273A JP2010054207A JP2010054207A JP2011184273A JP 2011184273 A JP2011184273 A JP 2011184273A JP 2010054207 A JP2010054207 A JP 2010054207A JP 2010054207 A JP2010054207 A JP 2010054207A JP 2011184273 A JP2011184273 A JP 2011184273A
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- Prior art keywords
- perovskite oxide
- organic solvent
- flaky
- oxide particles
- solvent dispersion
- Prior art date
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- Granted
Links
- 239000002245 particle Substances 0.000 title claims abstract description 100
- 239000006185 dispersion Substances 0.000 title claims abstract description 96
- 239000003960 organic solvent Substances 0.000 title claims abstract description 96
- 239000010409 thin film Substances 0.000 title claims description 53
- 238000004519 manufacturing process Methods 0.000 title claims description 17
- 150000002892 organic cations Chemical class 0.000 claims abstract description 19
- 239000007787 solid Substances 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 17
- 239000010408 film Substances 0.000 claims description 57
- 239000010410 layer Substances 0.000 claims description 39
- 239000002356 single layer Substances 0.000 claims description 32
- 239000002135 nanosheet Substances 0.000 claims description 24
- 239000011248 coating agent Substances 0.000 claims description 21
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 14
- 229920005989 resin Polymers 0.000 claims description 13
- 239000011347 resin Substances 0.000 claims description 13
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 12
- 229910052791 calcium Inorganic materials 0.000 claims description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- 229910052758 niobium Inorganic materials 0.000 claims description 9
- 229910052715 tantalum Inorganic materials 0.000 claims description 8
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 claims description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- 239000011342 resin composition Substances 0.000 claims description 3
- 229910052712 strontium Inorganic materials 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 238000010030 laminating Methods 0.000 claims 1
- JYVLIDXNZAXMDK-UHFFFAOYSA-N methyl propyl carbinol Natural products CCCC(C)O JYVLIDXNZAXMDK-UHFFFAOYSA-N 0.000 claims 1
- 239000000463 material Substances 0.000 description 43
- 239000000523 sample Substances 0.000 description 40
- -1 tetraalkylammonium ion Chemical class 0.000 description 37
- 239000000758 substrate Substances 0.000 description 22
- 239000000843 powder Substances 0.000 description 17
- 239000010955 niobium Substances 0.000 description 16
- 229910052783 alkali metal Inorganic materials 0.000 description 15
- 239000002585 base Substances 0.000 description 15
- 230000015572 biosynthetic process Effects 0.000 description 12
- 238000000576 coating method Methods 0.000 description 12
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 description 12
- 239000011575 calcium Substances 0.000 description 11
- 229910052739 hydrogen Inorganic materials 0.000 description 11
- 239000001257 hydrogen Substances 0.000 description 11
- 239000006228 supernatant Substances 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 10
- 150000007514 bases Chemical class 0.000 description 10
- 239000002270 dispersing agent Substances 0.000 description 10
- 238000002835 absorbance Methods 0.000 description 9
- 238000009835 boiling Methods 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 9
- 239000011230 binding agent Substances 0.000 description 8
- 229910052746 lanthanum Inorganic materials 0.000 description 8
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 7
- 239000002253 acid Substances 0.000 description 7
- 229910001413 alkali metal ion Inorganic materials 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 7
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 7
- 238000006386 neutralization reaction Methods 0.000 description 7
- 229920001296 polysiloxane Polymers 0.000 description 7
- 238000005119 centrifugation Methods 0.000 description 6
- CUZYJNBUPITPEI-UHFFFAOYSA-N europium lanthanum Chemical compound [La][Eu] CUZYJNBUPITPEI-UHFFFAOYSA-N 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 239000004033 plastic Substances 0.000 description 6
- 229920003023 plastic Polymers 0.000 description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- VIUKNDFMFRTONS-UHFFFAOYSA-N distrontium;niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[Sr+2].[Sr+2].[Nb+5].[Nb+5] VIUKNDFMFRTONS-UHFFFAOYSA-N 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 description 5
- 239000011941 photocatalyst Substances 0.000 description 5
- 125000001453 quaternary ammonium group Chemical group 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 230000004888 barrier function Effects 0.000 description 4
- 229910010293 ceramic material Inorganic materials 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000013256 coordination polymer Substances 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 239000003989 dielectric material Substances 0.000 description 4
- 239000007772 electrode material Substances 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 229910017604 nitric acid Inorganic materials 0.000 description 4
- 229910001414 potassium ion Inorganic materials 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 150000001340 alkali metals Chemical class 0.000 description 3
- 150000003973 alkyl amines Chemical class 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 239000000908 ammonium hydroxide Substances 0.000 description 3
- 238000003618 dip coating Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000010304 firing Methods 0.000 description 3
- 238000004108 freeze drying Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 238000001000 micrograph Methods 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- 235000021317 phosphate Nutrition 0.000 description 3
- 239000013049 sediment Substances 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000004606 Fillers/Extenders Substances 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- 238000011481 absorbance measurement Methods 0.000 description 2
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 2
- CBTVGIZVANVGBH-UHFFFAOYSA-N aminomethyl propanol Chemical compound CC(C)(N)CO CBTVGIZVANVGBH-UHFFFAOYSA-N 0.000 description 2
- 239000003125 aqueous solvent Substances 0.000 description 2
- 229910052792 caesium Inorganic materials 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000003995 emulsifying agent Substances 0.000 description 2
- 238000004299 exfoliation Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 238000010191 image analysis Methods 0.000 description 2
- 238000003475 lamination Methods 0.000 description 2
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000007761 roller coating Methods 0.000 description 2
- 229910052701 rubidium Inorganic materials 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 238000004528 spin coating Methods 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 2
- 230000008961 swelling Effects 0.000 description 2
- 150000005622 tetraalkylammonium hydroxides Chemical class 0.000 description 2
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 2
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 2
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 2
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 description 2
- 239000002562 thickening agent Substances 0.000 description 2
- UXFQFBNBSPQBJW-UHFFFAOYSA-N 2-amino-2-methylpropane-1,3-diol Chemical compound OCC(N)(C)CO UXFQFBNBSPQBJW-UHFFFAOYSA-N 0.000 description 1
- MOMKYJPSVWEWPM-UHFFFAOYSA-N 4-(chloromethyl)-2-(4-methylphenyl)-1,3-thiazole Chemical compound C1=CC(C)=CC=C1C1=NC(CCl)=CS1 MOMKYJPSVWEWPM-UHFFFAOYSA-N 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- KWIUHFFTVRNATP-UHFFFAOYSA-N Betaine Natural products C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- KWIUHFFTVRNATP-UHFFFAOYSA-O N,N,N-trimethylglycinium Chemical compound C[N+](C)(C)CC(O)=O KWIUHFFTVRNATP-UHFFFAOYSA-O 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 230000003373 anti-fouling effect Effects 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000003429 antifungal agent Substances 0.000 description 1
- 229940121375 antifungal agent Drugs 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 229960003237 betaine Drugs 0.000 description 1
- 229920006167 biodegradable resin Polymers 0.000 description 1
- QHIWVLPBUQWDMQ-UHFFFAOYSA-N butyl prop-2-enoate;methyl 2-methylprop-2-enoate;prop-2-enoic acid Chemical compound OC(=O)C=C.COC(=O)C(C)=C.CCCCOC(=O)C=C QHIWVLPBUQWDMQ-UHFFFAOYSA-N 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 238000007607 die coating method Methods 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- 238000009503 electrostatic coating Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 229910001940 europium oxide Inorganic materials 0.000 description 1
- AEBZCFFCDTZXHP-UHFFFAOYSA-N europium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Eu+3].[Eu+3] AEBZCFFCDTZXHP-UHFFFAOYSA-N 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 238000007716 flux method Methods 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 239000000417 fungicide Substances 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical group [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
- BDAGIHXWWSANSR-NJFSPNSNSA-N hydroxyformaldehyde Chemical compound O[14CH]=O BDAGIHXWWSANSR-NJFSPNSNSA-N 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 229910000484 niobium oxide Inorganic materials 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 230000003204 osmotic effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 description 1
- 235000019983 sodium metaphosphate Nutrition 0.000 description 1
- 229940048086 sodium pyrophosphate Drugs 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 235000019832 sodium triphosphate Nutrition 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 229910000018 strontium carbonate Inorganic materials 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010345 tape casting Methods 0.000 description 1
- DZLFLBLQUQXARW-UHFFFAOYSA-N tetrabutylammonium Chemical compound CCCC[N+](CCCC)(CCCC)CCCC DZLFLBLQUQXARW-UHFFFAOYSA-N 0.000 description 1
- CBXCPBUEXACCNR-UHFFFAOYSA-N tetraethylammonium Chemical compound CC[N+](CC)(CC)CC CBXCPBUEXACCNR-UHFFFAOYSA-N 0.000 description 1
- 235000019818 tetrasodium diphosphate Nutrition 0.000 description 1
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 239000012780 transparent material Substances 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Landscapes
- Inorganic Compounds Of Heavy Metals (AREA)
- Pigments, Carbon Blacks, Or Wood Stains (AREA)
- Paints Or Removers (AREA)
- Inorganic Insulating Materials (AREA)
Abstract
Description
本発明は、薄片状ペロブスカイト酸化物粒子を有機溶媒に配合した分散体及びその製造方法に関する。また、前記の有機溶媒分散体を用いた、ペロブスカイト酸化物薄膜及びその製造方法に関する。 The present invention relates to a dispersion in which flaky perovskite oxide particles are blended in an organic solvent and a method for producing the same. The present invention also relates to a perovskite oxide thin film using the organic solvent dispersion and a method for producing the same.
薄片状ペロブスカイト酸化物粒子は、厚さに対する幅及び長さの比が比較的大きな形状を有するものであり、例えば厚さが０．５〜１００ｎｍ程度、幅及び長さが０．１〜５００μｍ程度のものが知られている。中でも、その厚みをより薄くしたもの、例えば層状ペロブスカイト酸化物のホスト層を一枚単位に剥離して得られるような厚さが１０ｎｍ以下、幅及び長さが０．１〜１００μｍ程度のものはペロブスカイト酸化物ナノシートと呼ばれる。このような薄片状ペロブスカイト酸化物粒子は、従来のペロブスカイト酸化物と同じ用途、例えば、光触媒、誘電体、圧電体等のファインセラミックス材料、光電変換材料、フォトクロミック材料、赤外線反射材料、電池の電極材料、各種センサー、更には他物質の配向結晶成長のためのシードレイヤーなどに用いられる。特に、ペロブスカイト酸化物ナノシートを用いると薄層が形成できることから基材上にペロブスカイト酸化物薄膜を形成して誘電体材料、光触媒として好適に用いられる。また、ペロブスカイト酸化物ナノシートをプラスチックに配合するとプラスチックの機械的強度、耐熱性、ガスバリヤー性等を高めることができる。 The flaky perovskite oxide particles have a shape in which the ratio of width and length to thickness is relatively large. For example, the thickness is about 0.5 to 100 nm, and the width and length are about 0.1 to 500 μm. Things are known. Among them, those having a smaller thickness, such as those having a thickness of 10 nm or less and a width and length of about 0.1 to 100 μm, which are obtained by peeling off a layered perovskite oxide host layer as a single unit, It is called perovskite oxide nanosheet. Such flaky perovskite oxide particles are used in the same applications as conventional perovskite oxides, for example, photocatalysts, dielectrics, fine ceramic materials such as piezoelectrics, photoelectric conversion materials, photochromic materials, infrared reflective materials, battery electrode materials , Various sensors, and seed layers for the growth of oriented crystals of other materials. In particular, when a perovskite oxide nanosheet is used, a thin layer can be formed. Therefore, a perovskite oxide thin film is formed on a substrate and is suitably used as a dielectric material and a photocatalyst. Further, when the perovskite oxide nanosheet is blended with plastic, the mechanical strength, heat resistance, gas barrier property, etc. of the plastic can be improved.
下記の非特許文献１は、炭酸カリウム、炭酸カルシウム、酸化ニオブを混合粉砕し、大気中で焼成して得られる層状ペロブスカイト酸化物（ＫＣａ２Ｎｂ３Ｏ１０）の層間のＫ＋を硝酸によりＨ＋と交換し、水酸化テトラブチルアンモニウムと反応させることでＮｂＯ６八面体が厚み方向に２層分だけ頂点共有した薄片状ペロブスカイト酸化物の水性分散体が得られることを記載している。 Non-Patent Document 1 below shows that K + between layers of a layered perovskite oxide (KCa 2 Nb 3 O 10 ) obtained by mixing and pulverizing potassium carbonate, calcium carbonate, and niobium oxide and firing in the atmosphere with H 2 by nitric acid. It is described that an aqueous dispersion of flaky perovskite oxide in which two NbO 6 octahedrons share a vertex in the thickness direction is obtained by exchanging with + and reacting with tetrabutylammonium hydroxide.
非特許文献１は、薄片状ペロブスカイト酸化物の水性分散体を開示しているものの、有機溶剤分散体については記載していない。
金属酸化物ナノシートが単層で稠密に配列した膜（稠密単層膜）の作製方法としては、交互積層法と超音波処理を組み合わせた方法、Langmuir-Blodgett法等が知られているが、これらの方法は装置上の問題から大きなスケールの成膜が難しく、工業的に不向きである。また、従来の金属酸化物ナノシートを配合した水分散体では表面張力の高さなど種々の影響で基材とのなじみが悪いことから、基材にコートすることは難しく、稠密単層膜は得られなかった。
Non-Patent Document 1 discloses an aqueous dispersion of flaky perovskite oxide, but does not describe an organic solvent dispersion.
As a method for producing a film in which metal oxide nanosheets are densely arranged in a single layer (dense single layer film), a method combining alternating lamination method and ultrasonic treatment, Langmuir-Blodgett method, etc. are known. This method is not suitable industrially because it is difficult to form a large scale film due to problems in the apparatus. In addition, conventional aqueous dispersions containing metal oxide nanosheets have poor compatibility with the substrate due to various effects such as high surface tension, making it difficult to coat the substrate and obtaining a dense monolayer film. I couldn't.
そこで、本発明は、工業的に有利に実施できる、薄片状ペロブスカイト酸化物粒子を配合した有機溶媒分散体及びその製造方法を提供する。また、本発明は、工業的に有利に実施でき、しかも広範囲の基材に適用できるペロブスカイト酸化物薄膜、特にそのペロブスカイト酸化物ナノシートが単層で稠密に配列した膜（稠密単層膜）、その稠密単層膜が積層したペロブスカイト酸化物薄膜及びその製造方法を提供する。 Then, this invention provides the organic-solvent dispersion which mix | blended the flaky perovskite oxide particle | grains which can be implemented industrially advantageously, and its manufacturing method. Further, the present invention can be carried out industrially advantageously and can be applied to a wide range of substrates, particularly a film in which the perovskite oxide nanosheets are densely arranged in a single layer (dense single layer film), Provided are a perovskite oxide thin film in which a dense single layer film is laminated and a method for manufacturing the same.
本発明者らは、薄片状ペロブスカイト酸化物粒子を有機溶媒に配合した分散体を得るべく種々研究した結果、ホスト層がペロブスカイト構造である層状酸化物を有機カチオンと接触させ、層状構造を剥離して、薄片状ペロブスカイト酸化物粒子の水性分散体を予め調製し、それを遠心分離して得られた沈降物を有機溶媒に添加すると、比較的簡単に薄片状ペロブスカイト酸化物粒子を有機溶媒に分散させられること、また、薄片状ペロブスカイト酸化物粒子の水性分散体を凍結乾燥した後、得られた凍結乾燥物を有機溶媒に混合しても同様の分散体が得られることなどを見出した。
また、この方法で得られた薄片状ペロブスカイト酸化物粒子を含む有機溶媒分散体を用いるとペロブスカイト酸化物薄膜が簡単に得られること、特にペロブスカイト酸化物ナノシート有機溶媒分散体を基材にコートし、乾燥させるという簡便な方法でペロブスカイト酸化物ナノシート（以下、ナノシートということがある。）が単層で稠密に配列した膜を得ることができることなどを見出し、本発明を完成した。
As a result of various researches to obtain a dispersion in which flaky perovskite oxide particles are blended in an organic solvent, the present inventors contacted a layered oxide having a perovskite structure with an organic cation to release the layered structure. If an aqueous dispersion of flaky perovskite oxide particles is prepared in advance and the precipitate obtained by centrifuging it is added to an organic solvent, the flaky perovskite oxide particles are dispersed in an organic solvent relatively easily. It was also found that a similar dispersion can be obtained by lyophilizing an aqueous dispersion of flaky perovskite oxide particles and then mixing the resulting lyophilized product with an organic solvent.
In addition, by using an organic solvent dispersion containing flaky perovskite oxide particles obtained by this method, a perovskite oxide thin film can be easily obtained, in particular, a perovskite oxide nanosheet organic solvent dispersion is coated on a substrate, The present invention has been completed by discovering that a film in which perovskite oxide nanosheets (hereinafter sometimes referred to as nanosheets) are densely arranged in a single layer can be obtained by a simple method of drying.
すなわち、本発明は、
（１）有機溶媒及び前記有機溶媒に分散されたペロブスカイト構造を有する薄片状酸化物粒子を含む有機溶媒分散体、
（２）層状ペロブスカイト酸化物粒子を有機カチオンと接触させ、層状構造を剥離して、薄片状ペロブスカイト酸化物粒子の水性分散体を製造する第一工程、
前記水性分散体から、薄片状ペロブスカイト酸化物粒子を含む固形分を抽出する第二工程、及び
薄片状ペロブスカイト酸化物粒子を含む固形分を有機溶媒に分散させる第三工程、
を含む有機溶媒分散体の製造方法、
（３）前記の有機溶媒分散体を用いて成膜されたペロブスカイト酸化物薄膜などである。
That is, the present invention
(1) An organic solvent dispersion comprising an organic solvent and flaky oxide particles having a perovskite structure dispersed in the organic solvent,
(2) a first step of producing an aqueous dispersion of flaky perovskite oxide particles by bringing the layered perovskite oxide particles into contact with an organic cation and peeling off the layered structure;
A second step of extracting solids containing flaky perovskite oxide particles from the aqueous dispersion, and a third step of dispersing solids containing flaky perovskite oxide particles in an organic solvent,
A method for producing an organic solvent dispersion comprising
(3) A perovskite oxide thin film formed using the organic solvent dispersion.
本発明の有機溶媒分散体によれば、薄片状ペロブスカイト酸化物粒子を有機溶媒に長期間にわたって安定して分散させることができる。このため、薄片状ペロブスカイト酸化物粒子を種々の用途に用いることができ、水性分散体よりも、有機溶剤系コーティング剤やプラスチック等への配合の際に有利であり、薄片状ペロブスカイト酸化物粒子の適用拡大を図ることができる。また、溶媒を有機溶剤とすることで基材とのなじみが良くなり、基材へコートすることができるため、ペロブスカイト酸化物薄膜、特にペロブスカイト酸化物ナノシートの稠密単層膜、その稠密単層膜が積層したペロブスカイト酸化物薄膜などが得られる。しかも、このようなペロブスカイト酸化物薄膜の製造は有機溶媒の使用により低温度で行うことができ、温度に脆弱な基材への適用が可能となる。
具体的な用途としては、光触媒、ガスバリヤー性材料、誘電体、圧電体等のファインセラミックス材料、光電変換材料、熱電変換材料、電池の電極材料、各種センサー、更には他物質の配向結晶成長のためのシードレイヤー等の種々の用途が挙げられる。また、プラスチック等の樹脂に薄片状ペロブスカイト酸化物粒子を配合して、樹脂に機械的強度等を付与することができる。
また、本発明の有機溶媒分散体は、薄片状ペロブスカイト酸化物粒子の水性分散体を遠心分離するか、凍結乾燥した後、有機溶媒と混合して得られるため、水分をほとんど含まない有機溶媒分散体を比較的簡便に製造することができる。
また、前記の有機溶媒分散体を基材にコートし、室温〜３００℃の範囲の温度下で成膜するなどの比較的簡便な方法によりペロブスカイト酸化物薄膜を製造することができる。
According to the organic solvent dispersion of the present invention, flaky perovskite oxide particles can be stably dispersed in an organic solvent for a long period of time. For this reason, flaky perovskite oxide particles can be used in various applications, and are more advantageous than organic dispersions when blended with organic solvent-based coating agents and plastics. The application can be expanded. Also, since the compatibility with the base material is improved by using the solvent as the solvent, and the base material can be coated, a dense single layer film of a perovskite oxide thin film, particularly a perovskite oxide nanosheet, and the dense single layer film thereof A perovskite oxide thin film or the like laminated can be obtained. Moreover, such a perovskite oxide thin film can be produced at a low temperature by using an organic solvent, and can be applied to a temperature-fragile substrate.
Specific applications include photocatalysts, gas barrier materials, fine ceramic materials such as dielectrics and piezoelectrics, photoelectric conversion materials, thermoelectric conversion materials, battery electrode materials, various sensors, and growth of oriented crystals of other substances. Various uses such as a seed layer for the purpose. In addition, flaky perovskite oxide particles can be blended in a resin such as plastic to impart mechanical strength and the like to the resin.
The organic solvent dispersion of the present invention is obtained by centrifuging an aqueous dispersion of flaky perovskite oxide particles or lyophilizing and then mixing with an organic solvent. The body can be manufactured relatively easily.
In addition, a perovskite oxide thin film can be produced by a relatively simple method such as coating the organic solvent dispersion on a substrate and forming a film at a temperature in the range of room temperature to 300 ° C.
薄片状ペロブスカイト酸化物粒子は、一般に板状、シート状、フレーク状と呼ばれる形状を有するものを包含する。大きさは、薄片状ペロブスカイト酸化物粒子の薄片面の幅方向のサイズ（具体的には最長幅を「長さ」といい、長さに対して、最短幅を「幅」ということがある）と、薄片面に対する垂直方向の厚みとで規定して、幅方向のサイズは１００ｎｍ以上が好ましく、０．１〜５００μｍ程度のものが分散性の観点から好ましく、０．１〜３０μｍ程度がより好ましい。厚さは０．５〜１００ｎｍ程度が好ましく、０．５〜５０ｎｍ程度がより好ましい。薄膜を作製し易いため薄いものが好ましく１０ｎｍ以下がより好ましい。幅（最短幅）／厚みは１０以上が好ましく、３０以上がより好ましい。薄片状ペロブスカイト酸化物粒子のうち、厚さ１０ｎｍ以下、幅及び長さが０．１〜１００μｍ程度のものを、ペロブスカイト酸化物ナノシートという。
薄片の形状や大きさは、後述する薄片状ペロブスカイト酸化物粒子の製造条件、剥離条件等を変更して適宜調整することができ、走査プローブ顕微鏡によって求めることができる。
The flaky perovskite oxide particles include those generally having a shape called a plate shape, a sheet shape, or a flake shape. The size is the size in the width direction of the flaky perovskite oxide particles (specifically, the longest width is referred to as “length” and the shortest width is sometimes referred to as “width”). And the thickness in the width direction is preferably 100 nm or more, preferably about 0.1 to 500 μm from the viewpoint of dispersibility, and more preferably about 0.1 to 30 μm. . The thickness is preferably about 0.5 to 100 nm, and more preferably about 0.5 to 50 nm. Since it is easy to produce a thin film, a thin one is preferable and 10 nm or less is more preferable. The width (shortest width) / thickness is preferably 10 or more, and more preferably 30 or more. Of the flaky perovskite oxide particles, those having a thickness of 10 nm or less and a width and length of about 0.1 to 100 μm are referred to as perovskite oxide nanosheets.
The shape and size of the flakes can be adjusted as appropriate by changing the production conditions, exfoliation conditions, and the like of the flaky perovskite oxide particles described later, and can be determined by a scanning probe microscope.
具体的には薄片状ペロブスカイト酸化物は、ＲＥＭ２Ｏ７（式中、ＲＥは少なくとも一種の希土類元素、ＭはＮｂ及びＴａから選ばれる少なくとも一種）の組成式を有するものが好ましく、ＲＥは希土類元素単体もしくは少なくとも二種以上の希土類元素が任意の比率で固溶したものでもよく、ＭはＮｂ単体又はＴａ単体もしくはＮｂとＴａが任意の比率で固溶したものでも良い。このようなペロブスカイト酸化物粒子は、ＭＯ６八面体が厚み方向に２層分頂点共有したものである。より具体的には、組成式で表してＬａ０．９０Ｅｕ０．０５Ｎｂ２Ｏ７、Ｅｕ０．５６Ｔａ２Ｏ７、ＬａＮｂ２Ｏ７からなる群より選ばれる少なくとも一種がより好ましい。
また具体的には、薄片状ペロブスカイト酸化物は、Ａ２Ｎａｎ−３ＭｎＯ３ｎ＋１（式中、ＡはＣａ及びＳｒから選ばれる少なくとも一種ＭはＮｂ及びＴａから選ばれる少なくとも一種、ｎは３〜７の整数）の組成式を有するものが好ましく、ＭはＮｂ又はＴａ単体もしくはＮｂとＴａが任意の比率で固溶したものでも良い。このようなペロブスカイト酸化物粒子は、ＭＯ６八面体が厚み方向にｎ層分頂点共有したものである。より具体的には、組成式で表してＣａ２Ｎｂ３Ｏ１０、Ｃａ２Ｔａ３Ｏ１０、Ｓｒ２Ｎｂ３Ｏ１０、Ｃａ２ＮａＮｂ４Ｏ１３からなる群より選ばれる少なくとも一種がより好ましい。
Specifically, the flaky perovskite oxide preferably has a composition formula of REM 2 O 7 (wherein RE is at least one kind of rare earth element, M is at least one kind selected from Nb and Ta), and RE is a rare earth element. An elemental element or at least two or more rare earth elements may be dissolved in an arbitrary ratio, and M may be an elemental element of Nb, Ta elemental, or an element in which Nb and Ta are dissolved in an arbitrary ratio. Such perovskite oxide particles are those in which the MO 6 octahedrons share vertices for two layers in the thickness direction. More specifically, at least one selected from the group consisting of La 0.90 Eu 0.05 Nb 2 O 7 , Eu 0.56 Ta 2 O 7 and LaNb 2 O 7 is more preferable.
More specifically, the flaky perovskite oxide is A 2 Na n-3 M n O 3n + 1 (wherein A is at least one selected from Ca and Sr, M is at least one selected from Nb and Ta, and n is 3 is preferably an integer of 3 to 7, and M may be Nb or Ta alone or Nb and Ta in a solid solution at an arbitrary ratio. Such perovskite oxide particles are MO 6 octahedrons that share vertices for n layers in the thickness direction. More specifically, at least one selected from the group consisting of Ca 2 Nb 3 O 10 , Ca 2 Ta 3 O 10 , Sr 2 Nb 3 O 10 , and Ca 2 NaNb 4 O 13 is more preferable.
薄片状ペロブスカイト酸化物粒子は後述の通り層状ペロブスカイト酸化物粒子を剥離して得られるものである。層状ペロブスカイト酸化物粒子の状態では層間にアルカリ金属などのカチオンが存在し、ホスト層のペロブスカイト酸化物との電荷バランスを保っているが、剥離して得られた薄片状ペロブスカイト酸化物は負電荷を帯びており、不安定な状態である。そこで有機カチオンを共存させ電荷バランスを中性にすることで、薄片状ペロブスカイト酸化物は安定な分散状態を維持することができる。有機カチオンの含有量は、後述する層状ペロブスカイト酸化物に含まれる水素（Ｈ）に対して０．０５〜３当量の範囲が好ましく、０．１〜３当量の範囲がより好ましく、０．９〜１．５当量が更に好ましい。有機カチオンとしては、４級アンモニウムイオン、アルキルアミンが好ましく、炭素数の合計が７以上、好ましくは９以上のものが更に好ましい。炭素数の合計が７以上の有機カチオンを含有すると、多くの有機溶媒にも分散が可能となる。なお、上記４級アンモニウムイオンとしては、テトラアルキルアンモニウムイオンが好ましいが、そのうち、テトラエチルアンモニウムイオンが好ましく、テトラプロピルアンモニウムイオンがより好ましく、テトラブチルアンモニウムイオンが更に好ましい。アルキル基の有する炭素数が多くなるほど分子形状が大きくなり、層状ペロブスカイト酸化物粒子の層間に挿入された際に層間隔を広げ易くなるからである。一方、テトラアルキルアンモニウムイオンのうち、テトラメチルアンモニウムイオンを用いる場合は、コストパフォーマンスの点で好ましい。また、薄片状ペロブスカイト酸化物の粒子表面には、有機溶媒への分散性、樹脂の親和性等の観点から、従来の界面活性剤、カップリング剤等の有機化合物やシリカ、アルミナ等の無機化合物を被覆しても良い。 The flaky perovskite oxide particles are obtained by peeling off the layered perovskite oxide particles as described later. In the state of the layered perovskite oxide particles, cations such as alkali metals exist between the layers, and the charge balance with the perovskite oxide of the host layer is maintained, but the flaky perovskite oxide obtained by exfoliation has a negative charge. It is tinged and unstable. Therefore, the flaky perovskite oxide can maintain a stable dispersion state by coexisting an organic cation to neutralize the charge balance. The content of the organic cation is preferably in the range of 0.05 to 3 equivalents, more preferably in the range of 0.1 to 3 equivalents, relative to hydrogen (H) contained in the layered perovskite oxide described later, and 0.9 to 1.5 equivalents are more preferred. As the organic cation, a quaternary ammonium ion and an alkylamine are preferable, and those having a total carbon number of 7 or more, preferably 9 or more are more preferable. When an organic cation having a total carbon number of 7 or more is contained, it can be dispersed in many organic solvents. The quaternary ammonium ion is preferably a tetraalkylammonium ion, of which a tetraethylammonium ion is preferred, a tetrapropylammonium ion is more preferred, and a tetrabutylammonium ion is still more preferred. This is because the molecular shape increases as the number of carbon atoms of the alkyl group increases, and the interlaminar spacing is easily increased when inserted between the layers of the layered perovskite oxide particles. On the other hand, among tetraalkylammonium ions, the use of tetramethylammonium ions is preferable in terms of cost performance. In addition, on the particle surface of the flaky perovskite oxide, from the viewpoint of dispersibility in an organic solvent, affinity of the resin, etc., conventional organic compounds such as surfactants and coupling agents, and inorganic compounds such as silica and alumina May be coated.
有機溶媒分散体中の薄片状ペロブスカイト酸化物粒子の含有量は適宜調整することができるが、有機溶媒分散体の重量に対して０．００１重量％以上が好ましく、０．０１重量％以上がより好ましく、０．０２重量％以上がより好ましく、０．０５重量％以上がより好ましく、０．１重量％以上が更に好ましい。含有量が高くなりすぎると層間に有機カチオンを挟んだ層状チタン酸化物（オスモティック膨潤相）となり、分散の点で好ましくない。そのため、有機溶媒分散体の重量に対して１０重量％以下が好ましく、より好ましくは１．０重量％以下である。このことから、有機溶媒分散体中の重量に対して０．００１〜１０重量％がより好ましく、０．０１〜１０重量％がより好ましく、０．０２〜１０重量％がより好ましく、０．０５〜１０重量％が更に好ましく、０．０５〜１．０重量％が更に好ましく、０．１〜１．０重量％が特により好ましい。 The content of the flaky perovskite oxide particles in the organic solvent dispersion can be adjusted as appropriate, but is preferably 0.001% by weight or more, more preferably 0.01% by weight or more based on the weight of the organic solvent dispersion. Preferably, 0.02% by weight or more is more preferable, 0.05% by weight or more is more preferable, and 0.1% by weight or more is still more preferable. If the content is too high, a layered titanium oxide (osmotic swelling phase) in which an organic cation is sandwiched between layers is formed, which is not preferable in terms of dispersion. Therefore, it is preferably 10% by weight or less, more preferably 1.0% by weight or less, based on the weight of the organic solvent dispersion. From this, 0.001-10 weight% is more preferable with respect to the weight in an organic-solvent dispersion, 0.01-10 weight% is more preferable, 0.02-10 weight% is more preferable, 0.05 10 to 10% by weight is more preferable, 0.05 to 1.0% by weight is further preferable, and 0.1 to 1.0% by weight is particularly preferable.
有機溶媒は、用途に応じて適宜選択することができ、例えばアルコール、ニトリル、アミド、ケトン、スルホキシド等の極性溶媒が好ましく、誘電率が５以上の有機溶媒であると薄片状ペロブスカイト酸化物粒子が分散し易いためより好ましく、誘電率が１０以上の有機溶媒がより好ましい。このような有機溶媒としてはアセトニトリル（誘電率３７、沸点８２℃）、メタノール（誘電率３３、沸点６５℃）、ジメチルスルホキシド（誘電率４７、沸点１８９℃）、エタノール（誘電率２４、沸点７８．３℃）、２−プロパノール（誘電率１８、沸点８２．５℃）、Ｎ，Ｎ−ジメチルホルムアミド（誘電率３８、沸点１５３℃）、メチルエチルケトン（誘電率１８．５、沸点８０℃）、１−ブタノール（誘電率１７．８、沸点１１８℃）及びホルムアミド（誘電率１０９、沸点２１０℃）からなる群より選ばれる少なくとも一種がより好ましい。 The organic solvent can be appropriately selected depending on the application. For example, polar solvents such as alcohols, nitriles, amides, ketones, and sulfoxides are preferable. When the organic solvent has a dielectric constant of 5 or more, the flaky perovskite oxide particles An organic solvent having a dielectric constant of 10 or more is more preferable because it is easily dispersed. Examples of such organic solvents include acetonitrile (dielectric constant 37, boiling point 82 ° C.), methanol (dielectric constant 33, boiling point 65 ° C.), dimethyl sulfoxide (dielectric constant 47, boiling point 189 ° C.), ethanol (dielectric constant 24, boiling point 78. 3 ° C), 2-propanol (dielectric constant 18, boiling point 82.5 ° C), N, N-dimethylformamide (dielectric constant 38, boiling point 153 ° C), methyl ethyl ketone (dielectric constant 18.5, boiling point 80 ° C), 1- More preferred is at least one selected from the group consisting of butanol (dielectric constant 17.8, boiling point 118 ° C.) and formamide (dielectric constant 109, boiling point 210 ° C.).
本発明の有機溶媒分散体は、薄片状ペロブスカイト酸化物粒子の重量に対する薄片状ナノシートの重量（以下、剥離率ということがある。）が、５０重量％以上であることが好ましく、７０重量％以上であることがより好ましく、９０％であることが更に好ましい。
剥離率は、本発明の有機溶媒分散体を遠心分離に掛けてナノシート以外の粒子を分離除去したものの固形分と、遠心分離前のものの固形分とを、重量について比較することで求めることができる。
遠心分離の回転数は、薄片状ペロブスカイト酸化物粒子の大きさ等によって適宜設定するが、ナノシートの大きさがサブミクロンオーダーであれば、３０００ｒｐｍ、１０分程度の条件で、ナノシートのみを含んだ有機溶媒分散体と、ナノシート以外の薄片状ペロブスカイト酸化物粒子を含んだ沈降物に分離することができる。
In the organic solvent dispersion of the present invention, the weight of the flaky nanosheet with respect to the weight of the flaky perovskite oxide particles (hereinafter sometimes referred to as a peeling rate) is preferably 50% by weight or more, and 70% by weight or more. More preferably, it is more preferably 90%.
The peeling rate can be determined by comparing the solid content of the organic solvent dispersion of the present invention by centrifuging to separate and remove particles other than the nanosheet and the solid content of the material before centrifugation. .
The number of rotations of the centrifugation is appropriately set depending on the size of the flaky perovskite oxide particles, etc. If the size of the nanosheet is on the order of submicrons, the organic material containing only the nanosheet under the condition of 3000 rpm for about 10 minutes. It can be separated into a solvent dispersion and a sediment containing flaky perovskite oxide particles other than nanosheets.
本発明の有機溶媒分散体は、水分をほとんど含有しておらず、好ましい含水率は１０重量％以下であり、５重量％以下がより好ましく、１重量％以下がより好ましく、０．５重量％以下が更に好ましく、０．１重量％以下が更により好ましい。 The organic solvent dispersion of the present invention contains almost no water, and the preferred moisture content is 10% by weight or less, more preferably 5% by weight or less, more preferably 1% by weight or less, and 0.5% by weight. The following is more preferable, and 0.1% by weight or less is even more preferable.
有機溶媒分散体には、薄片状ペロブスカイト酸化物粒子、有機溶媒以外にも、本発明の効果を阻害しない範囲で、上述の有機カチオンのほか、樹脂バインダー、分散剤、表面調整剤（レベリング剤、濡れ性改良剤）、ｐＨ調整剤、消泡剤、乳化剤、着色剤、増量剤、防カビ剤、硬化助剤、増粘剤等の各種添加剤、充填剤等が第三成分として含まれていても良い。具体的には、樹脂バインダーとしては、（１）無機系バインダー（（ａ）重合性ケイ素化合物（加水分解性シラン又はその加水分解生成物又はその部分縮合物、水ガラス、コロイダルシリカ、オルガノポリシロキサン等）、（ｂ）金属アルコキシド類等）、（２）有機系バインダー（アルキド系樹脂、アクリル系樹脂、ポリエステル系樹脂、エポキシ系樹脂、フッ素系樹脂、変性シリコーン系樹脂）等が挙げられる。分散剤としては、（１）界面活性剤（（ａ）アニオン系（カルボン酸塩、硫酸エステル塩、スルホン酸塩、リン酸エステル塩等）、（ｂ）カチオン系（アルキルアミン塩、アルキルアミンの４級アンモニウム塩、芳香族４級アンモニウム塩、複素環４級アンモニウム塩等）、（ｃ）両性（ベタイン型、アミノ酸型、アルキルアミンオキシド、含窒素複素環型等）、（ｄ）ノニオン系（エーテル型、エーテルエステル型、エステル型、含窒素型等）等、（２）シリコーン系分散剤（アルキル変性ポリシロキサン、ポリオキシアルキレン変性ポリシロキサン等）、（３）リン酸塩系分散剤（リン酸ナトリウム、ピロリン酸ナトリウム、オルトリン酸ナトリウム、メタリン酸ナトリウム、トリポリリン酸ナトリウム等）、（４）アルカノールアミン類（アミノメチルプロパノール、アミノメチルプロパンジオール等）等が挙げられる。表面調整剤は有機溶媒分散体の表面張力をコントロールして、ハジキ、クレーター等の欠陥を防止するものであり、アクリル系表面調整剤、ビニル系表面調整剤、シリコーン系表面調整剤、フッ素系表面調整剤等が挙げられる。 In the organic solvent dispersion, in addition to the above-mentioned organic cation, in addition to the flaky perovskite oxide particles and the organic solvent, in addition to the above-mentioned organic cation, a resin binder, a dispersant, a surface conditioner (leveling agent, Wetability improvers), pH adjusters, antifoaming agents, emulsifiers, colorants, extenders, fungicides, curing aids, thickeners and other additives, fillers, etc. are included as the third component. May be. Specifically, as the resin binder, (1) inorganic binder ((a) polymerizable silicon compound (hydrolyzable silane or hydrolysis product thereof or partial condensate thereof, water glass, colloidal silica, organopolysiloxane) Etc.), (b) metal alkoxides, etc.) and (2) organic binders (alkyd resins, acrylic resins, polyester resins, epoxy resins, fluorine resins, modified silicone resins) and the like. Dispersants include (1) surfactants ((a) anionic (carboxylates, sulfates, sulfonates, phosphates, etc.), (b) cationics (alkylamine salts, alkylamines) Quaternary ammonium salt, aromatic quaternary ammonium salt, heterocyclic quaternary ammonium salt, etc.), (c) amphoteric (betaine type, amino acid type, alkylamine oxide, nitrogen-containing heterocyclic type, etc.), (d) nonionic type ( Ether type, ether ester type, ester type, nitrogen-containing type, etc.) (2) Silicone dispersant (alkyl modified polysiloxane, polyoxyalkylene modified polysiloxane, etc.), (3) Phosphate dispersant (phosphorus) Acid sodium, sodium pyrophosphate, sodium orthophosphate, sodium metaphosphate, sodium tripolyphosphate, etc.), (4) alkanolamine (Aminomethylpropanol, aminomethylpropanediol, etc.) etc. The surface conditioner controls the surface tension of the organic solvent dispersion to prevent defects such as repellency and craters. , Vinyl based surface conditioners, silicone based surface conditioners, fluorine based surface conditioners, and the like.
本発明の有機溶媒分散体は、薄片状ペロブスカイト酸化物粒子を基材にコートするためのコーティング剤として好適である。コーティング剤には、薄片状ペロブスカイト酸化物粒子を有機溶媒に分散した分散体の他、更に、前記の樹脂バインダー、分散剤、表面調整剤（レベリング剤、濡れ性改良剤）、ｐＨ調整剤、消泡剤、乳化剤、着色剤、増量剤、防カビ剤、硬化助剤、増粘剤等の各種添加剤、充填剤等を第三成分として含むものが含まれる。分散剤等の第三成分の添加量は適宜調整することができ、例えば分散剤として前記の界面活性剤、シリコーン系分散剤、リン酸塩系分散剤、アルカノールアミン類を用いる場合は、薄片状ペロブスカイト酸化物粒子の重量に対して０．００５〜２．０重量％程度が好ましく、０．０１〜０．２重量％程度がより好ましい。表面調整剤としては前記のシリコーン系表面調整剤等を用いることができ、薄片状ペロブスカイト酸化物粒子の重量に対して０．００５〜２．０重量％程度が好ましく、０．０１〜０．２重量％程度がより好ましい。このようなコーティング剤を用いて基材にコートすると、幅及び長さの大きい前記の薄片状ペロブスカイト酸化物粒子が基材に平行に配向して配置するため基材の被覆率が高いペロブスカイト酸化物薄膜、具体的には被覆率が９０％以上、好ましくは９５％以上の稠密なペロブスカイト酸化物薄膜を作製することができる。しかも、薄片状ペロブスカイト酸化物粒子の重なりが少ない状態、具体的には大半は粒子の重なりがない１粒子の厚みで膜が形成され、残りの部分においても、せいぜい２〜３粒子程度が重なり合った厚みで形成された単層ペロブスカイト酸化物薄膜を作製することができ、Langmuir-Blodgett膜に近い品質の稠密単層膜が得られる。コーティング剤中の薄片状ペロブスカイト酸化物粒子の含有量は適宜調整することができるが、稠密単層膜を得ようとする場合には、有機溶媒分散体の重量に対して０．００１〜１．０重量％がより好ましく、０．０１〜１．０重量％がより好ましく、０．０２〜１．０重量％が更に好ましく、０．０２〜０．５重量％が特により好ましい。高品質のペロブスカイト酸化物ナノシート多層膜を得ようとする場合に、最も好適なのは、上記の稠密単層コーティングを繰り返し、重ね塗りする方法である。また、簡便には、コーティング剤中の薄片状ペロブスカイト酸化物粒子の含有量を高くすることによっても酸化物ナノシート多層膜を作成することができる。 The organic solvent dispersion of the present invention is suitable as a coating agent for coating flaky perovskite oxide particles on a substrate. In addition to a dispersion in which flaky perovskite oxide particles are dispersed in an organic solvent, the coating agent further includes the resin binder, dispersant, surface conditioner (leveling agent, wettability improver), pH adjuster, Those containing various additives such as foaming agents, emulsifiers, colorants, extenders, antifungal agents, curing aids, thickeners, fillers and the like as the third component are included. The addition amount of the third component such as a dispersant can be appropriately adjusted. For example, when the surfactant, the silicone-based dispersant, the phosphate-based dispersant, or the alkanolamines are used as the dispersant, a flaky shape is used. About 0.005 to 2.0 weight% is preferable with respect to the weight of the perovskite oxide particles, and about 0.01 to 0.2 weight% is more preferable. As the surface conditioner, the aforementioned silicone-based surface conditioner can be used, and is preferably about 0.005 to 2.0% by weight with respect to the weight of the flaky perovskite oxide particles, 0.01 to 0.2 A weight percentage is more preferred. When the base material is coated using such a coating agent, the above-mentioned flaky perovskite oxide particles having a large width and length are arranged in parallel with the base material, and thus the perovskite oxide has a high base material coverage. A thin perovskite oxide thin film having a thin film, specifically, a coverage of 90% or more, preferably 95% or more can be produced. In addition, a film is formed with a small thickness of flaky perovskite oxide particles, specifically, a single particle thickness where most of the particles do not overlap, and in the remaining part, a few particles overlap at most. A single-layer perovskite oxide thin film formed with a thickness can be produced, and a dense single-layer film having a quality close to that of a Langmuir-Blodgett film can be obtained. The content of the flaky perovskite oxide particles in the coating agent can be adjusted as appropriate. However, when a dense single layer film is to be obtained, 0.001 to 1. 0 wt% is more preferable, 0.01 to 1.0 wt% is more preferable, 0.02 to 1.0 wt% is still more preferable, and 0.02 to 0.5 wt% is particularly preferable. In order to obtain a high-quality perovskite oxide nanosheet multilayer film, the most suitable method is a method in which the above-mentioned dense single layer coating is repeated and applied repeatedly. In addition, an oxide nanosheet multilayer film can also be prepared simply by increasing the content of flaky perovskite oxide particles in the coating agent.
本発明の有機溶媒分散体の製造方法は、ホスト層がペロブスカイト構造である層状酸化物を有機カチオンと接触させ、層状構造を剥離して、薄片状ペロブスカイト酸化物粒子の水性分散体を製造する工程（第一工程ということがある）、
前記水性分散体から薄片状ペロブスカイト酸化物粒子を含む固形分を抽出する工程（第二工程ということがある）、及び
前記固形分と有機溶媒とを混合して分散させる工程（第三工程ということがある）、を含む。
The method for producing an organic solvent dispersion of the present invention comprises a step of producing an aqueous dispersion of flaky perovskite oxide particles by contacting a layered oxide whose host layer has a perovskite structure with an organic cation and peeling the layered structure. (Sometimes referred to as the first step),
A step of extracting a solid content containing flaky perovskite oxide particles from the aqueous dispersion (sometimes referred to as a second step), and a step of mixing and dispersing the solid content and an organic solvent (referred to as a third step) Including).
前記の第一工程は、ホスト層がペロブスカイト構造である層状酸化物を有機カチオンと接触させ、層状構造を剥離して、薄片状ペロブスカイト酸化物粒子、好ましくはペロブスカイト酸化物のナノシートの水性分散体を製造する工程である。この第一工程で使用する層状ペロブスカイト酸化物としては、層状ペロブスカイト酸化物であればいずれのものでも使用でき、水素イオンやアルカリ金属を含んでいても良い。
層状ペロブスカイト酸化物はまず、ホスト層がペロブスカイト構造を有する酸化物であって、層間にアルカリ金属イオンを含む層状ペロブスカイト酸化物アルカリ金属塩を合成し、次いで、得られた層状ペロブスカイト酸化物アルカリ金属塩を水溶媒に懸濁した後、塩酸、硫酸、硝酸などの酸を添加し、アルカリ金属イオンを抽出し水素イオンで置換して製造することができる。
In the first step, a layered oxide whose host layer has a perovskite structure is brought into contact with an organic cation, and the layered structure is peeled off to form an aqueous dispersion of flaky perovskite oxide particles, preferably a nanosheet of perovskite oxide. It is a manufacturing process. As the layered perovskite oxide used in the first step, any layered perovskite oxide can be used, and hydrogen ions and alkali metals may be included.
The layered perovskite oxide is an oxide in which the host layer has a perovskite structure, and a layered perovskite oxide alkali metal salt containing an alkali metal ion between layers is synthesized, and then the obtained layered perovskite oxide alkali metal salt Is suspended in an aqueous solvent, and then an acid such as hydrochloric acid, sulfuric acid or nitric acid is added to extract alkali metal ions and replace them with hydrogen ions.
前記の層状ペロブスカイト酸化物アルカリ金属塩は、アルカリ金属として例えば、Ｌｉ、Ｎａ、Ｋ、Ｒｂ又はＣｓからなる群より選ばれる少なくとも一種を含むものが好ましく、具体的には、ＫＣａ２Ｎｂ３Ｏ１０、ＫＬａＮｂ２Ｏ７、ＫＬａ０．９０Ｅｕ０．０５Ｎｂ２Ｏ７、ＫＣａ２ＮａＮｂ４Ｏ１３、ＫＳｒ２Ｎｂ３Ｏ１０等で表わされるニオブ酸アルカリ金属塩やタンタル酸アルカリ金属塩を好適に用いることができる。このような層状ペロブスカイト酸化物アルカリ金属塩は、アルカリ金属酸化物又は加熱によりアルカリ金属酸化物に分解される化合物、たとえば、Ｌｉ、Ｋ、Ｒｂ、Ｃｓなどの元素を含む酸化物、炭酸塩、水酸化物、硫酸塩、好ましくは炭酸塩と、ペロブスカイト酸化物を構成する金属酸化物又は加熱によりペロブスカイト酸化物を生ずる化合物とを混合し、５００〜１７００℃、更に好ましくは６００〜１５００℃の温度で焼成して製造することが好ましい。反応を十分に行って原料組成物の残存量を少なくし、また、別の組成の物質の生成を抑えるには、上記温度範囲が好ましい。
それぞれの化合物の混合割合は、目的とする組成に応じて適宜設定することができる。
均一で単相の化合物を得るためには、前記合成工程の中、混合を十分に行うことが好ましく、原料粉末を自動乳鉢などで摩砕混合することが好ましい。また、層状ペロブスカイト酸化物アルカリ金属塩を製造する際の焼成温度を適宜選択したり、焼成の際に融剤を添加する所謂フラックス法を採用することによって、層状ペロブスカイト酸化物アルカリ金属塩の粒子の大きさを適宜調整することができ、これにより薄片状ペロブスカイト酸化物の粒子の大きさを適宜制御することができる。
The layered perovskite oxide alkali metal salt preferably contains at least one selected from the group consisting of Li, Na, K, Rb or Cs as an alkali metal, specifically, KCa 2 Nb 3 O 10. , KLaNb 2 O 7 , KLa 0.90 Eu 0.05 Nb 2 O 7 , KCa 2 NaNb 4 O 13 , KSr 2 Nb 3 O 10, etc. Can be used. Such layered perovskite oxide alkali metal salts include alkali metal oxides or compounds that decompose into alkali metal oxides upon heating, such as oxides, carbonates, water containing elements such as Li, K, Rb, and Cs. Oxides, sulfates, preferably carbonates, and metal oxides that constitute perovskite oxides or compounds that produce perovskite oxides upon heating are mixed at a temperature of 500-1700 ° C., more preferably 600-1500 ° C. It is preferable to manufacture by baking. The above-mentioned temperature range is preferable in order to sufficiently carry out the reaction to reduce the remaining amount of the raw material composition and to suppress the formation of a substance having another composition.
The mixing ratio of each compound can be appropriately set according to the intended composition.
In order to obtain a uniform and single-phase compound, it is preferable to sufficiently mix in the synthesis step, and it is preferable to grind and mix the raw material powder in an automatic mortar or the like. In addition, by appropriately selecting the firing temperature when producing the layered perovskite oxide alkali metal salt, or by adopting a so-called flux method in which a flux is added during firing, the particles of the layered perovskite oxide alkali metal salt The size can be appropriately adjusted, whereby the size of the flaky perovskite oxide particles can be appropriately controlled.
次いで、得られた層状ペロブスカイト酸化物アルカリ金属塩を水溶媒に懸濁した後、塩酸、硫酸、硝酸などの酸を添加し、アルカリ金属イオンを抽出して、水素イオンで置換した層状ペロブスカイト酸化物を得るのが好ましい。前記の方法で得られた層状ペロブスカイト酸化物アルカリ金属塩のアルカリ金属イオンは活性であるので、他の陽イオンとの交換反応や有機物のインターカレーションによる取り込みを起こす。このため、酸水溶液と接触させると、層間のアルカリ金属イオンが、短時間で水素イオン（存在形態はヒドロニウムイオン）と交換され、工業的に生産する場合に効率良く、生産コストの低い薄片状ペロブスカイト酸化物の水性分散体を得ることができる。酸の添加量、酸濃度、反応温度、反応時間等の条件はアルカリ金属イオンの抽出の程度に応じて適宜設定することができる。アルカリ金属イオンの抽出量は、７５％以上が好ましく、９０％以上がより好ましい。 Next, after suspending the obtained layered perovskite oxide alkali metal salt in an aqueous solvent, acid such as hydrochloric acid, sulfuric acid, nitric acid was added, the alkali metal ion was extracted, and the layered perovskite oxide substituted with hydrogen ion Is preferably obtained. Since the alkali metal ion of the layered perovskite oxide alkali metal salt obtained by the above method is active, it causes uptake by exchange reaction with other cations or organic intercalation. For this reason, when it is brought into contact with an acid aqueous solution, the alkali metal ions between the layers are exchanged with hydrogen ions (the presence form is hydronium ions) in a short time, and it is efficient for industrial production, and is a flaky shape with low production cost. An aqueous dispersion of perovskite oxide can be obtained. Conditions such as the amount of acid added, acid concentration, reaction temperature, reaction time, etc. can be appropriately set according to the degree of extraction of alkali metal ions. The extracted amount of alkali metal ions is preferably 75% or more, and more preferably 90% or more.
次に、層状ペロブスカイト酸化物を有機カチオン（塩基性化合物）と接触させ、層状構造を剥離して、薄片状ペロブスカイト酸化物粒子の水性分散体を製造する。具体的には、この層状ペロブスカイト酸化物に含まれる水素（Ｈ）に対して好ましくは０．０５〜３中和当量の範囲の有機カチオン源である塩基性化合物を媒液中で混合して、層状ペロブスカイト酸化物に含まれる水素を脱離させるとともに塩基性化合物を層間に挿入させ、次いで、層を剥離させて薄片状ペロブスカイト酸化物粒子を製造するのが好ましい。塩基性化合物の量が前記範囲より少ないと水素イオンが十分脱離せず、多すぎると膨潤はするが却って有機カチオンを介した層間相互作用が強くなり剥離が困難になる。より好ましい量は０．１〜３中和当量、更に好ましくは０．９〜１．５中和当量である。このような塩基性化合物の一部は有機カチオンとして薄片状ペロブスカイト酸化物に、好ましくは粒子表面に含まれる。 Next, the layered perovskite oxide is contacted with an organic cation (basic compound), and the layered structure is peeled off to produce an aqueous dispersion of flaky perovskite oxide particles. Specifically, a basic compound which is an organic cation source preferably in a range of 0.05 to 3 neutralization equivalent to hydrogen (H) contained in the layered perovskite oxide is mixed in a liquid medium, It is preferable to produce flaky perovskite oxide particles by desorbing hydrogen contained in the layered perovskite oxide and inserting a basic compound between the layers, and then separating the layers. When the amount of the basic compound is less than the above range, hydrogen ions are not sufficiently desorbed. When the amount is too large, swelling occurs, but the interlayer interaction via the organic cation becomes strong and peeling becomes difficult. A more preferable amount is 0.1 to 3 neutralization equivalent, and still more preferably 0.9 to 1.5 neutralization equivalent. A part of such a basic compound is contained as an organic cation in the flaky perovskite oxide, preferably on the particle surface.
塩基性化合物としては、（１）水酸化４級アンモニウム化合物（水酸化テトラメチルアンモニウム、水酸化テトラエチルアンモニウム、水酸化テトラプロピルアンモニウム、水酸化テトラブチルアンモニウム等）、（２）アルキルアミン化合物（プロピルアミン、ジエチルアミン等）、（３）アルカノールアミン化合物（エタノールアミン、アミノメチルプロパノール等）等が挙げられ、中でも水酸化４級アンモニウム化合物、アルキルアミン化合物が反応性に優れ好ましく、炭素数の合計が７以上、好ましくは９以上のものを用いると有機溶媒分散体としたときにも薄片状ペロブスカイト酸化物粒子の分散剤として有効に働くためより好ましい。上記水酸化４級アンモニウム化合物としては、水酸化テトラアルキルアンモニウムが好ましいが、そのうち、剥離率を向上させるためには、水酸化テトラエチルアンモニウムが好ましく、水酸化テトラプロピルアンモニウムがより好ましく、水酸化テトラブチルアンモニウムが更に好ましい。このように、水酸化テトラアルキルアンモニウムを用いる場合は、個々のアルキル基が含有する炭素数が増えるに従い剥離率が増加する。一方、テトラメチルアンモニウム化合物を用いる場合は、コストパフォーマンスを向上させることができるため、好ましい。
この工程で使用される媒液としては、水を用いるのが好ましい。媒液への層状ペロブスカイト酸化物及び塩基性化合物の添加の順序は特に限定されず、例えば水に層状ペロブスカイト酸化物と塩基性化合物を加え、撹拌して混合することができる。また層状ペロブスカイト酸化物を水に分散させたスラリーに塩基性化合物を加えても、塩基性化合物水溶液に層状ペロブスカイト酸化物を加えても良い。次いで、撹拌を続けると層状ペロブスカイト酸化物の層が剥離して、薄片状ペロブスカイト酸化物粒子が得られる。また、層間剥離の程度をより高めるため、溶液を入れた容器を振とうしても良い。この振とうにより、層状ペロブスカイト酸化物のホスト層一枚単位まで剥離した長さ及び幅がそれぞれ０．１μｍ以上、厚みが１０ｎｍ以下程度のナノシートを効率よく製造することができる。振とうには、振とう器、ペイントコンディショナー、シェーカー等を用いることができる。
Basic compounds include (1) quaternary ammonium hydroxide compounds (tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, etc.), (2) alkylamine compounds (propylamine) , Diethylamine, etc.), (3) alkanolamine compounds (ethanolamine, aminomethylpropanol, etc.), etc. Among them, quaternary ammonium hydroxide compounds and alkylamine compounds are preferred because of their excellent reactivity, and the total number of carbons is 7 or more. It is more preferable to use 9 or more, since it effectively works as a dispersant for the flaky perovskite oxide particles even when an organic solvent dispersion is used. As the quaternary ammonium hydroxide compound, tetraalkylammonium hydroxide is preferable. Among them, tetraethylammonium hydroxide is preferable, tetrapropylammonium hydroxide is more preferable, and tetrabutylhydroxide is preferable in order to improve the peeling rate. Ammonium is more preferred. Thus, when tetraalkylammonium hydroxide is used, the peel rate increases as the number of carbons contained in each alkyl group increases. On the other hand, the use of a tetramethylammonium compound is preferable because cost performance can be improved.
As the medium used in this step, it is preferable to use water. The order of addition of the layered perovskite oxide and the basic compound to the liquid medium is not particularly limited. For example, the layered perovskite oxide and the basic compound can be added to water and mixed by stirring. Further, the basic compound may be added to the slurry in which the layered perovskite oxide is dispersed in water, or the layered perovskite oxide may be added to the basic compound aqueous solution. Next, when stirring is continued, the layer of the layered perovskite oxide is peeled off to obtain flaky perovskite oxide particles. In order to further increase the degree of delamination, the container containing the solution may be shaken. By this shaking, it is possible to efficiently produce a nanosheet having a length and a width of 0.1 μm or more and a thickness of about 10 nm or less, each peeled up to a unit of the layered perovskite oxide host layer. For shaking, a shaker, a paint conditioner, a shaker, or the like can be used.
次に、第二工程では、薄片状ペロブスカイト酸化物粒子の水性分散体から薄片状ペロブスカイト酸化物粒子を含む固形分を抽出する。抽出方法は薄片状ペロブスカイト酸化物粒子の分散状態に応じて適宜選択することができ、高度に分散している場合には、遠心分離及び／又は凍結乾燥するのが好ましい。水性分散体を遠心分離すると、沈降物と媒液を分取することができる。遠心分離には通常の遠心分離器を用いることができる。所望の含水率に調整するために、遠心分離を２回以上繰り返しても良い。あるいは、薄片状ペロブスカイト酸化物粒子の水性分散体を凍結乾燥すると凍結乾燥物を得ることができる。凍結乾燥には通常の凍結乾燥機を用いることができる。遠心分離と凍結乾燥はそれぞれを組み合わせることができ、遠心分離を行った沈降物を凍結乾燥しても良い。 Next, in the second step, a solid content containing the flaky perovskite oxide particles is extracted from the aqueous dispersion of flaky perovskite oxide particles. The extraction method can be appropriately selected according to the dispersion state of the flaky perovskite oxide particles. When the flaky perovskite oxide particles are highly dispersed, it is preferable to perform centrifugation and / or freeze-drying. When the aqueous dispersion is centrifuged, the sediment and the liquid medium can be separated. A normal centrifuge can be used for centrifugation. Centrifugation may be repeated two or more times to adjust to the desired moisture content. Alternatively, a freeze-dried product can be obtained by lyophilizing an aqueous dispersion of flaky perovskite oxide particles. A normal freeze dryer can be used for freeze drying. Centrifugation and lyophilization can be combined with each other, and the sediment after centrifuging may be lyophilized.
次に、第三工程では、得られた沈降物や凍結乾燥物を有機溶媒と混合し、薄片状ペロブスカイト酸化物粒子を分散させて、有機溶媒分散体を得る。薄片状ペロブスカイト酸化物粒子を分散させるには、前記と同様の通常の撹拌機、コロイドミル、ボールミル、ビーズミル等の分散機、振とう器、ペイントコンディショナー、シェーカー等を用いることができ、その際、上記の第三成分を添加することができる。 Next, in the third step, the obtained precipitate or lyophilized product is mixed with an organic solvent, and the flaky perovskite oxide particles are dispersed to obtain an organic solvent dispersion. In order to disperse the flaky perovskite oxide particles, the same conventional stirrer as described above, colloid mill, ball mill, bead mill and other dispersing machines, shaker, paint conditioner, shaker, etc. can be used. The third component can be added.
前記の薄片状ペロブスカイト酸化物粒子を含む有機溶媒分散体やコーティング剤を基材上にコートして成膜してペロブスカイト酸化物薄膜とする。また、ペロブスカイト酸化物薄膜の厚みは、コート方法を適宜選択して任意の厚みとすることができる。基材の材質には、プラスチックス、ガラス、セラミックス、金属、木材、繊維等特に制限を受けない。基材の表面には、ペロブスカイト酸化物薄膜と基材との密着性を向上させたり、基材を保護する等の目的で、予めプライマー層を形成しておいても、ペロブスカイト酸化物薄膜を保護する等の目的で、膜の表面にトップコート層を形成しても良い。プライマー層やトップコート層の形成には、前述の無機系バインダー、有機系バインダー等を用いることができる。 The organic solvent dispersion containing the flaky perovskite oxide particles and the coating agent are coated on a base material to form a perovskite oxide thin film. Moreover, the thickness of the perovskite oxide thin film can be set to an arbitrary thickness by appropriately selecting a coating method. The material of the base material is not particularly limited, such as plastics, glass, ceramics, metal, wood, and fiber. Even if a primer layer is formed in advance on the surface of the base material for the purpose of improving the adhesion between the perovskite oxide thin film and the base material or protecting the base material, the perovskite oxide thin film is protected. For this purpose, a top coat layer may be formed on the surface of the film. For the formation of the primer layer and the topcoat layer, the above-mentioned inorganic binders, organic binders and the like can be used.
ペロブスカイト酸化物薄膜の好ましい態様は、前記の薄片状ペロブスカイト酸化物粒子が基材に平行に配向して配置した基材の被覆率が高いペロブスカイト酸化物薄膜、具体的には被覆率が９０％以上、好ましくは９５％以上のペロブスカイト酸化物薄膜である。このように被覆率が９０％以上の膜を稠密膜といい、被覆率は走査プローブ顕微鏡写真の画像解析から求める。また、薄片状ペロブスカイト酸化物粒子の重なりが少ない状態、具体的には、大半は粒子の重なりがない１粒子の厚みで膜が形成され残りの部分もせいぜい２〜３粒子程度が重なり合った厚みで形成された単層ペロブスカイト酸化物薄膜が好ましく、Langmuir-Blodgett膜に近い品質の稠密単層膜がより好ましい。既知の濃度の薄片状ペロブスカイト酸化物ゾルの吸光度測定と、薄片状ペロブスカイト酸化物の単位格子から薄片状ペロブスカイト酸化物の単層膜の理論吸光度を算出し、この理論吸光度と実際に測定されたペロブスカイト酸化物の吸光度とを比較することで単層膜であることを確認することができる。具体的には本発明においてはペロブスカイト酸化物の単層膜の理論吸光度に対し、８０〜１２０％、好ましくは９０〜１１０％の吸光度を示す膜を単層膜とする。ペロブスカイト酸化物薄膜の厚みは、薄片状ペロブスカイト酸化物粒子の厚みや粒子の重なり具合により適宜設定することができる。 A preferred embodiment of the perovskite oxide thin film is a perovskite oxide thin film having a high coverage of a base material in which the flaky perovskite oxide particles are arranged in parallel with the base material, specifically, the coverage is 90% or more. Preferably, it is a perovskite oxide thin film of 95% or more. A film having a coverage of 90% or more is called a dense film, and the coverage is obtained from image analysis of a scanning probe micrograph. In addition, there is little overlap of the flaky perovskite oxide particles, specifically, the film is formed with the thickness of one particle with most of the particles not overlapping, and the remaining portion has a thickness where at most about 2 to 3 particles overlap. The formed single layer perovskite oxide thin film is preferable, and a dense single layer film having a quality close to that of a Langmuir-Blodgett film is more preferable. Absorbance measurement of flaky perovskite oxide sol with a known concentration and the theoretical absorbance of the flaky perovskite oxide monolayer from the unit cell of flaky perovskite oxide were calculated, and this theoretical absorbance and the actual measured perovskite By comparing the absorbance of the oxide, it can be confirmed that it is a single layer film. Specifically, in the present invention, a film having an absorbance of 80 to 120%, preferably 90 to 110% with respect to the theoretical absorbance of the single layer film of perovskite oxide is defined as a single layer film. The thickness of the perovskite oxide thin film can be appropriately set depending on the thickness of the flaky perovskite oxide particles and the degree of particle overlap.
また、前記の単層ペロブスカイト酸化物薄膜を積み重ねた積層ペロブスカイト酸化物薄膜とすると種々の用途に用いることができ、好ましい。積層ペロブスカイト酸化物薄膜は、単層ペロブスカイト酸化物薄膜が積層した多層構造を有するペロブスカイト酸化物薄膜であって、各ペロブスカイト酸化物薄膜において薄片状ペロブスカイト酸化物粒子が配向した状態を保持しているため単層ペロブスカイト酸化物薄膜の性状を維持し、しかも、多層構造により多くの薄片状ペロブスカイト酸化物粒子を有することから、薄片状ペロブスカイト酸化物粒子の特性を一層引き出すことができる。各層は、前記の稠密単層ペロブスカイト酸化物薄膜で形成するのが好ましい。積層ペロブスカイト酸化物薄膜の膜厚は、積層回数により適宜調整することができ、１〜５０ｎｍの範囲が好ましく、１〜３０ｎｍの範囲がより好ましい。ペロブスカイト酸化物ナノシートを用いると、積層数（膜厚）の精密な制御が可能となり、より優れた特性を得ることができる。一方、１回のコートによって２０ｎｍ程度の膜厚とすることもできるが、このような厚膜ペロブスカイト酸化物膜では、薄片状ペロブスカイト酸化物粒子がランダムに配置されるため、前記のような透明の膜は得られ難い。 In addition, a laminated perovskite oxide thin film in which the single-layer perovskite oxide thin films are stacked is preferable because it can be used for various applications. The laminated perovskite oxide thin film is a perovskite oxide thin film having a multilayer structure in which single-layer perovskite oxide thin films are laminated, and the flaky perovskite oxide particles maintain an oriented state in each perovskite oxide thin film. The properties of the single layer perovskite oxide thin film are maintained, and more flaky perovskite oxide particles are provided in the multilayer structure, so that the characteristics of the flaky perovskite oxide particles can be further extracted. Each layer is preferably formed of the dense single layer perovskite oxide thin film. The film thickness of the laminated perovskite oxide thin film can be appropriately adjusted depending on the number of laminations, preferably in the range of 1 to 50 nm, more preferably in the range of 1 to 30 nm. When the perovskite oxide nanosheet is used, the number of stacked layers (film thickness) can be precisely controlled, and more excellent characteristics can be obtained. On the other hand, the film thickness can be about 20 nm by one coating. However, in such a thick perovskite oxide film, the flaky perovskite oxide particles are randomly arranged. A film is difficult to obtain.
基材に前記の有機溶媒分散体やコーティング剤をコートする方法としては、スピンコート、スプレー塗装、ローラーコート、ディップコート、フローコート、ナイフコート、静電塗装、バーコート、ダイコート、ハケ塗り、液滴を滴下する方法等、一般的な方法を制限無く用いることができる。ディップコートであれば、基材の両面にペロブスカイト酸化物薄膜を作製することができ、スピンコート、スプレー塗装、ローラーコート、フローコート等であれば基材の片面にペロブスカイト酸化物薄膜を作製することができる。膜厚をより厚くするのであれば、重ね塗りを行っても良い。コートしたものから有機溶媒を除去すればペロブスカイト酸化物薄膜が成膜するが、成膜は５〜３００℃の範囲の温度下で行うのが好ましい。前記の温度範囲の下限はそれぞれ室温が好ましい。また、湿度を５０〜１００％程度に保持した状態、好ましくは６０〜９５％程度の湿度で成膜しても良い。前記の成膜条件、具体的にはコーティング剤中の薄片状ペロブスカイト酸化物粒子の濃度、成膜温度、成膜の際の湿度、成膜の際の基材の配置等の条件を適宜設定することにより、成膜速度、有機溶媒の蒸発速度を適宜制御すると、薄片状ペロブスカイト酸化物粒子による基材の被覆率が高いペロブスカイト酸化物薄膜、具体的には被覆率が９０％以上、好ましくは９５％以上のペロブスカイト酸化物薄膜を製造することができる。また、薄片状ペロブスカイト酸化物粒子の重なりが少ない状態、具体的には大半の粒子の重なりがない１粒子の厚みで形成され残りの部分においてもせいぜい２〜３粒子程度が重なり合った厚みで形成された単層ペロブスカイト酸化物薄膜を製造することができ、Langmuir-Blodgett膜に近い品質の稠密単層膜を製造することができる。具体的には好ましい条件として、有機溶媒にジメチルスルホキシドを用いる場合、薄片状ペロブスカイト酸化物粒子の濃度を０．０２〜０．１重量％とし、成膜温度を１０〜３５℃、湿度を６０％以上とすると稠密単層ペロブスカイト酸化物薄膜を製造することができる。また、有機溶媒にＮ，Ｎ−ジメチルホルムアミドを用いる場合、薄片状ペロブスカイト酸化物粒子の濃度を０．０２〜０．１重量％、成膜温度を１５〜３５℃、湿度を９０％以上とすると稠密単層ペロブスカイト酸化物薄膜を製造することができる。また、成膜の際に基材を斜めあるいは垂直に配置することにより、有機溶媒が下方向に流れるとともに上方から徐々に有機溶媒が蒸発しゆっくりとした成膜が進み、余分な薄片状ペロブスカイト酸化物は基材から流れ落ちるため稠密単層ペロブスカイト酸化物薄膜が得られ易い。斜めあるいは垂直とは具体的には基材を、水平面を基準に１５〜９０°の角度に保持することをいい、好ましくは３０〜９０°程度、より好ましくは６０〜８０°程度である。一方、基材を水平（角度０°）に配置すると基材の中心に向かって溶媒が乾燥し、余分な薄片状ペロブスカイト酸化物が基材中央へ寄せ集められるため、基材全体にわたって単層稠密配列したペロブスカイト酸化物薄膜は得られ難い。 Examples of the method for coating the base material with the organic solvent dispersion or coating agent include spin coating, spray coating, roller coating, dip coating, flow coating, knife coating, electrostatic coating, bar coating, die coating, brush coating, and liquid. A general method such as a method of dropping a droplet can be used without limitation. For dip coating, perovskite oxide thin film can be prepared on both sides of the substrate, and for perovskite oxide thin film on one side of the substrate for spin coating, spray coating, roller coating, flow coating, etc. Can do. If the film thickness is to be increased, overcoating may be performed. If the organic solvent is removed from the coated material, a perovskite oxide thin film is formed, but the film formation is preferably performed at a temperature in the range of 5 to 300 ° C. The lower limit of the temperature range is preferably room temperature. Further, the film may be formed in a state where the humidity is maintained at about 50 to 100%, preferably at a humidity of about 60 to 95%. Appropriately set the film formation conditions, specifically, the concentration of the flaky perovskite oxide particles in the coating agent, the film formation temperature, the humidity during the film formation, the arrangement of the base material during the film formation, and the like. Accordingly, when the film formation rate and the evaporation rate of the organic solvent are appropriately controlled, a perovskite oxide thin film having a high substrate coverage with flaky perovskite oxide particles, specifically, a coverage of 90% or more, preferably 95 % Or more perovskite oxide thin film can be produced. In addition, the flaky perovskite oxide particles are formed with a small overlap, specifically, with a thickness of one particle where most of the particles do not overlap, and with the remaining portion formed with a thickness where at most about 2 to 3 particles overlap. A single-layer perovskite oxide thin film can be manufactured, and a dense single-layer film having a quality close to that of a Langmuir-Blodgett film can be manufactured. Specifically, as preferred conditions, when dimethyl sulfoxide is used as the organic solvent, the concentration of the flaky perovskite oxide particles is 0.02 to 0.1% by weight, the film forming temperature is 10 to 35 ° C., and the humidity is 60%. With the above, a dense single layer perovskite oxide thin film can be produced. When N, N-dimethylformamide is used as the organic solvent, the concentration of the flaky perovskite oxide particles is 0.02 to 0.1% by weight, the film forming temperature is 15 to 35 ° C., and the humidity is 90% or more. A dense single layer perovskite oxide thin film can be produced. In addition, by placing the substrate diagonally or vertically during film formation, the organic solvent flows downward and the organic solvent gradually evaporates from above, so that slow film formation proceeds, and excess flaky perovskite oxidation occurs. Since the material flows down from the substrate, a dense single layer perovskite oxide thin film is easily obtained. Specifically, the term “oblique or vertical” means that the substrate is held at an angle of 15 to 90 ° with respect to the horizontal plane, preferably about 30 to 90 °, more preferably about 60 to 80 °. On the other hand, when the substrate is placed horizontally (angle 0 °), the solvent dries toward the center of the substrate, and excess flaky perovskite oxide is gathered to the center of the substrate, so that the single layer dense throughout the substrate. It is difficult to obtain an aligned perovskite oxide thin film.
また、前記の有機溶媒分散体やコーティング剤を基材にコートし、次いで、５〜３００℃の範囲の温度下で成膜する操作を少なくとも２回繰り返して、薄片状ペロブスカイト酸化物粒子の多層膜を積層させることができる。コートの回数は適宜設定することができる。各層の成膜は、前記のペロブスカイト酸化物薄膜の成膜条件に準じて行うことができ、各層を稠密単層ペロブスカイト酸化物薄膜で形成するのが好ましい。また、前記の積層ペロブスカイト酸化物薄膜を基材の耐熱性に応じて必要であれば焼成しても良く、密着性を高めるために２００〜８００℃程度の温度で焼成しても良い。 In addition, a multilayer film of flaky perovskite oxide particles is obtained by coating an organic solvent dispersion or a coating agent on a substrate and then repeating the operation of forming a film at a temperature in the range of 5 to 300 ° C. at least twice. Can be laminated. The number of coatings can be set as appropriate. Each layer can be formed in accordance with the above-described film formation conditions of the perovskite oxide thin film, and each layer is preferably formed of a dense single layer perovskite oxide thin film. Further, the laminated perovskite oxide thin film may be fired if necessary according to the heat resistance of the substrate, and may be fired at a temperature of about 200 to 800 ° C. in order to improve adhesion.
前記のペロブスカイト酸化物薄膜を形成した基材は種々の用途に用いることができる。例えば、紫外線遮蔽剤、透明性材料、反射防止材料、光触媒性材料、フォトクロミック性材料、エレクトロクロミック性材料、ガスバリヤー性材料、誘電体、圧電体等のファインセラミックス材料、熱電変換材料、光電変換材料、フォトクロミック材料、導電性材料、赤外線反射材料、磁性半導体、電池の電極材料、各種センサー、更には他物質の配向結晶成長のためのシードレイヤー等の機能性材料に用いることができる。これらの用途への使用は従来から用いられている形態、担持状態、配合割合に応じて薄片状ペロブスカイト酸化物等を適用すれば良く、例えば光触媒体として用いる場合には、ペロブスカイト酸化物のバンドギャップ以上のエネルギーを有する波長の光を照射して、有害物質、悪臭物質、汚れ等を除去したり、超親水性効果による防汚、防曇作用等を活用することができる。また、薄片状ペロブスカイト酸化物粒子を含む有機溶媒分散体は樹脂と混合して、塗料、インキ等の液状樹脂組成物とすることもでき、あるいは、それを成形してプラスチック成形体、シート、フィルム等の固体樹脂組成物とすることもできる。このような樹脂としては前記の樹脂バインダーや生分解性樹脂、紫外線硬化性樹脂、熱硬化性樹脂等を適宜用いることができ、薄片状ペロブスカイト酸化物粒子の配合量、その他の添加剤の配合量等は適宜設定することができる。 The base material on which the perovskite oxide thin film is formed can be used for various applications. For example, UV shielding agent, transparency material, antireflection material, photocatalytic material, photochromic material, electrochromic material, gas barrier material, dielectric, piezoelectric ceramic and other fine ceramic materials, thermoelectric conversion material, photoelectric conversion material , Photochromic materials, conductive materials, infrared reflective materials, magnetic semiconductors, battery electrode materials, various sensors, and functional materials such as seed layers for growth of oriented crystals of other substances. For use in these applications, a flaky perovskite oxide or the like may be applied according to the form, loading state, and blending ratio conventionally used. For example, when used as a photocatalyst, the band gap of the perovskite oxide is used. By irradiating light having a wavelength having the above energy, harmful substances, malodorous substances, dirt, etc. can be removed, and antifouling and antifogging effects due to the superhydrophilic effect can be utilized. In addition, the organic solvent dispersion containing flaky perovskite oxide particles can be mixed with a resin to form a liquid resin composition such as paint or ink, or it can be molded into a plastic molded body, sheet or film. It can also be set as a solid resin composition. As such a resin, the above-mentioned resin binder, biodegradable resin, ultraviolet curable resin, thermosetting resin and the like can be used as appropriate, the amount of flaky perovskite oxide particles, the amount of other additives Etc. can be appropriately set.
以下に本発明の実施例を示すが、本発明はこれらに制限されるものではない。 Examples of the present invention are shown below, but the present invention is not limited thereto.
（１）薄片状ペロブスカイト酸化物の有機溶剤分散体の調製 (1) Preparation of organic solvent dispersion of flaky perovskite oxide
実施例１
炭酸カリウム（Ｋ２ＣＯ３）と炭酸カルシウム（ＣａＣＯ３）と酸化ニオブ（Ｎｂ２Ｏ５）をＫＣａ２Ｎｂ３Ｏ１０のモル比となるように混合し、十分に摩砕した。これを１２００℃の温度で１２時間焼成し、ニオブ酸カルシウムアルカリ金属塩粉末（ＫＣａ２Ｎｂ３Ｏ１０）を得た。
前記の粉末１ｇに対して、５規定の硝酸４０ｃｍ３を加え、３日間室温で撹拌しながら反応させた。その後、濾過、水洗、乾燥して、活性なカリウムイオンを水素イオンで置換した層状ニオブ酸カルシウムの粉末を得た。
次いで、層状ニオブ酸カルシウムの粉末０．４ｇを、層状ニオブ酸カルシウム中のＨ＋量に対して１中和当量の水酸化テトラブチルアンモニウムを溶解した水溶液０．１リットルに加え層間を膨潤させ、シェーカーで１５０回転／分程度の振とうを１０日間行って層間を剥離して、乳白色の薄片状ニオブ酸カルシウム水性分散体（試料ａ）を得た。
次に、試料ａを遠心分離機（日立工機株式会社製、CP 100MX）を使用して、１５０００ｒｐｍ、３０分間遠心分離した。透明な上澄みを捨て、捨てた上澄みと同量のジメチルスルホキシドを追加して軽く振とうして、薄片状ニオブ酸カルシウムの有機溶媒分散体（試料Ａ）を得た。試料Ａは、無色透明ではなく、試料ａと同様の色を呈していた。
Example 1
Potassium carbonate (K 2 CO 3 ), calcium carbonate (CaCO 3 ) and niobium oxide (Nb 2 O 5 ) were mixed at a molar ratio of KCa 2 Nb 3 O 10 and thoroughly ground. This was calcined at a temperature of 1200 ° C. for 12 hours to obtain a calcium niobate alkali metal salt powder (KCa 2 Nb 3 O 10 ).
To 1 g of the powder, 40 cm 3 of 5 N nitric acid was added and reacted for 3 days at room temperature with stirring. Thereafter, filtration, washing with water, and drying were performed to obtain a layered calcium niobate powder in which active potassium ions were replaced with hydrogen ions.
Next, 0.4 g of layered calcium niobate powder was added to 0.1 liter of an aqueous solution in which 1 neutralization equivalent of tetrabutylammonium hydroxide was dissolved with respect to the amount of H + in the layered calcium niobate, and the layers were swollen. The layer was peeled off by shaking at about 150 rpm for 10 days with a shaker to obtain a milky white flaky calcium niobate aqueous dispersion (sample a).
Next, the sample a was centrifuged at 15000 rpm for 30 minutes using a centrifuge (manufactured by Hitachi Koki Co., Ltd., CP 100MX). The transparent supernatant was discarded, the same amount of dimethyl sulfoxide as the discarded supernatant was added, and the mixture was shaken lightly to obtain an organic solvent dispersion of flaky calcium niobate (sample A). Sample A was not colorless and transparent, and had the same color as sample a.
実施例２
炭酸カリウム（Ｋ２ＣＯ３）と酸化ランタン（Ｌａ２Ｏ３）と酸化ニオブ（Ｎｂ２Ｏ５）をＫＬａＮｂ２Ｏ７のモル比となるように混合し、十分に摩砕した。これを１０００℃の温度で２４時間焼成し、ニオブ酸ランタンアルカリ金属塩粉末（ＫＬａＮｂ２Ｏ７）を得た。
前記の粉末１ｇに対して、１規定の塩酸１００ｃｍ３を加え、１日間室温で撹拌しながら反応させ、沈降した固形分を残して上澄みを捨てた。次に、得られた固形分に対して同様の処理を９回行い、その後、水洗、乾燥して、カリウムイオンを水素イオンで置換した層状ニオブ酸ランタンの粉末を得た。
次いで、層状ニオブ酸ランタンの粉末０．４ｇを、層状ニオブ酸ランタン中のＨ＋量に対して１中和当量の水酸化テトラブチルアンモニウムを溶解した水溶液０．１リットルに加え層間を膨潤させ、シェーカーで１５０回転／分程度の振とうを１０日間行って層間を剥離して、乳白色の薄片状ニオブ酸ランタン水性分散体（試料ｂ）を得た。
次に、試料ｂを遠心分離機（日立工機株式会社製、CP 100MX）を使用して、１５０００ｒｐｍ、３０分間遠心分離した。透明な上澄みを捨て、捨てた上澄みと同量のジメチルスルホキシドを追加して軽く振とうして、薄片状ニオブ酸ランタンの有機溶媒分散体（試料Ｂ）を得た。試料Ｂは、無色透明ではなく、試料ｂと同様の色を呈していた。
Example 2
Potassium carbonate (K 2 CO 3 ), lanthanum oxide (La 2 O 3 ), and niobium oxide (Nb 2 O 5 ) were mixed at a molar ratio of KLaNb 2 O 7 and thoroughly ground. This was calcined at a temperature of 1000 ° C. for 24 hours to obtain a lanthanum niobate alkali metal salt powder (KLaNb 2 O 7 ).
To 1 g of the above powder, 100 cm 3 of 1N hydrochloric acid was added and allowed to react with stirring at room temperature for 1 day, and the supernatant was discarded leaving the precipitated solid content. Next, the obtained solid content was subjected to the same treatment nine times, and then washed with water and dried to obtain a layered lanthanum niobate powder in which potassium ions were replaced with hydrogen ions.
Next, 0.4 g of layered lanthanum niobate powder was added to 0.1 liter of an aqueous solution in which 1 neutralization equivalent of tetrabutylammonium hydroxide was dissolved with respect to the amount of H + in the layered lanthanum niobate, and the layers were swollen. The layer was peeled off by shaking at about 150 rpm for 10 days with a shaker to obtain a milky white flaky lanthanum niobate aqueous dispersion (sample b).
Next, the sample b was centrifuged at 15000 rpm for 30 minutes using a centrifuge (manufactured by Hitachi Koki Co., Ltd., CP 100MX). The transparent supernatant was discarded, the same amount of dimethyl sulfoxide as the discarded supernatant was added, and the mixture was gently shaken to obtain an organic solvent dispersion of flaky lanthanum niobate (sample B). Sample B was not colorless and transparent, and had the same color as sample b.
実施例３
炭酸カリウム（Ｋ２ＣＯ３）と酸化ランタン（Ｌａ２Ｏ３）と酸化ユウロピウム（Ｅｕ２Ｏ３）と酸化ニオブ（Ｎｂ２Ｏ５）をＫＬａ０．９０Ｅｕ０．０５Ｎｂ２Ｏ７のモル比となるように混合し、十分に摩砕した。これを１１５０℃の温度で１時間焼成し、ニオブ酸ランタンユウロピウムアルカリ金属塩粉末（ＫＬａ０．９０Ｅｕ０．０５Ｎｂ２Ｏ７）を得た。
前記の粉末１ｇに対して、１規定の塩酸１００ｃｍ３を加え、１日間室温で撹拌しながら反応させ、沈降した固形分を残して上澄みを捨てた。次に、得られた固形分に対して同様の処理を９回行い、その後、水洗、乾燥して、カリウムイオンを水素イオンで置換した層状ニオブ酸ランタンユウロピウム化合物の粉末を得た。
次いで、層状ニオブ酸ランタンユウロピウムの粉末０．４ｇを、層状ニオブ酸ランタンユウロピウム中のＨ＋量に対して１中和当量の水酸化テトラブチルアンモニウムを溶解した水溶液０．１リットルに加え層間を膨潤させ、シェーカーで１５０回転／分程度の振とうを１０日間行って層間を剥離して、乳白色の薄片状ニオブ酸ランタンユウロピウム水性分散体（試料ｃ）を得た。
次に、試料ｃを遠心分離機（日立工機株式会社製、CP 100MX）を使用して、１５０００ｒｐｍ、３０分間遠心分離した。透明な上澄みを捨て、捨てた上澄みと同量のジメチルスルホキシドを追加して軽く振とうして、薄片状ニオブ酸ランタンユウロピウムの有機溶媒分散体（試料Ｃ）を得た。試料Ｃは、無色透明ではなく、試料ｃと同様の色を呈していた。
Example 3
Potassium carbonate (K 2 CO 3 ), lanthanum oxide (La 2 O 3 ), europium oxide (Eu 2 O 3 ) and niobium oxide (Nb 2 O 5 ) in moles of KLa 0.90 Eu 0.05 Nb 2 O 7 Mix to ratio and triturate well. This was calcined at a temperature of 1150 ° C. for 1 hour to obtain a lanthanum europium alkali metal salt metal powder (KLa 0.90 Eu 0.05 Nb 2 O 7 ).
To 1 g of the above powder, 100 cm 3 of 1N hydrochloric acid was added and allowed to react with stirring at room temperature for 1 day, and the supernatant was discarded leaving the precipitated solid content. Next, the same treatment was performed 9 times on the obtained solid content, and then washed with water and dried to obtain a powder of layered lanthanum europium niobate compound in which potassium ions were replaced with hydrogen ions.
Next, 0.4 g of layered lanthanum europium niobate powder was added to 0.1 liter of an aqueous solution in which tetrabutylammonium hydroxide equivalent to 1 neutralization equivalent was dissolved in the amount of H + in the layered lanthanum europium niobate, and the layers were swollen. The layer was peeled off by shaking at about 150 rpm for 10 days with a shaker to obtain a milky white flaky lanthanum europium niobate aqueous dispersion (sample c).
Next, the sample c was centrifuged at 15000 rpm for 30 minutes using a centrifuge (manufactured by Hitachi Koki Co., Ltd., CP 100MX). The transparent supernatant was discarded, the same amount of dimethyl sulfoxide as the discarded supernatant was added, and the mixture was shaken lightly to obtain an organic solvent dispersion (sample C) of flaky lanthanum europium niobate. Sample C was not colorless and transparent, and had the same color as sample c.
実施例４
炭酸カリウム（Ｋ２ＣＯ３）と炭酸ストロンチウム（ＳｒＣＯ３）と酸化ニオブ（Ｎｂ２Ｏ５）をＫＳｒ２Ｎｂ３Ｏ１０のモル比となるように混合し、十分に摩砕した。これを１２００℃の温度で１２時間焼成し、ニオブ酸ストロンチウムアルカリ金属塩粉末（ＫＳｒ２Ｎｂ３Ｏ１０）を得た。
前記の粉末１ｇに対して、１規定の塩酸１００ｃｍ３を加え、１日間室温で撹拌しながら反応させ、沈降した固形分を残して上澄みを捨てた。次に、得られた固形分に対して同様の処理を９回行い、その後、水洗、乾燥して、カリウムイオンを水素イオンで置換した層状ニオブ酸ストロンチウムの粉末を得た。
次いで、層状ニオブ酸ストロンチウムの粉末０．４ｇを、層状ニオブ酸ストロンチウム中のＨ＋量に対して１中和当量の水酸化テトラブチルアンモニウムを溶解した水溶液０．１リットルに加え層間を膨潤させ、シェーカーで１５０回転／分程度の振とうを１０日間行って層間を剥離して、乳白色の薄片状ニオブ酸ストロンチウム水性分散体（試料ｄ）を得た。
次に、試料ｄを遠心分離機（日立工機株式会社製、CP 100MX）を使用して、１５０００ｒｐｍ、３０分間遠心分離した。透明な上澄みを捨て、捨てた上澄みと同量のジメチルスルホキシドを追加して軽く振とうして、薄片状ニオブ酸ストロンチウムの有機溶媒分散体（試料Ｄ）を得た。試料Ｄは、無色透明ではなく、試料ｄと同様の色を呈していた。
Example 4
Potassium carbonate (K 2 CO 3 ), strontium carbonate (SrCO 3 ), and niobium oxide (Nb 2 O 5 ) were mixed in a molar ratio of KSr 2 Nb 3 O 10 and thoroughly ground. This was calcined at a temperature of 1200 ° C. for 12 hours to obtain a strontium niobate alkali metal salt powder (KSr 2 Nb 3 O 10 ).
To 1 g of the above powder, 100 cm 3 of 1N hydrochloric acid was added and allowed to react with stirring at room temperature for 1 day, and the supernatant was discarded leaving the precipitated solid content. Next, the obtained solid content was subjected to the same treatment nine times, then washed with water and dried to obtain a layered strontium niobate powder in which potassium ions were replaced with hydrogen ions.
Next, 0.4 g of the layered strontium niobate powder was added to 0.1 liter of an aqueous solution in which 1 neutralization equivalent of tetrabutylammonium hydroxide was dissolved with respect to the amount of H + in the layered strontium niobate, and the layers were swollen. The layer was peeled off by shaking at about 150 rpm for 10 days with a shaker to obtain a milky white flaky strontium niobate aqueous dispersion (sample d).
Next, the sample d was centrifuged at 15000 rpm for 30 minutes using a centrifuge (manufactured by Hitachi Koki Co., Ltd., CP 100MX). The transparent supernatant was discarded, the same amount of dimethyl sulfoxide as the discarded supernatant was added, and the mixture was gently shaken to obtain an organic solvent dispersion of flaky strontium niobate (sample D). Sample D was not colorless and transparent, and had the same color as sample d.
実施例５〜８
実施例１〜４において、使用した有機溶媒をジメチルスルホキシドからアセトニトリルに代えること以外は同様の方法を用いて、それぞれの有機溶媒分散体（試料Ａ１〜Ｄ１）を得た。
Examples 5-8
In Examples 1 to 4, respective organic solvent dispersions (samples A1 to D1) were obtained using the same method except that the organic solvent used was changed from dimethyl sulfoxide to acetonitrile.
前記の試料Ａ１〜Ｄ１にアセトニトリルを追加して２５０倍希釈ゾルとした後、分光光度計（日立ハイテクノロジーズ製、U-4000）を用いて吸光度を測定した。また実施例１〜４にて作成した水性分散体（試料ａ〜ｄ）に純水を加えて２５０倍希釈した水溶液について、同様の吸光度測定を行った。その結果を併せて図１〜４に示す。図中、実線は有機溶媒分散体の吸光度を示し、破線は水性分散体の吸光度を示す。有機溶媒分散体のスペクトルプロファイルと水系分散体のパターンが一致することから、それぞれの薄片状ペロブスカイト酸化物は有機溶媒中においても水と同様の分散状態を示すことが示唆された。なお、有機溶媒分散体で見られる２１０ｎｍ付近の吸光度減少は溶媒の影響によるものと考えられる。 Acetonitrile was added to the samples A1 to D1 to form a 250-fold diluted sol, and the absorbance was measured using a spectrophotometer (manufactured by Hitachi High-Technologies Corporation, U-4000). Further, the same absorbance measurement was performed on the aqueous solutions prepared by adding pure water to the aqueous dispersions (samples a to d) prepared in Examples 1 to 4 and diluted 250 times. The results are also shown in FIGS. In the figure, the solid line indicates the absorbance of the organic solvent dispersion, and the broken line indicates the absorbance of the aqueous dispersion. Since the spectrum profile of the organic solvent dispersion and the pattern of the aqueous dispersion coincided, it was suggested that each flaky perovskite oxide exhibits a dispersion state similar to water in the organic solvent. Note that the decrease in absorbance near 210 nm observed in the organic solvent dispersion is considered to be due to the influence of the solvent.
（２）ペロブスカイト酸化物薄膜の調製 (2) Preparation of perovskite oxide thin film
実施例９〜１２
試料Ａ〜Ｄのそれぞれに４倍の重量のジメチルスルホキシドを追加して５倍希釈ゾルを作製した。その５倍希釈ゾルをシリコンウェハーにディップコートし、室温で溶媒を揮発させて、ニオブ酸カルシウム膜（試料Ａ２）、ニオブ酸ランタン膜（試料Ｂ２）、ニオブ酸ランタンユウロピウム膜（試料Ｃ２）、ニオブ酸ストロンチウム膜（試料Ｄ２）を得た。
Examples 9-12
A 4-fold weight dimethyl sulfoxide was added to each of the samples A to D to prepare a 5-fold diluted sol. The silicon wafer is dip-coated with the 5-fold diluted sol, and the solvent is volatilized at room temperature to obtain a calcium niobate film (sample A2), a lanthanum niobate film (sample B2), a lanthanum europium niobate film (sample C2), niobium A strontium acid film (sample D2) was obtained.
試料Ａ２〜Ｄ２の薄片状酸化物の配列を走査プローブ顕微鏡により観察した。試料の写真を図５〜図８に示す。図５〜図８を見ると、得られた酸化物膜はサブミクロン〜ミクロンオーダーの幅および長さを有するシート状の酸化物が隙間なく敷き詰められた状態となっていることが分かる。画像解析からシート状酸化物の厚さは１ｎｍ〜３ｎｍ、酸化物による基板の被覆率はいずれも９０％以上であった。走査プローブ顕微鏡観察の結果から、実施例に記載の方法により、各種薄片状ペロブスカイト酸化物が原子にして数個分の厚みしか有さない状態で均一に分散している有機溶媒分散体が作製可能であることが確認された。またこの有機溶媒分散体を基板にディップコートするだけで薄片状酸化物が稠密に配列した酸化物薄膜が作製可能であることが確認された。 The arrangement of the flaky oxides of Samples A2 to D2 was observed with a scanning probe microscope. Photographs of the samples are shown in FIGS. 5 to 8, it can be seen that the obtained oxide film is in a state in which sheet-like oxides having a width and length on the order of submicron to micron are spread without gaps. From the image analysis, the thickness of the sheet oxide was 1 nm to 3 nm, and the coverage of the substrate with the oxide was 90% or more. From the results of scanning probe microscope observation, it is possible to produce an organic solvent dispersion in which various flaky perovskite oxides are uniformly dispersed in a state of having only a few thicknesses as atoms by the method described in the examples. It was confirmed that. It was also confirmed that an oxide thin film in which flaky oxides were densely arranged could be produced simply by dip-coating this organic solvent dispersion on a substrate.
本発明の薄片状ペロブスカイト酸化物の有機溶剤分散体は、例えば、光触媒、紫外線遮蔽剤、透明性材料、反射防止材料、ガスバリヤー性材料、誘電体、圧電体等のファインセラミックス材料、光電変換材料、フォトクロミック材料、導電性材料、赤外線反射材料、磁性半導体、電池の電極材料、各種センサー、更には他物質の配向結晶成長のためのシードレイヤー等の種々の用途に用いることができるペロブスカイト酸化物薄膜を作製するために、有用である。 The organic solvent dispersion of the flaky perovskite oxide of the present invention includes, for example, a photocatalyst, an ultraviolet shielding agent, a transparent material, an antireflection material, a gas barrier material, a dielectric material, a fine ceramic material such as a piezoelectric material, and a photoelectric conversion material. Perovskite oxide thin films that can be used for various applications such as seed layers for oriented crystal growth of other materials, photochromic materials, conductive materials, infrared reflective materials, magnetic semiconductors, battery electrode materials, various sensors Is useful for making.
Claims (16)
前記水性分散体から薄片状ペロブスカイト酸化物粒子を含む固形分を抽出する第二工程、及び
前記固形分を有機溶媒に分散させる第三工程、
を含む有機溶媒分散体の製造方法。 A first step of producing an aqueous dispersion of flaky perovskite oxide particles by contacting the layered perovskite oxide particles with an organic cation and peeling off the layered structure;
A second step of extracting solids containing flaky perovskite oxide particles from the aqueous dispersion, and a third step of dispersing the solids in an organic solvent,
The manufacturing method of the organic-solvent dispersion containing this.
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