JP2014229690A - Piezoelectric element and method for manufacturing the same - Google Patents
Piezoelectric element and method for manufacturing the same Download PDFInfo
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- JP2014229690A JP2014229690A JP2013107011A JP2013107011A JP2014229690A JP 2014229690 A JP2014229690 A JP 2014229690A JP 2013107011 A JP2013107011 A JP 2013107011A JP 2013107011 A JP2013107011 A JP 2013107011A JP 2014229690 A JP2014229690 A JP 2014229690A
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- 238000000034 method Methods 0.000 title claims description 62
- 238000004519 manufacturing process Methods 0.000 title claims description 41
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- 150000001875 compounds Chemical class 0.000 claims abstract description 73
- 239000013078 crystal Substances 0.000 claims abstract description 70
- 229910052984 zinc sulfide Inorganic materials 0.000 claims abstract description 66
- 239000002245 particle Substances 0.000 claims abstract description 34
- 239000002861 polymer material Substances 0.000 claims abstract description 21
- 239000002585 base Substances 0.000 claims description 55
- 238000000576 coating method Methods 0.000 claims description 50
- 239000000126 substance Substances 0.000 claims description 49
- 239000000758 substrate Substances 0.000 claims description 45
- 239000011248 coating agent Substances 0.000 claims description 43
- 238000001035 drying Methods 0.000 claims description 41
- 238000010304 firing Methods 0.000 claims description 26
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- 229920001721 polyimide Polymers 0.000 claims description 18
- 238000002360 preparation method Methods 0.000 claims description 17
- -1 polyethylene terephthalate Polymers 0.000 claims description 14
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 9
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 9
- 239000002033 PVDF binder Substances 0.000 claims description 6
- 239000004696 Poly ether ether ketone Substances 0.000 claims description 6
- 239000004697 Polyetherimide Substances 0.000 claims description 6
- 239000004734 Polyphenylene sulfide Substances 0.000 claims description 6
- 229910052783 alkali metal Inorganic materials 0.000 claims description 6
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 6
- 229910052795 boron group element Inorganic materials 0.000 claims description 6
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 6
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 6
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 6
- 229920001230 polyarylate Polymers 0.000 claims description 6
- 229920002530 polyetherether ketone Polymers 0.000 claims description 6
- 229920001601 polyetherimide Polymers 0.000 claims description 6
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 6
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- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 6
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 6
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 6
- 238000004528 spin coating Methods 0.000 claims description 6
- 150000001340 alkali metals Chemical class 0.000 claims description 5
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 5
- 229910004613 CdTe Inorganic materials 0.000 claims description 4
- 229910007709 ZnTe Inorganic materials 0.000 claims description 4
- UHYPYGJEEGLRJD-UHFFFAOYSA-N cadmium(2+);selenium(2-) Chemical compound [Se-2].[Cd+2] UHYPYGJEEGLRJD-UHFFFAOYSA-N 0.000 claims description 4
- SBIBMFFZSBJNJF-UHFFFAOYSA-N selenium;zinc Chemical compound [Se]=[Zn] SBIBMFFZSBJNJF-UHFFFAOYSA-N 0.000 claims description 4
- 239000004793 Polystyrene Substances 0.000 claims description 3
- 239000004760 aramid Substances 0.000 claims description 3
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- 238000010292 electrical insulation Methods 0.000 abstract description 21
- 230000006866 deterioration Effects 0.000 abstract description 2
- 239000010408 film Substances 0.000 description 149
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 35
- 239000011701 zinc Substances 0.000 description 20
- 239000011787 zinc oxide Substances 0.000 description 17
- 238000000224 chemical solution deposition Methods 0.000 description 15
- 229910052751 metal Inorganic materials 0.000 description 12
- 239000002184 metal Substances 0.000 description 12
- 239000002904 solvent Substances 0.000 description 11
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 10
- 239000012298 atmosphere Substances 0.000 description 9
- 238000009826 distribution Methods 0.000 description 9
- 238000004544 sputter deposition Methods 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 6
- 238000010586 diagram Methods 0.000 description 6
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 5
- 239000007772 electrode material Substances 0.000 description 5
- 239000003381 stabilizer Substances 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- 239000011575 calcium Substances 0.000 description 4
- 239000011261 inert gas Substances 0.000 description 4
- 239000011777 magnesium Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 229910052725 zinc Inorganic materials 0.000 description 4
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 229910002601 GaN Inorganic materials 0.000 description 3
- JMASRVWKEDWRBT-UHFFFAOYSA-N Gallium nitride Chemical compound [Ga]#N JMASRVWKEDWRBT-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 229910052950 sphalerite Inorganic materials 0.000 description 3
- YZYKBQUWMPUVEN-UHFFFAOYSA-N zafuleptine Chemical compound OC(=O)CCCCCC(C(C)C)NCC1=CC=C(F)C=C1 YZYKBQUWMPUVEN-UHFFFAOYSA-N 0.000 description 3
- XNDZQQSKSQTQQD-UHFFFAOYSA-N 3-methylcyclohex-2-en-1-ol Chemical compound CC1=CC(O)CCC1 XNDZQQSKSQTQQD-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 2
- 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 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 229910052788 barium Inorganic materials 0.000 description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 150000001925 cycloalkenes Chemical class 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 229910052733 gallium Inorganic materials 0.000 description 2
- CHPZKNULDCNCBW-UHFFFAOYSA-N gallium nitrate Chemical compound [Ga+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O CHPZKNULDCNCBW-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910001026 inconel Inorganic materials 0.000 description 2
- 229910052738 indium Inorganic materials 0.000 description 2
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 2
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- MFUVDXOKPBAHMC-UHFFFAOYSA-N magnesium;dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MFUVDXOKPBAHMC-UHFFFAOYSA-N 0.000 description 2
- 239000008204 material by function Substances 0.000 description 2
- 238000001451 molecular beam epitaxy Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 230000002265 prevention Effects 0.000 description 2
- 238000004549 pulsed laser deposition Methods 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 229910052712 strontium Inorganic materials 0.000 description 2
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 2
- DHEQXMRUPNDRPG-UHFFFAOYSA-N strontium nitrate Chemical compound [Sr+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DHEQXMRUPNDRPG-UHFFFAOYSA-N 0.000 description 2
- 238000010897 surface acoustic wave method Methods 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- LJDSTRZHPWMDPG-UHFFFAOYSA-N 2-(butylamino)ethanol Chemical compound CCCCNCCO LJDSTRZHPWMDPG-UHFFFAOYSA-N 0.000 description 1
- PIGFYZPCRLYGLF-UHFFFAOYSA-N Aluminum nitride Chemical compound [Al]#N PIGFYZPCRLYGLF-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- NGMCLZSBKVXVQH-UHFFFAOYSA-N O.O.[Li].C(C)(=O)O Chemical compound O.O.[Li].C(C)(=O)O NGMCLZSBKVXVQH-UHFFFAOYSA-N 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 description 1
- HDYRYUINDGQKMC-UHFFFAOYSA-M acetyloxyaluminum;dihydrate Chemical compound O.O.CC(=O)O[Al] HDYRYUINDGQKMC-UHFFFAOYSA-M 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001339 alkali metal compounds Chemical class 0.000 description 1
- 150000001341 alkaline earth metal compounds Chemical class 0.000 description 1
- 229940009827 aluminum acetate Drugs 0.000 description 1
- 229940063656 aluminum chloride Drugs 0.000 description 1
- 238000003491 array Methods 0.000 description 1
- ITHZDDVSAWDQPZ-UHFFFAOYSA-L barium acetate Chemical compound [Ba+2].CC([O-])=O.CC([O-])=O ITHZDDVSAWDQPZ-UHFFFAOYSA-L 0.000 description 1
- XQKKWWCELHKGKB-UHFFFAOYSA-L calcium acetate monohydrate Chemical compound O.[Ca+2].CC([O-])=O.CC([O-])=O XQKKWWCELHKGKB-UHFFFAOYSA-L 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- YZZFBYAKINKKFM-UHFFFAOYSA-N dinitrooxyindiganyl nitrate;hydrate Chemical compound O.[In+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YZZFBYAKINKKFM-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 229920005570 flexible polymer Polymers 0.000 description 1
- 229940044658 gallium nitrate Drugs 0.000 description 1
- UPWPDUACHOATKO-UHFFFAOYSA-K gallium trichloride Chemical compound Cl[Ga](Cl)Cl UPWPDUACHOATKO-UHFFFAOYSA-K 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- PSCMQHVBLHHWTO-UHFFFAOYSA-K indium(iii) chloride Chemical compound Cl[In](Cl)Cl PSCMQHVBLHHWTO-UHFFFAOYSA-K 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- IAQLJCYTGRMXMA-UHFFFAOYSA-M lithium;acetate;dihydrate Chemical compound [Li+].O.O.CC([O-])=O IAQLJCYTGRMXMA-UHFFFAOYSA-M 0.000 description 1
- 229940097364 magnesium acetate tetrahydrate Drugs 0.000 description 1
- XKPKPGCRSHFTKM-UHFFFAOYSA-L magnesium;diacetate;tetrahydrate Chemical compound O.O.O.O.[Mg+2].CC([O-])=O.CC([O-])=O XKPKPGCRSHFTKM-UHFFFAOYSA-L 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 238000005240 physical vapour deposition Methods 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920000307 polymer substrate Polymers 0.000 description 1
- 235000011056 potassium acetate Nutrition 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000029058 respiratory gaseous exchange Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- RXSHXLOMRZJCLB-UHFFFAOYSA-L strontium;diacetate Chemical compound [Sr+2].CC([O-])=O.CC([O-])=O RXSHXLOMRZJCLB-UHFFFAOYSA-L 0.000 description 1
- 125000001174 sulfone group Chemical group 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- RMZAYIKUYWXQPB-UHFFFAOYSA-N trioctylphosphane Chemical compound CCCCCCCCP(CCCCCCCC)CCCCCCCC RMZAYIKUYWXQPB-UHFFFAOYSA-N 0.000 description 1
- GPTWCNIDKQZDFF-UHFFFAOYSA-H trizinc;diphosphate;hydrate Chemical compound O.[Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O GPTWCNIDKQZDFF-UHFFFAOYSA-H 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 210000000707 wrist Anatomy 0.000 description 1
- 239000011667 zinc carbonate Substances 0.000 description 1
- 235000004416 zinc carbonate Nutrition 0.000 description 1
- 229910000010 zinc carbonate Inorganic materials 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- JDLYKQWJXAQNNS-UHFFFAOYSA-L zinc;dibenzoate Chemical compound [Zn+2].[O-]C(=O)C1=CC=CC=C1.[O-]C(=O)C1=CC=CC=C1 JDLYKQWJXAQNNS-UHFFFAOYSA-L 0.000 description 1
- RNZCSKGULNFAMC-UHFFFAOYSA-L zinc;hydrogen sulfate;hydroxide Chemical compound O.[Zn+2].[O-]S([O-])(=O)=O RNZCSKGULNFAMC-UHFFFAOYSA-L 0.000 description 1
- NHXVNEDMKGDNPR-UHFFFAOYSA-N zinc;pentane-2,4-dione Chemical compound [Zn+2].CC(=O)[CH-]C(C)=O.CC(=O)[CH-]C(C)=O NHXVNEDMKGDNPR-UHFFFAOYSA-N 0.000 description 1
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Abstract
Description
本発明は、圧電体素子、およびその製造方法に関する。 The present invention relates to a piezoelectric element and a manufacturing method thereof.
昨今、薄膜状の圧電体を用いた圧電体素子が注目されている。特に、六方晶系ウルツ鉱型結晶構造を取る酸化亜鉛（ＺｎＯ）系、窒化アルミニウム（ＡｌＮ）系、窒化ガリウム（ＧａＮ）系化合物等の化合物を膜状にしたウルツ鉱型結晶膜からなる圧電体膜およびこの圧電体膜を用いた圧電体素子が注目されている。 In recent years, a piezoelectric element using a thin film-like piezoelectric body has attracted attention. In particular, a piezoelectric body comprising a wurtzite crystal film in which a compound such as a zinc oxide (ZnO), aluminum nitride (AlN), or gallium nitride (GaN) compound having a hexagonal wurtzite crystal structure is formed into a film. A film and a piezoelectric element using this piezoelectric film have attracted attention.
例えば、ＺｎＯ圧電体膜は、表面弾性波（ＳＡＷ）素子として実用化され、またエンジン用燃焼圧センサへの応用が提案されている（非特許文献１参照）。ＡｌＮ圧電体膜はバルク弾性波（ＢＡＷ）フィルタとして実用化されている。また、ＺｎＯナノワイヤーアレイを基にした圧電性ナノ発電機の展望として、風、波、体の動き、交通など機械的エネルギーからの発電が提案されている（非特許文献２参照）。 For example, a ZnO piezoelectric film has been put into practical use as a surface acoustic wave (SAW) element, and application to a combustion pressure sensor for engines has been proposed (see Non-Patent Document 1). The AlN piezoelectric film has been put into practical use as a bulk acoustic wave (BAW) filter. As a prospect of piezoelectric nanogenerators based on ZnO nanowire arrays, power generation from mechanical energy such as wind, waves, body movements, and traffic has been proposed (see Non-Patent Document 2).
ウルツ鉱型結晶は、ｃ軸に沿った［０００１］および［０００−１］の２つの極性方向を有する。例えば、図９にウルツ鉱型ＺｎＯ結晶を示す。ＺｎＯ膜が、基材面から垂直方向に（０００１）面が配向した場合にはＺｎ極性を、基材面から垂直方向に（０００−１）面が配向した場合にはＯ極性を有する。ウルツ鉱型結晶膜の圧電応答特性は、極性分布割合に直線的に依存するため（非特許文献３参照）、極性分布割合を制御することは、ウルツ鉱型結晶膜の圧電特性を制御し向上させるための重要な要素である。 Wurtzite crystals have two polar directions [0001] and [000-1] along the c-axis. For example, FIG. 9 shows a wurtzite type ZnO crystal. The ZnO film has Zn polarity when the (0001) plane is oriented in the vertical direction from the substrate surface, and O polarity when the (000-1) plane is oriented in the vertical direction from the substrate surface. Since the piezoelectric response characteristics of the wurtzite crystal film linearly depend on the polarity distribution ratio (see Non-Patent Document 3), controlling the polarity distribution ratio controls and improves the piezoelectric characteristics of the wurtzite crystal film. It is an important element for making it happen.
ウルツ鉱型結晶からなる圧電体膜の製造方法として、主にスパッタ法、その他、ＰＬＤ（Ｐｕｌｓｅｄ Ｌａｓｅｒ Ｄｅｐｏｓｉｔｉｏｎ）法、ＭＢＥ（Ｍｏｌｅｃｕｌａｒ Ｂｅａｍ Ｅｐｉｔａｘｙ）法、ＣＶＤ（Ｃｈｅｍｉｃａｌ Ｖａｐｏｒ Ｄｅｐｏｓｉｔｉｏｎ）法等が知られている。 As a method for producing a piezoelectric film made of wurtzite crystal, a sputtering method, a PLD (Pulsed Laser Deposition) method, an MBE (Molecular Beam Epitaxy) method, a CVD (Chemical Vapor Deposition) method, etc. are known. .
しかしながら、これらの製造方法は真空チャンバーもしくは一般的なチャンバーを必要とするため、大面積の基材上に圧電体膜を成膜することが難しく、また装置導入などの経費も掛かるため、上記の製造方法で得られる圧電体膜は高価であるという問題点を有している。さらに、小規模生産や多品種生産に対応することが難しいという問題点もある。 However, since these manufacturing methods require a vacuum chamber or a general chamber, it is difficult to form a piezoelectric film on a large-area substrate, and the cost for introducing the apparatus is high. The piezoelectric film obtained by the manufacturing method has a problem that it is expensive. Furthermore, there is a problem that it is difficult to cope with small-scale production and multi-product production.
このため、低コストで大面積の基材上に成膜可能な実用的な成膜方法が強く求められている。このニーズに応える成膜方法として、化学溶液堆積法あるいはゾルゲル法と呼ばれる手法がある。本手法は、ウルツ鉱型結晶膜の成膜法として、透明導電膜や半導体素子等への応用を目指した研究開発が活発に行われている。 For this reason, there is a strong demand for a practical film forming method capable of forming a film on a large area substrate at low cost. As a film forming method that meets this need, there is a method called a chemical solution deposition method or a sol-gel method. This method has been actively researched and developed for application to transparent conductive films and semiconductor elements as a method for forming a wurtzite crystal film.
しかしながら、この化学溶液堆積法を用いた圧電体膜の成膜に関する報告は、かなり少ない。また、先述したように、圧電特性にとって重要な、ウルツ鉱型結晶膜の極性やその分布を、化学溶液堆積法で製造された膜に対して評価した報告は一報（非特許文献４）のみで、極性制御に関する知見はほとんどない。 However, there are quite a few reports on the formation of a piezoelectric film using this chemical solution deposition method. In addition, as described above, only one report (Non-patent Document 4) reports the evaluation of the polarity and distribution of the wurtzite crystal film, which is important for the piezoelectric characteristics, with respect to the film manufactured by the chemical solution deposition method. There is little knowledge about polarity control.
このように、圧電体膜の成膜においては、ｃ軸配向性だけでなく極性分布の制御までが求められるため、化学溶液堆積法は、これまで圧電体膜の成膜法としてはほとんど適用されてこなかった。 As described above, since the film formation of the piezoelectric film requires not only the c-axis orientation but also the control of the polarity distribution, the chemical solution deposition method has been mostly applied as a film formation method of the piezoelectric film so far. I did not come.
最近、ウルツ鉱型結晶膜からなる圧電体膜の新たな応用として、脈波や呼吸などの生体信号を検出するための生体センサへの応用が期待されている。生体センサは、センサ素子を、被験者の手首や胴体等に装着して使用される。このため、可撓性のある高分子基材上に成膜された圧電体膜が必要となる。 Recently, a new application of a piezoelectric film made of a wurtzite crystal film is expected to be applied to a biosensor for detecting a biosignal such as a pulse wave and respiration. A biosensor is used by attaching a sensor element to a wrist, a trunk, or the like of a subject. For this reason, a piezoelectric film formed on a flexible polymer substrate is required.
ここで、例えば、非特許文献６には、経済的に有利な化学溶液堆積法を用いて、ＩＴＯ（酸化インジウムスズ）／ＰＥＴ（Polyethylene terephthalate）基材上に粒子状構造を有するＺｎＯ圧電体膜を用いてフレキシブルな圧電体素子を作製することについて記載されている。ただし、非特許文献６に記載のＺｎＯ圧電体膜は、ＰＥＴ上に形成されたＩＴＯ下部電極上に作製され、さらに、ＺｎＯ圧電体膜上に上部電極が形成されている。このような圧電体膜のみを挟み込むように２つ電極が形成された圧電体素子の構造では、圧電体素子の圧電応答性の低下若しくは喪失するという問題が生じる。 Here, for example, Non-Patent Document 6 discloses a ZnO piezoelectric film having a particulate structure on an ITO (indium tin oxide) / PET (Polyethylene terephthalate) substrate by using an economically advantageous chemical solution deposition method. It describes that a flexible piezoelectric element is produced using the above. However, the ZnO piezoelectric film described in Non-Patent Document 6 is produced on an ITO lower electrode formed on PET, and further, an upper electrode is formed on the ZnO piezoelectric film. In the structure of a piezoelectric element in which two electrodes are formed so as to sandwich only such a piezoelectric film, there arises a problem that the piezoelectric response of the piezoelectric element is reduced or lost.
なぜなら、化学溶液堆積法で作製された膜は、一般的には、粒子が疎に充填した粒子状構造であるため、膜の上面から下面まで連続する間隙が存在する可能性が高く、このような間隙を有する膜に上部電極を形成すると、電極材料の成分である導電性化合物が上記間隙を通じて基材近傍若しくは基材上に堆積し、電極間の電気絶縁性の低下若しくは短絡を引き起こすためである。 This is because a film produced by chemical solution deposition generally has a granular structure in which particles are loosely filled, and therefore there is a high possibility that a continuous gap exists from the upper surface to the lower surface of the film. If the upper electrode is formed on a film having a large gap, the conductive compound that is a component of the electrode material is deposited in the vicinity of the base material or on the base material through the gap, causing a decrease in electrical insulation between the electrodes or a short circuit. is there.
圧電体素子の圧電応答性の低下若しくは喪失という問題は、圧電体膜中に問題となる間隙が１か所でも存在すると起こる。そのため、大面積の圧電体膜を成膜しそれを用いて作製された圧電体素子の場合には、より深刻な問題となる。また、このような問題は、スパッタ法を用いて製造された、ウルツ鉱型結晶からなる圧電体膜は、柱状晶からなる膜構造であるため、同様に起こりうる問題である。そのため、特許文献１に記載されているように、絶縁体であるポリイミド基材の直上に、ＡｌＮ圧電体膜が製造されている。しかしながら、スパッタ法を用いて製造された圧電体膜は、上述したように、その価格が高く、大面積のものを得ることが困難であるため、実用化を阻む大きな障壁となっている。 The problem of lowering or losing the piezoelectric response of the piezoelectric element occurs when there is even one problematic gap in the piezoelectric film. Therefore, in the case of a piezoelectric element produced by forming a large-area piezoelectric film and using it, it becomes a more serious problem. In addition, such a problem is a problem that can occur in the same manner because a piezoelectric film made of a wurtzite crystal manufactured by sputtering has a film structure made of columnar crystals. Therefore, as described in Patent Document 1, an AlN piezoelectric film is manufactured directly on a polyimide base material that is an insulator. However, as described above, the piezoelectric film manufactured by using the sputtering method is expensive, and it is difficult to obtain a film having a large area.
化学溶液堆積法を用いたＺｎＯ圧電体膜の製造に関する、そのほかの報告では、基材として、インコネル合金板やシリコン基板が用いられており、可撓性のある圧電体素子を提供していない。例えば、非特許文献４には、化学溶液堆積法を用いて、ウルツ鉱型結晶構造を有する化合物に他元素をドープすることにより、その極性分布割合を制御し、その結果、圧電特性向上したウルツ鉱型結晶膜、及びその製造方法について記載されているが、これは、インコネル合金板の基材上に、９２３Ｋの高温で焼成して製造するものである。すなわち、高分子基材の直上に圧電体膜を形成する手法として、化学溶液堆積法が用いられることはなかった。 In other reports regarding the production of ZnO piezoelectric films using chemical solution deposition, Inconel alloy plates and silicon substrates are used as substrates, and flexible piezoelectric elements are not provided. For example, in Non-Patent Document 4, a chemical solution deposition method is used to control the polarity distribution ratio by doping other elements into a compound having a wurtzite crystal structure, and as a result, wurtz with improved piezoelectric characteristics. An ore type crystal film and a manufacturing method thereof are described, but this is manufactured by firing at a high temperature of 923 K on a base material of an Inconel alloy plate. That is, the chemical solution deposition method has not been used as a method for forming a piezoelectric film directly on a polymer substrate.
本発明は、前記課題に鑑みてなされたもので、小規模生産や多品種生産に対応可能であること、電極間の電気絶縁性の低下や短絡の問題を解決すること、及び、大面積の基材上に経済的に成膜すること、の少なくとも１つを解決した、可撓性のある圧電体素子、及び当該圧電体素子の製造方法を提供することを目的とする。 The present invention has been made in view of the above-mentioned problems, is capable of dealing with small-scale production and multi-product production, solves the problem of electrical insulation degradation and short-circuit between electrodes, and has a large area. An object of the present invention is to provide a flexible piezoelectric element that solves at least one of economical film formation on a substrate and a method of manufacturing the piezoelectric element.
本発明の態様の１つは、少なくとも高分子材料を含む基材と、ウルツ鉱型結晶構造の化合物を含み、前記基材の直上に形成された圧電体膜と、を備え、前記圧電体膜は、前記基材面と垂直方向に少なくとも２つのウルツ鉱型結晶構造の化合物の粒子を充填及び堆積し、前記粒子が互いに結合してなる結合層を有することを特徴とする圧電体素子である。当該態様によれば、前記基材と前記圧電体膜を間に挟んで電極を形成した場合に、圧電体膜の上面から下面まで連続する間隙を通じて基材近傍若しくは基材上に電極材料の成分である導電性化合物が堆積したとしても、電極間の電気絶縁性の低下若しくは短絡を引き起こすおそれがない、可撓性を備えた圧電体素子を実現することができる。また、圧電体膜をスパッタ法にて形成すると、例えば非特許文献２で報告されているように前記基材面と垂直方向に１つの柱状晶が成長しその柱状晶の高さは膜厚に匹敵しているが、当該態様に係る圧電体素子は、前記基材面と垂直方向に少なくとも２つの粒子が充填及び堆積された構造であり、従来とは全く異なる構造の圧電体素子を実現できる。 One aspect of the present invention includes: a base material including at least a polymer material; and a piezoelectric film including a compound having a wurtzite crystal structure and formed directly on the base material. Is a piezoelectric element comprising a bonding layer formed by filling and depositing particles of a compound having a wurtzite crystal structure in a direction perpendicular to the substrate surface, and the particles are bonded to each other. . According to this aspect, when the electrode is formed with the base material and the piezoelectric film interposed therebetween, the component of the electrode material in the vicinity of the base material or on the base material through the gap continuous from the upper surface to the lower surface of the piezoelectric film Even if the conductive compound is deposited, it is possible to realize a flexible piezoelectric element that does not cause a decrease in electrical insulation between electrodes or cause a short circuit. Further, when the piezoelectric film is formed by the sputtering method, for example, as reported in Non-Patent Document 2, one columnar crystal grows in the direction perpendicular to the substrate surface, and the height of the columnar crystal is the film thickness. Although comparable, the piezoelectric element according to this aspect has a structure in which at least two particles are filled and deposited in a direction perpendicular to the base material surface, and a piezoelectric element having a completely different structure from the conventional one can be realized. .
本発明の選択的な態様の１つとして、前記基材は、１０８Ωｃｍ以上の電気抵抗を有することを特徴とする。当該態様によれば、前記基材と前記圧電体膜を間に挟んで電極を形成した場合に、圧電体膜の上面から下面まで連続する間隙を通じて基材近傍若しくは基材上に電極材料の成分である導電性化合物が堆積したとしても、電極間の電気絶縁性の低下若しくは短絡を引き起こすおそれがない圧電体素子を実現することが出来る。 As one of optional embodiments of the present invention, the substrate has an electric resistance of 10 8 Ωcm or more. According to this aspect, when the electrode is formed with the base material and the piezoelectric film interposed therebetween, the component of the electrode material in the vicinity of the base material or on the base material through the gap continuous from the upper surface to the lower surface of the piezoelectric film Even when the conductive compound is deposited, it is possible to realize a piezoelectric element that does not cause a decrease in electrical insulation between electrodes or cause a short circuit.
本発明の選択的な態様の１つとして、前記ウルツ鉱型結晶構造の化合物は、ＺｎＯ、ＺｎＳ、ＺｎＳｅ、ＺｎＴｅ、ＭｇＯ、ＣｄＯ、ＣｄＳ、ＣｄＳｅ、ＣｄＴｅ、ＡｌＮ、ＧａＮ、ＩｎＮ及びＩｎＰのうち少なくとも１つを含むことを特徴とする。当該態様によれば、圧電特性を示す圧電体膜を備えた圧電体素子を実現することができる。 As one of the selective embodiments of the present invention, the compound having the wurtzite crystal structure is at least one of ZnO, ZnS, ZnSe, ZnTe, MgO, CdO, CdS, CdSe, CdTe, AlN, GaN, InN, and InP. It is characterized by including one. According to this aspect, it is possible to realize a piezoelectric element including a piezoelectric film exhibiting piezoelectric characteristics.
本発明の選択的な態様の１つとして、前記高分子材料は、ポリイミド（ＰＩ）、アラミド（ＰＡ）、ポリフェニレンスルフィド（ＰＰＳ）、ポリエチレンナフタレート（ＰＥＮ）、ポリエーテルイミド（ＰＥＩ）、ポリエーテルサルフォン（ＰＥＳ）、ポリエチレンテレフタレート（ＰＥＴ）、ポリアリレート（ＰＡＲ）、ポリカーボネート（ＰＣ）、ポリメタクリル酸メチル（ＰＭＭＡ）、ポリスチレン（ＰＳ）、ポリエーテルエーテルケトン（ＰＥＥＫ）、ポリテトラフルオロエチレン（ＰＴＦＥ）、ポリジメチルシロキサン（ＰＤＭＳ）、ポリフッ化ビニリデン（ＰＶＤＦ）及びシクロオレフィン系ポリマーの少なくとも１種を含むことを特徴とする。当該態様によれば、前記基材が可撓性を有する圧電体素子を実現できる。 As one of the selective embodiments of the present invention, the polymer material is polyimide (PI), aramid (PA), polyphenylene sulfide (PPS), polyethylene naphthalate (PEN), polyetherimide (PEI), polyether. Sulphone (PES), polyethylene terephthalate (PET), polyarylate (PAR), polycarbonate (PC), polymethyl methacrylate (PMMA), polystyrene (PS), polyetheretherketone (PEEK), polytetrafluoroethylene (PTFE) ), Polydimethylsiloxane (PDMS), polyvinylidene fluoride (PVDF), and a cycloolefin-based polymer. According to this aspect, it is possible to realize a piezoelectric element in which the base material has flexibility.
本発明の選択的な態様の１つとして、前記ウルツ鉱型結晶構造の化合物は、他種元素を含むことを特徴とする。「他種元素」とは、前記ウルツ鉱型結晶構造の化合物に含まれる元素以外の元素を指す。当該態様によれば、前記他種元素が含むことにより、極性分布割合が高くなり、より高い圧電特性、電気特性、発光特性、化学的安定性等を有する圧電体膜を備えた圧電体素子を実現することができる。 As one of the selective embodiments of the present invention, the compound having the wurtzite crystal structure includes other kinds of elements. “Other element” refers to an element other than the element contained in the compound having the wurtzite crystal structure. According to the aspect, the piezoelectric element including the piezoelectric film having a higher polarity distribution ratio and higher piezoelectric characteristics, electrical characteristics, light emitting characteristics, chemical stability, and the like due to the inclusion of the other kinds of elements. Can be realized.
本発明の選択的な態様の１つとして、前記他種元素は、アルカリ金属元素、アルカリ土類金属元素及び第１３族元素の少なくとも１種を含むことを特徴とする。このような他種元素を含むことにより、圧電体膜がより高い極性分布割合を示すため、より高い圧電特性、電気特性、発光特性、化学的安定性等を有する圧電体素子を実現することができる。 As one of selective aspects of the present invention, the other species element includes at least one of an alkali metal element, an alkaline earth metal element, and a Group 13 element. By including such other elements, since the piezoelectric film exhibits a higher polarity distribution ratio, it is possible to realize a piezoelectric element having higher piezoelectric characteristics, electrical characteristics, light emission characteristics, chemical stability, and the like. it can.
本発明の選択的な態様の１つとして、前記圧電体膜及び前記基材を間に挟んで配置される、第１電極及び第２電極を更に備えることを特徴とする。当該態様によれば、電極間の電気絶縁性の低下や短絡のおそれが無い前記第１電極と前記第２電極を備えた圧電体素子を実現することができる。 One of the selective aspects of the present invention is characterized by further comprising a first electrode and a second electrode disposed with the piezoelectric film and the substrate interposed therebetween. According to this aspect, it is possible to realize a piezoelectric element including the first electrode and the second electrode that do not cause a decrease in electrical insulation between the electrodes or a short circuit.
本発明の他の態様は、ウルツ鉱型結晶構造を有する化合物を構成する元素種を含有する化学溶液を調製する調製工程と、少なくとも高分子材料を含む基材の上に、前記化学溶液を塗布する塗布工程と、前記塗布工程により形成した塗布膜を乾燥する乾燥工程と、前記乾燥工程により乾燥した塗布膜を焼成する焼成工程と、を含むことを特徴とする圧電体素子の製造方法である。当該製造方法によれば、可撓性を備えつつ、前記基材と前記圧電体膜を間に挟んで電極を形成した場合に、電極間の電気絶縁性の低下や短絡が防止される圧電体素子を製造することができる。 According to another aspect of the present invention, there is provided a preparation step of preparing a chemical solution containing an element species constituting a compound having a wurtzite crystal structure, and applying the chemical solution on a substrate containing at least a polymer material. A method for manufacturing a piezoelectric element, comprising: a coating step for drying; a drying step for drying the coating film formed by the coating step; and a firing step for firing the coating film dried by the drying step. . According to the manufacturing method, a piezoelectric body that is flexible and prevents a decrease in electrical insulation or a short circuit between the electrodes when the electrode is formed with the base material and the piezoelectric film interposed therebetween. An element can be manufactured.
本発明の選択的な態様の１つとして、前記調製工程において調製する前記化学溶液に、更に、前記元素種以外の他種元素を含有することを特徴とする。ウルツ鉱型結晶構造を有する化合物の薄膜を基材上に形成する場合、上述したようにスパッタ法で行われていたが、スパッタ法では単価が高価なターゲットを用いるため、成膜する圧電体膜を構成する元素や分子の構成比率の調整における自由度が低い。これに対し、化学溶液を用いる、いわゆる化学溶液堆積法であれば、化学溶液への他種元素の添加量の調整が容易であり、前記元素種に対する前記他種元素の比率の調整における自由度が大きく向上する。そして、前記元素種に前記他種元素を添加した化学溶液を用いた前記調整工程から前記焼成工程を経て製造される圧電体素子は、前記圧電体膜における極性分布割合の制御特性が向上し、圧電応答性が高い。また、電気特性、発光特性、化学的安定性及びエッチング特性も向上する。 As one of the selective aspects of the present invention, the chemical solution prepared in the preparation step further contains another kind of element other than the element kind. When a thin film of a compound having a wurtzite crystal structure is formed on a substrate, the sputtering method is used as described above. However, the sputtering method uses a target with an expensive unit price. The degree of freedom in adjusting the constituent ratio of the elements and molecules constituting the is low. In contrast, the so-called chemical solution deposition method using a chemical solution makes it easy to adjust the amount of other elements added to the chemical solution, and the degree of freedom in adjusting the ratio of the other elements to the element species. Is greatly improved. And the piezoelectric element manufactured through the baking process from the adjustment process using the chemical solution in which the other species element is added to the element type has improved control characteristics of the polarity distribution ratio in the piezoelectric film, High piezoelectric response. In addition, electrical characteristics, light emission characteristics, chemical stability, and etching characteristics are also improved.
本発明の選択的な態様の１つとして、前記焼成工程においては、前記基材の耐熱温度以下で、前記塗布膜を焼成することを特徴とする。また、本発明の選択的な態様の１つとして、前記乾燥工程においては、前記基材の耐熱温度以下で、前記塗布膜を乾燥することを特徴とする。これら態様に係る圧電体素子では、前記基材を熱で変質又は焼損させること無く、化学溶液堆積法にて前記基材の上に前記圧電体膜を形成することが出来る。 As one of selective aspects of the present invention, in the baking step, the coating film is baked at a temperature lower than the heat-resistant temperature of the base material. Moreover, as one of the selective aspects of the present invention, in the drying step, the coating film is dried at a temperature lower than the heat resistant temperature of the substrate. In the piezoelectric element according to these embodiments, the piezoelectric film can be formed on the base material by a chemical solution deposition method without causing the base material to be altered or burned by heat.
本発明の選択的な態様の１つとして、前記塗布工程における前記化学溶液の塗布は、スピンコート法、スプレーコート法、ディップコート法、ドクターブレード法、シルクスクリーン印刷法、またはインクジェット印刷法を用いて行われることを特徴とする。当該態様によれば、より均質で、且つ、信頼性の高い圧電体素子の製造方法を実現することができる。 As one of selective embodiments of the present invention, the chemical solution is applied in the application step by using a spin coating method, a spray coating method, a dip coating method, a doctor blade method, a silk screen printing method, or an ink jet printing method. It is characterized by being performed. According to this aspect, it is possible to realize a method for manufacturing a piezoelectric element that is more homogeneous and highly reliable.
なお、以上説明した圧電体素子は、他の機器に組み込まれた状態で実施されたり他の方法とともに実施されたりする等の各種の態様を含むものである。また、上述した圧電体素子の製造方法は、他の方法の一環として実施されたりする等の各種の態様を含むものである。 In addition, the piezoelectric element demonstrated above includes various aspects, such as being implemented in the state integrated in another apparatus, or being implemented with another method. The above-described method for manufacturing a piezoelectric element includes various aspects such as being carried out as part of another method.
本発明によれば、小規模生産や多品種生産に対応可能であること、電極間の電気絶縁性の低下や短絡の問題を解決すること、及び、大面積の基材上に経済的に成膜すること、の少なくとも１つを解決した、可撓性のある圧電体素子、及び当該圧電体素子の製造方法を提供することができる。 According to the present invention, it is possible to cope with small-scale production and multi-product production, to solve the problem of deterioration of electrical insulation between electrodes and short circuit, and economically on a large-area substrate. It is possible to provide a flexible piezoelectric element and a method for manufacturing the piezoelectric element, in which at least one of filming is solved.
以下、下記の順序に従って本発明を説明する。
（１）第１の実施形態：
（２）第２の実施形態：
（３）第３の実施形態：
（４）第４の実施形態：
（５）第５の実施形態：
（６）まとめ：
Hereinafter, the present invention will be described in the following order.
(1) First embodiment:
(2) Second embodiment:
(3) Third embodiment:
(4) Fourth embodiment:
(5) Fifth embodiment:
(6) Summary:
（１）第１の実施形態：
図１は、本実施形態に係る圧電体素子の断面を模式的に示した図である。同図に示すように、圧電体素子１００は、少なくとも高分子材料を含む基材１０と、ウルツ鉱型結晶構造の化合物を含み、基材１０の直上に直接形成された圧電体膜２０と、を備える。
(1) First embodiment:
FIG. 1 is a diagram schematically showing a cross section of the piezoelectric element according to the present embodiment. As shown in the figure, the piezoelectric element 100 includes a base material 10 containing at least a polymer material, a piezoelectric film 20 containing a compound having a wurtzite crystal structure, and formed directly on the base material 10; Is provided.
基材１０は、電気絶縁性を有することが好ましく、例えば、その電気抵抗を１０８Ωｃｍ以上とする。基材１０が電気絶縁性を有することにより、図２に示すように、電極間の電気絶縁性の低下若しくは短絡を防止できる。 The base material 10 preferably has electrical insulation, and for example, its electrical resistance is 10 8 Ωcm or more. When the base material 10 has electrical insulation, as shown in FIG. 2, the electrical insulation fall or short circuit between electrodes can be prevented.
図２は、電極間の電気絶縁性の低下若しくは短絡の防止を説明する図である。同図に示すように、圧電体膜２０と基材１０を挟んで両側に第１電極３０及び第２電極４０を形成した場合に、圧電体膜２０に亀裂や局所的に貫通する間隙５０のような欠陥が生じるおそれがある。 FIG. 2 is a diagram for explaining a reduction in electrical insulation between electrodes or prevention of a short circuit. As shown in the figure, when the first electrode 30 and the second electrode 40 are formed on both sides of the piezoelectric film 20 and the base material 10, the piezoelectric film 20 is cracked or has a gap 50 that penetrates locally. Such a defect may occur.
ここで、本実施形態に係る圧電体素子１００は、圧電体膜２０と第２電極４０の間に、電気絶縁性を有する基材１０が配置されている。従って、仮に、圧電体膜２０の間隙５０を通じて基材１０近傍若しくは基材１０上に電極材料の成分である導電性化合物が堆積しても、電極間の電気絶縁性の低下若しくは短絡を引き起こすおそれがない。 Here, in the piezoelectric element 100 according to the present embodiment, the base material 10 having electrical insulation is disposed between the piezoelectric film 20 and the second electrode 40. Therefore, even if a conductive compound that is a component of the electrode material is deposited near or on the base material 10 through the gap 50 of the piezoelectric film 20, there is a risk of causing a decrease in electrical insulation between the electrodes or a short circuit. There is no.
基材１０に含まれる高分子材料は、特に限定されるものではないが、ポリイミド（ＰＩ）、アラミド（ＰＡ）、ポリフェニレンスルフィド（ＰＰＳ）、ポリエチレンナフタレート（ＰＥＮ）、ポリエーテルイミド（ＰＥＩ）、ポリエーテルサルフォン（ＰＥＳ）、ポリエチレンテレフタレート（ＰＥＴ）、ポリアリレート（ＰＡＲ）、ポリカーボネート（ＰＣ）、ポリメタクリル酸メチル（ＰＭＭＡ）、ポリスチレン（ＰＳ）、ポリエーテルエーテルケトン（ＰＥＥＫ）、ポリテトラフルオロエチレン（ＰＴＦＥ）、ポリジメチルシロキサン（ＰＤＭＳ）、ポリフッ化ビニリデン（ＰＶＤＦ）及びシクロオレフィン系ポリマー、の何れか又は組み合わせが例示される。 The polymer material contained in the substrate 10 is not particularly limited, but polyimide (PI), aramid (PA), polyphenylene sulfide (PPS), polyethylene naphthalate (PEN), polyetherimide (PEI), Polyethersulfone (PES), polyethylene terephthalate (PET), polyarylate (PAR), polycarbonate (PC), polymethyl methacrylate (PMMA), polystyrene (PS), polyetheretherketone (PEEK), polytetrafluoroethylene Any one or a combination of (PTFE), polydimethylsiloxane (PDMS), polyvinylidene fluoride (PVDF), and a cycloolefin-based polymer is exemplified.
基材１０は、このような高分子材料を含むことが、可撓性及び電気絶縁性の確保の観点から好ましい。また、基材１０は、このような高分子材料を主成分とすることが更に好ましい。ここで、「主成分」とは、高分子材料が略５０重量％以上含まれていることを指す。つまり、可撓性及び上述した電気絶縁性を有する材料であれば、高分子材料の含有率に関わらず、各種の材料を基材１０として用いることができる。例えば、ポリイミドマトリックス中にシリカナノ粒子を分散させた材料等のように、高分子材料と無機材料を複合化した材料も、基材１０として用いることができる。 The base material 10 preferably contains such a polymer material from the viewpoint of ensuring flexibility and electrical insulation. Further, it is more preferable that the base material 10 contains such a polymer material as a main component. Here, the “main component” means that approximately 50% by weight or more of the polymer material is contained. That is, as long as the material has flexibility and the above-described electrical insulation properties, various materials can be used as the base material 10 regardless of the content of the polymer material. For example, a material in which a polymer material and an inorganic material are combined, such as a material in which silica nanoparticles are dispersed in a polyimide matrix, can also be used as the substrate 10.
圧電体膜２０は、基材１０面と垂直方向に少なくとも２つのウルツ鉱型結晶構造の化合物の粒子２１を有し、粒子２１が互いに結合してなる結合層２２を有することが好ましい。粒子２１の粒子径ｄは、２〜１０００ｎｍの範囲であることが好ましい。粒子２１の形状は特に限定されない。 The piezoelectric film 20 preferably includes at least two wurtzite crystal structure compound particles 21 in a direction perpendicular to the surface of the base material 10, and a bonding layer 22 formed by bonding the particles 21 to each other. The particle diameter d of the particles 21 is preferably in the range of 2 to 1000 nm. The shape of the particle 21 is not particularly limited.
ウルツ鉱型結晶構造の化合物としては、特に限定されるものではないが、ＺｎＯ、ＺｎＳ、ＺｎＳｅ、ＺｎＴｅ、ＭｇＯ、ＣｄＯ、ＣｄＳ、ＣｄＳｅ、ＣｄＴｅ、ＡｌＮ、ＧａＮ、ＩｎＮ及びＩｎＰ、の何れか又は組み合わせが例示される。 The wurtzite crystal structure compound is not particularly limited, but any one or combination of ZnO, ZnS, ZnSe, ZnTe, MgO, CdO, CdS, CdSe, CdTe, AlN, GaN, InN, and InP. Is exemplified.
圧電体膜２０を構成するウルツ鉱型結晶構造の化合物は、ウルツ鉱型結晶構造の化合物の構成元素以外の他種元素を含んでいてもよい。圧電体膜２０を構成するウルツ鉱型結晶構造の化合物が他種元素を含むことにより、圧電体膜２０における極性分布割合の制御特性が向上し、圧電応答性が高い圧電体素子が実現される。なお、このようなウルツ鉱型結晶構造の化合物は、電気特性、発光特性、化学的安定性及びエッチング特性も向上する。 The compound of the wurtzite crystal structure that constitutes the piezoelectric film 20 may contain other elements than the constituent elements of the compound of the wurtzite crystal structure. When the compound of the wurtzite crystal structure that constitutes the piezoelectric film 20 contains other kinds of elements, the control characteristics of the polarity distribution ratio in the piezoelectric film 20 are improved, and a piezoelectric element having high piezoelectric response is realized. . Note that such a wurtzite crystal structure compound also improves electrical characteristics, light emission characteristics, chemical stability, and etching characteristics.
他種元素としては、特に限定されるものではないが、アルカリ金属元素、アルカリ土類金属元素及び第１３族元素、何れか又は組み合わせが例示される。他種元素としてのアルカリ金属元素は、リチウム（Ｌｉ）、ナトリウム（Ｎａ）及びカリウム（Ｋ）、が例示される。他種元素としてのアルカリ土類金属元素は、マグネシウム（Ｍｇ）、カルシウム（Ｃａ）、ストロンチウム（Ｓｒ）、バリウム（Ｂａ）が例示される。他種元素としての第１３族元素は、アルミニウム（Ａｌ）、ガリウム（Ｇａ）及びインジウム（Ｉｎ）が例示される。 Although it does not specifically limit as another kind element, An alkali metal element, an alkaline-earth metal element, a Group 13 element, or any combination is illustrated. Examples of the alkali metal element as the other species include lithium (Li), sodium (Na), and potassium (K). Examples of the alkaline earth metal element as the other element include magnesium (Mg), calcium (Ca), strontium (Sr), and barium (Ba). Examples of Group 13 elements as other elements include aluminum (Al), gallium (Ga), and indium (In).
他種元素の濃度は、ウルツ鉱型結晶構造の化合物と、当該他種元素との関係、目的とする応用物性に応じて設定すればよい。例えば、ウルツ鉱型結晶構造の化合物がＺｎＯで、他種元素がＬｉの場合には、ＺｎとＬｉの原子濃度の和に対して、Ｌｉの原子濃度が２〜７．５ａｔ．％の範囲内であることが好ましい。Ｌｉの原子濃度を、このような範囲内に設定することにより、圧電体膜における圧電応答性が向上し、より圧電応答性が高い圧電体素子が実現される。 What is necessary is just to set the density | concentration of another kind element according to the relationship between the compound of a wurtzite type crystal structure, the said other kind element, and the target applied physical property. For example, when the compound having a wurtzite crystal structure is ZnO and the other element is Li, the atomic concentration of Li is 2 to 7.5 at. % Is preferable. By setting the atomic concentration of Li within such a range, the piezoelectric response in the piezoelectric film is improved, and a piezoelectric element with higher piezoelectric response is realized.
圧電体膜２０を構成するウルツ鉱型結晶構造の化合物の電気抵抗率は、１×１０６Ωｃｍ以上であることが好ましく、１×１０７Ωｃｍ以上であることがより好ましい。このような範囲内に設定することにより、ウルツ鉱型結晶構造の化合物の圧電特性が向上し、より優れた圧電体膜２０を実現可能となる。 The electric resistivity of the compound having a wurtzite crystal structure constituting the piezoelectric film 20 is preferably 1 × 10 6 Ωcm or more, and more preferably 1 × 10 7 Ωcm or more. By setting within this range, the piezoelectric characteristics of the compound having a wurtzite crystal structure are improved, and a more excellent piezoelectric film 20 can be realized.
以上説明した本実施形態によれば、少なくとも高分子材料を含む基材１０と、ウルツ鉱型結晶構造の化合物を含み、基材１０の直上に直接形成された圧電体膜２０と、を備える圧電体素子１００が実現される。この圧電体素子１００は、高分子材料を含むため可撓性を有する基材１０を実現可能である。また、基材１０と圧電体膜２０を間に挟んで電極３０，４０を形成した場合に、圧電体膜２０の上面から下面まで連続する間隙５０を通じて基材１０近傍若しくは基材１０上に電極材料の成分である導電性化合物が堆積したとしても、電極３０、４０間の電気絶縁性の低下若しくは短絡を引き起こすおそれがない。 According to the present embodiment described above, a piezoelectric device comprising: a base material 10 including at least a polymer material; and a piezoelectric film 20 including a compound having a wurtzite crystal structure and formed directly on the base material 10. The body element 100 is realized. Since the piezoelectric element 100 includes a polymer material, the flexible substrate 10 can be realized. Further, when the electrodes 30 and 40 are formed with the base material 10 and the piezoelectric film 20 interposed therebetween, the electrodes are provided in the vicinity of the base material 10 or on the base material 10 through the gap 50 continuous from the upper surface to the lower surface of the piezoelectric film 20. Even if the conductive compound which is a component of the material is deposited, there is no possibility of causing a decrease in electrical insulation between the electrodes 30 and 40 or a short circuit.
（２）第２の実施形態：
次に、上述した第１の実施形態に係る圧電体素子１００の製造方法について説明する。
図３は、本実施形態に係る圧電体素子の製造方法の流れを示す図である。同図に示す圧電体素子の製造方法は、化学溶液調製工程Ｓ１、塗布工程Ｓ２、乾燥工程Ｓ３、焼成工程Ｓ４を含む。
(2) Second embodiment:
Next, a method for manufacturing the piezoelectric element 100 according to the first embodiment will be described.
FIG. 3 is a diagram showing a flow of a method for manufacturing a piezoelectric element according to the present embodiment. The method for manufacturing a piezoelectric element shown in the figure includes a chemical solution preparation step S1, a coating step S2, a drying step S3, and a firing step S4.
［化学溶液調製工程Ｓ１］
化学溶液調製工程Ｓ１においては、圧電体膜を構成するウルツ鉱型結晶構造の化合物となる金属種を含有する化合物を特定の割合で溶剤に溶解させた化学溶液を調製する。この化学溶液には、必要に応じて、後述する他種元素を含有する化合物を添加する。
[Chemical solution preparation step S1]
In the chemical solution preparation step S1, a chemical solution is prepared in which a compound containing a metal species that is a compound of a wurtzite crystal structure constituting the piezoelectric film is dissolved in a solvent at a specific ratio. If necessary, a compound containing other elements described later is added to the chemical solution.
ウルツ鉱型結晶構造の化合物としては、特に限定されるものではないが、ＺｎＯ、ＺｎＳ、ＺｎＳｅ、ＺｎＴｅ、ＭｇＯ、ＣｄＯ、ＣｄＳ、ＣｄＳｅ、ＣｄＴｅ、ＡｌＮ、ＧａＮ、ＩｎＮ及びＩｎＰ、の何れか又は組み合わせが例示される。 The wurtzite crystal structure compound is not particularly limited, but any one or combination of ZnO, ZnS, ZnSe, ZnTe, MgO, CdO, CdS, CdSe, CdTe, AlN, GaN, InN, and InP. Is exemplified.
ウルツ鉱型結晶構造の化合物となる金属種を含有する化合物としては、本実施形態に係る製造方法によってウルツ鉱型結晶構造を有する化合物に変換されるものであって、溶剤に可溶もしくは分散可能な化合物であれば、様々なものを用いることができる。 As a compound containing a metal species that becomes a compound of a wurtzite crystal structure, it is converted into a compound having a wurtzite crystal structure by the manufacturing method according to this embodiment, and is soluble or dispersible in a solvent. Various compounds can be used as long as they are compounds.
具体的には、金属種がＺｎである場合には、ウルツ鉱型結晶構造の化合物となる金属種を含有する化合物としては、例えば、酢酸亜鉛二水和物、酸化亜鉛微粒子、アセチルアセトナート亜鉛水和物、硫酸亜鉛水和物、安息香酸亜鉛、炭酸亜鉛、塩化亜鉛、リン酸亜鉛水和物、等が例示される。 Specifically, when the metal species is Zn, examples of the compound containing a metal species that becomes a wurtzite crystal structure compound include zinc acetate dihydrate, zinc oxide fine particles, and zinc acetylacetonate. Examples include hydrate, zinc sulfate hydrate, zinc benzoate, zinc carbonate, zinc chloride, zinc phosphate hydrate, and the like.
化学溶液に添加する他種元素としては、特に限定される物ではないが、アルカリ金属元素、アルカリ土類金属元素及び第１３族元素、何れか又は組み合わせが例示される。 The other elements added to the chemical solution are not particularly limited, and examples thereof include alkali metal elements, alkaline earth metal elements and Group 13 elements, or combinations thereof.
他種元素としてのアルカリ金属元素は、リチウム（Ｌｉ）、ナトリウム（Ｎａ）及びカリウム（Ｋ）が例示される。他種元素としてのアルカリ土類金属元素は、マグネシウム（Ｍｇ）、カルシウム（Ｃａ）、ストロンチウム（Ｓｒ）、バリウム（Ｂａ）が例示される。他種元素としての第１３族元素は、アルミニウム（Ａｌ）、ガリウム（Ｇａ）及びインジウム（Ｉｎ）が例示される。 Examples of the alkali metal element as the other species include lithium (Li), sodium (Na), and potassium (K). Examples of the alkaline earth metal element as the other element include magnesium (Mg), calcium (Ca), strontium (Sr), and barium (Ba). Examples of Group 13 elements as other elements include aluminum (Al), gallium (Ga), and indium (In).
他種元素を含有する化合物としてのアルカリ金属化合物及びアルカリ土類金属化合物としては、具体的には、酢酸リチウム二水和物、硝酸リチウム、酢酸ナトリウム、硝酸ナトリウム、酢酸カリウム、硝酸カリウム、塩化カリウム、酢酸マグネシウム四水和物、硝酸マグネシウム六水和物、酢酸カルシウム水和物、酢酸ストロンチウム、硝酸ストロンチウム、酢酸バリウム、等が例示される。 Specific examples of the alkali metal compound and the alkaline earth metal compound containing a compound containing other elements include lithium acetate dihydrate, lithium nitrate, sodium acetate, sodium nitrate, potassium acetate, potassium nitrate, potassium chloride, Examples thereof include magnesium acetate tetrahydrate, magnesium nitrate hexahydrate, calcium acetate hydrate, strontium acetate, strontium nitrate, and barium acetate.
また、他種元素を含有する化合物としての第１３族化合物としては、具体的には、硝酸アルミニウム九水和物、酢酸アルミニウム、塩化アルミニウム、硝酸ガリウム水和物、塩化ガリウム、硝酸インジウム水和物、塩化インジウム、等が例示される。 In addition, as a Group 13 compound as a compound containing other elements, specifically, aluminum nitrate nonahydrate, aluminum acetate, aluminum chloride, gallium nitrate hydrate, gallium chloride, indium nitrate hydrate , Indium chloride, and the like.
化学溶液に用いる溶剤としては、ウルツ鉱型結晶構造の化合物となる金属種を含有する化合物を溶解させることができる溶剤であればよく、化学溶液に他種元素を添加する場合は、更に、当該他種元素を含有する化合物を溶解できる溶剤であればよい。具体的には、２−メトキシエタノール、２−プロパノール、エタノール、１−ブタノール、トリオクチルフォスフィン、水等が例示される。 The solvent used in the chemical solution may be any solvent that can dissolve a compound containing a metal species that is a compound of a wurtzite crystal structure. When adding other elements to the chemical solution, Any solvent can be used as long as it can dissolve a compound containing another element. Specifically, 2-methoxyethanol, 2-propanol, ethanol, 1-butanol, trioctylphosphine, water and the like are exemplified.
化学溶液に用いる溶剤には、ウルツ鉱型結晶構造の化合物となる金属種を含有する化合物を安定的に溶解させるため、安定化剤を加えてもよい。安定化剤としては、２−アミノエタノール、Ｎ−ブチルエタノールアミン等が例示される。安定化剤の使用量は、特に限定されるものではないが、ウルツ鉱型結晶構造の化合物となる金属種を含有する化合物と当モル程度とすればよい。 A stabilizer may be added to the solvent used for the chemical solution in order to stably dissolve a compound containing a metal species that becomes a compound of a wurtzite crystal structure. Examples of the stabilizer include 2-aminoethanol, N-butylethanolamine and the like. The amount of the stabilizer used is not particularly limited, but may be about the same mole as that of the compound containing a metal species that becomes a compound having a wurtzite crystal structure.
化学溶液におけるウルツ鉱型結晶構造の化合物となる金属種を含有する化合物、及び、他種元素を含有する化合物の合計の濃度は、０．１〜１０モル／Ｌの範囲内であることが好ましく、０．２〜１．０モル／Ｌの範囲内であることが更に好ましい。濃度が低すぎるとウルツ鉱型結晶構造の化合物を含む圧電体膜の膜厚を効率的に稼ぐことが出来ない可能性があり、濃度が高すぎると良質なウルツ鉱型結晶構造の化合物を含む圧電体膜を得ることが出来ない可能性があるためである。 It is preferable that the total concentration of the compound containing a metal species and a compound containing other elements as a compound having a wurtzite crystal structure in the chemical solution is in the range of 0.1 to 10 mol / L. More preferably, it is in the range of 0.2 to 1.0 mol / L. If the concentration is too low, there is a possibility that the film thickness of the piezoelectric film containing the compound having the wurtzite crystal structure cannot be efficiently obtained. If the concentration is too high, a compound having a good wurtzite crystal structure is included. This is because a piezoelectric film may not be obtained.
なお、以上説明した化学溶液調製工程Ｓ１は、後述するように塗布工程Ｓ２を繰り返し行う場合には、最初の塗布工程Ｓ２の前に一度だけ行うようにしてもよい。この場合、成膜プロセスの最初に、繰り返し行う塗布工程Ｓ２で必要とされる量の化学溶液が確保されるように調製しておき、その後繰り返し行う塗布工程Ｓ２では、最初に調製して保存しておいた化学溶液を使用する。 The chemical solution preparation step S1 described above may be performed only once before the first coating step S2 when the coating step S2 is repeatedly performed as described later. In this case, it is prepared at the beginning of the film forming process so as to secure an amount of chemical solution required in the repeated coating step S2, and then prepared and stored in the repeated coating step S2. Use the chemical solution.
［塗布工程Ｓ２］
塗布工程Ｓ２では、化学溶液調製工程Ｓ１において調製した化学溶液を基材１０に塗布する。塗布方法は、基材１０上に化学溶液を均一に塗布できる塗布方法であればよい。
[Coating step S2]
In the application step S2, the chemical solution prepared in the chemical solution preparation step S1 is applied to the substrate 10. The coating method may be any coating method that can uniformly coat the chemical solution on the substrate 10.
具体的には、公知の、スピンコート法、スプレーコート法、ディップコート法、ドクターブレード法、シルクスクリーン印刷法、又はインクジェット印刷法、等が例示される。これらの塗布方法によれば、大面積の基材上にも均一な膜厚の塗布膜を形成することが出来る。 Specific examples include known spin coating methods, spray coating methods, dip coating methods, doctor blade methods, silk screen printing methods, and ink jet printing methods. According to these coating methods, a coating film having a uniform film thickness can be formed on a large-area substrate.
塗布条件は、化学溶液の組成（溶剤の種類、化合物の種類や濃度、等）に応じて設定すればよいが、一回の塗布工程で成膜される塗布膜は、より厚い方が好ましい。塗布雰囲気は特に限定されず、空気中で行うことも出来る。 The application conditions may be set according to the composition of the chemical solution (the type of solvent, the type and concentration of the compound, etc.), but the coating film formed in a single application step is preferably thicker. The application atmosphere is not particularly limited, and can be performed in air.
［乾燥工程Ｓ３］
乾燥工程Ｓ３においては、塗布工程Ｓ２において基材１０の表面に形成された化学溶液の塗布膜を乾燥させる。
[Drying step S3]
In the drying step S3, the coating film of the chemical solution formed on the surface of the substrate 10 in the coating step S2 is dried.
乾燥条件は、塗布膜の組成（溶剤の種類等）に応じて適宜に設定すればよいが、乾燥温度は、化学溶液から緻密層の圧電体膜を形成する場合に必要な乾燥温度（ＺｎＯの緻密層を形成する場合は約４００℃以上）に比べて低い乾燥温度（例えば、３００℃以下）とする。ただし、乾燥温度は基材１０の耐熱温度以下であればよく、３００℃以下に限らず、基材１０の耐熱温度に応じて適宜に設定することができる。乾燥時間は、塗布膜の種類や状態、乾燥温度等に応じて適宜に設定される。乾燥雰囲気は、特に限定されないが、大気中の他に、アルゴンや窒素等の不活性ガス雰囲気中、あるいは酸素と不活性ガスの混合ガス雰囲気中で行うことができる。蒸発した溶剤を回収する場合は、ドラフト等の機体回収装置内で乾燥工程Ｓ３を行う。 The drying conditions may be appropriately set according to the composition of the coating film (such as the type of solvent), but the drying temperature is the drying temperature (ZnO of ZnO) required for forming a dense piezoelectric film from a chemical solution. When the dense layer is formed, the drying temperature is lower than that of about 400 ° C. (for example, 300 ° C. or lower). However, the drying temperature should just be below the heat-resistant temperature of the base material 10, and is not restricted to 300 degrees C or less, It can set suitably according to the heat-resistant temperature of the base material 10. The drying time is appropriately set according to the type and state of the coating film, the drying temperature, and the like. The drying atmosphere is not particularly limited, but may be performed in an inert gas atmosphere such as argon or nitrogen, or in a mixed gas atmosphere of oxygen and inert gas, in addition to the air. When recovering the evaporated solvent, the drying step S3 is performed in a body recovery device such as a draft.
基材１０の表面に塗布した後、乾燥させると析出及び凝集して、通常、平均粒子径が１〜５００ｎｍの範囲内の大きさの粒子になる。すなわち、乾燥工程Ｓ３によって乾燥された塗布膜（以下、乾燥塗布膜と記載する。）は、ウルツ鉱型結晶構造の化合物の粒子が充填及び堆積した集合体である。 After being applied to the surface of the substrate 10, when dried, it precipitates and aggregates to form particles having an average particle size in the range of 1 to 500 nm. That is, the coating film dried in the drying step S3 (hereinafter referred to as a dry coating film) is an aggregate in which particles of a compound having a wurtzite crystal structure are filled and deposited.
［焼成工程Ｓ４］
焼成工程Ｓ４においては、乾燥工程Ｓ３において形成された乾燥塗布膜を焼成して、基材１０上に、ウルツ鉱型結晶構造の化合物の結晶を形成する。
[Baking step S4]
In the firing step S <b> 4, the dried coating film formed in the drying step S <b> 3 is fired to form a compound crystal having a wurtzite crystal structure on the substrate 10.
焼成条件は、乾燥塗布膜の組成（金属種の種類等）に応じて適宜に設定すればよいが、焼成温度は、化学溶液から緻密層の圧電体膜を形成する場合に必要な焼成温度（ＺｎＯの緻密層を焼成する場合は約６００℃以上）よりも低い焼成温度（例えば、４５０℃以下）とする。ただし、焼成温度は基材１０の耐熱温度以下であればよく、４５０℃以下に限らず、基材１０の耐熱温度に応じて適宜に設定することができる。焼成時間は、乾燥塗布膜の種類や状態、焼成温度等に応じて適宜に設定される。焼成雰囲気は、特に限定されないが、大気中の他に、アルゴンや窒素等の不活性ガス雰囲気中、あるいは酸素と不活性ガスの混合ガス雰囲気中で行うことができる。 The firing conditions may be set as appropriate according to the composition of the dry coating film (type of metal species, etc.), but the firing temperature is the firing temperature required when a dense piezoelectric film is formed from a chemical solution ( When firing a dense layer of ZnO, the firing temperature is lower than about 600 ° C. (for example, 450 ° C. or lower). However, the firing temperature only needs to be equal to or lower than the heat resistance temperature of the base material 10, and is not limited to 450 ° C. or lower, and can be appropriately set according to the heat resistance temperature of the base material 10. The firing time is appropriately set according to the type and state of the dry coating film, the firing temperature, and the like. The firing atmosphere is not particularly limited, but can be performed in an inert gas atmosphere such as argon or nitrogen, or in a mixed gas atmosphere of oxygen and inert gas, in addition to the air.
焼成工程Ｓ４により、充填及び堆積した集合体となっている粒子は互いに焼結する。これにより、粒子が互いに結合してなる多孔体である結合層が形成される。この結合層は、ウルツ鉱型結晶構造の化合物の結晶の粒子が無秩序（構造上においては規則性無く）に充填された構造であり、基材１０面と垂直方向に少なくとも２つのウルツ鉱型結晶構造の化合物の粒子が堆積する。 By the firing step S4, the filled and deposited particles are sintered together. As a result, a bonded layer that is a porous body in which particles are bonded to each other is formed. This bonding layer has a structure in which particles of a compound of a wurtzite crystal structure are packed randomly (no regularity in the structure), and at least two wurtzite crystals are perpendicular to the surface of the substrate 10. Particles of structured compounds are deposited.
ただし、本実施形態では、化学溶液を通常よりも低い乾燥温度で乾燥し、また、通常よりも低い焼成温度で焼成するため、粒子径が２〜１０００ｎｍの範囲の粒子の形状を残した状態で焼結する。すなわち、焼成工程Ｓ４によって焼成された結合層は、ウルツ鉱型結晶構造の化合物の粒子が充填及び堆積した集合体である。なお、乾燥条件や焼成条件次第ではあるが、実際には、粒子径が１０〜５００ｎｍの範囲内の粒子の形状を残した状態で焼結することが多い。 However, in the present embodiment, the chemical solution is dried at a lower drying temperature than usual, and is baked at a lower firing temperature than usual, so that the shape of particles having a particle diameter in the range of 2 to 1000 nm remains. Sinter. That is, the bonding layer fired in the firing step S4 is an aggregate in which particles of a compound having a wurtzite crystal structure are filled and deposited. In addition, although it depends on drying conditions and firing conditions, in practice, sintering is often performed in a state where the shape of the particles having a particle diameter in the range of 10 to 500 nm remains.
ここで、一回の塗布工程Ｓ２及び乾燥工程Ｓ３で、圧電体膜２０として十分な膜厚の乾燥塗布膜が形成されない場合は、塗布工程Ｓ２と乾燥工程Ｓ３を複数回繰り返す。具体的には、塗布工程Ｓ２及び乾燥工程Ｓ３を１セットとして複数回繰り返して十分な膜厚の乾燥塗布膜を累積的に形成してから焼成工程Ｓ４を行ってもよいし、塗布工程Ｓ２、乾燥工程Ｓ３及び焼成工程Ｓ４を１セットとして複数回繰り返して十分な膜厚の圧電体膜２０を累積的に形成してもよいし、これらの組み合わせとしてもよい。 Here, when a dry coating film having a sufficient film thickness is not formed as the piezoelectric film 20 in one coating process S2 and drying process S3, the coating process S2 and the drying process S3 are repeated a plurality of times. Specifically, the baking step S4 may be performed after the coating step S2 and the drying step S3 are repeated a plurality of times as a set to cumulatively form a dry coating film having a sufficient thickness, or the coating step S2, The drying step S3 and the firing step S4 may be repeated a plurality of times to form the piezoelectric film 20 having a sufficient film thickness, or a combination thereof.
以上説明した化学溶液を用いる製造方法では、化学溶液の調製段階でドープする元素の添加量及びその添加割合の制御を簡便に行えるため、得られる圧電体膜の圧電応答特性や電気抵抗などの物性制御を容易に行う事が出来る。また、乾燥や焼成を低温で行うため、化学溶液堆積法を用いて、高分子材料を含む基材上に圧電体膜を形成することができる。 In the manufacturing method using the chemical solution described above, the addition amount and the addition ratio of the element to be doped in the chemical solution preparation stage can be easily controlled, so that the physical properties such as piezoelectric response characteristics and electrical resistance of the obtained piezoelectric film are obtained. Control can be easily performed. In addition, since drying and baking are performed at a low temperature, a piezoelectric film can be formed on a base material containing a polymer material using a chemical solution deposition method.
以下、実施例によって第２の実施形態、及び、これにより製造される圧電体素子の具体的な一例を説明するが、本発明は、これに限定されるものではない。 Hereinafter, although a specific example of 2nd Embodiment and a piezoelectric element manufactured by this is demonstrated by an Example, this invention is not limited to this.
［実施例１］
実施例１においては、３ａｔ．％のドープ濃度でＬｉドープされたＬｉ０．０３Ｚｎ０．９７Ｏを、ポリイミド基材上に化学溶液堆積法を用いて成膜した。
[Example 1]
In Example 1, 3 at. Li 0.03 Zn 0.97 O doped with Li at a doping concentration of% was deposited on a polyimide substrate using chemical solution deposition.
塗布に用いる化学溶液は、酢酸亜鉛二水和物、リチウム酢酸二水和物を出発原料として、２−メトキシエタノールを溶媒とし、２−アミノエタノール安定化剤として調製した（化学溶液調製工程Ｓ１）。亜鉛及びリチウムのモル濃度の総和は、０．６モル／リットル濃度で一定となるように調製した。２−アミノエタノールの亜鉛に対するモル比を１に保った。 The chemical solution used for coating was prepared using zinc acetate dihydrate and lithium acetic acid dihydrate as starting materials, 2-methoxyethanol as a solvent, and 2-aminoethanol stabilizer (chemical solution preparation step S1). . The total molar concentration of zinc and lithium was adjusted to be constant at a concentration of 0.6 mol / liter. The molar ratio of 2-aminoethanol to zinc was kept at 1.
得られた化学溶液を、保持板に張り付けたポリイミド基材（大きさ：１２０ｍｍ×９０ｍｍ、厚さ：５μｍ）上にスピンコート法で塗布して成膜し（塗布工程Ｓ２）、その膜を２００℃のホットプレート上で乾燥した（乾燥工程Ｓ３）。 The obtained chemical solution was applied by spin coating on a polyimide substrate (size: 120 mm × 90 mm, thickness: 5 μm) attached to a holding plate (application step S2). It dried on the hotplate of 0 degreeC (drying process S3).
これら塗布工程Ｓ２及び乾燥工程Ｓ３を１セットとして６回繰り返して得られた乾燥塗布膜を、大気中、４００℃の電気炉中で焼成した（焼成工程Ｓ４）。これらの塗布工程Ｓ２、乾燥工程Ｓ３及び焼成工程Ｓ４の組み合わせを、更に３セット繰り返すことにより、膜厚がおよそ５００ｎｍの圧電体膜を得た。このようにして厚さ５μｍのポリイミド基材上に形成したＺｎ０．９７Ｌｉ０．０３Ｏ圧電体膜を用いた圧電体素子は、可撓性を有していた。 The dry coating film obtained by repeating these coating step S2 and drying step S3 six times as a set was fired in an electric furnace at 400 ° C. in the atmosphere (firing step S4). A combination of these coating step S2, drying step S3 and firing step S4 was repeated three more times to obtain a piezoelectric film having a thickness of about 500 nm. Thus, the piezoelectric element using the Zn 0.97 Li 0.03 O piezoelectric film formed on the polyimide substrate having a thickness of 5 μm had flexibility.
図４は、このようにしてポリイミド基材上に形成したＺｎ０．９７Ｌｉ０．０３Ｏ圧電体膜を用いた圧電体素子の破断面を、電界放射型走査電子顕微鏡（ＦＥ−ＳＥＭ）で観察した観察画像である。同図において、Ｚｎ０．９７Ｌｉ０．０３Ｏ圧電体膜は、粒子径が２５〜５０ｎｍの結晶の粒子が充填及び堆積した構造を有する。 FIG. 4 is a field emission scanning electron microscope (FE-SEM) showing a fracture surface of a piezoelectric element using a Zn 0.97 Li 0.03 O piezoelectric film thus formed on a polyimide substrate. It is the observed image observed. In the figure, the Zn 0.97 Li 0.03 O piezoelectric film has a structure in which crystal particles having a particle diameter of 25 to 50 nm are filled and deposited.
また、Ｚｎ０．９７Ｌｉ０．０３Ｏ圧電体膜の圧電応答性を測定するため、圧電体膜を銅箔で挟み、治具に６０Ｎの初期荷重で固定し、振動荷重（振幅：５０Ｎ、周波数：５Ｈｚ）を印加に対して、発生する電荷量を測定した。その結果、得られたＺｎ０．９７Ｌｉ０．０３Ｏ膜は、およそ０．１ｐＣ／Ｎの圧電応答性を示した。 Further, in order to measure the piezoelectric response of the Zn 0.97 Li 0.03 O piezoelectric film, the piezoelectric film is sandwiched between copper foils, fixed to a jig with an initial load of 60 N, and a vibration load (amplitude: 50 N, (Frequency: 5 Hz), and the amount of generated charge was measured. As a result, the obtained Zn 0.97 Li 0.03 O film exhibited a piezoelectric response of about 0.1 pC / N.
［実施例２］
実施例２においては、２ａｔ．％のドープ濃度でＡｌドープされたＺｎ０．９８Ａｌ０．０２Ｏを、ポリイミド基材上に化学溶液堆積法を用いて成膜した。
[Example 2]
In Example 2, 2 at. Zn 0.98 Al 0.02 O doped with Al at a doping concentration of% was deposited on a polyimide substrate using chemical solution deposition.
塗布に用いる化学溶液は、酢酸亜鉛二水和物、硝酸アルミニウム九水和物を出発原料として、２−メトキシエタノールを溶媒とし、２−アミノエタノールを安定化剤として用いて調製した（化学溶液調製工程Ｓ１）。添加した亜鉛およびアルミニウムのモル濃度の総和は、０．６モル／リットル濃度で一定となるようにした。２−アミノエタノールの亜鉛に対するモル比を１に保った。 The chemical solution used for coating was prepared using zinc acetate dihydrate and aluminum nitrate nonahydrate as starting materials, 2-methoxyethanol as a solvent, and 2-aminoethanol as a stabilizer (chemical solution preparation). Step S1). The total molar concentration of added zinc and aluminum was made constant at a concentration of 0.6 mol / liter. The molar ratio of 2-aminoethanol to zinc was kept at 1.
得られた化学溶液を、保持板に張り付けたポリイミド基材（大きさ：１２０ｍｍ×９０ｍｍ、厚さ：５μｍ）上にスピンコート法で塗布して成膜し（塗布工程Ｓ２）、その膜を２００℃のホットプレート上で乾燥した（乾燥工程Ｓ３）。 The obtained chemical solution was applied by spin coating on a polyimide substrate (size: 120 mm × 90 mm, thickness: 5 μm) attached to a holding plate (application step S2). It dried on the hotplate of 0 degreeC (drying process S3).
これら塗布工程Ｓ２及び乾燥工程Ｓ３を１セットとして３回繰り返して得られた乾燥塗布膜を、大気中、４００℃の電気炉中で焼成した（焼成工程Ｓ４）。これら塗布工程Ｓ２、乾燥工程Ｓ３及び焼成工程Ｓ４の組み合わせを、更に３セット繰り返すことにより、膜厚がおよそ４００ｎｍの圧電体膜を得た。このようにして厚さ５μｍのポリイミド基材上に形成したＺｎ０．９８Ａｌ０．０２Ｏ圧電体膜を用いた圧電体素子は、可撓性を有していた。 A dry coating film obtained by repeating these coating step S2 and drying step S3 three times as one set was baked in an electric furnace at 400 ° C. in the atmosphere (baking step S4). A combination of these coating step S2, drying step S3, and firing step S4 was repeated three more times to obtain a piezoelectric film having a film thickness of about 400 nm. Thus, the piezoelectric element using the Zn 0.98 Al 0.02 O piezoelectric film formed on the polyimide substrate having a thickness of 5 μm had flexibility.
図５は、このようにしてポリイミド基材上に形成したＺｎ０．９８Ａｌ０．０２Ｏ圧電体膜を用いた圧電体素子の破断面を、ＦＥ−ＳＥＭで観察した観察画像である。同図において、Ｚｎ０．９８Ａｌ０．０２Ｏ圧電体膜は、粒子径が２０〜５０ｎｍの結晶の粒子が充填及び堆積した構造を有する。 FIG. 5 is an observation image obtained by observing the fracture surface of the piezoelectric element using the Zn 0.98 Al 0.02 O piezoelectric film formed on the polyimide base material with the FE-SEM. In the figure, the Zn 0.98 Al 0.02 O piezoelectric film has a structure in which crystal particles having a particle diameter of 20 to 50 nm are filled and deposited.
また、Ｚｎ０．９８Ａｌ０．０２Ｏ圧電体膜の圧電応答性を測定するため、上述した実施例１と同様の方法で圧電応答性を測定した。その結果、得られたＺｎ０．９８Ａｌ０．０２Ｏ圧電体膜は、およそ０．０８ｐＣ／Ｎの圧電応答性を示した。 Further, in order to measure the piezoelectric response of the Zn 0.98 Al 0.02 O piezoelectric film, the piezoelectric response was measured by the same method as in Example 1 described above. As a result, the obtained Zn 0.98 Al 0.02 O piezoelectric film exhibited a piezoelectric response of approximately 0.08 pC / N.
（３）第３の実施形態：
上述した第２の実施形態では、基材１０上に化学溶液堆積法で圧電体膜２０を堆積する圧電体素子１００の製造方法について説明したが、圧電体素子１００の製造方法は、これに限るものではない。
(3) Third embodiment:
In the above-described second embodiment, the method for manufacturing the piezoelectric element 100 in which the piezoelectric film 20 is deposited on the base material 10 by the chemical solution deposition method has been described. However, the method for manufacturing the piezoelectric element 100 is not limited thereto. It is not a thing.
図６は、第３の実施形態に係る圧電体素子１００の製造方法を説明する図である。同図に示す例では、まず、ダミー基材３３０を用意する。このダミー基材３３０は、圧電体膜２０から剥がしやすい特性を有するものとする。 FIG. 6 is a diagram illustrating a method for manufacturing the piezoelectric element 100 according to the third embodiment. In the example shown in the figure, first, a dummy base material 330 is prepared. This dummy base material 330 is assumed to have a characteristic that it can be easily peeled off from the piezoelectric film 20.
このダミー基材３３０の上に、図６（ａ）に示すように、ウルツ鉱型結晶構造の化合物を含む圧電体膜２０を形成し、この圧電体膜２０の上に、ポリイミド等の高分子材料を含む基材１０の材料をスピンコート等の手法により積層する。圧電体膜２０は、上述した第２の実施形態に係る製造方法と同様の手法で形成することができる。 As shown in FIG. 6A, a piezoelectric film 20 containing a compound having a wurtzite crystal structure is formed on the dummy substrate 330, and a polymer such as polyimide is formed on the piezoelectric film 20. The material of the base material 10 including the material is laminated by a technique such as spin coating. The piezoelectric film 20 can be formed by the same method as the manufacturing method according to the second embodiment described above.
その後、図６（ｂ）に示すように、ダミー基材３３０を圧電体膜２０からリフトオフにより剥がす。これにより、上述した第１の実施形態と構造が同じ圧電体素子、すなわち、少なくとも高分子材料を含む基材１０と、ウルツ鉱型結晶構造の化合物を含み、基材１０の直上に形成された圧電体膜２０と、を備える圧電体素子１００を作製することができる。 Thereafter, as shown in FIG. 6B, the dummy base material 330 is peeled off from the piezoelectric film 20 by lift-off. Accordingly, the piezoelectric element having the same structure as that of the first embodiment described above, that is, the base material 10 including at least the polymer material and the compound of the wurtzite crystal structure is formed directly on the base material 10. A piezoelectric element 100 including the piezoelectric film 20 can be manufactured.
（４）第４の実施形態：
図７は、本実施形態に係る圧電体素子の断面を模式的に示した図である。同図に示す圧電体素子４００は、少なくとも高分子材料を含む基材４１０と、ウルツ鉱型結晶構造の化合物を含み、基材４１０の直上に直接形成された圧電体膜４２０と、圧電体膜４２０及び基材４１０を間に挟んで配置される第１電極４３０及び第２電極４４０と、を備える。なお、基材４１０及び圧電体膜４２０は、それぞれ第１の実施形態に係る基材１０及び圧電体膜２０と同様の構成であるため、以下では説明を省略する。
(4) Fourth embodiment:
FIG. 7 is a diagram schematically showing a cross section of the piezoelectric element according to the present embodiment. The piezoelectric element 400 shown in the figure includes a base material 410 containing at least a polymer material, a piezoelectric film 420 containing a compound having a wurtzite crystal structure, and formed directly on the base material 410, and a piezoelectric film. A first electrode 430 and a second electrode 440 disposed with the substrate 420 and the substrate 410 interposed therebetween. Note that the base material 410 and the piezoelectric film 420 have the same configurations as the base material 10 and the piezoelectric film 20 according to the first embodiment, respectively, and thus description thereof will be omitted.
第１電極４３０及び第２電極４４０は、金属、合金、金属酸化物、金属窒化物、等の導電材料を用いることができる。具体的には、金属であれば、Ａｌ、Ｎｉ、Ｐｔ、Ａｕ、Ａｇ、Ｃｕ、Ｔｉ等が例示される。 The first electrode 430 and the second electrode 440 can be formed using a conductive material such as a metal, an alloy, a metal oxide, or a metal nitride. Specifically, examples of the metal include Al, Ni, Pt, Au, Ag, Cu, and Ti.
このように、本実施形態に係る圧電体素子４００は、圧電体膜４２０と第２電極４４０の間に、電気絶縁性を有する基材４１０が配置されている。従って、仮に、圧電体膜４２０の間隙を通じて基材４１０近傍若しくは基材４１０上に電極材料の成分である導電性化合物が堆積しても、電極間の電気絶縁性の低下若しくは短絡を引き起こすおそれがない。 As described above, in the piezoelectric element 400 according to this embodiment, the base material 410 having electrical insulation is disposed between the piezoelectric film 420 and the second electrode 440. Therefore, even if a conductive compound that is a component of the electrode material is deposited near or on the base material 410 through the gap between the piezoelectric films 420, there is a risk of causing a decrease in electrical insulation between the electrodes or a short circuit. Absent.
（５）第５の実施形態：
次に、第４の実施形態に係る圧電体素子４００の製造方法について説明する。
図８は、第４の実施形態に係る圧電体素子４００の製造方法の流れを示す図である。同図に示す圧電体素子の製造方法は、第４の実施形態に係る圧電体素子４００の製造方法であり、化学溶液調製工程Ｓ５１、塗布工程Ｓ５２、乾燥工程Ｓ５３、焼成工程Ｓ５４、電極形成工程Ｓ５５を含む。
(5) Fifth embodiment:
Next, a method for manufacturing the piezoelectric element 400 according to the fourth embodiment will be described.
FIG. 8 is a diagram illustrating a flow of a manufacturing method of the piezoelectric element 400 according to the fourth embodiment. The method for manufacturing a piezoelectric element shown in the figure is a method for manufacturing a piezoelectric element 400 according to the fourth embodiment, and includes a chemical solution preparation step S51, a coating step S52, a drying step S53, a firing step S54, and an electrode forming step. Includes S55.
なお、化学溶液調製工程Ｓ５１、塗布工程Ｓ５２、乾燥工程Ｓ５３及び焼成工程Ｓ５４は、上述した第２の実施形態の化学溶液調製工程Ｓ１、塗布工程Ｓ２、乾燥工程Ｓ３及び焼成工程Ｓ４とそれぞれ同様であるため、以下では説明を省略する。 The chemical solution preparation step S51, the application step S52, the drying step S53, and the baking step S54 are the same as the chemical solution preparation step S1, the application step S2, the drying step S3, and the baking step S4 of the second embodiment described above, respectively. Therefore, the description is omitted below.
電極形成工程Ｓ５５では、第２の実施形態と同様の製造方法により得られた圧電体素子１００に対し、圧電体膜４２０が露出する側面である第１の面に第１電極４３０を形成し、基材４１０が露出する側面である第２の面に第２電極４４０を形成する。これにより、第１電極４３０及び第２電極４４０が、圧電体膜４２０及び基材４１０を間に挟んで配置される。 In the electrode formation step S55, the first electrode 430 is formed on the first surface, which is the side surface from which the piezoelectric film 420 is exposed, with respect to the piezoelectric element 100 obtained by the manufacturing method similar to the second embodiment. The second electrode 440 is formed on the second surface, which is the side surface where the substrate 410 is exposed. Accordingly, the first electrode 430 and the second electrode 440 are disposed with the piezoelectric film 420 and the base material 410 interposed therebetween.
なお、第１電極４３０及び第２電極４４０の形成方法は、特に限定される物ではないが、例えば、塗布処理、メッキ法、スパッタ法、又は真空蒸着等の物理蒸着法が例示される。 In addition, although the formation method of the 1st electrode 430 and the 2nd electrode 440 is not a thing specifically limited, For example, physical vapor deposition methods, such as a coating process, a plating method, a sputtering method, or vacuum evaporation, are illustrated.
以下、実施例によって第５の実施形態、及び、これにより製造される圧電体素子４００の具体的な一例を説明するが、本発明は、これに限定されるものではない。 Hereinafter, although a specific example of 5th Embodiment and the piezoelectric element 400 manufactured by this is demonstrated by an Example, this invention is not limited to this.
［実施例３］
実施例３においては、実施例１で製造されたＺｎ０．９７Ｌｉ０．０３Ｏ圧電体膜に対して、Ｚｎ０．９７Ｌｉ０．０３Ｏ圧電体膜の面、及びその反対面のポリイミド基材の面に、蒸着法を用いてＡｌを蒸着し、それぞれ第１電極４３０及び第２電極４４０を作製した。
[Example 3]
In Example 3, the surface of the Zn 0.97 Li 0.03 O piezoelectric film and the polyimide on the opposite surface of the Zn 0.97 Li 0.03 O piezoelectric film manufactured in Example 1 were used. Al was vapor-deposited on the surface of the base material using the vapor deposition method, and the 1st electrode 430 and the 2nd electrode 440 were produced, respectively.
第１電極４３０及び第２電極４４０に、ローノイズケーブルの信号線およびアース線を接続した。そして、得られたものを２つ折りにして、絶縁性接着剤で接着し、圧電体素子４００を作製した。 A signal line and a ground line of a low noise cable were connected to the first electrode 430 and the second electrode 440. Then, the obtained product was folded in two and adhered with an insulating adhesive to produce a piezoelectric element 400.
このようにして得られた、圧電体素子４００の圧電応答性を測定するため、上述した実施例１と同様の方法で圧電応答性を測定した結果、得られた圧電体素子４００の圧電応答性は、０．２ｐＣ／Ｎであった。２つ折りにして素子化することにより、２倍の感度で、圧力を検出できることを確認した。 In order to measure the piezoelectric response of the piezoelectric element 400 thus obtained, the piezoelectric response of the piezoelectric element 400 obtained as a result of measuring the piezoelectric response by the same method as in Example 1 described above. Was 0.2 pC / N. It was confirmed that pressure could be detected with double sensitivity by folding the element into two.
また、圧電体素子５００のどの部分も圧電応答性を示し、短絡や電気抵抗の低下による不安定な圧電応答性は示さなかった。これは、仮に圧電体膜に亀裂や膜の上面から下面まで連続する間隙など欠陥があっても、電気絶縁性の高分子基材を挟んで２つの電極が作製されているため、短絡や著しい電気抵抗の低下が防止されるためである。すなわち、センサ素子面を大面積化しても、信頼性の高い圧電体素子を提供することが可能であることが示されている。 In addition, any part of the piezoelectric element 500 showed piezoelectric response and did not show unstable piezoelectric response due to short circuit or reduction in electrical resistance. This is because, even if the piezoelectric film has a defect such as a crack or a continuous gap from the upper surface to the lower surface of the film, the two electrodes are produced with the electrically insulating polymer base material interposed therebetween, so that a short circuit or significant This is because a decrease in electrical resistance is prevented. That is, it is shown that it is possible to provide a highly reliable piezoelectric element even if the sensor element surface is enlarged.
（６）まとめ：
以上説明した第１の実施形態、第２の実施形態及び第３の実施形態によれば、少なくとも高分子材料を含む基材１０と、ウルツ鉱型結晶構造の化合物を含み、基材１０の直上に形成された圧電体膜２０と、を備え、圧電体膜２０は、基材１０面と垂直方向に少なくとも２つのウルツ鉱型結晶構造の化合物の粒子２１を充填及び堆積し、粒子２１が互いに結合してなる結合層２２を有する圧電体素子１００が実現される。また、上述した第４の実施形態及び第５の実施形態によれば、少なくとも高分子材料を含む基材４１０と、ウルツ鉱型結晶構造の化合物を含み、基材４１０の直上に形成された圧電体膜４２０と、圧電体膜４２０及び基材４１０を間に挟んで配置される第１電極４３０及び第２電極４４０と、備え、圧電体膜４２０は、基材４１０面と垂直方向に少なくとも２つのウルツ鉱型結晶構造の化合物の粒子を充填及び堆積し、当該粒子が互いに結合してなる結合層を有する圧電体素子４００が実現される。これら圧電体素子１００，４００は、可撓性を備えつつ、基材と圧電体膜を間に挟んで形成した電極間の電気絶縁性の低下や短絡が防止できる。
(6) Summary:
According to the first embodiment, the second embodiment, and the third embodiment described above, the substrate 10 includes at least a polymer material and a compound having a wurtzite crystal structure, and is directly above the substrate 10. The piezoelectric film 20 is filled and deposited with at least two particles 21 of a wurtzite crystal structure compound in a direction perpendicular to the surface of the base material 10, and the particles 21 are mutually attached. The piezoelectric element 100 having the bonding layer 22 formed by bonding is realized. In addition, according to the above-described fourth and fifth embodiments, the piezoelectric substrate is formed directly on the base material 410, which includes the base material 410 containing at least a polymer material and a compound having a wurtzite crystal structure. A body film 420, and a first electrode 430 and a second electrode 440 that are disposed with the piezoelectric film 420 and the base material 410 interposed therebetween, and the piezoelectric film 420 has at least two in a direction perpendicular to the surface of the base material 410. The piezoelectric element 400 having a bonding layer formed by filling and depositing two wurtzite type crystal structure compound particles and bonding the particles to each other is realized. These piezoelectric elements 100 and 400 have flexibility and can prevent a decrease in electrical insulation and a short circuit between electrodes formed with a base material and a piezoelectric film interposed therebetween.
なお、本発明は上述した実施形態や変形例に限られず、上述した実施形態および変形例の中で開示した各構成を相互に置換したり組み合わせを変更したりした構成、公知技術並びに上述した実施形態および変形例の中で開示した各構成を相互に置換したり組み合わせを変更したりした構成、等も含まれる。また，本発明の技術的範囲は上述した実施形態に限定されず，特許請求の範囲に記載された事項とその均等物まで及ぶものである。 Note that the present invention is not limited to the above-described embodiments and modifications, and the structures disclosed in the above-described embodiments and modifications are mutually replaced, the combinations are changed, the known technique, and the above-described implementations. Configurations in which the configurations disclosed in the embodiments and modifications are mutually replaced or the combinations are changed are also included. Further, the technical scope of the present invention is not limited to the above-described embodiments, but extends to the matters described in the claims and equivalents thereof.
１０…基材、２０…圧電体膜、２１…粒子、２２…結合層、３０…第１電極、４０…第２電極、５０…間隙、１００…圧電体素子、３３０…ダミー基材、４００…圧電体素子、４１０…基材、４２０…圧電体膜、４３０…第１電極、４４０…第２電極、５００…圧電体素子、Ｓ１…化学溶液調製工程、Ｓ２…塗布工程、Ｓ３…乾燥工程、Ｓ４…焼成工程、Ｓ５１…化学溶液調製工程、Ｓ５２…塗布工程、Ｓ５３…乾燥工程、Ｓ５４…焼成工程、Ｓ５５…電極形成工程 DESCRIPTION OF SYMBOLS 10 ... Base material, 20 ... Piezoelectric film, 21 ... Particle, 22 ... Bonding layer, 30 ... First electrode, 40 ... Second electrode, 50 ... Gap, 100 ... Piezoelectric element, 330 ... Dummy base material, 400 ... Piezoelectric element, 410 ... base material, 420 ... piezoelectric film, 430 ... first electrode, 440 ... second electrode, 500 ... piezoelectric element, S1 ... chemical solution preparation process, S2 ... coating process, S3 ... drying process, S4 ... Baking step, S51 ... Chemical solution preparation step, S52 ... Coating step, S53 ... Drying step, S54 ... Baking step, S55 ... Electrode forming step
Claims (12)
ウルツ鉱型結晶構造の化合物を含み、前記基材の直上に形成された圧電体膜と、
を備え、
前記圧電体膜は、前記基材面と垂直方向に少なくとも２つのウルツ鉱型結晶構造の化合物の粒子を充填及び堆積し、前記粒子が互いに結合してなる結合層を有することを特徴とする圧電体素子。 A base material comprising at least a polymer material;
A piezoelectric film comprising a compound having a wurtzite crystal structure and formed directly on the substrate;
With
The piezoelectric film has a bonding layer in which particles of a compound having at least two wurtzite crystal structures are filled and deposited in a direction perpendicular to the substrate surface, and the particles are bonded to each other. Body element.
少なくとも高分子材料を含む基材の上に、前記化学溶液を塗布する塗布工程と、
前記塗布工程により形成した塗布膜を乾燥する乾燥工程と、
前記乾燥工程により乾燥した塗布膜を焼成する焼成工程と、
を含むことを特徴とする圧電体素子の製造方法。 A preparation step of preparing a chemical solution containing elemental species constituting a compound having a wurtzite crystal structure;
An application step of applying the chemical solution on a base material containing at least a polymer material;
A drying step of drying the coating film formed by the coating step;
A firing step of firing the coating film dried by the drying step;
A method for manufacturing a piezoelectric element, comprising:
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