JP6172698B2 - Inorganic crystal film and method for producing the same - Google Patents
Inorganic crystal film and method for producing the same Download PDFInfo
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- JP6172698B2 JP6172698B2 JP2011246749A JP2011246749A JP6172698B2 JP 6172698 B2 JP6172698 B2 JP 6172698B2 JP 2011246749 A JP2011246749 A JP 2011246749A JP 2011246749 A JP2011246749 A JP 2011246749A JP 6172698 B2 JP6172698 B2 JP 6172698B2
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- 239000013078 crystal Substances 0.000 title claims description 124
- 238000004519 manufacturing process Methods 0.000 title claims description 34
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 112
- 238000000576 coating method Methods 0.000 claims description 63
- 239000011787 zinc oxide Substances 0.000 claims description 54
- 238000000034 method Methods 0.000 claims description 53
- 238000001035 drying Methods 0.000 claims description 40
- 239000000758 substrate Substances 0.000 claims description 39
- 239000000463 material Substances 0.000 claims description 37
- 239000011248 coating agent Substances 0.000 claims description 33
- 239000002245 particle Substances 0.000 claims description 21
- 238000010304 firing Methods 0.000 claims description 19
- 229910052751 metal Inorganic materials 0.000 claims description 18
- 239000002184 metal Substances 0.000 claims description 18
- 239000000126 substance Substances 0.000 claims description 18
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 9
- 239000010949 copper Substances 0.000 claims description 9
- 229910052782 aluminium Inorganic materials 0.000 claims description 7
- 239000011777 magnesium Substances 0.000 claims description 6
- 239000011572 manganese Substances 0.000 claims description 6
- 238000007650 screen-printing Methods 0.000 claims description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 5
- 229910052802 copper Inorganic materials 0.000 claims description 5
- 238000007641 inkjet printing Methods 0.000 claims description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 4
- 229910052733 gallium Inorganic materials 0.000 claims description 4
- 229910052744 lithium Inorganic materials 0.000 claims description 4
- 238000004528 spin coating Methods 0.000 claims description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 3
- 229910052797 bismuth Inorganic materials 0.000 claims description 3
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 3
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- 238000003618 dip coating Methods 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 229910052748 manganese Inorganic materials 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 claims description 3
- 239000010408 film Substances 0.000 description 185
- 239000010409 thin film Substances 0.000 description 51
- 230000004044 response Effects 0.000 description 25
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 20
- 230000008569 process Effects 0.000 description 20
- 239000002904 solvent Substances 0.000 description 20
- 150000001875 compounds Chemical class 0.000 description 16
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 13
- 150000002736 metal compounds Chemical class 0.000 description 13
- 239000010419 fine particle Substances 0.000 description 11
- 239000011701 zinc Substances 0.000 description 11
- 239000000203 mixture Substances 0.000 description 10
- YZYKBQUWMPUVEN-UHFFFAOYSA-N zafuleptine Chemical compound OC(=O)CCCCCC(C(C)C)NCC1=CC=C(F)C=C1 YZYKBQUWMPUVEN-UHFFFAOYSA-N 0.000 description 9
- IAQLJCYTGRMXMA-UHFFFAOYSA-M lithium;acetate;dihydrate Chemical compound [Li+].O.O.CC([O-])=O IAQLJCYTGRMXMA-UHFFFAOYSA-M 0.000 description 8
- 230000000593 degrading effect Effects 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 239000012298 atmosphere Substances 0.000 description 6
- 239000007788 liquid Substances 0.000 description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 5
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- 230000001747 exhibiting effect Effects 0.000 description 4
- 238000009413 insulation Methods 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- 229910052984 zinc sulfide Inorganic materials 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 3
- 238000000224 chemical solution deposition Methods 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 229910001026 inconel Inorganic materials 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- 238000010030 laminating Methods 0.000 description 3
- 238000001451 molecular beam epitaxy Methods 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000012827 research and development Methods 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical group CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 230000001133 acceleration Effects 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 239000012300 argon atmosphere Substances 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 230000006870 function Effects 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
- 229910052738 indium Inorganic materials 0.000 description 2
- 229910003437 indium oxide Inorganic materials 0.000 description 2
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-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
- 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
- 238000004549 pulsed laser deposition Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- 238000004544 sputter deposition Methods 0.000 description 2
- 238000010897 surface acoustic wave method Methods 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- QYIGOGBGVKONDY-UHFFFAOYSA-N 1-(2-bromo-5-chlorophenyl)-3-methylpyrazole Chemical compound N1=C(C)C=CN1C1=CC(Cl)=CC=C1Br QYIGOGBGVKONDY-UHFFFAOYSA-N 0.000 description 1
- LJDSTRZHPWMDPG-UHFFFAOYSA-N 2-(butylamino)ethanol Chemical compound CCCCNCCO LJDSTRZHPWMDPG-UHFFFAOYSA-N 0.000 description 1
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 1
- 229910017083 AlN Inorganic materials 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 229910002601 GaN Inorganic materials 0.000 description 1
- 229910001218 Gallium arsenide Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 description 1
- 229910007709 ZnTe Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 1
- 229910002113 barium titanate Inorganic materials 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 1
- 229940044175 cobalt sulfate Drugs 0.000 description 1
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 1
- JAWGVVJVYSANRY-UHFFFAOYSA-N cobalt(3+) Chemical compound [Co+3] JAWGVVJVYSANRY-UHFFFAOYSA-N 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 229940044658 gallium nitrate Drugs 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 229910052742 iron Inorganic materials 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
- 150000002739 metals Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000005297 pyrex Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052594 sapphire Inorganic materials 0.000 description 1
- 239000010980 sapphire Substances 0.000 description 1
- 150000003346 selenoethers Chemical class 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- -1 stainless steel Chemical class 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 description 1
- 150000004772 tellurides Chemical class 0.000 description 1
- 150000003568 thioethers Chemical class 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- IPCXNCATNBAPKW-UHFFFAOYSA-N zinc;hydrate Chemical compound O.[Zn] IPCXNCATNBAPKW-UHFFFAOYSA-N 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
Landscapes
- Crystals, And After-Treatments Of Crystals (AREA)
Description
本発明は、無機結晶膜およびその製造方法に関するものである。より詳しくは、当該無機結晶膜上に他種の膜を積層して素子化しても性能や信頼性の低下を招くことなく利用することができる膜構造を有する無機結晶膜およびその製造方法に関するものである。 The present invention relates to an inorganic crystal film and a method for producing the same. More specifically, the present invention relates to an inorganic crystal film having a film structure that can be used without degrading performance and reliability even if another type of film is laminated on the inorganic crystal film to form an element, and a method for manufacturing the same It is.
例えば圧力センサ等の機能性薄膜として用いられる無機結晶膜は、様々な技術分野で応用されると同時に、その活発な研究開発により新たな応用が提案されている。特に、ウルツ鉱型結晶構造を有する酸化亜鉛（ＺｎＯ）薄膜（無機結晶膜）は、幅広い分野で優れた特性を有する有用な物質である。ＺｎＯ膜は例えば表面弾性波（ＳＡＷ）フィルタとして実用化されており、また、研究開発においては例えばＺｎＯ圧電体膜を用いたエンジン用燃焼圧センサへの応用が具体的に提案されている（非特許文献１）。その他に、透明導電体としてガリウム（Ｇａ）若しくはアルミニウム（Ａｌ）をドープしたＺｎＯ薄膜は、スズ（Ｓｎ）をドープした酸化インジム（ＩＴＯ）薄膜を代替する材料として期待されており、また、半導体としてＺｎＯ薄膜の優れた電気特性および発光特性も注目されており、活発な研究開発が行われている。 For example, an inorganic crystal film used as a functional thin film such as a pressure sensor is applied in various technical fields, and at the same time, a new application is proposed due to its active research and development. In particular, a zinc oxide (ZnO) thin film (inorganic crystal film) having a wurtzite crystal structure is a useful substance having excellent characteristics in a wide range of fields. A ZnO film has been put into practical use as, for example, a surface acoustic wave (SAW) filter, and in research and development, for example, an application to a combustion pressure sensor for an engine using a ZnO piezoelectric film has been specifically proposed (non- Patent Document 1). In addition, a ZnO thin film doped with gallium (Ga) or aluminum (Al) as a transparent conductor is expected as a substitute for an indium oxide (ITO) thin film doped with tin (Sn). The excellent electrical properties and light emitting properties of ZnO thin films have also attracted attention, and active research and development are being conducted.
上記無機結晶膜の製造方法としては、スパッタ法、ＰＬＤ(Pulsed Laser Deposition) 法、ＭＢＥ(Molecular Beam Epitaxy)法、ＣＶＤ(Chemical Vapor Deposition) 法等があり、実用化や研究開発に用いられている。但し、これら製造方法では、真空チャンバー若しくは一般的なチャンバーを必要とするため、大面積の基材上に成膜をすることが難しく、またコストも掛かるという問題点を有している。それゆえ、大面積の薄膜を成膜することが可能で、特別な装置を必要としない、低コストの無機結晶膜の製造方法が強く求められている。 Examples of the method for producing the inorganic crystal film include sputtering, PLD (Pulsed Laser Deposition), MBE (Molecular Beam Epitaxy), and CVD (Chemical Vapor Deposition). . However, since these manufacturing methods require a vacuum chamber or a general chamber, there is a problem that it is difficult to form a film on a substrate having a large area and the cost is high. Therefore, there is a strong demand for a low-cost method for producing an inorganic crystal film that can form a thin film with a large area and does not require a special apparatus.
当該製造方法（成膜法）として、近年、化学溶液堆積法或いはゾル−ゲル法と称される手法が注目され、種々の無機結晶膜に対する研究が活発に行われている。上記化学溶液堆積法を用いて製造された無機結晶膜の構造としては、丸い粒子状の結晶粒が充填した構造が知られている（非特許文献２，３）。例えば、ゾル−ゲル法で成膜されたＺｎＯ薄膜の構造は、粒子径４０〜７５ｎｍの丸いＺｎＯ結晶粒子が疎に充填した構造であることが報告されている（非特許文献２）。 As the manufacturing method (film formation method), in recent years, a technique called chemical solution deposition method or sol-gel method has attracted attention, and research on various inorganic crystal films has been actively conducted. As a structure of an inorganic crystal film manufactured using the chemical solution deposition method, a structure in which round crystal grains are filled is known (Non-patent Documents 2 and 3). For example, it has been reported that the structure of a ZnO thin film formed by a sol-gel method is a structure in which round ZnO crystal particles having a particle diameter of 40 to 75 nm are loosely filled (Non-patent Document 2).
しかしながら、粒子が疎に充填した構造を有する無機結晶膜では、膜の上面から下面まで連続する間隙が存在することが多く、従って基材上に無機結晶膜を積層したり、或いは無機結晶膜上に他種の膜を積層して素子化したり、装置に応用したりする場合には問題点を生じる。具体的には、例えば、圧電特性を有する無機結晶膜を圧電素子として応用する場合には、高い電気導電性を示す基材上に無機結晶膜を積層することにより当該基材を下部電極として用い、さらに当該無機結晶膜上に上部電極を形成する構造が、簡単な構成で圧電体膜本来の圧電特性を利用することができる有効な構造である。ところが、上記構造の圧電素子を、膜の上面から下面まで連続する間隙が存在する無機結晶膜を用いて作製すると、上部電極に含まれ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析出し、その結果、上部電極と下部電極との間の絶縁性の低下若しくは短絡を引き起こし、圧電素子の圧電応答性が低下若しくは消失するという問題点を生じる。特許文献１に記載の圧電センサの発明においても、無機結晶膜が上記構造を有していると、圧電体薄膜（無機結晶膜）の形成時の不具合により欠損部分が生じ、電極間の短絡によって圧電センサが使用不能に陥ることが指摘されている。 However, in an inorganic crystal film having a structure in which particles are sparsely packed, there are many continuous gaps from the upper surface to the lower surface of the film, and therefore, an inorganic crystal film is laminated on a substrate, or an inorganic crystal film is formed on the inorganic crystal film. In the case of stacking other kinds of films into an element or applying to an apparatus, a problem arises. Specifically, for example, when an inorganic crystal film having piezoelectric characteristics is applied as a piezoelectric element, the base material is used as a lower electrode by laminating the inorganic crystal film on a base material exhibiting high electrical conductivity. Furthermore, the structure in which the upper electrode is formed on the inorganic crystal film is an effective structure that can utilize the piezoelectric characteristics inherent in the piezoelectric film with a simple configuration. However, when the piezoelectric element having the above structure is manufactured using an inorganic crystal film having a continuous gap from the upper surface to the lower surface of the film, the conductive compound contained in the upper electrode passes near the substrate or on the substrate through the gap. As a result, the insulation between the upper electrode and the lower electrode is deteriorated or short-circuited, and the piezoelectric response of the piezoelectric element is reduced or lost. Also in the invention of the piezoelectric sensor described in Patent Document 1, if the inorganic crystal film has the above-described structure, a defect portion is generated due to a defect at the time of forming the piezoelectric thin film (inorganic crystal film), and a short circuit between the electrodes causes It has been pointed out that the piezoelectric sensor becomes unusable.
また、例えばスパッタ法で成膜された従来のＺｎＯ圧電体膜は柱状晶からなる膜構造であるので、例えば、当該ＺｎＯ圧電体膜上に上部電極をシルクスクリーン印刷法により積層する場合には問題が生じる。つまり、電極材料となる金属微粒子を溶媒に分散させたインクを膜上面に塗布すると、このインクは柱状晶の粒界に沿って膜の下部方向に浸透し、その結果、金属微粒子が基材近傍若しくは基材上に析出する。従って、上記ＺｎＯ薄膜は、上部電極と下部電極との間の絶縁性の低下若しくは短絡を引き起こし、圧電応答性を示さなくなる場合がある。また、ＭＢＥ法では単結晶基材を用いて単結晶膜が得られるものの、コストが非常に掛かり、また単結晶膜の大面積化も困難であるため実用的でなく、工業的な製造方法には適さない。 In addition, since a conventional ZnO piezoelectric film formed by sputtering, for example, has a film structure made of columnar crystals, there is a problem when an upper electrode is laminated on the ZnO piezoelectric film by silk screen printing, for example. Occurs. In other words, when an ink in which metal fine particles used as an electrode material are dispersed in a solvent is applied to the upper surface of the film, the ink penetrates along the columnar crystal grain boundaries toward the lower part of the film, and as a result, the metal fine particles are in the vicinity of the substrate. Or it precipitates on a base material. Therefore, the ZnO thin film may cause a decrease in insulation or a short circuit between the upper electrode and the lower electrode, and may not exhibit piezoelectric response. Moreover, although a single crystal film can be obtained using a single crystal substrate in the MBE method, it is very expensive and difficult to increase the area of the single crystal film, which is not practical and is an industrial manufacturing method. Is not suitable.
本発明は、係る背景技術の問題点に鑑みてなされたものである。即ち、本発明は、上記背景技術の問題点を克服するためになされたものであり、その主たる目的は、大面積の薄膜を成膜することが可能で、特別な装置を必要としない、低コストの無機結晶膜の製造方法を提供することにある。また、本発明の主たる目的は、無機結晶膜上に他種の膜を積層して素子化しても性能や信頼性の低下を招くことなく利用することができる膜構造を有する無機結晶膜を提供することにある。 The present invention has been made in view of the problems of the background art. That is, the present invention has been made to overcome the above-mentioned problems of the background art, and its main purpose is to form a thin film with a large area, and does not require a special apparatus. An object of the present invention is to provide a cost-effective method for manufacturing an inorganic crystal film. In addition, the main object of the present invention is to provide an inorganic crystal film having a film structure that can be used without degrading performance and reliability even if another type of film is laminated on the inorganic crystal film to form an element. There is to do.
本発明者は、上記背景技術の問題点を克服するために鋭意研究を重ねた結果、基材上に形成された無機結晶膜であって、基材に接する下層は緻密層であり、膜の最上層は充填した粒子が互いに結合してなる結合層である少なくとも二層構造の無機結晶膜を用いることにより、上記問題点を解決することができることを見出し、この知見に基づいて本発明を完成させるに至った。 As a result of intensive studies in order to overcome the problems of the background art described above, the present inventor is an inorganic crystal film formed on a substrate, and the lower layer in contact with the substrate is a dense layer. We found that the above problem can be solved by using an inorganic crystal film having at least a two-layer structure, in which the uppermost layer is a bonded layer in which packed particles are bonded to each other, and the present invention has been completed based on this finding. I came to let you.
即ち、本発明に係る無機結晶膜は、上記課題を解決するために、基材上に形成された無機結晶膜であって、少なくとも二層構造であり、基材に接する下層は緻密層であり、膜の最上層は充填した粒子が互いに結合してなる結合層であることを特徴としている。 That is, the inorganic crystal film according to the present invention is an inorganic crystal film formed on a base material in order to solve the above-described problem, and has at least a two-layer structure, and a lower layer in contact with the base material is a dense layer. The uppermost layer of the membrane is characterized in that it is a bonding layer in which the filled particles are bonded to each other.
上記無機結晶膜は、一方の面から他方の面まで連続する間隙を有しないことがより好ましく、また、上記緻密層では粒子の粒界が認められないことがより好ましく、また、酸化物を主成分とすることがより好ましく、また、ウルツ鉱型結晶構造を有する化合物を主成分とすることがより好ましい。例えば、上記主成分が酸化亜鉛（ＺｎＯ）であることが特に好ましい。さらに、上記無機結晶膜は、上記酸化亜鉛に、リチウム（Ｌｉ）、マグネシウム（Ｍｇ）、鉄（Ｆｅ）、銅（Ｃｕ）、ニッケル（Ｎｉ）、コバルト（Ｃｏ）、マンガン（Ｍｎ）、アルミニウム（Ａｌ）、ガリウム（Ｇａ）、ビスマス（Ｂｉ）、およびプラセオジウム（Ｐｒ）からなる元素群より選択される少なくとも一種類の元素が添加されていることがより好ましく、また、膜厚が１００〜１００００ｎｍの範囲内であることがより好ましく、また、圧電特性を有することがより好ましい。 More preferably, the inorganic crystal film does not have a continuous gap from one surface to the other surface, more preferably no grain boundary is observed in the dense layer, and an oxide is mainly used. More preferably, the main component is a compound having a wurtzite crystal structure. For example, the main component is particularly preferably zinc oxide (ZnO). Furthermore, the inorganic crystal film is formed by adding lithium (Li), magnesium (Mg), iron (Fe), copper (Cu), nickel (Ni), cobalt (Co), manganese (Mn), aluminum ( More preferably, at least one element selected from the group consisting of Al), gallium (Ga), bismuth (Bi), and praseodymium (Pr) is added, and the film thickness is 100 to 10,000 nm. It is more preferable that it is within the range, and it is more preferable to have piezoelectric characteristics.
上記構成によれば、無機結晶膜は、基材に接する下層は緻密層であり、膜の最上層は充填した粒子が互いに結合してなる結合層であるので、当該無機結晶膜上に他種の膜を積層して素子化しても性能や信頼性の低下を招くことなく利用することができる。つまり、他種の膜を積層することができるので、例えば上部電極を直接形成することができ、無機結晶膜の圧電特性を効率的に利用することができる。それゆえ、上記構成によれば、他種の膜を直接積層して素子化しても性能や信頼性の低下を招くことなく利用することができる膜構造を有する無機結晶膜を提供することができる。 According to the above configuration, the inorganic crystal film is a dense layer in the lower layer in contact with the substrate, and the uppermost layer of the film is a bonded layer in which the filled particles are bonded to each other. Even if these films are stacked to form an element, it can be used without degrading performance and reliability. That is, since other types of films can be stacked, for example, the upper electrode can be directly formed, and the piezoelectric characteristics of the inorganic crystal film can be used efficiently. Therefore, according to the above configuration, it is possible to provide an inorganic crystal film having a film structure that can be used without degrading performance and reliability even if other types of films are directly stacked to form an element. .
また、上記構成によれば、無機結晶膜上に他種の膜を例えば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積層する場合にも利点がある。即ち、他種類の膜を形成する化合物および溶剤を含むインクが緻密層を通過することがない。それゆえ、例えば、各種機能性薄膜に応用するために、電気導電性を示す基材（基板）上に上記無機結晶膜を積層し、さらに上部電極を積層する場合においては、上部電極を形成するインクが緻密層を通過して基材上に達することがないので、上部電極を形成する化合物は最深でも緻密層より上（緻密層と基材との界面とは反対側の、緻密層における結合層側の境界面）に析出し、基材近傍若しくは基材上に析出することはない。従って、本発明に係る無機結晶膜を例えば圧電体として応用する場合に、上部電極と下部電極との間の絶縁性の低下若しくは短絡を引き起こさずに、良好な圧電応答性を示すことができる。 Moreover, according to the said structure, there exists an advantage also when laminating | stacking another kind of film | membrane on the inorganic crystal film, for example using a silk screen printing method or the inkjet printing method. That is, an ink containing a compound that forms another type of film and a solvent does not pass through the dense layer. Therefore, for example, in order to apply to various functional thin films, the above-mentioned inorganic crystal film is laminated on a base material (substrate) exhibiting electrical conductivity, and when the upper electrode is further laminated, the upper electrode is formed. Since the ink does not pass through the dense layer and reach the substrate, the compound forming the upper electrode is at the deepest level above the dense layer (the bond in the dense layer opposite to the interface between the dense layer and the substrate) It precipitates on the boundary surface on the layer side and does not deposit in the vicinity of the substrate or on the substrate. Therefore, when the inorganic crystal film according to the present invention is applied as, for example, a piezoelectric body, good piezoelectric response can be exhibited without causing a decrease in insulation or a short circuit between the upper electrode and the lower electrode.
また、本発明に係る無機結晶膜の製造方法は、上記課題を解決するために、上記無機結晶膜の製造方法であって、無機結晶膜となる金属種を含有する化学溶液を基材に塗布する塗布工程、塗布工程で得られた塗布膜を乾燥する乾燥工程、および、乾燥した膜を焼成する焼成工程、を備え、上記塗布工程、乾燥工程および焼成工程を１セットとして複数回繰り返すことを特徴としている。 Moreover, in order to solve the said subject, the manufacturing method of the inorganic crystal film which concerns on this invention is a manufacturing method of the said inorganic crystal film, Comprising: The chemical solution containing the metal seed | species used as an inorganic crystal film is apply | coated to a base material. A coating process, a drying process for drying the coating film obtained in the coating process, and a firing process for firing the dried film, and the coating process, the drying process, and the firing process are repeated multiple times as a set. It is a feature.
上記製造方法は、上記塗布工程および乾燥工程を１セットとして複数回繰り返した後、上記焼成工程を行うことがより好ましく、また、スピンコート法、ディップコート法、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上記塗布工程を行うことがより好ましい。 In the manufacturing method, it is more preferable to perform the baking step after repeating the coating step and the drying step a plurality of times as one set, and the spin coating method, dip coating method, silk screen printing method, or ink jet printing method. It is more preferable to carry out the coating step using
上記方法によれば、大面積の薄膜を成膜することが可能であり、特別な装置を必要としない、低コストの無機結晶膜の製造方法、即ち、他種の膜を積層して素子化しても性能や信頼性の低下を招くことなく利用することができる膜構造を有する無機結晶膜の製造方法を提供することができる。 According to the above method, a thin film having a large area can be formed, and a low-cost method for producing an inorganic crystal film that does not require a special apparatus, that is, by stacking other types of films into an element. However, it is possible to provide a method for manufacturing an inorganic crystal film having a film structure that can be used without degrading performance or reliability.
上記構成によれば、無機結晶膜上に他種の膜を積層して素子化しても性能や信頼性の低下を招くことなく利用することができる膜構造を有する無機結晶膜を提供することができるという効果を奏する。 According to the above configuration, it is possible to provide an inorganic crystal film having a film structure that can be used without degrading performance and reliability even if another type of film is stacked on the inorganic crystal film to form an element. There is an effect that can be done.
また、上記方法によれば、大面積の薄膜を成膜することが可能であり、特別な装置を必要としない、低コストの無機結晶膜の製造方法を提供することができるという効果を奏する。 Moreover, according to the said method, it is possible to form a thin film of a large area, and there exists an effect that the manufacturing method of a low cost inorganic crystal film which does not require a special apparatus can be provided.
＜無機結晶膜＞
本発明に係る無機結晶膜は、少なくとも二層構造であって、一方の外層は緻密層であり、他方の外層は充填した粒子が互いに結合してなる結合層である構成である。そして、本発明に係る無機結晶膜は、当該無機結晶膜となる金属種を含有する原料である金属化合物を用いて、本発明に係る製造方法によって成膜することによって形成されており、圧電特性を有している。
<Inorganic crystal film>
The inorganic crystal film according to the present invention has at least a two-layer structure, in which one outer layer is a dense layer and the other outer layer is a bonded layer formed by bonding packed particles to each other. The inorganic crystal film according to the present invention is formed by forming a film by the manufacturing method according to the present invention using a metal compound that is a raw material containing a metal species to be the inorganic crystal film, and has piezoelectric characteristics. have.
無機結晶膜となる金属種としては、例えば、亜鉛（Ｚｎ）、カドミウム（Ｃｄ）、チタン（Ｔｉ）、バリウム（Ｂａ）、インジウム（Ｉｎ）、アルミニウム（Ａｌ）が挙げられ、このうちＺｎがより好ましい。従って、無機結晶膜を構成する無機結晶としては、上記金属種を含有する従来公知の各種酸化物、並びに、硫化物、セレン化物、テルル化物、窒化物等が挙げられ、これら化合物は、一種類のみで無機結晶を構成していてもよく、二種類以上で無機結晶を構成していてもよい。絶縁体である無機結晶は、酸化亜鉛（ＺｎＯ）、酸化チタン（ＴｉＯ２）、チタン酸バリウム（ＢａＴｉＯ３）、酸化インジウム（Ｉｎ２Ｏ３）等の酸化物を主成分とすることがより好ましく、或いは、ウルツ鉱型結晶構造を有するＺｎＯ、ＡｌＮ、ＧａＮ、ＺｎＴｅ等の化合物を主成分とすることがより好ましい。さらに、無機結晶は、ＺｎＯを主成分とすることがより好ましい。ここで、本発明において「主成分」とは、無機結晶に当該成分が５０重量％以上含まれていることを指す。 Examples of the metal species used as the inorganic crystal film include zinc (Zn), cadmium (Cd), titanium (Ti), barium (Ba), indium (In), and aluminum (Al). preferable. Accordingly, examples of the inorganic crystals constituting the inorganic crystal film include conventionally known various oxides containing the above metal species, sulfides, selenides, tellurides, nitrides, and the like. The inorganic crystal may be constituted only by two or more kinds of inorganic crystals. The inorganic crystal as an insulator is more preferably composed mainly of an oxide such as zinc oxide (ZnO), titanium oxide (TiO 2 ), barium titanate (BaTiO 3 ), indium oxide (In 2 O 3 ). Alternatively, it is more preferable to use a compound such as ZnO, AlN, GaN, ZnTe or the like having a wurtzite crystal structure as a main component. Furthermore, the inorganic crystal is more preferably composed mainly of ZnO. Here, in the present invention, the “main component” means that the inorganic crystal contains the component in an amount of 50% by weight or more.
それゆえ、無機結晶膜となる金属種を含有する原料である金属化合物は、本発明に係る製造方法によって上記無機結晶に変換される金属化合物であればよく、具体的には、上記金属化合物を含有する化学溶液を調製することができる、溶剤に可溶若しくは分散することができる金属化合物であればよい。より具体的には、金属がＺｎである場合には、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、リン酸亜鉛水和物が挙げられる。 Therefore, the metal compound, which is a raw material containing a metal species that becomes an inorganic crystal film, may be any metal compound that can be converted into the inorganic crystal by the production method according to the present invention. Any metal compound can be used as long as the chemical solution can be prepared and can be dissolved or dispersed in a solvent. More specifically, when the metal is Zn, zinc acetate dihydrate, zinc oxide fine particles, acetylacetonate zinc hydrate, zinc sulfate hydrate, zinc benzoate, zinc carbonate, zinc chloride, A zinc phosphate hydrate is mentioned.
上記無機結晶には、絶縁性（電気抵抗）を向上させる（例えばＺｎＯの場合、３×１０６Ω・ｃｍ程度を１×１０８Ω・ｃｍ程度に向上させる）ために、必要に応じて、上記金属種とは異なる他の元素がドープされていてもよい。具体的には、上記無機結晶がＺｎＯである場合には、リチウム（Ｌｉ）、マグネシウム（Ｍｇ）、鉄（Ｆｅ）、銅（Ｃｕ）、ニッケル（Ｎｉ）、コバルト（Ｃｏ）、マンガン（Ｍｎ）、アルミニウム（Ａｌ）、ガリウム（Ｇａ）、ビスマス（Ｂｉ）、およびプラセオジウム（Ｐｒ）からなる元素群より選択される少なくとも一種類の元素がドープされていてもよい。無機結晶に他の元素をドープするには、原料である金属化合物に、上記元素を含有する化合物（ａ）を添加すればよい。当該化合物（ａ）としては、酢酸リチウム二水和物、硝酸リチウム、酢酸マグネシウム四水和物、硝酸マグネシウム六水和物、アセチルアセトナート鉄(II)、アセチルアセトナート鉄(III) 、酢酸銅(II)水和物、硫酸コバルト(II)水和物、アセチルアセトナートコバルト(III) 、硝酸ガリウム水和物、酢酸ビスマス(III) が挙げられる。 In order to improve the insulating property (electric resistance) of the inorganic crystal (for example, in the case of ZnO, about 3 × 10 6 Ω · cm is improved to about 1 × 10 8 Ω · cm), if necessary, Other elements different from the above metal species may be doped. Specifically, when the inorganic crystal is ZnO, lithium (Li), magnesium (Mg), iron (Fe), copper (Cu), nickel (Ni), cobalt (Co), manganese (Mn) , At least one element selected from the group consisting of aluminum (Al), gallium (Ga), bismuth (Bi), and praseodymium (Pr) may be doped. In order to dope other elements into the inorganic crystal, the compound (a) containing the above elements may be added to the metal compound as the raw material. Examples of the compound (a) include lithium acetate dihydrate, lithium nitrate, magnesium acetate tetrahydrate, magnesium nitrate hexahydrate, acetylacetonate iron (II), acetylacetonate iron (III), copper acetate (II) Hydrate, cobalt sulfate (II) hydrate, acetylacetonate cobalt (III), gallium nitrate hydrate, and bismuth acetate (III).
金属化合物に対する化合物（ａ）の添加量は、添加目的、および無機結晶膜の母体となる無機化合物とドープする元素種との組み合わせに応じて調整する必要がある。例えば、ＬｉドープしたＺｎＯ（Ｚｎ１−ｘＬｉｘＯ）結晶膜の場合には、ＺｎおよびＬｉの原子数の和を１００ａｔ．％としたとき、Ｌｉのドープ濃度ｘが、０を超え、２０ａｔ．％の範囲内であることがより好ましく、３〜６ａｔ．％の範囲内であることがさらに好ましい。このようなドープ濃度となるように、化合物（ａ）であるＬｉ化合物の添加量を決定する。 The amount of the compound (a) added to the metal compound needs to be adjusted according to the purpose of addition and the combination of the inorganic compound serving as the base of the inorganic crystal film and the element type to be doped. For example, in the case of a Li-doped ZnO (Zn 1-x Li x O) crystal film, the sum of the number of atoms of Zn and Li is set to 100 at. %, The doping concentration x of Li exceeds 0 and 20 at. % In the range of 3 to 6 at. More preferably, it is in the range of%. The addition amount of the Li compound, which is the compound (a), is determined so as to obtain such a dope concentration.
本発明に係る無機結晶膜が形成される基材としては、慣用の従来公知の各種基材が挙げられ、そのうち、後述する焼成工程を行うことができるように、耐熱性に優れている基材がより好ましく、無機結晶膜を圧電素子等の各種機能性薄膜に応用することができるように、電気導電性を示す基材（基板）がさらに好ましい。上記基材としては、具体的には、例えば、シリコン（Ｓｉ）やＧａＡｓ等の半導体基材、ＡｌやＣｕ、インコネル（Inconel ：登録商標）、ステンレス等の金属および合金の板若しくは箔、石英ガラスや耐熱ガラス（例えばパイレックスガラス：登録商標）等のガラス基材、アルミナ、シリカ、シリカアルミナ等のセラミックス基材、サファイア等の無機単結晶基材が挙げられる。また、上記基材上に白金（Ｐｔ）等の金属膜を積層した基材、当該金属膜と基材との密着性を向上させるためにチタン（Ｔｉ）等のバッファー層を上記基材上に成膜した上に金属膜を積層した基材、および、上記基材上にＩＴＯやＺｎＯ系の透明導電膜を積層した基材を用いてもよい。 Examples of the base material on which the inorganic crystal film according to the present invention is formed include various conventionally known base materials, and among them, a base material having excellent heat resistance so that a firing step described later can be performed. More preferably, a base material (substrate) exhibiting electrical conductivity is more preferable so that the inorganic crystal film can be applied to various functional thin films such as piezoelectric elements. Specific examples of the base material include semiconductor base materials such as silicon (Si) and GaAs, Al and Cu, Inconel (registered trademark), plates and foils of metals and alloys such as stainless steel, and quartz glass. And glass base materials such as heat resistant glass (for example, Pyrex glass: registered trademark), ceramic base materials such as alumina, silica and silica alumina, and inorganic single crystal base materials such as sapphire. Also, a base material obtained by laminating a metal film such as platinum (Pt) on the base material, and a buffer layer such as titanium (Ti) on the base material in order to improve the adhesion between the metal film and the base material. You may use the base material which laminated | stacked the metal film on film-forming, and the base material which laminated | stacked ITO and the ZnO type transparent conductive film on the said base material.
また、基材は、無機結晶膜を圧電素子等の各種機能性薄膜に応用することができるように、例えば、水道管やガス管等に装着して使用する場合には、上記金属および合金の板若しくは箔のように、可撓性を備えていることが好ましい。その場合に基材の厚さは、特に限定されないものの、その機能が損なわれない範囲においてより薄い方が好ましい。 In addition, the base material can be applied to various functional thin films such as a piezoelectric element such as an inorganic crystal film. It is preferable to have flexibility like a board or foil. In that case, the thickness of the substrate is not particularly limited, but it is preferably thinner as long as the function is not impaired.
本発明に係る無機結晶膜の具体的な膜構造については、後段の＜無機結晶膜の膜構造＞にて詳述する。 The specific film structure of the inorganic crystal film according to the present invention will be described in detail later in <Film structure of inorganic crystal film>.
＜無機結晶膜の製造方法＞
本発明に係る無機結晶膜の製造方法は、上記無機結晶膜の製造方法であって、無機結晶膜となる金属種を含有する化学溶液を基材に塗布する塗布工程、塗布工程で得られた塗布膜を乾燥する乾燥工程、および、乾燥した膜を焼成する焼成工程、を備え、上記塗布工程、乾燥工程および焼成工程を１セットとして複数回繰り返す方法である。以下、各工程について説明する。
<Method for producing inorganic crystal film>
The method for producing an inorganic crystal film according to the present invention is a method for producing the above inorganic crystal film, which is obtained by a coating process and a coating process in which a chemical solution containing a metal species to be an inorganic crystal film is applied to a substrate. The method includes a drying step of drying the coating film and a baking step of baking the dried film, and the coating step, the drying step, and the baking step are repeated a plurality of times as one set. Hereinafter, each step will be described.
（塗布工程）
無機結晶膜となる金属種を含有する化学溶液は、溶剤（溶媒とも称する）に上記金属化合物および必要に応じて上記化合物（ａ）を溶解させることにより、容易に調製することができる。上記溶剤としては、金属化合物および化合物（ａ）を溶解させることができる溶剤であればよく、特に限定されないものの、具体的には、例えば、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、水等が挙げられる。
(Coating process)
A chemical solution containing a metal species to be an inorganic crystal film can be easily prepared by dissolving the metal compound and, if necessary, the compound (a) in a solvent (also referred to as a solvent). The solvent is not particularly limited as long as it is a solvent capable of dissolving the metal compound and the compound (a). Specifically, for example, 2-methoxyethanol, 2-propanol, ethanol, 1-butanol , Trioctylphosphine, water and the like.
化学溶液における金属化合物の濃度は、無機結晶膜を効率的に成膜することができるように、より高い方が好ましく、具体的には、０．１〜１０モル／リットルの範囲内がより好ましく、０．２〜１．０モル／リットルの範囲内がさらに好ましい。 The concentration of the metal compound in the chemical solution is preferably higher so that the inorganic crystal film can be efficiently formed, specifically, more preferably in the range of 0.1 to 10 mol / liter. The range of 0.2 to 1.0 mol / liter is more preferable.
また、化学溶液における化合物（ａ）の濃度は、所望するドープ量に応じて設定すればよい。例えば、ＬｉドープしたＺｎＯ結晶膜の場合には、化合物（ａ）であるＬｉ化合物の濃度は、１×１０−３〜０．１モル／リットルの範囲内が好ましい。 Moreover, what is necessary is just to set the density | concentration of the compound (a) in a chemical solution according to the dope amount desired. For example, in the case of a Li-doped ZnO crystal film, the concentration of the Li compound as the compound (a) is preferably in the range of 1 × 10 −3 to 0.1 mol / liter.
さらに、金属化合物を溶剤に溶解させるために、２−アミノエタノール、Ｎ−ブチルエタノールアミン等の添加剤（安定化剤）を添加してもよい。当該添加剤の使用量は、特に限定されないものの、金属化合物と当モル以上であることが好ましい。例えば、金属化合物が酢酸亜鉛二水和物であり、添加剤が２−アミノエタノールである場合には、化学溶液中では、亜鉛は酢酸基と２−アミノエタノールとが配位した錯体として存在すると推定される。 Further, an additive (stabilizer) such as 2-aminoethanol or N-butylethanolamine may be added to dissolve the metal compound in the solvent. Although the usage-amount of the said additive is not specifically limited, It is preferable that it is a metal compound and an equimolar or more. For example, when the metal compound is zinc acetate dihydrate and the additive is 2-aminoethanol, zinc is present in the chemical solution as a complex in which an acetate group and 2-aminoethanol are coordinated. Presumed.
尚、化学溶液を調製する工程は、塗布工程の前に行われていればよく、従って、塗布工程内の一工程である必要は無い。つまり、化学溶液を予め調製しておき、塗布工程を行うまで保存しておいてもよい。 In addition, the process of preparing a chemical solution should just be performed before the application | coating process, Therefore, it is not necessary to be one process in an application | coating process. That is, a chemical solution may be prepared in advance and stored until the coating process is performed.
化学溶液を基材に塗布する方法としては、基材上に化学溶液を均一に塗布することができる塗布方法であればよく、特に限定されないものの、スピンコート法、ディップコート法、シルクスクリーン印刷法、またはインクジェット印刷法が簡便であるので好適である。これら塗布方法は、大面積の基材上に均一な膜厚の塗布膜を形成することができる。つまり、これら塗布方法を行うことにより、局所的な欠損部分を有しない、均一な膜厚の塗布膜が得られる。塗布条件は、化学溶液の組成（溶剤の種類、金属化合物の濃度等）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、より厚い方が効率的であるので好ましい。塗布は空気中で行えばよいが、塗布雰囲気は特に限定されない。 The method for applying the chemical solution to the substrate is not particularly limited as long as it is a coating method that can uniformly apply the chemical solution on the substrate, but the spin coating method, the dip coating method, and the silk screen printing method. Or, the inkjet printing method is preferable because it is simple. These coating methods can form a coating film having a uniform film thickness on a large-area substrate. That is, by performing these coating methods, a coating film having a uniform film thickness without having a local defect portion can be obtained. The coating conditions may be set according to the composition of the chemical solution (the type of solvent, the concentration of the metal compound, etc.), but a thicker coating film formed in a single coating process is more efficient. Therefore, it is preferable. Application may be performed in air, but the application atmosphere is not particularly limited.
（乾燥工程）
塗布工程で得られた塗布膜を乾燥する乾燥条件は、化学溶液の組成（溶剤の種類等）に応じて設定すればよいが、乾燥温度は７０℃〜３００℃の範囲内が好ましい。乾燥時間は乾燥温度に応じて設定すればよいが、３分〜３０分の範囲内が好ましい。また、乾燥は空気中で行えばよいが、乾燥雰囲気は特に限定されない。但し、蒸発した溶剤が大気中に放出されないように、ドラフト等で溶剤を回収することが望ましい。
(Drying process)
What is necessary is just to set the drying conditions which dry the coating film obtained at the application | coating process according to the composition (type of solvent, etc.) of a chemical solution, but the drying temperature has the preferable range of 70 to 300 degreeC. The drying time may be set according to the drying temperature, but is preferably in the range of 3 minutes to 30 minutes. The drying may be performed in the air, but the drying atmosphere is not particularly limited. However, it is desirable to recover the solvent by a draft or the like so that the evaporated solvent is not released into the atmosphere.
無機結晶膜となる金属種は化学溶液中ではイオン状態で存在し、塗布工程後、乾燥させると析出および凝集して、通常、平均粒子径が１〜５００ｎｍの範囲内、より好ましくは５〜２０ｎｍ程度の大きさの粒子（以下、微粒子とも称する）になる。つまり、塗布工程および乾燥工程を行うことによって得られる膜（乾燥した膜）は、微粒子が充填した集合体である。 The metal species that forms the inorganic crystal film exists in an ionic state in the chemical solution, and precipitates and aggregates when dried after the coating step, and usually has an average particle diameter in the range of 1 to 500 nm, more preferably 5 to 20 nm. It becomes a particle of a certain size (hereinafter also referred to as a fine particle). That is, the film (dried film) obtained by performing the coating process and the drying process is an aggregate filled with fine particles.
塗布工程および乾燥工程を一回行うことによって得られる膜（乾燥した膜）の膜厚は、５〜１００ｎｍの範囲内である。従って、膜厚をこれよりも厚くするには、塗布工程および乾燥工程を１セットとして複数回繰り返せばよい。焼成工程に至るまでに繰り返す回数は、特に限定されないものの、２〜１５回程度が好ましく、３〜１０回程度がより好ましい。 The film thickness (dried film) obtained by performing the coating process and the drying process once is in the range of 5 to 100 nm. Therefore, in order to make the film thickness thicker than this, the coating process and the drying process may be repeated multiple times as one set. The number of repetitions until the firing step is not particularly limited, but is preferably about 2 to 15 times, and more preferably about 3 to 10 times.
尚、塗布工程および乾燥工程を１セットとして複数回繰り返す場合において、それぞれの工程の条件（塗布条件、乾燥条件）同士は、互いに異なっていてもよいが、均一な無機結晶膜を形成するには互いに同一条件であることが好ましい。 In addition, in the case where the coating process and the drying process are repeated multiple times as one set, the conditions (coating conditions and drying conditions) of each process may be different from each other, but in order to form a uniform inorganic crystal film It is preferable that the conditions are the same.
（焼成工程）
上記塗布工程および乾燥工程を１セットとして少なくとも一回、好ましくは複数回繰り返した後、焼成工程を行って乾燥した膜を焼成する。これにより、基材上に無機結晶膜を形成する。
(Baking process)
The coating step and the drying step are repeated at least once, preferably a plurality of times as a set, and then the dried film is fired by performing the firing step. Thereby, an inorganic crystal film is formed on the substrate.
焼成条件は、膜（乾燥した膜）の組成（金属種の種類等）に応じて設定すればよいが、焼成温度は４５０℃〜８００℃の範囲内が好ましく、５５０℃〜７００℃の範囲内がより好ましい。具体的には、例えば基材がインコネル基材である場合には６５０℃程度が好ましい。焼成時間は焼成温度に応じて設定すればよいが、５分〜６０分の範囲内が好ましく、１０分〜３０分の範囲内がより好ましい。また、焼成は、大気中の他に、アルゴン雰囲気や窒素雰囲気等の不活性ガス中、或いは酸素と不活性ガスとの混合ガス雰囲気や、水素と不活性ガスとの混合ガス雰囲気中で行えばよいが、焼成雰囲気は特に限定されない。 The firing conditions may be set according to the composition of the film (dried film) (type of metal species, etc.), but the firing temperature is preferably within the range of 450 ° C to 800 ° C, and within the range of 550 ° C to 700 ° C. Is more preferable. Specifically, for example, when the substrate is an Inconel substrate, about 650 ° C. is preferable. The firing time may be set according to the firing temperature, but is preferably in the range of 5 minutes to 60 minutes, and more preferably in the range of 10 minutes to 30 minutes. In addition to the air, firing may be performed in an inert gas such as an argon atmosphere or a nitrogen atmosphere, a mixed gas atmosphere of oxygen and an inert gas, or a mixed gas atmosphere of hydrogen and an inert gas. Although it is good, the firing atmosphere is not particularly limited.
膜（乾燥した膜）を焼成することにより、充填した集合体となっている微粒子は互いに焼結する。つまり、充填した微粒子が互いに結合してなる多孔体である結合層を形成する。当該結合層は、微粒子が無秩序に（規則性無く）充填された構造である。 By firing the film (dried film), the filled fine particles are sintered together. That is, a bonding layer that is a porous body formed by bonding filled fine particles to each other is formed. The bonding layer has a structure in which fine particles are packed randomly (without regularity).
次いで、上記結合層が形成された基材を用いて上記塗布工程および乾燥工程を繰り返すと、新たに塗布された化学溶液が多孔体の間隙に入り込むので、当該結合層の間隙は乾燥工程で形成された微粒子によって埋められ、焼成（焼結）することによって粒子が緻密に充填された構造となっていく。つまり、その詳細な生成過程については不明であるものの、微粒子である微細な結晶粒子は、周囲の大きな結晶粒子に取り込まれながら成長すると推測され、基材上に先に形成されていた結合層は上記塗布工程、乾燥工程および焼成工程を１セットとして繰り返すことにより緻密な膜構造へと変化していき、この緻密な膜構造の上に、新たな結合層が形成されることになる。 Next, when the coating step and the drying step are repeated using the base material on which the bonding layer is formed, the newly applied chemical solution enters the gap between the porous bodies, so that the gap between the bonding layers is formed in the drying step. By being filled with the fine particles formed and fired (sintered), the particles are densely packed. In other words, although the detailed generation process is unknown, it is assumed that fine crystal particles, which are fine particles, grow while being taken into surrounding large crystal particles, and the bonding layer previously formed on the substrate is By repeating the coating process, the drying process and the baking process as one set, the film is changed into a dense film structure, and a new bonding layer is formed on the dense film structure.
塗布工程、乾燥工程および焼成工程を一回行うことによって得られる膜（無機結晶膜）の膜厚は、１０〜３００ｎｍの範囲内である。従って、膜厚をこれよりも厚くするには、塗布工程、乾燥工程および焼成工程を１セットとして複数回繰り返せばよい。繰り返す回数は、特に限定されないものの、無機結晶膜を機能性薄膜として用いる場合の膜厚が通常、１００〜１００００ｎｍの範囲内であることを考慮すれば、２〜２０回程度が好ましく、３〜１０回程度がより好ましい。 The film thickness (inorganic crystal film) obtained by performing the coating process, the drying process and the baking process once is in the range of 10 to 300 nm. Therefore, in order to make the film thickness thicker than this, the coating process, the drying process, and the baking process may be repeated multiple times as one set. Although the number of repetitions is not particularly limited, it is preferably about 2 to 20 times considering that the film thickness when an inorganic crystal film is used as a functional thin film is usually in the range of 100 to 10000 nm. About once is more preferable.
尚、塗布工程、乾燥工程および焼成工程を１セットとして複数回繰り返す場合において、それぞれの工程の条件（塗布条件、乾燥条件、焼成条件）同士は、互いに異なっていてもよいが、均一な無機結晶膜を形成するには互いに同一条件であることが好ましい。 In addition, when repeating a coating process, a drying process, and a baking process several times as one set, the conditions (coating conditions, drying conditions, baking conditions) of each process may be different from each other, but uniform inorganic crystals In order to form the film, it is preferable that the conditions are the same.
そして、上記塗布工程、乾燥工程および焼成工程を１セットとして複数回繰り返すことにより、ヘテロ構造の、つまり、少なくとも二層構造の無機結晶膜が得られる。 And the said application | coating process, a drying process, and a baking process are repeated several times as one set, and the inorganic crystal film of a heterostructure, ie, an at least 2 layer structure, is obtained.
本発明に係る製造方法によれば、大面積の薄膜を成膜することが可能であり、特別な装置を必要としない。従って、低コストの無機結晶膜の製造方法、即ち、他種の膜を積層して素子化しても性能や信頼性の低下を招くことなく利用することができる膜構造を有する無機結晶膜の製造方法を提供することができる。また、化学溶液堆積法を用いた本発明に係る製造方法によれば、無機結晶の結晶構造の極性を揃えることができる。それゆえ、得られる無機結晶膜は良好な圧電応答性を示す。 According to the manufacturing method of the present invention, a thin film having a large area can be formed, and no special apparatus is required. Therefore, a low-cost method for producing an inorganic crystal film, that is, production of an inorganic crystal film having a film structure that can be used without degrading performance and reliability even if other types of films are stacked to form an element. A method can be provided. Moreover, according to the manufacturing method according to the present invention using the chemical solution deposition method, the polarities of the crystal structures of the inorganic crystals can be made uniform. Therefore, the obtained inorganic crystal film exhibits good piezoelectric response.
＜無機結晶膜の膜構造＞
上記製造方法によって成膜することによって最終的に得られる基材に接する下層（基材に接している側の膜の最下層）は、塗布工程、乾燥工程および焼成工程を１セットとして複数回繰り返すことによって形成されているので、粒子の粒界が認められない緻密層となっている。これに対して、最終的に得られる膜の最上層（基材に接していない側の膜の最上層）は、塗布工程、乾燥工程および焼成工程を１セットとして一回繰り返すことによって形成されているので、充填した粒子が互いに結合してなる多孔体である結合層となっている。ここで、本発明において「粒子の粒界が認められない」とは、下記実施例に記載の観察条件で、膜断面をフィールドエミッション走査型電子顕微鏡（ＦＥ−ＳＥＭ）で観察しても、粒子の粒界が認められないことを指す。
<Film structure of inorganic crystal film>
The lower layer in contact with the base material finally obtained by forming the film by the above manufacturing method (the lowermost layer of the film in contact with the base material) is repeated a plurality of times with the coating process, drying process and firing process as one set. Therefore, it is a dense layer in which no grain boundary is observed. In contrast, the uppermost layer of the film finally obtained (the uppermost layer of the film not in contact with the substrate) is formed by repeating the coating process, the drying process, and the baking process once as one set. Therefore, it becomes a bonding layer which is a porous body in which the filled particles are bonded to each other. Here, in the present invention, “the grain boundary of the particle is not recognized” means that even when the film cross section is observed with a field emission scanning electron microscope (FE-SEM) under the observation conditions described in the following examples. This means that no grain boundary is recognized.
本発明に係る無機結晶膜では、基材に接している側に緻密層が形成されており、当該緻密層には膜表面（基材に接していない側の最上層の面）から連続する間隙が形成されないので、結合層から緻密層まで、即ち、基材に接していない側の膜表面から基材に接している側の膜表面まで、連続する間隙は形成されない。従って、無機結晶膜上に他種の膜を例えば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積層する場合には、他種の膜を形成するときに用いる溶剤が緻密層を通過することがない。それゆえ、例えば、各種機能性薄膜に応用するために、電気導電性を示す基材（基板）上に上記無機結晶膜を積層した場合においては、上記溶剤が緻密層を通過して基材上に達することがないので、他種の膜を形成する化合物は少なくとも緻密層上（基材が位置する面と反対側の結合層に近い面）に析出し、基材近傍若しくは基材上に析出することはない。従って、本発明に係る無機結晶膜を各種機能性薄膜に応用しても、上部電極と下部電極との間の絶縁性の低下若しくは短絡を引き起こさずに、良好な圧電応答性を示すことができる。 In the inorganic crystal film according to the present invention, a dense layer is formed on the side in contact with the substrate, and the dense layer has a gap continuous from the film surface (the surface of the uppermost layer on the side not in contact with the substrate). Therefore, a continuous gap is not formed from the bonding layer to the dense layer, that is, from the film surface on the side not in contact with the base material to the film surface on the side in contact with the base material. Therefore, when another type of film is laminated on the inorganic crystal film by using, for example, a silk screen printing method or an ink jet printing method, the solvent used when forming the other type of film does not pass through the dense layer. . Therefore, for example, when the inorganic crystal film is laminated on a base material (substrate) exhibiting electrical conductivity for application to various functional thin films, the solvent passes through the dense layer on the base material. Therefore, the compound that forms other types of film is deposited at least on the dense layer (the surface close to the bonding layer opposite to the surface on which the substrate is located) and deposited in the vicinity of the substrate or on the substrate. Never do. Therefore, even if the inorganic crystal film according to the present invention is applied to various functional thin films, good piezoelectric response can be exhibited without causing a decrease in insulation or a short circuit between the upper electrode and the lower electrode. .
本発明は上述した各実施形態に限定されるものではなく、請求項に示した範囲で種々の変更が可能であり、異なる実施形態にそれぞれ開示された技術的手段を適宜組み合わせて得られる実施形態についても本発明の技術的範囲に含まれる。 The present invention is not limited to the above-described embodiments, and various modifications are possible within the scope shown in the claims, and embodiments obtained by appropriately combining technical means disclosed in different embodiments. Is also included in the technical scope of the present invention.
以下、実施例に基づいて本発明をより詳細に説明するが、本発明は以下の実施例に限定されるものではない。 EXAMPLES Hereinafter, although this invention is demonstrated in detail based on an Example, this invention is not limited to a following example.
〔実施例１〕
２−メトキシエタノールを溶剤として用いて、酢酸亜鉛二水和物および２−アミノエタノール（添加剤）を各々０．５６４モル／リットルの濃度で、酢酸リチウム二水和物を０．０３６モル／リットルの濃度で含有する２−メトキシエタノール溶液からなるコート液を調製した（酢酸亜鉛二水和物および酢酸リチウム二水和物の合計ａｔ．数を１００ａｔ．％としたとき、酢酸リチウム二水和物のａｔ．数は６ａｔ．％）。
[Example 1]
Using 2-methoxyethanol as a solvent, zinc acetate dihydrate and 2-aminoethanol (additive) each at a concentration of 0.564 mol / liter and lithium acetate dihydrate 0.036 mol / liter A coating solution consisting of a 2-methoxyethanol solution contained at a concentration of (when the total at. Number of zinc acetate dihydrate and lithium acetate dihydrate is 100 at.%, Lithium acetate dihydrate At. Number of 6 at.%).
上記コート液を透過型電子顕微鏡（ＴＥＭ）観察用銅グリッドの上に滴下して乾燥させ、ＴＥＭ観察を行ったが、微結晶若しくはゲル微粒子の存在は認められなかった。観察条件は、加速電圧２００ｋＶ、倍率３０万倍とした。また、当該コート液の紫外−可視吸収スペクトルを測定した結果、ＺｎＯ結晶特有の吸収は認められなかった。従って、コート液中では亜鉛は酢酸基と２−アミノエタノールとが配位した錯体として存在していると推定された。 The coating solution was dropped onto a transmission electron microscope (TEM) observation copper grid, dried, and subjected to TEM observation. However, the presence of fine crystals or gel fine particles was not observed. The observation conditions were an acceleration voltage of 200 kV and a magnification of 300,000 times. Moreover, as a result of measuring the ultraviolet-visible absorption spectrum of the coating solution, no absorption specific to the ZnO crystal was observed. Accordingly, it was presumed that zinc was present in the coating solution as a complex in which an acetate group and 2-aminoethanol were coordinated.
得られたコート液を、インコネル（登録商標）６００で形成された基材（大きさ：２０ｍｍ角、厚さ：０．５ｍｍ）上にスピンコート法で塗布した（塗布工程）。その後、得られた塗布膜を、ホットプレート上で２００℃、５〜３０分程度乾燥した（乾燥工程）。 The obtained coating liquid was applied by spin coating on a base material (size: 20 mm square, thickness: 0.5 mm) formed of Inconel (registered trademark) 600 (application process). Thereafter, the obtained coating film was dried on a hot plate at 200 ° C. for about 5 to 30 minutes (drying step).
そして、上記塗布工程および乾燥工程を１セットとして６回繰り返して成膜した後、得られた膜を、アルゴン雰囲気中、電気炉内（昇温速度１０℃／分）で６５０℃、２０分間焼成した（焼成工程）。さらに、上記塗布工程（６回）、乾燥工程（６回）および焼成工程（１回）を１セットとして３回繰り返すことにより、膜厚が凡そ７００ｎｍの、ＬｉでドープされたＺｎＯ薄膜（無機結晶膜）を作成した（ＺｎＯ薄膜の組成はＺｎ０．９４Ｌｉ０．０６Ｏ）。得られた薄膜がウルツ鉱型結晶構造を有し、高いｃ軸配向性を示していることは、Ｘ線回析（ＸＲＤ）（Ｃｕ Ｋα 線照射）法を用いて確認した。 Then, after the above coating process and drying process were repeated six times as one set, the obtained film was baked in an electric furnace (heating rate: 10 ° C./min) for 20 minutes at 650 ° C. in an argon atmosphere. (Firing step). Furthermore, by repeating the coating process (6 times), the drying process (6 times), and the baking process (1 time) 3 times as a set, the LiO-doped ZnO thin film (inorganic crystal) having a film thickness of about 700 nm is obtained. (ZnO thin film has a composition of Zn 0.94 Li 0.06 O). It was confirmed using an X-ray diffraction (XRD) (Cu Kα ray irradiation) method that the obtained thin film had a wurtzite crystal structure and exhibited high c-axis orientation.
得られたＺｎＯ薄膜を基材ごと曲げることによって破断して、生じた膜断面をフィールドエミッション走査型電子顕微鏡（ＦＥ−ＳＥＭ）で観察した。観察条件は、加速電圧５．０ｋＶ、倍率５万倍とした。観察画像を図１に示す。当該観察画像においては、基材が下側、膜表面が上側になっている。観察画像から、以下のことが判った。 The obtained ZnO thin film was broken by bending the whole substrate, and the resulting film cross section was observed with a field emission scanning electron microscope (FE-SEM). The observation conditions were an acceleration voltage of 5.0 kV and a magnification of 50,000 times. An observation image is shown in FIG. In the observed image, the substrate is on the lower side and the film surface is on the upper side. From the observation image, the following was found.
即ち、ＺｎＯ薄膜における基材（膜裏面）から凡そ２００ｎｍの厚さ（高さ）までの下層（基材に接する下層に相当）では、均質な緻密層が形成されており、粒子の粒界は認められなかった。この下層は、塗布工程、乾燥工程および焼成工程を３回繰り返すことによって堆積された層に対応する。これに対して、ＺｎＯ薄膜における膜表面から凡そ５００ｎｍの厚さ（深さ）までの上層（膜の最上層に相当）では、充填した粒子が互いに結合してなる結合層が形成されていた（粒子の粒界が認められた）。そして、上層のうち膜表面から凡そ３００ｎｍの厚さ（深さ）までは、粒子径１００ｎｍ程度の丸い粒子が無秩序に充填して互いに結合した構造を有する層となっていた。この層は、３回目に行った塗布工程、乾燥工程および焼成工程によって堆積された層に対応しており、当該構造は、非特許文献１において１回の焼成工程で作成された膜の膜構造と類似していた。 That is, in the lower layer (corresponding to the lower layer in contact with the substrate) from the substrate (film back surface) to the thickness (height) of about 200 nm in the ZnO thin film, a homogeneous dense layer is formed, and the grain boundaries of the particles are I was not able to admit. This lower layer corresponds to a layer deposited by repeating the coating process, the drying process and the baking process three times. On the other hand, in the upper layer (corresponding to the uppermost layer of the film) from the surface of the ZnO thin film to the thickness (depth) of about 500 nm, a bonding layer formed by bonding the filled particles to each other was formed ( Grain boundaries were observed). The upper layer from the film surface to a thickness (depth) of about 300 nm is a layer having a structure in which round particles having a particle diameter of about 100 nm are randomly packed and bonded to each other. This layer corresponds to the layer deposited by the coating process, the drying process, and the baking process performed for the third time, and the structure is a film structure of a film created in one baking process in Non-Patent Document 1. It was similar.
次に、上記塗布工程、乾燥工程および焼成工程を３回繰り返すことにより得られたＺｎＯ薄膜を切断して、生じた膜断面をクロスセクションポリッシャで加工した後、フィールドエミッション走査型電子顕微鏡で観察した。観察画像を図２に示す。当該観察画像においては、基材（図２ではSubstrate）が下側、膜（図２ではFilm）表面が上側になっている。観察画像から、以下のことが判った。 Next, the ZnO thin film obtained by repeating the coating step, the drying step and the firing step three times was cut, and the resulting film cross section was processed with a cross section polisher, and then observed with a field emission scanning electron microscope. . An observation image is shown in FIG. In the observed image, the substrate (Substrate in FIG. 2) is on the lower side, and the surface of the film (Film) is on the upper side. From the observation image, the following was found.
即ち、ＺｎＯ薄膜における上層側では、粒子が無秩序に充填して互いに結合しているため、膜表面から凡そ３００ｎｍの厚さ（深さ）まで、連続する間隙が認められた。これに対して、それよりも下層側では、緻密層となっているため、閉じられた空隙（間隙）は幾つか存在するものの、膜表面から連続する間隙は認められなかった。つまり、膜表面から基材（膜裏面）まで、連続する間隙は認められなかった。 That is, on the upper layer side of the ZnO thin film, since the particles are randomly packed and bonded to each other, a continuous gap is recognized from the film surface to a thickness (depth) of about 300 nm. On the other hand, since it is a dense layer on the lower layer side, there are some closed voids (gap), but no continuous gap was observed from the film surface. That is, no continuous gap was recognized from the film surface to the base material (film back surface).
上記構造のＺｎＯ薄膜の膜表面に、Ｐｔからなる直径２ｍｍの上部電極を６箇所形成し、基材を下部電極として圧電素子を作製し、それぞれの上部電極に関して電気抵抗および圧電応答性を測定した。その結果、上記圧電素子の電気抵抗は、６箇所とも短絡は認められず、その平均の抵抗値は７×１０７Ω・ｃｍであった。ｄ３３メータを用いて測定した上記圧電素子の圧電定数は、６箇所とも圧電応答性を示し、その平均値は５．８ｐＣ／Ｎであった。一般的に実用化されている水晶（圧電定数は２．０ｐＣ／Ｎ程度）と比較すると、当該ＺｎＯ薄膜が良好な圧電応答性を示すことが確認された。 Six upper electrodes with a diameter of 2 mm made of Pt were formed on the surface of the ZnO thin film having the above structure, and piezoelectric elements were produced using the base material as the lower electrode. The electric resistance and piezoelectric response of each upper electrode were measured. . As a result, as for the electrical resistance of the piezoelectric element, no short circuit was observed at all six locations, and the average resistance value was 7 × 10 7 Ω · cm. d The piezoelectric constant of the piezoelectric element measured using a 33 meter showed piezoelectric response at all six locations, and the average value was 5.8 pC / N. It was confirmed that the ZnO thin film shows a good piezoelectric response when compared with a quartz crystal that is generally put into practical use (piezoelectric constant is about 2.0 pC / N).
〔実施例２〕
２−メトキシエタノールを溶剤として用いて、酢酸亜鉛二水和物および２−アミノエタノールを各々０．６００モル／リットルの濃度で含有する２−メトキシエタノール溶液からなるコート液を調製した以外は、実施例１と同様の方法を行うことにより、ＺｎＯ薄膜を作成した（ＺｎＯ薄膜の組成はＺｎＯ）。
[Example 2]
Implementation was conducted except that 2-methoxyethanol was used as a solvent, and a coating solution consisting of a 2-methoxyethanol solution containing zinc acetate dihydrate and 2-aminoethanol at a concentration of 0.600 mol / liter each was prepared. By performing the same method as in Example 1, a ZnO thin film was prepared (the composition of the ZnO thin film was ZnO).
上記構造のＺｎＯ薄膜を用いて、実施例１と同様の方法で圧電素子を作製し、電気抵抗および圧電応答性を測定した。その結果、上記圧電素子の電気抵抗は、６箇所のうち５箇所で短絡は認められず、その平均の抵抗値は３×１０６Ω・ｃｍであった。ｄ３３メータを用いて測定した上記圧電素子の圧電定数は、短絡が認められなかった５箇所で圧電応答性を示し、その平均値は３．９ｐＣ／Ｎであった。従って、当該ＺｎＯ薄膜は良好な圧電応答性を示した。 Using the ZnO thin film having the above structure, a piezoelectric element was produced in the same manner as in Example 1, and the electrical resistance and piezoelectric response were measured. As a result, the electrical resistance of the piezoelectric element was not found to be short-circuited at 5 out of 6 locations, and the average resistance value was 3 × 10 6 Ω · cm. d The piezoelectric constant of the piezoelectric element measured using a 33 meter showed piezoelectric response at five locations where no short circuit was observed, and the average value was 3.9 pC / N. Therefore, the ZnO thin film showed good piezoelectric response.
〔実施例３〕
２−メトキシエタノールを溶剤として用いて、酢酸亜鉛二水和物および２−アミノエタノールを各々０．５８２モル／リットルの濃度で、酢酸リチウム二水和物を０．０１８モル／リットルの濃度で含有する２−メトキシエタノール溶液からなるコート液を調製した以外は、実施例１と同様の方法を行うことにより、ＺｎＯ薄膜を作成した（ＺｎＯ薄膜の組成はＺｎ０．９７Ｌｉ０．０３Ｏ）。
Example 3
Using 2-methoxyethanol as a solvent, zinc acetate dihydrate and 2-aminoethanol each containing 0.582 mol / liter and lithium acetate dihydrate containing 0.018 mol / liter to except the preparation of the 2-methoxyethanol solution consisting coating liquid, by carrying out the same method as in example 1 to prepare a ZnO thin film (the composition of ZnO thin Zn 0.97 Li 0.03 O).
上記構造のＺｎＯ薄膜を用いて、実施例１と同様の方法で圧電素子を作製し、電気抵抗および圧電応答性を測定した。その結果、上記圧電素子の電気抵抗は、６箇所とも短絡は認められず、その平均の抵抗値は５×１０８Ω・ｃｍであった。ｄ３３メータを用いて測定した上記圧電素子の圧電定数は、６箇所とも圧電応答性を示し、その平均値は５．６ｐＣ／Ｎであった。従って、当該ＺｎＯ薄膜は良好な圧電応答性を示した。 Using the ZnO thin film having the above structure, a piezoelectric element was produced in the same manner as in Example 1, and the electrical resistance and piezoelectric response were measured. As a result, no short circuit was observed at any of the six electrical resistances of the piezoelectric element, and the average resistance value was 5 × 10 8 Ω · cm. d The piezoelectric constant of the piezoelectric element measured using a 33 meter showed piezoelectric response at all six locations, and the average value was 5.6 pC / N. Therefore, the ZnO thin film showed good piezoelectric response.
〔実施例４〕
２−メトキシエタノールを溶剤として用いて、酢酸亜鉛二水和物および２−アミノエタノールを各々０．５４０モル／リットルの濃度で、酢酸リチウム二水和物を０．０６０モル／リットルの濃度で含有する２−メトキシエタノール溶液からなるコート液を調製した以外は、実施例１と同様の方法を行うことにより、ＺｎＯ薄膜を作成した（ＺｎＯ薄膜の組成はＺｎ０．９０Ｌｉ０．１０Ｏ）。
Example 4
Using 2-methoxyethanol as solvent, zinc acetate dihydrate and 2-aminoethanol each containing 0.540 mol / liter and lithium acetate dihydrate containing 0.060 mol / liter to except the preparation of the 2-methoxyethanol solution consisting coating liquid, by carrying out the same method as in example 1 to prepare a ZnO thin film (the composition of ZnO thin Zn 0.90 Li 0.10 O).
上記構造のＺｎＯ薄膜を用いて、実施例１と同様の方法で圧電素子を作製し、電気抵抗および圧電応答性を測定した。その結果、上記圧電素子の電気抵抗は、６箇所とも短絡は認められず、その平均の抵抗値は１×１０７Ω・ｃｍであった。ｄ３３メータを用いて測定した上記圧電素子の圧電定数は、６箇所とも圧電応答性を示し、その平均値は３．０ｐＣ／Ｎであった。従って、当該ＺｎＯ薄膜は良好な圧電応答性を示した。 Using the ZnO thin film having the above structure, a piezoelectric element was produced in the same manner as in Example 1, and the electrical resistance and piezoelectric response were measured. As a result, as for the electrical resistance of the piezoelectric element, no short circuit was observed at all six locations, and the average resistance value was 1 × 10 7 Ω · cm. d Piezoelectric constants of the piezoelectric element measured using a 33 meter showed piezoelectric response at all six locations, and the average value was 3.0 pC / N. Therefore, the ZnO thin film showed good piezoelectric response.
〔実施例５〕
２−メトキシエタノールを溶剤として用いて、酢酸亜鉛二水和物および２−アミノエタノールを各々０．５１０モル／リットルの濃度で、酢酸リチウム二水和物を０．０９０モル／リットルの濃度で含有する２−メトキシエタノール溶液からなるコート液を調製した以外は、実施例１と同様の方法を行うことにより、ＺｎＯ薄膜を作成した（ＺｎＯ薄膜の組成はＺｎ０．８５Ｌｉ０．１５Ｏ）。
Example 5
Using 2-methoxyethanol as solvent, zinc acetate dihydrate and 2-aminoethanol each containing 0.510 mol / liter and lithium acetate dihydrate containing 0.090 mol / liter to except the preparation of the 2-methoxyethanol solution consisting coating liquid, by carrying out the same method as in example 1 to prepare a ZnO thin film (the composition of ZnO thin Zn 0.85 Li 0.15 O).
上記構造のＺｎＯ薄膜を用いて、実施例１と同様の方法で圧電素子を作製し、電気抵抗および圧電応答性を測定した。その結果、上記圧電素子の電気抵抗は、６箇所とも短絡は認められず、その平均の抵抗値は１×１０７Ω・ｃｍであった。ｄ３３メータを用いて測定した上記圧電素子の圧電定数は、６箇所とも圧電応答性を示し、その平均値は２．３ｐＣ／Ｎであった。従って、当該ＺｎＯ薄膜は良好な圧電応答性を示した。 Using the ZnO thin film having the above structure, a piezoelectric element was produced in the same manner as in Example 1, and the electrical resistance and piezoelectric response were measured. As a result, as for the electrical resistance of the piezoelectric element, no short circuit was observed at all six locations, and the average resistance value was 1 × 10 7 Ω · cm. d The piezoelectric constant of the above piezoelectric element measured using a 33 meter showed piezoelectric response at all six locations, and the average value was 2.3 pC / N. Therefore, the ZnO thin film showed good piezoelectric response.
〔実施例６〕
２−メトキシエタノールを溶剤として用いて、酢酸亜鉛二水和物および２−アミノエタノールを各々０．４８０モル／リットルの濃度で、酢酸リチウム二水和物を０．１２０モル／リットルの濃度で含有する２−メトキシエタノール溶液からなるコート液を調製した以外は、実施例１と同様の方法を行うことにより、ＺｎＯ薄膜を作成した（ＺｎＯ薄膜の組成はＺｎ０．８０Ｌｉ０．２０Ｏ）。
Example 6
Using 2-methoxyethanol as a solvent, each containing zinc acetate dihydrate and 2-aminoethanol at a concentration of 0.480 mol / liter and lithium acetate dihydrate at a concentration of 0.120 mol / liter to except the preparation of the 2-methoxyethanol solution consisting coating liquid, by carrying out the same method as in example 1 to prepare a ZnO thin film (the composition of ZnO thin Zn 0.80 Li 0.20 O).
上記構造のＺｎＯ薄膜を用いて、実施例１と同様の方法で圧電素子を作製し、電気抵抗および圧電応答性を測定した。その結果、上記圧電素子の電気抵抗は、６箇所とも短絡は認められず、その平均の抵抗値は１×１０７Ω・ｃｍであった。ｄ３３メータを用いて測定した上記圧電素子の圧電定数は、６箇所とも圧電応答性を示し、その平均値は１．８ｐＣ／Ｎであった。従って、当該ＺｎＯ薄膜は良好な圧電応答性を示した。 Using the ZnO thin film having the above structure, a piezoelectric element was produced in the same manner as in Example 1, and the electrical resistance and piezoelectric response were measured. As a result, as for the electrical resistance of the piezoelectric element, no short circuit was observed at all six locations, and the average resistance value was 1 × 10 7 Ω · cm. d The piezoelectric constant of the piezoelectric element measured using a 33 meter showed piezoelectric response at all six locations, and the average value was 1.8 pC / N. Therefore, the ZnO thin film showed good piezoelectric response.
〔比較例１〕
実施例１と同様の方法で、塗布工程（６回）、乾燥工程（６回）および焼成工程（１回）を１セットとして１回行うことにより、ＬｉでドープされたＺｎＯ薄膜を作成した（ＺｎＯ薄膜の組成はＺｎ０．９４Ｌｉ０．０６Ｏ）。
[Comparative Example 1]
In the same manner as in Example 1, a coating step (6 times), a drying step (6 times), and a baking step (1 time) were performed once as a set, thereby producing a ZnO thin film doped with Li ( The composition of the ZnO thin film is Zn 0.94 Li 0.06 O).
上記ＺｎＯ薄膜の膜表面に、Ｐｔからなる直径２ｍｍの上部電極を６箇所形成し、基材を下部電極として圧電素子を作製し、それぞれの上部電極に関して電気抵抗および圧電応答性を測定した。その結果、６箇所のうち５箇所で短絡が認められ、短絡が認められた箇所では圧電応答性を全く示さなかった。 Six upper electrodes made of Pt with a diameter of 2 mm were formed on the surface of the ZnO thin film, and piezoelectric elements were produced using the base material as the lower electrode. The electric resistance and piezoelectric response of each upper electrode were measured. As a result, a short circuit was observed at five of the six locations, and no piezoelectric response was exhibited at the locations where the short circuit was observed.
本発明に係る無機結晶膜およびその製造方法は、例えば、圧力センサ、圧電センサ（圧電材料）、機械的エネルギーを電気エネルギーに変換する圧電発電装置に組み込まれる圧電体膜、強誘電体メモリに組み込まれる強誘電体膜、タッチパネル装置に組み込まれる圧電体膜および透明導電膜、各種ディスプレーや太陽電池装置に組み込まれる透明導電膜、バリスタ素子に組み込まれる誘電体膜、発光素子の発光体膜等の機能性薄膜に応用される無機結晶膜およびその製造方法として、利用することができる。 The inorganic crystal film and the manufacturing method thereof according to the present invention are incorporated into, for example, a pressure sensor, a piezoelectric sensor (piezoelectric material), a piezoelectric film incorporated in a piezoelectric power generation device that converts mechanical energy into electric energy, and a ferroelectric memory. Functions such as a ferroelectric film, a piezoelectric film and a transparent conductive film incorporated in a touch panel device, a transparent conductive film incorporated in various displays and solar cell devices, a dielectric film incorporated in a varistor element, and a light emitter film of a light emitting element It can utilize as an inorganic crystal film applied to a conductive thin film, and its manufacturing method.
Claims (6)
上記無機結晶膜は基材上に形成され、少なくとも二層構造であり、基材に接する下層は粒子間の間隙が認められない緻密層であり、膜の最上層は充填した粒子が互いに結合してなる多孔体である結合層であり、酸化亜鉛（ＺｎＯ）を主成分とし、
無機結晶膜となる金属種を含有する化学溶液を基材に塗布する塗布工程、
７０〜３００℃の温度にて、塗布工程で得られた塗布膜を乾燥する乾燥工程、および、
５５０〜７００℃の温度にて、乾燥した膜を焼成する焼成工程、
を備え、上記塗布工程および上記乾燥工程をセットとして複数回繰り返した後、上記焼成工程を１回行うことを１セットとして複数回繰り返すことを特徴とする無機結晶膜の製造方法。 A method for producing an inorganic crystal film , comprising:
The inorganic crystal film is formed on a substrate and has at least a two-layer structure. The lower layer in contact with the substrate is a dense layer in which no gap between particles is observed, and the uppermost layer of the film is formed by bonding packed particles to each other. A bonding layer that is a porous body comprising zinc oxide (ZnO) as a main component,
A coating process for coating a base material with a chemical solution containing a metal species to be an inorganic crystal film;
A drying step of drying the coating film obtained in the coating step at a temperature of 70 to 300 ° C., and
A firing step of firing the dried film at a temperature of 550 to 700 ° C .;
The method for producing an inorganic crystal film is characterized in that after repeating the coating step and the drying step a plurality of times as a set, the firing step is repeated a plurality of times as a set.
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