JP2015107905A - Non-lead dielectric thin film, composition for forming this film, and method for forming this film - Google Patents
Non-lead dielectric thin film, composition for forming this film, and method for forming this film Download PDFInfo
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- JP2015107905A JP2015107905A JP2014172455A JP2014172455A JP2015107905A JP 2015107905 A JP2015107905 A JP 2015107905A JP 2014172455 A JP2014172455 A JP 2014172455A JP 2014172455 A JP2014172455 A JP 2014172455A JP 2015107905 A JP2015107905 A JP 2015107905A
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- 239000010409 thin film Substances 0.000 title claims abstract description 148
- 239000000203 mixture Substances 0.000 title claims description 127
- 238000000034 method Methods 0.000 title claims description 28
- 239000010408 film Substances 0.000 title claims description 20
- 241000877463 Lanio Species 0.000 claims abstract description 9
- 239000007788 liquid Substances 0.000 claims description 31
- 239000000758 substrate Substances 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 12
- 238000000576 coating method Methods 0.000 claims description 11
- 238000010587 phase diagram Methods 0.000 claims description 11
- 229910004121 SrRuO Inorganic materials 0.000 claims description 10
- 239000011248 coating agent Substances 0.000 claims description 10
- 239000003990 capacitor Substances 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 8
- 238000002425 crystallisation Methods 0.000 claims description 6
- 230000008025 crystallization Effects 0.000 claims description 6
- 238000000224 chemical solution deposition Methods 0.000 claims description 5
- 239000002131 composite material Substances 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 230000001590 oxidative effect Effects 0.000 claims description 3
- 239000012212 insulator Substances 0.000 claims description 2
- 238000010897 surface acoustic wave method Methods 0.000 claims description 2
- 239000013078 crystal Substances 0.000 abstract description 28
- 229910017682 MgTi Inorganic materials 0.000 abstract 2
- 239000010936 titanium Substances 0.000 description 27
- 239000011777 magnesium Substances 0.000 description 25
- 238000010304 firing Methods 0.000 description 11
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 10
- 239000002994 raw material Substances 0.000 description 10
- 150000004703 alkoxides Chemical class 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- -1 barium carboxylate Chemical class 0.000 description 8
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 229910004298 SiO 2 Inorganic materials 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 229910052719 titanium Inorganic materials 0.000 description 4
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 4
- 229910052797 bismuth Inorganic materials 0.000 description 3
- 150000007942 carboxylates Chemical class 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 238000001755 magnetron sputter deposition Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- RVDLHGSZWAELAU-UHFFFAOYSA-N 5-tert-butylthiophene-2-carbonyl chloride Chemical compound CC(C)(C)C1=CC=C(C(Cl)=O)S1 RVDLHGSZWAELAU-UHFFFAOYSA-N 0.000 description 2
- 229910004356 Ti Raw Inorganic materials 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- DPASUYABUPGRDP-UHFFFAOYSA-K [Bi+3].CCC(CC)C([O-])=O.CCC(CC)C([O-])=O.CCC(CC)C([O-])=O Chemical compound [Bi+3].CCC(CC)C([O-])=O.CCC(CC)C([O-])=O.CCC(CC)C([O-])=O DPASUYABUPGRDP-UHFFFAOYSA-K 0.000 description 2
- 229910052788 barium Inorganic materials 0.000 description 2
- ITHZDDVSAWDQPZ-UHFFFAOYSA-L barium acetate Chemical compound [Ba+2].CC([O-])=O.CC([O-])=O ITHZDDVSAWDQPZ-UHFFFAOYSA-L 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- NUMHJBONQMZPBW-UHFFFAOYSA-K bis(2-ethylhexanoyloxy)bismuthanyl 2-ethylhexanoate Chemical compound [Bi+3].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O NUMHJBONQMZPBW-UHFFFAOYSA-K 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- AQBLLJNPHDIAPN-LNTINUHCSA-K iron(3+);(z)-4-oxopent-2-en-2-olate Chemical compound [Fe+3].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O AQBLLJNPHDIAPN-LNTINUHCSA-K 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 150000002902 organometallic compounds Chemical class 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000004528 spin coating Methods 0.000 description 2
- 239000002344 surface layer Substances 0.000 description 2
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 description 2
- 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 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- FWPJKASAXSYLKP-UHFFFAOYSA-L barium(2+);2-ethylbutanoate Chemical compound [Ba+2].CCC(CC)C([O-])=O.CCC(CC)C([O-])=O FWPJKASAXSYLKP-UHFFFAOYSA-L 0.000 description 1
- VJFFDDQGMMQGTQ-UHFFFAOYSA-L barium(2+);2-ethylhexanoate Chemical compound [Ba+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O VJFFDDQGMMQGTQ-UHFFFAOYSA-L 0.000 description 1
- TVSNZOUKUFGNLK-UHFFFAOYSA-N barium(2+);butan-1-olate Chemical compound [Ba+2].CCCC[O-].CCCC[O-] TVSNZOUKUFGNLK-UHFFFAOYSA-N 0.000 description 1
- CPUJSIVIXCTVEI-UHFFFAOYSA-N barium(2+);propan-2-olate Chemical compound [Ba+2].CC(C)[O-].CC(C)[O-] CPUJSIVIXCTVEI-UHFFFAOYSA-N 0.000 description 1
- 238000005234 chemical deposition Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- CRGZYKWWYNQGEC-UHFFFAOYSA-N magnesium;methanolate Chemical compound [Mg+2].[O-]C.[O-]C CRGZYKWWYNQGEC-UHFFFAOYSA-N 0.000 description 1
- WNJYXPXGUGOGBO-UHFFFAOYSA-N magnesium;propan-1-olate Chemical compound CCCO[Mg]OCCC WNJYXPXGUGOGBO-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 238000009283 thermal hydrolysis Methods 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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Abstract
Description
本発明は、鉛フリーで、高い結晶配向性と高い比誘電率を有し、ＢａＴｉＯ3の成分、Ｂｉ(Ｍｇ0.5Ｔｉ0.5)Ｏ3の成分及びＢｉＦｅＯ3の成分のうち少なくとも２成分を含有する非鉛誘電体薄膜及びこの薄膜形成用組成物並びにこの薄膜の形成方法に関する。更に詳しくは、化学溶液堆積法(Chemical Solution Deposition法)により形成された非鉛誘電体薄膜に関する。 The present invention is lead-free, has a high crystal orientation and a high dielectric constant, and contains at least two components of a BaTiO 3 component, a Bi (Mg 0.5 Ti 0.5 ) O 3 component, and a BiFeO 3 component. The present invention relates to a lead-free dielectric thin film, a composition for forming the thin film, and a method for forming the thin film. More specifically, the present invention relates to a lead-free dielectric thin film formed by a chemical solution deposition method.
近年、鉛含有の誘電体薄膜を用いた各種電子機器の廃棄後の環境負荷を危惧し、鉛フリーの誘電体薄膜が求められている。こうした鉛フリーの誘電体薄膜として、これまでＢａＴｉＯ3とＢｉ(Ｍｇ0.5Ｔｉ0.5)Ｏ3の二元系組成物をパルスレーザ蒸着法によりエピタキシャル成長させて形成された薄膜が示されている（例えば、非特許文献１参照。）。 In recent years, there has been a demand for lead-free dielectric thin films in view of the environmental impact after disposal of various electronic devices using lead-containing dielectric thin films. As such a lead-free dielectric thin film, a thin film formed by epitaxially growing a binary composition of BaTiO 3 and Bi (Mg 0.5 Ti 0.5 ) O 3 by a pulse laser deposition method has been shown (for example, (Refer nonpatent literature 1.).
しかしながら、上記非特許文献１に示される薄膜は、高価な真空プロセスの１種であるパルスレーザ蒸着法で作製されるため量産成膜性に課題があり、かつ複雑な組成を成膜するため大きな基板上での膜組成の均一性に問題があった。 However, the thin film shown in Non-Patent Document 1 has a problem in mass production film formation because it is produced by a pulse laser vapor deposition method which is one of expensive vacuum processes, and is large because a complicated composition is formed. There was a problem with the uniformity of the film composition on the substrate.
本発明の目的は、鉛フリーで、高い結晶配向性と高い比誘電率を有する非鉛誘電体薄膜を提供することにある。 An object of the present invention is to provide a lead-free dielectric thin film that is lead-free and has high crystal orientation and high relative dielectric constant.
本発明の第１の観点は、ＢａＴｉＯ3の成分、Ｂｉ(Ｍｇ0.5Ｔｉ0.5)Ｏ3の成分及びＢｉＦｅＯ3の成分のうち少なくとも２成分を含有して（１１１）配向に制御された非鉛誘電体薄膜である。 The first aspect of the present invention is a lead-free dielectric controlled to have a (111) orientation by containing at least two of a BaTiO 3 component, a Bi (Mg 0.5 Ti 0.5 ) O 3 component, and a BiFeO 3 component. It is a body thin film.
本発明の第２の観点は、ＢａＴｉＯ3の成分、Ｂｉ(Ｍｇ0.5Ｔｉ0.5)Ｏ3の成分及びＢｉＦｅＯ3の成分のうち少なくとも２成分を含有して（１００）配向に制御された非鉛誘電体薄膜である。 The second aspect of the present invention is a lead-free dielectric controlled to have a (100) orientation, containing at least two of the components BaTiO 3 , Bi (Mg 0.5 Ti 0.5 ) O 3 , and BiFeO 3. It is a body thin film.
本発明の第３の観点は、第１の観点に基づく発明であって、（１１１）配向したＳｒＲｕＯ3上に形成された非鉛誘電体薄膜である。 A third aspect of the present invention is an invention based on the first aspect, and is a lead-free dielectric thin film formed on (111) -oriented SrRuO 3 .
本発明の第４の観点は、第２の観点に基づく発明であって、（１００）配向したＬａＮｉＯ3上に形成された非鉛誘電体薄膜である。 A fourth aspect of the present invention is an invention based on the second aspect, and is a lead-free dielectric thin film formed on (100) oriented LaNiO 3 .
本発明の第５の観点は、第１の観点に基づく発明であって、前記少なくとも２成分の組成が、ｘ[ＢａＴｉＯ3]・ｙ[Ｂｉ(Ｍｇ0.5Ｔｉ0.5)Ｏ3]・ｚ[ＢｉＦｅＯ3]、かつｘ＋ｙ＋ｚ＝１とするとき、[ＢａＴｉＯ3]・[Ｂｉ(Ｍｇ0.5Ｔｉ0.5)Ｏ3]・[ＢｉＦｅＯ3]の三元相図上で、ｘ＝０．９０・ｙ＝０．１０と、ｘ＝０．３０・ｚ＝０．７０と、ｙ＝０．１０・ｚ＝０．９０と、ｘ＝０．３０・ｙ＝０．７０とで囲まれた第１領域内の組成である非鉛誘電体薄膜である。 A fifth aspect of the present invention is the invention based on the first aspect, wherein the composition of the at least two components is x [BaTiO 3 ] · y [Bi (Mg 0.5 Ti 0.5 ) O 3 ] · z [BiFeO. 3 ] and x + y + z = 1, on the ternary phase diagram of [BaTiO 3 ] · [Bi (Mg 0.5 Ti 0.5 ) O 3 ] · [BiFeO 3 ], x = 0.90 · y = 0. 10, x = 0.30 · z = 0.70, y = 0.10 · z = 0.90, and x = 0.30 · y = 0.70. A lead-free dielectric thin film having a composition.
本発明の第６の観点は、第２の観点に基づく発明であって、前記少なくとも２成分の組成が、ｘ[ＢａＴｉＯ3]・ｙ[Ｂｉ(Ｍｇ0.5Ｔｉ0.5)Ｏ3]・ｚ[ＢｉＦｅＯ3]、かつｘ＋ｙ＋ｚ＝１とするとき、[ＢａＴｉＯ3]・[Ｂｉ(Ｍｇ0.5Ｔｉ0.5)Ｏ3]・[ＢｉＦｅＯ3]の三元相図上で、ｘ＝０．９０・ｙ＝０．１０と、ｘ＝０．３０・ｚ＝０．７０と、ｙ＝０．１０・ｚ＝０．９０と、ｘ＝０．３０・ｙ＝０．７０とで囲まれた第１領域内の組成である非鉛誘電体薄膜である。 A sixth aspect of the present invention is the invention based on the second aspect, wherein the composition of the at least two components is x [BaTiO 3 ] · y [Bi (Mg 0.5 Ti 0.5 ) O 3 ] · z [BiFeO. 3 ] and x + y + z = 1, on the ternary phase diagram of [BaTiO 3 ] · [Bi (Mg 0.5 Ti 0.5 ) O 3 ] · [BiFeO 3 ], x = 0.90 · y = 0. 10, x = 0.30 · z = 0.70, y = 0.10 · z = 0.90, and x = 0.30 · y = 0.70. A lead-free dielectric thin film having a composition.
本発明の第７の観点は、第３の観点に基づく発明であって、前記少なくとも２成分の組成が、ｘ[ＢａＴｉＯ3]・ｙ[Ｂｉ(Ｍｇ0.5Ｔｉ0.5)Ｏ3]・ｚ[ＢｉＦｅＯ3]、かつｘ＋ｙ＋ｚ＝１とするとき、[ＢａＴｉＯ3]・[Ｂｉ(Ｍｇ0.5Ｔｉ0.5)Ｏ3]・[ＢｉＦｅＯ3]の三元相図上で、ｘ＝０．９０・ｙ＝０．１０と、ｘ＝０．３０・ｚ＝０．７０と、ｙ＝０．１０・ｚ＝０．９０と、ｘ＝０．３０・ｙ＝０．７０とで囲まれた第１領域内の組成である非鉛誘電体薄膜である。 A seventh aspect of the present invention is the invention based on the third aspect, wherein the composition of the at least two components is x [BaTiO 3 ] · y [Bi (Mg 0.5 Ti 0.5 ) O 3 ] · z [BiFeO. 3 ] and x + y + z = 1, on the ternary phase diagram of [BaTiO 3 ] · [Bi (Mg 0.5 Ti 0.5 ) O 3 ] · [BiFeO 3 ], x = 0.90 · y = 0. 10, x = 0.30 · z = 0.70, y = 0.10 · z = 0.90, and x = 0.30 · y = 0.70. A lead-free dielectric thin film having a composition.
本発明の第８の観点は、第４の観点に基づく発明であって、前記少なくとも２成分の組成が、ｘ[ＢａＴｉＯ3]・ｙ[Ｂｉ(Ｍｇ0.5Ｔｉ0.5)Ｏ3]・ｚ[ＢｉＦｅＯ3]、かつｘ＋ｙ＋ｚ＝１とするとき、[ＢａＴｉＯ3]・[Ｂｉ(Ｍｇ0.5Ｔｉ0.5)Ｏ3]・[ＢｉＦｅＯ3]の三元相図上で、ｘ＝０．９０・ｙ＝０．１０と、ｘ＝０．３０・ｚ＝０．７０と、ｙ＝０．１０・ｚ＝０．９０と、ｘ＝０．３０・ｙ＝０．７０とで囲まれた第１領域内の組成である非鉛誘電体薄膜である。 An eighth aspect of the present invention is the invention based on the fourth aspect, wherein the composition of the at least two components is x [BaTiO 3 ] · y [Bi (Mg 0.5 Ti 0.5 ) O 3 ] · z [BiFeO. 3 ] and x + y + z = 1, on the ternary phase diagram of [BaTiO 3 ] · [Bi (Mg 0.5 Ti 0.5 ) O 3 ] · [BiFeO 3 ], x = 0.90 · y = 0. 10, x = 0.30 · z = 0.70, y = 0.10 · z = 0.90, and x = 0.30 · y = 0.70. A lead-free dielectric thin film having a composition.
本発明の第９の観点は、第５の観点に基づく発明であって、前記少なくとも２成分の組成が、前記第１領域内の組成であって、ｘ＝０．７０・ｙ＝０．０９・ｚ＝０．２１と、ｘ＝０．３０・ｚ＝０．７０と、ｘ＝０．１５・ｙ＝０．１０・ｚ＝０．７５と、ｘ＝０．３０・ｙ＝０．５０・ｚ＝０．２０とで囲まれた第２領域内の組成である非鉛誘電体薄膜である。 A ninth aspect of the present invention is the invention based on the fifth aspect, wherein the composition of the at least two components is a composition in the first region, and x = 0.70 · y = 0.09. Z = 0.21, x = 0.30 · z = 0.70, x = 0.15 · y = 0.10 · z = 0.75, and x = 0.30 · y = 0. A lead-free dielectric thin film having a composition in the second region surrounded by 50 · z = 0.20.
本発明の第１０の観点は、第６の観点に基づく発明であって、前記少なくとも２成分の組成が、前記第１領域内の組成であって、ｘ＝０．７０・ｙ＝０．０９・ｚ＝０．２１と、ｘ＝０．３０・ｚ＝０．７０と、ｘ＝０．１５・ｙ＝０．１０・ｚ＝０．７５と、ｘ＝０．３０・ｙ＝０．５０・ｚ＝０．２０とで囲まれた第２領域内の組成である非鉛誘電体薄膜である。 A tenth aspect of the present invention is the invention based on the sixth aspect, wherein the composition of the at least two components is a composition in the first region, and x = 0.70 · y = 0.09. Z = 0.21, x = 0.30 · z = 0.70, x = 0.15 · y = 0.10 · z = 0.75, and x = 0.30 · y = 0. A lead-free dielectric thin film having a composition in the second region surrounded by 50 · z = 0.20.
本発明の第１１の観点は、第７の観点に基づく発明であって、前記少なくとも２成分の組成が、前記第１領域内の組成であって、ｘ＝０．７０・ｙ＝０．０９・ｚ＝０．２１と、ｘ＝０．３０・ｚ＝０．７０と、ｘ＝０．１５・ｙ＝０．１０・ｚ＝０．７５と、ｘ＝０．３０・ｙ＝０．５０・ｚ＝０．２０とで囲まれた第２領域内の組成である非鉛誘電体薄膜である。 An eleventh aspect of the present invention is the invention based on the seventh aspect, wherein the composition of the at least two components is a composition in the first region, and x = 0.70 · y = 0.09. Z = 0.21, x = 0.30 · z = 0.70, x = 0.15 · y = 0.10 · z = 0.75, and x = 0.30 · y = 0. A lead-free dielectric thin film having a composition in the second region surrounded by 50 · z = 0.20.
本発明の第１２の観点は、第８の観点に基づく発明であって、前記少なくとも２成分の組成が、前記第１領域内の組成であって、ｘ＝０．７０・ｙ＝０．０９・ｚ＝０．２１と、ｘ＝０．３０・ｚ＝０．７０と、ｘ＝０．１５・ｙ＝０．１０・ｚ＝０．７５と、ｘ＝０．３０・ｙ＝０．５０・ｚ＝０．２０とで囲まれた第２領域内の組成である非鉛誘電体薄膜である。 A twelfth aspect of the present invention is the invention based on the eighth aspect, wherein the composition of the at least two components is a composition in the first region, and x = 0.70 · y = 0.09. Z = 0.21, x = 0.30 · z = 0.70, x = 0.15 · y = 0.10 · z = 0.75, and x = 0.30 · y = 0. A lead-free dielectric thin film having a composition in the second region surrounded by 50 · z = 0.20.
本発明の第１３の観点は、第９の観点に基づく発明であって、前記少なくとも２成分の組成が、前記第２領域内の組成であって、ｘ＝０．４０・ｙ＝０．１０・ｚ＝０．５０と、ｘ＝０．３０・ｙ＝０．１０・ｚ＝０．６０と、ｘ＝０．３０・ｙ＝０．５０・ｚ＝０．２０とで囲まれた第３領域内の組成である非鉛誘電体薄膜である。 A thirteenth aspect of the present invention is the invention based on the ninth aspect, wherein the composition of the at least two components is a composition in the second region, and x = 0.40 · y = 0.10.・ Z = 0.50, x = 0.30 ・ y = 0.10 ・ z = 0.60, and x = 0.30 ・ y = 0.50 ・ z = 0.20 A lead-free dielectric thin film having a composition in three regions.
本発明の第１４の観点は、第１０の観点に基づく発明であって、前記少なくとも２成分の組成が、前記第２領域内の組成であって、ｘ＝０．４０・ｙ＝０．１０・ｚ＝０．５０と、ｘ＝０．３０・ｙ＝０．１０・ｚ＝０．６０と、ｘ＝０．３０・ｙ＝０．５０・ｚ＝０．２０とで囲まれた第３領域内の組成である非鉛誘電体薄膜である。 A fourteenth aspect of the present invention is the invention based on the tenth aspect, wherein the composition of the at least two components is a composition in the second region, and x = 0.40 · y = 0.10.・ Z = 0.50, x = 0.30 ・ y = 0.10 ・ z = 0.60, and x = 0.30 ・ y = 0.50 ・ z = 0.20 A lead-free dielectric thin film having a composition in three regions.
本発明の第１５の観点は、第１１の観点に基づく発明であって、前記少なくとも２成分の組成が、前記第２領域内の組成であって、ｘ＝０．４０・ｙ＝０．１０・ｚ＝０．５０と、ｘ＝０．３０・ｙ＝０．１０・ｚ＝０．６０と、ｘ＝０．３０・ｙ＝０．５０・ｚ＝０．２０とで囲まれた第３領域内の組成である非鉛誘電体薄膜である。 A fifteenth aspect of the present invention is the invention based on the eleventh aspect, wherein the composition of the at least two components is a composition in the second region, and x = 0.40 · y = 0.10.・ Z = 0.50, x = 0.30 ・ y = 0.10 ・ z = 0.60, and x = 0.30 ・ y = 0.50 ・ z = 0.20 A lead-free dielectric thin film having a composition in three regions.
本発明の第１６の観点は、第１２の観点に基づく発明であって、前記少なくとも２成分の組成が、前記第２領域内の組成であって、ｘ＝０．４０・ｙ＝０．１０・ｚ＝０．５０と、ｘ＝０．３０・ｙ＝０．１０・ｚ＝０．６０と、ｘ＝０．３０・ｙ＝０．５０・ｚ＝０．２０とで囲まれた第３領域内の組成である非鉛誘電体薄膜である。 A sixteenth aspect of the present invention is the invention based on the twelfth aspect, wherein the composition of the at least two components is a composition in the second region, and x = 0.40 · y = 0.10.・ Z = 0.50, x = 0.30 ・ y = 0.10 ・ z = 0.60, and x = 0.30 ・ y = 0.50 ・ z = 0.20 A lead-free dielectric thin film having a composition in three regions.
本発明の第１７の観点は、第５の観点に基づく発明であって、前記少なくとも２成分の組成が、前記第１領域内の組成であって、ｘ＝０．９０・ｙ＝０．１０と、ｘ＝０．８０・ｙ＝０．０９・ｚ＝０．２１と、ｘ＝０．６０・ｙ＝０．０９・ｚ＝０．３１と、ｘ＝０．６０・ｙ＝０．４０とで囲まれた第４領域内の組成である非鉛誘電体薄膜である。 A seventeenth aspect of the present invention is the invention based on the fifth aspect, wherein the composition of the at least two components is a composition in the first region, and x = 0.90 · y = 0.10. X = 0.80 · y = 0.09 · z = 0.21, x = 0.60 · y = 0.09 · z = 0.31, and x = 0.60 · y = 0. 40 is a lead-free dielectric thin film having a composition in the fourth region surrounded by 40.
本発明の第１８の観点は、第６の観点に基づく発明であって、前記少なくとも２成分の組成が、前記第１領域内の組成であって、ｘ＝０．９０・ｙ＝０．１０と、ｘ＝０．８０・ｙ＝０．０９・ｚ＝０．２１と、ｘ＝０．６０・ｙ＝０．０９・ｚ＝０．３１と、ｘ＝０．６０・ｙ＝０．４０とで囲まれた第４領域内の組成である非鉛誘電体薄膜である。 An eighteenth aspect of the present invention is the invention based on the sixth aspect, wherein the composition of the at least two components is a composition in the first region, and x = 0.90 · y = 0.10. X = 0.80 · y = 0.09 · z = 0.21, x = 0.60 · y = 0.09 · z = 0.31, and x = 0.60 · y = 0. 40 is a lead-free dielectric thin film having a composition in the fourth region surrounded by 40.
本発明の第１９の観点は、第７の観点に基づく発明であって、前記少なくとも２成分の組成が、前記第１領域内の組成であって、ｘ＝０．９０・ｙ＝０．１０と、ｘ＝０．８０・ｙ＝０．０９・ｚ＝０．２１と、ｘ＝０．６０・ｙ＝０．０９・ｚ＝０．３１と、ｘ＝０．６０・ｙ＝０．４０とで囲まれた第４領域内の組成である非鉛誘電体薄膜である。 A nineteenth aspect of the present invention is the invention based on the seventh aspect, wherein the composition of the at least two components is a composition in the first region, and x = 0.90 · y = 0.10. X = 0.80 · y = 0.09 · z = 0.21, x = 0.60 · y = 0.09 · z = 0.31, and x = 0.60 · y = 0. 40 is a lead-free dielectric thin film having a composition in the fourth region surrounded by 40.
本発明の第２０の観点は、第８の観点に基づく発明であって、前記少なくとも２成分の組成が、前記第１領域内の組成であって、ｘ＝０．９０・ｙ＝０．１０と、ｘ＝０．８０・ｙ＝０．０９・ｚ＝０．２１と、ｘ＝０．６０・ｙ＝０．０９・ｚ＝０．３１と、ｘ＝０．６０・ｙ＝０．４０とで囲まれた第４領域内の組成である非鉛誘電体薄膜である。 A twentieth aspect of the present invention is the invention based on the eighth aspect, wherein the composition of the at least two components is a composition in the first region, and x = 0.90 · y = 0.10. X = 0.80 · y = 0.09 · z = 0.21, x = 0.60 · y = 0.09 · z = 0.31, and x = 0.60 · y = 0. 40 is a lead-free dielectric thin film having a composition in the fourth region surrounded by 40.
本発明の第２１の観点は、第１の観点ないし第２０の観点のいずれかに基づく発明であって、化学溶液堆積法により形成された非鉛誘電体薄膜である。 A twenty-first aspect of the present invention is an invention based on any one of the first to twentieth aspects, and is a lead-free dielectric thin film formed by a chemical solution deposition method.
本発明の第２２の観点は、第１ないし第２０の観点のいずれかに基づく誘電体薄膜を、化学溶液堆積法により形成するための非鉛誘電体薄膜形成用液組成物である。 A twenty-second aspect of the present invention is a liquid composition for forming a lead-free dielectric thin film for forming a dielectric thin film according to any of the first to twentieth aspects by a chemical solution deposition method.
本発明の第２３の観点は、第２２の観点に基づく非鉛誘電体薄膜形成用液組成物を基板に塗布して塗膜を形成する塗布工程と、前記基板に形成された塗膜を、空気中、酸化雰囲気中又は含水蒸気雰囲気中で加熱して乾燥する乾燥工程と、前記乾燥工程の途中から或いは完了後に前記塗膜を、Ｏ2，Ｎ2，Ａｒ，Ｎ2Ｏ，Ｈ2若しくはこれらの混合ガス中又は乾燥空気中或いは水蒸気を含む前記雰囲気中で結晶化温度以上で焼成する焼成工程とを含む非鉛誘電体薄膜の形成方法である。 According to a twenty-third aspect of the present invention, there is provided a coating process in which a liquid composition for forming a lead-free dielectric thin film according to the twenty-second aspect is applied to a substrate to form a coating film, and a coating film formed on the substrate. A drying step of heating and drying in air, an oxidizing atmosphere or a steam-containing atmosphere, and the coating film from the middle of or after completion of the drying step, O 2 , N 2 , Ar, N 2 O, H 2 or A non-lead dielectric thin film forming method including a firing step of firing at a temperature equal to or higher than a crystallization temperature in the mixed gas or in the air containing dry air or water vapor.
本発明の第２４の観点は、第２３の観点に基づく発明であって、前記塗布工程及び前記乾燥工程が複数回繰り返され、前記焼成工程が前記複数回繰り返された最終乾燥工程の途中から或いは完了後に前記塗膜を、Ｏ2，Ｎ2，Ａｒ，Ｎ2Ｏ，Ｈ2若しくはこれらの混合ガス中又は乾燥空気中或いは水蒸気を含む前記雰囲気中で結晶化温度以上で焼成する焼成工程である非鉛誘電体薄膜の形成方法である。 A twenty-fourth aspect of the present invention is the invention based on the twenty-third aspect, wherein the coating step and the drying step are repeated a plurality of times, and the baking step is repeated halfway through the final drying step. It is a firing step in which the coating film is fired at a temperature equal to or higher than the crystallization temperature in O 2 , N 2 , Ar, N 2 O, H 2 or a mixed gas thereof, in dry air, or in an atmosphere containing water vapor after completion. This is a method for forming a lead-free dielectric thin film.
本発明の第２５の観点は、第１ないし第２１の観点のいずれかに基づく非鉛誘電体薄膜を有する薄膜コンデンサ、キャパシタ、ＩＰＤ、ＤＲＡＭメモリ用コンデンサ、積層コンデンサ、ＬＣノイズフィルタ素子、トランジスタのゲート絶縁体、不揮発性メモリ、又は焦電型赤外線検出素子のいずれかからなる複合電子部品である。 According to a twenty-fifth aspect of the present invention, there is provided a thin film capacitor, a capacitor, an IPD, a DRAM memory capacitor, a multilayer capacitor, an LC noise filter element, a transistor having a lead-free dielectric thin film according to any of the first to twenty-first aspects. It is a composite electronic component comprising any one of a gate insulator, a nonvolatile memory, and a pyroelectric infrared detection element.
本発明の第２６の観点は、第１ないし第２１の観点のいずれかに基づく非鉛誘電体薄膜を有する圧電素子、電気光学素子、アクチュエータ、共振子、超音波モータ、表面弾性波素子、又はトランスジューサのいずれかからなる複合電子部品である。 According to a twenty-sixth aspect of the present invention, there is provided a piezoelectric element, an electro-optic element, an actuator, a resonator, an ultrasonic motor, a surface acoustic wave element, or the like having a lead-free dielectric thin film according to any of the first to twenty-first aspects. It is a composite electronic component consisting of one of the transducers.
本発明の第１の観点の非鉛誘電体薄膜は、鉛フリーであって、（１１１）配向し高い比誘電率を有する。 The lead-free dielectric thin film according to the first aspect of the present invention is lead-free and has a (111) orientation and a high relative dielectric constant.
本発明の第２の観点の非鉛誘電体薄膜は、鉛フリーであって、（１００）配向し比較的高い比誘電率を有する。 The lead-free dielectric thin film according to the second aspect of the present invention is lead-free and has a (100) orientation and a relatively high relative dielectric constant.
本発明の第３の観点の非鉛誘電体薄膜は、鉛フリーであって、（１１１）配向したＳｒＲｕＯ3上に形成されるため、下層の結晶配向性を引きずりやすいため、強く（１１１）配向する特長がある。 Since the lead-free dielectric thin film according to the third aspect of the present invention is lead-free and is formed on (111) -oriented SrRuO 3 , it tends to drag the crystal orientation of the lower layer, and thus strongly (111) -oriented. There is a feature to do.
本発明の第４の観点の非鉛誘電体薄膜は、鉛フリーであって、（１００）配向したＬａＮｉＯ3上に形成されるため、下層の結晶配向性を引きずりやすいため、強く（１００）配向する特長がある。 The lead-free dielectric thin film according to the fourth aspect of the present invention is lead-free and is formed on (100) -oriented LaNiO 3, so that it is easy to drag the crystal orientation of the lower layer, and therefore strongly (100) -oriented. There is a feature to do.
本発明の第５ないし第８の観点のいずれかの非鉛誘電体薄膜は、鉛フリーであって、少なくとも２成分の組成を三元図上の第１領域内の組成にすることにより、高い比誘電率を有するようになる特長がある。 The lead-free dielectric thin film according to any one of the fifth to eighth aspects of the present invention is lead-free, and is high by making the composition of at least two components into the composition in the first region on the ternary diagram. There is a feature of having a relative dielectric constant.
本発明の第９ないし第１２の観点のいずれかの非鉛誘電体薄膜は、鉛フリーであって、少なくとも２成分の組成を三元図上の第２領域内の組成にすることにより、より高い比誘電率を有するようになる特長がある。 The lead-free dielectric thin film according to any one of the ninth to twelfth aspects of the present invention is lead-free, and has a composition of the at least two components in the second region on the ternary diagram. It has the feature of having a high relative dielectric constant.
本発明の第１３ないし第１６の観点のいずれかの非鉛誘電体薄膜は、鉛フリーであって、少なくとも２成分の組成を三元図上の第３領域内の組成にすることにより、より一層高い比誘電率を有するようになる特長がある。 The lead-free dielectric thin film according to any one of the thirteenth to sixteenth aspects of the present invention is lead-free, and the composition of at least two components is made to be the composition in the third region on the ternary diagram, so that It has a feature that it has a higher dielectric constant.
本発明の第１７ないし第２０の観点のいずれかの非鉛誘電体薄膜は、鉛フリーであって、２５℃の比誘電率と比べて高温雰囲気下で比誘電率がほぼ一定であって、温度依存性の小さい特長がある。 The lead-free dielectric thin film according to any one of the seventeenth to twentieth aspects of the present invention is lead-free and has a substantially constant relative dielectric constant in a high temperature atmosphere as compared with a relative dielectric constant of 25 ° C. There is a small temperature dependency.
次に本発明を実施するための形態を図面に基づいて説明する。 Next, an embodiment for carrying out the present invention will be described with reference to the drawings.
＜非鉛誘電体薄膜形成用液組成物の調製＞
本発明の非鉛誘電体薄膜形成用液組成物は、ＢａＴｉＯ3と、Ｂｉ(Ｍｇ0.5Ｔｉ0.5)Ｏ3と、ＢｉＦｅＯ3をそれぞれ形成可能な液組成物を含有してなり、それぞれ以下のように調製される。
<Preparation of a liquid composition for forming a lead-free dielectric thin film>
The liquid composition for forming a lead-free dielectric thin film of the present invention contains a liquid composition capable of forming BaTiO 3 , Bi (Mg 0.5 Ti 0.5 ) O 3 , and BiFeO 3 , respectively. To be prepared.
（１）ＢａＴｉＯ3用液組成物
ＢａＴｉＯ3用液組成物は、Ｂａ原料としてカルボン酸塩やアルコキシドを、Ｔｉ原料としてアルコキシドをそれぞれ用い、これらの原料を２−メトキシエタノールや酢酸等の溶剤に、所定のモル比で、かつ、金属酸化物換算の合計濃度が１〜２５質量％程度となるように混合溶解させることにより調製される。カルボン酸バリウムとしては、２−エチル酪酸バリウム、２−エチルヘキサン酸バリウム、酢酸バリウム等が挙げられ、バリウムアルコキシドとしては、バリウムジイソプロポキシド、バリウムジブトキシド等が挙げられる。またチタンアルコキシドとしては、チタニウムテトラエトキシド、チタニウムテトライソプロポキシド、チタニウムテトラブトキシド、チタニウムジメトキシジイソプロポキシド等が挙げられる。上記金属アルコキシドはそのまま使用しても良いが、分解を促進させるためにその部分加水分解物を使用しても良い。また安定化剤としてアセチルアセトン等を加えても良い。
(1) Liquid composition for BaTiO 3 The liquid composition for BaTiO 3 uses a carboxylate or alkoxide as a Ba raw material, and an alkoxide as a Ti raw material, and these raw materials are used in a solvent such as 2-methoxyethanol or acetic acid. It is prepared by mixing and dissolving at a predetermined molar ratio so that the total concentration in terms of metal oxide is about 1 to 25% by mass. Examples of the barium carboxylate include barium 2-ethylbutyrate, barium 2-ethylhexanoate, and barium acetate. Examples of the barium alkoxide include barium diisopropoxide and barium dibutoxide. Examples of the titanium alkoxide include titanium tetraethoxide, titanium tetraisopropoxide, titanium tetrabutoxide, titanium dimethoxydiisopropoxide, and the like. The above metal alkoxide may be used as it is, but a partially hydrolyzed product thereof may be used to promote decomposition. Moreover, you may add acetylacetone etc. as a stabilizer.
（２）Ｂｉ(Ｍｇ0.5Ｔｉ0.5)Ｏ3用液組成物
Ｂｉ(Ｍｇ0.5Ｔｉ0.5)Ｏ3用液組成物は、Ｂｉ原料としてカルボン酸塩やアルコキシドを、Ｍｇ原料としてアルコキシドを、Ｔｉ原料としてアルコキシドをそれぞれ用い、これらの原料を２−メトキシエタノール等の溶剤に、所定のモル比で、かつ、金属酸化物換算の合計濃度が１〜２５質量％程度となるように混合溶解させることにより調製される。カルボン酸ビスマスとしては、２−エチル酪酸ビスマス、２−エチルヘキサン酸ビスマス等が、ビスマスアルコキシドとしては、Ｂｉ(ＯＣ(ＣＨ3)3)3（以下、Ｂｉ(Ｏｔ-Ｂｕ)3と略記する。）、Ｂｉ(ＯＣ(ＣＨ3)2Ｃ2Ｈ5)3（以下、Ｂｉ(Ｏｔ-Ａｍ)3と略記する。）等が挙げられる。またマグネシウムアルコキシドとしては、マグネシウムエトキシド、マグネシウムメトキシド、マグネシウムプロポキシド等が挙げられる。更にチタンアルコキシドとしては、チタニウムテトラエトキシド、チタニウムテトライソプロポキシド、チタニウムテトラブトキシド、チタニウムジメトキシジイソプロポキシド等が挙げられる。上記金属アルコキシドはそのまま使用しても良いが、分解を促進させるためにその部分加水分解物を使用しても良い。また安定化剤としてアセチルアセトン等を加えても良い。
(2) Liquid composition for Bi (Mg 0.5 Ti 0.5 ) O 3 The liquid composition for Bi (Mg 0.5 Ti 0.5 ) O 3 is composed of carboxylate or alkoxide as Bi raw material, alkoxide as Mg raw material, and Ti raw material. Each alkoxide is used, and these raw materials are mixed and dissolved in a solvent such as 2-methoxyethanol at a predetermined molar ratio so that the total concentration in terms of metal oxide is about 1 to 25% by mass. Is done. As bismuth carboxylate, bismuth 2-ethylbutyrate, bismuth 2-ethylhexanoate and the like are abbreviated as Bi (OC (CH 3 ) 3 ) 3 (hereinafter referred to as Bi (Ot—Bu) 3 ). ), Bi (OC (CH 3 ) 2 C 2 H 5 ) 3 (hereinafter abbreviated as Bi (Ot-Am) 3 ) and the like. Examples of the magnesium alkoxide include magnesium ethoxide, magnesium methoxide, magnesium propoxide and the like. Further, examples of the titanium alkoxide include titanium tetraethoxide, titanium tetraisopropoxide, titanium tetrabutoxide, titanium dimethoxydiisopropoxide, and the like. The above metal alkoxide may be used as it is, but a partially hydrolyzed product thereof may be used to promote decomposition. Moreover, you may add acetylacetone etc. as a stabilizer.
（３）ＢｉＦｅＯ3用液組成物
ＢｉＦｅＯ3用液組成物は、Ｂｉ原料としてカルボン酸塩やアルコキシドを、Ｆｅ原料としてアセチルアセトナートや硝酸塩をそれぞれ用い、これらの原料を２−メトキシエタノール等の溶剤に、所定のモル比で、かつ、金属酸化物換算の合計濃度が１〜２５質量％程度となるように混合溶解させることにより調製される。カルボン酸ビスマスとしては、２−エチル酪酸ビスマス、２−エチルヘキサン酸ビスマス等が、ビスマスアルコキシドとしては、Ｂｉ(Ｏｔ-Ｂｕ)3、Ｂｉ(Ｏｔ-Ａｍ)3等が挙げられ、Ｆｅ原料としては、鉄(III)アセチルアセトナート錯体、硝酸鉄等が挙げられる。上記金属アルコキシドはそのまま使用しても良いが、分解を促進させるためにその部分加水分解物を使用しても良い。また安定化剤としてアセチルアセトン等を加えても良い。
(3) Liquid composition for BiFeO 3 The liquid composition for BiFeO 3 uses carboxylate and alkoxide as Bi raw materials, acetylacetonate and nitrate as Fe raw materials, and these raw materials are solvents such as 2-methoxyethanol. In addition, it is prepared by mixing and dissolving at a predetermined molar ratio so that the total concentration in terms of metal oxide is about 1 to 25% by mass. Examples of the bismuth carboxylate include bismuth 2-ethylbutyrate and bismuth 2-ethylhexanoate. Examples of the bismuth alkoxide include Bi (Ot-Bu) 3 and Bi (Ot-Am) 3. Iron (III) acetylacetonate complex, iron nitrate and the like. The above metal alkoxide may be used as it is, but a partially hydrolyzed product thereof may be used to promote decomposition. Moreover, you may add acetylacetone etc. as a stabilizer.
（４）非鉛誘電体薄膜形成用液組成物の調製
上述したＢａＴｉＯ3用液組成物、Ｂｉ(Ｍｇ0.5Ｔｉ0.5)Ｏ3用液組成物及びＢｉＦｅＯ3用液組成物の二者又は三者を所定の割合で秤量し、均一に混合することにより、本発明の非鉛誘電体薄膜を形成するための液組成物が調製される。
(4) Preparation of liquid composition for forming a lead-free dielectric thin film Two or three of the liquid composition for BaTiO 3 , the liquid composition for Bi (Mg 0.5 Ti 0.5 ) O 3 , and the liquid composition for BiFeO 3 Are weighed at a predetermined ratio and uniformly mixed to prepare a liquid composition for forming the lead-free dielectric thin film of the present invention.
＜非鉛誘電体薄膜の形成＞
得られた非鉛誘電体薄膜形成用液組成物を用いて、非鉛誘電体薄膜を形成するには、上記組成物をスピンコート、ディップコート、ＬＳＭＣＤ（Liquid Source Misted Chemical Deposition）法等の塗布法により耐熱性基板上に塗布し、乾燥（仮焼成）及び本焼成を行う。
<Formation of lead-free dielectric thin film>
In order to form a lead-free dielectric thin film using the obtained liquid composition for forming a lead-free dielectric thin film, the composition is applied by spin coating, dip coating, LSMCD (Liquid Source Misted Chemical Deposition), or the like. It is applied onto a heat-resistant substrate by the method, followed by drying (preliminary firing) and main firing.
使用される耐熱性基板としては、基板表層部に、（１１１）配向したＳｒＲｕＯ3を有するか、又は（１００）配向したＬａＮｉＯ3を有するものが好ましい。耐熱性絶縁基板の具体例としては、（１１１）配向したＳｒＲｕＯ3／Ｐｔ／ＴｉＯX／ＳｉＯ2／Ｓｉ又は（１００）配向したＬａＮｉＯ3／Ｐｔ／ＴｉＯX／ＳｉＯ2／Ｓｉ等が挙げられる。 As the heat-resistant substrate to be used, those having (111) -oriented SrRuO 3 or (100) -oriented LaNiO 3 in the substrate surface layer portion are preferable. Specific examples of the heat-resistant insulating substrate include (111) oriented SrRuO 3 / Pt / TiO x / SiO 2 / Si or (100) oriented LaNiO 3 / Pt / TiO x / SiO 2 / Si.
なお、１回の塗布では、所望の膜厚が得られない場合には、塗布、乾燥の工程を複数回繰返し行った後、本焼成を行う。ここで、所望の膜厚とは、本焼成後に得られる誘電体薄膜の厚さをいい、高容量密度の薄膜キャパシタ用途の場合、本焼成後の誘電体薄膜の膜厚が５０〜５００ｎｍの範囲である。 In addition, when a desired film thickness cannot be obtained by one application, the application and drying steps are repeated a plurality of times, followed by firing. Here, the desired film thickness refers to the thickness of the dielectric thin film obtained after the main firing, and in the case of high capacity density thin film capacitor applications, the thickness of the dielectric thin film after the main firing is in the range of 50 to 500 nm. It is.
また、仮焼成は、溶媒を除去するとともに有機化合物や有機金属化合物を熱分解又は加水分解して複合酸化物に転化させるために行うことから、空気中、酸化雰囲気中、又は含水蒸気雰囲気中で行う。空気中での加熱でも、加水分解に必要な水分は空気中の湿気により十分に確保される。この加熱は、溶媒の除去のための低温加熱と、有機金属化合物や有機化合物の分解のための高温加熱の２段階で実施しても良い。 In addition, pre-baking is performed in order to remove the solvent and to convert the organic compound or organometallic compound into a composite oxide by thermal decomposition or hydrolysis, and therefore, in the air, in an oxidizing atmosphere, or in a steam-containing atmosphere. Do. Even in heating in the air, the moisture required for hydrolysis is sufficiently secured by the humidity in the air. This heating may be performed in two stages: low temperature heating for removing the solvent and high temperature heating for decomposing the organometallic compound or organic compound.
本焼成は、仮焼成で得られた薄膜を結晶化温度以上の温度で焼成して結晶化させるための工程であり、これにより誘電体薄膜が得られる。この結晶化工程の焼成雰囲気はＯ2、Ｎ2、Ａｒ、Ｎ2Ｏ又はＨ2等或いはこれらの混合ガス等が好適である。 The main baking is a process for baking and crystallizing the thin film obtained by the preliminary baking at a temperature equal to or higher than the crystallization temperature, whereby a dielectric thin film is obtained. The firing atmosphere in this crystallization step is preferably O 2 , N 2 , Ar, N 2 O, H 2, or a mixed gas thereof.
仮焼成は、１５０〜５５０℃で１〜３０分間程度行われ、本焼成は４５０〜８００℃で１〜６０分間程度行われる。本焼成は、急速加熱処理（ＲＴＡ処理）やマッフル炉で行っても良い。ＲＴＡ処理で本焼成する場合、その昇温速度は１０〜１００℃／秒が好ましい。 The pre-baking is performed at 150 to 550 ° C. for about 1 to 30 minutes, and the main baking is performed at 450 to 800 ° C. for about 1 to 60 minutes. The main baking may be performed in a rapid heating process (RTA process) or a muffle furnace. When the main baking is performed by the RTA treatment, the heating rate is preferably 10 to 100 ° C./second.
このようにして形成された非鉛誘電体薄膜は、ＢａＴｉＯ3用液組成物、Ｂｉ(Ｍｇ0.5Ｔｉ0.5)Ｏ3用液組成物及びＢｉＦｅＯ3用液組成物の二者又は三者を所定の割合にすることにより、高い比誘電率が得られ、また基板表層部にペロブスカイト型導電性酸化物、例えばＳｒＲｕＯ3やＬａＮｉＯ3を設けた場合、それらの結晶配向性を引きずることで強い結晶配向性を有する。 The lead-free dielectric thin film thus formed has two or three of a liquid composition for BaTiO 3 , a liquid composition for Bi (Mg 0.5 Ti 0.5 ) O 3 , and a liquid composition for BiFeO 3 . By setting the ratio, a high relative dielectric constant can be obtained, and when a perovskite type conductive oxide such as SrRuO 3 or LaNiO 3 is provided on the surface layer portion of the substrate, strong crystal orientation is achieved by dragging those crystal orientations. Have
＜非鉛誘電体薄膜の評価方法＞
上記のようにして得られた非鉛誘電体薄膜について、以下のようにして結晶配向性と比誘電率と誘電正接（tanδ）が評価される。具体的には、誘電体薄膜の結晶配向性の評価は、結晶配向面の評価と、結晶配向度の評価をそれぞれ行う。結晶配向面の評価はθ−２θスキャン法により行う。一方、結晶配向度の評価は２θ−χスキャン法によるχ≒４６°の（１１０）ピークの半値幅により、行う（測定機器メーカー：ブルカー社、薄膜Ｘ線回折装置 (D8-discover)）。この場合、図１（ａ）に示すようにχ方向にストリークを引くピークが確認されれば結晶配向度は低く（上記ピーク半値幅は大きく）、一方、図１（ｂ）に示すようにスポット上のピークが確認されれば結晶配向度は高い（上記ピーク半値幅は小さい）と判断される。図１（ａ）は後述する比較例１の誘電体薄膜の結晶配向度を示し、図１（ｂ）は後述する実施例６の誘電体薄膜の結晶配向度を示す。誘電体薄膜の比誘電率をインピーダンス・アナライザにより、周波数１ｋＨｚにて測定する（測定機器メーカー：アジレントテクノロジー、HP4194A）。
<Evaluation method of lead-free dielectric thin film>
The lead-free dielectric thin film obtained as described above is evaluated for crystal orientation, relative permittivity, and dielectric loss tangent (tan δ) as follows. Specifically, the evaluation of the crystal orientation of the dielectric thin film is performed by evaluating the crystal orientation plane and evaluating the degree of crystal orientation, respectively. The crystal orientation plane is evaluated by the θ-2θ scan method. On the other hand, the degree of crystal orientation is evaluated based on the half width of the (110) peak at χ≈46 ° by the 2θ-χ scan method (measuring instrument manufacturer: Bruker, thin film X-ray diffractometer (D8-discover)). In this case, if a peak that streaks in the χ direction is confirmed as shown in FIG. 1A, the degree of crystal orientation is low (the peak half-value width is large), whereas a spot as shown in FIG. If the upper peak is confirmed, it is judged that the degree of crystal orientation is high (the peak half width is small). 1A shows the crystal orientation of a dielectric thin film of Comparative Example 1 described later, and FIG. 1B shows the crystal orientation of a dielectric thin film of Example 6 described later. The dielectric constant of the dielectric thin film is measured with an impedance analyzer at a frequency of 1 kHz (measuring equipment manufacturer: Agilent Technologies, HP4194A).
次に本発明の実施例を比較例とともに詳しく説明する。 Next, examples of the present invention will be described in detail together with comparative examples.
＜実施例１〜１２＞
先ずチタニウムテトラブトキシド０．００２５モルに２−メトキシエタノール１０ｍｌを添加し、室温で６０分間攪拌した。この混合液に酢酸バリウムを０．００２５モル加え、室温で１２０分間攪拌した。続いてアセチルアセトン０．２ｍｌと酢酸５ｍｌを加え、室温で一昼夜攪拌し、ＢａＴｉＯ3用液組成物を調製した。次にチタニウムテトラブトキシド０．００１２５モルに２−メトキシエタノール５ｍｌを添加し、室温で６０分間攪拌した。この混合液にアセチルアセトンで安定化させたマグネシウムエトキシドを０．００１２５モル加え、室温で３０分間攪拌した。続いてＢｉ(Ｏｔ-Ａｍ)3を０．００２５モルを加え、室温で６０分間攪拌し、Ｂｉ(Ｍｇ0.5Ｔｉ0.5)Ｏ3用液組成物を調製した。更に、鉄(III)アセチルアセトナート０．００２５モルに２−メトキシエタノール１０ｍｌを添加し、室温で６０分間攪拌し、８０℃に昇温して６０分間攪拌し、室温で６０分間攪拌した。続いてＢｉ(Ｏｔ-Ａｍ)3を０．００２５モルを加え、室温で３０分間攪拌し、ＢｉＦｅＯ3用液組成物を調製した。
<Examples 1 to 12>
First, 10 ml of 2-methoxyethanol was added to 0.0025 mol of titanium tetrabutoxide and stirred at room temperature for 60 minutes. To this mixed solution, 0.0025 mol of barium acetate was added and stirred at room temperature for 120 minutes. Subsequently, 0.2 ml of acetylacetone and 5 ml of acetic acid were added, and the mixture was stirred overnight at room temperature to prepare a liquid composition for BaTiO 3 . Next, 5 ml of 2-methoxyethanol was added to 0.00125 mol of titanium tetrabutoxide and stirred at room temperature for 60 minutes. To this mixed solution, 0.00125 mol of magnesium ethoxide stabilized with acetylacetone was added and stirred at room temperature for 30 minutes. Subsequently, 0.0025 mol of Bi (Ot—Am) 3 was added and stirred at room temperature for 60 minutes to prepare a liquid composition for Bi (Mg 0.5 Ti 0.5 ) O 3 . Furthermore, 10 ml of 2-methoxyethanol was added to 0.0025 mol of iron (III) acetylacetonate, stirred at room temperature for 60 minutes, heated to 80 ° C., stirred for 60 minutes, and stirred at room temperature for 60 minutes. Subsequently, 0.0025 mol of Bi (Ot-Am) 3 was added and stirred at room temperature for 30 minutes to prepare a BiFeO 3 liquid composition.
このように調製されたＢａＴｉＯ3用液組成物、Ｂｉ(Ｍｇ0.5Ｔｉ0.5)Ｏ3用液組成物及びＢｉＦｅＯ3用液組成物の二者又は三者を表１に示す酸化物換算の割合で秤量し、均一に混合することにより、実施例１〜１２の非鉛誘電体薄膜形成用液組成物を得た。 Two or three of the liquid composition for BaTiO 3 , the liquid composition for Bi (Mg 0.5 Ti 0.5 ) O 3 , and the liquid composition for BiFeO 3 prepared in this way are in the ratio in terms of oxide shown in Table 1. The liquid compositions for forming a lead-free dielectric thin film of Examples 1 to 12 were obtained by weighing and mixing uniformly.
基板として、（１１１）ＳｒＲｕＯ3／（１１１）Ｐｔ／ＴｉＯX／ＳｉＯ2／（１００）Ｓｉを用意した。ここでＳｒＲｕＯ3膜は、ＲＦマグネトロンスパッタ装置により基板温度５５０℃にて成膜し、膜厚２５ｎｍの（１１１）結晶配向膜とした。この（１１１）ＳｒＲｕＯ3上にスピンコート法により、三者の割合の異なる誘電体薄膜形成用液組成物を塗布した。（１１１）ＳｒＲｕＯ3は高周波マグネトロンスパッタリング装置により成膜した。塗布後、大気雰囲気中、４００℃、１分間、仮焼成を行い、更に大気雰囲気中、７５０℃、５分間、本焼成を行った。本焼成後、厚さ３００ｎｍの１２種類の誘電体薄膜を作製した。 As a substrate, (111) SrRuO 3 / (111) Pt / TiO x / SiO 2 / (100) Si was prepared. Here, the SrRuO 3 film was formed by an RF magnetron sputtering apparatus at a substrate temperature of 550 ° C. to obtain a (111) crystal orientation film having a film thickness of 25 nm. On this (111) SrRuO 3 , liquid compositions for forming a dielectric thin film with different ratios were applied by spin coating. (111) SrRuO 3 was deposited by a high-frequency magnetron sputtering apparatus. After the application, pre-baking was performed at 400 ° C. for 1 minute in the air atmosphere, and then main baking was performed at 750 ° C. for 5 minutes in the air atmosphere. After the main firing, 12 types of dielectric thin films having a thickness of 300 nm were prepared.
＜実施例１３＞
基板として、（１００）ＬａＮｉＯ3／（１１１）Ｐｔ／ＴｉＯX／ＳｉＯ2／（１００）Ｓｉを用い、本焼成を７００℃、５分間行った以外は、実施例１〜１２同様にして誘電体薄膜を作製した。ここでＬａＮｉＯ3膜は、ＲＦマグネトロンスパッタ装置により基板温度４５０℃にて成膜し、膜厚２５ｎｍの（１００）結晶配向膜とした。
<Example 13>
A dielectric material was used in the same manner as in Examples 1 to 12 except that (100) LaNiO 3 / (111) Pt / TiO x / SiO 2 / (100) Si was used as the substrate and the main firing was performed at 700 ° C. for 5 minutes. A thin film was prepared. Here, the LaNiO 3 film was formed by an RF magnetron sputtering apparatus at a substrate temperature of 450 ° C. to obtain a (100) crystal orientation film having a film thickness of 25 nm.
＜比較例１＞
基板として、（１１１）Ｐｔ／ＴｉＯX／ＳｉＯ2／（１００）Ｓｉを用いた以外は、実施例１〜１２と同様にして誘電体薄膜を作製した。
<Comparative Example 1>
As the substrate, except for using (111) Pt / TiO X / SiO 2 / (100) Si, to prepare a dielectric thin film in the same manner as in Example 1-12.
＜室温下での評価・測定試験＞
実施例１〜１２及び比較例１の各誘電体薄膜を室温の大気雰囲気下において、θ−２θスキャン法により結晶配向面を評価し、２θ−χスキャン法により結晶配向度を評価し、更に比誘電率と誘電正接（tanδ）を上述したインピーダンス・アナライザにより測定し、確認した。その結果を表１及び図２の三元相図に示す。なお、表１中、ｘはＢａＴｉＯ3のモル比を、ｙはＢｉ(Ｍｇ0.5Ｔｉ0.5)Ｏ3のモル比を、ｚはＢｉＦｅＯ3のモル比をそれぞれ示す。また図２の丸数字の１〜７は実施例１〜７を、図２の丸数字８は実施例１２を、図２の丸数字９〜１２は実施例８〜１１をそれぞれ示す。
<Evaluation and measurement test at room temperature>
In each of the dielectric thin films of Examples 1 to 12 and Comparative Example 1, the crystal orientation plane was evaluated by the θ-2θ scan method in the air atmosphere at room temperature, the degree of crystal orientation was evaluated by the 2θ-χ scan method, and the ratio The dielectric constant and dielectric loss tangent (tan δ) were measured and confirmed by the impedance analyzer described above. The results are shown in Table 1 and the ternary phase diagram of FIG. In Table 1, x represents the molar ratio of BaTiO 3 , y represents the molar ratio of Bi (Mg 0.5 Ti 0.5 ) O 3 , and z represents the molar ratio of BiFeO 3 . 2 are examples 1 to 7, circle numbers 8 in FIG. 2 are examples 12, and circles 9 to 12 in FIG. 2 are examples 8 to 11.
＜評価１＞
実施例１〜１２及び比較例１の誘電体薄膜に対してＸ線回折法によりθ−２θスキャンを実施し、回折線のピーク強度を測定し、これらの誘電体薄膜の結晶配向面を調べた。その結果を図３（ａ）及び（ｂ）に示す。図３（ａ）から明らかなように、実施例１(1)〜実施例７(7)及び実施例１２(8)の各誘電体薄膜が３８度付近で（１１１）面に配向し、図３（ｂ）から明らかなように、実施例６(6)及び実施例８(9)〜実施例１１(12)の各誘電体薄膜が３８度付近で（１１１）面に配向していることが判った。
<Evaluation 1>
The dielectric thin films of Examples 1 to 12 and Comparative Example 1 were subjected to θ-2θ scan by X-ray diffraction method, the peak intensity of the diffraction lines was measured, and the crystal orientation planes of these dielectric thin films were examined. . The results are shown in FIGS. 3 (a) and 3 (b). As is clear from FIG. 3A, the dielectric thin films of Example 1 (1) to Example 7 (7) and Example 12 (8) are oriented in the (111) plane at around 38 degrees. As is apparent from 3 (b), the dielectric thin films of Example 6 (6) and Example 8 (9) to Example 11 (12) are oriented in the (111) plane at around 38 degrees. I understood.
次に、これらの誘電体薄膜のうち、実施例１(1)、５(5)、６(6)の各誘電体薄膜に対してＸ線回折法により２θ−χスキャンを実施し、χ方向にストリークが現れるか、スポットが現れるか否かを測定し、これらの誘電体薄膜の結晶配向度が高いか低いかを調べた。その結果を図４（ａ）〜（ｃ）に示す。図４（ａ）から明らかなように、実施例１(1)の誘電体薄膜は２θが３１．５度付近でχ方向にストリークが現れ、配向度が低かった。一方、図４（ｂ）及び（ｃ）から明らかなように、実施例５(5)及び実施例６(6)の各誘電体薄膜は２θが３１．５度付近でχ方向にストリークは僅かに現れるけれども、スポットの方がはっきりと見られ、配向度が高かった。 Next, among these dielectric thin films, each dielectric thin film of Examples 1 (1), 5 (5), and 6 (6) was subjected to 2θ-χ scan by X-ray diffraction, and the χ direction Whether or not streaks appear or spots appear is measured, and it is examined whether the crystal orientation degree of these dielectric thin films is high or low. The results are shown in FIGS. As is clear from FIG. 4A, the dielectric thin film of Example 1 (1) had a streak in the χ direction when 2θ was around 31.5 degrees, and the degree of orientation was low. On the other hand, as is clear from FIGS. 4B and 4C, the dielectric thin films of Examples 5 (5) and 6 (6) have a slight streak in the χ direction when 2θ is around 31.5 degrees. However, the spot was clearly seen and the degree of orientation was high.
更に詳細に結晶配向度を調査するため、実施例１(1)、５(5)、６(6)の各誘電体薄膜に対してＸ線回折法により２θ−χスキャンを実施し、２θが３０度から３５度までの積算強度とχの関係を調査した。その結果を図５（ａ）〜（ｃ）に示す。図５（ａ）から明らかなように、実施例１(1)の誘電体薄膜は（１１０）面に帰属されるχが４５度付近のピーク強度は弱くかつ半値幅が大きく（配向度が低く）、一方、図５（ｂ）及び（ｃ）から明らかなように、実施例５(5)及び実施例６(6)の各誘電体薄膜は（１１０）面に帰属されるχが４５度付近のピーク強度は強くかつ半値幅が小さい（配向度が高い）ことが判った。 In order to investigate the degree of crystal orientation in more detail, 2θ-χ scan was performed on each dielectric thin film of Examples 1 (1), 5 (5), and 6 (6) by the X-ray diffraction method. The relationship between the integrated intensity from 30 degrees to 35 degrees and χ was investigated. The results are shown in FIGS. As is clear from FIG. 5A, the dielectric thin film of Example 1 (1) has a weak peak intensity around 45 degrees χ attributed to the (110) plane and a large half-value width (low degree of orientation). On the other hand, as is clear from FIGS. 5B and 5C, each dielectric thin film of Example 5 (5) and Example 6 (6) has a χ attributed to the (110) plane of 45 degrees. It was found that the peak intensity in the vicinity was strong and the half width was small (the degree of orientation was high).
実施例１(1)と実施例８(9)と実施例１２(8)と実施例１１(12)で得られた値で囲んだ第１領域（図２参照）は、表１から明らかなように（１１０）ピーク半値幅が２２．０度以下と良好で、比誘電率の平均が６００であり、誘電特性が良好であった。実施例３(3)と実施例８(9)と実施例７(7)と実施例１０(11)で得られた値で囲んだ第２領域（図２参照）は、表１から明らかなように（１１０）ピーク半値幅が９．６度以下と良好で、比誘電率の平均が６３２．５であり、誘電特性が良好であった。特に、実施例５(5)と実施例６(6)と実施例１０(11)で得られた値で囲んだ第３領域（図２参照）は、表１から明らかなように（１１０）ピーク半値幅が３．３度以下と極めて小さく、比誘電率の平均が８８２．５と比誘電率に極めて優れていた。 The first region (see FIG. 2) surrounded by the values obtained in Example 1 (1), Example 8 (9), Example 12 (8) and Example 11 (12) is apparent from Table 1. Thus, the (110) peak half-value width was as good as 22.0 degrees or less, the average relative dielectric constant was 600, and the dielectric characteristics were good. The second region (see FIG. 2) surrounded by the values obtained in Example 3 (3), Example 8 (9), Example 7 (7) and Example 10 (11) is apparent from Table 1. As described above, the (110) peak half width was as good as 9.6 degrees or less, the average relative dielectric constant was 632.5, and the dielectric properties were good. In particular, the third region (see FIG. 2) surrounded by the values obtained in Example 5 (5), Example 6 (6), and Example 10 (11) is (110) as apparent from Table 1. The peak half-value width was as small as 3.3 degrees or less, and the average relative dielectric constant was 882.5, which was extremely excellent in relative dielectric constant.
＜実施例６、実施例１３、比較例１＞
表１から明らかなように、膜組成が同一で結晶配向性のみが異なる実施例６、実施例１３、比較例１を比較すると、実施例６、実施例１３では（１１０）ピーク半値幅がそれぞれ３．０、１０．０と良好で、比誘電率はそれぞれ１０５０、４７０と高い値を示した。一方、ランダム配向の比較例１は（１１０）ピーク半値幅が極めて大きくて悪く、その結果、比誘電率は１００と小さい値を示した。このことから、結晶配向性を向上させることが、比誘電率向上に大きく影響することが判った。
<Example 6, Example 13, Comparative Example 1>
As is clear from Table 1, when Example 6, Example 13, and Comparative Example 1 having the same film composition but different crystal orientations are compared, in Example 6 and Example 13, the (110) peak half width is The dielectric constant was as good as 3.0 and 10.0, and the relative dielectric constants were as high as 1050 and 470, respectively. On the other hand, in Comparative Example 1 with random orientation, the (110) peak half width was extremely large and bad, and as a result, the relative dielectric constant was as small as 100. From this, it was found that improving the crystal orientation greatly affects the improvement of the dielectric constant.
図６に実施例１３の７００℃で焼成した誘電体薄膜に対してＸ線回折法によりθ−２θスキャンを実施し、Ｘ線回折線のピーク強度を測定した結果を示す。図６から明らかなように、実施例１３の誘電体薄膜は（１００）面に配向していることが判った。 FIG. 6 shows the result of measuring the peak intensity of the X-ray diffraction line by performing a θ-2θ scan on the dielectric thin film fired at 700 ° C. in Example 13 by the X-ray diffraction method. As is apparent from FIG. 6, it was found that the dielectric thin film of Example 13 was oriented in the (100) plane.
＜実施例１〜１２、実施例１４＞
室温下での測定試験で作製した実施例１〜１２の非鉛誘電体薄膜に加えて、ＢａＴｉＯ3のモル比(ｘ)が０．６０、Ｂｉ(Ｍｇ0.5Ｔｉ0.5)Ｏ3のモル比(ｙ)が０．４０、ＢｉＦｅＯ3のモル比(ｚ)が０．００である実施例１４の非鉛誘導体薄膜を作製した。モル比を変更した以外、実施例１４の非鉛誘導体薄膜は、実施例１〜１２と同様に作製した。
<Examples 1 to 12 and Example 14>
In addition to the lead-free dielectric thin films of Examples 1 to 12 produced in the measurement test at room temperature, the molar ratio (x) of BaTiO 3 is 0.60, and the molar ratio of Bi (Mg 0.5 Ti 0.5 ) O 3 ( A lead-free derivative thin film of Example 14 in which y) was 0.40 and the molar ratio (z) of BiFeO 3 was 0.00 was produced. The lead-free derivative thin film of Example 14 was produced in the same manner as in Examples 1 to 12 except that the molar ratio was changed.
＜高温下での測定試験＞
こうして作製した１３種類の非鉛誘導体薄膜のうち、実施例１〜４の４種類の非鉛誘導体薄膜について、大気雰囲気下、２５℃、５０℃、１００℃、１５０℃、２００℃、２５０℃、３００℃、３５０℃及び４００℃の各温度における比誘電率を上述したインピーダンス・アナライザによりそれぞれ測定した。実施例１〜４以外の実施例５〜１１と実施例１４の８種類の非鉛誘導体薄膜について、大気雰囲気下、２５℃、５０℃、１００℃、１５０℃、２００℃及び２５０℃の各温度における比誘電率を上述したインピーダンス・アナライザによりそれぞれ測定した。また実施例１２の非鉛誘導体薄膜について、大気雰囲気下、２５℃、５０℃及び１００℃の各温度における比誘電率を上述したインピーダンス・アナライザにより測定周波数を100 kHzにてそれぞれ測定した。三元図上における実施例１〜実施例４、実施例８、実施例１１、実施例１２及び実施例１４を図７に示す。また１３種類の非鉛誘導体薄膜の各温度における比誘電率を表２に示す。更に実施例１(1)〜実施例７(7)及び実施例１２(8)の誘導体薄膜の２５℃以上の各温度における比誘電率を図８に示し、実施例６(6)及び実施例８(9)〜実施例１１(12)及び実施例１４(13)の誘導体薄膜の２５℃以上の各温度における比誘電率を図９に示す。図７及び図９の丸数字の１３は実施例１４を示す。
<Measurement test under high temperature>
Among the 13 types of lead-free derivative thin films prepared in this way, the four types of lead-free derivative thin films of Examples 1 to 4 were 25 ° C., 50 ° C., 100 ° C., 150 ° C., 200 ° C., 250 ° C. The relative dielectric constant at each temperature of 300 ° C., 350 ° C. and 400 ° C. was measured by the impedance analyzer described above. About 8 types of non-lead derivative thin films of Examples 5-11 and Example 14 other than Examples 1-4, each temperature of 25 degreeC, 50 degreeC, 100 degreeC, 150 degreeC, 200 degreeC, and 250 degreeC in air | atmosphere atmosphere The relative dielectric constant was measured with the impedance analyzer described above. In addition, with respect to the lead-free derivative thin film of Example 12, the relative dielectric constant at each temperature of 25 ° C., 50 ° C., and 100 ° C. was measured at 100 kHz with the above-described impedance analyzer in the air atmosphere. Example 1 to Example 4, Example 8, Example 11, Example 12, and Example 14 on the ternary diagram are shown in FIG. Table 2 shows the relative dielectric constants of the 13 types of lead-free thin films at various temperatures. Further, the relative dielectric constants at temperatures of 25 ° C. or more of the derivative thin films of Example 1 (1) to Example 7 (7) and Example 12 (8) are shown in FIG. 8, and Example 6 (6) and Example 6 FIG. 9 shows the relative dielectric constants of the derivative thin films of 8 (9) to 11 (12) and 14 (13) at each temperature of 25 ° C. or higher. The numeral 13 in FIG. 7 and FIG.
＜評価２＞
表２及び図８、図９に示される実施例１(1)と実施例２(2)と実施例３(3)と実施例４(4)で得られた非鉛誘導体薄膜の２５℃から４００℃までの温度範囲における各比誘電率と実施例１４(13)で得られた非鉛誘導体薄膜の２５℃から２５０℃までの温度範囲における各比誘電率を見ると、実施例１〜４の４００℃における比誘電率又は実施例１４の２５０℃における比誘電率は、それぞれ２５℃における比誘電率とほぼ一定であり、温度依存性が小さく、高温雰囲気下で使用される誘導体薄膜に適することが判った。図７において、実施例１(1)と実施例２(2)と実施例３(3)と実施例４(4)と実施例１４(13)で囲まれた領域は第４領域として示される。図７において、第１領域は、第４領域が第１領域内にあることを明らかにするために示している。
<Evaluation 2>
From the lead-free derivative thin films obtained in Example 1 (1), Example 2 (2), Example 3 (3) and Example 4 (4) shown in Table 2 and FIGS. When the relative dielectric constants in the temperature range up to 400 ° C. and the relative dielectric constants in the temperature range from 25 ° C. to 250 ° C. of the lead-free derivative thin film obtained in Example 14 (13) are seen, Examples 1-4 The specific dielectric constant at 400 ° C. or the specific dielectric constant at 250 ° C. of Example 14 is almost constant with the specific dielectric constant at 25 ° C., has a small temperature dependence, and is suitable for a derivative thin film used in a high-temperature atmosphere. I found out. In FIG. 7, the region surrounded by Example 1 (1), Example 2 (2), Example 3 (3), Example 4 (4), and Example 14 (13) is shown as the fourth region. . In FIG. 7, the first area is shown to clarify that the fourth area is in the first area.
Claims (26)
前記乾燥工程の途中から或いは完了後に前記塗膜を、Ｏ2，Ｎ2，Ａｒ，Ｎ2Ｏ，Ｈ2若しくはこれらの混合ガス中又は乾燥空気中或いは水蒸気を含む前記雰囲気中で結晶化温度以上で焼成する焼成工程と
を含む非鉛誘電体薄膜の形成方法。 An application step of applying the liquid composition for forming a lead-free dielectric thin film according to claim 22 to a substrate to form a coating film, and the coating film formed on the substrate in air, in an oxidizing atmosphere, or in a water-containing atmosphere A drying step of heating and drying in,
In the middle of or after completion of the drying step, the coating film is heated to a crystallization temperature or higher in O 2 , N 2 , Ar, N 2 O, H 2 or a mixed gas thereof, in dry air, or in the atmosphere containing water vapor. A method for forming a lead-free dielectric thin film, comprising:
前記焼成工程が前記複数回繰り返された最終乾燥工程の途中から或いは完了後に前記塗膜を、Ｏ2，Ｎ2，Ａｒ，Ｎ2Ｏ，Ｈ2若しくはこれらの混合ガス中又は乾燥空気中或いは水蒸気を含む前記雰囲気中で結晶化温度以上で焼成する工程である請求項２３記載の非鉛誘電体薄膜の形成方法。 The coating step and the drying step are repeated multiple times,
The coating is applied in the middle of or after completion of the final drying process in which the baking process is repeated a plurality of times, in O 2 , N 2 , Ar, N 2 O, H 2, a mixed gas thereof, in dry air, or in steam. 24. The method for forming a lead-free dielectric thin film according to claim 23, wherein the method is a step of baking in the atmosphere containing at least a crystallization temperature.
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| US20170032893A1 (en) * | 2014-01-21 | 2017-02-02 | Epcos Ag | Dielectric composition, dielectric element, electronic component and laminated electronic component |
| US9776925B2 (en) | 2014-01-21 | 2017-10-03 | Epcos Ag | Dielectric composition, dielectric element, electronic component and laminated electronic component |
| JP2018157182A (en) * | 2017-03-15 | 2018-10-04 | 三菱マテリアル株式会社 | Method for manufacturing liquid composition for piezoelectric film formation, and method for forming piezoelectric film by use thereof |
| CN110981467A (en) * | 2019-12-09 | 2020-04-10 | 华中科技大学 | Lead-free pyroelectric composite ceramic material and preparation method thereof |
| CN112670086A (en) * | 2020-10-27 | 2021-04-16 | 西安交通大学 | Silicon integrated thin film capacitor with high energy storage density and preparation method thereof |
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| JP6063672B2 (en) * | 2011-09-06 | 2017-01-18 | キヤノン株式会社 | Piezoelectric ceramics, piezoelectric ceramic manufacturing method, piezoelectric element, liquid discharge head, liquid discharge device, ultrasonic motor, optical device, vibration device, dust removing device, imaging device, piezoelectric acoustic component, and electronic device |
| WO2013146303A1 (en) * | 2012-03-26 | 2013-10-03 | 国立大学法人山梨大学 | Dielectric material, dielectric element, capacitor, multilayer capacitor, and power storage device |
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| US20170032893A1 (en) * | 2014-01-21 | 2017-02-02 | Epcos Ag | Dielectric composition, dielectric element, electronic component and laminated electronic component |
| US9773616B2 (en) * | 2014-01-21 | 2017-09-26 | Epcos Ag | Dielectric composition, dielectric element, electronic component and laminated electronic component |
| US9776925B2 (en) | 2014-01-21 | 2017-10-03 | Epcos Ag | Dielectric composition, dielectric element, electronic component and laminated electronic component |
| JP2018157182A (en) * | 2017-03-15 | 2018-10-04 | 三菱マテリアル株式会社 | Method for manufacturing liquid composition for piezoelectric film formation, and method for forming piezoelectric film by use thereof |
| US11276813B2 (en) | 2018-06-20 | 2022-03-15 | Canon Kabushiki Kaisha | Coating liquid composition for orientational piezoelectric film, orientational piezoelectric film and liquid ejection head |
| CN110981467A (en) * | 2019-12-09 | 2020-04-10 | 华中科技大学 | Lead-free pyroelectric composite ceramic material and preparation method thereof |
| CN110981467B (en) * | 2019-12-09 | 2020-12-29 | 华中科技大学 | Lead-free pyroelectric composite ceramic material and preparation method thereof |
| CN112670086A (en) * | 2020-10-27 | 2021-04-16 | 西安交通大学 | Silicon integrated thin film capacitor with high energy storage density and preparation method thereof |
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