JP6800450B2 - Method for manufacturing metal oxide nanocrystals, method for manufacturing metal oxide nanocrystal film-immobilized substrate - Google Patents
Method for manufacturing metal oxide nanocrystals, method for manufacturing metal oxide nanocrystal film-immobilized substrate Download PDFInfo
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- 239000002159 nanocrystal Substances 0.000 title claims description 241
- 239000000758 substrate Substances 0.000 title claims description 101
- 229910044991 metal oxide Inorganic materials 0.000 title claims description 85
- 150000004706 metal oxides Chemical class 0.000 title claims description 85
- 238000004519 manufacturing process Methods 0.000 title claims description 50
- 238000000034 method Methods 0.000 title claims description 20
- 229910052451 lead zirconate titanate Inorganic materials 0.000 claims description 76
- HFGPZNIAWCZYJU-UHFFFAOYSA-N lead zirconate titanate Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ti+4].[Zr+4].[Pb+2] HFGPZNIAWCZYJU-UHFFFAOYSA-N 0.000 claims description 74
- 239000010936 titanium Substances 0.000 claims description 67
- 238000010438 heat treatment Methods 0.000 claims description 52
- NKZSPGSOXYXWQA-UHFFFAOYSA-N dioxido(oxo)titanium;lead(2+) Chemical compound [Pb+2].[O-][Ti]([O-])=O NKZSPGSOXYXWQA-UHFFFAOYSA-N 0.000 claims description 48
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 46
- 229910052719 titanium Inorganic materials 0.000 claims description 45
- 239000007788 liquid Substances 0.000 claims description 37
- 239000006185 dispersion Substances 0.000 claims description 35
- 239000011259 mixed solution Substances 0.000 claims description 32
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 31
- 229910052726 zirconium Inorganic materials 0.000 claims description 31
- 239000007864 aqueous solution Substances 0.000 claims description 24
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 22
- 239000013078 crystal Substances 0.000 claims description 21
- 238000001035 drying Methods 0.000 claims description 19
- 239000003446 ligand Substances 0.000 claims description 14
- 150000003856 quaternary ammonium compounds Chemical class 0.000 claims description 13
- 239000000243 solution Substances 0.000 claims description 13
- 229940046892 lead acetate Drugs 0.000 claims description 12
- 239000006228 supernatant Substances 0.000 claims description 11
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical group OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- 238000000926 separation method Methods 0.000 claims description 6
- 238000005119 centrifugation Methods 0.000 claims description 5
- 230000003100 immobilizing effect Effects 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- 230000002378 acidificating effect Effects 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 claims 1
- 238000007254 oxidation reaction Methods 0.000 claims 1
- 239000000523 sample Substances 0.000 description 36
- 238000001878 scanning electron micrograph Methods 0.000 description 33
- 239000010408 film Substances 0.000 description 32
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 30
- 229910052710 silicon Inorganic materials 0.000 description 30
- 239000010703 silicon Substances 0.000 description 30
- 238000005259 measurement Methods 0.000 description 23
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 21
- 238000003786 synthesis reaction Methods 0.000 description 21
- 230000015572 biosynthetic process Effects 0.000 description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 12
- 239000000843 powder Substances 0.000 description 11
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 8
- 238000000634 powder X-ray diffraction Methods 0.000 description 8
- 239000004642 Polyimide Substances 0.000 description 7
- 238000009826 distribution Methods 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 229920001721 polyimide Polymers 0.000 description 7
- 238000005464 sample preparation method Methods 0.000 description 7
- 230000003746 surface roughness Effects 0.000 description 7
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 239000010419 fine particle Substances 0.000 description 6
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 230000004044 response Effects 0.000 description 6
- 230000002194 synthesizing effect Effects 0.000 description 6
- 229910052697 platinum Inorganic materials 0.000 description 5
- LVRFTAZAXQPQHI-UHFFFAOYSA-N 2-hydroxy-4-methylvaleric acid Chemical compound CC(C)CC(O)C(O)=O LVRFTAZAXQPQHI-UHFFFAOYSA-N 0.000 description 4
- VEGSIXIYQSUOQG-UHFFFAOYSA-N azane;2-hydroxypropanoic acid;zirconium Chemical compound [NH4+].[Zr].CC(O)C([O-])=O VEGSIXIYQSUOQG-UHFFFAOYSA-N 0.000 description 4
- 238000010979 pH adjustment Methods 0.000 description 4
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 3
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 3
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 3
- 238000005530 etching Methods 0.000 description 3
- 238000001027 hydrothermal synthesis Methods 0.000 description 3
- 230000001678 irradiating effect Effects 0.000 description 3
- 239000004310 lactic acid Substances 0.000 description 3
- 235000014655 lactic acid Nutrition 0.000 description 3
- 239000001630 malic acid Substances 0.000 description 3
- 235000011090 malic acid Nutrition 0.000 description 3
- QBYIENPQHBMVBV-HFEGYEGKSA-N (2R)-2-hydroxy-2-phenylacetic acid Chemical compound O[C@@H](C(O)=O)c1ccccc1.O[C@@H](C(O)=O)c1ccccc1 QBYIENPQHBMVBV-HFEGYEGKSA-N 0.000 description 2
- AAWZDTNXLSGCEK-LNVDRNJUSA-N (3r,5r)-1,3,4,5-tetrahydroxycyclohexane-1-carboxylic acid Chemical compound O[C@@H]1CC(O)(C(O)=O)C[C@@H](O)C1O AAWZDTNXLSGCEK-LNVDRNJUSA-N 0.000 description 2
- LVRFTAZAXQPQHI-RXMQYKEDSA-N (R)-2-hydroxy-4-methylpentanoic acid Chemical compound CC(C)C[C@@H](O)C(O)=O LVRFTAZAXQPQHI-RXMQYKEDSA-N 0.000 description 2
- AFENDNXGAFYKQO-VKHMYHEASA-N (S)-2-hydroxybutyric acid Chemical compound CC[C@H](O)C(O)=O AFENDNXGAFYKQO-VKHMYHEASA-N 0.000 description 2
- RBNPOMFGQQGHHO-UHFFFAOYSA-N -2,3-Dihydroxypropanoic acid Natural products OCC(O)C(O)=O RBNPOMFGQQGHHO-UHFFFAOYSA-N 0.000 description 2
- AAWZDTNXLSGCEK-UHFFFAOYSA-N Cordycepinsaeure Natural products OC1CC(O)(C(O)=O)CC(O)C1O AAWZDTNXLSGCEK-UHFFFAOYSA-N 0.000 description 2
- RBNPOMFGQQGHHO-UWTATZPHSA-N D-glyceric acid Chemical compound OC[C@@H](O)C(O)=O RBNPOMFGQQGHHO-UWTATZPHSA-N 0.000 description 2
- AAWZDTNXLSGCEK-ZHQZDSKASA-N Quinic acid Natural products O[C@H]1CC(O)(C(O)=O)C[C@H](O)C1O AAWZDTNXLSGCEK-ZHQZDSKASA-N 0.000 description 2
- IWYDHOAUDWTVEP-UHFFFAOYSA-N R-2-phenyl-2-hydroxyacetic acid Natural products OC(=O)C(O)C1=CC=CC=C1 IWYDHOAUDWTVEP-UHFFFAOYSA-N 0.000 description 2
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 2
- 235000015165 citric acid Nutrition 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 238000005755 formation reaction Methods 0.000 description 2
- 229960002510 mandelic acid Drugs 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000011975 tartaric acid Substances 0.000 description 2
- 235000002906 tartaric acid Nutrition 0.000 description 2
- 239000004251 Ammonium lactate Substances 0.000 description 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- 241000549556 Nanos Species 0.000 description 1
- 229910020684 PbZr Inorganic materials 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 229940059265 ammonium lactate Drugs 0.000 description 1
- 235000019286 ammonium lactate Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- RZOBLYBZQXQGFY-HSHFZTNMSA-N azanium;(2r)-2-hydroxypropanoate Chemical compound [NH4+].C[C@@H](O)C([O-])=O RZOBLYBZQXQGFY-HSHFZTNMSA-N 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000002611 lead compounds Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 150000004686 pentahydrates Chemical class 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229940095064 tartrate Drugs 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 150000003755 zirconium compounds Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G25/00—Compounds of zirconium
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N30/00—Piezoelectric or electrostrictive devices
- H10N30/01—Manufacture or treatment
- H10N30/07—Forming of piezoelectric or electrostrictive parts or bodies on an electrical element or another base
- H10N30/074—Forming of piezoelectric or electrostrictive parts or bodies on an electrical element or another base by depositing piezoelectric or electrostrictive layers, e.g. aerosol or screen printing
- H10N30/077—Forming of piezoelectric or electrostrictive parts or bodies on an electrical element or another base by depositing piezoelectric or electrostrictive layers, e.g. aerosol or screen printing by liquid phase deposition
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N30/00—Piezoelectric or electrostrictive devices
- H10N30/80—Constructional details
- H10N30/85—Piezoelectric or electrostrictive active materials
- H10N30/853—Ceramic compositions
Description
この発明は、金属酸化物ナノ結晶膜固定化基板、金属酸化物ナノ結晶の製造方法、金属酸化物ナノ結晶膜固定化基板の製造方法に関する。
本願は、２０１７年６月３０日に、日本に出願された特願２０１７−１２９７１６号に基づき優先権を主張し、その内容をここに援用する。The present invention relates to a metal oxide nanocrystal film-immobilized substrate, a method for producing metal oxide nanocrystals, and a method for producing a metal oxide nanocrystal film-immobilized substrate.
The present application claims priority based on Japanese Patent Application No. 2017-129716 filed in Japan on June 30, 2017, the contents of which are incorporated herein by reference.
金属酸化物であるチタン酸鉛（ＰＴ）やチタン酸ジルコン酸鉛（ＰＺＴ）は、優れた圧電効果を示す圧電体として知られている。こうしたチタン酸鉛やチタン酸ジルコン酸鉛のナノ結晶（ナノキューブ）は、サイズに起因した特徴的な物性を発現し、新規材料としての応用が期待されている。 Lead titanate (PT) and lead zirconate titanate (PZT), which are metal oxides, are known as piezoelectric bodies that exhibit an excellent piezoelectric effect. Such nanocrystals (nanocubes) of lead titanate and lead zirconate titanate exhibit characteristic physical properties due to their size, and are expected to be applied as new materials.
従来のチタン酸ジルコン酸鉛の製造方法として、例えば、非特許文献１には、酢酸鉛粉末およびＥＤＴＡを水に分散し、これに酸化チタン粉末およびオキシ塩化ジルコニウムを水に分散した原料粉末を加えて、オートクレーブを用いて水熱合成することにより、チタン酸ジルコン酸鉛の粉末を製造することが記載されている。
非特許文献１に記載されたチタン酸ジルコン酸鉛の製造方法によれば、立方体形状であり、サイズが数μｍ程度に揃ったチタン酸ジルコン酸鉛の微粒子を製造できるとされている。As a conventional method for producing lead zirconate titanate, for example, in Non-Patent Document 1, lead acetate powder and EDTA are dispersed in water, and titanium oxide powder and raw material powder in which zirconium oxychloride is dispersed in water are added thereto. It is described that a powder of lead zirconate titanate is produced by hydrothermal synthesis using an autoclave.
According to the method for producing lead zirconate titanate described in Non-Patent Document 1, it is said that fine particles of lead zirconate titanate having a cubic shape and having a size of about several μm can be produced.
また、特許文献１には、鉛化合物、チタン化合物、およびジルコニウム化合物を特定範囲の混合比率で混合し、この混合原料を特定のｐＨ範囲で熟成してから塩基性物質を加えて水熱合成することにより、０．５〜１０μｍなどのミクロンサイズの粒子のチタン酸ジルコン酸鉛が得られることが記載されている。 Further, in Patent Document 1, a lead compound, a titanium compound, and a zirconium compound are mixed at a mixing ratio in a specific range, and the mixed raw material is aged in a specific pH range, and then a basic substance is added for hydrothermal synthesis. It is described that the lead zirconate titanate having micron size particles such as 0.5 to 10 μm can be obtained.
しかしながら、非特許文献１や特許文献１に記載されているチタン酸ジルコン酸鉛の微粒子の製造方法では、そのサイズに起因した特徴的な物性の発現が期待される、例えばサイズが数十ｎｍから数百ｎｍ程度のチタン酸鉛およびチタン酸ジルコン酸鉛のナノ結晶（ナノキューブ）を安定して製造することが困難である。 However, in the method for producing fine particles of lead zirconate titanate described in Non-Patent Document 1 and Patent Document 1, it is expected that characteristic physical properties due to the size thereof are exhibited, for example, the size is from several tens of nm. It is difficult to stably produce nanocrystals (nanocubes) of lead titanate and lead zirconate titanate having a size of several hundred nm.
また、従来、こうしたチタン酸鉛やチタン酸ジルコン酸鉛の微粒子を用いて、基板の表面にチタン酸鉛やチタン酸ジルコン酸鉛の微粒子を配列集積させた膜や、単独で基板上に分散させた膜の形成（以下、固定化という）の際には、膜を形成した後の基板の焼成や、基板に凹凸を形成するためにエッチングを行うなどの複雑な工程が必要であった。このため、チタン酸鉛やチタン酸ジルコン酸鉛の微粒子を含む膜が形成された基板を低コストで簡易に製造する方法が望まれている。 In addition, conventionally, such fine particles of lead titanate and lead zirconate titanate are used to form a film in which fine particles of lead titanate and lead zirconate titanate are arranged and accumulated on the surface of a substrate, or the fine particles are dispersed alone on a substrate. In the formation of the film (hereinafter referred to as immobilization), complicated steps such as firing the substrate after forming the film and etching to form irregularities on the substrate were required. Therefore, a method for easily producing a substrate on which a film containing fine particles of lead titanate or lead zirconate titanate is formed at low cost is desired.
本発明は、金属酸化物であるチタン酸鉛やチタン酸ジルコン酸鉛のナノ結晶（ナノキューブ）を製造することが可能な金属酸化物ナノ結晶の製造方法、および簡易な工程で金属酸化物ナノ結晶の膜を基板の表面に固定化することが可能な金属酸化物ナノ結晶膜固定化基板の製造方法を提供することを目的とする。 The present invention is a method for producing metal oxide nanocrystals capable of producing nanocrystals (nanocubes) of lead titanate and lead zirconate titanate, which are metal oxides, and metal oxide nanos by a simple process. An object of the present invention is to provide a method for producing a metal oxide nanocrystal film-immobilized substrate capable of immobilizing a crystal film on the surface of the substrate.
本発明者は、上記目的を達成するべく鋭意検討を行なった結果、酢酸鉛水溶液と、水溶性チタン錯体の水溶液、または水溶性チタン錯体の水溶液および水溶性ジルコニウム錯体の水溶液と、四級アンモニウム化合物とを混合して混合溶液を得て、この混合溶液を加熱して合成することによって、六面体状の構造を有するナノサイズのチタン酸鉛ナノ結晶、チタン酸ジルコン酸鉛ナノ結晶が得られることを見出し、本発明に想到した。 As a result of diligent studies to achieve the above object, the present inventor has obtained an aqueous solution of lead acetate and an aqueous solution of a water-soluble titanium complex, an aqueous solution of a water-soluble titanium complex, an aqueous solution of a water-soluble zirconate complex, and a quaternary ammonium compound. By mixing with and to obtain a mixed solution and heating and synthesizing this mixed solution, nano-sized lead titanate nanocrystals and lead zirconate titanate nanocrystals having a hexahedral structure can be obtained. I found it and came up with the present invention.
［１］本発明の一態様に係る金属酸化物ナノ結晶の製造方法は、チタン酸鉛またはチタン酸ジルコン酸鉛からなる金属酸化物を含む金属酸化物ナノ結晶の製造方法であって、酢酸鉛水溶液と、水溶性チタン錯体水溶液、または水溶性チタン錯体水溶液および水溶性ジルコニウム錯体水溶液と、四級アンモニウム化合物と、を混合して混合溶液を形成する混合溶液形成工程と、前記混合溶液を加熱して金属酸化物ナノ結晶を合成する加熱工程と、前記金属酸化物ナノ結晶と残液とを分離する分離工程と、を備えている。 [ 1 ] The method for producing a metal oxide nanocrystal according to one aspect of the present invention is a method for producing a metal oxide nanocrystal containing a metal oxide composed of lead titanate or lead zirconate titanate. A mixed solution forming step of mixing an aqueous solution, a water-soluble titanium complex aqueous solution, a water-soluble titanium complex aqueous solution, a water-soluble zirconium complex aqueous solution, and a quaternary ammonium compound to form a mixed solution, and heating the mixed solution. It includes a heating step for synthesizing the metal oxide nanocrystals and a separation step for separating the metal oxide nanocrystals from the residual solution.
上記態様によれば、簡易な方法で、チタン酸鉛およびチタン酸ジルコン酸鉛のナノ結晶（ナノキューブ）を安定して合成することが可能になる。 According to the above aspect, nanocrystals (nanocubes) of lead titanate and lead zirconate titanate can be stably synthesized by a simple method.
［２］上記［１］に記載の金属酸化物ナノ結晶の製造方法において、前記水溶性チタン錯体の配位子がヒドロキシカルボン酸であることが好ましい。 [ 2 ] In the method for producing metal oxide nanocrystals according to the above [ 1 ], it is preferable that the ligand of the water-soluble titanium complex is a hydroxycarboxylic acid.
[３]上記［１］または［２］のいずれかに記載の金属酸化物ナノ結晶の製造方法において、前記水溶性ジルコニウム錯体の配位子がヒドロキシカルボン酸であることが好ましい。 [ 3 ] In the method for producing metal oxide nanocrystals according to any one of [ 1 ] or [ 2 ] above, it is preferable that the ligand of the water-soluble zirconium complex is a hydroxycarboxylic acid.
［４］上記［１］〜［３］のいずれか一つに記載の金属酸化物ナノ結晶の製造方法において、前記四級アンモニウム化合物がテトラメチルアンモニウムヒドロキシドであることが好ましい。 [ 4 ] In the method for producing metal oxide nanocrystals according to any one of the above [ 1 ] to [ 3 ], it is preferable that the quaternary ammonium compound is tetramethylammonium hydroxide.
［５］上記［１］〜［４］のいずれか一つに記載の金属酸化物ナノ結晶の製造方法において、前記混合溶液において、チタンとジルコニウムとのモル比が、１００：０〜３０：７０の範囲であることが好ましい。 [ 5 ] In the method for producing metal oxide nanocrystals according to any one of the above [ 1 ] to [ 4 ], the molar ratio of titanium and zirconium in the mixed solution is 100: 0 to 30:70. It is preferably in the range of.
［６］上記［１］〜［５］のいずれか一つに記載の金属酸化物ナノ結晶の製造方法において、前記混合溶液において、鉛と、チタンまたはチタンおよびジルコニウムと、のモル比が１：１以上、２：１以下であることが好ましい。 [6] In the method for producing metal oxide nanocrystals according to any one of [ 1 ] to [ 5 ] above, the molar ratio of lead to titanium or titanium and zirconium in the mixed solution is 1: 1. It is preferably 1 or more and 2: 1 or less.
［７］上記［１］〜［６］のいずれか一つに記載の金属酸化物ナノ結晶の製造方法において、前記混合溶液は、鉛１モルに対する四級アンモニウム化合物のモル数が２以上１００以下であることが好ましい。 [ 7 ] In the method for producing metal oxide nanocrystals according to any one of [ 1 ] to [ 6 ] above, the mixed solution has 2 or more and 100 or less moles of the quaternary ammonium compound with respect to 1 mol of lead. Is preferable.
［８］上記［１］〜［７］のいずれか一つに記載の金属酸化物ナノ結晶の製造方法において、前記加熱工程は、１４０℃以上２４０℃以下の温度範囲で、かつ１時間以上１２０時間以下の時間範囲で実施することが好ましい。 [ 8 ] In the method for producing metal oxide nanocrystals according to any one of [ 1 ] to [ 7 ] above, the heating step is performed in a temperature range of 140 ° C. or higher and 240 ° C. or lower, and for 1 hour or longer and 120. It is preferable to carry out in a time range of less than an hour.
［９］上記［１］〜［８］のいずれか一つに記載の金属酸化物ナノ結晶の製造方法において、前記分離工程は、前記残液から遠心分離によって前記金属酸化物ナノ結晶を分離回収する工程であることが好ましい。 [ 9 ] In the method for producing metal oxide nanocrystals according to any one of [ 1 ] to [ 8 ] above, in the separation step, the metal oxide nanocrystals are separated and recovered by centrifugation from the residual liquid. It is preferable that the process is performed.
［１０］本発明の一態様に係る金属酸化物ナノ結晶膜固定化基板の製造方法は、基板と、該基板上に配列あるいは固定化した金属酸化物ナノ結晶からなるナノ結晶膜と、を備え、前記金属酸化物ナノ結晶を構成する金属酸化物は、チタン酸鉛またはチタン酸ジルコン酸鉛である金属酸化物ナノ結晶膜固定化基板の製造方法であって、前記各項記載の上記［１］〜［９］のいずれか一つに記載の金属酸化物ナノ結晶の製造方法で得た金属酸化物ナノ結晶を、アルコール溶媒またはｐＨ３以下の酸性溶媒に分散させてから遠心分離を行い、上澄みを回収してナノ結晶分散液を得る分散工程と、前記ナノ結晶分散液を前記基板上に塗布した後に乾燥させることによって、前記ナノ結晶膜を前記基板上に固定化させる固定化工程と、を有する。 [ 10 ] The method for producing a metal oxide nanocrystal film-immobilized substrate according to one aspect of the present invention includes a substrate and a nanocrystal film composed of metal oxide nanocrystals arranged or immobilized on the substrate. The metal oxide constituting the metal oxide nanocrystals is a method for producing a metal oxide nanocrystal film-immobilized substrate which is lead titanate or lead zirconate titanate, and is described in each of the above items [ 1]. ] To [ 9 ] The metal oxide nanocrystals obtained by the method for producing metal oxide nanocrystals according to any one of [ 9 ] are dispersed in an alcohol solvent or an acidic solvent having a pH of 3 or less, and then centrifuged to obtain a supernatant. A dispersion step of recovering the nanocrystal dispersion liquid to obtain a nanocrystal dispersion liquid, and an immobilization step of immobilizing the nanocrystal film on the substrate by applying the nanocrystal dispersion liquid on the substrate and then drying it. Have.
本発明によれば、チタン酸鉛やチタン酸ジルコン酸鉛のナノ結晶（ナノキューブ）を製造することが可能な金属酸化物ナノ結晶の製造方法、および簡易な工程で金属酸化物ナノ結晶の膜を基板の表面に固定化することが可能な、金属酸化物ナノ結晶膜固定化基板の製造方法を提供することが可能になる。 According to the present invention, a method for producing metal oxide nanocrystals capable of producing nanocrystals (nanocubes) of lead titanate or lead zirconate titanate, and a film of metal oxide nanocrystals in a simple process. It becomes possible to provide a method for producing a metal oxide nanocrystal film-immobilized substrate, which can be immobilized on the surface of the substrate.
以下、図面を参照して、本発明の一実施形態の金属酸化物ナノ結晶膜固定化基板、金属酸化物ナノ結晶の製造方法、金属酸化物ナノ結晶膜固定化基板の製造方法について説明する。なお、以下に示す各実施形態は、発明の趣旨をより良く理解させるために具体的に説明するものであり、特に指定のない限り、本発明を限定するものではない。また、以下の説明で用いる図面は、本発明の特徴をわかりやすくするために、便宜上、要部となる部分を拡大して示している場合があり、各構成要素の寸法比率などが実際と同じであるとは限らない。なお、本明細書において、「〜」を用いて数値範囲を示す時、両端の数値を含む。 Hereinafter, with reference to the drawings, a metal oxide nanocrystal film-immobilized substrate, a method for producing metal oxide nanocrystals, and a method for producing a metal oxide nanocrystal film-immobilized substrate according to an embodiment of the present invention will be described. It should be noted that each of the embodiments shown below is specifically described in order to better understand the gist of the invention, and is not limited to the present invention unless otherwise specified. Further, in the drawings used in the following description, in order to make the features of the present invention easy to understand, the main parts may be enlarged for convenience, and the dimensional ratios of the respective components are the same as the actual ones. Is not always the case. In this specification, when the numerical range is indicated by using "~", the numerical values at both ends are included.
まず、本発明の金属酸化物ナノ結晶の製造方法と、それによって得られる金属酸化物ナノ結晶について説明する。
なお、本明細書において「ナノ結晶」とは、六面体状の結晶である、いわゆるナノキューブの他、ナノキューブの合成若しくは作製工程において同時に合成される、六面体の頂点が面取りされた不完全な六面体状の結晶をも含む。なお、この六面体の頂点が面取りされた不完全な六面体状の結晶は六面体状の結晶になる途上のものである。また、そのサイズとしては、チタン酸鉛やチタン酸ジルコン酸鉛が六面体状になりえるナノメートルサイズであれば、結晶のサイズに制限はないが、例えば、１０ｎｍ以上、１５００ｎｍ以下の範囲を想定することができる。また、このサイズは、１００ｎｍ以上、１５００ｎｍ以下であることが好ましく、８００ｎｍ以上、１５００ｎｍ以下であればより好ましい。なお、ここでのサイズは、各ナノ結晶の各面を平面視した際の最大の一辺の長さを意味している。First, the method for producing metal oxide nanocrystals of the present invention and the metal oxide nanocrystals obtained by the method will be described.
In addition to the so-called nanocube, which is a hexahedral crystal, the term "nanocrystal" as used herein refers to an incomplete hexahedron in which the apex of the hexahedron is chamfered, which is simultaneously synthesized in the process of synthesizing or producing the nanocube. Also includes shaped crystals. The incomplete hexahedral crystal in which the apex of the hexahedron is chamfered is in the process of becoming a hexahedral crystal. The size of the crystal is not limited as long as it is a nanometer size in which lead titanate or lead zirconate titanate can be hexahedral, but it is assumed to be in the range of 10 nm or more and 1500 nm or less, for example. be able to. Further, this size is preferably 100 nm or more and 1500 nm or less, and more preferably 800 nm or more and 1500 nm or less. The size here means the maximum length of one side when each surface of each nanocrystal is viewed in a plan view.
また、本明細書において「チタン酸ジルコン酸鉛」は、一般式ＰｂＺｒｘＴｉ（１−ｘ）Ｏ３（０≦ｘ≦０．７）で表わされる。そして、この一般式においてｘ＝０の場合がチタン酸鉛である。Further, in the present specification, "lead zirconate titanate" is represented by the general formula PbZr x Ti (1-x) O 3 (0 ≦ x ≦ 0.7). Then, in this general formula, the case of x = 0 is lead titanate.
本発明の金属酸化物ナノ結晶の製造方法において、結晶サイズがナノメートルサイズであるチタン酸鉛ナノ結晶を製造する場合、その原料として、酢酸鉛水溶液と、水溶性チタン錯体水溶液と、四級アンモニウム化合物と、を用意し、それらを混合して、ナノ結晶の合成原料である混合溶液を形成する（混合溶液形成工程）。
また、結晶サイズがナノメートルサイズであるチタン酸ジルコン酸鉛を製造する場合、その原料として、酢酸鉛水溶液と、水溶性チタン錯体水溶液および水溶性ジルコニウム錯体水溶液と、四級アンモニウム化合物と、を用意し、それらを混合して、ナノ結晶の合成原料である混合溶液を形成する（混合溶液形成工程）。In the method for producing metal oxide nanocrystals of the present invention, when producing lead titanoate nanocrystals having a crystal size of nanometer size, lead acetate aqueous solution, water-soluble titanium complex aqueous solution, and quaternary ammonium are used as raw materials. Compounds and compounds are prepared and mixed to form a mixed solution which is a raw material for synthesizing nanocrystals (mixed solution forming step).
When producing lead zirconate titanate having a crystal size of nanometer size, a lead acetate aqueous solution, a water-soluble titanium complex aqueous solution, a water-soluble zirconium complex aqueous solution, and a quaternary ammonium compound are prepared as raw materials. Then, they are mixed to form a mixed solution which is a synthetic raw material for nanocrystals (mixed solution forming step).
本発明で用いる水溶性チタン錯体としては、水に溶解された後チタン原子から配位子がはずれてチタン原子と酸素原子との結合が形成されるような化合物を用いることができる。そのような化合物としては、水溶性チタン錯体の配位子がヒドロキシカルボン酸であることが好ましい。 As the water-soluble titanium complex used in the present invention, a compound can be used in which the ligand is removed from the titanium atom after being dissolved in water to form a bond between the titanium atom and the oxygen atom. As such a compound, it is preferable that the ligand of the water-soluble titanium complex is a hydroxycarboxylic acid.
ヒドロキシカルボン酸の具体例としては、乳酸、リンゴ酸、クエン酸、酒石酸、グリセリン酸、２−ヒドロキシ酪酸、ロイシン酸（＝２−ヒドロキシ−４−メチルペンタン酸）、キナ酸、マンデル酸（＝２−ヒドロキシ−２−フェニル酢酸）、グリコール酸等を挙げることができる。水溶性チタン錯体としては例えば、配位子が乳酸であるチタニウムビス（アンモニウムラクテート）ジヒドロキシド（Titanium bis(ammonium lactate) dihydroxide、以下「ＴＡＬＨ」）、配位子がグリコール酸（HOCH2COOH）である(NH4)6[Ti4(C2H2O3)4(C2H3O3)2(O2)4O2]・6H2O、配位子がクエン酸（（CH2COOH)2C(OH)COOH）である(NH4)8[Ti4(C6H4O7)4(O2)4]・8H2O、又は配位子がリンゴ酸（CH2CHOH(COOH)2）若しくは酒石酸（(CHOH)2(COOH)2）であるチタン錯体などが挙げられる。Specific examples of hydroxycarboxylic acid include lactic acid, malic acid, citric acid, tartaric acid, glyceric acid, 2-hydroxybutyric acid, leucic acid (= 2-hydroxy-4-methylpentanoic acid), quinic acid, and mandelic acid (= 2). -Hydroxy-2-phenylacetic acid), glycolic acid and the like can be mentioned. Examples of the water-soluble titanium complex include Titanium bis (ammonium lactate) dihydroxide (hereinafter referred to as "TALH") in which the ligand is lactic acid, and glycolic acid (HOCH 2 COOH) in the ligand. Yes (NH 4 ) 6 [Ti 4 (C 2 H 2 O 3 ) 4 (C 2 H 3 O 3 ) 2 (O 2 ) 4 O 2 ] ・ 6H 2 O, ligand is citrate ((CH 2) COOH) 2 C (OH) COOH) (NH 4 ) 8 [Ti 4 (C 6 H 4 O 7 ) 4 (O 2 ) 4 ] ・ 8H 2 O, or ligand is malic acid (CH 2 CHOH) Examples include a titanium complex which is (COOH) 2 ) or tartrate ((CHOH) 2 (COOH) 2 ).
本実施形態では、水溶性チタン錯体としてＴＡＬＨを用いている。ＴＡＬＨは水に可溶なチタンを含む酸化物の前駆体であり、ＴＡＬＨを用いた酸化物の形成反応は、他の方法と比べて穏やかな条件で反応が進行し、ＴＡＬＨが水に可溶であるため水溶液中での反応が可能である。こうした配位子がヒドロキシカルボン酸である水溶性チタン錯体を用いることにより、制御されたナノメートルサイズの六面体状の構造を有するチタン酸鉛ナノ結晶やチタン酸ジルコン酸鉛ナノ結晶の合成に寄与する。 In this embodiment, TALH is used as the water-soluble titanium complex. TALH is a precursor of an oxide containing titanium that is soluble in water, and the oxide formation reaction using TALH proceeds under mild conditions as compared with other methods, and TALH is soluble in water. Therefore, the reaction in an aqueous solution is possible. By using a water-soluble titanium complex in which such a ligand is a hydroxycarboxylic acid, it contributes to the synthesis of lead titanate nanocrystals and lead zirconate titanate nanocrystals having a controlled nanometer-sized hexahedral structure. ..
本発明で用いる水溶性ジルコニウム錯体としては、水に溶解された後ジルコニウム原子から配位子がはずれてジルコニウム原子と酸素原子との結合が形成されるような化合物を用いることができる。そのような化合物としては、水溶性ジルコニウム錯体の配位子がヒドロキシカルボン酸であることが好ましい。 As the water-soluble zirconium complex used in the present invention, a compound that is dissolved in water and then the ligand is removed from the zirconium atom to form a bond between the zirconium atom and the oxygen atom can be used. As such a compound, it is preferable that the ligand of the water-soluble zirconium complex is a hydroxycarboxylic acid.
ヒドロキシカルボン酸の具体例としては、乳酸、リンゴ酸、クエン酸、酒石酸、グリセリン酸、２−ヒドロキシ酪酸、ロイシン酸（＝２−ヒドロキシ−４−メチルペンタン酸）、キナ酸、マンデル酸（＝２−ヒドロキシ−２−フェニル酢酸）、グリコール酸等を挙げることができる。水溶性ジルコニウム錯体としては例えば、ジルコニウムラクテートアンモニウム塩などが挙げられる。 Specific examples of hydroxycarboxylic acid include lactic acid, malic acid, citric acid, tartaric acid, glyceric acid, 2-hydroxybutyric acid, leucic acid (= 2-hydroxy-4-methylpentanoic acid), quinic acid, and mandelic acid (= 2). -Hydroxy-2-phenylacetic acid), glycolic acid and the like can be mentioned. Examples of the water-soluble zirconium complex include zirconium lactate ammonium salt and the like.
本実施形態では、水溶性ジルコニウム錯体としてジルコニウムラクテートアンモニウム塩（Zr(OH)[(OCH(CH3)COO-]3(NH4 +)3）を用いている。具体的には、オルガチックスＺＣ−３００（商品名、マツモトファインケミカル製）が挙げられる。こうした配位子がヒドロキシカルボン酸である水溶性ジルコニウム錯体を用いることにより、制御されたナノメートルサイズの六面体状の構造を有するチタン酸ジルコン酸鉛ナノ結晶の合成に寄与する。In this embodiment, zirconium lactate ammonium salt as the water-soluble zirconium complex (Zr (OH) [(OCH (CH 3) COO -]. 3 (NH 4 +) 3) is used specifically, Orgatics ZC -300 (trade name, manufactured by Matsumoto Fine Chemicals). Zirconic acid titanate having a controlled nanometer-sized hexahedral structure by using a water-soluble zirconium complex in which such a ligand is a hydroxycarboxylic acid. Contributes to the synthesis of lead nanocrystals.
本発明では、上述した混合溶液において、チタンとジルコニウムとのモル比が、１００：０〜３０：７０の範囲になるように、水溶性チタン錯体と水溶性ジルコニウム錯体とを混合する。すなわち、チタンのモル比が３０以上１００以下、ジルコニウムのモルが０以上７０以下であり、かつチタンとジルコニウムのモル比の合計が１００の範囲になるように、水溶性チタン錯体と水溶性ジルコニウム錯体とを混合する。なお、ジルコニウムのモル比が０の場合は、チタン酸鉛ナノ結晶を合成する場合に相当する。 In the present invention, the water-soluble titanium complex and the water-soluble zirconium complex are mixed so that the molar ratio of titanium and zirconium is in the range of 100: 0 to 30:70 in the above-mentioned mixed solution. That is, the water-soluble titanium complex and the water-soluble zirconium complex so that the molar ratio of titanium is 30 or more and 100 or less, the molar ratio of zirconium is 0 or more and 70 or less, and the total molar ratio of titanium and zirconium is in the range of 100. And mix. When the molar ratio of zirconium is 0, it corresponds to the case of synthesizing lead titanate nanocrystals.
また、本発明では、製造後（合成後）に、チタンのモル数が、鉛のモル数の０．３倍以上１倍以下となるように、かつチタンおよびジルコニウムのモル数の合計が、鉛のモル数と同じになるように、酢酸鉛と、水溶性チタン錯体、水溶性ジルコニウム錯体とを混合する。そのために、上述した混合溶液において、鉛とチタン、または、鉛とチタンおよびジルコニウムとのモル比（Ｐｂ：Ｔｉ＋Ｚｒ）が、１：１以上、２：１以下の範囲となるように、酢酸鉛と、水溶性チタン錯体、水溶性ジルコニウム錯体とを混合する。すなわち、混合開始時おいては、チタン１モル、または、チタンおよびジルコニウムの混合物１モルに対して、鉛を１モル以上２モル以下とする。 Further, in the present invention, after production (after synthesis), the number of moles of titanium is 0.3 times or more and 1 times or less the number of moles of lead, and the total number of moles of titanium and zirconium is lead. Lead acetate, a water-soluble titanium complex, and a water-soluble zirconium complex are mixed so as to have the same number of moles. Therefore, in the above-mentioned mixed solution, lead acetate is used so that the molar ratio of lead to titanium or lead to titanium and zirconium (Pb: Ti + Zr) is in the range of 1: 1 or more and 2: 1 or less. , A water-soluble titanium complex and a water-soluble zirconium complex are mixed. That is, at the start of mixing, the amount of lead is 1 mol or more and 2 mol or less with respect to 1 mol of titanium or 1 mol of a mixture of titanium and zirconium.
本発明で用いる四級アンモニウム化合物としては、例えば、テトラメチルアンモニウムヒドロキシド（Tetramethylammonium hydroxide）以下「ＴＭＡＨ」）が挙げられる。ＴＭＡＨは比較的安定した固体の五水和物の形で存在し、水に溶解すると水溶液は強塩基性を示す。 Examples of the quaternary ammonium compound used in the present invention include tetramethylammonium hydroxide (“TMAH”). TMAH exists in the form of a relatively stable solid pentahydrate, and when dissolved in water, the aqueous solution is strongly basic.
本発明では、上述した混合溶液において、鉛１モルに対する四級アンモニウム化合物のモル数が２以上１００以下の範囲になるように、酢酸鉛と、四級アンモニウム化合物とを混合する。これにより、後述する加熱工程においてナノ結晶の合成反応を十分に進行させることができ、かつ合成するナノ結晶の凝集を十分に抑制して、ナノメートルサイズにすることができる。 In the present invention, lead acetate and a quaternary ammonium compound are mixed so that the number of moles of the quaternary ammonium compound with respect to 1 mol of lead is in the range of 2 or more and 100 or less in the above-mentioned mixed solution. As a result, the nanocrystal synthesis reaction can be sufficiently advanced in the heating step described later, and the aggregation of the nanocrystals to be synthesized can be sufficiently suppressed to achieve a nanometer size.
鉛１モルに対する四級アンモニウム化合物のモル数が２未満の場合には、後述する加熱工程において合成反応が十分に進行せず、また、ナノ結晶の形状が十分に制御されず、きれいな六面体にならないという問題点がある。また、鉛１モルに対する四級アンモニウム化合物のモル数が１００を超える場合、加熱工程での合成反応終了後に残渣を完全に取り除くのが困難になるという問題点がある。 When the number of moles of the quaternary ammonium compound with respect to 1 mole of lead is less than 2, the synthesis reaction does not proceed sufficiently in the heating step described later, and the shape of the nanocrystals is not sufficiently controlled, resulting in a clean hexahedron. There is a problem. Further, when the number of moles of the quaternary ammonium compound with respect to 1 mole of lead exceeds 100, there is a problem that it becomes difficult to completely remove the residue after the completion of the synthesis reaction in the heating step.
次に、上述した混合溶液を加熱して、金属酸化物ナノ結晶を合成する（加熱工程）。
本発明で用いる反応溶液の加熱は、１４０℃以上、２４０℃以下の温度で実施されることが好ましい。また、２００℃以上２３０℃以下の温度で実施されることがより好ましい。加熱温度が１４０℃未満の場合には、ナノ結晶の合成反応が十分に進行しないという問題点がある。また、加熱温度が２４０℃を超える場合には、制御された六面体状の構造が最終的に得られないという問題点がある。Next, the above-mentioned mixed solution is heated to synthesize metal oxide nanocrystals (heating step).
The reaction solution used in the present invention is preferably heated at a temperature of 140 ° C. or higher and 240 ° C. or lower. Further, it is more preferable to carry out at a temperature of 200 ° C. or higher and 230 ° C. or lower. When the heating temperature is less than 140 ° C., there is a problem that the synthesis reaction of nanocrystals does not proceed sufficiently. Further, when the heating temperature exceeds 240 ° C., there is a problem that a controlled hexahedral structure cannot be finally obtained.
本発明で用いる反応溶液の加熱は、１時間以上１２０時間以下の間実施されることが好ましく、７０時間以上１００時間以下の間実施されることがより好ましい。加熱時間が１時間未満の場合には、ナノ結晶の合成反応が十分に進行しないという問題点がある。また、加熱時間が１２０時間を超えてもナノ結晶の形状はさほど変化しないため、これ以上の加熱は必要ではないと考えられる。 The heating of the reaction solution used in the present invention is preferably carried out for 1 hour or more and 120 hours or less, and more preferably 70 hours or more and 100 hours or less. If the heating time is less than 1 hour, there is a problem that the nanocrystal synthesis reaction does not proceed sufficiently. Further, since the shape of the nanocrystals does not change so much even if the heating time exceeds 120 hours, it is considered that further heating is not necessary.
本発明の反応溶液を加熱して反応を進行させるには既に知られている様々な方法を適宜使用することができるが、水熱合成を用いることが好ましい。 Various already known methods can be appropriately used to heat the reaction solution of the present invention to allow the reaction to proceed, but hydrothermal synthesis is preferred.
本発明の金属酸化物ナノ結晶の製造方法によれば、加熱工程を１４０℃以上２４０℃以下の温度で、かつ１時間以上１２０時間以下の間実施することにより、ナノ結晶の合成反応を十分に進行させかつ無駄な加熱を実施することなく、制御された六面体状の構造を成すナノメートルサイズのチタン酸鉛ナノ結晶、チタン酸ジルコン酸鉛ナノ結晶を得ることができる。 According to the method for producing metal oxide nanocrystals of the present invention, the nanocrystal synthesis reaction is sufficiently carried out by carrying out the heating step at a temperature of 140 ° C. or higher and 240 ° C. or lower and for 1 hour or longer and 120 hours or lower. It is possible to obtain nanometer-sized lead titanate nanocrystals and lead zirconate titanate nanocrystals having a controlled hexahedral structure without advancing and unnecessary heating.
この後、金属酸化物ナノ結晶を合成した後の混合溶液の遠心分離を行う。そして、金属酸化物ナノ結晶を沈殿させ、濾過などによって残液と分離（分離回収）する（分離工程）。こうした分離工程によって、不要な小さな結晶などを取り除き、サイズが制御された六面体状の構造を持つチタン酸鉛ナノ結晶、チタン酸ジルコン酸鉛ナノ結晶を得ることができる。 After that, the mixed solution is centrifuged after synthesizing the metal oxide nanocrystals. Then, the metal oxide nanocrystals are precipitated and separated (separated and recovered) from the residual liquid by filtration or the like (separation step). By such a separation step, unnecessary small crystals and the like can be removed to obtain lead titanate nanocrystals and lead zirconate titanate nanocrystals having a hexahedral structure whose size is controlled.
以上の本発明の金属酸化物ナノ結晶の製造方法によって得られた、金属酸化物ナノ結晶（チタン酸鉛ナノ結晶、チタン酸ジルコン酸鉛ナノ結晶）は、以下の特性を備えている。
（１）結晶形状が六面体（状）であり、かつ、結晶サイズが１０ｎｍ以上、１５００ｎｍ以下である。また、好ましくは１００ｎｍ以上、１５００ｎｍ以下である。更に、より好ましくは８００ｎｍ以上、１５００ｎｍ以下である。なお、このサイズとは、各ナノ結晶を平面視した際の最大の一辺の長さを意味する。
（２）圧電応答顕微鏡（ＰＦＭ）測定によって求まる圧電定数（ｄ３３−ＰＦＭ）の飽和値の絶対値の平均が２５ｐｍ／Ｖ以上である。ｄ定数は電圧を印加した際の変形のし易さを表す量であり、ｄ３３は電極面に垂直（厚み方向）の伸縮を示す。
（３）ＳＰＭ（走査型プローブ顕微鏡）により測定した形状像において、六面体の任意の一面（六面体を構成する各面）の対角線における中心線平均粗さが５ｎｍ以下となり、かつ六面体の任意の一面の面積の４０％以上の領域における平均面粗さが３０ｎｍ以下となるような表面平滑性を有している。なお、ＳＥＭによるナノ結晶の観察像から推察すると基本的に平滑性は六面体の全面で保たれている。The metal oxide nanocrystals (lead titanate nanocrystals, lead zirconate titanate nanocrystals) obtained by the above method for producing metal oxide nanocrystals of the present invention have the following characteristics.
(1) The crystal shape is hexahedron (shaped), and the crystal size is 10 nm or more and 1500 nm or less. Further, it is preferably 100 nm or more and 1500 nm or less. Further, it is more preferably 800 nm or more and 1500 nm or less. In addition, this size means the length of the maximum side when each nanocrystal is viewed in a plane.
(2) The average of the absolute values of the saturation values of the piezoelectric constants (d 33-PFM ) obtained by the piezoelectric response microscope (PFM) measurement is 25 pm / V or more. The d constant is a quantity indicating the ease of deformation when a voltage is applied, and d 33 indicates expansion and contraction perpendicular to the electrode surface (thickness direction).
(3) In the shape image measured by SPM (scanning probe microscope), the average roughness of the center line on the diagonal of any one surface of the hexahedron (each surface constituting the hexahedron) is 5 nm or less, and any one surface of the hexahedron It has surface smoothness such that the average surface roughness in a region of 40% or more of the area is 30 nm or less. Inferring from the observation image of nanocrystals by SEM, the smoothness is basically maintained on the entire surface of the hexahedron.
次に、本発明の金属酸化物ナノ結晶膜固定化基板の製造方法について説明する。
本発明の金属酸化物ナノ結晶膜固定化基板の製造方法によって得られる金属酸化物ナノ結晶膜固定化基板は、基板と、この基板上に配列あるいは固定化した金属酸化物ナノ結晶からなるナノ結晶膜と、を備えたものである。金属酸化物ナノ結晶を構成する金属酸化物は、チタン酸鉛またはチタン酸ジルコン酸鉛である。Next, a method for manufacturing the metal oxide nanocrystal film-immobilized substrate of the present invention will be described.
The metal oxide nanocrystal film-immobilized substrate obtained by the method for producing a metal oxide nanocrystal film-immobilized substrate of the present invention is a nanocrystal composed of a substrate and metal oxide nanocrystals arranged or immobilized on the substrate. It is equipped with a membrane. The metal oxide constituting the metal oxide nanocrystal is lead titanate or lead zirconate titanate.
基板としては、溶媒に対して安定でかつ吸湿性がないものであれば適用可能であり、平坦な表面を有するものが好ましく、例えば、ＦＴＯ、ＩＴＯ、ガラス、シリコン、金属、セラミックス、ポリマー、紙、ゴム、及び、低耐熱性基材の群から選択されたものを用いることができる。 As the substrate, any substrate that is stable to a solvent and has no hygroscopicity can be applied, and a substrate having a flat surface is preferable. For example, FTO, ITO, glass, silicon, metal, ceramics, polymer, paper. , Rubber, and those selected from the group of low heat resistant substrates can be used.
また、基板の表面には、エッチングによって除去可能な凹凸を形成しておくことができる。こうした凹凸によって、ナノ結晶膜を基板上で任意の形状に形成することができる。基板の厚さ方向からの平面視における凹凸の形状としては、例えば、直線状、曲線状、円形状のうち、いずれか１つのパターン形状にすることができる。 Further, unevenness that can be removed by etching can be formed on the surface of the substrate. Due to these irregularities, the nanocrystal film can be formed into an arbitrary shape on the substrate. As the shape of the unevenness in a plan view from the thickness direction of the substrate, for example, any one of a linear shape, a curved shape, and a circular shape can be used.
本実施形態では、こうした基板として、シリコンウェハに白金薄膜を形成したものを用いた。そして、ナノ結晶膜をこの基板上に多数の線状に形成するために、基板の表面に凹凸として、例えば、ポリイミドからなるモールドを幅数ミクロンのストライプ状に予め形成した。 In the present embodiment, as such a substrate, a silicon wafer on which a platinum thin film is formed is used. Then, in order to form a large number of linear nanocrystal films on the substrate, a mold made of polyimide, for example, was formed in advance on the surface of the substrate in the form of stripes having a width of several microns.
次に、前述した本発明の金属酸化物ナノ結晶の製造方法によって得られたチタン酸鉛ナノ結晶またはチタン酸ジルコン酸鉛ナノ結晶を、アルコール溶媒またはｐＨ３以下の酸性溶媒に分散させてから遠心分離を行い、上澄みを回収してナノ結晶分散液を得る（分散工程）。 Next, the lead titanate nanocrystals or lead zirconate titanate nanocrystals obtained by the method for producing metal oxide nanocrystals of the present invention described above are dispersed in an alcohol solvent or an acidic solvent having a pH of 3 or less, and then centrifuged. To obtain a nanocrystal dispersion liquid by recovering the supernatant (dispersion step).
そして、この分散工程で得られたナノ結晶分散液を基板上に塗布し、乾燥させる。これにより、ナノ結晶分散液が乾燥したナノ結晶膜が、基板上に固定化される（固定化工程）。この後、本実施形態のように、ストライプ状に形成したモールドを除去すれば、線状のモールド同士の間の溝に入り込んで固定化されたナノ結晶膜が残り、基板上にストライプパターンのナノ結晶膜を備えた金属酸化物ナノ結晶膜固定化基板を得ることができる。 Then, the nanocrystal dispersion liquid obtained in this dispersion step is applied onto the substrate and dried. As a result, the nanocrystal film in which the nanocrystal dispersion liquid is dried is immobilized on the substrate (immobilization step). After that, if the striped molds are removed as in the present embodiment, the nanocrystal films that have entered the grooves between the linear molds and are fixed remain, and the nanocrystals of the stripe pattern are left on the substrate. A metal oxide nanocrystal film-immobilized substrate provided with a crystal film can be obtained.
本発明の金属酸化物ナノ結晶膜固定化基板の製造方法によれば、チタン酸鉛ナノ結晶やチタン酸ジルコン酸鉛ナノ結晶を分散したナノ結晶膜を基板上に形成する際に、ナノ結晶分散液を基板に塗布して乾燥させるだけで、ナノ結晶膜が基板上に固定化されるので、従来のように、微細な結晶膜を基板上に形成するために焼成などの熱処理を行う必要が無い。これにより、例えばポリマー、紙、ゴム、などの低耐熱性基材で形成された基板であっても、チタン酸鉛ナノ結晶やチタン酸ジルコン酸鉛ナノ結晶を分散したナノ結晶膜を固定化させることができる。 According to the method for producing a metal oxide nanocrystal film-immobilized substrate of the present invention, nanocrystal dispersion occurs when a nanocrystal film in which lead titanate nanocrystals and lead zirconate nanocrystals are dispersed is formed on the substrate. Since the nanocrystal film is immobilized on the substrate simply by applying the liquid to the substrate and drying it, it is necessary to perform heat treatment such as firing in order to form a fine crystal film on the substrate as in the conventional case. No. As a result, even if the substrate is formed of a low heat resistant substrate such as polymer, paper, or rubber, the nanocrystal film in which lead titanate nanocrystals and lead zirconate titanate nanocrystals are dispersed is immobilized. be able to.
また、ナノ結晶分散液を基板に塗布して乾燥させるといった簡易な工程で、低コストに、かつ容易に金属酸化物ナノ結晶膜固定化基板を得ることができる。
更に、基板上に予め任意のパターンのモールドなど、除去が容易な凹凸を形成しておけば、基板を予めエッチングしなくても、任意のパターンでチタン酸鉛ナノ結晶やチタン酸ジルコン酸鉛ナノ結晶を分散したナノ結晶膜を固定化させた金属酸化物ナノ結晶膜固定化基板を容易に形成することができる。Further, a metal oxide nanocrystal film-immobilized substrate can be easily obtained at low cost by a simple process of applying the nanocrystal dispersion liquid to the substrate and drying it.
Further, if irregularities that can be easily removed such as a mold of an arbitrary pattern are formed on the substrate in advance, lead titanate nanocrystals and lead zirconate titanate nanocrystals can be formed in an arbitrary pattern without etching the substrate in advance. A metal oxide nanocrystal film-immobilized substrate on which a nanocrystal film in which crystals are dispersed is immobilized can be easily formed.
以上、本発明の実施形態を説明したが、これらの実施形態は、例として提示したものであり、発明の範囲を限定することは意図していない。これら実施形態は、その他の様々な形態で実施されることが可能であり、発明の要旨を逸脱しない範囲で、種々の省略、置き換え、変更を行うことができる。これら実施形態やその変形は、発明の範囲や要旨に含まれると同様に、特許請求の範囲に記載された発明とその均等の範囲に含まれるものである。 Although the embodiments of the present invention have been described above, these embodiments are presented as examples and are not intended to limit the scope of the invention. These embodiments can be implemented in various other forms, and various omissions, replacements, and changes can be made without departing from the gist of the invention. These embodiments and modifications thereof are included in the scope and gist of the invention, as well as in the scope of the invention described in the claims and the equivalent scope thereof.
〔チタン酸鉛ナノ結晶の合成及び同定〕
（１）チタン酸鉛ナノ結晶の合成（製造）
以下の手順に従ってチタン酸鉛ナノ結晶を合成した。酢酸鉛（Pb(CH3COO)2・3H2O）６ｍｍｏｌを水１５ｍｌに溶解した。この酢酸鉛水溶液に濃度６ｍｍｏｌのＴＡＬＨ水溶液を攪拌しながら添加し、次いでＴＭＡＨ６．７２６ｇを水１５ｍｌに溶解したＴＭＡＨ水溶液を添加して混合溶液（反応液）を調製した。この段階において、混合溶液に含まれる鉛とチタンとのモル比（Ｐｂ：Ｔｉ）を、２：１となるようにした。得られた混合溶液をオートクレーブに入れて密閉し、２４時間加熱した後に室温まで冷却した。この時の加熱温度が１８０℃のものを実施例１、加熱温度が２００℃のものを実施例２とした。[Synthesis and identification of lead titanate nanocrystals]
(1) Synthesis (manufacturing) of lead titanate nanocrystals
Lead titanate nanocrystals were synthesized according to the following procedure. Lead acetate (Pb (CH 3 COO) 2 · 3H 2 O) 6mmol dissolved in water 15 ml. A TALH aqueous solution having a concentration of 6 mmol was added to the lead acetate aqueous solution with stirring, and then a TMAH aqueous solution in which 6.726 g of TMAH was dissolved in 15 ml of water was added to prepare a mixed solution (reaction solution). At this stage, the molar ratio (Pb: Ti) of lead and titanium contained in the mixed solution was adjusted to 2: 1. The resulting mixed solution was placed in an autoclave, sealed, heated for 24 hours and then cooled to room temperature. The one having a heating temperature of 180 ° C. at this time was designated as Example 1, and the one having a heating temperature of 200 ° C. was designated as Example 2.
（２）チタン酸鉛ナノ結晶の同定
チタン酸鉛ナノ結晶は、走査電子顕微鏡（日本電子株式会社製ＪＥＯＬ、ＪＳＭ−６３３５ＦＭ、１０ｋＶ）を用いて解析した。結晶相の同定をＸ線回折装置（株式会社リガク製、ＳｍａｒｔＬａｂ、４０ｋＶ／３０ｍＡ）を用いて同定した。(2) Identification of lead titanate nanocrystals The lead titanate nanocrystals were analyzed using a scanning electron microscope (JEOL, JSM-6335FM, 10 kV manufactured by JEOL Ltd.). The crystal phase was identified using an X-ray diffractometer (SmartLab, 40 kV / 30 mA, manufactured by Rigaku Co., Ltd.).
実施例１および実施例２のチタン酸鉛ナノ結晶の各種同定用サンプルは、遠心分離により回収した粉末をイソプロピルアルコールに再分散させたコロイド溶液を用い、シリコンウェハ基板へ室温にて滴下乾燥することにより作製した。サンプルに紫外線照射２時間を行った後、インキュベータ内において２００℃で１．５時間保持して、表面の清浄化を行った。 The various identification samples of lead titanate nanocrystals of Examples 1 and 2 are dried by dropping on a silicon wafer substrate at room temperature using a colloidal solution in which the powder recovered by centrifugation is redispersed in isopropyl alcohol. Made by After irradiating the sample with ultraviolet rays for 2 hours, the sample was kept at 200 ° C. for 1.5 hours in an incubator to clean the surface.
図１に、上記のサンプル作製方法によって、実施例１で作製したチタン酸鉛ナノ結晶（混合開始時のモル比Ｐｂ：Ｔｉ＝２：１、加熱温度１８０℃）を含む分散液を、シリコンウェハ基板上に室温にて滴下乾燥することにより作製した、サンプルの表面のＳＥＭ像を示す。
ＳＥＭ像から、実施例１において、ほぼ六面体状でかつ、ほぼ１００ｎｍのサイズのナノ結晶を合成できたことが確認できた。ナノ結晶のサイズ及びその分布は合成条件に依存するが、実施例１においては、１００ｎｍのサイズのナノ結晶は全体の９０％程度であった。FIG. 1 shows a silicon wafer containing a dispersion containing lead titanate nanocrystals (molar ratio Pb: Ti = 2: 1 at the start of mixing, heating temperature 180 ° C.) prepared in Example 1 by the above sample preparation method. The SEM image of the surface of the sample prepared by dropping and drying on a substrate at room temperature is shown.
From the SEM image, it was confirmed that in Example 1, nanocrystals having a hexahedral shape and a size of about 100 nm could be synthesized. The size of the nanocrystals and their distribution depend on the synthesis conditions, but in Example 1, nanocrystals having a size of 100 nm accounted for about 90% of the total.
図２に、上記のサンプル作製方法によって、実施例２で作製したチタン酸鉛ナノ結晶（混合開始時のモル比Ｐｂ：Ｔｉ＝２：１、加熱温度２００℃）を含む分散液を、シリコンウェハ基板上に室温にて滴下乾燥することにより作製した、サンプルの表面のＳＥＭ像を示す。
ＳＥＭ像から、実施例２において、ほぼ六面体状でかつほぼ１００ｎｍのサイズのナノ結晶を合成できたことが確認できた。ナノ結晶のサイズ及びその分布は合成条件に依存するが、実施例２においては、１００ｎｍサイズのナノ結晶は全体の８０％程度であった。FIG. 2 shows a silicon wafer containing a dispersion liquid containing lead titanate nanocrystals (molar ratio Pb: Ti = 2: 1 at the start of mixing, heating temperature 200 ° C.) prepared in Example 2 by the above sample preparation method. The SEM image of the surface of the sample prepared by dropping and drying on a substrate at room temperature is shown.
From the SEM image, it was confirmed that in Example 2, nanocrystals having a hexahedral shape and a size of about 100 nm could be synthesized. The size of the nanocrystals and their distribution depend on the synthesis conditions, but in Example 2, the nanocrystals having a size of 100 nm accounted for about 80% of the total.
図３に、実施例２で作製したチタン酸鉛ナノ結晶について、Ｘ線回折装置を用いて粉末ＸＲＤ測定を行った結果を示す。実施例１で作製したチタン酸鉛ナノ結晶は、ＰｂＴｉＯ３とほぼ同じ位置にピークを有しており、結晶構造及びその格子定数が近い。この結果から、作製（合成）されたチタン酸鉛ナノ結晶のうち、鉛とチタンとのモル比（Ｐｂ：Ｔｉ）が、１：１となっていることを確認することができる。FIG. 3 shows the results of powder XRD measurement of the lead titanate nanocrystals produced in Example 2 using an X-ray diffractometer. The lead titanate nanocrystals produced in Example 1 have a peak at substantially the same position as PbTiO 3 , and the crystal structure and its lattice constant are close to each other. From this result, it can be confirmed that among the produced (synthesized) lead titanate nanocrystals, the molar ratio (Pb: Ti) of lead to titanium is 1: 1.
〔チタン酸ジルコン酸鉛ナノ結晶（Ｐｂ（Ｚｒ０．５２Ｔｉ０．４８）Ｏ３）の合成及び同定：組成１〕
（１）チタン酸ジルコン酸鉛ナノ結晶（Ｚｒ：Ｔｉ＝５２：４８）の合成（製造）
以下の手順に従ってチタン酸ジルコン酸鉛ナノ結晶（組成１）を合成した。酢酸鉛（Pb(CH3COO)2・3H2O）０．３ｍｍｏｌ、ＴＡＬＨ０．０７２ｍｍｏｌ、ジルコニウムラクテートアンモニウム塩（マツモトファインケミカル株式会社製、ＺＣ−３００（商品名））０．０７８ｍｍｏｌを水１５ｍｌに溶解した。この水溶液にＴＭＡＨ１．６８１５ｇを水１５ｍｌに溶解したＴＭＡＨ水溶液を添加して混合溶液（反応液）を調製した。この段階において、混合溶液に含まれる鉛とジルコニウムおよびチタンとのモル比（Ｐｂ：Ｚｒ＋Ｔｉ）を、２：１となるようにした。得られた混合溶液をオートクレーブに入れて密閉し加熱した後に室温まで冷却した。この時の加熱温度が１８０℃、加熱時間が２４時間のものを実施例３、加熱温度が１８０℃、加熱時間が６時間のものを実施例４、加熱温度が２００℃、加熱時間が６時間のものを実施例５、加熱温度が２２０℃、加熱時間が６時間のものを実施例６とした。[Synthesis and identification of lead nanocrystals of lead zirconate titanate (Pb (Zr 0.52 Ti 0.48 ) O 3 ): Composition 1]
(1) Synthesis (manufacturing) of lead nanocrystals of lead zirconate titanate (Zr: Ti = 52: 48)
Lead zirconate titanate nanocrystals (composition 1) were synthesized according to the following procedure. Lead acetate (Pb (CH 3 COO) 2 · 3H 2 O) 0.3mmol, TALH0.072mmol, dissolved zirconium lactate ammonium salt (Matsumoto Fine Chemical Co., ZC-300 (trade name)) 0.078 mmol of water 15ml did. A mixed solution (reaction solution) was prepared by adding an aqueous TMAH solution prepared by dissolving 1.6815 g of TMAH in 15 ml of water to this aqueous solution. At this stage, the molar ratio (Pb: Zr + Ti) of lead to zirconium and titanium contained in the mixed solution was adjusted to 2: 1. The obtained mixed solution was placed in an autoclave, sealed, heated, and then cooled to room temperature. At this time, the heating temperature is 180 ° C. and the heating time is 24 hours in Example 3, the heating temperature is 180 ° C. and the heating time is 6 hours in Example 4, the heating temperature is 200 ° C. and the heating time is 6 hours. The one with the heating temperature of 220 ° C. and the heating time of 6 hours was designated as Example 5.
（２）チタン酸ジルコン酸鉛ナノ結晶（Ｚｒ：Ｔｉ＝５２：４８）の同定
チタン酸ジルコン酸鉛ナノ結晶は、走査電子顕微鏡（日本電子株式会社製ＪＥＯＬ、ＪＳＭ−６３３５ＦＭ、１０ｋＶ）を用いて解析した。結晶相の同定をＸ線回折装置（株式会社リガク製、ＳｍａｒｔＬａｂ、４０ｋＶ／３０ｍＡ）を用いて同定した。(2) Identification of lead zirconate titanate nanocrystals (Zr: Ti = 52: 48) Lead zirconate titanate nanocrystals were prepared using a scanning electron microscope (JEOL, JSM-6335FM, 10 kV, manufactured by JEOL Ltd.). Analyzed. The crystal phase was identified using an X-ray diffractometer (SmartLab, 40 kV / 30 mA, manufactured by Rigaku Co., Ltd.).
実施例３〜６のチタン酸ジルコン酸鉛ナノ結晶の各種同定用サンプルは、遠心分離により回収した粉末を、イソプロピルアルコールに再分散させたコロイド溶液を用い、シリコンウェハ基板へ室温にて滴下乾燥することにより作製した。サンプルに紫外線照射２時間を行った後、インキュベータ内において２００℃で１．５時間保持して、表面の清浄化を行った。 The various identification samples of lead zirconate titanate nanocrystals of Examples 3 to 6 are dried by dropping the powder recovered by centrifugation onto a silicon wafer substrate at room temperature using a colloidal solution in which the powder is redispersed in isopropyl alcohol. It was made by. After irradiating the sample with ultraviolet rays for 2 hours, the sample was kept at 200 ° C. for 1.5 hours in an incubator to clean the surface.
図４に、上記のサンプル作製方法によって、実施例３で作製したチタン酸ジルコン酸鉛ナノ結晶（加熱温度１８０℃、加熱時間２４時間）を含む分散液をシリコンウェハ基板上に室温にて滴下乾燥することにより作製したサンプルの表面のＳＥＭ像を示す。
ＳＥＭ像から、実施例３において、ほぼ六面体状でかつ、８００ｎｍ〜１０００ｎｍのサイズのナノ結晶を合成できたことが確認できた。ナノ結晶のサイズ及びその分布は合成条件に依存するが、実施例３においては、８００ｎｍ〜１０００ｎｍのサイズのナノ結晶は全体の９０％程度であった。In FIG. 4, a dispersion liquid containing lead zirconate titanate nanocrystals (heating temperature 180 ° C., heating time 24 hours) prepared in Example 3 by the above sample preparation method is dropped and dried on a silicon wafer substrate at room temperature. The SEM image of the surface of the sample prepared by the above is shown.
From the SEM image, it was confirmed that in Example 3, nanocrystals having a substantially hexahedral shape and a size of 800 nm to 1000 nm could be synthesized. The size of the nanocrystals and their distribution depend on the synthesis conditions, but in Example 3, nanocrystals having a size of 800 nm to 1000 nm accounted for about 90% of the total.
図５に、上記のサンプル作製方法によって、実施例４で作製したチタン酸ジルコン酸鉛ナノ結晶（加熱温度１８０℃、加熱時間６時間）を含む分散液をシリコンウェハ基板上に室温にて滴下乾燥することにより作製したサンプルの表面のＳＥＭ像を示す。
ＳＥＭ像から、実施例４において、ほぼ六面体状でかつ、１０００ｎｍのサイズのナノ結晶を合成できたことが確認できた。ナノ結晶のサイズ及びその分布は合成条件に依存するが、実施例４においては、１０００ｎｍのサイズのナノ結晶は全体の９０％程度であった。In FIG. 5, the dispersion liquid containing the lead zirconate titanate nanocrystals (heating temperature 180 ° C., heating time 6 hours) prepared in Example 4 by the above sample preparation method is dropped and dried on a silicon wafer substrate at room temperature. The SEM image of the surface of the sample prepared by the above is shown.
From the SEM image, it was confirmed that in Example 4, nanocrystals having a substantially hexahedral shape and a size of 1000 nm could be synthesized. The size of the nanocrystals and their distribution depend on the synthetic conditions, but in Example 4, the nanocrystals having a size of 1000 nm accounted for about 90% of the total.
図６に、上記のサンプル作製方法によって、実施例５で作製したチタン酸ジルコン酸鉛ナノ結晶（加熱温度２００℃、加熱時間６時間）を含む分散液をシリコンウェハ基板上に室温にて滴下乾燥することにより作製したサンプルの表面のＳＥＭ像を示す。
ＳＥＭ像から、実施例５において、ほぼ六面体状でかつ、１２００ｎｍ〜１３００ｎｍのサイズのナノ結晶を合成できたことが確認できた。ナノ結晶のサイズ及びその分布は合成条件に依存するが、実施例５においては、１２００ｎｍ〜１３００ｎｍのサイズのナノ結晶は全体の９０％程度であった。In FIG. 6, the dispersion liquid containing the lead zirconate titanate nanocrystals (heating temperature 200 ° C., heating time 6 hours) prepared in Example 5 by the above sample preparation method is dropped and dried on a silicon wafer substrate at room temperature. The SEM image of the surface of the sample prepared by the above is shown.
From the SEM image, it was confirmed that in Example 5, nanocrystals having a substantially hexahedral shape and a size of 1200 nm to 1300 nm could be synthesized. The size of the nanocrystals and their distribution depend on the synthesis conditions, but in Example 5, nanocrystals having a size of 1200 nm to 1300 nm accounted for about 90% of the total.
図７に、上記のサンプル作製方法によって、実施例６で作製したチタン酸ジルコン酸鉛ナノ結晶（加熱温度２２０℃、加熱時間６時間）を含む分散液をシリコンウェハ基板上に室温にて滴下乾燥することにより作製したサンプルの表面のＳＥＭ像を示す。
ＳＥＭ像から、実施例６において、ほぼ四角柱状でかつ、幅1μｍ、長さ５〜１０μｍのサイズのナノ結晶を合成できたことが確認できた。ナノ結晶のサイズ及びその分布は合成条件に依存するが、実施例６においては、四角柱状でかつ、幅1μｍ、長さ５〜１０μｍのサイズのナノ結晶は全体の９０％程度であった。In FIG. 7, the dispersion liquid containing the lead zirconate titanate nanocrystals (heating temperature 220 ° C., heating time 6 hours) prepared in Example 6 by the above sample preparation method is dropped and dried on a silicon wafer substrate at room temperature. The SEM image of the surface of the sample prepared by the above is shown.
From the SEM image, it was confirmed that in Example 6, nanocrystals having a size of approximately square columnar, 1 μm in width and 5 to 10 μm in length could be synthesized. The size of the nanocrystals and their distribution depend on the synthesis conditions, but in Example 6, nanocrystals having a size of 1 μm in width and 5 to 10 μm in length were about 90% of the total.
図８に、実施例３で作製したチタン酸ジルコン酸鉛ナノ結晶についてＸ線回折装置を用いて粉末ＸＲＤ測定を行った結果を示す。実施例３で作製したチタン酸鉛ナノ結晶は、Ｐｂ（Ｚｒ０．５２Ｔｉ０．４８）Ｏ３とほぼ同じ位置にピークを有しており、結晶構造及びその格子定数が近い。この結果から、作製（合成）されたチタン酸ジルコン酸鉛ナノ結晶のうち、鉛とジルコニウムおよびチタンとのモル比（Ｐｂ：Ｚｒ＋Ｔｉ）が、１：１となっていることを確認することができる。FIG. 8 shows the results of powder XRD measurement of the lead zirconate titanate nanocrystals produced in Example 3 using an X-ray diffractometer. The lead titanate nanocrystals prepared in Example 3, Pb (Zr 0.52 Ti 0.48 ) O 3 and has a peak at substantially the same position, it is closer crystal structure and the lattice constants. From this result, it can be confirmed that the molar ratio (Pb: Zr + Ti) of lead to zirconium and titanium among the prepared (synthesized) lead zirconate titanate nanocrystals is 1: 1. ..
図９に、実施例４〜６で作製したチタン酸鉛ナノ結晶についてＸ線回折装置を用いて粉末ＸＲＤ測定を行った結果を示す。実施例４〜６で作製したチタン酸鉛ナノ結晶のうち、実施例６（加熱温度２２０℃、加熱時間６時間）は、３元系遷移金属酸化物を示すペロブスカイト構造が得られなかった。一方、実施例４、５は、ペロブスカイト構造が得られた。 FIG. 9 shows the results of powder XRD measurement of the lead titanate nanocrystals produced in Examples 4 to 6 using an X-ray diffractometer. Among the lead titanate nanocrystals produced in Examples 4 to 6, in Example 6 (heating temperature 220 ° C., heating time 6 hours), a perovskite structure showing a ternary transition metal oxide was not obtained. On the other hand, in Examples 4 and 5, a perovskite structure was obtained.
〔チタン酸ジルコン酸鉛ナノ結晶（Ｐｂ（Ｚｒ０．７Ｔｉ０．３）Ｏ３）の合成及び同定：組成２〕
（１）チタン酸ジルコン酸鉛ナノ結晶（Ｚｒ：Ｔｉ＝７０：３０）の合成（製造）
以下の手順に従ってチタン酸ジルコン酸鉛ナノ結晶（組成２）を合成した。酢酸鉛（Pb(CH3COO)2・3H2O）０．３ｍｍｏｌ、ＴＡＬＨ０．０４５ｍｍｏｌ、ジルコニウムラクテートアンモニウム塩（マツモトファインケミカル株式会社製、ＺＣ−３００（商品名））０．１０５ｍｍｏｌを水１５ｍｌに溶解した。この水溶液にＴＭＡＨ１．６８１５ｇを水１５ｍｌに溶解したＴＭＡＨ水溶液を添加して混合溶液（反応液）を調製した。この段階において、混合溶液に含まれる鉛とジルコニウムおよびチタンとのモル比（Ｐｂ：Ｚｒ＋Ｔｉ）を、２：１となるようにした。得られた混合溶液をオートクレーブに入れて密閉し、加熱温度１８０℃、加熱時間６時間の条件で加熱した後に室温まで冷却したものを実施例７とした。[Synthesis and identification of lead nanocrystals of lead zirconate titanate (Pb (Zr 0.7 Ti 0.3 ) O 3 ): Composition 2]
(1) Synthesis (manufacturing) of lead nanocrystals of lead zirconate titanate (Zr: Ti = 70: 30)
Lead zirconate titanate nanocrystals (composition 2) were synthesized according to the following procedure. Lead acetate (Pb (CH 3 COO) 2 · 3H 2 O) 0.3mmol, TALH0.045mmol, dissolved zirconium lactate ammonium salt (Matsumoto Fine Chemical Co., ZC-300 (trade name)) 0.105 mmol of water 15ml did. A mixed solution (reaction solution) was prepared by adding an aqueous TMAH solution prepared by dissolving 1.6815 g of TMAH in 15 ml of water to this aqueous solution. At this stage, the molar ratio (Pb: Zr + Ti) of lead to zirconium and titanium contained in the mixed solution was adjusted to 2: 1. The obtained mixed solution was placed in an autoclave, sealed, heated at a heating temperature of 180 ° C. and a heating time of 6 hours, and then cooled to room temperature as Example 7.
（２）チタン酸ジルコン酸鉛ナノ結晶（Ｚｒ：Ｔｉ＝７０：３０）の同定
チタン酸ジルコン酸鉛ナノ結晶は、走査電子顕微鏡（日本電子株式会社製ＪＥＯＬ、ＪＳＭ−６３３５ＦＭ、１０ｋＶ）を用いて解析した。結晶相の同定をＸ線回折装置（株式会社リガク製、ＳｍａｒｔＬａｂ、４０ｋＶ／３０ｍＡ）を用いて同定した。(2) Identification of lead zirconate titanate nanocrystals (Zr: Ti = 70: 30) Lead zirconate titanate nanocrystals were prepared using a scanning electron microscope (JEOL, JSM-6335FM, 10 kV, manufactured by JEOL Ltd.). Analyzed. The crystal phase was identified using an X-ray diffractometer (SmartLab, 40 kV / 30 mA, manufactured by Rigaku Co., Ltd.).
実施例７のチタン酸ジルコン酸鉛ナノ結晶の同定用サンプルは、遠心分離により回収した粉末をイソプロピルアルコールに再分散させたコロイド溶液を用い、シリコンウェハ基板へ室温にて滴下乾燥することにより作製した。サンプルに紫外線照射２時間を行った後、インキュベータ内において２００℃で１．５時間保持して、表面の清浄化を行った。 The sample for identifying the lead nanocrystals of lead zirconate titanate of Example 7 was prepared by dropping and drying the powder recovered by centrifugation on a silicon wafer substrate at room temperature using a colloidal solution in which the powder was redispersed in isopropyl alcohol. .. After irradiating the sample with ultraviolet rays for 2 hours, the sample was kept at 200 ° C. for 1.5 hours in an incubator to clean the surface.
図１０に、上記のサンプル作製方法によって、実施例７で作製したチタン酸ジルコン酸鉛ナノ結晶（加熱温度１８０℃、加熱時間６時間）を含む分散液をシリコンウェハ基板上に室温にて滴下乾燥することにより作製したサンプルの表面のＳＥＭ像を示す。
ＳＥＭ像から、実施例７において、ほぼ六面体状でかつ、１０００ｎｍのサイズのナノ結晶を合成できたことが確認できた。ナノ結晶のサイズ及びその分布は合成条件に依存するが、実施例７においては、１０００ｎｍのサイズのナノ結晶は全体の９０％程度であった。In FIG. 10, a dispersion liquid containing lead zirconate titanate nanocrystals (heating temperature 180 ° C., heating time 6 hours) prepared in Example 7 by the above sample preparation method is dropped and dried on a silicon wafer substrate at room temperature. The SEM image of the surface of the sample prepared by the above is shown.
From the SEM image, it was confirmed that in Example 7, nanocrystals having a substantially hexahedral shape and a size of 1000 nm could be synthesized. The size of the nanocrystals and their distribution depend on the synthesis conditions, but in Example 7, nanocrystals having a size of 1000 nm accounted for about 90% of the total.
図１１に、実施例７で作製したチタン酸ジルコン酸鉛ナノ結晶についてＸ線回折装置を用いて粉末ＸＲＤ測定を行った結果を示す。実施例７で作製したチタン酸鉛ナノ結晶は、Ｐｂ（Ｚｒ０．７Ｔｉ０．３）Ｏ３とほぼ同じ位置にピークを有しており、結晶構造及びその格子定数が近く、ペロブスカイト構造が得られている。この結果から、作製（合成）されたチタン酸ジルコン酸鉛ナノ結晶のうち、鉛とジルコニウムおよびチタンとのモル比（Ｐｂ：Ｚｒ＋Ｔｉ）が、１：１となっていることを確認することができる。FIG. 11 shows the results of powder XRD measurement of the lead zirconate titanate nanocrystals produced in Example 7 using an X-ray diffractometer. The lead titanate nanocrystal produced in Example 7 has a peak at almost the same position as Pb (Zr 0.7 Ti 0.3 ) O 3 , the crystal structure and its lattice constant are close, and the perovskite structure is similar. Has been obtained. From this result, it can be confirmed that the molar ratio (Pb: Zr + Ti) of lead to zirconium and titanium among the prepared (synthesized) lead zirconate titanate nanocrystals is 1: 1. ..
〔金属酸化物ナノ結晶膜固定化基板の作製〕
上述した実施例３で得られたチタン酸ジルコン酸鉛ナノ結晶（Ｐｂ（Ｚｒ０．５２Ｔｉ０．４８）Ｏ３）の粉末０．１ｇをイソプロピルアルコール（２−プロパノール）に加えて超音波によって分散させ、ナノ結晶分散液を得た。次に、シリコンウェハに白金膜を形成した基板を用意し、この基板に、ポリイミドからなるストライプ状のマイクロパターン（幅２〜３μｍ）をもつモールド（凹凸）を形成した。そして、このモールドを備えた基板にナノ結晶分散液を滴下した後、乾燥させた。
[Preparation of metal oxide nanocrystal film-immobilized substrate]
0.1 g of powder of lead zirconate titanate nanocrystals (Pb (Zr 0.52 Ti 0.48 ) O 3 ) obtained in Example 3 described above is added to isopropyl alcohol (2-propanol) by ultrasonic waves. It was dispersed to obtain a nanocrystal dispersion liquid. Next, a substrate having a platinum film formed on a silicon wafer was prepared, and a mold (concavo-convex) having a striped micropattern (width 2-3 μm ) made of polyimide was formed on this substrate. Then, the nanocrystal dispersion liquid was dropped onto the substrate provided with this mold, and then dried.
この乾燥後のモールドが付いた状態でナノ結晶膜が基板上に固定化されたサンプルのＳＥＭ像を図１２に示す。図１２によれば、モールドの溝の中にチタン酸ジルコン酸鉛ナノ結晶が集積している個所（丸囲い点線部）が見られた。 FIG. 12 shows an SEM image of a sample in which the nanocrystal film is immobilized on the substrate with the dried mold attached. According to FIG. 12, a portion (circled dotted line portion) where lead zirconate titanate nanocrystals were accumulated was observed in the groove of the mold.
次に、上述したサンプルのＳＰＭ（走査型プローブ顕微鏡、日立ハイテクサイエンス社製ＮａｎｏＮａｖｉＲｅａｌ）像を図１３に示す。図１３によれば、ナノ結晶分散液を滴下して乾燥させることでチタン酸ジルコン酸鉛のナノ結晶膜が基板上に固定化されたため、ＳＰＭ（走査型プローブ顕微鏡）によって形状測定が可能になっている。 Next, an SPM (scanning probe microscope, NanoNaviReal manufactured by Hitachi High-Tech Science Corporation) image of the above-mentioned sample is shown in FIG. According to FIG. 13, since the nanocrystal film of lead zirconate titanate was immobilized on the substrate by dropping the nanocrystal dispersion liquid and drying it, the shape can be measured by SPM (scanning probe microscope). ing.
〔圧電応答顕微鏡を用いたチタン酸ジルコン酸鉛ナノ結晶の圧電特性の測定〕
上述した金属酸化物ナノ結晶膜固定化基板をサンプルとして、圧電応答顕微鏡（ＰＦＭ）を用いてチタン酸ジルコン酸鉛ナノ結晶の圧電特性の測定を行った。
圧電応答顕微鏡としては、日立ハイテクサイエンス社製ＮａｎｏＮａｖｉＲｅａｌ圧電応答顕微鏡を用いて解析した。それぞれ基板上で測定位置を４か所設定し、それぞれ複数回の測定を行った。
それぞれの測定位置のＳＰＭ像と、圧電特性の測定結果（１）〜（４）を図１４〜図１７に示す。[Measurement of piezoelectric characteristics of lead zirconate titanate nanocrystals using a piezoelectric response microscope]
Using the above-mentioned metal oxide nanocrystal film-immobilized substrate as a sample, the piezoelectric characteristics of lead zirconate titanate nanocrystals were measured using a piezoelectric response microscope (PFM).
As the piezoelectric response microscope, a NanoNaviReal piezoelectric response microscope manufactured by Hitachi High-Tech Science Corporation was used for analysis. Four measurement positions were set on the substrate, and each measurement was performed a plurality of times.
The SPM images of the respective measurement positions and the measurement results (1) to (4) of the piezoelectric characteristics are shown in FIGS. 14 to 17.
図１４〜図１７に示す圧電特性の測定結果から、本発明のチタン酸ジルコン酸鉛ナノ結晶の圧電応答顕微鏡測定によって求まる圧電定数（ｄ３３−ＰＦＭ）の飽和値の絶対値の平均が２５ｐｍ／Ｖ以上であることが確認された。From the measurement results of the piezoelectric characteristics shown in FIGS. 14 to 17, the average of the absolute values of the saturation values of the piezoelectric constants (d 33-PFM ) obtained by the piezoelectric response microscope measurement of the lead zirconate titanate nanocrystals of the present invention is 25 pm /. It was confirmed that it was V or higher.
〔ナノ結晶分散液の調整と、ナノ結晶膜の基板への固定化手法と、基板表面の微細構造の観察〕
上述した実施例４のチタン酸ジルコン酸鉛ナノ結晶（Ｐｂ（Ｚｒ０．５２Ｔｉ０．４８）Ｏ３：加熱温度１８０℃、加熱時間６時間）の粉末０．１ｇをイソプロピルアルコール（２−プロパノール）に加えて洗浄し、塩酸（１０ｍｍｏｌ）を１５ｍｌ添加してｐＨ調整を行い、チタン酸ジルコン酸鉛ナノ結晶の分散を試みた。そして、５８００ｒｐｍの回転数で５分間撹拌し、上澄み液を採取した。この上澄み液のｐＨは１．９であった。なお、ｐＨ調整を行わない上澄み液のｐＨは１２．５３であった。[Preparation of nanocrystal dispersion, method of immobilizing nanocrystal film on substrate, observation of microstructure on substrate surface]
0.1 g of powder of lead zirconate titanate nanocrystals (Pb (Zr 0.52 Ti 0.48 ) O 3 : heating temperature 180 ° C., heating time 6 hours) of Example 4 described above was added to isopropyl alcohol (2-propanol). ), And 15 ml of hydrochloric acid (10 mmol) was added to adjust the pH, and an attempt was made to disperse lead nanocrystals of lead zirconate titanate. Then, the mixture was stirred at a rotation speed of 5800 rpm for 5 minutes, and the supernatant was collected. The pH of this supernatant was 1.9. The pH of the supernatant without pH adjustment was 12.53.
図１８に、塩酸によるｐＨ調整後の上澄み液を１日静置したものをシリコンウェハ基板上に室温にて滴下乾燥することにより作製したサンプルのＳＥＭ像を示す。
図１８のＳＥＭ像では、サイズが８００ｎｍ〜１５００ｎｍ程度の整った六面体が観察できた。FIG. 18 shows an SEM image of a sample prepared by allowing the supernatant liquid adjusted for pH with hydrochloric acid to stand for one day and then dropping and drying it on a silicon wafer substrate at room temperature.
In the SEM image of FIG. 18, a well-organized hexahedron having a size of about 800 nm to 1500 nm could be observed.
次に、シリコンウェハに白金膜を形成した基板に、ポリイミドからなるストライプ状のマイクロパターン（幅２〜３μｍ）をもつモールド（凹凸）を形成し、塩酸によるｐＨ調整後の上澄み液（ナノ結晶分散液）を滴下した後、乾燥させた。
また、シリコンウェハに白金膜を形成した基板に、シリコンからなるストライプ状のマイクロパターン（幅２〜３μｍ）をもつモールド（凹凸）を形成し、塩酸によるｐＨ調整後の上澄み液（ナノ結晶分散液）を滴下した後、乾燥させた。
Next, a mold (concavo-convex) having a striped micropattern (width 2-3 μm ) made of polyimide is formed on a substrate on which a platinum film is formed on a silicon wafer, and a supernatant liquid (nanocrystal) after pH adjustment with hydrochloric acid is formed. The dispersion liquid) was added dropwise and then dried.
In addition, a mold (unevenness) having a striped micropattern (width 2-3 μm ) made of silicon is formed on a substrate having a platinum film formed on a silicon wafer, and a supernatant liquid (nanocrystal dispersion) after pH adjustment with hydrochloric acid is formed. After dropping the liquid), it was dried.
上述したポリイミドのモールドが付いた状態でナノ結晶膜が基板上に固定化されたサンプルのＳＥＭ像を図１９および図２０に示す。また、シリコンモールドが付いた状態でナノ結晶膜が基板上に固定化されたサンプルのＳＥＭ像を図２１に示す。
図１９〜図２１によれば、ポリイミドおよびシリコンのいずれのモールドであっても、モールドの溝の中にチタン酸ジルコン酸鉛ナノ結晶が集積している個所が観察された。19 and 20 show SEM images of the sample in which the nanocrystal film is immobilized on the substrate with the above-mentioned polyimide mold attached. Further, FIG. 21 shows an SEM image of a sample in which the nanocrystal film is immobilized on the substrate with the silicon mold attached.
According to FIGS. 19 to 21, in both the polyimide and silicon molds, the locations where lead zirconate titanate nanocrystals were accumulated were observed in the grooves of the mold.
〔金属酸化物ナノ結晶の中心線平均粗さおよび平均面粗さの観察〕
上述した塩酸によるｐＨ調整後の上澄み液（ナノ結晶分散液）を、シリコンからなるストライプ状のマイクロパターン（幅２〜３μｍ）をもつモールド（凹凸）を形成した２つの基板（シリコンウェハに白金膜を形成）に、それぞれ滴下して乾燥させた。これらの金属酸化物ナノ結晶膜固定化基板を用いて、チタン酸ジルコン酸鉛ナノ結晶（Ｐｂ（Ｚｒ０．５２Ｔｉ０．４８）Ｏ３：加熱温度１８０℃、加熱時間６時間）の中心線平均粗さおよび平均面粗さを測定した。[Observation of centerline average roughness and average surface roughness of metal oxide nanocrystals]
The above-mentioned supernatant liquid (nanocrystal dispersion liquid) after pH adjustment with hydrochloric acid is applied to two substrates (platinum film on a silicon wafer) on which a mold (concavo-convex) having a striped micro pattern (width 2-3 μm) made of silicon is formed. Was formed), and each was dropped and dried. Using these metal oxide nanocrystal film-immobilized substrates, the center line of lead zirconate titanate nanocrystals (Pb (Zr 0.52 Ti 0.48 ) O 3 : heating temperature 180 ° C., heating time 6 hours) The average roughness and the average surface roughness were measured.
２つの測定の結果を、それぞれ図２２、２３に示す。チタン酸ジルコン酸鉛ナノ結晶（Ｐｂ（Ｚｒ０．５２Ｔｉ０．４８）Ｏ３：加熱温度１８０℃、加熱時間６時間）の六面体の任意の一面の対角線における中心線平均粗さは４．７ｎｍ（図２２）、３．９ｎｍ（図２３）であった。また、チタン酸ジルコン酸鉛ナノ結晶の六面体の任意の一面の平均面粗さは２７ｎｍ（図２２）、２８ｎｍ（４４％）（図２３）であった。これらの結果から、本発明のチタン酸ジルコン酸鉛ナノ結晶は、六面体の任意の一面の対角線における中心線平均粗さが５ｎｍ以下、かつ六面体の任意の一面の４０％以上の領域における平均面粗さが３０ｎｍ以下であることが確認された。The results of the two measurements are shown in FIGS. 22 and 23, respectively. Lead zirconate titanate nanocrystals (Pb (Zr 0.52 Ti 0.48 ) O 3 : heating temperature 180 ° C., heating time 6 hours) The average roughness of the center line on the diagonal of any one side of the hexahedron is 4.7 nm. (FIG. 22) was 3.9 nm (FIG. 23). The average surface roughness of any one surface of the hexahedron of lead zirconate titanate nanocrystals was 27 nm (FIG. 22) and 28 nm (44%) (FIG. 23). From these results, the lead zirconate titanate nanocrystal of the present invention has a center line average roughness of 5 nm or less on the diagonal line of any one surface of the hexahedron, and an average surface roughness in a region of 40% or more of any one surface of the hexahedron. It was confirmed that the diameter was 30 nm or less.
本ＰＺＴキューブは、圧電デバイス素子および強誘電体メモリ素子に、好適に利用される。 The PZT cube is suitably used for piezoelectric device elements and ferroelectric memory elements.
Claims (10)
酢酸鉛水溶液と、水溶性チタン錯体水溶液、または水溶性チタン錯体水溶液および水溶性ジルコニウム錯体水溶液と、四級アンモニウム化合物と、を混合して混合溶液を形成する混合溶液形成工程と、前記混合溶液を加熱して金属酸化物ナノ結晶を合成する加熱工程と、前記金属酸化物ナノ結晶と残液とを分離する分離工程と、を備えたことを特徴とする金属酸化物ナノ結晶の製造方法。 A method for producing metal oxide nanocrystals containing a metal oxide composed of lead titanate or lead zirconate titanate.
A mixed solution forming step of mixing a lead acetate aqueous solution, a water-soluble titanium complex aqueous solution, a water-soluble titanium complex aqueous solution, a water-soluble zirconium complex aqueous solution, and a quaternary ammonium compound to form a mixed solution, and the mixed solution. A method for producing a metal oxide nanocrystal, which comprises a heating step of heating to synthesize a metal oxide nanocrystal and a separation step of separating the metal oxide nanocrystal and a residual solution.
請求項１ないし９いずれか一項に記載の金属酸化物ナノ結晶の製造方法で得た金属酸化物ナノ結晶を、アルコール溶媒またはｐＨ３以下の酸性溶媒に分散させてから遠心分離を行い、上澄みを回収してナノ結晶分散液を得る分散工程と、前記ナノ結晶分散液を前記基板上に塗布した後に乾燥させることによって、前記ナノ結晶膜を前記基板上に固定化させる固定化工程と、を有することを特徴とする金属酸化物ナノ結晶膜固定化基板の製造方法。 The metal oxide comprising a substrate and a nanocrystal film composed of metal oxide nanocrystals arranged or immobilized on the substrate and constituting the metal oxide nanocrystals is lead titanate or lead zirconate titanate. This is a method for manufacturing a metal oxide nanocrystal film-immobilized substrate.
The metal oxide nanocrystals obtained by the method for producing metal oxide nanocrystals according to any one of claims 1 to 9 are dispersed in an alcohol solvent or an acidic solvent having a pH of 3 or less, and then centrifuged to obtain a supernatant. It has a dispersion step of collecting and obtaining a nanocrystal dispersion liquid, and an immobilization step of immobilizing the nanocrystal film on the substrate by applying the nanocrystal dispersion liquid on the substrate and then drying it. A method for manufacturing a metal oxide nanocrystal film-immobilized substrate.
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