JP7498938B2 - Thin film manufacturing method - Google Patents
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- 239000010409 thin film Substances 0.000 title claims description 58
- 238000004519 manufacturing process Methods 0.000 title claims description 11
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims description 34
- 239000004094 surface-active agent Substances 0.000 claims description 32
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 28
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 25
- 239000013078 crystal Substances 0.000 claims description 23
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical group [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 13
- 239000001099 ammonium carbonate Substances 0.000 claims description 13
- 229910021529 ammonia Inorganic materials 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 11
- 239000007864 aqueous solution Substances 0.000 claims description 10
- -1 cerium ions Chemical class 0.000 claims description 10
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 7
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 6
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 150000003863 ammonium salts Chemical class 0.000 claims description 4
- 229910052684 Cerium Inorganic materials 0.000 claims description 3
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 claims description 3
- 239000002131 composite material Substances 0.000 claims description 3
- 238000000354 decomposition reaction Methods 0.000 claims description 3
- 239000010436 fluorite Substances 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 239000006104 solid solution Substances 0.000 claims description 2
- 229940125782 compound 2 Drugs 0.000 description 24
- 239000002135 nanosheet Substances 0.000 description 17
- 150000002736 metal compounds Chemical class 0.000 description 16
- 229910021645 metal ion Inorganic materials 0.000 description 13
- AICOOMRHRUFYCM-ZRRPKQBOSA-N oxazine, 1 Chemical compound C([C@@H]1[C@H](C(C[C@]2(C)[C@@H]([C@H](C)N(C)C)[C@H](O)C[C@]21C)=O)CC1=CC2)C[C@H]1[C@@]1(C)[C@H]2N=C(C(C)C)OC1 AICOOMRHRUFYCM-ZRRPKQBOSA-N 0.000 description 11
- 229940125904 compound 1 Drugs 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 238000010586 diagram Methods 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- 238000001878 scanning electron micrograph Methods 0.000 description 6
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- 229910001868 water Inorganic materials 0.000 description 5
- 238000003917 TEM image Methods 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 238000000089 atomic force micrograph Methods 0.000 description 4
- NWZBFJYXRGSRGD-UHFFFAOYSA-M sodium;octadecyl sulfate Chemical compound [Na+].CCCCCCCCCCCCCCCCCCOS([O-])(=O)=O NWZBFJYXRGSRGD-UHFFFAOYSA-M 0.000 description 4
- 239000003945 anionic surfactant Substances 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000000604 cryogenic transmission electron microscopy Methods 0.000 description 3
- 238000001000 micrograph Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 150000001768 cations Chemical group 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000002524 electron diffraction data Methods 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 239000010408 film Substances 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- 229910000000 metal hydroxide Inorganic materials 0.000 description 2
- 150000004692 metal hydroxides Chemical class 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000002411 thermogravimetry Methods 0.000 description 2
- IBMCQJYLPXUOKM-UHFFFAOYSA-N 1,2,2,6,6-pentamethyl-3h-pyridine Chemical compound CN1C(C)(C)CC=CC1(C)C IBMCQJYLPXUOKM-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 229910004631 Ce(NO3)3.6H2O Inorganic materials 0.000 description 1
- 229910052688 Gadolinium Inorganic materials 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 238000001237 Raman spectrum Methods 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910052768 actinide Inorganic materials 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 229910001420 alkaline earth metal ion Inorganic materials 0.000 description 1
- 150000008051 alkyl sulfates Chemical class 0.000 description 1
- 150000008052 alkyl sulfonates Chemical class 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 229910001422 barium ion Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 150000001785 cerium compounds Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002593 electrical impedance tomography Methods 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 229910021644 lanthanide ion Inorganic materials 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000003852 thin film production method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Landscapes
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
- Catalysts (AREA)
- Fuel Cell (AREA)
Description
本開示は、薄膜及びその製造方法に関する。 This disclosure relates to thin films and methods for producing the same.
セリア（酸化セリウム（ＩＶ）、ＣｅＯ２）は、高いイオン伝導性を有することから、固体酸化物形燃料電池（ＳＯＦＣ）などへの応用が注目されている。また、表面におけるプロトンホッピングを利用して、触媒、センサーなどへの応用が注目されている。 Ceria (cerium (IV) oxide, CeO 2 ) has attracted attention for its application to solid oxide fuel cells (SOFCs) and other devices due to its high ionic conductivity. It is also attracting attention for its application to catalysts, sensors, and other devices that utilize proton hopping on the surface.
セリアをＳＯＦＣや触媒などとして好適に利用するために、優れた特性を有するセリアの薄膜を製造する技術が求められている。また、その他の金属酸化物や金属水酸化物などの金属化合物についても、薄膜にすることによって特性が向上することが期待される。 In order to use ceria effectively in SOFCs and catalysts, there is a demand for technology to manufacture thin films of ceria with excellent properties. It is also expected that the properties of other metal compounds such as metal oxides and metal hydroxides can be improved by forming them into thin films.
本開示は、このような課題に鑑みてなされ、その目的は、優れた特性を有する金属化合物の薄膜を提供することである。 This disclosure has been made in light of these problems, and its purpose is to provide a thin film of a metal compound with excellent properties.
上記課題を解決するために、本開示のある態様は、薄膜の製造方法である。この方法は、界面活性剤の層状結晶の層間に金属イオンが含まれた複合体を生成するステップと、複合体に塩基の蒸気を作用させることにより層間に金属化合物を生成するステップと、界面活性剤を溶媒に溶解させることにより金属化合物の薄膜を生成するステップと、薄膜を熱処理することにより金属化合物の結晶構造を変換するステップと、を備える。 To solve the above problems, one aspect of the present disclosure is a method for producing a thin film. This method includes the steps of: generating a complex containing metal ions between layers of a layered crystal of a surfactant; generating a metal compound between the layers by applying base vapor to the complex; generating a thin film of the metal compound by dissolving the surfactant in a solvent; and converting the crystal structure of the metal compound by heat-treating the thin film.
本開示の別の態様もまた、薄膜の製造方法である。この方法は、界面活性剤の層状結晶の層間に金属イオンが含まれた複合体を生成するステップと、複合体とアンモニウム塩の固体又は水溶液とを容器内に並置して複合体にアンモニアの蒸気を作用させることにより層間に金属化合物を生成するステップと、界面活性剤を溶媒に溶解させることにより金属化合物の薄膜を生成するステップと、を備える。 Another aspect of the present disclosure is also a method for producing a thin film. This method includes the steps of: producing a complex containing metal ions between layers of layered crystals of a surfactant; arranging the complex and a solid or aqueous solution of an ammonium salt side by side in a container and applying ammonia vapor to the complex to produce a metal compound between the layers; and producing a thin film of the metal compound by dissolving the surfactant in a solvent.
本開示のさらに別の態様は、薄膜である。この薄膜は、蛍石型の結晶構造を有する酸化セリウム（ＩＶ）を含み、膜厚が２ｎｍ未満である。 Yet another aspect of the present disclosure is a thin film. The thin film includes cerium(IV) oxide having a fluorite-type crystal structure and has a thickness of less than 2 nm.
本開示によれば、優れた特性を有する金属化合物の薄膜を提供することができる。 This disclosure makes it possible to provide a thin film of a metal compound with excellent properties.
本開示では、セリアの特性を高めるために、ナノメーターオーダーの薄膜（ナノシート）を製造する技術を開示する。セリアを薄膜化することにより、蛍石型の結晶構造が歪んで、酸化物イオンが移動する際の活性化エネルギーが変化すると考えられるので、イオン伝導性の向上が期待できる。また、セリアを薄膜化することにより、表面積を増加させることができるので、表面におけるプロトンホッピングによる触媒効果の向上が期待できる。 This disclosure discloses a technique for producing a thin film (nanosheet) on the nanometer order in order to enhance the properties of ceria. By thinning ceria, the fluorite-type crystal structure is distorted, which is thought to change the activation energy when oxide ions move, and therefore improved ion conductivity can be expected. In addition, by thinning ceria, the surface area can be increased, and therefore improved catalytic effects due to proton hopping on the surface can be expected.
これまでの研究により、セリアのイオン伝導性が薄膜の膜厚に強く依存することが示唆されているが、膜厚が２ｎｍ未満のナノシートは報告されていない。蒸着法やゾル－ゲル法などによって作製可能なセリアのナノシートの膜厚はせいぜい２～３ｎｍ程度であり、それよりも薄いセリアのナノシートを作製するのは困難であった。また、横幅も数μｍ程度であり、ＳＯＦＣや触媒などの応用に好適な、大きなナノシートを作製するのは困難であった。 Previous research has suggested that the ionic conductivity of ceria is strongly dependent on the thickness of the thin film, but no nanosheets with a thickness of less than 2 nm have been reported. Ceria nanosheets that can be produced by deposition or sol-gel methods have a thickness of at most 2-3 nm, and it has been difficult to produce ceria nanosheets thinner than this. In addition, the width is only a few micrometers, making it difficult to produce large nanosheets suitable for applications such as SOFCs and catalysts.
界面活性剤のラメラー型の液晶をテンプレートとして、層間にナノシートを作製する技術が知られているが、２ｎｍ未満のナノシートを作製する場合には適用できない。 There is a known technique for creating nanosheets between layers using lamellar surfactant liquid crystals as a template, but this is not applicable to creating nanosheets smaller than 2 nm.
したがって、本開示に係る薄膜の製造方法では、界面活性剤の層状結晶をテンプレートとして薄膜を製造する。液晶相よりも狭い界面活性剤の層間で薄膜を生成するので、厚み方向への成長を制限することができ、２ｎｍ未満のナノシートを製造することができる。また、横サイズの大きな界面活性剤の層状結晶をテンプレートとして使用することにより、数十μｍ以上の横サイズを有する大きなナノシートを製造することができる。 Therefore, in the method for producing a thin film according to the present disclosure, a thin film is produced using layered crystals of a surfactant as a template. Since a thin film is produced between surfactant layers narrower than the liquid crystal phase, growth in the thickness direction can be restricted, and nanosheets of less than 2 nm can be produced. In addition, by using layered crystals of a surfactant with a large lateral size as a template, large nanosheets with lateral sizes of several tens of μm or more can be produced.
図１は、実施の形態に係る薄膜の製造方法を模式的に示す。まず、界面活性剤の層状結晶の層間に金属イオンが含まれた複合体を生成する。この複合体を化合物１とする。つづいて、複合体に塩基の蒸気を作用させることにより層間に金属化合物を生成する。この複合体を化合物２とする。界面活性剤を溶媒に溶解させることにより金属化合物を含む薄膜を生成する。最後に、薄膜を熱処理することにより金属化合物の結晶構造を変換する。 Figure 1 shows a schematic diagram of a method for producing a thin film according to an embodiment. First, a complex containing metal ions is generated between the layers of the layered crystals of the surfactant. This complex is called compound 1. Next, a metal compound is generated between the layers by applying base vapor to the complex. This complex is called compound 2. A thin film containing a metal compound is generated by dissolving the surfactant in a solvent. Finally, the crystal structure of the metal compound is transformed by heat-treating the thin film.
界面活性剤は、層状結晶を形成可能な任意のアニオン界面活性剤であってもよく、例えば、アルキル硫酸塩、アルキルスルホン酸塩、アルキルリン酸塩などであってもよい。界面活性剤は、結晶構造、層間のサイズ、製造する薄膜の膜厚や特性、金属化合物の種類や量などに応じて選択されてもよい。 The surfactant may be any anionic surfactant capable of forming layered crystals, such as an alkyl sulfate, an alkyl sulfonate, or an alkyl phosphate. The surfactant may be selected depending on the crystal structure, the size between the layers, the thickness and characteristics of the thin film to be produced, the type and amount of the metal compound, etc.
複合体は、界面活性剤の水溶液と、金属イオンを含む水溶液とを混合して、界面活性剤に含まれていた陽イオンを金属イオンに置換することにより生成されてもよい。複合体に含まれる金属イオンは、水溶液中で安定な任意の金属イオンであってもよく、例えば、セリウムイオン、ランタンイオン、ガリウムイオン、ジルコニウムイオン、バリウムイオン、ガドリニウムイオン、又はそれらの２以上の組合せであってもよい。複合体に含まれる金属イオンは、アルカリ金属イオン、アルカリ土類金属イオン、ランタノイドイオン、アクチノイドイオン、遷移金属イオンなどであってもよい。アニオン界面活性剤の対イオンは、置換する金属イオンの価数よりも低い価数の陽イオンであってもよい。これにより、金属イオンを含む界面活性剤の複合体を析出しやすくすることができる。界面活性剤に対して過剰量の金属イオンを含む水溶液が界面活性剤の水溶液に混合されてもよい。これによっても、金属イオンを含む界面活性剤の複合体を析出しやすくすることができる。 The complex may be produced by mixing an aqueous solution of a surfactant with an aqueous solution containing a metal ion to replace the cations contained in the surfactant with metal ions. The metal ions contained in the complex may be any metal ion stable in an aqueous solution, such as cerium ions, lanthanum ions, gallium ions, zirconium ions, barium ions, gadolinium ions, or a combination of two or more thereof. The metal ions contained in the complex may be alkali metal ions, alkaline earth metal ions, lanthanide ions, actinide ions, transition metal ions, etc. The counter ion of the anionic surfactant may be a cation with a lower valence than the valence of the metal ion to be replaced. This makes it easier to precipitate the surfactant complex containing the metal ion. An aqueous solution containing an excess amount of metal ions relative to the surfactant may be mixed with the aqueous solution of the surfactant. This also makes it easier to precipitate the surfactant complex containing the metal ion.
複合体に作用させる塩基は、アンモニアであってもよい。複合体と、アンモニア又はアンモニウム塩の水溶液を入れた容器とを、より大きな容器内に並置して静置することにより、複合体にアンモニアの蒸気を作用させてもよい。アンモニアの蒸気と水蒸気が複合体に作用することにより、層間の金属イオンを加水分解して、金属酸化物や金属水酸化物などの金属化合物を層間に析出させることができる。アンモニアと水を蒸気で複合体に作用させることにより、複合体の層状構造を崩さずに層間に金属化合物を生成することができる。 The base to be applied to the complex may be ammonia. The complex and a container containing an aqueous solution of ammonia or an ammonium salt may be placed side by side in a larger container and allowed to stand, allowing ammonia vapor to be applied to the complex. By allowing ammonia vapor and water vapor to act on the complex, metal ions between the layers can be hydrolyzed, and metal compounds such as metal oxides and metal hydroxides can be precipitated between the layers. By allowing ammonia and water vapor to act on the complex, metal compounds can be generated between the layers without destroying the layered structure of the complex.
複合体と、炭酸アンモニウム又は炭酸水素アンモニウムの固体とを容器内に並置して、炭酸アンモニウム又は炭酸水素アンモニウムの分解温度以上の温度に加熱してもよい。炭酸アンモニウム及び炭酸水素アンモニウムは、分解温度以上の温度に加熱すると、アンモニア、水、二酸化炭素に分解する。したがって、複合体に作用させるアンモニアと水の量を制御することができる。このような方法により、特性の良好な薄膜が製造できることが本発明者らの実験により明らかになっている。 The complex and ammonium carbonate or ammonium bicarbonate solid may be placed side by side in a container and heated to a temperature equal to or higher than the decomposition temperature of ammonium carbonate or ammonium bicarbonate. When ammonium carbonate and ammonium bicarbonate are heated to a temperature equal to or higher than their decomposition temperature, they decompose into ammonia, water, and carbon dioxide. Therefore, the amounts of ammonia and water that are applied to the complex can be controlled. Experiments by the present inventors have demonstrated that thin films with good properties can be produced by this method.
界面活性剤を溶解させて除去するための溶媒の種類や量は、界面活性剤の種類や量などに応じて任意に選択されてもよい。 The type and amount of the solvent used to dissolve and remove the surfactant may be selected as appropriate depending on the type and amount of the surfactant.
熱処理は、金属化合物を所望の結晶構造に変換させるのに必要な温度、時間、雰囲気などの条件で実施されてもよい。例えば、蛍石型の結晶構造を有するセリアのナノシートを製造する場合、熱処理は、９００℃以上の温度で６時間以上実施されてもよい。熱処理は、溶媒に溶解しなかった界面活性剤を除去するために実施されてもよい。複合体の層間で生成された金属化合物が、界面活性剤を除去した段階で既に所望の結晶構造を有している場合は、熱処理は実施されなくてもよい。 The heat treatment may be performed under conditions such as temperature, time, and atmosphere required to convert the metal compound into the desired crystal structure. For example, when producing ceria nanosheets having a fluorite-type crystal structure, the heat treatment may be performed at a temperature of 900°C or higher for 6 hours or more. The heat treatment may be performed to remove the surfactant that was not dissolved in the solvent. If the metal compound generated between the layers of the composite already has the desired crystal structure at the stage when the surfactant is removed, the heat treatment may not be performed.
［実施例］
実施の形態に係る薄膜の製造方法にしたがってセリアのナノシートを製造し、特性を評価した。
[Example]
A ceria nanosheet was produced according to the thin film production method of the embodiment, and its characteristics were evaluated.
［化合物１の調整］
アニオン界面活性剤である硫酸ナトリウムオクタデシル（Sodium Octadecyl Sulfate：ＳＯＳ）の水溶液に、過剰量（Ｃｅ：ＳＯＳ＝２０：１）の硝酸セリウム（ＩＩＩ）六水和物（Ｃｅ（ＮＯ３）３・６Ｈ２Ｏ）の水溶液を加えた。生成した沈殿を洗浄して乾燥し、化合物１を得た。
[Preparation of Compound 1]
An excess amount (Ce:SOS=20:1) of an aqueous solution of cerium (III) nitrate hexahydrate (Ce( NO3 ) 3.6H2O ) was added to an aqueous solution of sodium octadecyl sulfate (SOS), an anionic surfactant. The resulting precipitate was washed and dried to obtain compound 1.
［化合物２の調整］
化合物１の結晶を入れたバイアル瓶と、アンモニア水を入れたバイアル瓶を、それぞれ蓋を開けた状態で容器中に封入し、室温で２日静置した。生成した化合物２を８０℃で乾燥した。
[Preparation of Compound 2]
The vial containing the crystals of Compound 1 and the vial containing the aqueous ammonia were sealed in a container with their lids open, and left to stand at room temperature for 2 days. The resulting Compound 2 was dried at 80°C.
［ナノシートの生成］
化合物２をホルムアミドに分散させて化合物２に含まれる界面活性剤を溶解させ、ナノシートを得た。
[Nanosheet generation]
Compound 2 was dispersed in formamide to dissolve the surfactant contained in Compound 2, thereby obtaining nanosheets.
［結晶構造の変換］
ナノシートをシリコン基板の上に載置し、９００℃で６時間熱処理した。これにより、後述するように、蛍石型の結晶構造を有するセリアの薄膜が製造された。
[Crystal structure conversion]
The nanosheet was placed on a silicon substrate and heat-treated for 6 hours at 900° C. This produced a thin film of ceria with a fluorite-type crystal structure, as described below.
図２は、化合物１のＳＥＭ像及びＴＥＭ像を示す。図２（ａ）に示したＳＥＭ像から、化合物１が板状の結晶であることが分かる。図２（ｂ）に示したＴＥＭ像において、直線状の黒い部分はセリウムイオン、直線間のやや白い部分は界面活性剤であると考えられる。これらから、化合物１が約５ｎｍ周期の層状構造を有することが分かる。 Figure 2 shows SEM and TEM images of compound 1. From the SEM image shown in Figure 2(a), it can be seen that compound 1 is a plate-like crystal. In the TEM image shown in Figure 2(b), the straight black parts are thought to be cerium ions, and the slightly white parts between the lines are thought to be surfactants. From these, it can be seen that compound 1 has a layered structure with a periodicity of about 5 nm.
図３は、化合物１を対象とする各種の測定データを示す。図３（ａ）は、化合物１の元素分析結果を示す。図３（ｂ）は、化合物１の熱重量分析結果を示す。図３（ｃ）は、化合物１のＸＰＳスペクトルを示す。ＳＯＳに含まれていたＮａは、化合物１では失われており、代わって、界面活性剤に由来するＳの１／３の量のＣｅが含まれている。ＸＰＳスペクトルでは、Ｃｅ３＋に対応するピークが観測されている。熱重量曲線における１００℃付近の重量減少は、結晶水の離脱に由来すると考えられる。 FIG. 3 shows various measurement data for compound 1. FIG. 3(a) shows the elemental analysis results for compound 1. FIG. 3(b) shows the thermogravimetric analysis results for compound 1. FIG. 3(c) shows the XPS spectrum for compound 1. The Na contained in SOS is lost in compound 1, and instead, Ce is contained in an amount 1/3 of the S derived from the surfactant. In the XPS spectrum, a peak corresponding to Ce 3+ is observed. The weight loss around 100° C. in the thermogravimetric curve is thought to be due to the removal of water of crystallization.
図４は、化合物１の予想される構造を示す。化合物１は、界面活性剤の層状構造の層間に、Ｃｅ３＋をＣｅ３＋：ＯＳ－＝１：３の比で含む構造を有すると考えられる。また、Ｈ２Ｏ：ＯＳ－＝１：２の比で結晶水が含まれていると考えられる。 4 shows the predicted structure of compound 1. Compound 1 is believed to have a structure containing Ce 3+ between the layers of the surfactant layer structure in a ratio of Ce 3+ :OS − =1:3. It is also believed to contain water of crystallization in a ratio of H 2 O:OS − =1:2.
図５は、化合物２のＳＥＭ像とＸ線回折パターンを示す。図５（ａ）に示したＳＥＭ像から、化合物２も板状の結晶であることが分かる。図５（ｂ）に示したＸ線回折パターンから、化合物２が約４．２ｎｍ周期の層状構造を有することが分かる。化合物２では、約５ｎｍの周期に対応するブロードなピークも観測されている。なお、化合物１にアンモニアの蒸気を作用させる際に、炭酸アンモニウムを加熱することによりアンモニアの蒸気を生成した場合は、このブロードなピークは観測されなかった。なお、化合物２は不安定であり、ＴＥＭ像を撮影することはできなかった。 Figure 5 shows the SEM image and X-ray diffraction pattern of compound 2. From the SEM image shown in Figure 5(a), it can be seen that compound 2 is also a plate-like crystal. From the X-ray diffraction pattern shown in Figure 5(b), it can be seen that compound 2 has a layered structure with a period of about 4.2 nm. In compound 2, a broad peak corresponding to a period of about 5 nm is also observed. Note that when ammonia vapor is applied to compound 1 by heating ammonium carbonate to generate ammonia vapor, this broad peak is not observed. Note that compound 2 is unstable, and a TEM image could not be taken.
図６は、化合物２を対象とする各種の測定データを示す。図６（ａ）は、化合物２の元素分析結果を示す。図６（ｂ）は、化合物２の熱重量分析結果を示す。図６（ｃ）は、化合物２のＸＰＳスペクトルを示す。化合物２に含まれるＣとＳの比は化合物１と同じであり、界面活性剤はそのまま化合物２にも含まれていると考えられる。化合物２には、アンモニアに由来すると考えられるＮが含まれる。ＸＰＳスペクトルにおいて、Ｃｅ３＋に対応するピークに加えて、Ｃｅ４＋に対応するピークも観測されている。 FIG. 6 shows various measurement data for compound 2. FIG. 6(a) shows the elemental analysis results for compound 2. FIG. 6(b) shows the thermogravimetric analysis results for compound 2. FIG. 6(c) shows the XPS spectrum for compound 2. The ratio of C and S contained in compound 2 is the same as that in compound 1, and it is considered that the surfactant is also contained in compound 2 as it is. Compound 2 contains N that is considered to be derived from ammonia. In addition to the peak corresponding to Ce 3+ , a peak corresponding to Ce 4+ is also observed in the XPS spectrum.
図７は、化合物２の予想される構造を示す。化合物２は、界面活性剤の層状構造の層間に、対イオンとしてアンモニウムイオンがＮＨ４＋：ＯＳ－＝０．９：１の比で含み、さらに、Ｃｅ３＋及びＣｅ４＋を含む層状のセリウム化合物を含む構造を有すると考えられる。 7 shows a predicted structure of compound 2. Compound 2 is considered to have a structure containing ammonium ions as counter ions at a ratio of NH4+:OS−=0.9:1 between layers of the layered structure of the surfactant, and further containing a layered cerium compound containing Ce3 + and Ce4 + .
図８は、化合物２から界面活性剤を除去して得られた薄膜のＣｒｙｏ－ＴＥＭ像及び電子線回折パターンを示す。図８（ａ）に示すＣｒｙｏ－ＴＥＭ像及び図８（ｂ）に示す電子線回折パターンから、薄膜が蛍石型ではない単結晶性材料であることが示唆される。 Figure 8 shows a Cryo-TEM image and an electron diffraction pattern of a thin film obtained by removing the surfactant from compound 2. The Cryo-TEM image shown in Figure 8(a) and the electron diffraction pattern shown in Figure 8(b) suggest that the thin film is a single-crystalline material that is not of the fluorite type.
図９は、熱処理を実施した後の薄膜を対象とする各種の測定データを示す。図９（ａ）は、薄膜のラマンスペクトルを示す。蛍石型のセリアのＣｅ－Ｏ振動に対応するピークが観測されている。図９（ｂ）は、薄膜のＩｎ－Ｐｌａｎｅ Ｘ線回折パターンを示す。蛍石型のセリアの（２００）に対応するピークが観測されている。蛍石型のセリアの（１１１）に対応するピークが観測されていないが、これは、セリアが二次元平面構造を有することを示唆している。図９（ｃ）は、薄膜のＸＰＳスペクトルを示す。Ｃｅ４＋に対応するピークが観測されている。これらから、薄膜を熱処理することによりセリアの結晶構造が蛍石型に変換されたことが示された。 FIG. 9 shows various measurement data for the thin film after heat treatment. FIG. 9(a) shows the Raman spectrum of the thin film. A peak corresponding to the Ce-O vibration of fluorite-type ceria is observed. FIG. 9(b) shows the in-plane X-ray diffraction pattern of the thin film. A peak corresponding to (200) of fluorite-type ceria is observed. No peak corresponding to (111) of fluorite-type ceria is observed, which suggests that ceria has a two-dimensional planar structure. FIG. 9(c) shows the XPS spectrum of the thin film. A peak corresponding to Ce 4+ is observed. These results show that the crystal structure of ceria was converted to the fluorite type by heat treatment of the thin film.
図１０は、熱処理を実施した後の薄膜の共焦点レーザー顕微鏡画像及び原子間力顕微鏡画像を示す。図１０（ａ）は、薄膜の共焦点レーザー顕微鏡画像を示す。薄膜は、折り畳まれたシート状の形状を有する。図１０（ｂ）は、図１０（ａ）の破線で囲った部分を拡大した原子間力顕微鏡画像を示し、図１０（ｃ）は、図１０（ｂ）の破線で囲った部分を更に拡大した原子間力顕微鏡画像を示す。薄膜は、多数の微少な結晶を含む多結晶体であることが示唆される。図１０（ｄ）は、原子間力顕微鏡によって測定された薄膜の表面形状を示す。折り畳まれた部分における厚みの差から、薄膜の膜厚は約１．５ｎｍであることが示された。表面吸着水などの影響を加味すると、セリアの単位格子１～２個分の膜厚であると予想される。 Figure 10 shows confocal laser microscope images and atomic force microscope images of the thin film after heat treatment. Figure 10(a) shows a confocal laser microscope image of the thin film. The thin film has a folded sheet shape. Figure 10(b) shows an atomic force microscope image of an enlarged portion enclosed by a dashed line in Figure 10(a), and Figure 10(c) shows an atomic force microscope image of an enlarged portion enclosed by a dashed line in Figure 10(b). It is suggested that the thin film is a polycrystalline body containing many minute crystals. Figure 10(d) shows the surface shape of the thin film measured by an atomic force microscope. The difference in thickness in the folded portion indicated that the film thickness was about 1.5 nm. Taking into account the effects of surface adsorbed water, etc., it is expected that the film thickness is equivalent to one or two unit cells of ceria.
図１１は、薄膜の予想される構造を示す。薄膜は、膜厚が約１．５ｎｍで、幅が数十ｎｍのセリアの多結晶を含む、幅数十μｍのシート状の構造を有すると考えられる。 Figure 11 shows the expected structure of the thin film. The thin film is thought to have a thickness of about 1.5 nm and a sheet-like structure several tens of μm wide, containing polycrystals of ceria several tens of nm wide.
蛍石型のセリアのナノシートのイオン伝導性を評価するために、金の櫛形電極を作製し、実施例の薄膜の上に櫛形電極を載置して、電気化学インピーダンス測定を行った。図１２は、櫛形電極を薄膜の上に載置した様子を模式的に示す。櫛形電極のそれぞれの櫛の間における薄膜のイオン伝導性が測定される。図１３は、測定されたインピーダンスのナイキストプロットを示す。実施例の薄膜がイオン伝導性を有することが示唆される。薄膜における伝導の形態として、薄膜に含まれるセリアの多結晶の粒子内及び粒子間におけるプロトン及び酸化物イオンによる伝導が考えられるが、表面におけるプロトンのグロッタス機構による伝導が支配的であると仮定して、プロトンの伝導性を解析した。 To evaluate the ionic conductivity of the fluorite-type ceria nanosheet, a gold comb electrode was prepared and placed on the thin film of the example to perform electrochemical impedance measurement. Figure 12 shows a schematic diagram of the comb electrode placed on the thin film. The ionic conductivity of the thin film between each comb of the comb electrode was measured. Figure 13 shows a Nyquist plot of the measured impedance. It is suggested that the thin film of the example has ionic conductivity. As a form of conduction in the thin film, conduction by protons and oxide ions within and between the polycrystalline particles of ceria contained in the thin film is considered, but the proton conductivity was analyzed assuming that conduction by the Grotthuss mechanism of protons on the surface is dominant.
図１４は、薄膜におけるプロトンの伝導性を示す。図１４（ａ）は、プロトンの電気伝導率の温度依存性を示す。図１４（ｂ）は、アレニウスプロットを示す。プロトン移動の活性化エネルギーは、０．２１ｅＶであった。蛍石型のセリアのナノシートがバルクの同等物よりも高いイオン伝導性を有することが示された。 Figure 14 shows the proton conductivity in the thin film. Figure 14(a) shows the temperature dependence of the proton electrical conductivity. Figure 14(b) shows the Arrhenius plot. The activation energy for proton transfer was 0.21 eV. It was shown that fluorite-type ceria nanosheets have higher ionic conductivity than their bulk counterparts.
以上、本開示を、実施例をもとに説明した。この実施例は例示であり、それらの各構成要素や各処理プロセスの組合せにいろいろな変形例が可能なこと、またそうした変形例も本開示の範囲にあることは当業者に理解されるところである。 The present disclosure has been described above based on examples. These examples are merely illustrative, and those skilled in the art will understand that various modifications are possible in the combination of each component and each processing process, and that such modifications are also within the scope of the present disclosure.
Claims (4)
前記複合体とアンモニウム塩の固体又は水溶液とを容器内に並置して前記複合体にアンモニアの蒸気を作用させることにより前記層間に酸化セリウム（ＩＶ）を生成するステップと、
前記界面活性剤を溶媒に溶解させることにより酸化セリウム（ＩＶ）を含む薄膜を生成するステップと、
前記薄膜を熱処理することにより酸化セリウム（ＩＶ）の結晶構造を蛍石型に変換するステップと、
を備える薄膜の製造方法。 A step of forming a complex containing cerium ions between layers of a layered crystal of a surfactant;
A step of juxtaposing the composite and a solid or aqueous solution of an ammonium salt in a container and applying ammonia vapor to the composite to generate cerium (IV) oxide between the layers;
forming a thin film comprising cerium (IV) oxide by dissolving the surfactant in a solvent;
heat-treating the thin film to convert the crystal structure of cerium (IV) oxide into a fluorite type;
A method for producing a thin film comprising the steps of:
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004031550A (en) | 2002-06-25 | 2004-01-29 | Takeshi Kawabata | Superconducting wire with high critical current characteristics |
| JP2004263066A (en) | 2003-02-28 | 2004-09-24 | National Institute Of Advanced Industrial & Technology | Layered organosilica nanocomposite and method for producing the same |
| JP2007311194A (en) | 2006-05-18 | 2007-11-29 | Sumitomo Electric Ind Ltd | Superconducting thin film material and method for producing superconducting thin film material |
| JP2011129380A (en) | 2009-12-17 | 2011-06-30 | Toyota Central R&D Labs Inc | Lamella porous electrolyte |
| JP2014091646A (en) | 2012-11-01 | 2014-05-19 | National Institute For Materials Science | Fluorite type undoped cerium oxide nanoparticle having high concentration cerium trivalence excellent in atmospheric stability, and manufacture method of the same |
| JP2017226580A (en) | 2016-06-23 | 2017-12-28 | 日産自動車株式会社 | Method for producing crystalline metal oxide film |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3076613B2 (en) * | 1991-03-07 | 2000-08-14 | 科学技術振興事業団 | Method for producing metal oxide thin film |
-
2020
- 2020-03-04 JP JP2020036782A patent/JP7498938B2/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004031550A (en) | 2002-06-25 | 2004-01-29 | Takeshi Kawabata | Superconducting wire with high critical current characteristics |
| JP2004263066A (en) | 2003-02-28 | 2004-09-24 | National Institute Of Advanced Industrial & Technology | Layered organosilica nanocomposite and method for producing the same |
| JP2007311194A (en) | 2006-05-18 | 2007-11-29 | Sumitomo Electric Ind Ltd | Superconducting thin film material and method for producing superconducting thin film material |
| JP2011129380A (en) | 2009-12-17 | 2011-06-30 | Toyota Central R&D Labs Inc | Lamella porous electrolyte |
| JP2014091646A (en) | 2012-11-01 | 2014-05-19 | National Institute For Materials Science | Fluorite type undoped cerium oxide nanoparticle having high concentration cerium trivalence excellent in atmospheric stability, and manufacture method of the same |
| JP2017226580A (en) | 2016-06-23 | 2017-12-28 | 日産自動車株式会社 | Method for producing crystalline metal oxide film |
Non-Patent Citations (3)
| Title |
|---|
| E．YAMAMOTO et al.，"Bottom-up preparation of ceria based nanosheet using solid surfactant crystals"，第58回セラミックス基礎科学討論会 講演要旨集，2020年01月09日，p.113，2A03 |
| Haruo IMAGAWA et al.，"Controlled Synthesis of Monodisperse CeO2 Nanoplates Developed from Assembled Nanoparticles"，The Journal of Physical Chemistry C，2012年01月03日，Vol. 116, No. 4，p.2761-2765，DOI: 10.1021/jp210324x |
| Jia Cai NIE et al.，"Quantum confinement effect in high quality nanostructured CeO2 thin films"，Journal of Applied Physics，2008年03月06日，Vol. 103, No. 5，054308，DOI: 10.1063/1.2841719 |
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