JP2001129389A - Method for manufacturing fine particles and method for forming coating film - Google Patents
Method for manufacturing fine particles and method for forming coating filmInfo
- Publication number
- JP2001129389A JP2001129389A JP31250499A JP31250499A JP2001129389A JP 2001129389 A JP2001129389 A JP 2001129389A JP 31250499 A JP31250499 A JP 31250499A JP 31250499 A JP31250499 A JP 31250499A JP 2001129389 A JP2001129389 A JP 2001129389A
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- Prior art keywords
- fine particles
- supercritical
- metal oxide
- oxide fine
- nozzle
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Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、微粒子の製造方法
及び膜の形成方法に関する。[0001] The present invention relates to a method for producing fine particles and a method for forming a film.
【０００２】[0002]
【従来の技術】金属酸化物微粒子は、従来からセラミッ
ク材料、研磨剤、顔料、塗料、触媒として用いられ、最
近では、磁気材料、磁性流体、化粧品、医薬品、各種セ
ンサー材料、燃料電池材料、二次イオン電池材料等の磁
気的、電気的及び光学的機能性を有する材料及び静電
体、磁性体、絶縁体等の機能素子材料として幅広い分野
で用いられている。また、金属酸化物微粒子は、量子ド
ットに代表されるナノオーダーの構造（ナノ微粒子も含
む）による量子サイズ効果の発現に注目が集まってお
り、その製造方法の開発研究が世界中で盛んに進められ
ている。2. Description of the Related Art Metal oxide fine particles have conventionally been used as ceramic materials, abrasives, pigments, paints, and catalysts. Recently, magnetic materials, magnetic fluids, cosmetics, pharmaceuticals, various sensor materials, fuel cell materials, It is used in a wide range of fields as materials having magnetic, electrical and optical functions such as secondary ion battery materials and functional element materials such as electrostatics, magnetics and insulators. In metal oxide fine particles, attention has been focused on the development of quantum size effects due to nano-order structures (including nanoparticles) represented by quantum dots. Have been.
【０００３】従来、このような酸化物微粒子は、液相法
により、例えば、１〜１００μｍの比較的大きな結晶粒
子を合成し、それを粉砕、分級操作により合成してき
た。このように、金属酸化物微粒子を、先に挙げたよう
な機能性材料又は基板上に均一な金属酸化物層を被膜さ
せた電子材料等に用いる場合、金属酸化物微粒子の組成
や結晶構造が均質であるだけでなく、金属酸化物微粒子
の形状やサイズを制御する必要があった。Conventionally, such oxide fine particles have been synthesized by a liquid phase method, for example, by synthesizing relatively large crystal particles of, for example, 1 to 100 μm, and pulverizing and classifying them. As described above, when the metal oxide fine particles are used as a functional material as described above or an electronic material in which a uniform metal oxide layer is coated on a substrate, the composition and the crystal structure of the metal oxide fine particles are In addition to being homogeneous, it was necessary to control the shape and size of the metal oxide fine particles.
【０００４】しかしながら、上記のように合成した金属
酸化物微粒子は、サイズ制御が十分でなく、形状の制御
やナノサイズ微粒子の合成が非常に困難であった。However, the metal oxide fine particles synthesized as described above do not have sufficient size control, and it is very difficult to control the shape and synthesize nano-sized fine particles.
【０００５】[0005]
【発明が解決しようとする課題】本発明は上記した従来
の課題に鑑みてなされたものであり、その目的とすると
ころは、金属酸化物微粒子の組成、結晶構造、形状及び
サイズを制御することができ、単分散且つ乾燥状態であ
るナノサイズの金属酸化物微粒子を合成することができ
る微粒子の製造方法と、組成、結晶構造、形状及びサイ
ズが制御された金属酸化物微粒子の合成と、基板上に均
一な金属酸化物層を被膜する工程とを連続して行うこと
ができる膜の形成方法を提供することにある。SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned conventional problems, and has as its object to control the composition, crystal structure, shape, and size of metal oxide fine particles. Method of producing fine particles capable of synthesizing nano-sized metal oxide fine particles in a monodispersed and dry state, synthesis of metal oxide fine particles having controlled composition, crystal structure, shape and size, and substrate An object of the present invention is to provide a film forming method capable of continuously performing a step of coating a uniform metal oxide layer thereon.
【０００６】[0006]
【課題を解決するための手段】すなわち、本発明によれ
ば、金属塩水溶液、金属アルコキシドアルコール水又は
これらの混合溶液であり、且つ超臨界状態になる液状物
を、水熱反応温度まで急速に昇温し、水熱合成反応によ
り金属酸化物微粒子を発生させ、更に超臨界状態に昇温
して粒子径を制御した金属酸化物微粒子を含有した超臨
界のスラリー状液を、過熱超臨界ノズルから粉体回収装
置内に噴出させることにより、単分散且つ乾燥状態の金
属酸化物微粒子を製造することを特徴とする微粒子の製
造方法が提供される。このとき、本発明では、金属酸化
物微粒子の平均粒子径が、５〜１００ｎｍであることが
好ましく、過熱超臨界ノズルの出口温度を、水又は超臨
界液の凝縮点よりも高くすることが好ましい。That is, according to the present invention, a liquid material which is a metal salt aqueous solution, a metal alkoxide alcohol aqueous solution or a mixed solution thereof and which is in a supercritical state is rapidly cooled to a hydrothermal reaction temperature. The temperature is raised, the metal oxide fine particles are generated by a hydrothermal synthesis reaction, and the supercritical slurry-like liquid containing the metal oxide fine particles whose particle diameter is controlled by further raising the temperature to a supercritical state is supplied to a superheated supercritical nozzle. A monodispersed metal oxide fine particle in a dry state by jetting the fine particles into a powder recovery device. At this time, in the present invention, the average particle diameter of the metal oxide fine particles is preferably 5 to 100 nm, and the outlet temperature of the superheated supercritical nozzle is preferably higher than the condensation point of water or the supercritical liquid. .
【０００７】また、本発明によれば、金属塩水溶液、金
属アルコキシドアルコール水又はこれらの混合溶液であ
り、且つ超臨界状態になる液状物を、水熱反応温度まで
急速に昇温し、水熱合成反応により金属酸化物微粒子を
発生させ、更に超臨界状態に昇温して粒子径を制御した
金属酸化物微粒子を含有した超臨界のスラリー状液を、
過熱超臨界ノズルから基板上に噴出させることにより、
基板の表面上に金属酸化物微粒子を堆積させ、該基板上
に均一な金属酸化物層を被膜させることを特徴とする膜
の形成方法が提供される。このとき、本発明では、金属
酸化物層の厚さが、１〜５００μｍであることが好まし
く、過熱超臨界ノズルの出口温度を、水又は超臨界液の
凝縮点よりも高くすることが好ましい。Further, according to the present invention, a liquid material which is a metal salt aqueous solution, a metal alkoxide alcohol aqueous solution or a mixed solution thereof and which becomes a supercritical state is rapidly heated to a hydrothermal reaction temperature, A metal oxide fine particle is generated by a synthesis reaction, and further heated to a supercritical state, a supercritical slurry-like liquid containing the metal oxide fine particle whose particle diameter is controlled,
By jetting from the superheated supercritical nozzle onto the substrate,
A method for forming a film is provided, wherein metal oxide fine particles are deposited on a surface of a substrate, and a uniform metal oxide layer is coated on the substrate. At this time, in the present invention, the thickness of the metal oxide layer is preferably 1 to 500 μm, and the outlet temperature of the superheated supercritical nozzle is preferably higher than the condensation point of water or the supercritical liquid.
【０００８】[0008]
【発明の実施の形態】本発明の微粒子の製造方法は、金
属塩水溶液、金属アルコキシドアルコール水又はこれら
の混合溶液であり、且つ超臨界状態になる液状物を、水
熱反応温度まで急速に昇温し、水熱合成反応により金属
酸化物微粒子を発生させ、更に超臨界状態に昇温して粒
子径を制御した金属酸化物微粒子を含有した超臨界のス
ラリー状液を、過熱超臨界ノズルから粉体回収装置内に
噴出させることにより、単分散且つ乾燥状態の金属酸化
物微粒子を製造することにある。これにより、金属酸化
物微粒子の組成、結晶構造、形状及びサイズを制御する
ことができ、単分散且つ乾燥状態であるナノサイズの金
属酸化物微粒子を合成することができる。BEST MODE FOR CARRYING OUT THE INVENTION In the method for producing fine particles of the present invention, a supercritical liquid, which is an aqueous solution of a metal salt, an aqueous solution of a metal alkoxide or a mixed solution thereof, is rapidly raised to a hydrothermal reaction temperature. The metal oxide fine particles are generated by a hydrothermal synthesis reaction, and the supercritical slurry-like liquid containing the metal oxide fine particles whose particle diameter is controlled by further raising the temperature to a supercritical state is passed through a superheated supercritical nozzle. The object of the present invention is to produce metal oxide fine particles in a monodispersed and dry state by jetting them into a powder recovery device. As a result, the composition, crystal structure, shape and size of the metal oxide fine particles can be controlled, and nano-sized metal oxide fine particles that are monodisperse and dry can be synthesized.
【０００９】以上のことから、本発明の微粒子の製造方
法は、特に、触媒（例えば、ＴｉＯ 2等）、蛍光体（例
えば、ＹＡＧ：Ｔｂ等）、磁気材料（例えば、ＢａＯ・
６Ｆｅ2Ｏ3等）、電子材料（例えば、チタン酸バリウ
ム、ＰＺＴ、酸化チタン、インジウム酸化スズ等）等の
ナノサイズ（例えば、５〜１００ｎｍ）の金属酸化物微
粒子の製造に好適に用いることができる。From the above, it can be seen that the method for producing the fine particles of the present invention
The method is particularly suitable for catalysts (eg, TiO 2). TwoEtc.), phosphors (examples
For example, YAG: Tb or the like, a magnetic material (for example, BaO.
6FeTwoOThreeEtc.), electronic materials (for example, barium titanate)
, PZT, titanium oxide, indium tin oxide, etc.)
Nano-sized (for example, 5 to 100 nm) metal oxide fine particles
It can be suitably used for the production of particles.
【００１０】また、本発明の膜の形成方法は、金属塩水
溶液、金属アルコキシドアルコール水又はこれらの混合
溶液であり、且つ超臨界状態になる液状物を、水熱反応
温度まで急速に昇温し、水熱合成反応により金属酸化物
微粒子を発生させ、更に超臨界状態に昇温して粒子径を
制御した金属酸化物微粒子を含有した超臨界のスラリー
状液を、過熱超臨界ノズルから基板上に噴出させること
により、基板の表面上に金属酸化物微粒子を堆積させ、
基板上に均一な金属酸化物層（厚さ：１〜５００μｍ）
を被膜させることにある。これにより、組成、結晶構
造、形状及びサイズが制御された金属酸化物微粒子の合
成と、基板上に均一な金属酸化物層を被膜する工程とを
連続して行うことができる。The method for forming a film according to the present invention is characterized in that a liquid material which is a metal salt aqueous solution, a metal alkoxide alcohol aqueous solution or a mixed solution thereof and which is in a supercritical state is rapidly heated to a hydrothermal reaction temperature. Then, a metal oxide fine particle is generated by a hydrothermal synthesis reaction, and a supercritical slurry-like liquid containing the metal oxide fine particle whose particle diameter is controlled by further raising the temperature to a supercritical state is placed on a substrate from a superheated supercritical nozzle. By spraying metal oxide particles on the surface of the substrate,
Uniform metal oxide layer on substrate (thickness: 1-500 μm)
Is to be coated. Accordingly, the synthesis of the metal oxide fine particles having a controlled composition, crystal structure, shape, and size and the step of coating a uniform metal oxide layer on the substrate can be continuously performed.
【００１１】以上のことから、本発明の膜の形成方法
は、特に、触媒（例えば、ＴｉＯ2等）、蛍光体（例え
ば、ＹＡＧ：Ｔｂ等）、磁気材料（例えば、ＢａＯ・６
Ｆｅ2Ｏ3等）、電子材料（例えば、チタン酸バリウム、
ＰＺＴ、酸化チタン、インジウム酸化スズ等）等を基板
上に均一に被膜させることができるため、触媒や電子部
品等の製造に好適に用いることができる。From the above, the method of forming a film of the present invention is particularly suitable for a catalyst (for example, TiO 2 ), a phosphor (for example, YAG: Tb), a magnetic material (for example, BaO.6).
Fe 2 O 3, etc.), electronic materials (eg, barium titanate,
Since PZT, titanium oxide, indium tin oxide, and the like can be uniformly coated on the substrate, it can be suitably used for manufacturing catalysts, electronic components, and the like.
【００１２】次に、超臨界流体として水を用いた場合に
おける本発明の微粒子の生成機構の一例について説明す
る。まず、微粒子の生成機構の第１段階は、亜臨界水
（３００℃，３０ＭＰａ）中で、液状物である金属塩水
溶液の水熱合成反応を行うことにより、ナノサイズ前後
の金属酸化物微粒子を合成する。更に、上記金属塩水溶
液を超臨界状態（４００℃、３０ＭＰａ）に昇温して、
粒子径制御を行い、平均粒子径が５〜１００ｎｍの金属
酸化物微粒子を含有した超臨界のスラリー状液を得る。Next, an example of a mechanism for producing fine particles of the present invention when water is used as a supercritical fluid will be described. First, the first step of the fine particle generation mechanism is to perform a hydrothermal synthesis reaction of a liquid metal salt aqueous solution in subcritical water (300 ° C., 30 MPa) to convert metal oxide fine particles of approximately nano-size into fine particles. Combine. Further, the temperature of the aqueous metal salt solution is raised to a supercritical state (400 ° C., 30 MPa),
The particle diameter is controlled to obtain a supercritical slurry-like liquid containing metal oxide fine particles having an average particle diameter of 5 to 100 nm.
【００１３】尚、超臨界状態では、水の誘電率が有機溶
媒並に低くなるため、溶解度が大幅に変化する。これ
は、臨界点近傍での水の物性、特に、誘電率の低下に大
きく依存しており、常温で８０程度である誘電率が、臨
界点近傍で２〜５程度に極めて小さくなるため、反応場
の化学平衡がイオンから電荷の無い粒子が生成する方向
へシフトしたためであると考えられる。また、超臨界状
態では、金属水酸化物の溶解度が小さいため、水酸化物
の取り込みによる粒子成長を防止することができるた
め、ナノサイズの金属酸化物微粒子を生成させることが
できる。以上のことから、亜臨界水中及び超臨界水中で
の金属塩水溶液の水熱合成反応は、極めて高い過飽和が
瞬時に得られ、高い核発生速度が得られるため、ナノサ
イズ（例えば、５〜１００ｎｍ）の金属酸化物微粒子を
合成することができる。In the supercritical state, since the dielectric constant of water is as low as that of an organic solvent, the solubility is greatly changed. This greatly depends on the physical properties of water near the critical point, particularly, on the decrease in the dielectric constant. Since the dielectric constant, which is about 80 at room temperature, becomes extremely small at about 2 to 5 near the critical point, the reaction It is considered that the chemical equilibrium of the field was shifted in a direction in which particles without charge were generated from the ions. In the supercritical state, since the solubility of the metal hydroxide is low, the particle growth due to the incorporation of the hydroxide can be prevented, so that nano-sized metal oxide fine particles can be generated. From the above, in the hydrothermal synthesis reaction of the metal salt aqueous solution in the subcritical water and the supercritical water, an extremely high supersaturation is instantaneously obtained, and a high nucleation rate is obtained. ) Metal oxide fine particles can be synthesized.
【００１４】次に、微粒子の生成機構の第２段階は、第
１段階で得られた金属酸化物微粒子を含有した超臨界水
溶液を、過熱超臨界ノズルから粉体回収装置内に噴出さ
せることにより、媒体である水が液滴になることなく、
単分散且つ乾燥状態であるナノサイズの金属酸化物微粒
子を析出させる。Next, the second stage of the fine particle generation mechanism is to eject the supercritical aqueous solution containing the metal oxide fine particles obtained in the first stage from a superheated supercritical nozzle into a powder recovery device. , Without the medium water becoming droplets,
The nano-sized metal oxide fine particles in a monodispersed and dry state are precipitated.
【００１５】以上のことから、本発明の微粒子の生成機
構の一例は、第１段階で得られた金属酸化物微粒子を含
有した超臨界水溶液を冷却・減圧して、金属酸化物微粒
子をスラリーとして回収する必要がないため、乾燥・分
散処理等を行う必要がなく、極めて効率的に単分散且つ
乾燥状態であるナノサイズ（例えば、５〜１００ｎｍ）
の金属酸化物微粒子を得ることができる。From the above, one example of the fine particle generation mechanism of the present invention is that the supercritical aqueous solution containing the metal oxide fine particles obtained in the first stage is cooled and depressurized to convert the metal oxide fine particles into a slurry. Since there is no need to collect, there is no need to perform drying / dispersion treatment, etc., and nano-sizes (eg, 5 to 100 nm) that are monodispersed and in a dry state extremely efficiently.
Can be obtained.
【００１６】尚、本発明で適用できる液状物は、金属塩
水溶液（例えば、硝酸塩、塩酸塩、硫酸塩の水溶液）、
金属アルコキシドアルコール水又はこれらの混合溶液で
あり、且つ超臨界状態になるものであることが好まし
い。The liquid substance applicable to the present invention is an aqueous solution of a metal salt (eg, an aqueous solution of a nitrate, a hydrochloride, or a sulfate).
It is preferable that the metal alkoxide alcohol water or a mixed solution thereof be in a supercritical state.
【００１７】次に、本発明を図面に基づいて詳細に説明
する。図１は、本発明で用いた微粒子の製造装置の一例
を示す概要図である。図１に示すように、液状物である
金属塩水溶液（例えば、四塩化チタン水溶液）は、液状
物用貯槽３から供給され、ポンプ７で接触混合部９に送
液される。超臨界水は、超臨界液用貯槽１から供給され
た蒸留水を、ポンプ６で臨界圧力以上に加圧した後、ヒ
ータ８で臨界温度以上に加熱することにより得られ、接
触混合部９に送液される。接触混合部９は、金属塩水溶
液と超臨界水とを直接接触させることにより、亜臨界状
態で水熱合成反応を生じさせ、金属酸化物微粒子の合成
を行う。Next, the present invention will be described in detail with reference to the drawings. FIG. 1 is a schematic diagram showing an example of a device for producing fine particles used in the present invention. As shown in FIG. 1, a liquid metal salt aqueous solution (for example, titanium tetrachloride aqueous solution) is supplied from a liquid storage tank 3 and sent to a contact mixing unit 9 by a pump 7. The supercritical water is obtained by pressurizing the distilled water supplied from the supercritical liquid storage tank 1 to a pressure higher than the critical pressure by the pump 6 and then heating it to a temperature higher than the critical temperature by the heater 8. It is sent. The contact mixing section 9 causes a hydrothermal synthesis reaction in a subcritical state by directly contacting the aqueous metal salt solution and supercritical water, thereby synthesizing metal oxide fine particles.
【００１８】次に、接触混合部９から得られた金属酸化
物微粒子を含有した亜臨界水溶液は、更に加熱され、超
臨界状態に維持された反応管１０内を所定の時間をかけ
て移動する。これにより、超臨界水溶液中に含有してい
る金属酸化物微粒子の粒子径は、制御され、平均粒子径
１〜１００ｎｍサイズの金属酸化物微粒子の収率を向上
させることができる。Next, the subcritical aqueous solution containing the metal oxide fine particles obtained from the contact mixing section 9 is further heated and moves for a predetermined time in the reaction tube 10 maintained in a supercritical state. . Thereby, the particle diameter of the metal oxide fine particles contained in the supercritical aqueous solution is controlled, and the yield of the metal oxide fine particles having an average particle diameter of 1 to 100 nm can be improved.
【００１９】最後に、金属酸化物微粒子を含有した超臨
界水溶液は、反応管１０から過熱超臨界ノズル２０のフ
ィードライン１４に導入され、過熱用ヒータ１２で所定
の温度（ノズル出口温度が水の凝縮点よりも高い温度）
に過熱された後、所定の口径の超臨界ノズル１６から粉
体回収装置であるチャンバー７０の空間部に噴出させる
ことにより、金属酸化物微粒子（例えば、平均粒子径：
８ｎｍの酸化チタン）が得られた。これにより、単分散
且つ乾燥状態であるナノサイズ（例えば、５〜１００ｎ
ｍ）の金属酸化物微粒子を析出させることができる。
尚、析出した金属酸化物微粒子は、粉体回収装置の一部
であるバグフィルター等の粉体分離捕集設備７２で分離
捕集され、製品として取り出される。Finally, the supercritical aqueous solution containing the metal oxide fine particles is introduced from the reaction tube 10 to the feed line 14 of the superheated supercritical nozzle 20, and a predetermined temperature (the nozzle outlet temperature is set to water) by the superheater 12. Higher than the condensation point)
After being superheated, the metal oxide fine particles (for example, average particle diameter:
8 nm of titanium oxide) was obtained. Thereby, the nano-size (for example, 5 to 100 n) which is monodispersed and in a dry state
m) The metal oxide fine particles can be precipitated.
The precipitated metal oxide fine particles are separated and collected by a powder separation and collection equipment 72 such as a bag filter which is a part of the powder recovery device, and are taken out as a product.
【００２０】次に、本発明で用いた膜の形成装置の一例
を図２に示す。図２に示すように、液状物である金属塩
水溶液（例えば、塩酸化ジルコニウム、硝酸鉛、四塩化
チタンの混合水溶液）は、液状物用貯槽３から供給さ
れ、ポンプ７で接触混合部９に送液される。超臨界水
は、超臨界液用貯槽１から供給された蒸留水を、ポンプ
６で臨界圧力以上に加圧した後、ヒータ８で臨界温度以
上に加熱することにより得られ、接触混合部９に送液さ
れる。接触混合部９は、金属塩水溶液と超臨界水とを直
接接触させることにより、亜臨界状態で水熱合成反応を
生じさせ、金属酸化物微粒子の合成を行う。Next, FIG. 2 shows an example of a film forming apparatus used in the present invention. As shown in FIG. 2, a liquid metal salt aqueous solution (for example, a mixed aqueous solution of zirconium hydrochloride, lead nitrate, and titanium tetrachloride) is supplied from a liquid storage tank 3, and is supplied to a contact mixing section 9 by a pump 7. It is sent. The supercritical water is obtained by pressurizing the distilled water supplied from the supercritical liquid storage tank 1 to a pressure higher than the critical pressure by the pump 6 and then heating it to a temperature higher than the critical temperature by the heater 8. It is sent. The contact mixing section 9 causes a hydrothermal synthesis reaction in a subcritical state by directly contacting the aqueous metal salt solution and supercritical water to synthesize metal oxide fine particles.
【００２１】次に、接触混合部９から得られた金属酸化
物微粒子を含有した亜臨界水溶液は、更に加熱され、超
臨界状態に維持された反応管１０内を所定の時間をかけ
て移動する。Next, the subcritical aqueous solution containing the metal oxide fine particles obtained from the contact mixing section 9 is further heated and moves over a predetermined time in the reaction tube 10 maintained in a supercritical state. .
【００２２】最後に、金属酸化物微粒子を含有した超臨
界水溶液は、反応管１０から過熱超臨界ノズル２０のフ
ィードライン１４に導入され、過熱用ヒータ１２で所定
の温度（ノズル出口温度が水の凝縮点よりも高い温度）
に過熱された後、所定の口径の超臨界ノズル１６からチ
ャンバー７０中の基板８０上に噴出させる。これによ
り、単分散且つ乾燥状態であるナノサイズの金属酸化物
微粒子を基板８０の表面上に均一な金属酸化物層（例え
ば、膜厚：５０μｍのＰＺＴ［チタン酸ジルコン酸
鉛］）を被膜させることができる。尚、基板上に形成さ
れた金属酸化物膜の厚さは、１〜５００μｍ程度にする
ことが可能である。このとき、粉体回収装置の一部であ
るチャンバー７０内部は、減圧にすることがより好まし
い。Finally, the supercritical aqueous solution containing the metal oxide fine particles is introduced into the feed line 14 of the superheated supercritical nozzle 20 from the reaction tube 10 and is heated by the superheater 12 at a predetermined temperature (when the nozzle outlet temperature becomes water). Higher than the condensation point)
After being superheated, the supercritical nozzle 16 having a predetermined diameter is ejected onto the substrate 80 in the chamber 70. As a result, the nano-sized metal oxide fine particles in a monodispersed and dry state are coated on the surface of the substrate 80 with a uniform metal oxide layer (for example, PZT [lead zirconate titanate] having a thickness of 50 μm). be able to. Incidentally, the thickness of the metal oxide film formed on the substrate can be about 1 to 500 μm. At this time, it is more preferable to reduce the pressure inside the chamber 70 which is a part of the powder recovery device.
【００２３】尚、本発明で用いた過熱超臨界ノズルは、
超臨界ノズルから噴出した媒体である水又は超臨界液が
液滴になることがないため、単分散且つ乾燥状態である
ナノサイズの金属酸化物微粒子とすることができる。こ
れは、ノズル出口温度Ｔ1を、水又は超臨界液の凝縮点
よりも高くすることより、液滴や氷塊が発生しても、水
又は超臨界液の微少な核（クラスターと呼ばれる集合
体）となり、より微細な金属酸化物微粒子の生成を妨げ
ることがないからである。尚、ノズル出口温度Ｔ1が液
化又は固化温度を下回る場合、液滴や氷塊ができやすく
なり、粒子又は成膜の均一性がなくなる。The superheated supercritical nozzle used in the present invention is:
Since the water or the supercritical liquid, which is the medium ejected from the supercritical nozzle, does not become droplets, the nanosized metal oxide fine particles can be monodisperse and dry. This is because, by making the nozzle outlet temperature T 1 higher than the condensation point of water or supercritical liquid, even if droplets or ice blocks are generated, minute nuclei of water or supercritical liquid (an aggregate called a cluster) ), And does not hinder the generation of finer metal oxide fine particles. Incidentally, when the nozzle outlet temperature T 1 is below the liquefaction or solidification temperature, easily it can drop and ice blocks, there is no uniformity of particles or film forming.
【００２４】また、本発明で用いた過熱超臨界ノズル
は、過熱超臨界ノズル近傍のごく狭い領域で成膜が主に
行われており、具体的には、過熱超臨界ノズルから、多
数の微少な金属酸化物微粒子を、基板の表面上に噴出さ
せて堆積させることにより、基板上に均一な金属酸化物
層を被膜させることができる。In the superheated supercritical nozzle used in the present invention, film formation is mainly performed in a very small area near the superheated supercritical nozzle. By spraying and depositing such fine metal oxide particles on the surface of the substrate, a uniform metal oxide layer can be coated on the substrate.
【００２５】このとき、基板に均質かつ一定の厚さの成
膜を行うためには、超臨界噴出法の原理を考慮して、基
板と過熱超臨界ノズルとの距離をできるだけ短く（例え
ば、５ｍｍ）するとともに、十分な成膜時間を取ること
が好ましい。尚、ノズル出口温度Ｔ1は、ノズル入口１
６ｂでの圧力及び温度Ｔ2が高いほど上昇する。ノズル
出口温度Ｔ1が上昇すると、水又は超臨界液がガス状に
高速で噴出されるため、金属酸化物粒子を乾燥状態で基
板上に均質且つ均一に成膜することができる。At this time, in order to form a film having a uniform and uniform thickness on the substrate, the distance between the substrate and the superheated supercritical nozzle is made as short as possible (for example, 5 mm) in consideration of the principle of the supercritical ejection method. ) And at the same time, it is preferable to take a sufficient film formation time. Note that the nozzle outlet temperature T 1 is the nozzle inlet 1
It rises higher pressure and temperature T 2 at 6b. When the nozzle outlet temperature T 1 is increased, since the water or supercritical fluid is ejected at a high speed gaseous, it can be homogeneously and uniformly deposited on a substrate of metal oxide particles in the dry state.
【００２６】ここで、過熱超臨界ノズルは、超臨界噴出
法に基づいて開発されたものであり、図３に示すよう
に、ノズル出口温度Ｔ1を水又は超臨界液の凝縮点より
も高くするため、ノズル入口１６ｂ付近のフィードライ
ン１４に過熱用ヒータ１２を配設したことが最大の特徴
である。これにより、本発明で用いた過熱超臨界ノズル
は、水又は超臨界液が液滴になることがないため、単分
散且つ乾燥状態の微粒子を得ることができ、超臨界液が
ノズル周辺で凝固することもないため、超臨界ノズルの
詰まりや装置の不具合を防止することができる。Here, the superheated supercritical nozzle has been developed based on the supercritical jet method, and as shown in FIG. 3, the nozzle outlet temperature T 1 is higher than the condensation point of water or the supercritical liquid. Therefore, the greatest feature is that the superheater heater 12 is disposed in the feed line 14 near the nozzle inlet 16b. Accordingly, the superheated supercritical nozzle used in the present invention can obtain monodispersed and dry fine particles because water or supercritical liquid does not become droplets, and the supercritical liquid solidifies around the nozzle. Therefore, clogging of the supercritical nozzle and malfunction of the device can be prevented.
【００２７】超臨界噴出法（ＲＥＳＳ法：Rapid Expans
ion of Supercritical Fluid Solutions)は、溶媒であ
る超臨界流体に溶質を溶かした溶液を、微細な口径のノ
ズルから大気中に噴出させて、上記溶液を断熱膨脹さ
せ、上記溶液の圧力及び温度が急激に低下させて、上記
溶液中の溶媒の溶解力を激減させることにより、溶質の
みを析出させることができるものである。尚、本発明で
は、溶質でなく、固体粒子を先に析出させ、残りの微量
の溶質を、超臨界噴出法で固体単独又は析出した固体に
付着した形等で回収するものである。Supercritical injection method (RESS method: Rapid Expans
(Ion of Supercritical Fluid Solutions) is a solution in which a solute is dissolved in a supercritical fluid, which is a solvent, is ejected from a fine-diameter nozzle into the atmosphere, and the solution is adiabatically expanded. To drastically reduce the dissolving power of the solvent in the solution to precipitate only the solute. In the present invention, not solutes but solid particles are precipitated first, and the remaining trace amount of solutes is recovered by a supercritical squirting method alone or in a form attached to the precipitated solids.
【００２８】尚、超臨界流体とは、臨界点よりも高い温
度と圧力下にある流体であり、液体のように高密度状態
であるにもかかわらず、気体のように運動することが可
能であるものである。また、超臨界流体は、物質をかな
り溶解又は分散させることができるとともに、臨界点近
傍で少しの温度あるいは圧力を変化させることにより、
超臨界流体の密度を大きく変化させ、物質の溶解度又は
分散度を大きく変えることができることが知られてい
る。The supercritical fluid is a fluid at a temperature and pressure higher than the critical point, and can move like a gas despite being in a high density state like a liquid. There is something. In addition, supercritical fluids can considerably dissolve or disperse substances, and by slightly changing the temperature or pressure near the critical point,
It is known that the density of a supercritical fluid can be significantly changed to greatly change the solubility or dispersity of a substance.
【００２９】[0029]
【発明の効果】本発明の微粒子の製造方法は、金属酸化
物微粒子の組成、結晶構造、形状及びサイズを制御する
ことができ、単分散且つ乾燥状態であるナノサイズの金
属酸化物微粒子を合成することができる。また、本発明
の膜の形成方法は、組成、結晶構造、形状及びサイズが
制御された金属酸化物微粒子の合成と、基板上に均一な
金属酸化物層を被膜する工程を連続して行うことができ
る。According to the method for producing fine particles of the present invention, the composition, crystal structure, shape and size of fine metal oxide particles can be controlled, and nano-sized fine metal oxide particles that are monodisperse and dry can be synthesized. can do. The method for forming a film according to the present invention includes the steps of continuously synthesizing metal oxide fine particles having a controlled composition, crystal structure, shape and size, and coating a uniform metal oxide layer on a substrate. Can be.
【図１】 本発明で用いた微粒子の製造装置の一例を示
す断面概要図である。FIG. 1 is a schematic sectional view showing an example of an apparatus for producing fine particles used in the present invention.
【図２】 本発明で用いた膜の形成方法の一例を示す断
面概要図である。FIG. 2 is a schematic sectional view showing an example of a film forming method used in the present invention.
【図３】 本発明で用いた過熱超臨界ノズルの一例を示
す概略断面図である。FIG. 3 is a schematic sectional view showing an example of a superheated supercritical nozzle used in the present invention.
【符号の説明】 １…液状物用貯槽、３…超臨界液用貯槽、６，７…ポン
プ 、８…ヒータ、９…接触混合部、１０…反応管、１
１…ヒータ、１２…過熱用ヒータ、１４…フィードライ
ン、１６…超臨界ノズル、１６ａ…ノズル出口、１６ｂ
…ノズル入口、２０…過熱超臨界ノズル、７０…チャン
バー（粉体回収装置）、７２…排風機、７４…粉体分離
捕集設備、８０…基板。[Description of Signs] 1 ... storage tank for liquid material, 3 ... storage tank for supercritical liquid, 6, 7 ... pump, 8 ... heater, 9 ... contact mixing unit, 10 ... reaction tube, 1
DESCRIPTION OF SYMBOLS 1 ... Heater, 12 ... Heating heater, 14 ... Feed line, 16 ... Supercritical nozzle, 16a ... Nozzle outlet, 16b
... Nozzle inlet, 20 ... Superheated supercritical nozzle, 70 ... Chamber (powder recovery device), 72 ... Air blower, 74 ... Powder separation and collection equipment, 80 ... Substrate.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 堤 敦司 東京都文京区本郷７−３−１ 東京大学大 学院工学系研究科内 Ｆターム(参考） 4D075 AA01 EC08 4F033 AA01 HA01 4G075 AA24 AA27 BB02 BB08 BD09 CA02 CA65 CA66 EA06 EB01 EC01 ──────────────────────────────────────────────────続 き Continuing from the front page (72) Inventor Atsushi Tsutsumi 7-3-1 Hongo, Bunkyo-ku, Tokyo F-term in the Graduate School of Engineering, University of Tokyo 4D075 AA01 EC08 4F033 AA01 HA01 4G075 AA24 AA27 BB02 BB08 BD09 CA02 CA65 CA66 EA06 EB01 EC01
Claims (6)
ル水又はこれらの混合溶液であり、且つ超臨界状態にな
る液状物を、水熱反応温度まで急速に昇温し、水熱合成
反応により金属酸化物微粒子を発生させ、更に超臨界状
態に昇温して粒子径を制御した金属酸化物微粒子を含有
した超臨界のスラリー状液を、過熱超臨界ノズルから粉
体回収装置内に噴出させることにより、単分散且つ乾燥
状態の金属酸化物微粒子を製造することを特徴とする微
粒子の製造方法。An aqueous metal salt solution, an aqueous metal alkoxide alcohol solution or a mixed solution thereof, and a liquid material in a supercritical state is rapidly heated to a hydrothermal reaction temperature, and the metal oxide is subjected to a hydrothermal synthesis reaction. By generating fine particles, and further raising the temperature to a supercritical state and discharging a supercritical slurry-like liquid containing metal oxide fine particles having a controlled particle size from a superheated supercritical nozzle into a powder recovery device, A method for producing fine particles, comprising producing metal oxide fine particles in a monodispersed and dry state.
００ｎｍである請求項１に記載の微粒子の製造方法。2. The metal oxide fine particles having an average particle size of 5 to 1
The method for producing fine particles according to claim 1, which has a thickness of 00 nm.
臨界液の凝縮点よりも高くした請求項１又は２に記載の
微粒子の製造方法。3. The method for producing fine particles according to claim 1, wherein the outlet temperature of the superheated supercritical nozzle is higher than the condensation point of water or the supercritical liquid.
ル水又はこれらの混合溶液であり、且つ超臨界状態にな
る液状物を、水熱反応温度まで急速に昇温し、水熱合成
反応により金属酸化物微粒子を発生させ、更に超臨界状
態に昇温して粒子径を制御した金属酸化物微粒子を含有
した超臨界のスラリー状液を、過熱超臨界ノズルから基
板上に噴出させることにより、基板の表面上に金属酸化
物微粒子を堆積させ、該基板上に均一な金属酸化物層を
被膜させることを特徴とする膜の形成方法。4. A metal salt aqueous solution, a metal alkoxide alcohol aqueous solution, or a mixed solution thereof, and a liquid material in a supercritical state is rapidly heated to a hydrothermal reaction temperature, and the metal oxide is subjected to a hydrothermal synthesis reaction. Fine particles are generated, and a supercritical slurry-like liquid containing metal oxide fine particles whose particle diameter is controlled by raising the temperature to a supercritical state is jetted from the superheated supercritical nozzle onto the substrate, thereby forming a surface of the substrate. A method for forming a film, comprising depositing metal oxide fine particles on the substrate and coating a uniform metal oxide layer on the substrate.
ある請求項４に記載の膜の形成方法。5. The method according to claim 4, wherein the thickness of the metal oxide layer is 1 to 500 μm.
臨界液の凝縮点よりも高くした請求項４又は５に記載の
膜の形成方法。6. The method according to claim 4, wherein the outlet temperature of the superheated supercritical nozzle is higher than the condensation point of water or the supercritical liquid.
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|---|---|---|---|
| JP31250499A JP2001129389A (en) | 1999-11-02 | 1999-11-02 | Method for manufacturing fine particles and method for forming coating film |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP31250499A JP2001129389A (en) | 1999-11-02 | 1999-11-02 | Method for manufacturing fine particles and method for forming coating film |
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ID=18030026
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