JP2006256916A - Method of manufacturing rare earth-containing metal oxide thin film - Google Patents
Method of manufacturing rare earth-containing metal oxide thin film Download PDFInfo
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本発明は、希土類を含有する金属酸化物の薄膜ないし微細構造体の製造方法に関する。 The present invention relates to a method for producing a thin film or microstructure of a metal oxide containing a rare earth.
機能性材料の薄膜を得る方法としては、例えば特許文献１は、二酸化ケイ素薄膜に関して、ケイフッ化水素酸水溶液を二酸化ケイ素で過飽和状態にする工程、有機物の添加、有機物含有二酸化ケイ素薄膜の形成、の３つの工程からなる、有機物を含んだ二酸化ケイ素薄膜の製造方法を開示している。
ところで、金属酸化物は、その電子、光学、磁性材料としての可能性から数多くの研究開発がなされてきており、この金属酸化物についても、上記と同様に薄膜等として用いることが多くなってきている。 By the way, many researches and developments have been made on metal oxides because of their potential as electronic, optical, and magnetic materials, and these metal oxides are also often used as thin films as described above. Yes.
また、強い磁石や強強度の光を得られる蛍光体は、電気・電子機器の小型化や高性能化に貢献するとともに、省電力即ちエネルギーの有効利用にも貢献するものである。また、酸素のみが固体中を選択的に遊離・移動できる材料は、エンジン内で燃料を効率よく燃焼させるための酸素センサとして機能するだけでなく、排気ガスとして放出される有害物質を無害化する浄化用触媒の主要成分として、広く使用されている。このような優れた機能を有する材料となるのが希土類系物質である。ここで希土類とは、周期律表の欄外に位置するＬａからＬｕまでの１５個の元素に、ＳｃとＹとを加えた１７個の元素の総称である。 In addition, strong magnets and phosphors capable of obtaining high-intensity light contribute to miniaturization and high performance of electric / electronic devices, and also contribute to power saving, that is, effective use of energy. In addition, a material that can selectively release and move only oxygen in the solid not only functions as an oxygen sensor for efficiently burning fuel in the engine, but also detoxifies harmful substances released as exhaust gas. Widely used as the main component of purification catalysts. A material having such an excellent function is a rare earth material. Here, the rare earth is a general term for 17 elements obtained by adding Sc and Y to 15 elements from La to Lu located outside the column of the periodic table.
そして、このような希土類を含有する金属酸化物の薄膜等の機能性材料の設計については、その有力な手法の一つとして、溶液内での金属フッ化物錯体の加水分解平衡反応を利用する液相析出法（Liquid Phase Deposition, ＬＰＤ法）が考えられる。この反応を下記に示す。 And, for designing functional materials such as metal oxide thin films containing rare earths, as one of the promising methods, liquids utilizing hydrolysis equilibrium reaction of metal fluoride complexes in solution are used. A phase precipitation method (Liquid Phase Deposition, LPD method) can be considered. This reaction is shown below.
この［化１］の式（１）で示される加水分解平衡反応は、式（２ａ），（２ｂ）で示されるようなより安定なホウ素もしくはアルミニウムからなるフッ化物錯体を形成することにより、酸化物と遊離フッ素が形成される方向に進行する。ＬＰＤ法は、金属フッ化物錯体を母液とし、その系内にホウ酸又は金属アルミニウム（フッ素イオン消費剤）を添加することにより、酸化物を基板上に直接析出させることを特徴とする。 The hydrolysis equilibrium reaction represented by the formula (1) in [Chemical Formula 1] is performed by forming a more stable fluoride complex composed of boron or aluminum as represented by the formulas (2a) and (2b). It proceeds in the direction in which free fluorine is formed. The LPD method is characterized in that an oxide is directly deposited on a substrate by using a metal fluoride complex as a mother liquor and adding boric acid or metal aluminum (fluorine ion consumer) into the system.
しかし、このＬＰＤ法の反応においては、上記［化１］の式（１）に示す液相中の平衡反応が成立することが前提である。一方、フッ素錯体が系内に存在するということは、フッ化物の溶解度が非常に小さい希土類含有物質の薄膜を合成する上で、直ちにフッ化物の沈殿を生じさせるという問題が生じている。 However, in the reaction of the LPD method, it is premised that an equilibrium reaction in the liquid phase represented by the formula (1) of the above [Chemical Formula 1] is established. On the other hand, the presence of the fluorine complex in the system causes a problem that a precipitate of fluoride is immediately generated in synthesizing a thin film of a rare earth-containing material having a very low solubility of fluoride.
本発明の解決しようとする課題は以上の如くであり、次にこの課題を解決するための手段とその効果を説明する。 The problems to be solved by the present invention are as described above. Next, means for solving the problems and the effects thereof will be described.
◆本発明の第１の観点によれば、以下のような、ＬＰＤ法により基板上に希土類含有金属酸化物薄膜を直接析出させる希土類含有金属酸化物薄膜の製造方法が提供される。前記ＬＰＤ法における反応溶液が、希土類イオンキレート錯体と金属フッ化物錯体とを混合する工程を含む方法で製造されている。上記反応溶液にフッ素イオン消費剤を添加することにより、前記基板上に希土類含有金属酸化物薄膜をＬＰＤ法により析出させる。生成した薄膜を高温加熱処理する。 The first aspect of the present invention provides a method for producing a rare earth-containing metal oxide thin film by which a rare earth-containing metal oxide thin film is directly deposited on a substrate by the LPD method as follows. The reaction solution in the LPD method is manufactured by a method including a step of mixing a rare earth ion chelate complex and a metal fluoride complex. By adding a fluorine ion consumer to the reaction solution, a rare earth-containing metal oxide thin film is deposited on the substrate by the LPD method. The produced thin film is heat-treated at a high temperature.
これにより、フッ化物の沈殿を生じさせることなく、希土類含有金属酸化物薄膜を容易かつ安定的に製造することができる。 Thereby, the rare earth-containing metal oxide thin film can be easily and stably produced without causing precipitation of fluoride.
◆本発明の第２の観点によれば、以下のような、希土類含有金属酸化物構造体の製造方法が提供される。前述の製造方法により希土類含有金属酸化物薄膜を製造し、その薄膜の表面にポリスチレン粒子を自己集積化させることで三次元周期構造のテンプレートを形成する。前記反応溶液に前記テンプレートを浸漬することにより、前記ポリスチレン粒子の隙間に希土類含有金属酸化物を析出させる。加熱処理によってポリスチレン粒子を除去することで三次元反転オパール構造体を得る。 -According to the second aspect of the present invention, the following method for producing a rare earth-containing metal oxide structure is provided. A rare earth-containing metal oxide thin film is produced by the above-described production method, and polystyrene particles are self-assembled on the surface of the thin film to form a template having a three-dimensional periodic structure. By immersing the template in the reaction solution, a rare earth-containing metal oxide is deposited in the gaps between the polystyrene particles. By removing the polystyrene particles by heat treatment, a three-dimensional inverted opal structure is obtained.
これにより、表面積の大きい希土類含有金属酸化膜構造体を容易かつ安定的に製造することができる。 Thereby, a rare earth-containing metal oxide film structure having a large surface area can be produced easily and stably.
◆前記の希土類含有金属酸化物薄膜又は構造体の製造方法においては、前記希土類含有金属酸化物薄膜又は構造体が、酸化ジルコニウム：ユーロプウム付活（ＺｒＯ2；Ｅｕ）結晶、酸化ジルコニウム：イットリウム付活（ＺｒＯ2；Ｙ）結晶、酸化ジルコニウム：ランタン付活（ＺｒＯ2；Ｌａ）結晶、酸化ジルコニウム：プラセオジウム付活（ＺｒＯ2；Ｐｒ）結晶、酸化ジルコニウム：ネオジウム付活（ＺｒＯ2；Ｎｄ）結晶、酸化ジルコニウム：テリビウム付活（ＺｒＯ2；Ｔｂ）結晶、のいずれか１種類又は２種類以上の組み合わせからなることが好ましい。 In the method for producing the rare earth-containing metal oxide thin film or structure, the rare earth-containing metal oxide thin film or structure is composed of zirconium oxide: europium activated (ZrO 2 ; Eu) crystal, zirconium oxide: yttrium activated. (ZrO 2 ; Y) crystal, zirconium oxide: lanthanum activated (ZrO 2 ; La) crystal, zirconium oxide: praseodymium activated (ZrO 2 ; Pr) crystal, zirconium oxide: neodymium activated (ZrO 2 ; Nd) crystal, It is preferably composed of any one kind or a combination of two or more kinds of zirconium oxide: terbium activated (ZrO 2 ; Tb) crystal.
これにより、希土類含有金属酸化物薄膜又は構造体の製造方法が広範囲において実用可能になる。 Thereby, the manufacturing method of the rare earth-containing metal oxide thin film or structure becomes practical in a wide range.
◆前記の希土類含有金属酸化物薄膜又は構造体の製造方法においては、以下のようにすることが好ましい。前記ＬＰＤ法における反応溶液には、金属フッ化物錯体溶液と、希土類イオンをジエチレントリアミン五酢酸キレート錯体によりマスクした溶液と、を混合したものが含まれている。前記フッ素イオン消費剤はアルミニウム又はホウ酸である。 In the method for producing the rare earth-containing metal oxide thin film or structure, it is preferable to do the following. The reaction solution in the LPD method includes a mixture of a metal fluoride complex solution and a solution obtained by masking rare earth ions with a diethylenetriaminepentaacetic acid chelate complex. The fluorine ion consumer is aluminum or boric acid.
これにより、希土類含有金属酸化物薄膜の製造方法の広範囲の応用が期待できる。 Thereby, the wide range application of the manufacturing method of a rare earth metal oxide thin film can be expected.
◆前記の希土類含有金属酸化物薄膜又は構造体の製造方法においては、前記高温加熱処理が４００℃以上７００℃以下の温度範囲で行われることが好ましい。 In the method for producing the rare earth-containing metal oxide thin film or structure, the high-temperature heat treatment is preferably performed in a temperature range of 400 ° C. or higher and 700 ° C. or lower.
これにより、ＺｒＯ2の正方晶からなる希土類含有金属酸化物薄膜又は構造体を得ることができる。 As a result, a rare earth-containing metal oxide thin film or structure made of tetragonal ZrO 2 can be obtained.
◆前記の希土類含有金属酸化物薄膜又は構造体の製造方法においては、前記高温加熱処理が７００℃以上更に好ましくは８００℃以上１０００℃以下の温度範囲で行われることが好ましい。 In the method for producing the rare earth-containing metal oxide thin film or structure, the high-temperature heat treatment is preferably performed at a temperature range of 700 ° C. or higher, more preferably 800 ° C. or higher and 1000 ° C. or lower.
これにより、ＺｒＯ2の正方晶に相変化を起こさせて、かつ結晶格子の内部に希土類イオンが挿入固溶体化され、ＺｒＯ2の立方晶からなる希土類含有金属酸化物薄膜又は構造体を得ることができる。 As a result, a phase change is caused in the tetragonal crystal of ZrO 2 , and the rare earth ions are inserted into a solid solution inside the crystal lattice to obtain a rare earth-containing metal oxide thin film or structure made of cubic ZrO 2. it can.
◆前記の希土類含有金属酸化物構造体の製造方法においては、前記ポリスチレン粒子の粒径が８０nm以上３２０nm以下であることが好ましい。 In the method for producing the rare earth-containing metal oxide structure, the polystyrene particles preferably have a particle size of 80 nm or more and 320 nm or less.
これにより、三次元反転オパール構造の最適化によって表面積が大きくかつ均質な構造体が得られ、構造体の各種特性の向上が期待できる。 As a result, by optimizing the three-dimensional inverted opal structure, a uniform structure having a large surface area can be obtained, and improvement of various characteristics of the structure can be expected.
◆前記の希土類含有金属酸化物薄膜又は構造体の製造方法においては、前記基板が、ソーダライムガラス、溶融石英板、シリコンウェハ、シリコンカーバイドのうち何れか１つとされていることが好ましい。 In the method for producing a rare earth-containing metal oxide thin film or structure, the substrate is preferably one of soda lime glass, fused quartz plate, silicon wafer, and silicon carbide.
これにより、希土類含有金属酸化物薄膜又は構造体とそれぞれの用途に合わせた基板とを組み合わせることで、応用範囲の拡大が期待される。 Thereby, the expansion of the application range is expected by combining the rare earth-containing metal oxide thin film or structure with the substrate suitable for each application.
次に、発明の実施の形態を説明する。図１は液相析出法（ＬＰＤ法）の装置を示した模式図である。図２は本実施形態で製造された薄膜の様子を示すＡＦＭ写真である。図３は種々の温度で焼成した薄膜のＸ線回折パターンを示すグラフ図である。 Next, embodiments of the invention will be described. FIG. 1 is a schematic view showing an apparatus for a liquid phase precipitation method (LPD method). FIG. 2 is an AFM photograph showing the state of the thin film manufactured in this embodiment. FIG. 3 is a graph showing X-ray diffraction patterns of thin films fired at various temperatures.
〔薄膜の製造〕
本実施形態では、希土類含有金属酸化物として、透明な酸化ジルコニウム：ユーロプウム付活（ＺｒＯ2；Ｅｕ）薄膜をＬＰＤ法（液相析出法）により製造した。この酸化ジルコニウム（ＺｒＯ2）は、Ａｌ2Ｏ3やＳｉＯ2等と比較して低いフォノン振動を有すること、高誘電性であり、融点も多く、安定性に優れていることから、マトリックスとしての有用性が高いと期待されている。しかしながら従来は、ＬＰＤ法における溶液内反応に用いるフッ化ジルコン酸溶液中では、溶液中に存在するＦ-イオンのため、希土類イオンを共存させると直ちに沈殿が生じてしまっていた。
[Manufacture of thin film]
In this embodiment, a transparent zirconium oxide: europium activated (ZrO 2 ; Eu) thin film was produced as a rare earth-containing metal oxide by the LPD method (liquid phase deposition method). This zirconium oxide (ZrO 2 ) has low phonon vibration compared to Al 2 O 3 , SiO 2, etc., has high dielectric properties, has a high melting point, and is excellent in stability. Expected to be highly useful. However the prior art, the solution in the fluoride zirconate solution used for the reaction in the LPD method, F present in solution - for ion was incorrectly caused immediately precipitated coexists with rare earth ions.
本実施形態では、この沈殿生成を回避するために、Ｅｕ3+イオンをジエチレントリアミン五酢酸（ＤＴＰＡ）キレート錯体によりマスクして安定化することで、フッ化物共存下においても沈殿を生じさせずに可溶化させることができ、結果として基板上にＥｕ3+／ＺｒＯ2薄膜を形成することができたのである。 In this embodiment, in order to avoid this precipitation, the Eu 3+ ion is masked with a diethylenetriaminepentaacetic acid (DTPA) chelate complex and stabilized, so that precipitation can be avoided even in the presence of fluoride. As a result, an Eu 3+ / ZrO 2 thin film could be formed on the substrate.
具体的な薄膜の製造方法を以下に示す。ＺｒＯ2の薄膜生成における出発物質としては、森田化学株式会社製のフッ化ジルコン酸（Ｈ2ＺｒＦ6）を使用した。また、酸化ユーロプウム（Ｅｕ2Ｏ3）を１０％塩酸中にて溶解させ、Ｅｕ3+イオンを０．２mol dm-3 とした。そして、この溶液にＤＴＰＡキレート水溶液を、Ｅｕ3+：ＤＴＰＡ＝１：１となるように混合した。また、溶液を所定の組成比にてジルコニウムフッ化物錯体と混合し、反応溶液とした。 A specific method for producing a thin film is shown below. As a starting material in forming a thin film of ZrO 2 , fluorinated zirconic acid (H 2 ZrF 6 ) manufactured by Morita Chemical Co., Ltd. was used. Europium oxide (Eu 2 O 3 ) was dissolved in 10% hydrochloric acid to make Eu 3+ ions 0.2 mol dm −3 . And the DTPA chelate aqueous solution was mixed with this solution so that it might become Eu3 + : DTPA = 1: 1. The solution was mixed with a zirconium fluoride complex at a predetermined composition ratio to obtain a reaction solution.
この反応溶液に、フッ素イオン消費剤として板状の金属アルミニウム（ホウ酸を用いても良い）を添加し、反応を進行させた。最終的な反応溶液中のＺｒ4+イオン濃度は０．０６mol dm-3とした。Ｅｕ2+のＤＴＰＡ錯体濃度は２mmol dm-3とした。 To this reaction solution, plate-like metal aluminum (boric acid may be used) was added as a fluorine ion consumer, and the reaction was allowed to proceed. The final Zr 4+ ion concentration in the reaction solution was 0.06 mol dm −3 . The DTPA complex concentration of Eu 2+ was 2 mmol dm −3 .
基板としては、本実施形態ではソーダライムガラスを用いたが、それに限定されず、溶融石英板、シリコンウェハ、シリコンカーバイドを用いることもできる。基板はケイ酸ナトリウム中でのアルカリ脱脂を行い、３０℃、２４時間の超音波洗浄を行った後、前記反応溶液中に浸漬して薄膜形成を行った。 As the substrate, soda lime glass is used in the present embodiment, but is not limited thereto, and a fused quartz plate, a silicon wafer, or silicon carbide can also be used. The substrate was subjected to alkali degreasing in sodium silicate, subjected to ultrasonic cleaning at 30 ° C. for 24 hours, and then immersed in the reaction solution to form a thin film.
この薄膜の形成は、図１に示すＬＰＤ法の装置２１を用いて行った。具体的には、Ｈ2ＺｒＦ6水溶液及びＥｕ3+イオンを含む塩酸水溶液及びＤＴＰＡキレート水溶液及び蒸留水の混合物としての反応溶液２６をポンプ２４で吸い上げ、配管２５を通して、アルミニウム板が内壁に沿って設置された容器２３に流し込んで処理液２２とし、上下搬送機構２７の基板保持金具２９に取り付けた基板１を垂直に下降させて速やかに容器２３内の処理液２２に浸漬し、所定の時間だけ反応させた。その後、基板１を取り出し、蒸留水にて洗浄後、室温にて乾燥させた。その後、焼成を所定の温度（５００℃から９００℃まで、１００℃刻み）にて１時間行った。 This thin film was formed using the LPD method apparatus 21 shown in FIG. Specifically, a reaction solution 26 as a mixture of an aqueous solution of H 2 ZrF 6, an aqueous solution of hydrochloric acid containing Eu 3+ ions, an aqueous solution of DTPA chelate and distilled water is sucked up by a pump 24, and an aluminum plate passes along the inner wall through a pipe 25. Pour into the installed container 23 to make the processing liquid 22, and the substrate 1 attached to the substrate holding metal fitting 29 of the vertical transport mechanism 27 is vertically lowered and immediately immersed in the processing liquid 22 in the container 23 for a predetermined time. Reacted. Thereafter, the substrate 1 was taken out, washed with distilled water, and dried at room temperature. Thereafter, firing was performed at a predetermined temperature (from 500 ° C. to 900 ° C. in increments of 100 ° C.) for 1 hour.
得られた薄膜表面を原子間力顕微鏡（ＡＦＭ）で撮影した様子を図２に示す。なお図２には、（ａ）焼成前、（ｂ）５００℃で焼成した場合、（ｃ）７００℃で焼成した場合、（ｄ）９００℃で焼成した場合の４つの場合の様子が示されている。 FIG. 2 shows a state where the obtained thin film surface was photographed with an atomic force microscope (AFM). FIG. 2 shows four cases: (a) before firing, (b) when fired at 500 ° C., (c) when fired at 700 ° C., and (d) when fired at 900 ° C. ing.
図２（ａ）によると、形成した薄膜におけるＥｕ／ＺｒＯ2は数十nm程度の微細な粒子からなり、基板１の表面に緻密に析出していることが判る。析出直後（焼成前）の薄膜は、約８０nmの平均粒径を有する球状粒子が緻密かつ一様に基板１の表面を被覆しており、亀裂は認められなかった。 According to FIG. 2A, it can be seen that Eu / ZrO 2 in the formed thin film consists of fine particles of about several tens of nm and is densely deposited on the surface of the substrate 1. In the thin film immediately after deposition (before firing), spherical particles having an average particle diameter of about 80 nm covered the surface of the substrate 1 densely and uniformly, and no cracks were observed.
また図２の（ｂ）〜（ｄ）を比較すれば、焼成温度が上昇するに伴い、基板１の表面に存在する微小な粒子が互いに凝集し、９００℃での焼成時には粒径が２００nm程度まで増大することが判る。ただし、凝集するといっても粒径が数百nm程度であり、基板１の表面に亀裂も生じていないことから、これらの薄膜は（焼成の前後を問わず）可視光透過性に優れていることが判る。 2 (b) to 2 (d), the fine particles present on the surface of the substrate 1 aggregate with each other as the firing temperature rises, and when firing at 900 ° C., the particle size is about 200 nm. It turns out that it increases to. However, since the particle size is about several hundreds of nanometers and no cracks are formed on the surface of the substrate 1, these thin films are excellent in visible light transparency (regardless of before and after firing). I understand that.
次に、焼成後の薄膜についてＸ線回折測定を行い、得られたＸ線回折パターンを図３に示した。この図３をみると、薄膜が、正方晶もしくは立法晶からなるＺｒＯ2結晶に同定されることが考えられる。また、各温度で焼成した後の薄膜は相変化することなく、室温において正方晶（または立法晶）で安定化されていることが判る。 Next, X-ray diffraction measurement was performed on the fired thin film, and the obtained X-ray diffraction pattern was shown in FIG. Referring to FIG. 3, it is considered that the thin film is identified as a ZrO 2 crystal composed of tetragonal crystals or cubic crystals. It can also be seen that the thin film after firing at each temperature is stabilized with tetragonal crystals (or cubic crystals) at room temperature without phase change.
また、このＸ線回折測定において認められる回折ピークのうち、２θ＝３０．５°付近において認められるピークは、焼成時に８００℃以上の温度まで加熱した場合、低角度側にシフトしている（図３のグラフの中の小グラフは、横軸を拡大して示したものである）。これは、Ｚｒ4+（イオン半径：８７pm）より大きなイオン半径を有するＥｕ3+（イオン半径：９８pm）が結晶格子内に挿入され、固溶体化したものと考えられる。
更にまた、５００℃、６００℃、７００℃、８００℃、９００℃と焼成温度を高めていく事でスペクトル強度が大幅に向上されており、ＺｒＯ２の結晶格子の中にＥｕイオンの挿入が進み活性剤としての働きをしてフォトルミネッセンスが向上しているものと考えられる。
Of the diffraction peaks observed in this X-ray diffraction measurement, the peak observed near 2θ = 30.5 ° is shifted to the lower angle side when heated to a temperature of 800 ° C. or higher during firing (FIG. The small graph in graph 3 is shown with the horizontal axis enlarged). This is considered that Eu 3+ (ion radius: 98 pm) having an ionic radius larger than Zr 4+ (ion radius: 87 pm) was inserted into the crystal lattice to form a solid solution.
Furthermore, the spectral intensity is greatly improved by increasing the firing temperature to 500 ° C, 600 ° C, 700 ° C, 800 ° C, 900 ° C, and Eu ions are inserted into the crystal lattice of ZrO2 and activated. It is considered that the photoluminescence is improved by acting as an agent.
一方、ラマン散乱スペクトルにおいては、７００℃以下の焼成を行った場合、２６１，３３０，４６１，６１２，および６３６cm-1にＺｒＯ2の正方晶に基づくピークが認められたが、９００℃まで焼成した場合、６３０cm-1において立法晶に帰属されるピークが生じた。従って、８００℃付近において相変化が認められ、それ以上の温度で焼成すると正方晶から立法晶へ変化すると考えられる。 On the other hand, in the Raman scattering spectrum, when firing at 700 ° C. or lower, peaks based on ZrO 2 tetragonal crystals were observed at 261, 330, 461, 612, and 636 cm −1 , but the firing was performed to 900 ° C. In this case, a peak attributed to the cubic crystal occurred at 630 cm −1 . Therefore, a phase change is recognized at around 800 ° C., and it is considered that the tetragonal crystal changes to the cubic crystal when fired at a temperature higher than that.
〔周期構造体の製造〕
次に、上述の方法で製造された希土類含有金属酸化物薄膜３の表面に、図４に示すように単分散ポリスチレン粒子２を自己集積化させることで、テンプレートを作成した。ポリスチレン粒子２の粒径は、３０７nm，１９１nm，１７８nm，８８nmの４種類を用いた。このテンプレートを図１の装置の前述の処理液２２に再び浸漬して所定の時間だけ反応させ、図５に示すように、ポリスチレン粒子２の間隙に酸化ジルコニウム：ユーロプウム付活（ＺｒＯ2；Ｅｕ）４を析出させた（液相充填法）。その後、４００℃の高温で熱処理することで、ポリスチレン粒子２を分解除去し、基板１の表面に構造体を形成した。
[Manufacture of periodic structures]
Next, as shown in FIG. 4, monodisperse polystyrene particles 2 were self-assembled on the surface of the rare earth-containing metal oxide thin film 3 manufactured by the above-described method, thereby creating a template. As the particle size of the polystyrene particle 2, four types of 307 nm, 191 nm, 178 nm, and 88 nm were used. This template is immersed again in the above-described treatment liquid 22 of the apparatus of FIG. 1 and reacted for a predetermined time. As shown in FIG. 5, zirconium oxide: europium activated (ZrO 2 ; Eu) is inserted into the gaps of the polystyrene particles 2. 4 was deposited (liquid phase filling method). Thereafter, the polystyrene particles 2 were decomposed and removed by heat treatment at a high temperature of 400 ° C., and a structure was formed on the surface of the substrate 1.
図６に、粒径３０７nmのポリスチレン粒子２を使用した場合の上記構造体のＳＥＭによる観察結果を示す。この図６からは、ポリスチレン粒子２の間といった非常に微細な空間や間隙にも隙間なくＺｒＯ2が析出し、上記のポリスチレン粒子２を配列させたテンプレートの三次元形状が、基板１上に正確に転写されていることが判る。また、ポリスチレン粒子２は自己集積化により六方細密充填に配列し、これが転写された結果、構造体の表面が三次元反転オパール構造となっていることが判る。このように、三次元周期を有する希土類含有金属酸化物構造体が容易に作成可能であることが明らかになった。なお上記の結果は、他の粒径のポリスチレン粒子２（１９１nm，１７８nm，８８nm）を用いた場合でも同様であった。 In FIG. 6, the observation result by SEM of the said structure at the time of using the polystyrene particle 2 with a particle size of 307 nm is shown. From FIG. 6, ZrO 2 is deposited without gaps even in very fine spaces and gaps between the polystyrene particles 2, and the three-dimensional shape of the template in which the polystyrene particles 2 are arranged is accurately displayed on the substrate 1. It can be seen that it has been transferred to. Further, the polystyrene particles 2 are arranged in a hexagonal close packing by self-assembly, and as a result of the transfer, it can be seen that the surface of the structure has a three-dimensional inverted opal structure. Thus, it became clear that a rare earth-containing metal oxide structure having a three-dimensional period can be easily produced. The above results were the same even when polystyrene particles 2 (191 nm, 178 nm, 88 nm) having other particle sizes were used.
また、得られた酸化物の結晶性について検討するため、上記構造体の断面のＴＥＭ観察を行った。すると、析出したＥｕ／ＺｒＯ2はアナターゼ型を呈しており、微細領域及びポリスチレン粒子２との境界面においては、通常得られる薄膜と比較して特異的に高い結晶性を有することが確認された。 In addition, in order to examine the crystallinity of the obtained oxide, TEM observation of a cross section of the structure was performed. Then, the deposited Eu / ZrO 2 has an anatase type, and it has been confirmed that the interface between the fine region and the polystyrene particles 2 has a particularly high crystallinity as compared with the usually obtained thin film. .
更に、上記の三次元反転オパール構造体を蛍光体膜として用いた場合の、２４０nmＵＶ励起フォトルミネッセンス発光特性を計測した。計測値を、通常の市販の蛍光灯用希土類蛍光体膜のそれと比較したグラフを図７に示す。この図７に示すように、本発明の構造体は、２４０nmの光で励起した場合、非常に強度の強い発光スペクトルが得られていることが判る。この良好な結果は、上記の三次元反転オパール構造体４が形成されることによって、単位容積あたりの表面積が極めて大きくなっていることが一因であると考えられる。 Furthermore, 240 nm UV excitation photoluminescence emission characteristics were measured when the above three-dimensional inverted opal structure was used as a phosphor film. FIG. 7 shows a graph comparing the measured values with those of a normal commercially available rare earth phosphor film for a fluorescent lamp. As shown in FIG. 7, it can be seen that the structure of the present invention has a very strong emission spectrum when excited by light of 240 nm. This good result is considered to be due in part to the fact that the surface area per unit volume is extremely large due to the formation of the three-dimensional inverted opal structure 4 described above.
本発明で利用するＬＰＤ法は、大面積・複雑形状を有する基板に対して追随性が良く、また、低コスト且つ低温での合成が可能であり、組成の制御が容易でプロセスが簡便であるなど、他の方法と比較して様々な優位性を有している。本発明の方法により、このように有用なＬＰＤ法を、希土類含有金属酸化物の薄膜ないし構造体の作製に適用する際の障害を克服することができた。 The LPD method used in the present invention has good followability with respect to a substrate having a large area and a complicated shape, can be synthesized at a low cost and at a low temperature, can easily control the composition, and has a simple process. It has various advantages compared to other methods. According to the method of the present invention, it was possible to overcome the obstacles in applying the useful LPD method to the production of a rare earth-containing metal oxide thin film or structure.
また、本発明では、上記のように希土類含有金属酸化物の薄膜、ないし大きな表面積を有する構造体を容易に得られることから、蛍光体のほかにもフォトニクス結晶、磁性体、触媒担持体、色素増感型太陽電池、センサー等、種々のデバイスへの応用が期待される。 Further, in the present invention, since a thin film of a rare earth-containing metal oxide or a structure having a large surface area can be easily obtained as described above, in addition to a phosphor, a photonic crystal, a magnetic material, a catalyst carrier, a dye Applications to various devices such as sensitized solar cells and sensors are expected.
１ 基板
２ ポリスチレン粒子
３ 希土類含有金属酸化物薄膜
４ 希土類含有金属酸化物構造体（三次元反転オパール構造）
２１ ＬＰＤ法による希土類含有金属酸化物製造装置
２２ 処理液
２３ 容器
２４ ポンプ
２５ 配管
２６ 反応溶液
２７ 上下搬送機構
２９ 基板保持金具
1 Substrate 2 Polystyrene particles 3 Rare earth-containing metal oxide thin film 4 Rare earth-containing metal oxide structure (three-dimensional inverted opal structure)
21 Rare earth-containing metal oxide production apparatus by LPD method 22 Treatment liquid 23 Container 24 Pump 25 Piping 26 Reaction solution 27 Vertical transport mechanism 29 Substrate holding bracket
Claims (8)
前記ＬＰＤ法における反応溶液が、希土類イオンキレート錯体と金属フッ化物錯体とを混合する工程を含む方法で製造されており、
上記反応溶液にフッ素イオン消費剤を添加することにより、前記基板上に希土類含有金属酸化物薄膜をＬＰＤ法により析出させ、
生成した薄膜を高温加熱処理することを特徴とする、希土類含有金属酸化物薄膜の製造方法。 A method for producing a rare earth-containing metal oxide thin film by directly depositing a rare earth-containing metal oxide thin film on a substrate by an LPD method,
The reaction solution in the LPD method is manufactured by a method including a step of mixing a rare earth ion chelate complex and a metal fluoride complex,
By adding a fluorine ion consumer to the reaction solution, a rare earth-containing metal oxide thin film is deposited on the substrate by the LPD method,
A method for producing a rare earth-containing metal oxide thin film, wherein the produced thin film is subjected to high-temperature heat treatment.
前記反応溶液に前記テンプレートを浸漬することにより、前記ポリスチレン粒子の隙間に希土類含有金属酸化物を析出させ、
加熱処理によってポリスチレン粒子を除去することで三次元反転オパール構造体を得ることを特徴とする、希土類含有金属酸化物構造体の製造方法。 A rare earth-containing metal oxide thin film is produced by the production method according to claim 1, and a template having a three-dimensional periodic structure is formed by self-integrating polystyrene particles on the surface of the thin film.
By immersing the template in the reaction solution, the rare earth-containing metal oxide is precipitated in the gaps between the polystyrene particles,
A method for producing a rare earth-containing metal oxide structure, comprising obtaining a three-dimensional inverted opal structure by removing polystyrene particles by heat treatment.
前記希土類含有金属酸化物薄膜又は構造体が、
酸化ジルコニウム：ユーロプウム付活（ＺｒＯ2；Ｅｕ）結晶、
酸化ジルコニウム：イットリウム付活（ＺｒＯ2；Ｙ）結晶、
酸化ジルコニウム：ランタン付活（ＺｒＯ2；Ｌａ）結晶、
酸化ジルコニウム：プラセオジウム付活（ＺｒＯ2；Ｐｒ）結晶、
酸化ジルコニウム：ネオジウム付活（ＺｒＯ2；Ｎｄ）結晶、
酸化ジルコニウム：テリビウム付活（ＺｒＯ2；Ｔｂ）結晶、
のいずれか１種類又は２種類以上の組み合わせからなることを特徴とする、希土類含有金属酸化物薄膜又は構造体の製造方法。 A method for producing a rare earth-containing metal oxide thin film or structure according to claim 1 or 2,
The rare earth-containing metal oxide thin film or structure is
Zirconium oxide: Europium activated (ZrO 2 ; Eu) crystal,
Zirconium oxide: Yttrium activated (ZrO 2 ; Y) crystal,
Zirconium oxide: Lanthanum activated (ZrO 2 ; La) crystal,
Zirconium oxide: praseodymium activated (ZrO 2 ; Pr) crystal,
Zirconium oxide: neodymium activated (ZrO 2 ; Nd) crystal,
Zirconium oxide: Terbium activated (ZrO 2 ; Tb) crystal,
A method for producing a rare earth-containing metal oxide thin film or structure comprising any one of the above or a combination of two or more thereof.
前記ＬＰＤ法における反応溶液には、金属フッ化物錯体溶液と、希土類イオンをジエチレントリアミン五酢酸キレート錯体によりマスクした溶液と、を混合したものが含まれており、
前記フッ素イオン消費剤はアルミニウム又はホウ酸であることを特徴とする、希土類含有金属酸化物薄膜又は構造体の製造方法。 A method for producing a rare earth-containing metal oxide thin film or structure according to claim 1 or 2,
The reaction solution in the LPD method includes a mixture of a metal fluoride complex solution and a solution obtained by masking a rare earth ion with a diethylenetriaminepentaacetic acid chelate complex,
The method for producing a rare earth-containing metal oxide thin film or structure, wherein the fluorine ion consumable is aluminum or boric acid.
前記基板が、ソーダライムガラス、溶融石英板、シリコンウェハ、シリコンカーバイドのうち何れか１つとされていることを特徴とする、希土類含有金属酸化物薄膜又は構造体の製造方法。 A method for producing a rare earth-containing metal oxide thin film or structure according to any one of claims 1 to 7,
A method for producing a rare earth-containing metal oxide thin film or structure, wherein the substrate is any one of soda lime glass, fused quartz plate, silicon wafer, and silicon carbide.
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