JP2009155376A - Oxide phosphor epitaxial thin film - Google Patents
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Abstract
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本発明は、酸化物蛍光体エピタキシャル薄膜に係り、特に、赤色を発光することが可能な酸化物蛍光体エピタキシャル薄膜に関する。 The present invention relates to an oxide phosphor epitaxial thin film, and more particularly to an oxide phosphor epitaxial thin film capable of emitting red light.
従来、有機ＥＬや無機ＥＬ等多数の蛍光体が知られているが、大気中暴露によって結晶性が低下し、蛍光特性の経年劣化が著しいという問題がある。 Conventionally, many phosphors such as organic EL and inorganic EL are known. However, there is a problem that crystallinity is lowered by exposure to the atmosphere, and aged deterioration of fluorescence characteristics is remarkable.
特許文献1には、イットリウムアルミネート等の無機母材材料に金属イオンを置換した複酸化物蛍光体薄膜の製造方法が示されている。
特許文献2には、無機母体材料に希土類金属イオンや遷移金属イオンを含有した材料に機械的外力を印加することにより発光する薄膜の製造方法が示されている。
特許文献3には、多結晶体Snペロブスカイト酸化物系の蛍光特性が示されている。
非特許文献1には、多結晶体ASnO3 系ペロブスカイト構造（A=Ca,Sr,Ba）において、Eu3+で置換した際に赤色蛍光特性が得られることが示されている。
非特許文献2には、多結晶体Sn系層状ペロブスカイト構造において青色蛍光が得られることが示されている。
非特許文献3には、多結晶体CaSnO3において、Tbを置換した際に蛍光特性が得られることが示されている。
非特許文献4には、多結晶体層状層状ペロブスカイトSrn+1TiO3n+1系で赤色蛍光特性が得られることが示されている。
非特許文献5には、SrTiO3単結晶および薄膜に関し、酸素欠損により青白蛍光が得られることが示されている。
非特許文献6には、多結晶体SrTiO3 にPr原子を置換することにより、赤色蛍光特性が得られることが示されている。
非特許文献7には、多結晶体Pr原子置換(CaxSr1-x)TiO3において赤色蛍光特性が得られることが示されている。
非特許文献8には、薄膜MHfO3：Tm置換の青色蛍光特性が得られることが示されている。
非特許文献9には、Er原子で置換したBaTiO3薄膜において蛍光特性が得られることが示されている。
Patent Document 1 discloses a method for producing a double oxide phosphor thin film in which a metal ion is substituted for an inorganic base material such as yttrium aluminate.
Patent Document 2 discloses a method for producing a thin film that emits light by applying a mechanical external force to a material containing a rare earth metal ion or a transition metal ion in an inorganic base material.
Patent Document 3 shows fluorescence characteristics of a polycrystalline Sn perovskite oxide system.
Non-Patent Document 1 shows that red fluorescence characteristics can be obtained when a polycrystalline ASnO 3 perovskite structure (A = Ca, Sr, Ba) is substituted with Eu 3+ .
Non-Patent Document 2 shows that blue fluorescence can be obtained in a polycrystalline Sn-based layered perovskite structure.
Non-Patent Document 3 shows that in the polycrystalline CaSnO 3 , fluorescence characteristics can be obtained when Tb is substituted.
Non-Patent Document 4 shows that red fluorescence characteristics can be obtained with a polycrystalline layered layered perovskite Sr n + 1 TiO 3n + 1 system.
Non-Patent Document 5 shows that blue-white fluorescence can be obtained by oxygen deficiency for SrTiO 3 single crystals and thin films.
Non-Patent Document 6 shows that red fluorescence characteristics can be obtained by substituting Pr atoms for polycrystalline SrTiO 3 .
Non-Patent Document 7 shows that red fluorescence characteristics can be obtained in polycrystalline Pr atom substitution (Ca x Sr 1-x ) TiO 3 .
Non-Patent Document 8 shows that a blue fluorescent characteristic of a thin film MHfO 3 : Tm substitution can be obtained.
Non-Patent Document 9 shows that fluorescence characteristics can be obtained in a BaTiO 3 thin film substituted with Er atoms.
従来技術に示すように、酸化物多結晶体においては良好な蛍光体が得られることは知られているが、ディスプレイ作製上必要な赤色、緑色、及び青色の3原色の蛍光を発する酸化物蛍光体エピタキシャル薄膜は知られていない。特に、ディスプレイ応用の際には、薄膜によるＥＬの開発が必要不可欠であり、酸化物蛍光体エピタキシャル薄膜の開発が急務とされている。
本発明の目的は、ディスプレイ作製の基礎となる赤色の発色が可能な、酸化物蛍光体エピタキシャル薄膜を提供することにある。
As shown in the prior art, it is known that good phosphors can be obtained with oxide polycrystals, but oxide fluorescence that emits three primary colors of red, green, and blue, which are necessary for display production. No body epitaxial thin film is known. In particular, for display applications, the development of EL using thin films is indispensable, and the development of oxide phosphor epitaxial thin films is urgently required.
An object of the present invention is to provide an oxide phosphor epitaxial thin film capable of forming a red color, which is the basis of display production.
本発明は、上記の課題を解決するために、次のような手段を採用した。
第1の手段は、アルミニウム元素をペロブスカイトに置換した多結晶ターゲット材料としてパルスレーザー堆積法によって、600℃以上800℃以下の温度でエピタキシャル成長により基板上に薄膜が形成されたことを特徴とする酸化物蛍光体エピタキシャル薄膜である。
第2の手段は、第1の手段において、前記多結晶ターゲット材料が、(Sr1-xPrx)(Ti1-yAly)O3 :0≦ｘ≦0.1、0≦y≦0.2であり、赤色蛍光を得ることを特徴とする酸化物蛍光体エピタキシャル薄膜である。
第3の手段は、第1の手段または第2の手段において、前記基板が、SrTiO3、LaAlO3、LaGaO3、LaSrGaO4のいずれかからなるペロブスカイト関連構造を有する材料、またはMgO、MgAl2O4のいずれかからなる立方晶系もしくは正方晶系を有する材料であることを特徴とする酸化物蛍光体エピタキシャル薄膜である。
The present invention employs the following means in order to solve the above problems.
The first means is an oxide characterized in that a thin film is formed on a substrate by epitaxial growth at a temperature of 600 ° C. or higher and 800 ° C. or lower by a pulse laser deposition method as a polycrystalline target material in which aluminum element is replaced with perovskite. It is a phosphor epitaxial thin film.
The second means is that in the first means, the polycrystalline target material is (Sr 1-x Pr x ) (Ti 1-y Al y ) O 3 : 0 ≦ x ≦ 0.1, 0 ≦ y ≦ 0.2. It is an oxide phosphor epitaxial thin film characterized by obtaining red fluorescence.
A third means is the material according to the first means or the second means, wherein the substrate has a perovskite-related structure made of any one of SrTiO 3 , LaAlO 3 , LaGaO 3 , LaSrGaO 4 , or MgO, MgAl 2 O 4. An oxide phosphor epitaxial thin film characterized by being a material having a cubic system or a tetragonal system composed of any one of 4 above.
本発明によれば、赤色の優れた蛍光特性を有する酸化物蛍光体エピタキシャル薄膜が得られる。この結果、酸化物エピタキシャル薄膜によるエレクトロルミネッセンスデバイスの開発が期待される。薄膜によるエレクトロルミネッセンスデバイスは、低電圧駆動が可能なことから、システムの小型化が実現される。また酸化物を利用することによって、試料の大気中暴露による結晶性の劣化が極めて少ない利点を有する。 According to the present invention, an oxide phosphor epitaxial thin film having excellent red fluorescence properties can be obtained. As a result, development of an electroluminescence device using an oxide epitaxial thin film is expected. Since the electroluminescent device using a thin film can be driven at a low voltage, the size of the system can be reduced. Further, by using an oxide, there is an advantage that the deterioration of crystallinity due to exposure of the sample to the atmosphere is extremely small.
本発明に係る酸化物蛍光体エピタキシャル薄膜の作製には、パルスレーザー堆積法を用いた。この薄膜は酸素気流中で成膜することができるため、酸化物薄膜成長時には酸素欠損等による電気的特性、蛍光特性の劣化を極めて少なくすることができる。パルスレーザー堆積法は、1Torr以下の低圧酸素中で、酸化物からなるターゲット材料にArF（波長193nm）のエキシマレーザーを照射し、ターゲット材料をプラズマ化させプルームを形成し、そのターゲット材料に対向した面に過熱した基板を配置し、薄膜を堆積させる手法である。1000℃以下の温度ではクラスター成長が支配的であり、ターゲット材料をその化学量論組成で成膜させることができることを特徴とする。 A pulsed laser deposition method was used for producing the oxide phosphor epitaxial thin film according to the present invention. Since this thin film can be formed in an oxygen stream, degradation of electrical characteristics and fluorescence characteristics due to oxygen deficiency or the like can be extremely reduced during the growth of the oxide thin film. In the pulsed laser deposition method, an oxide target material is irradiated with an excimer laser of ArF (wavelength: 193 nm) in low-pressure oxygen of 1 Torr or less, and the target material is turned into plasma to form a plume, which faces the target material. In this method, a superheated substrate is placed on the surface and a thin film is deposited. Cluster growth is dominant at a temperature of 1000 ° C. or lower, and the target material can be deposited with its stoichiometric composition.
本発明の成膜法の詳細について述べる。レーザー照射周波数は８Ｈｚであり、成膜時間は30分である。また、基板とターゲット間距離は30ｍｍとした。レーザーエネルギーは約120mJである。基板は典型例としてSrTiO3(001)）単結晶研磨基板を用いた。SrTiO3の結晶構造は正方晶であり、格子定数は3.905nmである。ペロブスカイト酸化物の多くの材料はこの近傍の格子定数を持ち、その整合性が良いため、結晶性の優れた酸化物エピタキシャル薄膜の成長が期待される。 Details of the film forming method of the present invention will be described. The laser irradiation frequency is 8 Hz, and the film formation time is 30 minutes. The distance between the substrate and the target was 30 mm. The laser energy is about 120mJ. As a typical substrate, a SrTiO 3 (001)) single crystal polished substrate was used. The crystal structure of SrTiO 3 is tetragonal and the lattice constant is 3.905 nm. Since many materials of perovskite oxide have lattice constants in the vicinity of this material and have good matching, it is expected to grow an oxide epitaxial thin film with excellent crystallinity.
非特許文献４には、多結晶体層状ペロブスカイトSrn+1TiO3n+1系で赤色蛍光特性が示されている。また、非特許文献6には、多結晶体SrTiO3 にPr原子、Al原子を置換することで赤色蛍光特性が向上することが示されている。本発明は、これらの知見に基づいて、アルミニウム元素をペロブスカイトに置換した多結晶ターゲット材料として、(Sr1-xPrx)(Ti1-yAly)O3 :0≦ｘ≦0.1、0≦y≦0.2を用い、パルスレーザー堆積法によって、600℃以上800℃以下の温度でエピタキシャル成長により基板上に酸化物蛍光体エピタキシャル薄膜が形成したものである。 Non-Patent Document 4 shows red fluorescence characteristics in a polycrystalline layered perovskite Sr n + 1 TiO 3n + 1 system. Non-Patent Document 6 shows that red fluorescence characteristics are improved by replacing Pr atoms and Al atoms with polycrystalline SrTiO 3 . Based on these findings, the present invention provides (Sr 1-x Pr x ) (Ti 1-y Al y ) O 3 : 0 ≦ x ≦ 0.1, 0 as a polycrystalline target material in which an aluminum element is substituted with perovskite. An oxide phosphor epitaxial thin film is formed on a substrate by epitaxial growth at a temperature of 600 ° C. or higher and 800 ° C. or lower by pulse laser deposition using ≦ y ≦ 0.2.
ここでは、前記化学組成の蛍光特性において最も良い蛍光特性が得られると考えられるx=0.02、y=0.05における実施例について述べる。基板温度は600℃、700℃、800℃で成膜を行った。結晶構造を調べるためX線回折を測定した。その結果、全ての温度で(001)薄膜が成長していることからエピタキシャル成長が確認された。 Here, an example in which x = 0.02 and y = 0.05, which are considered to obtain the best fluorescence characteristics among the fluorescence characteristics of the chemical composition, will be described. Film formation was performed at substrate temperatures of 600 ° C., 700 ° C., and 800 ° C. X-ray diffraction was measured to investigate the crystal structure. As a result, the (001) thin film was grown at all temperatures, confirming epitaxial growth.
典型例として700℃成長時のX線回折パターンを図1に示す。計算結果と多結晶体で得られた結果に対し、薄膜のパターンは(001)方位のみが出現していることから、(001)方位にエピタキシャル成長していることが分かる。 As a typical example, an X-ray diffraction pattern during growth at 700 ° C. is shown in FIG. In contrast to the calculation results and the results obtained for the polycrystal, only the (001) orientation appears in the thin film pattern, indicating that the epitaxial growth has occurred in the (001) orientation.
次に、基板温度600℃、700℃、800℃で成膜を行った薄膜の蛍光特性の調査を行った。典型例として700℃成膜された試料で測定された蛍光特性を図2に示す（励起波長330nm）。615nmの波長で蛍光特性が得られ、赤色であることが分かる。最適な化学組成でこれらの結果が得られたことから、(Sr1-xPrx)(Ti1-yAly)O3 :0≦ｘ≦0.1、0≦y≦0.2の領域でも同様の蛍光特性が得られると考えられる。 Next, the fluorescence characteristics of the thin films formed at substrate temperatures of 600 ° C., 700 ° C., and 800 ° C. were investigated. As a typical example, fluorescence characteristics measured with a sample formed at 700 ° C. are shown in FIG. 2 (excitation wavelength: 330 nm). It can be seen that fluorescence characteristics are obtained at a wavelength of 615 nm and that the color is red. Since these results were obtained with an optimal chemical composition, the same applies to the region of (Sr 1-x Pr x ) (Ti 1-y Al y ) O 3 : 0 ≦ x ≦ 0.1 and 0 ≦ y ≦ 0.2. It is considered that fluorescence characteristics can be obtained.
また、上記実施例では基板材料として、酸化物系ぺロブスカイトSrTiO3単結晶基板を用いて(Sr1-xPrx)(Ti1-yAly)O3 :0≦ｘ≦0.1、0≦y≦0.2エピタキシャル薄膜を形成に成功したことから、LaAlO3、LaGaO3、LaSrGaO4などのペロブスカイト関連構造基板やMgO、MgAl2O4などの立方晶系もしくは正方晶系の基板でも、エピタキシャル成長は可能であることが予想される。 Further, in the above embodiment, an oxide-based perovskite SrTiO 3 single crystal substrate is used as the substrate material (Sr 1-x Pr x ) (Ti 1-y Al y ) O 3 : 0 ≦ x ≦ 0.1, 0 ≦ Since we successfully formed an y ≦ 0.2 epitaxial thin film, epitaxial growth is possible even with perovskite-related structural substrates such as LaAlO 3 , LaGaO 3 , LaSrGaO 4 and cubic or tetragonal substrates such as MgO and MgAl 2 O 4 It is expected that
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2012020704A1 (en) * | 2010-08-09 | 2012-02-16 | 独立行政法人産業技術総合研究所 | Inorganic-oxide fluorescent material and thin film of white fluorescent material |
| JP2012036305A (en) * | 2010-08-09 | 2012-02-23 | National Institute Of Advanced Industrial Science & Technology | Inorganic-oxide fluorescent material, method for producing the same, and light-emitting apparatus |
| JP2012046590A (en) * | 2010-08-25 | 2012-03-08 | National Institute Of Advanced Industrial Science & Technology | White fluorescent thin film, method for production thereof, and light-emitting device |
| CN104861969A (en) * | 2015-05-20 | 2015-08-26 | 中国科学院新疆理化技术研究所 | Aluminum calcium titanate solid-solution type red phosphor and preparation method thereof |
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| JP2004353072A (en) * | 2003-05-30 | 2004-12-16 | National Institute For Materials Science | Production method for dielectric |
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| JP2004353072A (en) * | 2003-05-30 | 2004-12-16 | National Institute For Materials Science | Production method for dielectric |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012020704A1 (en) * | 2010-08-09 | 2012-02-16 | 独立行政法人産業技術総合研究所 | Inorganic-oxide fluorescent material and thin film of white fluorescent material |
| JP2012036305A (en) * | 2010-08-09 | 2012-02-23 | National Institute Of Advanced Industrial Science & Technology | Inorganic-oxide fluorescent material, method for producing the same, and light-emitting apparatus |
| JP2012046590A (en) * | 2010-08-25 | 2012-03-08 | National Institute Of Advanced Industrial Science & Technology | White fluorescent thin film, method for production thereof, and light-emitting device |
| CN104861969A (en) * | 2015-05-20 | 2015-08-26 | 中国科学院新疆理化技术研究所 | Aluminum calcium titanate solid-solution type red phosphor and preparation method thereof |
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