JP2008019317A - Oxide phosphor epitaxial film - Google Patents

Oxide phosphor epitaxial film Download PDF

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JP2008019317A
JP2008019317A JP2006190755A JP2006190755A JP2008019317A JP 2008019317 A JP2008019317 A JP 2008019317A JP 2006190755 A JP2006190755 A JP 2006190755A JP 2006190755 A JP2006190755 A JP 2006190755A JP 2008019317 A JP2008019317 A JP 2008019317A
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thin film
oxide phosphor
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oxide
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JP4873464B2 (en
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Hiroshi Takashima
浩 高島
Kazushige Ueda
和茂 植田
Mitsuru Ito
満 伊藤
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National Institute of Advanced Industrial Science and Technology AIST
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Abstract

<P>PROBLEM TO BE SOLVED: To provide an oxide phosphor epitaxial film enabling color development of the three primary colors of red, green, and blue which come to the basis of manufacturing a display. <P>SOLUTION: The oxide phosphor epitaxial film is obtained by forming a film on a substrate at a temperature of 600-800°C by epitaxial growth using an oxide phosphor material as a target material by the pulse laser accumulation method and subjecting the film thus formed to heat treatment in oxygen or in the air at 900-1,200°C to improve fluorescence properties. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

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、緑色、及び青色の3原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 three primary colors of red, green, and blue.

従来、有機ELや無機EL等多数の蛍光体が知られているが、酸化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 the crystallinity is lowered by oxidation and the aging of the 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 manufacturing 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.

特開2003-183646号公報JP2003-183646 特開平11-219601号公報Japanese Patent Laid-Open No. 11-219601 特願2005-322286Japanese Patent Application 2005-322286 J. AlloyCompd. Vol.387, pp L1-4 (2005)J. AlloyCompd. Vol.387, pp L1-4 (2005) J. Mater.Sci. Lett., Vol.11, 1330 (1992)J. Mater.Sci. Lett., Vol. 11, 1330 (1992) MaterialsChemistry and Physics Vol.93, pp.129-132 (2005)MaterialsChemistry and Physics Vol.93, pp.129-132 (2005) J.J.Appl. Phys. Vol.44, pp. 761-764 (2005)J.J.Appl.Phys.Vol.44, pp.761-764 (2005) Naturematerials Vol 4, 816 (2005)Naturematerials Vol 4, 816 (2005) Appl.Phy. Lett Vol 78, 655 (2001)Appl.Phy. Lett Vol 78, 655 (2001) Chem.Mater. Vol 17, 3200 (2005)Chem. Mater. Vol 17, 3200 (2005) Appl.Surf. Sci. Vol 197-198, 402 (2002)Appl.Surf. Sci. Vol 197-198, 402 (2002) Appl.Phy. Lett Vol 65, 25 (1994)Appl.Phy. Lett Vol 65, 25 (1994)

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、緑色、青色の3原色の発色が可能な、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 a good phosphor can be obtained in an oxide polycrystal, but the oxide fluorescence that emits three primary colors of red, green, and blue 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 developing three primary colors of red, green, and blue, which is a basis for 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、酸化物蛍光材料を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、前記ターゲット材料が、希土類元素、遷移金属元素、アルカリ土類元素等をペロブスカイト構造に置換した多結晶ターゲット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。
第3の手段は、第1の手段または第2の手段において、前記ターゲット材料が、Sr2(Sn1-x
Tix)O4:0.01≦x≦0.1であり、青色蛍光が得られ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4の手段は、第1の手段または第2の手段において、前記ターゲット材料が、Pry(CaxSr1-x1-yTiO3:0.1≦x≦1.0、0.0005≦y≦0.05であり、赤色蛍光が得られ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5の手段は、第1の手段または第2の手段において、前記ターゲット材料が、(Sr1-x
Eu x)2(Sn1-y Ti y)O4:0.01≦x≦0.1、0.01≦y≦0.2であり、赤色蛍光が得られ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6の手段は、第1の手段または第2の手段において、前記ターゲット材料が、{(Ca1-x
Mg x) 1-yTby}SnO3:0.01≦x≦0.2、0.001≦y≦0.2であり、緑色蛍光が得られ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7の手段は、第1の手段または第2の手段において、前記ターゲット材料が、(PrxSr1-x)SnO3:0.001≦x≦0.2であり、波長490nm±10nmの蛍光が得られ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8の手段は、第1の手段ないし第7の手段いずれか1つの手段において、前記薄膜を、酸素中または大気中で、900℃以上1200℃以下の熱処理によって蛍光特性を向上させ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9の手段は、第1の手段ないし第8の手段いずれか1つの手段において、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もしくは正方晶系を有する材料からな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 phosphor epitaxial thin film 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 using an oxide fluorescent material as a target material. It is.
A second means is the oxide phosphor according to the first means, wherein the target material is a polycrystalline target material in which a rare earth element, a transition metal element, an alkaline earth element or the like is substituted with a perovskite structure. It is an epitaxial thin film.
The third means is the first means or the second means, wherein the target material is Sr 2 (Sn 1-x
Ti x ) O 4 : 0.01 ≦ x ≦ 0.1, which is an oxide phosphor epitaxial thin film characterized in that blue fluorescence is obtained.
The fourth means is the first means or the second means, wherein the target material is Pr y (Ca x Sr 1-x ) 1-y TiO 3 : 0.1 ≦ x ≦ 1.0, 0.0005 ≦ y ≦ 0.05 There is an oxide phosphor epitaxial thin film characterized in that red fluorescence is obtained.
The fifth means is the first means or the second means, wherein the target material is (Sr 1-x
Eu x ) 2 (Sn 1-y Ti y ) O 4 : 0.01 ≦ x ≦ 0.1, 0.01 ≦ y ≦ 0.2, and an oxide phosphor epitaxial thin film characterized in that red fluorescence is obtained.
A sixth means is the first means or the second means, wherein the target material is {(Ca 1-x
Mg x ) 1-y Tb y } SnO 3 : 0.01 ≦ x ≦ 0.2, 0.001 ≦ y ≦ 0.2, and is an oxide phosphor epitaxial thin film characterized in that green fluorescence is obtained.
A seventh means is that, in the first means or the second means, the target material is (Pr x Sr 1-x ) SnO 3 : 0.001 ≦ x ≦ 0.2, and fluorescence having a wavelength of 490 nm ± 10 nm is obtained. This is an oxide phosphor epitaxial thin film.
The eighth means is that in any one of the first means to the seventh means, the thin film is improved in fluorescence characteristics by heat treatment at 900 ° C. or more and 1200 ° C. or less in oxygen or air. It is a characteristic oxide phosphor epitaxial thin film.
A ninth means is the material according to any one of the first to eighth means, wherein the substrate has a perovskite-related structure made of any of SrTiO 3 , LaAlO 3 , LaGaO 3 , LaSrGaO 4 , or An oxide phosphor epitaxial thin film comprising a cubic or tetragonal material composed of either MgO or MgAl 2 O 4 .

本発明によれば、赤色、緑色、青色の3原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、その結果、酸化物蛍光体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可能となる。また酸化物蛍光体エピタキシャル薄膜を用いたエレクトロルミネッセンスデバイスによれば、低電圧駆動が可能となることから、システムの小型化が可能となる。   According to the present invention, an oxide phosphor epitaxial thin film having excellent fluorescence characteristics of three primary colors of red, green, and blue can be obtained, and as a result, an electroluminescence device using the oxide phosphor epitaxial thin film can be developed. . Moreover, according to the electroluminescence device using the oxide phosphor epitaxial thin film, it is possible to drive at a low voltage, and thus the system can be miniaturized.

はじめに、本発明に係る酸化物蛍光体エピタキシャル薄膜の作製の概要について説明する。薄膜の作製にはパルスレーザー堆積法を用いる。パルスレーザー堆積法は短時間(典型的成膜時間は1時間)で500nm程度の薄膜を形成することができることから、工業的応用に期待されている。また、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、ターゲット材料に対抗する面に加熱した基板を配置し、薄膜を堆積させるものである。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。   First, an outline of the production of the oxide phosphor epitaxial thin film according to the present invention will be described. Pulse laser deposition is used for the production of the thin film. The pulsed laser deposition method is expected for industrial application because it can form a thin film of about 500 nm in a short time (typical film formation time is 1 hour). Further, since the film can be formed in an oxygen stream, deterioration 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, the target material made of oxide 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. A heated substrate is placed on and a thin film is deposited. Cluster growth is dominant at temperatures below 1000 ° C., and the target material can be deposited with its stoichiometric composition.

パルスレーザー堆積法における、レーザー照射周波数は8Hzであり、成膜時間は30分である。基板とターゲット間距離は32mmとした。レーザーエネルギーは約120mJである。ターゲット材料としては、希土類元素、遷移金属元素、アルカリ土類元素をペロブスカイト構造に置換した多結晶ターゲット材料を用いる。また、基板としては、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もしくは正方晶系を有する材料を用いる。ここでは、典型的例として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、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できる。 In the pulsed laser deposition method, the laser irradiation frequency is 8 Hz, and the film formation time is 30 minutes. The distance between the substrate and the target was 32 mm. The laser energy is about 120mJ. As the target material, a polycrystalline target material in which a rare earth element, a transition metal element, or an alkaline earth element is substituted with a perovskite structure is used. In addition, as the substrate, a material having a perovskite-related structure composed of any of SrTiO 3 , LaAlO 3 , LaGaO 3 , LaSrGaO 4 , or a material having a cubic or tetragonal system composed of any of MgO and MgAl 2 O 4 Is used. Here, a SrTiO 3 (001) single crystal polishing substrate was used as a typical example. The crystal structure of SrTiO 3 is tetragonal and the lattice constant is 3.905 nm. Since many materials of perovskite oxide have a lattice constant in the vicinity of this material and have good matching, growth of an oxide epitaxial thin film having excellent crystallinity can be expected.

本発明の実施例1を図1ないし図5を用いて説明する。図1は、ターゲット材料としてSr2(Sn1-x Tix)O4: x=0.05を用い、パルスレーザー堆積法による800℃で成長時の酸化物蛍光体エピタキシャル薄膜、多結晶体および計算結果より得られた多結晶体のx線回折パターンを示す図、図2は、ターゲット材料としてSr2(Sn1-x Tix)O4: x=0.05を用い、パルスレーザー堆積法による850℃で成長後、および大気中1000℃、1100℃、1200℃で熱処理後の酸化物蛍光体エピタキシャル薄膜の蛍光特性の測定結果を示す図、図3は、ターゲット材料としてSr2(Sn1-x Tix)O4: x=0.05を用い、パルスレーザー堆積法による800℃で成長後、および大気中1000℃、1100℃、1200℃で熱処理後の酸化物蛍光体エピタキシャル薄膜の蛍光特性の測定結果を示す図、図4は、ターゲット材料としてSr2(Sn1-x Tix)O4: x=0.05を用い、パルスレーザー堆積法による600℃で成長後、および大気中1000℃で熱処理後の酸化物蛍光体エピタキシャル薄膜の蛍光特性の測定結果を示す図、図5は、図2ないし図4の蛍光特性の測定結果をまとめた図である。 A first embodiment of the present invention will be described with reference to FIGS. Figure 1 shows the oxide phosphor epitaxial thin film, polycrystal, and calculation results when grown at 800 ° C by pulsed laser deposition method using Sr 2 (Sn 1-x Ti x ) O 4 : x = 0.05 as the target material. Fig. 2 shows the x-ray diffraction pattern of the polycrystal obtained, and Fig. 2 shows that the target material is Sr 2 (Sn 1-x Ti x ) O 4 : x = 0.05 at 850 ° C by pulsed laser deposition. Fig. 3 shows the measurement results of the fluorescence characteristics of oxide phosphor epitaxial thin films after growth and after heat treatment at 1000 ° C, 1100 ° C, and 1200 ° C in the atmosphere. Fig. 3 shows Sr 2 (Sn 1-x Ti x ) Shows the measurement results of the fluorescence properties of oxide phosphor epitaxial thin films after growth at 800 ° C by pulsed laser deposition using O 4 : x = 0.05, and after heat treatment at 1000 ° C, 1100 ° C, and 1200 ° C in air FIG, 4, Sr 2 (Sn 1-x Ti x) O 4 as the target material: with x = 0.05, pulsed laser deposition Fig. 5 shows the measurement results of the fluorescence characteristics of oxide phosphor epitaxial thin films after growth at 600 ° C and after heat treatment at 1000 ° C in the air, and Fig. 5 summarizes the measurement results of the fluorescence characteristics of Figs. FIG.

特許文献3には、多結晶体Snペロブスカイト酸化物により、赤、青、緑色の蛍光特性が得られること、および多結晶体Sr2(Sn1-x Tix)O4:0.01≦x≦0.1において青色蛍光が得られることが示されている。これらの知見に基づいて、本実施例の発明で得られる酸化物蛍光体エピタキシャル薄膜は、ターゲット材料としてSr2(Sn1-x Tix)O4:0.01≦x≦0.1を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成膜したものである。 Patent Document 3 discloses that a polycrystalline Sn perovskite oxide provides red, blue, and green fluorescence characteristics, and that a polycrystalline Sr 2 (Sn 1-x Ti x ) O 4 : 0.01 ≦ x ≦ 0.1 Shows that blue fluorescence is obtained. Based on these findings, the oxide phosphor epitaxial thin film obtained by the invention of this example is obtained by using a pulse laser deposition method with Sr 2 (Sn 1-x Ti x ) O 4 : 0.01 ≦ x ≦ 0.1 as a target material. The film is formed on the substrate by epitaxial growth at a temperature of 600 ° C. or higher and 800 ° C. or lower.

以下においては、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x=0.05の場合について述べる。パルスレーザー堆積法によって前記化学組成のターゲットを基板温度が600℃、800℃、850℃において、エピタキシャル成長により基板上に成膜した。その後、成膜された酸化物蛍光体エピタキシャル薄膜の結晶構造を調べるためx線回折パターンを測定した。その結果、全ての温度で(110)薄膜が形成されていることからエピタキシャル成長が確認された。   In the following, a case where x = 0.05 is obtained in which the best fluorescence characteristic is obtained in the fluorescence characteristics of the chemical composition. A target having the above chemical composition was formed on the substrate by epitaxial growth at a substrate temperature of 600 ° C., 800 ° C., and 850 ° C. by a pulse laser deposition method. Thereafter, an x-ray diffraction pattern was measured in order to investigate the crystal structure of the formed oxide phosphor epitaxial thin film. As a result, (110) thin films were formed at all temperatures, confirming epitaxial growth.

図1は、典型的例として800℃で成長時の酸化物蛍光体エピタキシャル薄膜のx線回折パターンを示す図であり、同図に示すように、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(110)方位のみが出現していることから、(110)方位にエピタキシャル成長していることが分かる。   FIG. 1 is a diagram showing an x-ray diffraction pattern of an oxide phosphor epitaxial thin film grown at 800 ° C. as a typical example. As shown in FIG. On the other hand, since only the (110) orientation appears in the thin film pattern, it can be seen that the thin film pattern is epitaxially grown in the (110) orientation.

図2は、酸化物蛍光体エピタキシャル薄膜を850℃で成長後、および大気中1000℃、1100℃、1200℃で熱処理後の蛍光特性の測定結果を示す図であり、同図に示すように、それぞれにおいて410nmの波長で蛍光特性が得られていることが分かる。特に、1000℃の熱処理によって蛍光特性が顕著に向上していることから、1000℃による熱処理が最適と考えられる。   FIG. 2 is a diagram showing measurement results of fluorescence characteristics after growing an oxide phosphor epitaxial thin film at 850 ° C. and after heat treatment at 1000 ° C., 1100 ° C., and 1200 ° C. in the atmosphere. It can be seen that fluorescence characteristics are obtained at a wavelength of 410 nm in each. In particular, since the fluorescence characteristics are remarkably improved by the heat treatment at 1000 ° C., the heat treatment at 1000 ° C. is considered optimal.

図3は、酸化物蛍光体エピタキシャル薄膜を800℃で成長後、および大気中1000℃、1100℃、1200℃で熱処理後の蛍光特性の測定結果を示す図であり、同図に示すように、1000℃の熱処理によって、蛍光特性が顕著に改善していることが分かる。これらの結果から、薄膜成長後、大気中1000℃で熱処理を行うことによって、蛍光特性が顕著に向上することが分かる。   FIG. 3 is a diagram showing measurement results of fluorescence characteristics after growing an oxide phosphor epitaxial thin film at 800 ° C. and after heat treatment at 1000 ° C., 1100 ° C., and 1200 ° C. in the atmosphere. It can be seen that the fluorescence characteristics are remarkably improved by the heat treatment at 1000 ° C. From these results, it can be seen that the fluorescence characteristics are remarkably improved by performing a heat treatment at 1000 ° C. in the atmosphere after the thin film is grown.

図4は、酸化物蛍光体エピタキシャル薄膜を600℃で成長後、および大気中1000℃で熱処理後の蛍光特性の測定結果を示す図であり、同図に示すように、大気中1000℃で熱処理を行うことによって、蛍光特性が顕著に向上していることが分かる。   FIG. 4 is a diagram showing the measurement results of the fluorescence characteristics after growing the oxide phosphor epitaxial thin film at 600 ° C. and after heat treatment at 1000 ° C. in the atmosphere. As shown in FIG. It can be seen that the fluorescence characteristics are remarkably improved by performing.

図5は、図2ないし図4に示した測定結果を総合的にまとめた図である。同図に示すように、最も良好な蛍光特性は、600℃で上記化学組成のターゲットをパルスレーザー堆積法によって成膜後、大気中1000℃で熱処理することによって得られることが分かる。大気中には20%前後の酸素が含有されていることから、酸素中における熱処理でも同様の結果が得られると考えられる。最適な化学組成でこれらの結果が得られたことから、Sr2(Sn1-x
Tix)O4:0.01≦x≦0.1においても、同様の蛍光特性が得られると考えられる。
FIG. 5 is a diagram summarizing the measurement results shown in FIGS. As shown in the figure, it can be seen that the best fluorescence characteristics can be obtained by heat-treating the target having the above chemical composition at 600 ° C. at 1000 ° C. in the atmosphere after film formation by pulse laser deposition. Since about 20% of oxygen is contained in the atmosphere, it is considered that the same result can be obtained by heat treatment in oxygen. Since these results were obtained with an optimal chemical composition, Sr 2 (Sn 1-x
It is considered that similar fluorescence characteristics can be obtained even when Ti x ) O 4 : 0.01 ≦ x ≦ 0.1.

本発明の実施例2を図6および図7を用いて説明する。図6は、ターゲット材料としてPr0.002(Ca0.6Sr0.40.998TiO3を用い、パルスレーザー堆積法による800℃で成長時の酸化物蛍光体エピタキシャル薄膜のx線回折パターンを示す図、図7は、ターゲット材料としてPr0.002(Ca0.6Sr0.40.998TiO3を用い、パルスレーザー堆積法による600℃で成長後、および大気中1000℃、1100℃で熱処理後の酸化物蛍光体エピタキシャル薄膜の蛍光特性の測定結果を示す図である。 A second embodiment of the present invention will be described with reference to FIGS. Figure 6 shows the x-ray diffraction pattern of an oxide phosphor epitaxial thin film grown at 800 ° C by pulse laser deposition using Pr 0.002 (Ca 0.6 Sr 0.4 ) 0.998 TiO 3 as the target material. Fluorescence of oxide phosphor epitaxial thin films using Pr 0.002 (Ca 0.6 Sr 0.4 ) 0.998 TiO 3 as a target material, grown at 600 ° C. by pulsed laser deposition, and after heat treatment at 1000 ° C. and 1100 ° C. in air It is a figure which shows the measurement result of a characteristic.

非特許文献7には、多結晶体、Pry(CaxSr1-x1-yTiO3:0.1≦x≦1.0、0.0005≦y≦0.05において赤色蛍光特性が得られることが示されている。これらの知見に基づいて、本実施例の発明で得られる酸化物蛍光体エピタキシャル薄膜は、ターゲット材料として、Pry(CaxSr1-x1-yTiO3:0.1≦x≦1.0、0.0005≦y≦0.05を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成膜したものである。 Non-Patent Document 7 shows that red fluorescence characteristics can be obtained in a polycrystal, Pr y (Ca x Sr 1-x ) 1-y TiO 3 : 0.1 ≦ x ≦ 1.0, 0.0005 ≦ y ≦ 0.05. Yes. Based on these findings, the oxide phosphor epitaxial thin film obtained by the invention of the present example has Pr y (Ca x Sr 1-x ) 1-y TiO 3 : 0.1 ≦ x ≦ 1.0, 0.0005 as a target material. ≦ y ≦ 0.05 is formed on a substrate by epitaxial growth at a temperature of 600 ° C. or more and 800 ° C. or less by a pulse laser deposition method.

以下においては、前記非特許文献7において化学組成において最も良い蛍光特性が得られるx=0.6、y=0.002の場合について述べる。パルスレーザー堆積法によって前記化学組成のターゲットを基板温度が600℃および800℃において、エピタキシャル成長により基板上に成膜した。その後、成膜された酸化物蛍光体エピタキシャル薄膜の結晶構造を調べるためx線回折パターンを測定した。   In the following, the case where x = 0.6 and y = 0.002 at which the best fluorescence characteristics are obtained in the chemical composition in Non-Patent Document 7 will be described. A target having the above chemical composition was formed on the substrate by epitaxial growth at a substrate temperature of 600 ° C. and 800 ° C. by a pulse laser deposition method. Thereafter, an x-ray diffraction pattern was measured in order to investigate the crystal structure of the formed oxide phosphor epitaxial thin film.

図6は、典型的例として800℃で成長時の酸化物蛍光体エピタキシャル薄膜のx線回折パターンを示す図であり、同図は10度から80度までのx線回折パターンであり、(001)薄膜が形成されていることからエピタキシャル成長した薄膜であることが分かる。   FIG. 6 is a diagram showing an x-ray diffraction pattern of an oxide phosphor epitaxial thin film grown at 800 ° C. as a typical example, which is an x-ray diffraction pattern from 10 degrees to 80 degrees, (001 ) Since the thin film is formed, it is understood that the thin film is epitaxially grown.

図7は、酸化物蛍光体エピタキシャル薄膜を600℃で成膜後、および大気中1000℃、1100℃で熱処理後の蛍光特性の測定結果を示す図であり、同図に示すように、それぞれにおいて620nmの波長で蛍光特性が得られていることが分かる。酸化物蛍光体エピタキシャル薄膜の成長後のみの蛍光特性よりも大気中1000℃で熱処理後の薄膜、またはそれよりも高温の大気中1100℃で熱処理後の薄膜において蛍光特性が顕著に向上していることが分かる。なお、大気中1200℃で熱処理後の薄膜は、この材料を使用しても蛍光特性が劣化することが分かった。大気中には20%前後の酸素が含有されていることから、酸素中における熱処理でも同様の結果が得られると考えられる。最適な化学組成でこれらの結果が得られたことから、Pry(CaxSr1-x1-yTiO3:0.1≦x≦1.0、0.0005≦y≦0.05の領域でも蛍光特性が得られると考えられる。 FIG. 7 is a diagram showing the measurement results of the fluorescence characteristics after the oxide phosphor epitaxial thin film was formed at 600 ° C. and after heat treatment at 1000 ° C. and 1100 ° C. in the atmosphere. As shown in FIG. It can be seen that fluorescence characteristics are obtained at a wavelength of 620 nm. Fluorescence properties are significantly improved in the thin film after heat treatment at 1000 ° C in the atmosphere or in the thin film after heat treatment at 1100 ° C in the air at a higher temperature than the fluorescence property only after the growth of oxide phosphor epitaxial thin film I understand that. In addition, it was found that the thin film after heat treatment at 1200 ° C. in the atmosphere deteriorates the fluorescence characteristics even when this material is used. Since about 20% of oxygen is contained in the atmosphere, it is considered that the same result can be obtained by heat treatment in oxygen. Since these results were obtained with an optimum chemical composition, Pr y (Ca x Sr 1-x ) 1-y TiO 3 : Fluorescence characteristics can be obtained even in the region of 0.1 ≦ x ≦ 1.0 and 0.0005 ≦ y ≦ 0.05 it is conceivable that.

本発明の実施例3を図8ないし図10を用いて説明する。図8は、ターゲット材料として(Sr1-x Eu x)2(Sn1-y Ti y)O4:x=0.02、y=0.1を用い、パルスレーザー堆積法による600℃で成長時の酸化物蛍光体エピタキシャル薄膜および計算結果より得られた多結晶体のx線回折パターンを示す図、図9は、ターゲット材料として(Sr1-x Eu x)2(Sn1-y Ti y)O4:x=0.02、y=0.1を用い、パルスレーザー堆積法による800℃で成長時の酸化物蛍光体エピタキシャル薄膜および計算結果より得られた多結晶体のx線回折パターンを示す図、図10は、ターゲット材料として(Sr1-x Eu x)2(Sn1-y Ti y)O4:x=0.02、y=0.1を用い、パルスレーザー堆積法による600℃、800℃で成長後、および大気中1000℃、1100℃、1,200℃で熱処理後の酸化物蛍光体エピタキシャル薄膜の蛍光特性の測定結果を示す図である。 A third embodiment of the present invention will be described with reference to FIGS. Figure 8 shows the oxides grown at 600 ° C by pulsed laser deposition using (Sr 1-x Eu x ) 2 (Sn 1-y Ti y ) O 4 : x = 0.02, y = 0.1 as the target material. FIG. 9 shows an x-ray diffraction pattern of a polycrystalline body obtained from a phosphor epitaxial thin film and calculation results. FIG. 9 shows (Sr 1-x Eu x ) 2 (Sn 1-y Ti y ) O 4 : FIG. 10 is a diagram showing an x-ray diffraction pattern of an oxide phosphor epitaxial thin film grown at 800 ° C. by a pulsed laser deposition method using x = 0.02 and y = 0.1 and a polycrystal obtained from a calculation result, (Sr 1-x Eu x ) 2 (Sn 1-y Ti y ) O 4 : x = 0.02, y = 0.1 as target material, grown at 600 ° C, 800 ° C by pulsed laser deposition method, and in the atmosphere FIG. 6 is a diagram showing the measurement results of the fluorescence characteristics of oxide phosphor epitaxial thin films after heat treatment at 1000 ° C., 1100 ° C., and 1,200 ° C.

特許文献3には、多結晶体Snペロブスカイト酸化物により、赤、青、緑色の蛍光特性が得られること、および多結晶体(Sr1-x Eu x)2(Sn1-y Ti y)O4:0.01≦x≦0.1、0.01≦y≦0.2において赤色蛍光が得られたことが示されている。これらの知見に基づいて、本実施例の発明で得られる酸化物蛍光体エピタキシャル薄膜は、ターゲット材料として(Sr1-x Eu x)2(Sn1-y Ti y)O4:0.01≦x≦0.1、0.01≦y≦0.2を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成膜されたものである。 Patent Document 3 discloses that red, blue and green fluorescent properties can be obtained by polycrystalline Sn perovskite oxide, and that polycrystalline (Sr 1-x Eu x ) 2 (Sn 1-y Ti y ) O 4 : It is shown that red fluorescence was obtained at 0.01 ≦ x ≦ 0.1 and 0.01 ≦ y ≦ 0.2. Based on these findings, the oxide phosphor epitaxial thin film obtained in the invention of the present example is used as a target material (Sr 1-x Eu x ) 2 (Sn 1-y Ti y ) O 4 : 0.01 ≦ x ≦ 0.1 and 0.01 ≦ y ≦ 0.2 were formed on the substrate by epitaxial growth at a temperature of 600 ° C. or higher and 800 ° C. or lower by the pulse laser deposition method.

以下においては、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x=0.02、y=0.1の場合について述べる。パルスレーザー堆積法によって前記化学組成のターゲットを基板温度が600℃および800℃おいて、エピタキシャル成長により基板上に成膜した。その後、成膜された酸化物蛍光体エピタキシャル薄膜の結晶構造を調べるためx線回折パターンを測定した。   In the following, a case where x = 0.02 and y = 0.1 are obtained in which the best fluorescence characteristic is obtained in the fluorescence characteristics of the chemical composition. A target having the above chemical composition was formed on the substrate by epitaxial growth at a substrate temperature of 600 ° C. and 800 ° C. by a pulse laser deposition method. Thereafter, an x-ray diffraction pattern was measured in order to investigate the crystal structure of the formed oxide phosphor epitaxial thin film.

図8は、600℃で成長時の酸化物蛍光体エピタキシャル薄膜のx線回折パターンを示す図であり、同図に示すように、計算結果に対し、薄膜のx線回折パターンは(110)方位に配向した薄膜が成長していることから、エピタキシャル成長した薄膜であることが分かる。   FIG. 8 is a diagram showing an x-ray diffraction pattern of an oxide phosphor epitaxial thin film grown at 600 ° C. As shown in FIG. 8, the x-ray diffraction pattern of the thin film is (110) azimuth relative to the calculation result. It can be seen that the thin film is epitaxially grown from the fact that the thin film oriented in the direction is grown.

図9は、800℃で成長時の酸化物蛍光体エピタキシャル薄膜のx線回折パターンを示す図であり、同図に示すように、計算結果に対し、薄膜のx線回折パターンは(110)方位に配向した薄膜が成長していることから、エピタキシャル成長した薄膜であることが分かる。   FIG. 9 is a diagram showing an x-ray diffraction pattern of an oxide phosphor epitaxial thin film grown at 800 ° C. As shown in FIG. 9, the x-ray diffraction pattern of the thin film is (110) azimuth relative to the calculation result. It can be seen that the thin film is epitaxially grown from the fact that the thin film oriented in the direction is grown.

図10は、酸化物蛍光体エピタキシャル薄膜を800℃で成膜後、および大気中1000℃、1100℃、1200℃で熱処理後の蛍光特性の測定結果を示す図であり、同図に示すように、それぞれにおいて赤色を示す590 nmから610nmの波長で蛍光特性が得られていることが分かる。特に、600℃で成膜後、大気中1000℃で熱処理した蛍光特性が最も強度が強いことから、最適条件であることが分かる。大気中には20%前後の酸素が含有されていることから、酸素中における熱処理でも同様の結果が得られると考えられる。最適な化学組成でこれらの結果が得られたことから、(Sr1-x Eu x)2(Sn1-y Ti y)O4:0.01≦x≦0.1、0.01≦y≦0.2の領域でも蛍光特性が得られると考えられる。 FIG. 10 is a diagram showing measurement results of fluorescence characteristics after forming an oxide phosphor epitaxial thin film at 800 ° C. and after heat treatment at 1000 ° C., 1100 ° C., and 1200 ° C. in the atmosphere. It can be seen that fluorescence characteristics are obtained at wavelengths of 590 nm to 610 nm showing red in each. In particular, it can be seen that the optimum conditions are obtained because the fluorescence characteristics after film formation at 600 ° C. and heat treatment at 1000 ° C. in the atmosphere have the strongest intensity. Since about 20% of oxygen is contained in the atmosphere, it is considered that the same result can be obtained by heat treatment in oxygen. Since these results were obtained with the optimum chemical composition, (Sr 1-x Eu x ) 2 (Sn 1-y Ti y ) O 4 : Fluorescence was observed even in the region of 0.01 ≦ x ≦ 0.1 and 0.01 ≦ y ≦ 0.2. It is thought that characteristics can be obtained.

本発明の実施例4を図11ないし図13を用いて説明する。図11は、ターゲット材料として{(Ca1-x Mg x) 1-yTby}SnO3:x=0.03、y=0.005を用い、パルスレーザー堆積法による600℃で成長時の酸化物蛍光体エピタキシャル薄膜および計算結果より得られた多結晶体のx線回折パターンを示す図、図12は、ターゲット材料として{(Ca1-x Mg x) 1-yTby}SnO3:x=0.03、y=0.005を用い、パルスレーザー堆積法による800℃で成長時の酸化物蛍光体エピタキシャル薄膜および計算結果より得られた多結晶体のx線回折パターンを示す図、図13は、ターゲット材料として{(Ca1-x Mg x) 1-yTby}SnO3:x=0.03、y=0.005を用い、パルスレーザー堆積法による600℃、800℃で成長後、および大気中1000℃、1100℃、1200℃で熱処理後の酸化物蛍光体エピタキシャル薄膜の蛍光特性の測定結果を示す図である。 A fourth embodiment of the present invention will be described with reference to FIGS. Fig. 11 shows the oxide phosphor grown at 600 ° C by pulsed laser deposition using {(Ca 1-x Mg x ) 1-y Tb y } SnO 3 : x = 0.03, y = 0.005 as the target material. FIG. 12 shows an x-ray diffraction pattern of the polycrystalline thin film obtained from the epitaxial thin film and the calculation result. FIG. 12 shows {(Ca 1-x Mg x ) 1-y Tb y } SnO 3 : x = 0.03 as a target material. FIG. 13 shows an x-ray diffraction pattern of an oxide phosphor epitaxial thin film grown at 800 ° C. by a pulse laser deposition method using y = 0.005 and a polycrystal obtained from the calculation result. FIG. (Ca 1-x Mg x ) 1-y Tb y } SnO 3 : x = 0.03, y = 0.005, after growth at 600 ° C. and 800 ° C. by pulsed laser deposition, and in the atmosphere 1000 ° C., 1100 ° C., It is a figure which shows the measurement result of the fluorescence characteristic of the oxide fluorescent substance epitaxial thin film after heat processing at 1200 degreeC.

特許文献3には、多結晶体Snペロブスカイト酸化物により、赤、青、緑色の蛍光特性が得られること、および多結晶体{(Ca1-x Mg x) 1-yTby}SnO3:0.01≦x≦0.2、0.001≦y≦0.2において緑色蛍光が得られることが示されている。これらの知見に基づいて、本実施例の発明で得られる酸化物蛍光体エピタキシャル薄膜は、ターゲット材料として{(Ca1-x Mg x) 1-yTby}SnO3:0.01≦x≦0.2、0.001≦y≦0.2を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成膜したものである。 Patent Document 3 discloses that the polycrystalline Sn perovskite oxide provides red, blue, and green fluorescence characteristics, and that the polycrystalline {(Ca 1-x Mg x ) 1-y Tb y } SnO 3 : It is shown that green fluorescence is obtained when 0.01 ≦ x ≦ 0.2 and 0.001 ≦ y ≦ 0.2. Based on these findings, the oxide phosphor epitaxial thin film obtained by the invention of the present example, the target material is {(Ca 1-x Mg x ) 1-y Tb y } SnO 3 : 0.01 ≦ x ≦ 0.2, 0.001 ≦ y ≦ 0.2 was formed on the substrate by epitaxial growth at a temperature of 600 ° C. or more and 800 ° C. or less by the pulse laser deposition method.

以下においては、特許文献3に示す化学組成において最も良い蛍光特性が得られるx=0.03、y=0.005の場合について述べる。パルスレーザー堆積法によって前記化学組成のターゲットを基板温度が600℃および800℃において、エピタキシャル成長により基板上に成膜した。その後、成膜された酸化物蛍光体エピタキシャル薄膜の結晶構造を調べるためx線回折パターンを測定した。   In the following, the case where x = 0.03 and y = 0.005 are obtained in which the best fluorescence characteristics can be obtained with the chemical composition shown in Patent Document 3. A target having the above chemical composition was formed on the substrate by epitaxial growth at a substrate temperature of 600 ° C. and 800 ° C. by a pulse laser deposition method. Thereafter, an x-ray diffraction pattern was measured in order to investigate the crystal structure of the formed oxide phosphor epitaxial thin film.

図11は、600℃で成長時の酸化物蛍光体エピタキシャル薄膜のx線回折パターンを示す図であり、同図に示すように、計算結果に対し、薄膜のx線回折パターンは(110)方位に配向した薄膜が成長していることから、エピタキシャル成長した薄膜であることが分かる。   FIG. 11 is a diagram showing an x-ray diffraction pattern of an oxide phosphor epitaxial thin film grown at 600 ° C. As shown in FIG. 11, the x-ray diffraction pattern of the thin film is (110) azimuth relative to the calculation result. It can be seen that the thin film is epitaxially grown from the fact that the thin film oriented in the direction is grown.

図12は、800℃で成長時の酸化物蛍光体エピタキシャル薄膜のx線回折パターンを示す図であり、同図に示すように、計算結果に対し、薄膜のx線回折パターンは(110)方位に配向した薄膜が成長していることから、エピタキシャル成長した薄膜であることが分かる。   FIG. 12 is a diagram showing an x-ray diffraction pattern of an oxide phosphor epitaxial thin film grown at 800 ° C. As shown in FIG. 12, the x-ray diffraction pattern of the thin film is (110) azimuth relative to the calculation result. It can be seen that the thin film is epitaxially grown from the fact that the thin film oriented in the direction is grown.

図13は、酸化物蛍光体エピタキシャル薄膜を600℃、800℃で成膜後、大気中1000℃、1100℃、1200℃で熱処理後の蛍光特性の測定結果を示す図であり、同図に示すように、薄膜の蛍光特性測定の結果、800℃で成膜直後では、良好な結果は得られなかった。800℃で成膜後、大気中1000℃、1100℃、1200で熱処理を行った結果、および、600℃で成膜後、大気中1100℃で熱処理を行った結果、全ての場合において540nmの波長において顕著な蛍光特性が得られていることが分かる。特に、600℃で成膜後、大気中1100℃で熱処理を行った場合、最も顕著な蛍光特性が得られることが分かる。大気中には20%前後の酸素が含有されていることから、酸素中における熱処理でも同様の結果が得られると考えられる。最適な化学組成でこれらの結果が得られたことから、{(Ca1-x Mg x) 1-yTby}SnO3:0.01≦x≦0.2、0.001≦y≦0.2の領域でも蛍光特性が得られると考えられる。 FIG. 13 is a diagram showing measurement results of fluorescence characteristics after forming an oxide phosphor epitaxial thin film at 600 ° C. and 800 ° C., and after heat treatment at 1000 ° C., 1100 ° C., and 1200 ° C. in the atmosphere. Thus, as a result of measuring the fluorescence characteristics of the thin film, a good result was not obtained immediately after film formation at 800 ° C. As a result of heat treatment at 1000 ° C, 1100 ° C and 1200 ° C in the air after film formation at 800 ° C, and as a result of heat treatment at 1100 ° C in air after film formation at 600 ° C, a wavelength of 540 nm was used in all cases. It can be seen that a remarkable fluorescence characteristic is obtained. In particular, it can be seen that when the film is formed at 600 ° C. and then heat-treated at 1100 ° C. in the atmosphere, the most remarkable fluorescence characteristics can be obtained. Since about 20% of oxygen is contained in the atmosphere, it is considered that the same result can be obtained by heat treatment in oxygen. Since these results were obtained with an optimal chemical composition, {(Ca 1-x Mg x ) 1-y Tb y } SnO 3 : Fluorescence characteristics were also obtained in the region of 0.01 ≦ x ≦ 0.2 and 0.001 ≦ y ≦ 0.2. It is thought that it is obtained.

本発明の実施例5を図14および図15を用いて説明する。図14は、ターゲット材料として(PrxSr1-x)SnO3:x=0.005を用い、パルスレーザー堆積法による800℃で成長時の酸化物蛍光体エピタキシャル薄膜および計算結果より得られた多結晶体のx線回折パターンを示す図、図15は、ターゲット材料として(PrxSr1-x)SnO3:x=0.005を用い、パルスレーザー堆積法による600℃、800℃で成長後、および大気中1000℃、1100℃で熱処理後の酸化物蛍光体エピタキシャル薄膜の蛍光特性の測定結果を示す図である。 A fifth embodiment of the present invention will be described with reference to FIGS. FIG. 14 shows the polycrystalline oxide obtained from the oxide phosphor epitaxial thin film grown at 800 ° C. by pulsed laser deposition method and the calculation result using (Pr x Sr 1-x ) SnO 3 : x = 0.005 as the target material. FIG. 15 shows an x-ray diffraction pattern of the body, and (Pr x Sr 1-x ) SnO 3 : x = 0.005 is used as a target material, grown at 600 ° C. and 800 ° C. by the pulse laser deposition method, and the atmosphere It is a figure which shows the measurement result of the fluorescence characteristic of the oxide fluorescent substance epitaxial thin film after heat processing inside 1000 degreeC and 1100 degreeC.

特許文献3には、多結晶体Snペロブスカイト酸化物により、赤、青、緑色の蛍光特性が得られること、および多結晶体(PrxSr1-x)SnO3:0.001≦x≦0.2において波長490nm±10nm蛍光が得られることが示されている。これらの知見に基づいて、本実施例の発明で得られる酸化物蛍光体エピタキシャル薄膜は、ターゲット材料として(PrxSr1-x)SnO3:0.001≦x≦0.2を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成膜したものである。 Patent Document 3 describes that red, blue, and green fluorescence characteristics can be obtained by polycrystalline Sn perovskite oxide, and that polycrystalline (Pr x Sr 1-x ) SnO 3 : 0.001 ≦ x ≦ 0.2 wavelength. It has been shown that 490 nm ± 10 nm fluorescence can be obtained. Based on these findings, the oxide phosphor epitaxial thin film obtained by the invention of this example is obtained by applying (Pr x Sr 1-x ) SnO 3 : 0.001 ≦ x ≦ 0.2 as a target material by a pulse laser deposition method. The film is formed on the substrate by epitaxial growth at a temperature of from ℃.

以下においては、特許文献3に示す化学組成において最も良い蛍光特性が得られるx=0.005の場合について述べる。パルスレーザー堆積法によって前記化学組成のターゲットを基板温度が600℃および800℃において、エピタキシャル成長により基板上に成膜した。その後、800℃で成膜された酸化物蛍光体エピタキシャル薄膜の結晶構造を調べるためx線回折パターンを測定した。   In the following, the case where x = 0.005 is obtained in which the best fluorescence characteristic is obtained with the chemical composition shown in Patent Document 3. A target having the above chemical composition was formed on the substrate by epitaxial growth at a substrate temperature of 600 ° C. and 800 ° C. by a pulse laser deposition method. Thereafter, an x-ray diffraction pattern was measured in order to examine the crystal structure of the oxide phosphor epitaxial thin film formed at 800 ° C.

図14は、800℃で成長時の酸化物蛍光体エピタキシャル薄膜のx線回折パターンを示す図であり、同図に示すように、計算結果に対し、薄膜のx線回折パターンは(110)方位に配向した薄膜が成長していることから、エピタキシャル成長した薄膜であることが分かる。   FIG. 14 is a diagram showing an x-ray diffraction pattern of an oxide phosphor epitaxial thin film grown at 800 ° C. As shown in FIG. 14, the x-ray diffraction pattern of the thin film is (110) azimuth relative to the calculation result. It can be seen that the thin film is epitaxially grown from the fact that the thin film oriented in the direction is grown.

図15は、酸化物蛍光体エピタキシャル薄膜を600℃、800℃で成膜後、大気中1000℃、1100℃で熱処理後の蛍光特性の測定結果を示す図であり、同図に示すように、薄膜の蛍光特性測定の結果、600℃、800℃で成膜直後では、良好な結果は得られなかった。600℃、800℃で成膜後、大気中1000℃、1100℃で熱処理を行った結果、蛍光特性が改善し、490nmの波長において顕著な蛍光特性が得られていることが分かる。特に、600℃で成膜後、大気中1100℃で熱処理を行った場合、最も顕著な蛍光特性が得られることが分かる。大気中には20%前後の酸素が含有されていることから、酸素中における熱処理でも同様の結果が得られると考えられる。最適な化学組成でこれらの結果が得られたことから、(PrxSr1-x)SnO3:0.001≦x≦0.2の領域でも蛍光特性が得られると考えられる。 FIG. 15 is a diagram showing the measurement results of the fluorescence characteristics after forming the oxide phosphor epitaxial thin film at 600 ° C. and 800 ° C., and after heat treatment at 1000 ° C. and 1100 ° C. in the atmosphere. As a result of measuring the fluorescence characteristics of the thin film, good results were not obtained immediately after film formation at 600 ° C. and 800 ° C. As a result of heat treatment at 1000 ° C. and 1100 ° C. in the air after film formation at 600 ° C. and 800 ° C., it can be seen that the fluorescence properties are improved and remarkable fluorescence properties are obtained at a wavelength of 490 nm. In particular, it can be seen that when the film is formed at 600 ° C. and then heat-treated at 1100 ° C. in the atmosphere, the most remarkable fluorescence characteristics can be obtained. Since about 20% of oxygen is contained in the atmosphere, it is considered that the same result can be obtained by heat treatment in oxygen. Since these results were obtained with an optimal chemical composition, it is considered that fluorescence characteristics can be obtained even in the region of (Pr x Sr 1-x ) SnO 3 : 0.001 ≦ x ≦ 0.2.

ターゲット材料としてSr2(Sn1-x Tix)O4: x=0.05を用い、パルスレーザー堆積法による800℃で成長時の酸化物蛍光体エピタキシャル薄膜、多結晶体および計算結果より得られた多結晶体のx線回折パターンを示す図である。Using Sr 2 (Sn 1-x Ti x ) O 4 : x = 0.05 as the target material, obtained from the oxide phosphor epitaxial thin film, polycrystal, and calculation results grown at 800 ° C by pulsed laser deposition method It is a figure which shows the x-ray-diffraction pattern of a polycrystal. ターゲット材料としてSr2(Sn1-x Tix)O4: x=0.05を用い、パルスレーザー堆積法による850℃で成長後、および大気中1000℃、1100℃、1200℃で熱処理後の酸化物蛍光体エピタキシャル薄膜の蛍光特性の測定結果を示す図である。Sr 2 (Sn 1-x Ti x ) O 4 : x = 0.05 as the target material, grown at 850 ° C by pulsed laser deposition, and after heat treatment at 1000 ° C, 1100 ° C, and 1200 ° C in air It is a figure which shows the measurement result of the fluorescence characteristic of a fluorescent substance epitaxial thin film. ターゲット材料としてSr2(Sn1-x Tix)O4: x=0.05を用い、パルスレーザー堆積法による800℃で成長後、および大気中1000℃、1100℃、1200℃で熱処理後の酸化物蛍光体エピタキシャル薄膜の蛍光特性の測定結果を示す図である。Sr 2 (Sn 1-x Ti x ) O 4 : x = 0.05 as target material, grown at 800 ° C by pulsed laser deposition method, and oxide after heat treatment at 1000 ° C, 1100 ° C, 1200 ° C in air It is a figure which shows the measurement result of the fluorescence characteristic of a fluorescent substance epitaxial thin film. ターゲット材料としてSr2(Sn1-x Tix)O4: x=0.05を用い、パルスレーザー堆積法による600℃で成長後、および大気中1000℃で熱処理後の酸化物蛍光体エピタキシャル薄膜の蛍光特性の測定結果を示す図である。Fluorescence of oxide phosphor epitaxial thin films using Sr 2 (Sn 1-x Ti x ) O 4 : x = 0.05 as a target material, grown at 600 ° C by pulsed laser deposition, and heat-treated at 1000 ° C in air It is a figure which shows the measurement result of a characteristic. 図2ないし図4の蛍光特性の測定結果をまとめた図である。FIG. 5 summarizes the measurement results of the fluorescence characteristics of FIGS. ターゲット材料としてPr0.002(Ca0.6Sr0.40.998TiO3を用い、パルスレーザー堆積法による800℃で成長後の酸化物蛍光体エピタキシャル薄膜のx線回折パターンを示す図である。The Pr 0.002 (Ca 0.6 Sr 0.4) 0.998 TiO 3 used as a target material is a diagram showing an x-ray diffraction pattern of the oxide phosphor epitaxial thin film after growth at 800 ° C. by pulsed laser deposition. ターゲット材料としてPr0.002(Ca0.6Sr0.40.998TiO3を用い、パルスレーザー堆積法による600℃で成長後、および大気中1000℃、1100℃で熱処理後の酸化物蛍光体エピタキシャル薄膜の蛍光特性の測定結果を示す図である。Pr 0.002 (Ca 0.6 Sr 0.4 ) 0.998 TiO 3 as the target material, grown at 600 ° C by pulsed laser deposition, and after the heat treatment at 1000 ° C and 1100 ° C in the atmosphere, the fluorescence characteristics of the oxide phosphor epitaxial thin film It is a figure which shows a measurement result. ターゲット材料として(Sr1-x Eu x)2(Sn1-y Ti y)O4:x=0.02、y=0.1を用い、パルスレーザー堆積法による600℃で成長時の酸化物蛍光体エピタキシャル薄膜および計算結果より得られた多結晶体のx線回折パターンを示す図である。(Sr 1-x Eu x ) 2 (Sn 1-y Ti y ) O 4 : x = 0.02, y = 0.1 as the target material, oxide phosphor epitaxial thin film grown at 600 ° C. by pulsed laser deposition method It is a figure which shows the x-ray-diffraction pattern of the polycrystal obtained from the calculation result. ターゲット材料として(Sr1-x Eu x)2(Sn1-y Ti y)O4:x=0.02、y=0.1を用い、パルスレーザー堆積法による800℃で成長時の酸化物蛍光体エピタキシャル薄膜および計算結果より得られた多結晶体のx線回折パターンを示す図である。(Sr 1-x Eu x ) 2 (Sn 1-y Ti y ) O 4 : x = 0.02, y = 0.1 as the target material, oxide phosphor epitaxial thin film grown at 800 ° C. by pulsed laser deposition method It is a figure which shows the x-ray-diffraction pattern of the polycrystal obtained from the calculation result. ターゲット材料として(Sr1-x Eu x)2(Sn1-y Ti y)O4:x=0.02、y=0.1を用い、パルスレーザー堆積法による600℃、800℃で成長後、および大気中1000℃、1100℃、1,200℃で熱処理後の酸化物蛍光体エピタキシャル薄膜の蛍光特性の測定結果を示す図である。(Sr 1-x Eu x ) 2 (Sn 1-y Ti y ) O 4 : x = 0.02, y = 0.1 as target material, grown at 600 ° C, 800 ° C by pulsed laser deposition method, and in the atmosphere FIG. 6 is a diagram showing the measurement results of the fluorescence characteristics of oxide phosphor epitaxial thin films after heat treatment at 1000 ° C., 1100 ° C., and 1,200 ° C. ターゲット材料として{(Ca1-x Mg x) 1-yTby}SnO3:x=0.03、y=0.005を用い、パルスレーザー堆積法による600℃で成長時の酸化物蛍光体エピタキシャル薄膜および計算結果より得られた多結晶体のx線回折パターンを示す図である。Using {(Ca 1-x Mg x ) 1-y Tb y } SnO 3 : x = 0.03, y = 0.005 as the target material, and the oxide phosphor epitaxial thin film grown at 600 ° C. by pulse laser deposition and calculation It is a figure which shows the x-ray-diffraction pattern of the polycrystal obtained from the result. ターゲット材料として{(Ca1-x Mg x) 1-yTby}SnO3:x=0.03、y=0.005を用い、パルスレーザー堆積法による800℃で成長時の酸化物蛍光体エピタキシャル薄膜および計算結果より得られた多結晶体のx線回折パターンを示す図である。Using {(Ca 1-x Mg x ) 1-y Tb y } SnO 3 : x = 0.03, y = 0.005 as the target material, and the oxide phosphor epitaxial thin film grown at 800 ° C by pulsed laser deposition and calculation It is a figure which shows the x-ray-diffraction pattern of the polycrystal obtained from the result. ターゲット材料として{(Ca1-x Mg x) 1-yTby}SnO3:x=0.03、y=0.005を用い、パルスレーザー堆積法による600℃、800℃で成長後、および大気中1000℃、1100℃、1200℃で熱処理後の酸化物蛍光体エピタキシャル薄膜の蛍光特性の測定結果を示す図である。Using {(Ca 1-x Mg x ) 1-y Tb y } SnO 3 : x = 0.03, y = 0.005 as the target material, grown at 600 ° C and 800 ° C by pulsed laser deposition, and 1000 ° C in the atmosphere FIG. 3 is a graph showing measurement results of fluorescence characteristics of oxide phosphor epitaxial thin films after heat treatment at 1100 ° C. and 1200 ° C. FIG. ターゲット材料として(PrxSr1-x)SnO3:x=0.005を用い、パルスレーザー堆積法による800℃で成長時の酸化物蛍光体エピタキシャル薄膜および計算結果より得られた多結晶体のx線回折パターンを示す図である。Using (Pr x Sr 1-x ) SnO 3 : x = 0.005 as the target material, the oxide phosphor epitaxial thin film grown at 800 ° C by pulsed laser deposition and the x-ray of the polycrystalline material obtained from the calculation results It is a figure which shows a diffraction pattern. ターゲット材料として(PrxSr1-x)SnO3:x=0.005を用い、パルスレーザー堆積法による600℃、800℃で成長後、および大気中1000℃、1100℃で熱処理後の酸化物蛍光体エピタキシャル薄膜の蛍光特性の測定結果を示す図である。(Pr x Sr 1-x ) SnO 3 : x = 0.005 as target material, grown at 600 ° C and 800 ° C by pulsed laser deposition, and after heat treatment at 1000 ° C and 1100 ° C in air It is a figure which shows the measurement result of the fluorescence characteristic of an epitaxial thin film.

Claims (9)

酸化物蛍光材料を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。   An oxide phosphor epitaxial thin film 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 pulse laser deposition using an oxide fluorescent material as a target material. 前記ターゲット材料が、希土類元素、遷移金属元素、アルカリ土類元素をペロブスカイト構造に置換した多結晶ターゲット材料であることを特徴とする請求項1に記載の酸化物蛍光体エピタキシャル薄膜。   2. The oxide phosphor epitaxial thin film according to claim 1, wherein the target material is a polycrystalline target material in which a rare earth element, a transition metal element, or an alkaline earth element is substituted with a perovskite structure. 前記ターゲット材料が、Sr2(Sn1-x Tix)O4:0.01≦x≦0.1であり、青色蛍光が得られることを特徴とする請求項1または請求項2に記載の酸化物蛍光体エピタキシャル薄膜。 3. The oxide phosphor according to claim 1, wherein the target material is Sr 2 (Sn 1-x Ti x ) O 4 : 0.01 ≦ x ≦ 0.1, and blue fluorescence is obtained. Epitaxial thin film. 前記ターゲット材料が、Pry(CaxSr1-x1-yTiO3:0.1≦x≦1.0、0.0005≦y≦0.05であり、赤色蛍光が得られることを特徴とする請求項1または請求項2に記載の酸化物蛍光体エピタキシャル薄膜。 The target material is Pr y (Ca x Sr 1-x ) 1-y TiO 3 : 0.1 ≦ x ≦ 1.0, 0.0005 ≦ y ≦ 0.05, and red fluorescence is obtained. Item 3. The oxide phosphor epitaxial thin film according to Item 2. 前記ターゲット材料が、(Sr1-x Eu x)2(Sn1-y Ti y)O4:0.01≦x≦0.1、0.01≦y≦0.2であり、赤色蛍光が得られることを特徴とする請求項1または請求項2に記載の酸化物蛍光体エピタキシャル薄膜。 The target material is (Sr 1-x Eu x ) 2 (Sn 1-y Ti y ) O 4 : 0.01 ≦ x ≦ 0.1, 0.01 ≦ y ≦ 0.2, and red fluorescence is obtained. Item 3. The oxide phosphor epitaxial thin film according to Item 1 or 2. 前記ターゲット材料が、{(Ca1-x Mg x) 1-yTby}SnO3:0.01≦x≦0.2、0.001≦y≦0.2であり、緑色蛍光が得られることを特徴とする請求項1または請求項2に記載の酸化物蛍光体エピタキシャル薄膜。 2. The target material is {(Ca 1−x Mg x ) 1−y Tb y } SnO 3 : 0.01 ≦ x ≦ 0.2, 0.001 ≦ y ≦ 0.2, and green fluorescence is obtained. 3. The oxide phosphor epitaxial thin film according to claim 2. 前記ターゲット材料が、(PrxSr1-x)SnO3:0.001≦x≦0.2であり、波長490nm±10nmの蛍光が得られることを特徴とする請求項1または請求項2に記載の酸化物蛍光体エピタキシャル薄膜。 3. The oxide according to claim 1, wherein the target material is (Pr x Sr 1-x ) SnO 3 : 0.001 ≦ x ≦ 0.2, and fluorescence with a wavelength of 490 nm ± 10 nm is obtained. Phosphor epitaxial thin film. 前記薄膜を、酸素中または大気中で、900℃以上1200℃以下の熱処理によって蛍光特性を向上させたことを特徴とする請求項1ないし請求項7のいずれか1つの請求項に記載の酸化物蛍光体エピタキシャル薄膜。   8. The oxide according to claim 1, wherein the thin film has a fluorescent property improved by a heat treatment at 900 ° C. or more and 1200 ° C. or less in oxygen or air. Phosphor epitaxial thin film. 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もしくは正方晶系を有する材料からなることを特徴とする請求項1ないし請求項8のいずれか1つの請求項に記載の酸化物蛍光体エピタキシャル薄膜。
The substrate is made of a material having a perovskite-related structure made of any of SrTiO 3 , LaAlO 3 , LaGaO 3 , LaSrGaO 4 , or a material having a cubic or tetragonal system made of either MgO or MgAl 2 O 4. 9. The oxide phosphor epitaxial thin film according to any one of claims 1 to 8, wherein the oxide phosphor epitaxial thin film is characterized.
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JP2014038759A (en) * 2012-08-15 2014-02-27 National Institute Of Advanced Industrial & Technology Phosphor for electron beam excitation, light-emitting element, and light-emitting device
JP2017005092A (en) * 2015-06-09 2017-01-05 国立研究開発法人産業技術総合研究所 Light emitting diode and method for manufacturing the same
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