JP5563542B2 - Aluminate compound phosphor - Google Patents
Aluminate compound phosphor Download PDFInfo
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- JP5563542B2 JP5563542B2 JP2011246358A JP2011246358A JP5563542B2 JP 5563542 B2 JP5563542 B2 JP 5563542B2 JP 2011246358 A JP2011246358 A JP 2011246358A JP 2011246358 A JP2011246358 A JP 2011246358A JP 5563542 B2 JP5563542 B2 JP 5563542B2
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- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims description 28
- 150000004645 aluminates Chemical class 0.000 title claims description 10
- 150000001875 compounds Chemical class 0.000 title claims description 10
- 238000000034 method Methods 0.000 claims description 8
- 238000005245 sintering Methods 0.000 claims description 8
- 229910052746 lanthanum Inorganic materials 0.000 claims description 7
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical group [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 6
- 238000003746 solid phase reaction Methods 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 4
- 238000010586 diagram Methods 0.000 description 8
- 238000001228 spectrum Methods 0.000 description 8
- 239000000463 material Substances 0.000 description 5
- 238000009877 rendering Methods 0.000 description 5
- 239000004568 cement Substances 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
- 229910052693 Europium Inorganic materials 0.000 description 3
- 230000005284 excitation Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229910052684 Cerium Inorganic materials 0.000 description 2
- 229910052692 Dysprosium Inorganic materials 0.000 description 2
- 229910052691 Erbium Inorganic materials 0.000 description 2
- 229910052779 Neodymium Inorganic materials 0.000 description 2
- 229910052777 Praseodymium Inorganic materials 0.000 description 2
- 229910052772 Samarium Inorganic materials 0.000 description 2
- 229910052771 Terbium Inorganic materials 0.000 description 2
- 229910052769 Ytterbium Inorganic materials 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000000634 powder X-ray diffraction Methods 0.000 description 2
- 229910019655 synthetic inorganic crystalline material Inorganic materials 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 229910004261 CaF 2 Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910052688 Gadolinium Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910052765 Lutetium Inorganic materials 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910019990 cerium-doped yttrium aluminum garnet Inorganic materials 0.000 description 1
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000295 emission spectrum Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/77064—Aluminosilicates
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7704—Halogenides
- C09K11/7705—Halogenides with alkali or alkaline earth metals
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
- H01L33/50—Wavelength conversion elements
- H01L33/501—Wavelength conversion elements characterised by the materials, e.g. binder
- H01L33/502—Wavelength conversion materials
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B33/00—Electroluminescent light sources
- H05B33/12—Light sources with substantially two-dimensional radiating surfaces
- H05B33/14—Light sources with substantially two-dimensional radiating surfaces characterised by the chemical or physical composition or the arrangement of the electroluminescent material, or by the simultaneous addition of the electroluminescent material in or onto the light source
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- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Power Engineering (AREA)
- Luminescent Compositions (AREA)
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Description
本発明は、蛍光体材料の配合式に関し、特に光学性質の改善を可能にするため、Ｓｉ／Ｏ元素を一部のＡｌ／Ｆ元素に取り代わるアルミン酸塩化合物蛍光体の配合式に関する。チップの波長は、２００〜４００ｎｍの紫外光によって励起されるほか、Ｓｉ／Ｏ元素を一部のＡｌ／Ｆ元素に取り代わり、微調整を行い、蛍光体に含めるランタン系金属原子価の存在比率を改変することにより、発光性質を制御できるため、応用の潜在力と学術価値を有する。
The present invention relates to a formulation type of the phosphor material, in particular to allow for improved optical properties, concerns the formulation type of aluminate compounds phosphor replaces take Si / O elements in a part of the Al / F elements. The wavelength of the chip is excited by ultraviolet light of 200 to 400 nm, the Si / O element is replaced with some Al / F elements, fine adjustment is performed, and the abundance ratio of the lanthanum metal valence included in the phosphor The light emission properties can be controlled by modifying, so it has potential for application and academic value.
文明の進展及び省エネ、カーボン排出減量などの環境保護意識に従い、世界各国とも発光ダイオード（Ｌｉｇｈｔ Ｅｍｉｔｔｉｎｇ Ｄｉｏｄｅ， ＬＥＤ）が従来の光源に取り代わりつつある。発光ダイオードの体積が小さい、消費電力が低い（白熱灯球の１／１０、蛍光灯管の１／２）、寿命が長い、発光効率が極めて良い、稼動反応速度が速いなどの長所を備え、従来の光源が克服難しい問題を解決できる。よって、すでに交通信号灯、自動車のライト、表示装置などの素子に使用されている。さらに、現在で推進中の環境保護意識概念に符合していることから、２１世紀の「緑の照明光源」と称賛されている。 In accordance with the progress of civilization and environmental protection awareness such as energy saving and carbon emission reduction, light emitting diodes (LEDs) are being replaced by conventional light sources in all countries of the world. Features such as small volume of light emitting diode, low power consumption (1/10 of incandescent lamp bulb, 1/2 of fluorescent lamp tube), long life, extremely good luminous efficiency, fast operating reaction speed, etc. The conventional light source can solve problems that are difficult to overcome. Therefore, it is already used for elements such as traffic signal lights, automobile lights, and display devices. Furthermore, it is praised as a “green lighting source” in the 21st century because it matches the concept of environmental awareness that is currently being promoted.
日亜化学工業株式会社（以下は、日亜という）は１９９６年、青色ＬＥＤによって、セリウム添加イットリウムアルミニウムガーネット（Ｃｅｒｉｕｍ−ｄｏｐｅｄ ｙｔｔｒｉｕｍ ａｌｕｍｉｎｕｍ ｇａｒｎｅｔ；ＹＡＧ：Ｃｅ）蛍光体を励起して黄色の蛍光を発生させ、青色光と混合した後、冷色白光を発生する。これが世界初めの白色ＬＥＤである。しかし、この種の白色光は、赤色を欠けるため、演色性が低いほか、その特許は、日亜に限られている。白色ＬＥＤは、全スペクトル帯域発光でなければ、高い演色性と理想な色温度を実現することはできない。しかし、青色ＬＥＤにＹＡＧと、赤色蛍光体との組合せ方式のほか、青色ＬＥＤに緑色と青色蛍光体との組合せ方式、またはＵＶ−ＬＥＤに青、緑、赤３色の蛍光体との組合せによる白色光がある。そのうち、理想な色温度（暖色の白光）を発光させるには、ＵＶ−ＬＥＤと３色の蛍光体との組合せ方式がより良い発光効率が得られる。よって、紫外光に励起されやすい、青色、緑色、赤色蛍光体を開発することは、現在の重要な研究課題である。 Nichia Chemical Co., Ltd. (hereinafter referred to as Nichia) generated yellow fluorescence by exciting a cerium-doped yttrium aluminum garnet (YAG: Ce) phosphor with a blue LED in 1996 And cold white light is generated after mixing with blue light. This is the world's first white LED. However, this type of white light lacks red color and therefore has low color rendering properties, and its patent is limited to Nichia. A white LED cannot achieve high color rendering and an ideal color temperature unless it emits light in the entire spectrum band. However, in addition to the combination method of YAG and red phosphor for blue LED, the combination method of green and blue phosphor for blue LED or the combination of blue, green and red phosphor for UV-LED There is white light. Of these, in order to emit an ideal color temperature (warm white light), a combination of a UV-LED and three color phosphors can provide better luminous efficiency. Therefore, the development of blue, green, and red phosphors that are easily excited by ultraviolet light is a current important research subject.
現時点、蛍光体に関する研究は、新しいホスト格子の開発のほか、ホスト格子に他の元素をドープして、従来のホスト格子に取り代わり、発光性を改善することは、良く見かける研究方向である。一例として、Ｄｕａｎらは２０１１年に、Ｃｈｅｍｉｓｔｒｙ ｏｆ ｍａｔｅｒｉａｌ誌（Ｃｈｅｍｉｓｔｒｙ Ｍａｔｅｒｉａｌｓ， ｄｘ．ｄｏｉ．ｏｒｇ／１０．１０２１／ｃｍ１０３４９５ｊ）において、Ｒｅ2Ｓｉ4Ｎ6Ｃ （ＲＥ＝Ｌｕ， Ｙ， Ｇｄ）シリーズ蛍光体の研究を発表し、すなわち、ＲＥ／Ｃを従来ＭＲＥＳｉ4Ｎ7に含まれるＭ／Ｎ （Ｍ＝Ｂａ， Ｓｒ， Ｃａ）をＣ元素の共有結合性と、より剛性を持つ結合特性を利用し、ホスト格子の安定性改善も現時点の主な研究目標である。 At the present time, research on phosphors is not only the development of a new host lattice, but also the addition of other elements to the host lattice to replace the conventional host lattice and improve the light emission is a common research direction. As an example, Duan et al. In 2011 in Chemistry of materials (Chemistry Materials, dx.doi.org/10.1021/cm103495j), Re 2 Si 4 N 6 C (RE = Lu, Y, Gd) series fluorescence. Announcement of research on the body, that is, RE / C uses M / Si (M = Ba, Sr, Ca) that is included in conventional MRESi 4 N 7 and uses C element covalent bond and more rigid bond characteristics However, improving the stability of the host lattice is also the current main research goal.
Ｙｕらは、１９９７年、Ｃｅｍｅｎｔ ａｎｄ Ｃｏｎｃｒｅｔｅ Ｒｅｓｅａｒｃｈ誌（Ｃｅｍｅｎｔ Ｃｏｎｃｒｅｔｅ Ｒｅｓ， １９９７， ２７， １４３９−１４４９）において、Ｃａ12Ａｌ14Ｏ32Ｆ2の調製方法と単結晶構造を発表し、その構造は、［ＡｌＯ4］の四面体構成であり、単位格子は正方晶系に属し、空間群はＩ４３ｄである。四面体の間は、酸素原子をブリッジングとし、酸素原子と６つの酸素と一つのフッ素原子配位、合計７配位である。さらに、構造を形成するの欠け格子は、フッ素原子によって補う。この結晶質は、Ｃ１２Ａ７の構造に比べ、より安定性を有し、蛍光体に適している。
Yu et al., 1997, published a method and a single crystal structure of Ca 12 Al 14 O 32 F 2 in Cement and Concrete Research (Cement Concrete Res, 1997, 27, 1439-1449). [AlO 4 ] has a tetrahedral structure, the unit cell belongs to the tetragonal system, and the space group is I43d. Between tetrahedrons, oxygen atoms are bridged, and oxygen atoms, six oxygens, and one fluorine atom coordination, a total of seven coordinations. Furthermore, the missing lattice that forms the structure is supplemented by fluorine atoms. This crystalline material is more stable than the structure of C12A7 and is suitable for a phosphor.
本発明の一目的は、より安定性を有する蛍光体を提供する。 An object of the present invention is to provide a more stable phosphor.
本発明の次の目的は、演色性を向上できる蛍光体を提供する。 The next object of the present invention is to provide a phosphor capable of improving the color rendering.
本発明のもう一つの目的は、生産プロセスの簡素化及び原価を低減できる蛍光体を提供する。 Another object of the present invention is to provide a phosphor capable of simplifying the production process and reducing the cost.
前述目的を達成するため、本発明のアルミン酸塩化合物蛍光体は、焼結温度Ｔと焼結圧力Ｐの条件において、固相反応によって合成される。その化学式は、ＣａaＳｒbＢａcＡｌdＳｉeＯfＦgＲhである。そのうち、１０≦ａ＋ｂ＋ｃ＋ｈ≦１２（０≦ａ＜１２；０≦ｂ＜１２；０≦ｃ＜１２；０＜ｈ≦１）、１２＜ｄ＋ｅ≦１４（１２≦ｄ＜１４；０＜ｅ≦２）、３０≦ｆ≦３４；、０＜ｇ≦２，Ｒは、ランタン系金属の元素であり、蛍光体の発光主体である。そのうち、この固相反応法に使用する焼結温度Ｔは、１０００〜１４００℃であり、焼結圧力Ｙは、０．１〜０．９ＭＰａである。本発明の蛍光体は、波長が２００〜４００ｎｍの発光ダイオードによって、励起することができ、かつ出射の波長は、４００−７００ｎｍである。そのうち、ランタン系金属Ｒは、Ｃｅ、Ｅｕ、Ｐｒ、Ｎｄ、Ｓｍ、Ｔｂ、Ｅｒ、Ｙｂ、Ｄｙのいずれかである、様々な領域において発光できる。本発明の蛍光体は、Ｓｉ／Ｏを一部のＡｌ／Ｆに取り代わり、微調整を行い、発光中心の配位環境の改変により、ランタン系金属が結晶格子におけるそれぞれの価数の存在比率を調節し、光学性質を制御する。その発光領域は青色光、緑色光と赤色光を同時にカーバーし、ＵＶ−ＬＥＤと組合せて、白色光を合成し、演色性を向上できるほか、少ない種類の粉体を使用するため、生産プロセスを簡素化すると共に、コストを低減でき、応用の潜在力と学術価値を有する。 In order to achieve the above-mentioned object, the aluminate compound phosphor of the present invention is synthesized by a solid phase reaction under the conditions of a sintering temperature T and a sintering pressure P. Its chemical formula is Ca a Sr b Ba c Al d Si e O f F g R h. Among them, 10 ≦ a + b + c + h ≦ 12 (0 ≦ a <12; 0 ≦ b <12; 0 ≦ c <12; 0 <h ≦ 1), 12 <d + e ≦ 14 (12 ≦ d <14; 0 <e ≦ 2) ), 30 ≦ f ≦ 34; 0 <g ≦ 2, R is an element of a lanthanum-based metal and is a light emitting main body of the phosphor. Among them, the sintering temperature T used in this solid phase reaction method is 1000 to 1400 ° C., and the sintering pressure Y is 0.1 to 0.9 MPa. The phosphor of the present invention can be excited by a light emitting diode having a wavelength of 200 to 400 nm, and the emission wavelength is 400 to 700 nm. Among them, the lanthanum metal R can emit light in various regions which are any one of Ce, Eu, Pr, Nd, Sm, Tb, Er, Yb, and Dy. In the phosphor of the present invention, Si / O is replaced with a part of Al / F, fine adjustment is performed, and the abundance ratio of each valence in the crystal lattice of the lanthanum-based metal is changed by modifying the coordination environment of the emission center. Adjust the optical properties. Its light emitting area covers blue light, green light and red light at the same time, and combines with UV-LED to synthesize white light and improve color rendering. Simplify, reduce costs, and have application potential and academic value.
本発明の内容のさらなる理解を図るため、以下にて図面と合わせて説明する。 In order to further understand the contents of the present invention, the following description will be made with reference to the drawings.
本発明のアルミン酸塩化合物蛍光体は、固相反応法によって調製される。焼結温度Ｔは１０００〜１４００℃であり、焼結圧力Ｐは、０．１〜０．９ ＭＰａである。化学式ＣａaＳｒbＢａcＡｌdＳｉeＯfＦgＲhで表すことができる。そのうち、１０≦ａ＋ｂ＋ｃ＋ｈ≦１２ （ ０≦ａ＜１２；０≦ｂ＜１２；０≦ｃ＜１２；０＜ｈ≦１ ）、１２＜ｄ＋ｅ≦１４ （ １２≦ｄ＜１４；０＜ｅ≦２ ）、３０≦ｆ≦３４；、０＜ｇ≦２。そのうち、Ｒはランタン系金属元素Ｃｅ、Ｅｕ、Ｐｒ、Ｎｄ、Ｓｍ、Ｔｂ、Ｅｒ、Ｙｂ、Ｄｙのいずれかである。本発明の好ましい実施例（Ａ） 〜（Ｅ）はＣａ11.9Ａｌ14-xＳｉxＯ32+XＦ2-x：Ｅｕ0.1 （ｘ＝０．１、０．２、０．３、０．５、０．６）サンプルであり、配合方法は、下表に示す。 The aluminate compound phosphor of the present invention is prepared by a solid phase reaction method. The sintering temperature T is 1000-1400 ° C., and the sintering pressure P is 0.1-0.9 MPa. It can be represented by the chemical formula Ca a Sr b Ba c Al d Si e O f F g R h. Among them, 10 ≦ a + b + c + h ≦ 12 (0 ≦ a <12; 0 ≦ b <12; 0 ≦ c <12; 0 <h ≦ 1), 12 <d + e ≦ 14 (12 ≦ d <14; 0 <e ≦ 2) ), 30 ≦ f ≦ 34; 0 <g ≦ 2. Among them, R is any one of the lanthanum-based metal elements Ce, Eu, Pr, Nd, Sm, Tb, Er, Yb, and Dy. Preferred embodiments (A) to (E) of the present invention are Ca 11.9 Al 14 -x Si x O 32 + X F 2-x : Eu 0.1 (x = 0.1, 0.2, 0.3, 0. 5, 0.6) Sample, and the blending method is shown in the table below.
図１、本発明の好ましい実施例（Ａ）〜（Ｅ）のＸ線粉末回折スペクトル図を参照する。本発明の好ましい実施例（Ａ） 〜（Ｅ）に基づいて調製されたＣａ11.9Ａｌ14-xＳｉxＯ32+XＦ2-x：Ｅｕ0.1（ｘ＝０．１、０．２、０．３、０．５、０．６）サンプルをＸ線粉末回折スペクトル図によって、結晶相の純度を鑑定したところ、本発明によって、合成された蛍光体が純相（ｐｕｒｅ ｐｈａｓｅ）であることを観察できる。 Referring to FIG. 1, X-ray powder diffraction spectrum diagrams of preferred embodiments (A) to (E) of the present invention. Ca 11.9 Al 14-x Si x O 32 + X F 2-x prepared according to the preferred embodiments (A) to (E) of the present invention: Eu 0.1 (x = 0.1, 0.2, 0) .3, 0.5, 0.6) When the purity of the crystal phase of the sample was identified by an X-ray powder diffraction spectrum diagram, it was confirmed that the phosphor synthesized according to the present invention was a pure phase. Observe.
図３Ａ、３Ｂ、本発明の好ましい実施例（Ａ） 〜（Ｅ）の発光すベクトル図その１、その２である。本発明の好ましい実施例（Ａ） 〜（Ｅ）によって調製されたＣａ11.9Ａｌ14-xＳｉxＯ32+XＦ2-x：Ｅｕ0.1（ｘ＝０．１、０．２、０．３、０．５、０．６）サンプルは、波長が２００〜４００ｎｍの発光ダイオードによって励起される。特に、Ｓｉ／Ｏ量の増加に従い、波長が２５０ｎｍおよび３２５ｎｍ付近の光スペクトルの励起効果がより顕著的である。 FIGS. 3A and 3B are vector diagrams Nos. 1 and 2 of light emission of preferred embodiments (A) to (E) of the present invention. Ca 11.9 Al 14 -x Si x O 32 + x F 2 -x : Eu 0.1 (x = 0.1, 0.2, 0.3) prepared according to the preferred embodiments (A) to (E) of the present invention. 0.5, 0.6) The sample is excited by a light emitting diode with a wavelength of 200-400 nm. In particular, as the amount of Si / O increases, the excitation effect of the optical spectrum with wavelengths of around 250 nm and 325 nm is more remarkable.
図２および４、本発明の好ましい実施例（Ａ） 〜（Ｅ）の出射スペクトル図と色度座標図を参照する。図に示すように、本発明の好ましい実施例（Ａ） 〜（Ｅ）によって、調製されたＣａ11.9Ａｌ14-xＳｉxＯ32+XＦ2-x：Ｅｕ0.1（ｘ＝０．１、０．２、０．３、０．５、０．６）サンプルの出射波長は、４００〜７００ｎｍであり、かつＳｉ／Ｏを一部のＡｌ／Ｆに取り代わる量の改変に従い、Ｅｕ2+／Ｅｕ3+比例の構造微調整を行うことによって、青緑光と赤色光領域の光出射強度を調節し、Ｓｉ／Ｏの微量増に対して、Ａｌ／Ｆが相対的に減少し、青緑光の強度が大幅な増を示すと共に、赤色光の強度が相対に減少される。引き続き、出射スペクトルの数値を国際照明委員会が制定した色度座標図に従って、公式換算した各蛍光体の色度座標を、それぞれ座標図に表す。本発明の好ましい実施例によって、合成されたＣａ11.9Ａｌ14-xＳｉxＯ32+XＦ2-x：Ｅｕ0.1は、ｘ値の上昇に従い、出射光を赤色光領域から青色光領域に調節することができる。 2 and 4, reference is made to the emission spectrum diagrams and chromaticity coordinate diagrams of preferred embodiments (A) to (E) of the present invention. As shown in the figure, Ca 11.9 Al 14 -x Si x O 32 + X F 2-x : Eu 0.1 (x = 0.1, prepared according to the preferred embodiments (A) to (E) of the present invention. 0.2, 0.3, 0.5, 0.6) The emission wavelength of the sample is 400 to 700 nm, and according to the modification of the amount that replaces Si / O with some Al / F, Eu 2+ / Eu 3 + proportional structural fine adjustment to adjust the light emission intensity of blue-green light and red light region, Al / F decreases relatively with a slight increase of Si / O, blue-green light The intensity of the red light is significantly increased, and the intensity of the red light is relatively decreased. Subsequently, the chromaticity coordinates of the respective phosphors, which are officially converted according to the chromaticity coordinate diagram established by the International Commission on Illumination, are shown in the coordinate diagrams. According to a preferred embodiment of the present invention, synthesized Ca 11.9 Al 14 -x Si x O 32 + X F 2-x : Eu 0.1 adjusts the emitted light from the red light region to the blue light region as the x value increases. can do.
よって、本発明の蛍光体は、Ｓｉ／Ｏを一部のＡｌ／Ｆに取り替え、構造の微調整を行い、光出射中心の配位環境の改変によって、ランタン系金属が結晶格子におけるそれぞれの価数の存在比率を調節することによって、光学性質を制御する。その光出射領域は、青緑光と赤色光を同時にカーバーし、ＵＶ−ＬＥＤと組み合わせて、白色光を合成した場合、演色性を向上できる。本好ましい実施例のアルミン酸塩化合物蛍光体Ｃａ11.9Ａｌ14-xＳｉxＯ32+XＦ2-x：Ｅｕ0.1の使用原料は、ＣａＣＯ3、Ａｌ2Ｏ3、ＳｉＯ2、ＣａＦ2、Ｅｕ2Ｏ3を含み、化学式に従い、所定の原料を乳鉢に入れ、均一に混合し、すりつぶした後、温度１２５０℃、水素（５％）−窒素（９５％）の雰囲気において、６時間を焼結した後、製品が得られる。製造プロセスが簡単であり、大量生産に向き、少ない種類の粉体を使用することは、生産プロセスの簡素化並びにコスト低減できるほか、応用の潜在力と学術価値を有する。 Therefore, in the phosphor of the present invention, Si / O is replaced with a part of Al / F, the structure is finely adjusted, and the coordination environment of the light emission center is changed, so that the lanthanum metal in each crystal lattice has a different valence. The optical properties are controlled by adjusting the abundance ratio of the numbers. In the light emission region, when blue light and red light are simultaneously covered and combined with UV-LED, white light is synthesized, color rendering can be improved. The aluminate compound phosphor Ca 11.9 Al 14-x Si x O 32 + X F 2-x : Eu 0.1 used in this preferred embodiment is made of CaCO 3 , Al 2 O 3 , SiO 2 , CaF 2 , Eu. According to the chemical formula, containing 2 O 3 , put the specified raw material in a mortar, mix uniformly, grind, then sinter for 6 hours in the atmosphere of temperature 1250 ° C, hydrogen (5%)-nitrogen (95%) After that, the product is obtained. The simple manufacturing process, suitable for mass production, and the use of a small number of powders can simplify the production process and reduce costs, and have application potential and academic value.
以上に説明された各実施例は、本発明の好ましい実施例に過ぎず、本発明の特許請求範囲を制限するものではない。本発明の精神を逸脱されない範囲による修飾または変更は、本発明の特許請求範囲に含める。 Each embodiment described above is only a preferred embodiment of the present invention, and does not limit the scope of claims of the present invention. Modifications or alterations without departing from the spirit of the present invention are included in the claims of the present invention.
Claims (5)
Is synthesized by solid-phase reaction, its chemical formula is Ca a Sr b Ba c Al d Si e O f F g R h, of which, a + b + c + h = 12, d + e = 14, 0 ≦ a <12,0 ≦ b < 12, 0 ≦ c <12, 0 <h ≦ 1, 12 ≦ d <14, 0 <e ≦ 2, 32.1 ≦ f ≦ 32.6, 1.4 ≦ g ≦ 1.9, R is lanthanum An aluminate compound phosphor characterized in that it is an element of a metallic metal and is the main light emitting body of the phosphor.
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