JP2006083260A - Phosphor particle, phosphor particle dispersion, lighting device and display containing them - Google Patents

Phosphor particle, phosphor particle dispersion, lighting device and display containing them Download PDF

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JP2006083260A
JP2006083260A JP2004268203A JP2004268203A JP2006083260A JP 2006083260 A JP2006083260 A JP 2006083260A JP 2004268203 A JP2004268203 A JP 2004268203A JP 2004268203 A JP2004268203 A JP 2004268203A JP 2006083260 A JP2006083260 A JP 2006083260A
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phosphor
semiconductor
particles
energy
phosphor particles
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JP4785363B2 (en
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Tatsuya Morioka
達也 森岡
Hajime Saito
肇 齊藤
Mototaka Tanetani
元隆 種谷
Shigeo Fujita
茂夫 藤田
Shizuo Fujita
静雄 藤田
Yoichi Kawakami
養一 川上
Mitsuru Funato
充 船戸
Masafumi Harada
雅史 原田
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Sharp Corp
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Abstract

<P>PROBLEM TO BE SOLVED: To obtain a phosphor particle having high absorption efficiency and high luminance of exciting light and a phosphor particle dispersion having excellent color rendering properties and a lighting device and a display device comprising them. <P>SOLUTION: The phosphor particle 100 receives an exciting light 11 having an excitation energy E<SB>e</SB>, emits fluorescence, comprises a semiconductor core particle 101 having a band-gap energy E<SB>1</SB>and a semiconductor shell layer 102 having a band-gap energy E<SB>2</SB>, has relation of E<SB>1</SB><E<SB>2</SB>≤E<SB>e</SB>, forms a discrete energy level having an energy between E<SB>1</SB>and E<SB>2</SB>in the semiconductor core particle 101 by coating the semiconductor core particle 101 with the semiconductor shell layer 102 and emits fluorescence based on an energy E between ground states 111c and 111v at the energy level. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

本発明は、発光素子からの励起光を受けて発光する蛍光体粒子、蛍光体粒子分散体ならびにこれらを含む照明装置および表示装置に関する。   The present invention relates to a phosphor particle that emits light upon receiving excitation light from a light-emitting element, a phosphor particle dispersion, and an illumination device and a display device including these.

半導体中の量子効果によって形成される基底準位間のバンドギャップエネルギーによる蛍光を発する蛍光体を用いた照明装置および表示装置が提案されている（たとえば、特許文献１参照）。   An illumination device and a display device using a phosphor that emits fluorescence due to band gap energy between ground levels formed by quantum effects in a semiconductor have been proposed (for example, see Patent Document 1).

上記照明装置または表示装置は、具体的には、窒化物系ＩＩＩ−Ｖ族化合物半導体を用いた発光素子と、励起子ボーア半径の２倍以下の粒径を有するコア粒子（核粒子）とシェル層（外層）の２層構造を有する蛍光体とを含む照明装置または表示装置である。   Specifically, the lighting device or the display device includes a light-emitting element using a nitride III-V compound semiconductor, a core particle (nuclear particle) having a particle size equal to or smaller than an exciton Bohr radius, and a shell. It is an illuminating device or a display device including a phosphor having a two-layer structure of layers (outer layers).

さらに、詳しくは、窒化物系ＩＩＩ−Ｖ族化合物半導体を用いた発光素子としては、サファイア基板上に形成されたＧａxＩｎ1-xＮ（０≦ｘ≦１）／ＧａyＩｎ1-yＮ（０≦ｙ≦１）の対で構成される量子井戸構造の活性層を有するものが用いられている。そして、コア粒子とシェル層の２層構造を有する蛍光体としてはＣｄＳｅ（コア粒子）／ＺｎＳ（シェル層）構造からなり、ＣｄＳｅの粒径を変化させることによって生じる量子効果による基底準位の変化を利用して蛍光の波長（色）の制御を行うものが示されている。 Further, particularly, as a light emitting device using nitride III-V compound semiconductor, which is formed on a sapphire substrate Ga x In 1-x N ( 0 ≦ x ≦ 1) / Ga y In 1-y An active layer having a quantum well structure composed of N (0 ≦ y ≦ 1) pairs is used. The phosphor having a two-layer structure of a core particle and a shell layer has a CdSe (core particle) / ZnS (shell layer) structure, and changes in the ground level due to quantum effects caused by changing the particle size of CdSe. A device for controlling the wavelength (color) of fluorescence using the above is shown.

しかし、上記蛍光体は、励起光の吸収効率が必ずしも高くなく、この蛍光体と発光素子とを組み合わせた照明装置または表示装置においては、十分な輝度を得ることができない。また、上記蛍光体は、演色性が乏しい問題があった。
特開平１１−３４０５１６号公報 However, the phosphor does not necessarily have high absorption efficiency of excitation light, and a sufficient luminance cannot be obtained in an illumination device or a display device in which the phosphor and a light emitting element are combined. Further, the phosphor has a problem of poor color rendering.
JP 11-340516 A

上記状況を鑑みて、本発明は、励起光の吸収効率が高く輝度の高い蛍光体粒子および演色性に優れた蛍光体粒子分散体ならびにこれらを含む照明装置および表示装置を提供することを目的とする。   In view of the above circumstances, an object of the present invention is to provide phosphor particles having high excitation light absorption efficiency and high luminance, phosphor particle dispersions excellent in color rendering, and illumination devices and display devices including these. To do.

本発明は、励起エネルギーＥeを有する励起光を受けて蛍光を発する蛍光体粒子であって、バンドギャップエネルギーＥ1を有する半導体コア粒子と、半導体コア粒子を被覆するバンドギャップエネルギーＥ2を有する半導体シェル層を含み、半導体コア粒子のＥ1と半導体シェル層のＥ2と励起光のＥeとの関係がＥ1＜Ｅ2≦Ｅeであり、半導体シェル層で半導体コア粒子を被覆することにより半導体コア粒子中にＥ1とＥ2との間のエネルギーを有する離散的なエネルギー準位が形成され、エネルギー準位における基底準位間のエネルギーＥに基づく蛍光を発する蛍光体粒子である。 The present invention is a phosphor particle that emits fluorescence upon receiving excitation light having excitation energy E e , and has semiconductor core particles having band gap energy E 1 and band gap energy E 2 covering the semiconductor core particles. includes a semiconductor shell layer, the relationship between E 2 of E 1 and the semiconductor shell layer of the semiconductor core particles E e of the excitation light is E 1 <E 2 ≦ E e, covering the semiconductor core particles in the semiconductor shell layer Accordingly, discrete energy levels having energy between E 1 and E 2 are formed in the semiconductor core particles, and the phosphor particles emit fluorescence based on the energy E between the ground levels in the energy levels. .

本発明にかかる蛍光体粒子において、上記基底準位間のエネルギーを１．８５ｅＶ〜２．０６ｅＶ、２．２９ｅＶ〜２．４８ｅＶまたは２．５８ｅＶ〜３．０２ｅＶのいずれかの範囲とすることができる。また、半導体コア粒子はＩｎx1Ｇａy1Ａｌ1-x1-y1Ｎ（０＜ｘ１、０≦ｙ１、ｘ１＋ｙ１≦１）、Ｃｄz11Ｚｎ1-z11Ｓｅ（０＜ｚ１１≦１）およびＣｄz12Ｚｎ1-z12Ｓ（０＜ｚ１２≦１）からなる群から選ばれた１つの半導体であること、または、半導体シェル層はＩｎx2Ｇａy2Ａｌ1-x2-y2Ｎ（０＜ｘ２、０＜ｙ２、ｘ２＋ｙ２≦１）およびＣｄy21Ｚｎ1-y21Ｓｅ（０≦ｙ２１＜１）からなる群から選ばれた１つの半導体であることが好ましい。また、本発明にかかる蛍光体粒子は、半導体レーザまたは発光ダイオードからなる発光素子からの励起光を受けて発光することができる。 In the phosphor particles according to the present invention, the energy between the ground levels can be set in a range of 1.85 eV to 2.06 eV, 2.29 eV to 2.48 eV, or 2.58 eV to 3.02 eV. . The semiconductor core particles are In x1 Ga y1 Al 1-x1-y1 N (0 <x1, 0 ≦ y1, x1 + y1 ≦ 1), Cd z11 Zn 1-z11 Se (0 <z11 ≦ 1) and Cd z12 Zn 1 -z12 S (0 <z12 ≦ 1), or a semiconductor shell layer may be In x2 Ga y2 Al 1-x2-y2 N (0 < x2, 0 <y2, x2 + y2 ≦ 1) and Cd y21 Zn 1-y21 Se (0 ≦ y21 <1) are preferable. Moreover, the phosphor particles according to the present invention can emit light upon receiving excitation light from a light emitting element composed of a semiconductor laser or a light emitting diode.

本発明は、上記蛍光体粒子を２以上含む蛍光体粒子分散体であって、基底準位が異なる２以上の蛍光体粒子を含み、すべての蛍光体粒子の半導体シェル層のバンドギャップエネルギーＥ2が、すべての蛍光体粒子の半導体コア粒子中に形成される基底準位間のエネルギーＥよりも大きいことを特徴とする蛍光体粒子分散体である。さらに、本発明にかかる蛍光体粒子分散体は、２以上の蛍光体粒子が媒体中に分散されているものとすることができる。 The present invention is a phosphor particle dispersion containing two or more of the above phosphor particles, including two or more phosphor particles having different ground levels, and the band gap energy E 2 of the semiconductor shell layer of all the phosphor particles. Is a phosphor particle dispersion characterized by being larger than the energy E between the ground levels formed in the semiconductor core particles of all phosphor particles. Furthermore, the phosphor particle dispersion according to the present invention may have two or more phosphor particles dispersed in a medium.

本発明は、上記の蛍光体粒子または蛍光体粒子分散体と、発光素子とを含む照明装置である。   This invention is an illuminating device containing said fluorescent substance particle or fluorescent substance particle dispersion, and a light emitting element.

本発明は、上記の蛍光体粒子または蛍光体粒子分散体と、発光素子と、蛍光体粒子または蛍光体粒子分散体から発する蛍光および発光素子から発する励起光の少なくとも１つの光の光強度を変調する光強度変調手段を含む表示装置である。   The present invention modulates the light intensity of at least one of the phosphor particles or phosphor particle dispersion described above, a light emitting device, fluorescence emitted from the phosphor particles or phosphor particle dispersion and excitation light emitted from the light emitting device. The display device includes a light intensity modulating means.

上記のように、本発明によれば、励起光の吸収効率が高く輝度の高い蛍光体および演色性に優れた蛍光体粒子分散体ならびにこれらを含む照明装置および表示装置を提供することができる。   As described above, according to the present invention, it is possible to provide a phosphor with high excitation light absorption efficiency and high luminance, a phosphor particle dispersion excellent in color rendering, and an illumination device and a display device including these.

（実施形態１）
本発明の実施形態１による蛍光体粒子は、図１を参照して、励起エネルギーＥeを有する励起光１１を受けて蛍光１３を発する蛍光体粒子１００であって、バンドギャップエネルギーＥ1（伝導帯１０１ｃと価電子帯１０１ｖとの間のバンドギャップエネルギー）を有する半導体コア粒子１０１と、半導体コア粒子を被覆するバンドギャップエネルギーＥ2（伝導帯１０２ｃと価電子帯１０２ｖとの間のバンドギャップエネルギー）を有する半導体シェル層１０２とを含み、半導体コア粒子のＥ1と半導体シェル層のＥ2と励起光のＥeとの関係がＥ1＜Ｅ2≦Ｅeであり、半導体シェル層１０２で半導体コア粒子１０１を被覆することにより半導体コア粒子１０１中にＥ1とＥ2との間のエネルギーを有する離散的なエネルギー準位が形成され、エネルギー準位における基底準位１１１ｃ，１１１ｖ間のエネルギーＥに基づく蛍光１３を発する蛍光体粒子である。 (Embodiment 1)
Phosphor particles according to the first embodiment of the present invention, with reference to FIG. 1, the phosphor particles 100 that emit fluorescence 13 receives the excitation light 11 with excitation energy E e, the band gap energy E 1 (conductivity Semiconductor core particle 101 having a band gap energy between band 101c and valence band 101v) and band gap energy E 2 covering the semiconductor core particle (band gap energy between conduction band 102c and valence band 102v) ) and a semiconductor shell layer 102 having the relationship between E 2 of E 1 and the semiconductor shell layer of the semiconductor core particles E e of the excitation light is E 1 <E 2 ≦ E e, the semiconductor shell layer 102 discrete energy levels having an energy between E 1 and E 2 into the semiconductor core particle 101 is formed by coating the semiconductor core particles 101 Ground level 111c in energy levels, a phosphor particle emits fluorescence 13 based on the energy E between 111v.

本実施形態の蛍光体粒子が、励起光の吸収効率が高く輝度が高くなる理由を、従来の蛍光体粒子と対比させて、具体的に説明する。   The reason why the phosphor particles of this embodiment have high excitation light absorption efficiency and high luminance will be specifically described in comparison with conventional phosphor particles.

従来の蛍光体粒子は、たとえば、図２を参照して、半導体コア粒子２０１として１．７ｅＶ程度のバンドギャップエネルギーＥ1を有する直径６〜１０ｎｍ程度のＣｄＳｅコア粒子と、半導体コア粒子２０１を被覆する半導体シェル層２０２として３．８０ｅＶのバンドギャップエネルギーＥ2を有するＺｎＳシェル層とからなり、Ｉｎx3Ｇａ1-x3Ｎ（０≦ｘ３≦１）発光素子が発した励起エネルギーＥeが２．８８ｅＶ（波長４３０ｎｍ）の励起光１１を受けて、蛍光１３を発する蛍光体粒子である。なお、励起光の一部は、蛍光体粒子表面によって散乱され散乱光１２として反射される。 For example, referring to FIG. 2, conventional phosphor particles are coated with CdSe core particles having a band gap energy E 1 of about 1.7 eV and a diameter of about 6 to 10 nm as semiconductor core particles 201, and semiconductor core particles 201. The semiconductor shell layer 202 to be formed is a ZnS shell layer having a band gap energy E 2 of 3.80 eV, and the excitation energy E e emitted from the In x3 Ga 1-x3 N (0 ≦ x3 ≦ 1) light emitting element is 2. The phosphor particles emit fluorescence 13 in response to the excitation light 11 of 88 eV (wavelength 430 nm). A part of the excitation light is scattered by the phosphor particle surface and reflected as scattered light 12.

この従来の蛍光体粒子において、ＺｎＳシェル層でＣｄＳｅコア粒子を被覆することによってＣｄＳｅコア粒子中に形成された基底準位２１１ｃ，２１１ｖ間のエネルギーＥはたとえば１．９ｅＶ（６５０ｎｍ）であり、波長が６５０ｎｍの蛍光１３を発する。なお、図２（ｂ）において、Ｃ．Ｂは伝導帯、Ｖ．Ｂは価電子帯、白丸は電子１４、黒丸は正孔１５を示す。   In this conventional phosphor particle, the energy E between the ground levels 211c and 211v formed in the CdSe core particle by covering the CdSe core particle with the ZnS shell layer is, for example, 1.9 eV (650 nm), and the wavelength Emits fluorescence 13 at 650 nm. In FIG. 2B, C.I. B is the conduction band; B represents a valence band, white circles represent electrons 14, and black circles represent holes 15.

上記のように、従来の蛍光体粒子においては、ＥeとＥ2とＥとの関係はＥ＜Ｅe＜Ｅ2となり、このようなバンド構造においては、ＣｄＳｅコア粒子内に形成されるエネルギー準位、すなわち励起エネルギーＥeを有する励起光１１を吸収できるエネルギー状態密度は離散的にしか存在せず、このエネルギー準位から少しでも外れると励起光の吸収効率が低下し輝度が低下する。なお、Ｉｎx3Ｇａ1-x3Ｎ発光素子（０≦ｘ３≦１）において、ＩｎおよびＧａの組成をどのように変化させても、その励起エネルギーＥeは３．３８ｅＶ以下となり、上記と同様にＥe＜Ｅ2となってしまう。 As described above, in the conventional phosphor particles, the relationship between E e , E 2 and E is E <E e <E 2 , and in such a band structure, the energy formed in the CdSe core particles The energy state density capable of absorbing the excitation light 11 having the level, that is, the excitation energy E e exists only discretely, and if it deviates even a little from this energy level, the absorption efficiency of the excitation light is lowered and the luminance is lowered. In the In x3 Ga 1-x3 N light emitting device (0 ≦ x3 ≦ 1), the excitation energy E e is 3.38 eV or less regardless of how the composition of In and Ga is changed. E e <E 2

これに対し、本実施形態の蛍光体粒子は、たとえば、図１を参照して、半導体コア粒子１０１として２．００ｅＶ（波長６２０ｎｍ）のバンドギャップエネルギーＥ1を有するＩｎＮコア粒子と、半導体コア粒子１０１を被覆する半導体シェル層１０２として２．８０ｅＶ（波長４４２ｎｍ）のバンドギャップエネルギーＥ2を有するＩｎx2Ｇａ1-x2Ｎシェル層（０＜ｘ２＜１）とからなり、Ｉｎx3Ｇａ1-x3Ｎ発光素子（０≦ｘ３≦１）が発した励起エネルギーＥeが２．８８ｅＶ（４３０ｎｍ）の励起光１１を受けて蛍光１３を発する蛍光体粒子である。なお、励起光の一部は、蛍光体粒子表面によって散乱され散乱光１２として反射される。 In contrast, the phosphor particles according to the present embodiment include, for example, an InN core particle having a band gap energy E 1 of 2.00 eV (wavelength 620 nm) as a semiconductor core particle 101 and a semiconductor core particle with reference to FIG. The semiconductor shell layer 102 covering 101 includes an In x2 Ga 1-x2 N shell layer (0 <x2 <1) having a band gap energy E 2 of 2.80 eV (wavelength 442 nm), and In x3 Ga 1-x3 The phosphor particles emit fluorescence 13 upon receiving excitation light 11 having an excitation energy E e of 2.88 eV (430 nm) emitted from an N light emitting element (0 ≦ x3 ≦ 1). A part of the excitation light is scattered by the phosphor particle surface and reflected as scattered light 12.

この本実施形態の蛍光体粒子において、Ｉｎx2Ｇａ1-x2Ｎシェル層（０＜ｘ２＜１）でＩｎＮコア粒子を被覆することによって、ＩｎＮコア粒子中に形成された基底準位１１１ｃ，１１１ｖ間のエネルギーＥは、たとえば２．５８ｅＶ（波長４８０ｎｍ）となり、波長４８０ｎｍの蛍光１３を発する。 In the phosphor particles of this embodiment, the InN core particles are covered with an In x2 Ga 1-x2 N shell layer (0 <x2 <1), whereby ground levels 111c and 111v formed in the InN core particles are formed. The energy E between them is, for example, 2.58 eV (wavelength 480 nm), and emits fluorescence 13 having a wavelength of 480 nm.

上記のように、半導体シェル層であるＩｎx2Ｇａ1-x2Ｎシェル層（０＜ｘ２＜１）のＥ2が励起光のＥe以下になるように、Ｉｎx2Ｇａ1-x2Ｎシェル層の元素組成比ｘ２を設定することにより、励起光の大部分を半導体シェル層で吸収することができる。これにより、励起光を吸収し得る体積（半導体シェル層の体積）を増大することができ、蛍光体粒子の輝度が高くなる。 As described above, In x2 Ga 1-x2 N shell layer is a semiconductor shell layers as (0 <x2 <1) E 2 is less than or equal to E e of the excitation light, In x2 Ga 1-x2 N shell layer By setting the elemental composition ratio x2, most of the excitation light can be absorbed by the semiconductor shell layer. Thereby, the volume (volume of a semiconductor shell layer) which can absorb excitation light can be increased, and the brightness | luminance of fluorescent substance particle becomes high.

本実施形態は、半導体コア粒子内に形成された基底準位間のエネルギーＥが２．５８ｅＶ（波長４８０ｎｍ）である青色の蛍光を発する蛍光体粒子の例であるが、半導体コア粒子の粒径ならびに半導体コア粒子または半導体シェル層の構成元素または元素組成比などを調整することにより、上記基底準位間のエネルギーが、１．８５ｅＶ〜２．０６ｅＶ（波長６７０ｎｍ〜６００ｎｍ）の赤色の蛍光を発する蛍光体粒子、２．２９ｅＶ〜２．４８ｅＶ（波長５４０ｎｍ〜５００ｎｍ）の緑色の蛍光を発する蛍光体粒子、２．５８ｅＶ〜３．０２ｅＶ（波長４８０ｎｍ〜４１０ｎｍ）の青色の蛍光を発する蛍光体粒子を得ることができる。   The present embodiment is an example of phosphor particles that emit blue fluorescence whose energy E between ground levels formed in the semiconductor core particles is 2.58 eV (wavelength 480 nm). In addition, by adjusting the constituent element or element composition ratio of the semiconductor core particle or the semiconductor shell layer, the energy between the ground levels emits red fluorescence having a wavelength of 1.85 eV to 2.06 eV (wavelength 670 nm to 600 nm). Phosphor particles, phosphor particles emitting green fluorescence of 2.29 eV to 2.48 eV (wavelength 540 nm to 500 nm), phosphor particles emitting blue fluorescence of 2.58 eV to 3.02 eV (wavelength 480 nm to 410 nm) Obtainable.

本実施形態においては、半導体コア粒子としてＩｎＮからなるＩｎＮコア粒子を挙げたが、半導体コア粒子を構成する半導体としては、Ｉｎx1Ｇａy1Ａｌ1-x1-y1Ｎ（０＜ｘ１、０≦ｙ１、ｘ１＋ｙ１≦１）、Ｃｄz11Ｚｎ1-z11Ｓｅ（０＜ｚ１１≦１）またはＣｄz12Ｚｎ1-z12Ｓ（０＜ｚ１２≦１）なども好ましく用いられる。 In the present embodiment, InN core particles made of InN are used as the semiconductor core particles. However, as the semiconductor constituting the semiconductor core particles, In x1 Ga y1 Al 1-x1-y1 N (0 < x1, 0 ≦ y1) X1 + y1≤1 ), Cdz11Zn1 -z11Se (0 <z11≤1), Cdz12Zn1 -z12S (0 <z12≤1), etc. are also preferably used.

本実施形態においては、半導体シェル層としてＩｎx2Ｇａ1-x2Ｎシェル層（０＜ｘ２＜１）を挙げたが、Ｉｎx2Ｇａy2Ａｌ1-x2-y2Ｎ（０＜ｘ２、０＜ｙ２、ｘ２＋ｙ２≦１）またはＣｄy21Ｚｎ1-y21Ｓｅ（０≦ｙ２１＜１）なども好ましく用いられる。 In the present embodiment, an In x2 Ga 1-x2 N shell layer (0 <x2 <1) is used as the semiconductor shell layer, but In x2 Ga y2 Al 1-x2-y2 N (0 < x2, 0 <y2 X2 + y2 ≦ 1) or Cd y21 Zn 1-y21 Se (0 ≦ y21 <1) is also preferably used.

ここで、半導体コア粒子および半導体シェル層の元素組成比ｘ１、ｙ１、ｚ１１、ｚ１２、ｘ２、ｙ２、ｚ２１は、半導体コア粒子のＥ1と半導体シェル層のＥ2と励起光のＥeとの関係がＥ1＜Ｅ2≦ＥeとなるＥ1およびＥ2が得られるように設定する。また、半導体コア粒子の粒径は、半導体コア粒子のＥ1と半導体シェル層のＥ2とにより、所望のＥが得られるように設定する。 Here, the elemental composition ratio of the semiconductor core particles and semiconductor shell layers x1, y1, z11, z12, x2, y2, z21 is the E 2 of E 1 and the semiconductor shell layer of the semiconductor core particles E e of the excitation light E 1 and E 2 are set so that the relationship E 1 <E 2 ≦ E e is obtained. The particle size of the semiconductor core particles, by the E 2 of E 1 and the semiconductor shell layer of the semiconductor core particles are set as desired E is obtained.

本実施形態において用いられる発光素子は、特に制限はないが、半導体レーザまたは発光ダイオードが、安定したエネルギー（波長）を有する励起光が得られる点から、好ましい。   The light-emitting element used in the present embodiment is not particularly limited, but a semiconductor laser or a light-emitting diode is preferable because excitation light having stable energy (wavelength) can be obtained.

また、本実施形態の蛍光体粒子の製造方法には特に制限はないが、生成物質の構成元素を含む複数の出発物質を媒体に分散させ、これを反応させて目的の生成物質を得る化学合成法は簡便な手法であり低コストである点から好ましい。化学合成法には、ゾルゲル法(コロイド法)、逆ミセル法、分子プレカーサ法、水熱合成法、フラックス法などが含まれる。   The method for producing the phosphor particles of the present embodiment is not particularly limited, but a chemical synthesis in which a plurality of starting materials containing the constituent elements of the product substance are dispersed in a medium and reacted to obtain a target product substance. The method is preferable because it is a simple method and low cost. Chemical synthesis methods include sol-gel method (colloid method), reverse micelle method, molecular precursor method, hydrothermal synthesis method, flux method and the like.

（実施形態２）
本発明の実施形態２による蛍光体粒子分散体は、上記蛍光体粒子を２以上含む蛍光体粒子分散体であって、この蛍光体粒子分散体は、基底準位が異なる２以上の蛍光体粒子を含み、すべての蛍光体粒子の半導体シェル層のバンドギャップエネルギーＥ2が、すべての蛍光体粒子の半導体コア粒子中に形成される基底準位間のエネルギーＥよりも大きい蛍光体粒子分散体である。 (Embodiment 2)
A phosphor particle dispersion according to Embodiment 2 of the present invention is a phosphor particle dispersion including two or more of the phosphor particles, and the phosphor particle dispersion includes two or more phosphor particles having different ground levels. A phosphor particle dispersion in which the band gap energy E 2 of the semiconductor shell layer of all phosphor particles is larger than the energy E between the ground levels formed in the semiconductor core particles of all phosphor particles. is there.

さらに、具体的には、図３を参照して、図３（ａ）に示すような、基底準位が異なる２以上の蛍光体粒子が媒体３１００である透明なエポキシ樹脂中に分散された蛍光体粒子分散体３０００であって、すべての蛍光体粒子の半導体シェル層のバンドギャップエネルギーＥ2が、すべての蛍光体粒子の半導体コア粒子中に形成される基底準位間のエネルギーＥよりも大きい蛍光体粒子分散体について説明する。 More specifically, referring to FIG. 3, fluorescence in which two or more phosphor particles having different ground levels are dispersed in a transparent epoxy resin as medium 3100 as shown in FIG. In the body particle dispersion 3000, the band gap energy E 2 of the semiconductor shell layer of all the phosphor particles is larger than the energy E between the ground levels formed in the semiconductor core particles of all the phosphor particles. The phosphor particle dispersion will be described.

蛍光体粒子は、基底準位間のエネルギーＥの違いによって、異なる色の蛍光を発するため、たとえば、青色の蛍光を発する青色の蛍光体粒子、緑色の蛍光を発する緑色の蛍光体粒子および／または赤色の蛍光を発する赤色の蛍光体粒子を所定の割合で媒体に分散させることにより、蛍光色の色度を調整することができる。   Since the phosphor particles emit fluorescence of different colors depending on the difference in energy E between the ground levels, for example, blue phosphor particles that emit blue fluorescence, green phosphor particles that emit green fluorescence, and / or The chromaticity of the fluorescent color can be adjusted by dispersing the red phosphor particles emitting red fluorescence in the medium at a predetermined ratio.

たとえば、図３および図４を参照して、蛍光体粒子分散体３０００における青色の蛍光体粒子１００と赤色の蛍光体粒子３００との相互作用について説明する。   For example, with reference to FIG. 3 and FIG. 4, the interaction between the blue phosphor particles 100 and the red phosphor particles 300 in the phosphor particle dispersion 3000 will be described.

青色の蛍光体粒子１００は、半導体コア粒子１０１として２．００ｅＶ（波長６２０ｎｍ）のバンドギャップエネルギーＥ1Bを有するＩｎＮコア粒子と、半導体コア粒子１０１を被覆する半導体シェル層１０２として２．８２ｅＶ（波長４４０ｎｍ）のバンドギャップエネルギーＥ2Bを有するＩｎx21Ｇａ1-x21Ｎシェル層（０＜ｘ２１＜１）とからなり、Ｉｎx3Ｇａ1-x3Ｎ発光素子（０≦ｘ３≦１）が発した励起エネルギーＥeが２．８８ｅＶ（４３０ｎｍ）の励起光１１を受けて蛍光１３を発する蛍光体粒子である。本実施形態における青色の蛍光体粒子において、Ｉｎx21Ｇａ1-x21Ｎシェル層（０＜ｘ２１＜１）でＩｎＮコア粒子を被覆することによってＩｎＮコア粒子中に形成された基底準位１１１ｃ，１１１ｖ間のエネルギーＥBは２．５８ｅＶ（波長４８０ｎｍ）となり、波長４８０ｎｍの青色の蛍光１３を発する。 The blue phosphor particle 100 has an InN core particle having a band gap energy E 1B of 2.00 eV (wavelength 620 nm) as the semiconductor core particle 101 and 2.82 eV (wavelength as the semiconductor shell layer 102 covering the semiconductor core particle 101). 440 nm) of In x21 Ga 1-x21 N shell layer (0 <x21 <1) having a band gap energy E 2B and excited by an In x3 Ga 1-x3 N light emitting device (0 ≦ x3 ≦ 1) The phosphor particles emit fluorescence 13 upon receiving excitation light 11 having energy E e of 2.88 eV (430 nm). In the blue phosphor particles in the present embodiment, the ground levels 111c and 111v formed in the InN core particles by covering the InN core particles with an In x21 Ga 1 -x21 N shell layer (0 <x21 <1). energy E B between emits 2.58 eV (wavelength 480 nm), and the fluorescence 13 of the blue wavelength 480 nm.

また、赤色の蛍光体粒子３００は、半導体コア粒子３０１として２．００ｅＶ（波長６２０ｎｍ）のバンドギャップエネルギーＥ1Rを有するＩｎＮコア粒子と、半導体コア粒子３０１を被覆する半導体シェル層３０２として２．７６ｅＶ（波長４５０ｎｍ）のバンドギャップエネルギーＥ2Rを有するＩｎx22Ｇａ1-x22Ｎシェル層（０＜ｘ２２＜１）とからなり、Ｉｎx3Ｇａ1-x3Ｎ発光素子（０≦ｘ３≦１）が発した励起エネルギーＥeが２．８８ｅＶ（４３０ｎｍ）の励起光１１を受けて蛍光１３を発する蛍光体粒子である。本実施形態における赤色の蛍光体粒子において、Ｉｎx22Ｇａ1-x22Ｎシェル層（０＜ｘ２２＜１）でＩｎＮコア粒子を被覆することによってＩｎＮコア粒子中に形成された基底準位３１１ｃ，３１１ｖ間のエネルギーＥRは２．０３ｅＶ（波長６１０ｎｍ）となり、波長６１０ｎｍの赤色の蛍光１３を発する。 The red phosphor particles 300 have InN core particles having a band gap energy E 1R of 2.00 eV (wavelength 620 nm) as the semiconductor core particles 301 and 2.76 eV as the semiconductor shell layer 302 covering the semiconductor core particles 301. It consists of an In x22 Ga 1 -x22 N shell layer (0 <x22 <1) having a band gap energy E 2R (wavelength 450 nm), and an In x3 Ga 1-x3 N light emitting device (0 ≦ x3 ≦ 1) is emitted. The phosphor particles emit fluorescence 13 upon receiving excitation light 11 having an excitation energy E e of 2.88 eV (430 nm). In the red phosphor particles in the present embodiment, ground levels 311c and 311v formed in the InN core particles by covering the InN core particles with an In x22 Ga 1-x22 N shell layer (0 <x22 <1). energy between E R emits 2.03EV (wavelength 610 nm), and the fluorescence 13 of the red wavelength 610 nm.

すなわち、励起エネルギー２．８８ｅＶ（波長４３０ｎｍ）を有する励起光が上記蛍光体粒子分散体に照射されると、この励起光が青色の蛍光体粒子１００および赤色の蛍光体粒子３００のそれぞれに吸収されて、それぞれ、波長４８０ｎｍの青色の蛍光および６１０ｎｍの赤色の蛍光を発する。   That is, when excitation light having excitation energy of 2.88 eV (wavelength 430 nm) is irradiated onto the phosphor particle dispersion, the excitation light is absorbed by each of the blue phosphor particles 100 and the red phosphor particles 300. And emits blue fluorescence having a wavelength of 480 nm and red fluorescence having a wavelength of 610 nm, respectively.

上記のように、青色の蛍光体粒子および赤色の蛍光体粒子において、いずれの蛍光体粒子の半導体シェル層のＥ2B、Ｅ2Rを、いずれの蛍光体粒子の半導体コア粒子に形成される基底準位間のエネルギーＥB、ＥRよりも大きくすることによって、青色の蛍光体粒子からの青色の蛍光が赤色の蛍光体粒子に再吸収されることを抑制することができ、青色および赤色のそれぞれの色度を良好に保つことができる。 As described above, in the blue phosphor particles and the red phosphor particles, the E 2B and E 2R of the semiconductor shell layer of any phosphor particle are used as the base level formed on the semiconductor core particle of any phosphor particle. By making the interstitial energy E B or E R larger than the blue fluorescent particles, it is possible to suppress the blue fluorescent particles from being reabsorbed by the red fluorescent particles. Can maintain good chromaticity.

上記では青色の蛍光体粒子と赤色の蛍光体粒子との関係について説明したが、青色の蛍光体粒子と緑色の蛍光体粒子との関係および緑色の蛍光体粒子と赤色の蛍光体粒子との関係についても同様である。   In the above description, the relationship between the blue phosphor particles and the red phosphor particles is described. However, the relationship between the blue phosphor particles and the green phosphor particles and the relationship between the green phosphor particles and the red phosphor particles. The same applies to.

すなわち、基底準位が異なる２以上の上記蛍光体粒子を含む蛍光体粒子分散体において、すべての蛍光体粒子の半導体シェル層のバンドギャップエネルギーＥ2が、すべての蛍光体粒子の半導体コア粒子中に形成される基底準位間のエネルギーＥよりも大きくなるように蛍光体粒子を設計することにより、各蛍光体粒子の蛍光の色度が良好で、演色性に優れた蛍光体粒子分散体が得られる。 That is, in the phosphor particle dispersion including two or more phosphor particles having different ground levels, the band gap energy E 2 of the semiconductor shell layer of all phosphor particles is in the semiconductor core particles of all phosphor particles. By designing the phosphor particles so as to be larger than the energy E between the ground levels formed in the phosphor particles, a phosphor particle dispersion having excellent chromaticity of fluorescence of each phosphor particle and excellent color rendering properties can be obtained. can get.

ところで、上記のように複数の蛍光体粒子を分散させた場合の蛍光の光学特性について、以下に説明する。   By the way, the optical characteristics of fluorescence when a plurality of phosphor particles are dispersed as described above will be described below.

図３（ｂ）には、青色の蛍光体粒子１００および赤色の蛍光体粒子３００に、それぞれ励起光１１が照射され、半導体コア粒子の粒径に応じた基底準位間のエネルギーに基づく蛍光１３，３３と、励起光１３が蛍光体粒子表面によって散乱された散乱光１２，３２が発生する様子も示されている。   In FIG. 3B, the blue phosphor particles 100 and the red phosphor particles 300 are respectively irradiated with the excitation light 11, and the fluorescence 13 based on the energy between the ground levels according to the particle size of the semiconductor core particles. 33 and the scattered light 12 and 32 in which the excitation light 13 is scattered by the phosphor particle surface are also shown.

このような蛍光体粒子における励起光または他の蛍光体粒子から放射された蛍光に対する蛍光体粒子の散乱状態は、散乱角θ方向の強度をＩ（θ）とすると
Ｉ（θ）＝｜Σ(２ν＋１)／ν(ν＋１)｛ａνΠν(cosθ)＋ｂντν(cosθ)｝｜2
ν=１、∞
で表される。ここでａν、ｂνは複素振幅を表す係数で、粒子の屈折率およびサイズ因子（粒子サイズ）の関数である。また、Πν、τνは散乱角のみの関数で、ルジャンドルの多項式およびその導関数である。 The scattering state of the phosphor particles with respect to the excitation light in such phosphor particles or the fluorescence emitted from other phosphor particles is expressed as follows: I (θ) = | Σ ( 2ν + 1) / ν (ν + 1) {a ν Π ν (cosθ) + b ν τ ν (cosθ)} | 2
ν = 1, ∞
It is represented by Here, a ν and b ν are coefficients representing complex amplitudes, which are functions of the refractive index of the particles and the size factor (particle size). Further, ν ν and τ ν are functions of only the scattering angle, and are a Legendre polynomial and its derivatives.

このため、各色を発色する蛍光体粒子の粒径がそれぞれ異なる場合には、励起光や他の蛍光体粒子から放射される蛍光の散乱状態が蛍光体粒子の種類毎に異なってしまう。   For this reason, when the particle diameters of the phosphor particles that develop the respective colors are different, the scattering state of the fluorescence emitted from the excitation light and other phosphor particles is different for each type of the phosphor particles.

このとき、蛍光の散乱状態を調整するため、図５で示されるように、蛍光体粒子１００，３００において半導体シェル層１０２，３０２の厚さのみによって調整しようとすると、励起光を吸収する半導体シェル層１０２、３０２の体積が異なってしまい、励起光に対する吸収係数がそれぞれの蛍光体粒子で異なるという問題が生じる。   At this time, in order to adjust the scattering state of the fluorescence, as shown in FIG. 5, if the phosphor particles 100 and 300 are adjusted only by the thickness of the semiconductor shell layers 102 and 302, the semiconductor shell that absorbs excitation light is used. The volumes of the layers 102 and 302 are different, which causes a problem that the absorption coefficient for the excitation light is different for each phosphor particle.

この問題をするために、半導体コア粒子に形成される基底準位間のエネルギーＥの大きさを調節するためには、半導体シェル層１０２、３０２の厚さだけでなく、半導体コア粒子および／または半導体シェル層の構成元素種、組成比の調整が行われる。すなわち、本実施形態においては、蛍光体粒子分散体に含まれるすべての蛍光体粒子の半導体シェル層のバンドギャップエネルギーＥ2を、すべての蛍光体粒子の半導体コア粒子中に形成される基底準位間のエネルギーＥより大きくなるように、半導体コア粒子および／または半導体シェル層の構成元素種および／または組成比を調節する。 In order to adjust the magnitude of the energy E between the ground levels formed in the semiconductor core particle in order to solve this problem, not only the thickness of the semiconductor shell layers 102 and 302 but also the semiconductor core particle and / or The constituent element species and composition ratio of the semiconductor shell layer are adjusted. That is, in the present embodiment, the band gap energy E 2 of the semiconductor shell layers of all the phosphor particles contained in the phosphor particle dispersion is changed to the ground level formed in the semiconductor core particles of all the phosphor particles. The constituent element species and / or composition ratio of the semiconductor core particles and / or the semiconductor shell layer are adjusted so as to be larger than the energy E between them.

（実施形態３）
本発明の実施形態３による照明装置は、図６を参照して、励起エネルギーが２．８８ｅＶ（波長４３０ｎｍ）の励起光を発するＩｎx4Ｇａ1-x4Ｎ発光ダイオード（０≦ｘ４≦１）のチップ（図示せず）が実装されているリードフレーム６０１の上部に、２以上の青色の蛍光体粒子、緑色の蛍光体粒子および赤色の蛍光体粒子を媒体としての透明エポキシ樹脂に分散させた蛍光体粒子分散体６０２が形成された照明装置６００である。ここで、上記蛍光体粒子分散体６０２中に含まれるすべての蛍光体粒子の半導体シェル層のバンドギャップエネルギーＥ2を、すべての蛍光体粒子の半導体コア粒子中に形成される基底準位間のエネルギーＥより大きくなるように、すべての蛍光体粒子が設計されているため、各蛍光体粒子の蛍光の混色によって、演色性に優れた白色照明装置となる。なお、上記点状の照明装置をアレイ状に並べることにより面状の照明装置とすることもできる。 (Embodiment 3)
The illumination device according to Embodiment 3 of the present invention is an In x4 Ga 1-x4 N light emitting diode (0 ≦ x4 ≦ 1) that emits excitation light having an excitation energy of 2.88 eV (wavelength 430 nm) with reference to FIG. Fluorescence in which two or more blue phosphor particles, green phosphor particles, and red phosphor particles are dispersed in a transparent epoxy resin as a medium on top of a lead frame 601 on which a chip (not shown) is mounted. It is the illuminating device 600 in which the body particle dispersion 602 was formed. Here, the band gap energy E 2 of the semiconductor shell layers of all the phosphor particles contained in the phosphor particle dispersion 602 is determined between the ground levels formed in the semiconductor core particles of all the phosphor particles. Since all the phosphor particles are designed so as to be larger than the energy E, a white illumination device having excellent color rendering properties is obtained by the color mixture of the fluorescence of each phosphor particle. In addition, it can also be set as a planar illuminating device by arranging the said point-shaped illuminating device in an array form.

（実施形態４）
本発明の実施形態４による照明装置は、図７を参照して、図７（ａ）に示すように、励起エネルギーが２．８８ｅＶ（波長４３０ｎｍ）の励起光を発振するＩｎx5Ｇａ1-x5Ｎ半導体レーザ（０≦ｘ５≦１）のチップ（図示せず）が実装されたステム７０１が、樹脂７０７を介して導光体７０８に光学的に結合されている照明装置７００である。 (Embodiment 4)
Lighting device according to a fourth embodiment of the present invention, with reference to FIG. 7, as shown in FIG. 7 (a), In x5 Ga 1-x5 excitation energy oscillates excitation light of 2.88 eV (wavelength 430 nm) A stem 701 on which a chip (not shown) of an N semiconductor laser (0 ≦ x5 ≦ 1) is mounted is an illumination device 700 that is optically coupled to a light guide 708 via a resin 707.

ここで、図７（ａ）および図７（ｂ）を参照して、上記導光体７０８は、アクリルからなるコア７０２がこのコアより屈折率の低いフッ素系樹脂からなるクラッド７０４によって被覆された構造を有する。また、この導光体７０８の片方の端面にはＩｎx5Ｇａ1-x5Ｎ半導体レーザが、他方の端面には導光体内を伝播する励起光を反射するたとえば酸化シリコンからなる反射膜７０６が形成されている。さらに、上記コア７０２の一部にはＴｉＯ2粒子よりなる散乱体７０３が設けられており、半導体レーザよりこの導光体７０８に入射した励起光はこの散乱体７０３によって周りに拡散される。なお、ＴｉＯ2粒子からなる上記散乱体を用いる構成に換えて、コア７０２とクラッド７０４の界面に凹凸部を設け（図示せず）、この凹凸部を有する界面における乱反射を用いるような構成としてもよい。さらに、上記導光体７０８の外周に、２以上の青色の蛍光体粒子、緑色の蛍光体粒子および赤色の蛍光体粒子を媒体としての透明エポキシ樹脂に分散させた蛍光体粒子分散体７０５を形成して本照明装置７００の蛍光体層７０９とする。 Here, referring to FIG. 7A and FIG. 7B, in the light guide 708, a core 702 made of acrylic is covered with a clad 704 made of a fluororesin having a refractive index lower than that of the core. It has a structure. Further, an In x5 Ga 1 -x5 N semiconductor laser is formed on one end face of the light guide 708, and a reflection film 706 made of, for example, silicon oxide that reflects excitation light propagating through the light guide is formed on the other end face. Has been. Further, a scatterer 703 made of TiO 2 particles is provided on a part of the core 702, and excitation light incident on the light guide 708 from the semiconductor laser is diffused around by the scatterer 703. Instead of using the scatterer made of TiO 2 particles, an uneven portion (not shown) is provided at the interface between the core 702 and the clad 704, and irregular reflection at the interface having the uneven portion may be used. Good. Further, a phosphor particle dispersion 705 in which two or more blue phosphor particles, green phosphor particles, and red phosphor particles are dispersed in a transparent epoxy resin as a medium is formed on the outer periphery of the light guide 708. Thus, the phosphor layer 709 of the lighting device 700 is obtained.

以上の構成により、演色性に優れた線状の白色蛍光７１０を発する照明装置が得られる。また、蛍光体粒子分散体中の青色の蛍光体粒子、緑色の蛍光体粒子および／または赤色の蛍光体粒子の混合比を適宜変えることによって白色以外の所望とされる色度を有する照明装置を実現できる。   With the above configuration, an illumination device that emits linear white fluorescent light 710 excellent in color rendering can be obtained. An illumination device having a desired chromaticity other than white by appropriately changing the mixing ratio of blue phosphor particles, green phosphor particles, and / or red phosphor particles in the phosphor particle dispersion. realizable.

なお、実施形態３または実施形態４に示す点状または線状の照明装置は、一般家庭における照明装置や、更には液晶のバックライトや液晶プロジェクターの光源としての照明に用いることもできる。   Note that the dotted or linear illumination device shown in Embodiment 3 or Embodiment 4 can also be used for illumination as a lighting device in a general home, and further as a liquid crystal backlight or a light source of a liquid crystal projector.

（実施形態５）
本発明の実施形態５による表示装置は、図８を参照して、Ｉｎx5Ｇａ1-x5Ｎ半導体レーザ（０≦ｘ５≦１）のチップ（図示せず）が実装されたステム７０１が導光体８１１に光学的に結合され、この導光体８１１が別の導光体８０１に光学的に結合され、導光体８０１の上面部には光強度を変調するための光変調素子８０２を介してそれぞれの色の蛍光体粒子または蛍光粒子分散体を含む素子（具体的には、青色蛍光体粒子含有樹脂８０３、緑色蛍光体粒子含有樹脂８０４、赤色蛍光体粒子含有樹脂８０５）が形成された表示装置８００である。 (Embodiment 5)
In the display device according to the fifth embodiment of the present invention, referring to FIG. 8, a stem 701 on which a chip (not shown) of an In x5 Ga 1-x5 N semiconductor laser (0 ≦ x5 ≦ 1) is mounted is guided. The light guide body 811 is optically coupled to another light guide body 801, and an upper surface portion of the light guide body 801 is provided with a light modulation element 802 for modulating light intensity. Thus, an element (specifically, a blue phosphor particle-containing resin 803, a green phosphor particle-containing resin 804, and a red phosphor particle-containing resin 805) including phosphor particles or phosphor particle dispersions of respective colors is formed. This is a display device 800.

ここで、導光体８１１は、アクリルからなるコア７０２がこのコアより屈折率の低いフッ素系樹脂からなるクラッド７０４によって被覆され、このクラッド７０４は開口部８１１ａを有する金属Ａｌ膜からなる反射膜８１２によって被覆された構造を有する。このコア７０２の一部にはＴｉＯ2粒子からなる散乱体７０３が形成されている。さらに、この導光体８１１の一方の端面には、Ｉｎx5Ｇａ1-x5Ｎ半導体レーザを実装するステム７０１が配置され、他方の端面には、このＩｎx5Ｇａ1-x5Ｎ半導体レーザの光を反射するたとえば酸化シリコンからなる反射膜７０６が形成されている。かかる構成により、点状光源である半導体レーザから放射される励起光が線状光源に変換される。 Here, in the light guide 811, a core 702 made of acrylic is covered with a clad 704 made of a fluorine-based resin having a refractive index lower than that of the core, and the clad 704 is a reflective film 812 made of a metal Al film having an opening 811 a. It has a structure covered with. A scatterer 703 made of TiO 2 particles is formed on a part of the core 702. Further, the one end surface of the light guide 811, In x5 Ga 1-x5 N stem 701 for mounting the semiconductor laser is disposed on the other end face, the light of the In x5 Ga 1-x5 N semiconductor laser A reflective film 706 made of, for example, silicon oxide is formed. With this configuration, excitation light emitted from a semiconductor laser that is a point light source is converted into a linear light source.

そして、この導光体８１１は別の導光体８０１に光学的に結合されており、この導光体８１１の開口部８１１ａから放射される線状の励起光がこの導光体８０１に入射される。さらに、この導光体８０１の下面（裏面）側には金属Ａｌ膜からなる反射膜８０６が形成されており、線状の励起光はこの導光体８０１中を伝播しつつ、線状の励起光の一部が反射膜８０６によって上面方向に放射される。かかる構成により、線状の光源が面状の光源に変換される。   The light guide 811 is optically coupled to another light guide 801, and linear excitation light radiated from the opening 811 a of the light guide 811 is incident on the light guide 801. The Further, a reflective film 806 made of a metal Al film is formed on the lower surface (rear surface) side of the light guide 801, and linear excitation light propagates through the light guide 801 and is linearly excited. A part of the light is emitted in the upper surface direction by the reflective film 806. With this configuration, a linear light source is converted into a planar light source.

この導光体８０１の上面には、光変調素子８０２として放射された励起光の光強度を制御するよう偏光板に挟まれたアクティブマトリクス駆動型ＴＦＴ（薄膜トランジスタ）を含む液晶光変調素子が設けられており、この液晶光変調素子によって光強度が変調される。   On the upper surface of the light guide 801, a liquid crystal light modulation element including an active matrix driving type TFT (thin film transistor) sandwiched between polarizing plates so as to control the light intensity of the excitation light emitted as the light modulation element 802 is provided. The light intensity is modulated by the liquid crystal light modulation element.

光変調素子８０２の上面には、光変調素子上の各画素に対応して、媒体である透明エポキシ樹脂中に各色の蛍光体粒子が分散した蛍光体粒子含有素子（青色蛍光体粒子含有樹脂８０３、緑色蛍光体粒子含有樹脂８０４、赤色蛍光体粒子含有樹脂８０５）が配置されている。このため、光強度が変調された励起光が上記の青色蛍光体粒子含有樹脂８０３、緑色蛍光体粒子含有樹脂８０４および赤色蛍光体粒子含有樹脂８０５に照射されることにより、所望の画像を表示することができる。このようにして、演色性に優れた表示装置が得られる。なお、蛍光体から放射された蛍光の光強度を制御する手段としては、蛍光体より放射される蛍光を光電界吸収効果で吸収するような手段を用いることもできる。   On the upper surface of the light modulation element 802, a phosphor particle-containing element (blue phosphor particle-containing resin 803) in which phosphor particles of each color are dispersed in a transparent epoxy resin, which is a medium, corresponding to each pixel on the light modulation element. , Green phosphor particle-containing resin 804, red phosphor particle-containing resin 805). Therefore, a desired image is displayed by irradiating the blue phosphor particle-containing resin 803, the green phosphor particle-containing resin 804, and the red phosphor particle-containing resin 805 with the excitation light whose light intensity is modulated. be able to. In this way, a display device excellent in color rendering is obtained. In addition, as a means for controlling the light intensity of the fluorescence emitted from the phosphor, a means for absorbing the fluorescence emitted from the phosphor by the optical electric field absorption effect can be used.

今回開示された実施の形態はすべての点で例示であって制限的なものではないと考えられるべきである。本発明の範囲は、上記した説明でなくて特許請求の範囲によって示され、特許請求の範囲と均等の意味および範囲内のすべての変更が含まれることが意図される。   The embodiment disclosed this time should be considered as illustrative in all points and not restrictive. The scope of the present invention is defined by the terms of the claims, rather than the description above, and is intended to include any modifications within the scope and meaning equivalent to the terms of the claims.

上記のように、本発明は、励起光の吸収効率が高く輝度の高い蛍光体粒子および演色性に優れた蛍光体粒子分散体ならびにこれらを含む照明装置および表示装置に広く利用することができる。   As described above, the present invention can be widely used for phosphor particles with high excitation light absorption efficiency and high luminance, phosphor particle dispersions excellent in color rendering, and illumination devices and display devices including these.

（ａ）は本発明の実施形態１による蛍光体粒子の断面模式図である。（ｂ）は本発明の実施形態１による蛍光体粒子のバンド構造図である。(A) is a cross-sectional schematic diagram of the phosphor particles according to Embodiment 1 of the present invention. FIG. 2B is a band structure diagram of phosphor particles according to Embodiment 1 of the present invention. （ａ）は従来の蛍光体粒子の断面模式図である。（ｂ）は従来の蛍光体粒子のバンド構造図である。(A) is a cross-sectional schematic diagram of conventional phosphor particles. (B) is the band structure figure of the conventional fluorescent substance particle. （ａ）は本発明の実施形態２による蛍光体粒子分散体の立体透視模式図である。（ｂ）は本発明の実施形態２による蛍光体粒子分散体中における２つの蛍光体粒子の拡大断面模式図である。(A) is a three-dimensional perspective schematic diagram of the phosphor particle dispersion according to Embodiment 2 of the present invention. (B) is an expanded cross-sectional schematic diagram of two fluorescent substance particles in the fluorescent substance particle dispersion by Embodiment 2 of this invention. 本発明の実施形態２による蛍光体粒子分散体中における２つの蛍光体粒子のバンド構造図である。It is a band structure figure of two fluorescent substance particles in the fluorescent substance particle dispersion by Embodiment 2 of the present invention. 蛍光体粒子分散体中における２つの蛍光体粒子について、半導体シェル層の厚さの調節を説明する断面模式図である。It is a cross-sectional schematic diagram explaining adjustment of the thickness of a semiconductor shell layer about two fluorescent substance particles in a fluorescent substance particle dispersion. 本発明の実施形態３による照明装置の立体模式図である。It is a three-dimensional schematic diagram of the illuminating device by Embodiment 3 of this invention. （ａ）は本発明の実施形態４による照明装置の立体模式図である。（ｂ）本発明の実施形態４による照明装置のＶＩＩ方向からの断面模式図である。(A) is a three-dimensional schematic diagram of the illuminating device by Embodiment 4 of this invention. (B) It is a cross-sectional schematic diagram from the VII direction of the illuminating device by Embodiment 4 of this invention. （ａ）本発明の実施形態５による表示装置の立体模式図である。（ｂ）本発明の実施形態５による表示装置に用いられる導光体のＶＩＩＩ方向からの断面模色図である。(A) It is a three-dimensional schematic diagram of the display apparatus by Embodiment 5 of this invention. (B) It is a cross-sectional schematic diagram from the VIII direction of the light guide used for the display apparatus by Embodiment 5 of this invention.

符号の説明Explanation of symbols

１１ 励起光、１２，２２，３２ 散乱光、１３，２３，３３ 蛍光、１４ 電子、１５ 正孔、１００，２００，３００ 蛍光体粒子、１０１，２０１，３０１ 半導体コア粒子、１０１ｃ，１０２ｃ，２０１ｃ，２０２ｃ，３０１ｃ，３０２ｃ 伝導帯、１０１ｖ，１０２ｖ，２０１ｖ，２０２ｖ，３０１ｖ，３０２ｖ 価電子帯、１０２，２０２，３０２ 半導体シェル層、１１１ｃ，１１１ｖ，２１１ｃ，２１１ｖ，３１１ｃ，３１１ｖ 基底準位、６００，７００ 照明装置、６０２，７０５，３０００ 蛍光体粒子分散体、７０１ ステム、７０２ コア、７０３ 散乱体、７０４ クラッド、７０６，８０６，８１２ 反射膜、７０７ 樹脂、７０８，８０１，８１１ 導光体、７０９ 蛍光体層、７１０ 白色蛍光、８００ 表示装置、８０２ 光変調素子、８０３ 青色蛍光体粒子含有樹脂、８０４ 緑色蛍光体粒子含有樹脂、８０５ 赤色蛍光体粒子含有樹脂、８１１ａ 開口部、３１００ 媒体。   11 excitation light, 12, 22, 32 scattered light, 13, 23, 33 fluorescence, 14 electrons, 15 holes, 100, 200, 300 phosphor particles, 101, 201, 301 semiconductor core particles, 101c, 102c, 201c, 202c, 301c, 302c conduction band, 101v, 102v, 201v, 202v, 301v, 302v valence band, 102, 202, 302 semiconductor shell layer, 111c, 111v, 211c, 211v, 311c, 311v ground level, 600, 700 Illumination device, 602, 705, 3000 phosphor particle dispersion, 701 stem, 702 core, 703 scatterer, 704 clad, 706, 806, 812 reflective film, 707 resin, 708, 801, 811 light guide, 709 phosphor Layer, 710 white fluorescence, 800 display, 80 2 Light modulation element, 803 Blue phosphor particle-containing resin, 804 Green phosphor particle-containing resin, 805 Red phosphor particle-containing resin, 811a opening, 3100 medium.

Claims (9)

励起エネルギーＥeを有する励起光を受けて蛍光を発する蛍光体粒子であって、
バンドギャップエネルギーＥ1を有する半導体コア粒子と、前記半導体コア粒子を被覆するバンドギャップエネルギーＥ2を有する半導体シェル層を含み、
前記半導体コア粒子のＥ1と、前記半導体シェル層のＥ2と、前記励起光のＥeとの関係が、Ｅ1＜Ｅ2≦Ｅeであり、
前記半導体シェル層で前記半導体コア粒子を被覆することにより前記半導体コア粒子中にＥ1とＥ2との間のエネルギーを有する離散的なエネルギー準位が形成され、前記エネルギー準位における基底準位間のエネルギーＥに基づく蛍光を発する蛍光体粒子。 Phosphor particles that emit fluorescence in response to excitation light having excitation energy E e ,
Includes a semiconductor core particles having a band gap energy E 1, a semiconductor shell layer having a band gap energy E 2 covering the semiconductor core particles,
The relationship between E 1 of the semiconductor core particles, E 2 of the semiconductor shell layer, and E e of the excitation light is E 1 <E 2 ≦ E e ,
By covering the semiconductor core particle with the semiconductor shell layer, a discrete energy level having energy between E 1 and E 2 is formed in the semiconductor core particle, and a ground level in the energy level is formed. Phosphor particles emitting fluorescence based on the energy E between them. 前記基底準位間のエネルギーが、１．８５ｅＶ〜２．０６ｅＶ、２．２９ｅＶ〜２．４８ｅＶまたは２．５８ｅＶ〜３．０２ｅＶのいずれかの範囲にある請求項１に記載の蛍光体粒子。   The phosphor particles according to claim 1, wherein the energy between the ground levels is in a range of 1.85 eV to 2.06 eV, 2.29 eV to 2.48 eV, or 2.58 eV to 3.02 eV. 前記半導体コア粒子が、Ｉｎx1Ｇａy1Ａｌ1-x1-y1Ｎ（０＜ｘ１、０≦ｙ１、ｘ１＋ｙ１≦１）、Ｃｄz11Ｚｎ1-z11Ｓｅ（０＜ｚ１１≦１）およびＣｄz12Ｚｎ1-z12Ｓ（０＜ｚ１２≦１）からなる群から選ばれた１つの半導体からなる請求項１または請求項２に記載の蛍光体粒子。 The semiconductor core particles are In x1 Ga y1 Al 1-x1-y1 N (0 <x1, 0 ≦ y1, x1 + y1 ≦ 1), Cd z11 Zn 1-z11 Se (0 <z11 ≦ 1) and Cd z12 Zn 1 The phosphor particle according to claim 1 or 2, comprising a single semiconductor selected from the group consisting of -z12 S (0 <z12 ≦ 1). 前記半導体シェル層が、Ｉｎx2Ｇａy2Ａｌ1-x2-y2Ｎ（０＜ｘ２、０＜ｙ２、ｘ２＋ｙ２≦１）およびＣｄy21Ｚｎ1-y21Ｓｅ（０≦ｙ２１＜１）からなる群から選ばれた１つの半導体からなる請求項１〜請求項３のいずれかに記載の蛍光体粒子。 The semiconductor shell layer, selected from the In x2 Ga y2 Al 1-x2 -y2 N (0 <x2,0 <y2, x2 + y2 ≦ 1) and Cd y21 Zn 1-y21 group consisting Se (0 ≦ y21 <1) The phosphor particle according to any one of claims 1 to 3, which is made of a single semiconductor. 半導体レーザまたは発光ダイオードからなる発光素子からの励起光を受けて発光する請求項１〜請求項４のいずれかに記載の蛍光体粒子。   The phosphor particles according to claim 1, which emit light upon receiving excitation light from a light emitting element comprising a semiconductor laser or a light emitting diode. 請求項１〜請求項５のいずれかに記載の蛍光体粒子を２以上含む蛍光体粒子分散体であって、
前記基底準位が異なる２以上の前記蛍光体粒子を含み、すべての前記蛍光体粒子の半導体シェル層のバンドギャップエネルギーＥ2が、すべての前記蛍光体粒子の半導体コア粒子中に形成される基底準位間のエネルギーＥよりも大きいことを特徴とする蛍光体粒子分散体。 A phosphor particle dispersion comprising two or more phosphor particles according to any one of claims 1 to 5,
The base includes two or more phosphor particles having different ground levels, and the band gap energy E 2 of the semiconductor shell layer of all the phosphor particles is formed in the semiconductor core particles of all the phosphor particles. A phosphor particle dispersion characterized by being larger than energy E between levels. 前記２以上の蛍光体粒子が媒体中に分散されている請求項６に記載の蛍光体粒子分散体。   The phosphor particle dispersion according to claim 6, wherein the two or more phosphor particles are dispersed in a medium. 請求項１〜請求項７のいずれかに記載の蛍光体粒子または蛍光体粒子分散体と、発光素子とを含む照明装置。   The illuminating device containing the fluorescent substance particle or fluorescent substance particle dispersion in any one of Claims 1-7, and a light emitting element. 請求項１〜請求項７のいずれかに記載の蛍光体粒子または蛍光体粒子分散体と、発光素子と、前記蛍光体粒子または前記蛍光体粒子分散体から発する蛍光および発光素子から発する励起光の少なくとも１つの光の光強度を変調する光強度変調手段を含む表示装置。   The phosphor particles or phosphor particle dispersion according to any one of claims 1 to 7, a light emitting element, fluorescence emitted from the phosphor particles or phosphor particle dispersion, and excitation light emitted from the light emitting element. A display device comprising light intensity modulation means for modulating the light intensity of at least one light.
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