JP2009040944A - Phosphor, phosphor-containing composition, light emitter, lighting apparatus, and image display device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a blue to green color-emitting phosphor capable of being excited by near-ultraviolet light, having a half band width broader than that of the prior phosphor, and being preferable to obtain natural white light. <P>SOLUTION: This phosphor has a chemical composition represented by following formula (1): M<SP>1</SP><SB>3-3x</SB>Eu<SB>3x</SB>M<SP>2</SP><SB>1-y</SB>Ln<SB>y</SB>Si<SB>2</SB>O<SB>8-z</SB>N<SB>z</SB>(1), wherein M<SP>1</SP>represents at least one element selected from the group consisting of Ba, Sr and Ca, M<SP>2</SP>represents at least one element selected from the group consisting of Mg and Zn, Ln represents at least one element selected from the group consisting of La, Lu, Y, Sc and Gd, and x, y and z are each a positive number which satisfies 0<x<1, 0.05≤y<1, and 0≤z<1. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

The present invention relates to a phosphor that emits blue to green light by excitation with near-ultraviolet light, a phosphor-containing composition containing the phosphor, a light-emitting device, an illumination device using the light-emitting device, and an image display device.
More specifically, the phosphor has a wide emission wavelength range, and is preferable for obtaining white light closer to natural light. The phosphor, the phosphor-containing composition containing the phosphor, the light-emitting device, and illumination using the light-emitting device The present invention relates to an apparatus and an image display apparatus.

  In recent years, development of white light emitting devices for display and illumination using semiconductor light emitting devices has been actively conducted. As phosphors used in these apparatuses, those using blue light as an excitation light source and those using near ultraviolet light as an excitation light source are known. Currently, most of the above use blue light as an excitation light source, and those using near ultraviolet light as an excitation light source are limited.

(Ba, Sr) ₂ SiO ₄ : Eu, BaMgAl ₁₀ O ₁₇ : Eu, Mn, and the like are known as phosphors that emit near-ultraviolet light as an excitation light source and emit green light. White light closer to natural light is known. In order to obtain the above, a phosphor having a larger half width is desired (see Patent Documents 1 and 2).

Further, as one of the phosphors using near ultraviolet light as an excitation light source, a phosphor having a host crystal composition of a composition of Ba ₃ MgSi ₂ O ₈ is known (see Patent Documents 3 to 5). Also, only blue emission or red emission was performed. In addition, since the half width of the emission spectrum is narrow, white light closer to natural light could not be obtained.

US Pat. No. 6,982,045 Japanese Examined Patent Publication No. 52-22836 International Publication No. 2005/112135 Pamphlet JP 2002-332481 A JP 2006-124644 A

As described above, in order to obtain white light close to natural light with a phosphor that can be excited by near-ultraviolet light, a phosphor exhibiting an emission spectrum shape with a wider half-value width is desired.
The present invention has been made in view of the above-described problems. The object is to provide a blue to green phosphor that can be excited by near-ultraviolet light, has a half-value width wider than that of conventional phosphors, and is preferable for obtaining natural white light.

As a result of intensive studies to solve the above-mentioned problems, the inventors of the present invention have obtained a part of Mg sites of a phosphor having a merwinite structure and a base crystal composition of Ba ₃ MgSi ₂ O _8. The inventors have found that by substituting with a specific rare earth element, the full width at half maximum of the emission spectrum is increased and the emission peak wavelength is shifted to the longer wavelength side, and the present invention has been completed.

（前記式（１）において、Ｍ¹は、Ｂａ、Ｓｒ及びＣａからなる群より選ばれる１種以上の元素を示し、Ｍ²は、Ｍｇ及びＺｎからなる群より選ばれる１種以上の元素を示し、Ｌｎは、Ｌａ、Ｌｕ、Ｙ、Ｓｃ及びＧｄからなる群より選ばれる１種以上の元素を示し、ｘ、ｙ及びｚは、各々、０＜ｘ＜１、０．０５≦ｙ＜１、０≦ｚ＜１、を満たす正の数を示す。） That is, the gist of the present invention resides in a phosphor having a chemical composition represented by the following formula (1) (claim 1).

(In the formula (1), M ¹ represents one or more elements selected from the group consisting of Ba, Sr and Ca, and M ² represents one or more elements selected from the group consisting of Mg and Zn. Ln represents one or more elements selected from the group consisting of La, Lu, Y, Sc, and Gd, and x, y, and z represent 0 <x <1, 0.05 ≦ y <1, respectively. And a positive number satisfying 0 ≦ z <1.)

  At this time, when excited with light having a wavelength of 395 nm, it preferably has a peak wavelength of the emission spectrum in a wavelength range of 420 nm to 550 nm.

  Moreover, it is also preferable that the half width of the peak of the emission spectrum is 60 nm or more.

  Another gist of the present invention is an emission spectrum having one peak wavelength in a wavelength range of 420 nm or more and 550 nm or less when excited with light having a wavelength range of 250 nm or more and 480 nm or less, and half of the peak of the emission spectrum. It exists in the fluorescent substance characterized by having a value range of 145 nm or more.

（前記式（２）において、Ｍ³及びＭ⁴は、それぞれ独立にアルカリ金属元素、アルカリ土類金属元素、及び２価の遷移元素からなる群より選ばれる１種以上の元素を示し、Ｍ⁵は、Ｂ、Ａｌ、Ｓｉ、Ｇｅ、Ｐ、Ａｓ、及びＳｂからなる群より選ばれる１種以上の元素を示し、Ｍ⁶は、Ｏ、Ｎ、Ｓ、及びハロゲンからなる群より選ばれる１種以上の元素を示し、Ｌ¹は、Ｓｍ、Ｅｕ、Ｔｍ及びＹｂからなる群より選ばれる１種以上の元素を示し、Ｌ²は、希土類元素を示す。また、Ｍ³のイオン半径はＭ⁴のイオン半径より大きく、Ｌ²のイオン半径はＭ⁴の０．７倍以上１．３倍以下の範囲である。） At this time, it is preferable to have a chemical composition represented by the following formula (2).

(In the formula (2), M ³ and M ⁴ are respectively an alkali metal element independently, an alkaline earth metal element, and one or more elements selected from the group consisting of divalent transition element, M ⁵ Represents one or more elements selected from the group consisting of B, Al, Si, Ge, P, As, and Sb, and M ⁶ is one type selected from the group consisting of O, N, S, and halogen L ¹ represents one or more elements selected from the group consisting of Sm, Eu, Tm, and Yb, L ² represents a rare earth element, and M ^{3 has} an ionic radius of M ⁴ The ion radius of L ² is in the range of 0.7 to 1.3 times M ^4. )

  Another gist of the present invention resides in a phosphor-containing composition comprising the above-mentioned phosphor and a liquid medium (claim 6).

  Another gist of the present invention is provided with a first light emitter and a second light emitter that emits visible light by irradiation of light from the first light emitter, and the second light emitter is claimed in claim One or more types of the phosphors according to any one of 1 to 5 are contained as a first phosphor. The present invention resides in a light-emitting device.

  At this time, it is preferable that the second phosphor includes at least one phosphor having a different emission peak wavelength from the first phosphor as the second phosphor.

  The first light emitter has a light emission peak in a wavelength range of 300 nm to 420 nm, and the second light emitter emits light in a wavelength range of more than 490 nm and less than 570 nm as the second phosphor. It is also preferable to contain at least one kind of phosphor having a peak and at least one kind of phosphor having an emission peak in a wavelength range of more than 570 nm and not more than 780 nm (claim 9).

  Further, the first light emitter has a light emission peak in a wavelength range of 300 nm to 420 nm, and the second light emitter as the second phosphor has a light emission peak in a wavelength range of 420 nm to 490 nm. It is also preferable to contain at least one kind of phosphor having the above and at least one kind of phosphor having an emission peak in a wavelength range of more than 570 nm and not more than 780 nm (claim 10).

  Another subject matter of the present invention lies in an illumination device characterized by comprising the above light emitting device (claim 11).

  Another subject matter of the present invention lies in an image display device comprising the above light emitting device (claim 12).

  According to the present invention, a novel blue to green phosphor that can be excited by near-ultraviolet light, which has a wider half-value width than a conventional phosphor and is preferable for obtaining natural white light, and The phosphor-containing composition, the light emitting device, the lighting device, and the image display device used can be obtained.

  Hereinafter, embodiments of the present invention will be described in detail. However, the present invention is not limited to the following embodiments, and various modifications can be made within the scope of the gist of the present invention.

In the composition formula of the phosphors in this specification, each composition formula is delimited by a punctuation mark (,). In addition, when listing a plurality of elements separated by commas (,) in parentheses, it indicates that one or more of the listed elements may be contained in any combination and composition Yes. Further, the subscript representing the number of atoms (composition ratio) attached to the parenthesis represents the total number of atoms of the elements listed in the parenthesis.
For example, the composition formula of “(Ca, Sr, Ba) Al ₂ O ₄ : Eu” is “CaAl ₂ O ₄ : Eu”, “SrAl ₂ O ₄ : Eu”, and “BaAl ₂ O ₄ : Eu”. “Ca _1-x Sr _x Al ₂ O ₄ : Eu”, “Sr _1-x Ba _x Al ₂ O ₄ : Eu”, “Ca _1-x Ba _x Al ₂ O ₄ : Eu”, _{"Ca 1-xy Sr x Ba y} Al 2 O 4: Eu " and all assumed to generically indicated (in the above formula, 0 <x <1,0 <y <1,0 <x + y <1).

  The relationship between the color name and the chromaticity coordinates in this specification is all based on the JIS standard (JIS Z8110 and Z8701).

[1. Phosphor]
The phosphor according to one embodiment of the present invention (hereinafter sometimes referred to as “specific characteristic phosphor of the present invention” or simply “specific characteristic phosphor”) has an emission peak half-width when excited with light of a specific wavelength. It meets the provisions of
In addition, the phosphor according to another embodiment of the present invention (hereinafter sometimes referred to as “specific composition phosphor of the present invention” or simply “specific composition phosphor”) has a composition that satisfies the following rules. .

  The phosphor of the present invention corresponds to at least one of “specific characteristic phosphor” and “specific composition phosphor”, but corresponds to both “specific characteristic phosphor” and “specific composition phosphor”. It is preferable.

In the following description, the “specific characteristic phosphor” and the “specific composition phosphor” are separately described as necessary. Further, when the “specific phosphor” and the “specific composition phosphor” are not particularly distinguished, they are collectively referred to as “the phosphor of the present invention”.
It should be noted that the terms “specific characteristic phosphor” and “specific composition phosphor” are used for convenience of explanation, and do not affect the phosphor of the present invention.

[1-1. Specific composition phosphor]
On the other hand, the specific composition phosphor of the present invention has the characteristics described below.

<Composition>
The specific composition phosphor has a chemical composition represented by the following formula (1). Specific examples thereof include a structure in which a part of Mg sites of a phosphor having a base crystal composition of Ba ₃ MgSi ₂ O ₈ is substituted with a specific rare earth element.

（前記式（１）において、Ｍ¹は、Ｂａ、Ｓｒ及びＣａからなる群より選ばれる１種以上の元素を示し、Ｍ²は、Ｍｇ及びＺｎからなる群より選ばれる１種以上の元素を示し、Ｌｎは、Ｌａ、Ｌｕ、Ｙ、Ｓｃ及びＧｄからなる群より選ばれる１種以上の元素を示し、ｘ、ｙ及びｚは、各々、０＜ｘ＜１、０．０５≦ｙ＜１、０≦ｚ＜１を満たす正の数を示す。）

(In the formula (1), M ¹ represents one or more elements selected from the group consisting of Ba, Sr and Ca, and M ² represents one or more elements selected from the group consisting of Mg and Zn. Ln represents one or more elements selected from the group consisting of La, Lu, Y, Sc, and Gd, and x, y, and z represent 0 <x <1, 0.05 ≦ y <1, respectively. And a positive number satisfying 0 ≦ z <1.)

In the above formula (1), M ¹ represents one or more elements selected from the group consisting of Ba, Sr and Ca. As said M1, any ¹ type of these elements may be contained independently, and 2 or more types may be included together by arbitrary combinations and ratios.
Among these, at least Ba is preferably contained. Here, assuming that the molar ratios of Ba, Sr, and Ca to the entire M ¹ are [Ba], [Sr], and [Ca], respectively, the molar ratio of [Ba] to the entire M ¹ , that is, [Ba] / The value represented by ([Ba] + [Sr] + [Ca]) is usually 0 or more, preferably 0.2 or more, more preferably 0.5 or more, still more preferably 0.8 or more, and usually 1 It is as follows.

In said formula (1), Eu is europium which is an activation element. Eu exists as a divalent cation and / or a trivalent cation in the specific composition phosphor. At this time, Eu preferably has a higher proportion of divalent cations.
The ratio of Eu ^{2+ to} the total Eu amount is usually 20 mol% or more, preferably 50 mol% or more, more preferably 80 mol% or more, and particularly preferably 90 mol% or more.
Note that the ratio of Eu ^{2+ in} the total Eu contained in the specific composition phosphor can be examined, for example, by measuring an X-ray absorption fine structure (X-ray Absorption Fine Structure). That is, when the L3 absorption edge of Eu atom is measured, Eu ²⁺ and Eu ³⁺ show separate absorption peaks, and the ratio can be quantified from the area. In addition, the ratio of Eu ^{2+ in} the total Eu contained in the specific composition phosphor can be determined by measuring electron spin resonance (ESR).

In the formula (1), x is a numerical value indicating the substitution amount of Eu for M ¹ site. The numerical value is usually a value larger than 0, preferably 0.001 or more, more preferably 0.01 or more, and usually less than 1, preferably 0.8 or less, more preferably 0.5 or less, and still more preferably. Is 0.3 or less, particularly preferably 0.2 or less. If it exceeds this range, the emission intensity may decrease due to concentration quenching. In addition, if it falls below this range, the light emission intensity may be lowered.

In the above formula (1), M ² represents one or more elements selected from the group consisting of Mg and Zn. As M ² , any one of these elements may be contained alone, or two or more may be contained in any combination and ratio.
Among these, it is preferable to contain at least Mg. Here, assuming that the molar ratio of Mg and Zn to the whole M ² is [Mg] and [Zn], respectively, the molar ratio of [Mg] to the whole M ² , that is, [Mg] / ([Mg] + [Zn ]) Is usually 0 or more, preferably 0.2 or more, more preferably 0.5 or more, still more preferably 0.8 or more, and usually 1 or less.

In the above formula (1), Ln represents one or more elements selected from the group consisting of La, Lu, Y, Sc and Gd. As said Ln, any 1 type may be contained independently among these elements, and 2 or more types may be included together by arbitrary combinations and ratios.
Among these, it is preferable to contain Lu or Y. Here, when the molar ratios of La, Lu, Y, Sc and Gd to the whole Ln are [La], [Lu], [Y], [Sc] and [Gd], respectively, the [Lu] to the whole M ¹ The molar ratio, that is, the value represented by [Lu] / ([La] + [Lu] + [Y] + [Sc] + [Gd]) is usually 0 or more, preferably 0.2 or more, more preferably 0.5 or more, more preferably 0.8 or more, and usually 1 or less.

In the formula (1), y is a numerical value indicating the substitution amount of Ln for M ² sites. In order to obtain the effect that the half-value width of the emission spectrum is wide, which is a feature of the present invention, the numerical value is usually 0.05 or more, preferably 0.1 or more, more preferably 0.2 or more, and further preferably It is 0.3 or more, usually less than 1, preferably 0.9 or less, more preferably 0.8 or less, and further preferably 0.7 or less.
As the value of y increases, the full width at half maximum of the emission spectrum increases, but the emission peak wavelength shifts accordingly between the blue and green wavelength ranges. Therefore, when used as a blue phosphor, the numerical value is usually 0.05 or more, preferably 0.1 or more, and usually 0.25 or less, preferably 0.2 or less. Moreover, when using as a green fluorescent substance, it is 0.3 or more normally, Preferably it is 0.35 or more, and is 0.45 or less normally, Preferably it is 0.4 or less. When the value of y is out of the above range, the emission color is a blue-green phosphor.

  In the above formula (1), z is a numerical value indicating the composition ratio of N and O. The numerical value is usually 0 or more, preferably 0.05 or more, and usually less than 1, preferably 0.9 or less, more preferably 0.8 or less. Outside this range, lattice defects may occur.

Specific examples of preferred compositions of the specific composition phosphor are listed in the following table, but the composition of the phosphor of the present invention is not limited to the following examples.

In addition to the elements described in the formula [1], ie, M ¹ , Eu, M ² , Ln, Si, O, and N, the specific composition phosphor further includes a monovalent element and a divalent element. An element selected from the group consisting of a trivalent element, a −1 valent element, and a −3 valent element (hereinafter referred to as “trace element” as appropriate) may be contained.

  Among these, the trace element preferably contains at least one element selected from the group consisting of alkali metal elements, phosphorus (P), rare earth elements, and halogen elements.

  The total content of the trace elements is usually 1 ppm or more, preferably 3 ppm or more, more preferably 5 ppm or more, and usually 100 ppm or less, preferably 50 ppm or less, more preferably 30 ppm or less. When the specific composition phosphor contains plural kinds of trace elements, the total amount thereof satisfies the above range.

  Further, Si may be partially substituted by other elements such as Ge. However, from the viewpoint of blue to green emission intensity, etc., the ratio of Si being replaced by other elements is preferably as low as possible. Specifically, other elements such as Ge may be contained in an amount of 20 mol% or less of Si, and it is more preferable that all are made of Si.

  The specific composition phosphor may contain one or more elements selected from the group consisting of Tb, Ag, Sm, and Pr in addition to the above-described elements.

  The specific composition phosphor may contain Al in addition to the above elements. The Al content is usually 1 ppm or more, preferably 5 ppm or more, more preferably 10 ppm or more, and usually 500 ppm or less, preferably 200 ppm or less, more preferably 100 ppm or less.

  The specific composition phosphor may contain B (boron) in addition to the above elements. The content of B is usually 1 ppm or more, preferably 3 ppm or more, more preferably 5 ppm or more, and usually 100 ppm or less, preferably 50 ppm or less, more preferably 30 ppm or less.

  In addition to the above elements, the specific composition phosphor may contain Fe. The Fe content is usually 1 ppm or more, preferably 3 ppm or more, more preferably 5 ppm or more, and usually 100 ppm or less, preferably 50 ppm or less, more preferably 30 ppm or less.

<Characteristics related to emission spectrum>
The specific composition phosphor is not limited as long as it has the above-described characteristics (composition), but preferably has the following characteristics.

  When the specific composition phosphor is excited with light having a wavelength of 395 nm, an emission spectrum having the following characteristics is measured.

First, the specific composition phosphor has an emission peak wavelength λ _p (nm) in the above emission spectrum.
However, it is usually in the range of 420 nm or more, preferably 440 nm or more, more preferably 450 nm or more, and usually 550 nm or less, preferably 540 nm or less, more preferably 530 nm or less. When the emission peak wavelength λ _p is out of the above range, colors that are not blue to green tend to be mixed from the phosphor, and the characteristics of the phosphor may deteriorate in any case.

The relative intensity of the emission peak of the specific composition phosphor (hereinafter sometimes referred to as “relative emission peak intensity”) is usually 0.1 or more, preferably 0.3 or more, more preferably 0.5 or more, and still more preferably. Is 0.8 or more. Incidentally, the relative emission peak intensity Kasei Optonix Ltd. BaMgAl ₁₀ O _17: Eu represents the emission intensity when excited with (Product No. LP-B4) at 395nm as 100. A higher relative emission peak intensity is preferred.

  Further, the specific composition phosphor has a feature that the full width at half maximum (full width at half maximum, hereinafter abbreviated as “FWHM” as appropriate) in the above-described emission spectrum is 60 nm or more and is wide. A wide FWHM means that the phosphor is a preferable phosphor for obtaining natural white light. For example, the phosphor is excellent in applications such as illumination.

  Specifically, the FWHM of the specific composition phosphor is usually in the range of 60 nm or more, preferably 80 nm or more, more preferably 100 nm or more, further preferably 120 nm or more, particularly preferably 145 nm or more, and usually 200 nm or less. If the FWHM is too narrow, the luminance may decrease. On the other hand, if the FWHM is too wide, the color purity may decrease.

  For example, a GaN light emitting diode can be used to excite the phosphor with light having a peak wavelength of 395 nm or less.

  Further, the measurement of the emission spectrum of the phosphor and the calculation of the emission peak wavelength, the relative emission peak intensity, and the peak half-value width are performed, for example, using a 150 W xenon lamp as an excitation light source and a multi-channel CCD detector C7041 (Hamamatsu) as a spectrum measurement device. This can be carried out using a fluorescence measuring device (manufactured by JASCO Corporation) equipped with Photonics).

<Chromaticity coordinates>
The emission color of the specific composition phosphor can be expressed by one of the CIE chromaticity coordinates, the x, y color system (CIE 1931 color system).

Specifically, the value of the CIE chromaticity coordinate x of the specific characteristic phosphor is usually in the range of 0.15 or more, preferably 0.2 or more, and usually 0.35 or less, preferably 0.3 or less.
The value of CIE chromaticity coordinate y of the specific characteristic phosphor is usually 0.15 or more, preferably 0.2 or more, and usually 0.5 or less, preferably 0.45 or less, more preferably 0.4. The range is as follows.
The values of CIE chromaticity coordinates x and y of the phosphor can be calculated by calculating according to JIS Z8724 from the emission spectrum in the wavelength range of 480 nm to 800 nm.

<Others>
In addition to the features described above, the specific composition phosphor may include any one or two or more features among the features of the specific characteristic phosphor described later. Further, the specific composition phosphor may correspond to a specific characteristic phosphor described later.

[1-2. Specific characteristic phosphor]
The specific characteristic phosphor of the present invention has the characteristics described below.

<Characteristics related to emission spectrum>
In view of the use as a blue to green phosphor, the specific characteristic phosphor has the following characteristics when an emission spectrum is measured when excited with light having a peak wavelength of 250 nm or more and 480 nm or less.

  First, the specific characteristic phosphor has a feature that the emission peak half-width (FWHM) in the above-described emission spectrum is 145 nm or more and is wide. A wide FWHM means that the phosphor is a preferable phosphor for obtaining natural white light. For example, the phosphor is excellent in applications such as illumination.

  Specifically, the FWHM of the specific characteristic phosphor is usually in the range of 145 nm or more, preferably 150 nm or more, more preferably 155 nm or more, particularly preferably 160 nm or more, and usually 200 nm or less. If the FWHM is too narrow, the luminance may decrease. On the other hand, if the FWHM is too wide, the color purity may decrease.

The specific characteristic phosphor has an emission peak wavelength λ _p (nm) in the above-mentioned emission spectrum of usually 420 nm or more, preferably 450 nm or more, more preferably 480 nm or more, and usually 550 nm or less, preferably 540 nm or less, more preferably It is the range of 530 nm or less. When the emission peak wavelength λ _p is out of the above range, colors that are not blue to green tend to be mixed from the phosphor, and the characteristics of the phosphor may deteriorate in any case.

Further, the relative intensity of the emission peak of the specific characteristic phosphor (hereinafter sometimes referred to as “relative emission peak intensity”) is usually 0.1 or more, preferably 0.3 or more, more preferably 0.5 or more, still more preferably. Is 0.8 or more. Incidentally, the relative emission peak intensity Kasei Optonix Ltd. BaMgAl ₁₀ O _17: Eu represents the emission intensity when the (product number LP-B4) excited by light with a wavelength of 395nm as 100. A higher relative emission peak intensity is preferred.

  In order to excite the phosphor with light having a peak wavelength of 250 nm or more and 480 nm or less, for example, a GaN light emitting diode can be used.

  In addition, the measurement of the emission spectrum of the phosphor and the calculation of the emission peak wavelength, peak relative intensity, and peak half width are, for example, a 150 W xenon lamp as an excitation light source and a multichannel CCD detector C7041 (Hamamatsu Photonics) as a spectrum measurement device. And a fluorescence measuring apparatus (manufactured by JASCO Corporation).

<Chromaticity coordinates>
The emission color of the specific characteristic phosphor can be expressed by one of the CIE chromaticity coordinates, the x, y color system (CIE 1931 color system). Specifically, preferred ranges and the like are the same as those of the specific composition phosphor.

<Composition>
The specific characteristic phosphor is not limited as long as it has the above-described characteristics (emission spectrum), but preferably has a structure of the following formula (2).

（前記式（２）において、Ｍ³及びＭ⁴は、それぞれ独立にアルカリ金属元素、アルカリ土類金属元素、及び２価の遷移元素からなる群より選ばれる１種以上の元素を示し、Ｍ⁵は、Ｂ、Ａｌ、Ｓｉ、Ｇｅ、Ｐ、Ａｓ、及びＳｂからなる群より選ばれる１種以上の元素を示し、Ｍ⁶は、Ｏ、Ｎ、Ｓ、及びハロゲンからなる群より選ばれる１種以上の元素を示し、Ｌ¹は、Ｓｍ、Ｅｕ、Ｔｍ及びＹｂからなる群より選ばれる１種以上の元素を示し、Ｌ²は、Ｌ¹以外の希土類元素を示す。また、Ｍ³のイオン半径はＭ⁴のイオン半径より大きく、Ｌ²のイオン半径はＭ⁴の０．７倍以上１．３倍以下の範囲である。）

(In the formula (2), M ³ and M ⁴ are respectively an alkali metal element independently, an alkaline earth metal element, and one or more elements selected from the group consisting of divalent transition element, M ⁵ Represents one or more elements selected from the group consisting of B, Al, Si, Ge, P, As, and Sb, and M ⁶ is one type selected from the group consisting of O, N, S, and halogen L ¹ represents one or more elements selected from the group consisting of Sm, Eu, Tm and Yb, L ² represents a rare earth element other than L ¹ , and M ³ ions (The radius is larger than the ionic radius of M ^{4, and} the ionic radius of L ² is in the range of 0.7 to 1.3 times M ^4. )

In the above formula (2), M ³ and M ^{4 each} represent one or more elements selected from the group consisting of alkali metal elements, alkaline earth metal elements, and divalent transition elements. As said M < ³ > and M < ⁴ >, any one of these elements may be contained independently, and 2 or more types may be included in arbitrary combinations and ratios. In the present invention, the transition element refers to an element belonging to Group 3 to Group 12 in the long periodic table.
M ³ is an element having an ionic radius larger than that of M ⁴ . In addition, about this ion radius, R.I. D. SHANNON Acta Cryst. (1976) A32,751.

As M ³ , Ba, Sr, Ca, Cs, Pb, or K is preferable. Among these, at least Ba, Sr or Ca is preferably contained, and at least Ba is more preferably contained.
Here, the molar ratio of Ba to the total amount of M ³ is usually 0 or more, preferably 0.2 or more, more preferably 0.5 or more, still more preferably 0.8 or more, and usually 1 or less. .

As the ^{M 4, Mg, Zn, Ti} , Zr, Na, or Mn is preferred. Among these, at least Mg or Zn is preferably contained, and at least Mg is more preferably contained.
Here, the molar ratio of Mg to the total amount of M ⁴ is usually 0 or more, preferably 0.2 or more, more preferably 0.5 or more, still more preferably 0.8 or more, and usually 1 or less. .

In the above formula (2), L ¹ represents one or more elements selected from the group consisting of Sm, Eu, Tm and Yb. As said L1, any ¹ type of these elements may be contained independently, and 2 or more types may be included together by arbitrary combinations and ratios. Among these, it is preferable to contain Eu.
When Eu is contained, the molar ratio of Eu with respect to the total amount of L ¹ is usually 0 or more, preferably 0.5 or more, more preferably 0.8 or more, further preferably 0.9 or more, and usually 1 or less. is there.

L ¹ is an activator element and exists as a divalent cation and / or a trivalent cation in the specific characteristic phosphor. At this time, it is preferable that L ¹ has a higher proportion of divalent cations. For example, when L ¹ is Eu, the ratio of Eu ^{2+ to} the total Eu amount is usually 20 mol% or more, preferably 50 mol% or more, more preferably 80 mol% or more, and particularly preferably 90 mol% or more. .
The ratio of Eu ^{2+ in} the total Eu contained in the specific characteristic phosphor can be arbitrarily determined using a known measurement method. For example, the ratio described in the section of the specific composition phosphor should be used. Can do.

In the above formula (2), L ² represents a rare earth element other than L ¹ , and the ionic radius of L ² is usually 0.7 times or more, preferably 0.8 times or more of the ionic radius of M ^4. The range is preferably 0.9 times or more, and usually 1.3 times or less, preferably 1.2 times or less, more preferably 1.1 times or less. Above this range, there is a possibility that the substitution takes place in the M ³ site. On the other hand, if it is lower, the substitution to the target M ⁴ site may be reduced. In the present invention, it is presumed that the effect is obtained by the change in crystal structure caused by the substitution of the M ⁴ element with the L ² element.

As the L ^2, it may contain solely one type of rare earth element may be in having both of two or more kinds in any combination and in any ratio. In the present invention, the rare earth element refers to Sc, Y, and lanthanoids (La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu). .

In the above formula (2), M ⁵ represents one or more elements selected from the group consisting of B, Al, Si, Ge, P, As, and Sb. As M ⁵ , any one of these elements may be contained alone, or two or more thereof may be contained in any combination and ratio.
Among them, it is preferable to contain B, Al, Si, Ge, or P. Among them, it is more preferable to contain Al, Si, Ge, or P, and further, Si or Ge is contained. In particular, Si is preferable. When Si is contained, the molar ratio of Si to the total amount of M ⁵ is usually 0 or more, preferably 0.5 or more, more preferably 0.8 or more, further preferably 0.9 or more, and usually 1 or less. .

In the above formula (2), M ⁶ represents one or more elements selected from the group consisting of O, N, S, and halogen. As M ⁶ , any one of these elements may be contained alone, or two or more may be contained in any combination and ratio. Especially, it is preferable to contain 1 or more types chosen from the group which consists of O, N, and a halogen. In particular, at least O for all M ⁶ amount usually 0 or larger, preferably 0.2 or more, more preferably 0.5 or more, more preferably 0.8 or larger, and usually 1 or less, preferably 0. 95 or less, more preferably 0.9 or less.

<Others>
In addition to the features described above, the specific-characteristic phosphor may include any one or more of the features of the specific composition phosphor described above. For example, the specific characteristic phosphor may contain the trace element described in the section of the specific composition phosphor in the ratio described in the section. The specific characteristic phosphor may correspond to the above-described specific composition phosphor.

[1-3. Common features of phosphors of the present invention]
The phosphor of the present invention preferably has the following characteristics.

<Characteristics related to excitation wavelength>
The excitation wavelength of the phosphor of the present invention is not particularly limited, but it can be excited with light in a wavelength range of usually 200 nm or more, preferably 300 nm or more, and usually 500 nm or less, preferably 420 nm or less, more preferably 410 nm or less. Is preferred. For example, the semiconductor light emitting element or the like emits the first light if it can be excited by light in the blue region (wavelength range: 420 nm to 500 nm) and / or light in the near ultraviolet region (wavelength range: 300 nm to 420 nm). It can be suitably used for a light emitting device as a body.

  The excitation spectrum can be measured at room temperature, for example, 25 ° C., using a fluorescence spectrophotometer F-4500 type (manufactured by Hitachi, Ltd.). The excitation peak wavelength can be calculated from the obtained excitation spectrum.

<Weight median diameter>
The weight median diameter of the phosphor of the present invention is usually 0.01 μm or more, preferably 1 μm or more, more preferably 5 μm or more, further preferably 10 μm or more, and usually 100 μm or less, preferably 30 μm or less, more preferably 20 μm or less. It is preferable that it is the range of these. When the weight median diameter is too small, the luminance is lowered and the phosphor particles tend to aggregate. On the other hand, if the weight median diameter is too large, there is a tendency for coating unevenness and blockage of the dispenser to occur. The weight median diameter of the specific composition phosphor can be measured using an apparatus such as a laser diffraction / scattering particle size distribution measuring apparatus.

<Temperature characteristics>
The phosphor of the present invention is also excellent in temperature characteristics. Specifically, the ratio of the emission peak intensity value in the emission spectrum diagram at 150 ° C. to the emission peak intensity value in the emission spectrum diagram at 20 ° C. when irradiated with light having a wavelength of 400 nm is usually 40% or more. And preferably 50% or more, particularly preferably 60% or more.
Further, since the emission intensity of ordinary phosphors decreases with increasing temperature, it is unlikely that the ratio exceeds 100%, but it may exceed 100% for some reason. However, if it exceeds 150%, the color shift tends to occur due to a temperature change.

  The phosphor of the present invention is excellent not only in terms of the emission peak intensity but also in terms of luminance. Specifically, the ratio of the luminance at 150 ° C. to the luminance at 20 ° C. when irradiated with light having a wavelength of 400 nm is usually 40% or more, preferably 50% or more, particularly preferably 70% or more. is there.

  When measuring the temperature characteristics, for example, an MCPD7000 multi-channel spectrum measuring device manufactured by Otsuka Electronics as an emission spectrum device, a color luminance meter BM5A as a luminance measuring device, a cooling mechanism using a Peltier element, and a heating mechanism using a heater. And it can measure as follows using the apparatus provided with a 150W xenon lamp as a light source. A cell containing a phosphor sample is placed on the stage, and the temperature is changed in the range of 20 ° C to 150 ° C. It is confirmed that the surface temperature of the phosphor is constant at 20 ° C. or 150 ° C. Next, the phosphor is excited with light having a wavelength of 400 nm extracted from the light source by the diffraction grating, and the emission spectrum is measured. The emission peak intensity is obtained from the measured emission spectrum. Here, as the measured value of the surface temperature on the excitation light irradiation side of the phosphor, a value corrected using the measured temperature value by the radiation thermometer and the thermocouple is used.

[2. Method for producing phosphor of the present invention]
An example of a raw material, a phosphor production method and the like for obtaining the phosphor of the present invention will be shown. The method for producing the phosphor of the present invention is not limited to the following examples, and can be produced by any method as long as the effects of the present invention are not significantly impaired.

The phosphor of the present invention can be produced by firing a metal compound mixture containing a compound represented by formula (1) or formula (2) and an activator by firing. That is, it can be manufactured by weighing the metal compound so as to have a predetermined composition, mixing, and firing. For example, when producing the phosphor represented by the above formula (1), a raw material of M ¹ (hereinafter referred to as “M ¹ source” as appropriate), a raw material of Eu (hereinafter referred to as “Eu source” as appropriate), a raw material of M ² ( (Hereinafter referred to as “M ² source” as appropriate), Ln raw material (hereinafter referred to as “Ln source” as appropriate) and Si raw material (hereinafter referred to as “Si source” as appropriate) (mixing step), and the resulting mixture It can manufacture by baking (baking process).
Further, for example, when manufacturing the phosphor represented by the above formula (2), M ³ raw material (hereinafter referred to as “M ³ source” as appropriate), L ¹ raw material (hereinafter referred to as “L ¹ source” as appropriate), M ⁴ raw materials (hereinafter referred to as “M ⁴ source” as appropriate), L ² raw material (hereinafter referred to as “L ² source” as appropriate), and M ⁵ raw material (hereinafter referred to as “M ⁵ source” as appropriate) are mixed (mixing step) ) And firing the obtained mixture (firing step).

[2-1. Phosphor raw material]
Phosphor raw materials (M ¹ source, Eu source, M ² source, Ln source, Si source, M ³ source, L ¹ source, M ⁴ source, L ² source, and M used in the production of the phosphor of the present invention ⁵ sources) include metals, alloys, imide compounds, oxynitrides, nitrides of each element of M ¹ , Eu, M ² , Ln, Si, M ³ , L ¹ , M ⁴ , L ² , and M ⁵ Oxide, hydroxide, carbonate, nitrate, sulfate, oxalate, carboxylate, halide, and the like. From these compounds, the reactivity to the composite oxynitride, the low generation amount of NO _x , SO _{x and the} like during firing may be selected as appropriate.

M ⁶ is an anion constituent element of the phosphor represented by the above formula (2).
As the raw material of M ⁶ (hereinafter referred to as “M ⁶ source” as appropriate), among the specific compounds described as the above-mentioned M ³ source to M ⁵ source, L ¹ source, and L ² source, an M ⁶ element-containing compound is used. In addition to being used as an M ⁶ source, as an N source and an O source, a gas present in the phosphor firing atmosphere can also be an M ⁶ source.

(M ¹ source)
Specific examples of the M ¹ source are listed separately for each type of M ¹ as follows.

Specific examples of Ba raw materials (hereinafter referred to as “Ba source” where appropriate) include BaO, Ba (OH) ₂ .8H ₂ O, BaCO ₃ , Ba (NO ₃ ) ₂ , BaSO ₄ , Ba (C ₂ O ₄ ). Ba (OCOCH ₃ ) ₂ , BaCl ₂ , Ba ₃ N ₂ , BaNH and the like. Of these, carbonates, oxides, and the like can be preferably used, but carbonates are more preferable from the viewpoint of handling because oxides easily react with moisture in the air. Of these, BaCO ₃ is preferable. This is because the stability in the air is good, and it is easily decomposed by heating, so that undesired elements hardly remain and it is easy to obtain high-purity raw materials. When carbonate is used as a raw material, it is preferable to pre-calcinate the carbonate and use it as a raw material.

Specific examples of Ca raw materials (hereinafter referred to as “Ca source” where appropriate) include CaO, Ca (OH) ₂ , CaCO ₃ , Ca (NO ₃ ) ₂ .4H ₂ O, CaSO ₄ .2H ₂ O, and Ca (C ₂ O ₄ ) · H ₂ O, Ca (OCOCH ₃ ) ₂ .H ₂ O, CaCl ₂ , Ca ₃ N ₂ , CaNH and the like. Of these, CaCO ₃ , CaCl _{2 and the} like are preferable. When carbonate is used as a raw material, it is preferable to pre-calcinate the carbonate and use it as a raw material.

Specific examples of the raw material for Sr (hereinafter referred to as “Sr source” as appropriate) include SrO, Sr (OH) ₂ .8H ₂ O, SrCO ₃ , Sr (NO ₃ ) ₂ , SrSO ₄ , Sr (C ₂ O ₄ ). _{· H 2 O, Sr (OCOCH} 3) 2 · 0.5H 2 O, SrCl 2, Sr 3 N 2, SrNH and the like. Of these, SrCO ₃ is preferable. This is because the stability in the air is good, it is easily decomposed by heating, it is difficult for undesired elements to remain, and it is easy to obtain high-purity raw materials. When carbonate is used as a raw material, it is preferable to pre-calcinate the carbonate and use it as a raw material.

(Eu source)
Specific examples of the Eu source are as follows.

Specific examples of Eu raw materials (hereinafter referred to as “Eu source” as appropriate) include Eu ₂ O ₃ , Eu ₂ (SO ₄ ) ₃ , Eu ₂ (C ₂ O ₄ ) ₃ .10H ₂ O, EuCl ₂ and EuCl. ₃ , Eu (NO ₃ ) ₃ .6H ₂ O, EuN, EuNH and the like. Of these, Eu ₂ O ₃ , EuCl _{2 and the} like are preferable, and Eu ₂ O ₃ is particularly preferable.

(M ² source)
Specific examples of the M ² source are listed separately for each type of M ² as follows.

Specific examples of the Zn raw material (hereinafter referred to as “Zn source” as appropriate) include ZnO, ZnF ₂ , ZnCl ₂ , Zn (OH) ₂ , Zn ₃ N ₂ , ZnNH, Zn (C ₂ O ₄ ), ZnSO _4, etc. Zinc compound (however, it may be a hydrate). Of these, ZnF ₂ .4H ₂ O (however, may be an anhydride) is preferred from the viewpoint of high effect of promoting particle growth. When carbonate is used as a raw material, it is preferable to pre-calcinate the carbonate and use it as a raw material.

Specific examples of Mg raw materials (hereinafter referred to as “Mg source” as appropriate) include MgO, Mg (OH) ₂ , basic magnesium carbonate (mMgCO ₃ .Mg (OH) ₂ .nH ₂ O), Mg (NO ₃ ) ₂ · 6H ₂ O, MgSO ₄ , Mg (C ₂ O ₄ ) · 2H ₂ O, Mg (OCOCH ₃ ) ₂ · 4H ₂ O, MgCl ₂ , Mg ₃ N ₂ , MgNH, and the like. Of these, MgO and basic magnesium carbonate are preferred. When carbonate is used as a raw material, it is preferable to pre-calcinate the carbonate and use it as a raw material.

(Ln source)
Specific examples of the Ln source are listed for each type of Ln as follows.

Specific examples of Lu raw materials (hereinafter referred to as “Lu source” where appropriate) include Lu ₂ O ₃ , LuCl ₃ , LuF ₃ , Lu (NO ₃ ) ₃ , Lu ₂ (CO ₃ ) _{3 and the} like. Of these, Lu ₂ O ₃ is preferable. When carbonate is used as a raw material, it is preferable to pre-calcinate the carbonate and use it as a raw material.

  La raw material (hereinafter referred to as “La source”), Y raw material (hereinafter referred to as “Y source”), Sc raw material (hereinafter referred to as “Sc source”), and Gd raw material (hereinafter referred to as appropriate) Specific examples of other Ln sources such as “Gd source” include compounds in which Lu is replaced by La, Y, Sc, Gd, etc. in the respective compounds listed as specific examples of Lu sources.

(Si source)
Specific examples of the Si source are as follows.

As a specific example of the Si raw material (hereinafter referred to as “Si source” as appropriate), it is preferable to use SiO ₂ or Si ₃ N ₄ . A compound that becomes SiO ₂ can also be used. Specific examples of such a compound include SiO ₂ , H ₄ SiO ₄ , Si (OCOCH ₃ ) _{4 and the} like. Further, Si ₃ N ₄ is preferably one having a small particle diameter and high purity from the viewpoint of light emission efficiency from the viewpoint of reactivity. Furthermore, from the viewpoint of light emission efficiency, β-Si ₃ N ₄ is more preferable than α-Si ₃ N ₄ , and in particular, one having a small content of carbon element as an impurity is preferable. The smaller the carbon content, the better. However, the content is usually 0.01% by weight or more, usually 0.3% by weight or less, preferably 0.1% by weight or less, more preferably 0.05% or less. . In addition, when using carbonate as a raw material, it is preferable to pre-fire and use carbonate as a raw material.

(M ³ source and M ⁴ source)
Specific examples of the M ³ source and the M ⁴ source are listed for each type of M ^{3 and} M ⁴ as follows.

Among the alkali metal elements, specific examples of the raw material for Li (hereinafter referred to as “Li source” where appropriate) include Li ₂ CO ₃ , Li ₂ O, LiOH, LiCl, LiF, Li ₂ (C ₂ O ₄ ) ₂ , LiNO ₃ or the like is preferable. When carbonate is used as a raw material, it is preferable to pre-calcinate the carbonate and use it as a raw material.

  Na raw material (hereinafter referred to as “Na source” as appropriate), K raw material (hereinafter referred to as “K source” as appropriate), Rb raw material (hereinafter referred to as “Rb source” as appropriate), Cs raw material (hereinafter referred to as “ Specific examples of other alkali metal elements such as “Cs source” include compounds in which Li is replaced by Na, K, Rb, Cs, etc. in the respective compounds listed as specific examples of the Li source.

Mg raw material (hereinafter appropriately referred to as “Mg”), Ca raw material (hereinafter appropriately referred to as “Ca source”), Sr raw material (hereinafter appropriately referred to as “Sr source”), and Ba raw material (hereinafter appropriately referred to as “ Specific examples of other alkaline earth metal elements such as “Ba source” include those described in the section of the M ¹ source and the M ² source.

Among the divalent transition elements, specific examples of Zn raw materials (hereinafter referred to as “Zn sources” as appropriate) include ZnO, ZnCl ₂ , ZnF ₂ , Zn (NO ₃ ) ₂ .6H ₂ O, ZnS, Zn ( OH) ₂ , Zn (OCOCH ₃ ) _{2 and the} like are preferable. When carbonate is used as a raw material, it is preferable to pre-calcinate the carbonate and use it as a raw material.

  Cr raw material (hereinafter referred to as “Cr” as appropriate), Mn raw material (hereinafter referred to as “Mn source” as appropriate), Co raw material (hereinafter referred to as “Co source” as appropriate), Ni raw material (hereinafter referred to as “Ni” as appropriate) Source)), Cu source (hereinafter referred to as “Cu source”), Nb source (hereinafter referred to as “Nb source”), Mo source (hereinafter referred to as “Mo source”), and Cd Specific examples of other divalent transition elements such as raw materials (hereinafter referred to as “Cd source” where appropriate) include Mg, Cr, Mn, Co, Ni, Cu in the respective compounds listed as specific examples of the Ba source. , Nb, Mo, Cd, and the like.

(L ¹ source)
Specific examples of the L ¹ source are listed for each type of L ¹ as follows.

  Specific examples of the Eu source are the same as the compounds exemplified in the above description of the Eu source.

  In addition, other activations such as a raw material of Sm (hereinafter referred to as “Sm source” as appropriate), a raw material of Tm (hereinafter referred to as “Tm source” as appropriate), and a raw material of Yb (hereinafter referred to as “Yb source” as appropriate). Specific examples of the raw material of the agent element include compounds in which Eu is replaced with Sm, Tm, Yb, etc., in each of the compounds listed as specific examples of the Eu source.

(L ² source)
Specific examples of the L ² source are listed separately for each type of L ² as follows.

  Among the rare earth elements, specific examples of the Lu source are the same as the compounds exemplified in the above description of the Lu source. Similarly, specific examples of La source, Y source, Sc source, Gd source and the like are the same as the compounds exemplified in the above description.

  Ce raw material (hereinafter referred to as “Ce source” as appropriate), Nd raw material (hereinafter referred to as “Nd source” as appropriate), Pm raw material (hereinafter referred to as “Pm source” as appropriate), Dy raw material (hereinafter referred to as “ Specific examples of other rare earth elements such as “Dy source”, Ho raw material (hereinafter referred to as “Ho source” where appropriate), Er raw material (hereinafter referred to as “Er source”) as specific examples of Lu source In each of the compounds mentioned as above, compounds in which Lu is replaced with Ce, Nd, Pm, Dy, Ho, Er, etc., respectively.

Specific examples of Tb raw materials (hereinafter referred to as “Tb source” where appropriate) include Tb ₄ O ₇ , TbCl ₃ (including hydrates), TbF ₃ , Tb (NO ₃ ) ₃ .nH ₂ O, Tb ₂ (SiO ₄ ) ₃ , Tb ₂ (C ₂ O ₄ ) ₃ · 10H ₂ O, and the like. Among these, Tb ₄ O ₇ , TbCl ₃ and TbF ₃ are preferable, and Tb ₄ O ₇ is more preferable.

Specific examples of Pr raw materials (hereinafter referred to as “Pr source” as appropriate) include Pr ₂ O ₃ , PrCl ₃ , PrF ₃ , Pr (NO ₃ ) ₃ .6H ₂ O, Pr ₂ (SiO ₄ ) ₃ , Pr ₂ (C ₂ O ₄ ) ₃ · 10H ₂ O and the like. Among these, Pr ₂ O ₃ , PrCl ₃ , and PrF ₃ are exemplified, and Pr ₂ O ₃ is more preferable.

(M ⁵ source)
Specific examples of the M ⁵ source are listed separately for each type of M ⁵ as follows.

As a specific example of the raw material of Ge (hereinafter referred to as “Ge source” as appropriate), GeO ₂ or Ge ₃ N ₄ is preferably used. A compound of GeO ₂ can also be used. Specific examples of such a compound include GeO ₂ , Ge (OH) ₄ , Ge (OCOCH ₃ ) ₄ , GeCl _{4 and the} like. When carbonate is used as a raw material, it is preferable to pre-calcinate the carbonate and use it as a raw material.

Specific examples of other M ⁵ sources such as an As raw material (hereinafter referred to as “As source” where appropriate) and an Sb raw material (hereinafter referred to as “Sb source” as appropriate) include each of the specific examples of Ge source. Examples of the compound include compounds in which Ge is replaced with As, Sb, and the like.

  Specific examples of the Si source are the same as the compounds exemplified in the above description of the Si source.

Specific examples of the raw material of P (hereinafter referred to as “P source” as appropriate) include P ₂ O ₅ , Ba ₃ (PO ₄ ) ₂ , Sr ₃ (PO ₄ ) ₂ , (NH ₄ ) ₃ PO _{4 and the} like. It is done.

Specific examples of the raw material for B (hereinafter referred to as “B source” as appropriate) include B ₂ O ₃ and H ₃ BO ₃ .

Al raw material (hereinafter suitably referred to as "Al source") Examples _{of, α-Al 2 O 3,} γ-Al 2 O 3, Al 2 O 3 equal, Al (OH) _3, AlOOH, Al ( NO ₃ ) ₃ · 9H ₂ O, Al ₂ (SO ₄ ) ₃ , AlCl _{3 and the} like.

In addition, any one of the above-described M ¹ source, Eu source, M ² source, Ln source, Si source, M ³ source, L ¹ source, M ⁴ source, L ² source, M ⁵ source, and M ⁶ source May be used alone, or two or more of them may be used in any combination and ratio.

[2-2. Production method of phosphor: mixing step]
The phosphor raw material is weighed so as to obtain the target composition, mixed sufficiently using a ball mill or the like, then filled in a crucible, fired at a predetermined temperature and atmosphere, and the fired product is pulverized and washed, thereby producing the present invention. The phosphor can be obtained.

Although it does not specifically limit as said mixing method, Specifically, the method of following (A) and (B) is mentioned.
(A) Dry pulverizer such as hammer mill, roll mill, ball mill, jet mill, etc., or pulverization using mortar and pestle, and mixer such as ribbon blender, V-type blender, Henschel mixer, or mortar and pestle And a dry mixing method in which the above phosphor raw materials are pulverized and mixed.
(B) A solvent or dispersion medium such as water is added to the phosphor material described above, and mixed using, for example, a pulverizer, a mortar and a pestle, or an evaporating dish and a stirring rod, to obtain a solution or slurry. A wet mixing method in which drying is performed by spray drying, heat drying, or natural drying.
The phosphor raw material may be mixed by either the above wet method or dry method, but wet mixing using water or ethanol is more preferable.

[2-3. Production method of phosphor: firing step]
The obtained mixture is filled in a heat-resistant container such as a crucible or a tray made of a material having low reactivity with each phosphor raw material. Examples of the material of the heat-resistant container used at the time of firing include ceramics such as alumina, quartz, boron nitride, silicon nitride, silicon carbide, magnesium, mullite, platinum, molybdenum, tungsten, tantalum, niobium, iridium, rhodium, and the like. Examples thereof include metals, alloys containing them as main components, and carbon (graphite). Here, the heat-resistant container made of quartz can be used for heat treatment at a relatively low temperature, that is, 1200 ° C. or less, and a preferable use temperature range is 1000 ° C. or less.
Examples of such heat-resistant containers include preferably heat-resistant containers made of boron nitride, alumina, silicon nitride, silicon carbide, platinum, molybdenum, tungsten, and tantalum.

  Regarding the firing step, the fired powder usually sinters at a firing temperature exceeding 1600 ° C., and the light emission intensity may be lowered. However, a powder having good crystallinity is obtained at a firing temperature around 1400 ° C. . Therefore, the firing temperature for producing the phosphor of the present invention is usually 1000 ° C or higher, preferably 1100 ° C or higher, more preferably 1200 ° C or higher, and usually 1600 ° C or lower, preferably 1500 ° C. The temperature is not higher than ° C, more preferably not higher than 1450 ° C.

  Although it does not restrict | limit especially as a baking atmosphere, Usually, it carries out in inert gas atmosphere or reducing atmosphere. Here, as described above, the valence of the activating element is preferably a divalent one, so that a reducing atmosphere is preferable. In addition, only 1 type may be used for an inert gas and reducing gas, and 2 or more types may be used together by arbitrary combinations and a ratio.

Examples of the inert gas and the reducing gas include carbon monoxide, hydrogen, nitrogen, argon, and the like. Of these, a nitrogen gas atmosphere is preferable, and a hydrogen gas-containing nitrogen gas atmosphere is more preferable. As the nitrogen (N ₂ ) gas, it is preferable to use a purity of 99.9% or more. When using hydrogen-containing nitrogen, it is preferable to reduce the oxygen concentration in the electric furnace to 20 ppm or less. Furthermore, the hydrogen content in the atmosphere is preferably 1% by volume or more, more preferably 2% by volume or more, and preferably 5% by volume or less. This is because if the hydrogen content in the atmosphere is too high, the safety may decrease, and if it is too low, a sufficient reducing atmosphere may not be achieved.

  The firing time is usually 0.5 hours or longer, preferably 1 hour or longer, although it varies depending on the temperature and pressure during firing. The firing time is preferably longer, but is usually 100 hours or shorter, preferably 50 hours or shorter, more preferably 24 hours or shorter, and further preferably 12 hours or shorter.

Although the pressure at the time of firing varies depending on the firing temperature and the like, it is not particularly limited, but is usually 1 × 10 ⁻⁵ Pa or more, preferably 1 × 10 ⁻³ Pa or more, more preferably 0.01 MPa or more, and still more preferably 0.8. The upper limit is usually 5 GPa or less, preferably 1 GPa or less, more preferably 200 MPa or less, and still more preferably 100 MPa or less. Among these, the atmospheric pressure to about 1 MPa is industrially preferable in terms of cost and labor.

[2-4. flux]

  In the firing step, it is preferable that a flux coexists in the reaction system from the viewpoint of growing good crystals. The type of the flux is not particularly limited, but a compound containing a monovalent element or atomic group and a -1 valent element, a compound containing a monovalent element or atomic group and a -3 valent element or atomic group, Compound containing divalent element and −1 valent element, compound containing 2 valent element and -3 valent element or atomic group, compound containing 3 valent element and −1 valent element In addition, it is preferable to use as the flux a compound selected from the group consisting of a trivalent element and a compound containing a trivalent element or an atomic group.

The monovalent element or atomic group is preferably at least one element selected from the group consisting of an alkali metal element and an ammonium group (NH ₄ ), for example.
The divalent element is preferably, for example, at least one element selected from the group consisting of an alkaline earth metal element and zinc (Zn), and more preferably strontium (Sr) or barium (Ba). preferable.
The trivalent element is preferably at least one element selected from the group consisting of rare earth elements such as lanthanum (La), yttrium (Y), aluminum (Al), and scandium (Sc). (Y) or aluminum (Al) is more preferable.
The -1 valent element is preferably, for example, at least one element selected from the group consisting of halogen elements, and is preferably chlorine (Cl) or fluorine (F).
The −3 element or atomic group is preferably, for example, a phosphate group (PO ₄ ).

  Among the above, the flux is a trivalent selected from the group consisting of alkali metal halides, alkaline earth metal halides, zinc halides, yttrium (Y), aluminum (Al), scandium (Sc), and rare earth elements. Selected from the group consisting of elemental halides, alkali metal phosphates, alkaline earth metal phosphates, zinc phosphate, yttrium (Y), aluminum (Al), lanthanum (La), and scandium (Sc) It is preferable to use a compound selected from the group consisting of phosphates of trivalent elements.

More specific examples include, NH ₄ Cl, NH ₄ ammonium halides such as F · HF; alkali metal carbonate such as _{NaCO 3, LiCO 3; LiCl,} NaCl, KCl, CsCl, LiF, NaF, KF, such as CsF Alkali metal halides; alkaline earth metal halides such as CaCl ₂ , BaCl ₂ , SrCl ₂ , CaF ₂ , BaF ₂ , SrF ₂ ; alkaline earth metal oxides such as CaO, SrO, BaO; B ₂ O ₃ , Boron oxides such as H ₃ BO ₃ and NaB ₄ O ₇ , boric acid and borate compounds; phosphate compounds such as Li ₃ PO ₄ and NH ₄ H ₂ PO ₄ ; aluminum halides such as AlF ₃ ; ZnCl periodic table group 15 element compound such as _{Bi 2 O 3;; 2,} ZnF 2 such zinc halide, zinc oxide, zinc compounds such as zinc sulfide _{Li 3 N, Ca 3 N 2} , S _{3 N 2, Ba 3 N 2} , BN alkali metal such like, and the like nitride of alkaline earth metal or a Group 13 element. Of these, preferred are halides, and among these, alkali metal halides, alkaline earth metal halides, and Zn halides are preferred. Of these halides, fluorides and chlorides are preferred.

  The amount of flux used varies depending on the type of raw material and the material of the flux, but is usually 0.01% by weight or more, preferably 0.1% by weight or more, more preferably 1% by weight or more, and usually 20% by weight. Hereinafter, the range of 10% by weight or less is more preferable. If the amount of flux used is too small, the effect of the flux will not appear, and if the amount of flux used is too large, the flux effect will be saturated, or it will be incorporated into the host crystal and change the emission color or cause a decrease in brightness There is. These fluxes may be used individually by 1 type, and may use 2 or more types together by arbitrary combinations and ratios.

[2-5. Primary firing and secondary firing]
The firing step may be divided into primary firing and secondary firing, and the raw material mixture obtained by the mixing step may be first fired first, and then pulverized again with a ball mill or the like, followed by secondary firing.

The temperature of the primary firing is arbitrary as long as the effect of the present invention is not significantly impaired, but is usually 800 ° C. or higher, preferably 1000 ° C. or higher, and usually 1600 ° C. or lower, preferably 1400 ° C. or lower, more preferably 1300 ° C. or lower. Range.
Here, in order to obtain a phosphor having a uniform particle size, it is preferable to advance the solid phase reaction in a powder state by setting the primary firing temperature low. On the other hand, in order to obtain a high-luminance phosphor, it is preferable that the primary firing temperature is set high and the raw materials are sufficiently mixed and reacted in a molten state and then grown by secondary firing.
The time for the primary firing is arbitrary as long as the effect of the present invention is not significantly impaired, but is usually 1 hour or longer, preferably 2 hours or longer, and usually 100 hours or shorter, preferably 50 hours or shorter, more preferably 24 hours or shorter. More preferably, it is 12 hours or less.

The conditions such as the temperature and time of the secondary firing are basically the same as the conditions described in the above-mentioned firing step column.
The flux may be mixed before the primary firing or may be mixed before the secondary firing. Also, the firing conditions such as the atmosphere may be changed between the primary firing and the secondary firing.

[2-6. Post-processing]
After the heat treatment in the above-described firing step, washing, drying, pulverization, classification treatment, and the like are performed as necessary.
For the pulverization treatment, for example, pulverizers listed as being usable in the raw material mixing step can be used.
The washing can be performed, for example, with water such as deionized water, an organic solvent such as ethanol, or an alkaline aqueous solution such as ammonia water. Further, for the purpose of removing the used flux, for example, an inorganic acid such as hydrochloric acid, nitric acid, sulfuric acid, or an aqueous solution of an organic acid such as acetic acid can be used. In this case, it is preferable to further wash with water after washing in an acidic aqueous solution.
The classification treatment can be performed, for example, by performing water sieving or using various classifiers such as various air classifiers and vibrating sieves. In particular, when dry classification using a nylon mesh is used, a phosphor with good dispersibility having a weight median diameter of about 20 μm can be obtained.

  Moreover, it is preferable to perform a drying process after a washing process. Although there is no restriction | limiting in particular in the method of a drying process, It is preferable to select a drying process method suitably according to the property of fluorescent substance as needed. For example, when a specific composition phosphor is exposed to a high-temperature and high-humidity atmosphere (for example, hot water) for a long time, a part of the surface of the matrix of the phosphor is dissolved, and the dissolved part is dissolved in carbon dioxide in the air. May react to carbonate. Therefore, when subjecting a specific composition phosphor to a drying treatment, low temperature drying such as vacuum drying, reduced pressure drying, freeze drying, etc., and short time drying such as spray drying are preferable, and carbon dioxide such as nitrogen or argon gas is included. It is preferable to dry in a dry atmosphere, or to replace the moisture with a low boiling point solvent and air dry.

[2-7. surface treatment]
In addition, when manufacturing the light emitting device by the method described later using the phosphor of the present invention obtained by the above procedure, in order to further improve the weather resistance such as moisture resistance, or the light emitting device described later. In order to improve the dispersibility of the phosphor-containing portion with respect to the resin, a surface treatment such as coating the surface of the phosphor with a different substance may be performed as necessary.

  Examples of the substance that can be present on the surface of the phosphor (hereinafter, arbitrarily referred to as “surface treatment substance”) include organic compounds, inorganic compounds, and glass materials.

  Examples of the organic compound include hot-melt polymers such as acrylic resin, polycarbonate, polyamide, and polyethylene, latex, and polyorganosiloxane.

  Examples of inorganic compounds include magnesium oxide, aluminum oxide, silicon oxide, titanium oxide, zirconium oxide, tin oxide, germanium oxide, tantalum oxide, niobium oxide, vanadium oxide, boron oxide, antimony oxide, zinc oxide, yttrium oxide, and oxide. Examples thereof include metal oxides such as bismuth, metal nitrides such as silicon nitride and aluminum nitride, orthophosphates such as calcium phosphate, barium phosphate and strontium phosphate, and polyphosphates.

  Examples of the glass material include borosilicate, phosphosilicate, and alkali silicate.

  These surface treatment substances may be used alone or in combination of two or more in any combination and ratio.

The phosphor of the present invention obtained by the above surface treatment is premised on the presence of a surface treatment substance, and examples of the mode include the following.
(I) A mode in which the surface treatment substance constitutes a continuous film and covers the phosphor surface.
(Ii) A mode in which the surface treatment substance becomes a large number of fine particles and adheres to the surface of the phosphor to coat the phosphor surface.

  The adhesion amount or the coating amount of the surface treatment substance on the surface of the phosphor is arbitrary as long as the effect of the present invention is not significantly impaired, but is usually 0.1% by weight or more, preferably 1 with respect to the weight of the phosphor. % By weight or more, more preferably 5% by weight or more, further preferably 10% by weight or more, and usually 50% by weight or less, preferably 30% by weight or less, more preferably 20% by weight or less. If the amount of the surface treatment substance with respect to the phosphor is too large, the light emission characteristics of the phosphor may be impaired. If the amount is too small, the surface coating may be incomplete, and the moisture resistance and dispersibility may not be improved.

  Further, the film thickness (layer thickness) of the surface treatment substance formed by the surface treatment is arbitrary as long as the effects of the present invention are not significantly impaired, but is usually 10 nm or more, preferably 50 nm or more, and usually 2000 nm or less, preferably Is 1000 nm or less. If this film thickness is too thick, the light emission characteristics of the phosphor may be impaired. If it is too thin, the surface coating may be incomplete, and the moisture resistance and dispersibility may not be improved.

  The surface treatment method is not particularly limited, and examples thereof include a coating treatment method using a metal oxide (silicon oxide) as described below.

  The phosphor of the present invention is mixed in an alcohol such as ethanol and stirred, and further an alkaline aqueous solution such as ammonia water is mixed and stirred. Next, a hydrolyzable alkyl silicate such as tetraethylorthosilicate is mixed and stirred. The obtained solution is allowed to stand for 3 to 60 minutes, and then the supernatant containing silicon oxide particles that have not adhered to the phosphor surface is removed with a dropper or the like. Subsequently, after mixing alcohol, stirring, standing, and removing the supernatant several times, a surface-treated phosphor is obtained through a vacuum drying step at 120 ° C. to 150 ° C. for 10 minutes to 5 hours, for example, 2 hours.

  Other methods for surface treatment of the phosphor include, for example, a method in which spherical silicon oxide fine powder is adhered to the phosphor (JP-A-2-209998, JP-A-2-233794), and a phosphor-based silicon compound. A method of attaching a film (Japanese Patent Laid-Open No. 3-231987), a method of coating the surface of phosphor fine particles with polymer fine particles (Japanese Patent Laid-Open No. 6-314593), a phosphor with an organic material, an inorganic material, a glass material, etc. A coating method (Japanese Patent Laid-Open No. 2002-223008), a method of coating a phosphor surface by a chemical vapor reaction method (Japanese Patent Laid-Open No. 2005-82788), and a method of attaching metal compound particles (Japanese Patent Laid-Open No. 2006-2006) No. 28458) can be used.

[3. Use of phosphor]
The phosphor of the present invention can be used for any application that uses the phosphor. In particular, taking advantage of the fact that it can be excited by blue light or near-ultraviolet light, various light emitting devices (see “ The light-emitting device of the invention ") can be suitably used. By adjusting the types and usage ratios of the phosphors to be combined, light emitting devices having various emission colors can be manufactured.

  For example, when the phosphor of the present invention emits green fluorescence, an excitation light source that emits blue light and a phosphor that emits orange or red fluorescence (orange or red phosphor) are combined, or an excitation light source that emits near ultraviolet light And a phosphor emitting blue fluorescence (blue phosphor) and a phosphor emitting orange to red fluorescence, a white light emitting device can be manufactured. The emission color in this case can be changed to a desired emission color by adjusting the emission wavelength of the phosphor of the present invention or the combined orange or red phosphor. For example, so-called pseudo white (for example, blue LED and It is also possible to obtain an emission spectrum similar to the emission spectrum of the light emitting device combined with a yellow phosphor. Furthermore, combining this white light-emitting device with a phosphor that emits red fluorescence (red phosphor) realizes a light-emitting device that excels in red color rendering and a light-emitting device that emits light bulb color (warm white). can do.

  Further, when the phosphor of the present invention emits blue fluorescence, a white light emitting device can be obtained by combining an excitation light source that emits near ultraviolet light, a phosphor that emits green fluorescence (green phosphor), and a red phosphor. Can be manufactured.

  The emission color of the light-emitting device is not limited to white, and if necessary, a yellow phosphor (phosphor that emits yellow fluorescence), a blue phosphor, an orange to red phosphor, a green phosphor, or the like can be combined for fluorescence. A light-emitting device that emits light in an arbitrary color can be manufactured by adjusting the type and use ratio of the body. The light-emitting device thus obtained can be used as a light-emitting portion (particularly a liquid crystal backlight) or an illumination device of an image display device.

[4. Phosphor-containing composition]
The phosphor of the present invention can be used by mixing with a liquid medium. In particular, when the phosphor of the present invention is used for applications such as a light emitting device, it is preferably used in a form dispersed in a liquid medium. The phosphor of the present invention dispersed in a liquid medium will be referred to as “the phosphor-containing composition of the present invention” as appropriate.

[4-1. Phosphor]
There is no restriction | limiting in the kind of fluorescent substance of this invention contained in the fluorescent substance containing composition of this invention, It can select arbitrarily from what was mentioned above. Moreover, the fluorescent substance of this invention contained in the fluorescent substance containing composition of this invention may be only 1 type, and may use 2 or more types together by arbitrary combinations and a ratio. Furthermore, the phosphor-containing composition of the present invention may contain a phosphor other than the phosphor of the present invention as long as the effects of the present invention are not significantly impaired.

[4-2. Liquid medium]
The liquid medium used in the phosphor-containing composition of the present invention is not particularly limited as long as the performance of the phosphor is not impaired within the intended range. For example, any inorganic material and / or organic material may be used as long as it exhibits liquid properties under the desired use conditions, suitably disperses the phosphor of the present invention, and does not cause an undesirable reaction. it can.

  Examples of the inorganic material include a solution obtained by hydrolyzing a solution containing a metal alkoxide, a ceramic precursor polymer, or a metal alkoxide by a sol-gel method (for example, an inorganic material having a siloxane bond). it can.

  Examples of organic materials include thermoplastic resins, thermosetting resins, and photocurable resins. Specifically, for example, methacrylic resin such as polymethylmethacrylate; styrene resin such as polystyrene and styrene-acrylonitrile copolymer; polycarbonate resin; polyester resin; phenoxy resin; butyral resin; polyvinyl alcohol; Cellulose resins such as cellulose acetate butyrate; epoxy resins; phenol resins; silicone resins.

  Among these, when using a phosphor for a high-power light-emitting device such as illumination, it is preferable to use a silicon-containing compound for the purpose of heat resistance and light resistance.

  The silicon-containing compound refers to a compound having a silicon atom in the molecule, for example, an organic material (silicone material) such as polyorganosiloxane, an inorganic material such as silicon oxide, silicon nitride, silicon oxynitride, and borosilicate. And glass materials such as phosphosilicate and alkali silicate. Among these, silicone materials are preferable from the viewpoint of ease of handling.

The silicone material generally refers to an organic polymer having a siloxane bond as a main chain, and examples thereof include a compound represented by the following formula (i) and / or a mixture thereof.

In the above formula (i), R ¹ to R ⁶ may be the same or different and are selected from the group consisting of an organic functional group, a hydroxyl group and a hydrogen atom.
In the above formula (i), M, D, T, and Q are numbers that are 0 or more and less than 1, respectively, and that satisfy M + D + T + Q = 1.

  When used for sealing a semiconductor light emitting device, the silicone material can be used after being sealed with a liquid silicone material and then cured by heat or light.

  When silicone materials are classified according to the curing mechanism, silicone materials such as an addition polymerization curing type, a condensation polymerization curing type, an ultraviolet curing type, and a peroxide vulcanization type can be generally cited. Among these, addition polymerization curing type (addition type silicone resin), condensation curing type (condensation type silicone resin), and ultraviolet curing type are preferable. Hereinafter, the addition type silicone material and the condensation type silicone material will be described.

  The addition-type silicone material refers to a material in which polyorganosiloxane chains are crosslinked by organic addition bonds. A typical example is a compound having a Si—C—C—Si bond at a crosslinking point obtained by reacting vinylsilane and hydrosilane in the presence of an addition catalyst such as a Pt catalyst. As these, commercially available products can be used. Specific examples of addition polymerization curing type trade names include “LPS-1400”, “LPS-2410”, and “LPS-3400” manufactured by Shin-Etsu Chemical Co., Ltd.

On the other hand, examples of the condensation type silicone material include a compound having a Si—O—Si bond obtained by hydrolysis and polycondensation of an alkylalkoxysilane at a crosslinking point.
Specific examples include polycondensates obtained by hydrolysis and polycondensation of compounds represented by the following general formula (ii) and / or (iii) and / or oligomers thereof.

M ^{m +} X _n Y ¹ _mn (ii)
(In formula (ii), M represents at least one element selected from silicon, aluminum, zirconium, and titanium, X represents a hydrolyzable group, and Y ¹ represents a monovalent organic group. M represents one or more integers representing the valence of M, and n represents one or more integers representing the number of X groups, provided that m ≧ n.

_{^{(M s + X t Y 1}} st-1) u Y 2 (iii)
(In formula (iii), M represents at least one element selected from silicon, aluminum, zirconium, and titanium, X represents a hydrolyzable group, and Y ¹ represents a monovalent organic group. Y ² represents a u-valent organic group, s represents an integer of 1 or more representing the valence of M, t represents an integer of 1 or more and s−1 or less, and u represents 2 or more. Represents an integer.)

  Further, the condensation type silicone material may contain a curing catalyst. As this curing catalyst, for example, a metal chelate compound or the like can be suitably used. The metal chelate compound preferably contains one or more of Ti, Ta, and Zr, and more preferably contains Zr. In addition, only 1 type may be used for a curing catalyst and it may use 2 or more types together by arbitrary combinations and a ratio.

  As such a condensation-type silicone material, for example, semiconductor light-emitting device members described in JP-A Nos. 2007-112973 to 112975 and JP-A-2007-19459 are suitable.

Of the condensed silicone materials, particularly preferred materials will be described below.
Silicone materials generally have a problem of poor adhesion to semiconductor light emitting elements, substrates on which elements are arranged, packages, and the like, but as silicone materials having high adhesion, the following features [1] to A condensation type silicone material having one or more of [3] is preferred.

[1] The silicon content is 20% by weight or more.
[2] The solid Si-nuclear magnetic resonance (NMR) spectrum measured by the method described in detail later has at least one peak derived from Si in the following (a) and / or (b).
(A) A peak whose peak top position is in a region where the chemical shift is −40 ppm or more and 0 ppm or less with respect to tetramethoxysilane, and the half width of the peak is 0.3 ppm or more and 3.0 ppm or less.
(B) A peak whose peak top position is in a region where the chemical shift is −80 ppm or more and less than −40 ppm with respect to tetramethoxysilane, and the half width of the peak is 0.3 ppm or more and 5.0 ppm or less.
[3] The silanol content is 0.1% by weight or more and 10% by weight or less.

In the present invention, among the above features [1] to [3], a silicone material having the feature [1] is preferable, a silicone material having the above features [1] and [2] is more preferable, Particularly preferred are silicone materials having all the features [1] to [3].
Hereinafter, the above features [1] to [3] will be described.

<Characteristic [1] (silicon content)>
The basic skeleton of the conventional silicone-based material is an organic resin such as an epoxy resin having carbon-carbon and carbon-oxygen bonds as the basic skeleton, whereas the basic skeleton of the silicone-based material of the present invention is glass (silicate). It is the same inorganic siloxane bond as glass). This siloxane bond has the following excellent characteristics as a silicone-based material, as is apparent from the chemical bond comparison table shown in [Table 2] below.

(I) Since the binding energy is large and thermal decomposition and photolysis are difficult, light resistance is good.
(II) It is slightly polarized electrically.
(III) The degree of freedom of the chain structure is large, a structure with high flexibility is possible, and the chain structure can freely rotate around the center of the siloxane chain.
(IV) The degree of oxidation is large and no further oxidation occurs.
(V) Rich in electrical insulation.

  Because of these characteristics, silicone-based silicone materials that are formed with a skeleton in which siloxane bonds are three-dimensionally bonded with a high degree of crosslinking are close to inorganic materials such as glass or rock, and have a high heat resistance and light resistance. Can be understood. In particular, a silicone-based material having a methyl group as a substituent has no absorption in the ultraviolet region, so that photolysis hardly occurs and has excellent light resistance.

The silicon content of the silicone material suitable for the present invention is usually 20% by weight or more, preferably 25% by weight or more, and more preferably 30% by weight or more. On the other hand, the upper limit is usually in the range of 47% by weight or less because the silicon content of the glass composed solely of SiO ₂ is 47% by weight.

  Note that the silicon content of the silicone-based material is calculated based on the results obtained by performing inductively coupled plasma spectroscopy (hereinafter abbreviated as “ICP” where appropriate) using the following method, for example. Can do.

{Measurement of silicon content}
Silicone material is baked in a platinum crucible in the air at 450 ° C. for 1 hour, then at 750 ° C. for 1 hour, and at 950 ° C. for 1.5 hours to remove the carbon component, and then a small amount of residue is obtained. Add more than 10 times the amount of sodium carbonate and heat with a burner to melt, cool this, add demineralized water, and adjust the pH to neutral with hydrochloric acid to a few ppm as silicon. ICP analysis is performed.

<Feature [2] (Solid Si-NMR spectrum)>
When a solid Si-NMR spectrum of a silicone-based material suitable for the present invention is measured, at least one peak in the peak region of (a) and / or (b) derived from a silicon atom to which a carbon atom of an organic group is directly bonded, Preferably, a plurality of peaks are observed.

When arranged for each chemical shift, in the silicone-based material suitable for the present invention, the half width of the peak described in (a) is generally less than the peak described in (b) described later because molecular motion is less restricted. It is smaller than the case, usually in the range of 3.0 ppm or less, preferably 2.0 ppm or less, and usually 0.3 ppm or more.
On the other hand, the full width at half maximum of the peak described in (b) is usually 5.0 ppm or less, preferably 4.0 ppm or less, and usually 0.3 ppm or more, preferably 0.4 ppm or more.

  If the half-value width of the peak observed in the chemical shift region is too large, the molecular motion is constrained and the strain becomes large, cracks are likely to occur, and the member may be inferior in heat resistance and weather resistance. For example, in the case where a large amount of tetrafunctional silane is used, or in the state where rapid drying is performed in the drying process and a large internal stress is stored, the full width at half maximum is larger than the above range.

  In addition, if the half width of the peak is too small, Si atoms in the environment will not be involved in siloxane crosslinking, and heat resistance is higher than that of substances formed mainly from siloxane bonds, such as cases where trifunctional silane remains in an uncrosslinked state. -It may be a member inferior in weather resistance.

  However, in a silicone material containing a small amount of Si component in a large amount of organic component, good heat resistance / light resistance and coating performance can be obtained even if the peak of the above-mentioned half width range is observed at -80 ppm or more. There may not be.

  The chemical shift value of the silicone material suitable for the present invention can be calculated based on the results of solid Si-NMR measurement using the following method, for example. In addition, analysis of measurement data (half-width or silanol amount analysis) is performed by a method of dividing and extracting each peak by, for example, waveform separation analysis using a Gaussian function or a Lorentz function.

{Solid Si-NMR spectrum measurement and silanol content calculation}
When performing a solid Si-NMR spectrum about a silicone type material, a solid Si-NMR spectrum measurement and waveform separation analysis are performed on condition of the following. Further, from the obtained waveform data, the half width of each peak is determined for the silicone material. Also, from the ratio of the peak area derived from silanol to the total peak area, the ratio (%) of silicon atoms that are silanols in all silicon atoms is obtained, and the silanol content is determined by comparing with the silicon content analyzed separately. Ask.

{Device conditions}
Apparatus: Chemmagnetics Infinity CMX-400 Nuclear magnetic resonance spectrometer
²⁹ Si resonance frequency: 79.436 MHz
Probe: 7.5 mmφ CP / MAS probe Measurement temperature: room temperature Sample rotation speed: 4 kHz
Measurement method: Single pulse method
¹ H decoupling frequency: 50 kHz
²⁹ Si flip angle: 90 °
²⁹ Si 90 ° pulse width: 5.0μs
Repeat time: 600s
Integration count: 128 Observation width: 30 kHz
Broadening factor: 20Hz
Reference sample: Tetramethoxysilane

  For silicone-based materials, 512 points are taken as measurement data, zero-filled to 8192 points, and Fourier transformed.

{Waveform separation analysis method}
For each peak of the spectrum after Fourier transform, optimization calculation is performed by a non-linear least square method with the center position, height, and half width of the peak shape created by Lorentz waveform and Gaussian waveform or a mixture of both as variable parameters.
In addition, the identification of a peak is AIChE Journal, 44 (5), p. Refer to 1141, 1998, etc.

<Feature [3] (silanol content)>
The silicone material suitable for the present invention has a silanol content of usually 0.1% by weight or more, preferably 0.3% by weight or more, and usually 10% by weight or less, preferably 8% by weight or less, more preferably The range is 5% by weight or less. By reducing the silanol content, the silanol-based material has excellent performance with little change over time, excellent long-term performance stability, and low moisture absorption and moisture permeability. However, since a member containing no silanol is inferior in adhesion, there exists an optimum range for the silanol content as described above.

  In addition, the silanol content rate of a silicone type material uses the method demonstrated in the item of {the solid-state Si-NMR spectrum measurement and calculation of silanol content rate} of <characteristic [2] (solid Si-NMR spectrum)> above, for example. The solid Si-NMR spectrum measurement was performed, and the ratio (%) of silicon atoms that are silanols in the total silicon atoms was determined from the ratio of the peak area derived from silanol to the total peak area, and compared with the silicon content analyzed separately. This can be calculated.

  In addition, since the silicone-based material suitable for the present invention contains an appropriate amount of silanol, the silanol usually bonds with hydrogen at the polar portion present on the device surface, thereby exhibiting adhesion. Examples of the polar part include a hydroxyl group and a metalloxane-bonded oxygen.

  In addition, the silicone material suitable for the present invention is usually heated in the presence of an appropriate catalyst to form a covalent bond by dehydration condensation with the hydroxyl group on the device surface, thereby exhibiting stronger adhesion. can do.

  On the other hand, if there is too much silanol, the inside of the system will thicken and it will be difficult to apply, or it will become more active and solidify before the light-boiling components volatilize by heating, leading to increased foaming and internal stress. It may occur and induce cracks.

[4-3. Content of liquid medium]
The content of the liquid medium is arbitrary as long as the effect of the present invention is not significantly impaired, but is usually 50% by weight or more, preferably 75% by weight or more, based on the entire phosphor-containing composition of the present invention. It is 99 weight% or less, Preferably it is 95 weight% or less. When the amount of the liquid medium is large, no particular problem occurs. However, in order to obtain a desired chromaticity coordinate, color rendering index, luminous efficiency, etc. in the case of a semiconductor light emitting device, it is usually at a blending ratio as described above. It is desirable to use a liquid medium. On the other hand, if there is too little liquid medium, there is a possibility that it will be difficult to handle due to lack of fluidity.

  The liquid medium mainly has a role as a binder in the phosphor-containing composition of the present invention. The liquid medium may be used alone or in combination of two or more in any combination and ratio. For example, when a silicon-containing compound is used for the purpose of heat resistance, light resistance, etc., other thermosetting resins such as an epoxy resin may be contained to the extent that the durability of the silicon-containing compound is not impaired. In this case, the content of the other thermosetting resin is usually 25% by weight or less, preferably 10% by weight or less based on the total amount of the liquid medium as the binder.

[4-4. Other ingredients]
The phosphor-containing composition of the present invention may contain other components in addition to the phosphor and the liquid medium as long as the effects of the present invention are not significantly impaired. Moreover, only 1 type may be used for another component and it may use 2 or more types together by arbitrary combinations and a ratio.

[5. Light emitting device]
The light-emitting device of the present invention (hereinafter referred to as “light-emitting device” as appropriate) includes a first light-emitting body (excitation light source), and a second light-emitting body that emits visible light when irradiated with light from the first light-emitting body. A light-emitting device having the above-described [1. The phosphor of the present invention described in the section of “phosphor” contains at least one kind of the first phosphor.

  The phosphor of the present invention is the above-described specific-characteristic phosphor and / or a specific-composition phosphor, which usually emits fluorescence in the blue to green region under the irradiation of light from an excitation light source (hereinafter referred to as a phosphor). As appropriate, among the phosphors of the present invention, the phosphor that emits green fluorescence is the “green phosphor of the present invention”, and among the phosphors of the present invention, the phosphor that emits the blue fluorescence is “the blue phosphor of the present invention”. May be used). Specifically, the green phosphor of the present invention preferably has an emission peak in the range of 500 nm to 540 nm, and the blue phosphor of the present invention preferably has an emission peak in the range of 420 nm to 490 nm. Any one of the phosphors of the present invention may be used alone, or two or more thereof may be used in any combination and ratio.

  Moreover, as a preferable specific example of the phosphor of the present invention used in the light emitting device of the present invention, [1. Examples thereof include the phosphor of the present invention described in the “Phosphor” column and the phosphors used in the respective Examples in the “Example” column described later.

  The light-emitting device of the present invention has a first light emitter (excitation light source), and at least the phosphor of the present invention is used as the second light emitter. It is possible to arbitrarily adopt the apparatus configuration. A specific example of the device configuration will be described later.

As the light emission peak in the green region in the light emission spectrum of the light emitting device of the present invention, one having a light emission peak in the wavelength range of 500 nm to 540 nm is preferable.
Moreover, as a light emission peak of the blue region in the light emission spectrum of the light emitting device of the present invention, one having a light emission peak in a wavelength range of 420 nm to 490 nm is preferable.

Note that the emission spectrum of the light emitting device is measured by energizing 20 mA with a color / illuminance measurement software and USB2000 series spectroscope (integral sphere specification) manufactured by Ocean Optics in a room maintained at a temperature of 25 ± 1 ° C. Can be done. Chromaticity values (x, y, z) can be calculated as chromaticity coordinates in the XYZ color system defined by JIS Z8701 from data in the wavelength region of 380 nm to 780 nm of the emission spectrum. In this case, the relational expression x + y + z = 1 holds. In the present specification, the XYZ color system may be referred to as an XY color system, and is usually expressed as (x, y).

  The luminous efficiency is obtained by obtaining the total luminous flux from the result of the emission spectrum measurement using the light emitting device as described above, and dividing the lumen (lm) value by the power consumption (W). The power consumption is obtained by measuring a voltage using a True RMS Multimeters Model 187 & 189 manufactured by Fluke in a state in which 20 mA is energized, and obtaining the product of the current value and the voltage value.

  Among the light-emitting devices of the present invention, in particular, as a white light-emitting device, specifically, an excitation light source as described later is used as the first light emitter, and red fluorescence as described later is used in addition to the phosphor of the present invention. Phosphor that emits light (hereinafter referred to as “red phosphor” as appropriate), phosphor that emits blue fluorescence (hereinafter referred to as “blue phosphor” as appropriate), phosphor that emits yellow fluorescence (hereinafter referred to as “yellow phosphor” as appropriate) It can be obtained by using a known phosphor structure such as any combination of known phosphors.

  Here, the white color of the white light emitting device means all of (yellowish) white, (greenish) white, (blueish) white, (purple) white and white defined by JIS Z 8701 Of these, white is preferred.

[5-1. Configuration of Light Emitting Device (Light Emitter)]
[First luminous body]
The 1st light-emitting body in the light-emitting device of this invention light-emits the light which excites the 2nd light-emitting body mentioned later.

  The light emission wavelength of the first light emitter is not particularly limited as long as it overlaps with the absorption wavelength of the second light emitter described later, and a light emitter having a wide light emission wavelength region can be used. Usually, an illuminant having an emission wavelength from the ultraviolet region to the blue region is used, and it is particularly preferable to use an illuminant having an emission wavelength from the near ultraviolet region to the blue region.

  As a specific numerical value of the emission wavelength of the first luminous body, 200 nm or more is usually desirable. Among these, it is desirable to use an illuminant having a peak emission wavelength of usually 300 nm or more, preferably 330 nm or more, more preferably 360 nm or more, and usually 420 nm or less. This is from the viewpoint of color purity of the light emitting device.

  As the first light emitter, a semiconductor light emitting element is generally used, and specifically, a light emitting LED, a semiconductor laser diode (hereinafter abbreviated as “LD” as appropriate), or the like can be used. In addition, as a light-emitting body which can be used as a 1st light-emitting body, an organic electroluminescent light emitting element, an inorganic electroluminescent light emitting element, etc. are mentioned, for example. However, what can be used as a 1st light-emitting body is not restricted to what is illustrated by this specification.

Among these, as the first light emitter, a GaN LED or LD using a GaN compound semiconductor is preferable. This is because GaN-based LEDs and LDs have significantly higher light emission output and external quantum efficiency than SiC-based LEDs that emit light in this region, and are extremely bright with very low power when combined with the phosphor. This is because light emission can be obtained. For example, for a current load of 20 mA, GaN-based LEDs and LDs usually have a light emission intensity 100 times or more that of SiC-based. GaN-based LEDs and LDs preferably have an Al _x Ga _y N light emitting layer, a GaN light emitting layer, or an In _x Ga _y N light emitting layer. Among GaN-based LEDs, those having an In _X Ga _Y N light-emitting layer are particularly preferable because of their very high emission intensity. In GaN-based LEDs, a multiple quantum well structure of In _X Ga _Y N layers and GaN layers is preferred. Is particularly preferable because the emission intensity is very strong.

  In the above, the value of X + Y is usually a value in the range of 0.8 to 1.2. In the GaN-based LED, those in which the light emitting layer is doped with Zn or Si or those without a dopant are preferable for adjusting the light emission characteristics.

A GaN-based LED has these light-emitting layer, p-layer, n-layer, electrode, and substrate as basic components, and the light-emitting layer is composed of n-type and p-type Al _x Ga _y N layers, GaN layers, or In _x. Those having a hetero structure sandwiched by Ga _Y N layers or the like are preferable because of high light emission efficiency, and those having a hetero structure having a quantum well structure are more preferable because of high light emission efficiency.
Note that only one first light emitter may be used, or two or more first light emitters may be used in any combination and ratio.

[Second luminous body]
The second light emitter in the light emitting device of the present invention is a light emitter that emits visible light when irradiated with light from the first light emitter described above, and the phosphor of the present invention described above (for example, the first phosphor) (for example, And a second phosphor (for example, a red phosphor, a blue phosphor, an orange phosphor, etc.), which will be described later. Further, for example, the second light emitter is configured by dispersing the first and second phosphors in a sealing material.

Used for the in the second luminescent material is not particularly limited to the phosphor composition other than the phosphor of the present invention, the crystal _{matrix, Y 2 O 3, YVO 4} , Zn 2 SiO 4, Y 3 Metal oxides typified by Al ₅ O ₁₂ , Sr ₂ SiO ₄ , metal nitrides typified by Sr ₂ Si ₅ N ₈ , phosphates typified by Ca ₅ (PO ₄ ) ₃ Cl, etc. Ce, Pr, Nd, Pm, Sm, Eu, Tb, Dy, sulfides typified by ZnS, SrS, CaS, etc., oxysulfides typified by Y ₂ O ₂ S, La ₂ O ₂ S, etc. A combination of rare earth metal ions such as Ho, Er, Tm, and Yb, and metal ions such as Ag, Cu, Au, Al, Mn, and Sb as activators or coactivators.

Preferred examples of the crystal matrix include, for example, sulfides such as (Zn, Cd) S, SrGa ₂ S ₄ , SrS, ZnS; oxysulfides such as Y ₂ O ₂ S; (Y, Gd) ₃ Al ₅ O ₁₂ , YAlO ₃ , BaMgAl ₁₀ O ₁₇ , (Ba, Sr) (Mg, Mn) Al ₁₀ O ₁₇ , (Ba, Sr, Ca) (Mg, Zn, Mn) Al ₁₀ O ₁₇ , BaAl ₁₂ O ₁₉ , CeMgAl Aluminates such as ₁₁ O ₁₉ , (Ba, Sr, Mg) O.Al ₂ O ₃ , BaAl ₂ Si ₂ O ₈ , SrAl ₂ O ₄ , Sr ₄ Al ₁₄ O ₂₅ , Y ₃ Al ₅ O ₁₂ ; Y Silicates such as ₂ SiO ₅ and Zn ₂ SiO ₄ ; Oxides such as SnO ₂ and Y ₂ O ₃ ; Borates such as GdMgB ₅ O ₁₀ and (Y, Gd) BO ₃ ; Ca ₁₀ (PO ₄ ) ₆ ( _{F, Cl) 2, (Sr} , Ca, Ba, Mg) 10 (PO 4) 6 halophosphate of ₂ such as Cl; Sr ₂ P _{2 7,} it may be mentioned (La, Ce) phosphate PO _4, etc. and the like.

  However, the crystal matrix and the activator element or coactivator element are not particularly limited in element composition, and can be partially replaced with elements of the same family, and the obtained phosphor is light in the near ultraviolet to visible region. Any material that absorbs and emits visible light can be used.

  Specifically, the following phosphors can be used, but these are merely examples, and phosphors that can be used in the present invention are not limited to these. In the following examples, as described above, phosphors that differ only in part of the structure are omitted as appropriate.

<First phosphor>
The second light emitter in the light emitting device of the present invention contains at least the above-described phosphor of the present invention as the first phosphor. Any one of the phosphors of the present invention may be used alone, or two or more thereof may be used in any combination and ratio. In addition to the phosphor of the present invention, a phosphor that emits fluorescence of the same color as the phosphor of the present invention (same color combined phosphor) may be used as the first phosphor. Since the phosphor of the present invention is usually a blue to green phosphor, the first phosphor may be used in combination with the green phosphor of the present invention together with another type of green phosphor, or with the blue phosphor of the present invention. Other types of blue phosphors can be used in combination.

(Green phosphor)
As said green fluorescent substance, arbitrary things can be used unless the effect of this invention is impaired remarkably.
The emission peak wavelength λ _p (nm) is usually larger than 490 nm, preferably 500 nm or more, and usually 570 nm or less, especially 550 nm or less, and further preferably 540 nm or less. If this emission peak wavelength λ _p is too short, it tends to be bluish, while if it is too long, it tends to be yellowish, and the characteristics as green light may deteriorate.

Specifically, the green phosphor is composed of, for example, fractured particles having a fractured surface, and emits a green region (Mg, Ca, Sr, Ba) with europium represented by Si ₂ O ₂ N ₂ : Eu. Examples include active alkaline earth silicon oxynitride phosphors.

Other green phosphors include Eu-activated aluminate phosphors such as Sr ₄ Al ₁₄ O ₂₅ : Eu, (Ba, Sr, Ca) Al ₂ O ₄ : Eu, and (Sr, Ba) Al _{2. Si 2 O 8: Eu, (} Ba, Mg) 2 SiO 4: Eu, (Ba, Sr, Ca, Mg) 2 SiO 4: Eu, (Ba, Sr, Ca) 2 (Mg, Zn) Si 2 O 7 : Eu, (Ba, Ca, Sr, Mg) ₉ (Sc, Y, Lu, Gd) ₂ (Si, Ge) ₆ O ₂₄ : Eu-activated silicate phosphor such as Eu, Y ₂ SiO ₅ : Ce, Ce, Tb activated silicate phosphor such as Tb, Sr ₂ P ₂ O ₇ —Sr ₂ B ₂ O ₅ : Eu activated borate phosphate phosphor such as Eu, Sr ₂ Si ₃ O ₈ -2SrCl ₂ : Eu-activated halo silicate phosphor such as Eu, Zn ₂ SiO _4: Mn-activated silicate phosphors such as _{Mn, CeMgAl 11 O 19: Tb} , ₃ Al ₅ O _12: Tb-activated aluminate phosphors such as _{Tb, Ca 2 Y 8 (SiO} 4) 6 O 2: Tb, La 3 Ga 5 SiO 14: Tb -activated silicate phosphors such as Tb, (Sr, Ba, Ca) Ga ₂ S ₄ : Eu, Tb, Sm activated thiogallate phosphors such as Eu, Tb, Sm, Y ₃ (Al, Ga) ₅ O ₁₂ : Ce, (Y, Ga, Tb, La, Sm, Pr, Lu) ₃ (Al, Ga) ₅ O ₁₂ : Ce-activated aluminate phosphor such as Ce, Ca ₃ Sc ₂ Si ₃ O ₁₂ : Ce, Ca ₃ (Sc, Mg, Na, Li) ₂ Si ₃ O ₁₂ : Ce activated silicate phosphor such as Ce, Ce activated oxide phosphor such as CaSc ₂ O ₄ : Ce, Eu activated oxynitride phosphor such as Eu activated β sialon _{, BaMgAl 10 O 17: Eu,} Eu such as Mn, Mn-activated aluminate phosphor, SrAl ₂ O _4: Eu such as Eu Activated aluminate phosphors, (La, Gd, Y) 2 O 2 S: Tb Tsukekatsusan sulfide phosphor such as Tb, LaPO _4: Ce, Ce and Tb such, Tb-activated phosphate phosphor, Sulfide phosphors such as ZnS: Cu, Al, ZnS: Cu, Au, Al, (Y, Ga, Lu, Sc, La) BO ₃ : Ce, Tb, Na ₂ Gd ₂ B ₂ O ₇ : Ce, Tb (Ba, Sr) ₂ (Ca, Mg, Zn) B ₂ O ₆ : Ce, Tb activated borate phosphors such as K, Ce, Tb, Ca ₈ Mg (SiO ₄ ) ₄ Cl ₂ : Eu, Mn Eu, Mn activated halosilicate phosphors such as (Sr, Ca, Ba) (Al, Ga, In) ₂ S ₄ : Eu activated thioaluminate phosphors and thiogallate phosphors such as Eu, (Ca, Sr) ₈ (Mg, Zn) (SiO ₄ ) ₄ Cl ₂ : Eu, Mn activated halosilicate phosphor such as Eu, Mn, M ₃ S i ₆ O ₉ N ₄ : Eu, M ₃ Si ₆ O ₁₂ N ₂ : Eu (where M represents an alkaline earth metal element). It is also possible to use Eu-activated oxynitride phosphors such as

In addition, as the green phosphor, it is also possible to use a pyridine-phthalimide condensed derivative, a benzoxazinone-based, a quinazolinone-based, a coumarin-based, a quinophthalone-based, a nartaric imide-based fluorescent dye, or an organic phosphor such as a terbium complex. is there.
Any of the green phosphors exemplified above may be used alone, or two or more may be used in any combination and ratio.

(Blue phosphor)
Any blue phosphor may be used as long as the effects of the present invention are not significantly impaired.
The emission peak wavelength λ _p (nm) is usually larger than 420 nm, preferably 430 nm or more, more preferably 440 nm or more, and usually 490 nm or less, particularly preferably 480 nm or less, more preferably 470 nm or less, particularly 460 nm. The following is preferred. If the emission peak wavelength λ _p is too short, it is out of the range of visible light, while if it is too long, it tends to be greenish, and the characteristics as blue light may deteriorate.

As such a blue phosphor, europium represented by (Ba, Sr, Ca) MgAl ₁₀ O ₁₇ : Eu which is composed of growing particles having a substantially hexagonal shape as a regular crystal growth shape and emits light in a blue region. The activated barium magnesium aluminate phosphor is composed of growing particles having a substantially spherical shape as a regular crystal growth shape, and emits light in the blue region (Mg, Ca, Sr, Ba) ₅ (PO ₄ ) ₃ ( Cl, F): a europium-activated calcium halophosphate phosphor represented by Eu, composed of grown particles having a substantially cubic shape as a regular crystal growth shape, and emits light in a blue region (Ca, Sr, Ba) ₂ B ₅ O ₉ Cl: europium-activated alkaline earth represented by Eu aluminate-based phosphor is composed of fractured particles having a fractured surface Performing light emission in the blue-green region (Sr, Ca, Ba) Al 2 O 4: Eu or _{(Sr, Ca, Ba) 4} Al 14 O 25: europium-activated alkaline earth represented by Eu aluminate-based phosphor such as Is mentioned.

In addition, as the blue phosphor, Sn-activated phosphate phosphors such as Sr ₂ P ₂ O ₇ : Sn, (Sr, Ca, Ba) Al ₂ O ₄ : Eu or (Sr, Ca, Ba) ₄ Al ₁₄ O ₂₅ : Eu, BaMgAl ₁₀ O ₁₇ : Eu, (Ba, Sr, Ca) MgAl ₁₀ O ₁₇ : Eu, BaMgAl ₁₀ O ₁₇ : Eu, Tb, Sm, BaAl ₈ O ₁₃ : Eu attached Active aluminate phosphor, Ce-activated thiogallate phosphor such as SrGa ₂ S ₄ : Ce, CaGa ₂ S ₄ : Ce, Eu, Mn such as (Ba, Sr, Ca) MgAl ₁₀ O ₁₇ : Eu, Mn Active aluminate phosphor, (Sr, Ca, Ba, Mg) ₁₀ (PO ₄ ) ₆ Cl ₂ : Eu, (Ba, Sr, Ca) ₅ (PO ₄ ) ₃ (Cl, F, Br, OH): Eu, Mn, Eu-activated halophosphate phosphors such as Sb, BaAl ₂ Si _{2 8: Eu, (Sr, Ba} ) 3 MgSi 2 O 8: Eu -activated silicate phosphors such as _{Eu, Sr 2 P 2 O 7} : Eu -activated phosphate phosphor such as Eu, ZnS: Ag, ZnS : Sulfide phosphors such as Ag and Al, Y ₂ SiO ₅ : Ce activated silicate phosphors such as Ce, Tungsten phosphors such as CaWO ₄ , (Ba, Sr, Ca) BPO ₅ : Eu, Mn _{, (Sr, Ca) 10 (} PO 4) 6 · nB 2 O 3: Eu, 2SrO · 0.84P 2 O 5 · 0.16B 2 O 3: Eu such as Eu, Mn-activated borate phosphate phosphors Eu-activated halosilicate phosphors such as Sr ₂ Si ₃ O ₈ .2SrCl ₂ : Eu, Eu-activated oxynitride phosphors such as SrSi ₉ Al ₁₉ ON ₃₁ : Eu, EuSi ₉ Al ₁₉ ON _31, etc. It is also possible to use it.

  In addition, as the blue phosphor, for example, naphthalic acid imide-based, benzoxazole-based, styryl-based, coumarin-based, pyralizone-based, triazole-based compound fluorescent dyes, thulium complexes and other organic phosphors can be used. .

Among the above examples, as the blue phosphor, (Ca, Sr, Ba) MgAl ₁₀ O ₁₇ : Eu, (Sr, Ca, Ba, Mg) ₁₀ (PO ₄ ) ₆ (Cl, F) ₂ : Eu or It is preferable to contain (Ba, Ca, Mg, Sr) ₂ SiO ₄ : Eu, and (Ca, Sr, Ba) MgAl ₁₀ O ₁₇ : Eu, (Sr, Ca, Ba, Mg) ₁₀ (PO ₄ ) ₆ ( Cl, F) ₂ : Eu or (Ba, Ca, Sr) ₃ MgSi ₂ O ₈ : Eu is more preferable, and BaMgAl ₁₀ O ₁₇ : Eu, Sr ₁₀ (PO ₄ ) ₆ (Cl, F) ₂ : More preferably, Eu or Ba ₃ MgSi ₂ O ₈ : Eu is included. Of these, (Sr, Ca, Ba, Mg) ₁₀ (PO ₄ ) ₆ Cl ₂ : Eu or (Ca, Sr, Ba) MgAl ₁₀ O ₁₇ : Eu is particularly preferred for illumination and display applications.

<Second phosphor>
The second light emitter in the light emitting device of the present invention may contain a phosphor (that is, a second phosphor) in addition to the first phosphor described above, depending on the application. The second phosphor is a phosphor having an emission wavelength different from that of the first phosphor. Usually, since these second phosphors are used to adjust the color tone of light emitted from the second light emitter, the second phosphor emits fluorescence having a color different from that of the first phosphor. Often phosphors are used. For example, when a green phosphor is used as the first phosphor, a phosphor other than a green phosphor such as an orange to red phosphor, a blue phosphor, or a yellow phosphor is used as the second phosphor.

  The weight median diameter of the second phosphor used in the light emitting device of the present invention is usually in the range of 10 μm or more, especially 12 μm or more, and usually 30 μm or less, especially 25 μm or less. When the weight median diameter is too small, the luminance is lowered and the phosphor particles tend to aggregate. On the other hand, if the weight median diameter is too large, there is a tendency for coating unevenness and blockage of the dispenser to occur.

(Orange to red phosphor)
When an orange or red phosphor is used as the second phosphor, any orange or red phosphor can be used as long as the effects of the present invention are not significantly impaired. At this time, the emission peak wavelength of the orange to red phosphor is usually in the wavelength range of more than 570 nm, preferably 580 nm or more, more preferably 585 nm or more, and usually 780 nm or less, preferably 700 nm or less, more preferably 680 nm or less. Preferably it is.

Examples of such orange to red phosphors are europium composed of broken particles having a red fracture surface and emitting red region (Mg, Ca, Sr, Ba) ₂ Si ₅ N ₈ : Eu. The activated alkaline earth silicon nitride-based phosphor is composed of growing particles having a substantially spherical shape as a regular crystal growth shape, and emits light in the red region (Y, La, Gd, Lu) ₂ O ₂ S: Examples include europium activated rare earth oxychalcogenide phosphors represented by Eu.

  Furthermore, an oxynitride and / or an acid containing at least one element selected from the group consisting of Ti, Zr, Hf, Nb, Ta, W, and Mo described in JP-A No. 2004-300247 A phosphor containing a sulfide and containing an oxynitride having an alpha sialon structure in which a part or all of the Al element is substituted with a Ga element can also be used in the present invention. These are phosphors containing oxynitride and / or oxysulfide.

In addition, examples of red phosphors include Eu-activated oxysulfide phosphors such as (La, Y) ₂ O ₂ S: Eu, Y (V, P) O ₄ : Eu, Y ₂ O ₃ : Eu, and the like. Eu-activated oxide phosphors of (Ba, Mg) ₂ SiO ₄ : Eu, Mn, (Ba, Sr, Ca, Mg) ₂ SiO ₄ : Eu, Mn-activated silicate phosphors such as Eu and Mn, Eu-activated tungstate phosphors such as LiW ₂ O ₈ : Eu, LiW ₂ O ₈ : Eu, Sm, Eu ₂ W ₂ O ₉ , Eu ₂ W ₂ O ₉ : Nb, Eu ₂ W ₂ O ₉ : Sm Eu-activated sulfide phosphors such as (Ca, Sr) S: Eu, Eu-activated aluminate phosphors such as YAlO ₃ : Eu, Ca ₂ Y ₈ (SiO ₄ ) ₆ O ₂ : Eu, LiY _{9 (SiO 4) 6 O 2:} Eu, (Sr, Ba, Ca) 3 SiO 5: Eu, Sr 2 BaSiO 5: Eu -activated silicate phosphors such as Eu, _{Y, Gd) 3 Al 5 O} 12: Ce, (Tb, Gd) 3 Al 5 O 12: Ce -activated aluminate phosphor such as Ce, (Mg, Ca, Sr , Ba) 2 Si 5 (N, Eu-activated oxides such as O) ₈ : Eu, (Mg, Ca, Sr, Ba) Si (N, O) ₂ : Eu, (Mg, Ca, Sr, Ba) AlSi (N, O) ₃ : Eu , Nitride or oxynitride phosphor, (Mg, Ca, Sr, Ba) AlSi (N, O) ₃ : Ce activated oxide such as Ce, nitride or oxynitride phosphor, (Sr, Ca, Ba, Mg) ₁₀ (PO ₄ ) ₆ Cl ₂ : Eu, Mn-activated halophosphate phosphor such as Eu, Mn, Ba ₃ MgSi ₂ O ₈ : Eu, Mn, (Ba, Sr, Ca, Mg) ₃ (Zn, Mg) Si ₂ O ₈ : Eu, Mn activated silicate phosphor such as Eu, Mn, 3.5MgO.0.5MgF ₂ .GeO ₂ : Mn Mn-activated germanate phosphor such as Eu-activated α-sialon phosphor such as Eu-activated α-sialon, (Gd, Y, Lu, La) ₂ O ₃ : Eu, Bi-activated Eu, Bi, etc. Oxide phosphor, (Gd, Y, Lu, La) ₂ O ₂ S: Eu, Bi activated oxysulfide phosphor such as Eu, Bi, (Gd, Y, Lu, La) VO ₄ : Eu, Bi Eu, Bi activated vanadate phosphors such as SrY ₂ S ₄ : Eu, Ce activated sulfide phosphors such as Eu, Ce, Ce activated sulfide phosphors such as CaLa ₂ S ₄ : Ce, ( Ba, Sr, Ca) MgP ₂ O ₇ : Eu, Mn, (Sr, Ca, Ba, Mg, Zn) ₂ P ₂ O ₇ : Eu, Mn activated phosphate phosphor such as Eu, Mn, (Y _{, Lu) 2 WO 6: Eu} , Eu such as Mo, Mo-activated tungstate salt phosphor, (Ba, Sr, Ca) x Si y N z: Eu, Ce However, x, y, z are an integer of 1 or more. Eu, Ce-activated nitride phosphors such as (Ca, Sr, Ba, Mg) ₁₀ (PO ₄ ) ₆ (F, Cl, Br, OH): Eu, Mn-activated halophosphoric acid such as Eu, Mn Ce phosphors such as salt phosphors, ((Y, Lu, Gd, Tb) _1-xy Sc _x Ce _y ) ₂ (Ca, Mg) _1-r (Mg, Zn) _{2 + r} Si _zq Ge _q O _{12 + δ} It is also possible to use an activated silicate phosphor or the like.

  Examples of red phosphors include β-diketonates, β-diketones, aromatic carboxylic acids, red organic phosphors composed of rare earth element ion complexes having an anion such as Bronsted acid as a ligand, and perylene pigments (for example, Dibenzo {[f, f ′]-4,4 ′, 7,7′-tetraphenyl} diindeno [1,2,3-cd: 1 ′, 2 ′, 3′-lm] perylene), anthraquinone pigment, Lake pigments, azo pigments, quinacridone pigments, anthracene pigments, isoindoline pigments, isoindolinone pigments, phthalocyanine pigments, triphenylmethane basic dyes, indanthrone pigments, indophenol pigments, It is also possible to use a cyanine pigment or a dioxazine pigment.

Among these, as red phosphors, (Ca, Sr, Ba) ₂ Si ₅ (N, O) ₈ : Eu, (Ca, Sr, Ba) Si (N, O) ₂ : Eu, (Ca, Sr , Ba) AlSi (N, O) ₃ : Eu, (Ca, Sr, Ba) AlSi (N, O) ₃ : Ce, (Sr, Ba) ₃ SiO ₅ : Eu, (Ca, Sr) S: Eu, It is preferable to contain (La, Y) ₂ O ₂ S: Eu or Eu complex, more preferably (Ca, Sr, Ba) ₂ Si ₅ (N, O) ₈ : Eu, (Ca, Sr, Ba) Si. (N, O) ₂ : Eu, (Ca, Sr, Ba) AlSi (N, O) ₃ : Eu, (Ca, Sr, Ba) AlSi (N, O) ₃ : Ce, (Sr, Ba) ₃ SiO _{5: Eu, (Ca, Sr} ) S: Eu or _{(La, Y) 2 O 2} S: Eu or Eu (dibenzoylmethane) ₃ · 1, Preferably comprises a β- diketone Eu complex or carboxylic acid type Eu complex such as 10-phenanthroline complex, (Ca, Sr, Ba) 2 Si 5 (N, O) 8: Eu, (Sr, Ca) AlSiN 3 : Eu or (La, Y) ₂ O ₂ S: Eu is particularly preferred.

Of the above examples, (Sr, Ba) ₃ SiO ₅ : Eu is preferable as the orange phosphor.

(Yellow phosphor)
When a yellow phosphor is used as the second phosphor, any yellow phosphor can be used as long as the effects of the present invention are not significantly impaired. At this time, the emission peak wavelength of the yellow phosphor is usually in the wavelength range of 530 nm or more, preferably 540 nm or more, more preferably 550 nm or more, and usually 620 nm or less, preferably 600 nm or less, more preferably 580 nm or less. Is preferred.

Examples of such yellow phosphors include various oxide-based, nitride-based, oxynitride-based, sulfide-based, and oxysulfide-based phosphors.
In particular, RE ₃ M ₅ O ₁₂ : Ce (where RE represents at least one element selected from the group consisting of Y, Tb, Gd, Lu, and Sm, and M represents Al, Ga, and Sc. And M ^a ₃ M ^b ₂ ^Mc ₃ O ₁₂ : Ce (where M ^a is a divalent metal element and M ^b is a trivalent metal element) , M ^c represents a tetravalent metal element.) Garnet-based phosphor having a garnet structure represented by AE ₂ M ^d O ₄ : Eu (where AE is Ba, Sr, Ca, Mg, and And at least one element selected from the group consisting of Zn, M ^d represents Si and / or Ge), etc., and oxygen of constituent elements of the phosphors of these systems Oxynitride phosphor, part of which is replaced with nitrogen, AEAlS Ce such as nitride phosphors having a CaAlSiN ₃ structure such as iN ₃ : Ce (wherein AE represents at least one element selected from the group consisting of Ba, Sr, Ca, Mg and Zn). And the phosphor activated in step (b).

Other examples of yellow phosphors include sulfide-based fluorescence such as CaGa ₂ S ₄ : Eu, (Ca, Sr) Ga ₂ S ₄ : Eu, (Ca, Sr) (Ga, Al) ₂ S ₄ : Eu. A phosphor activated by Eu such as an oxynitride-based phosphor having a SiAlON structure such as Ca _x (Si, Al) ₁₂ (O, N) ₁₆ : Eu (0 ≦ x <1). Is possible.

  Examples of yellow phosphors include brilliant sulfoflavine FF (Color Index Number 56205), basic yellow HG (Color Index Number 46040), eosine (Color Index Number 45e 380a) Etc. can also be used.

(Blue phosphor)
When a blue phosphor is used as the second phosphor, any blue phosphor can be used as long as the effects of the present invention are not significantly impaired. At this time, the emission peak wavelength of the blue phosphor is usually 420 nm or more, preferably 430 nm or more, more preferably 440 nm or more, and usually 490 nm or less, particularly preferably 480 nm or less, more preferably 470 nm or less, particularly 460 nm or less is preferable. If the emission peak wavelength λ _p is too short, it is out of the range of visible light, while if it is too long, it tends to be greenish, and the characteristics as blue light may deteriorate. As such a blue phosphor, the blue phosphor described in the section of the first phosphor can be used.

(Green phosphor)
When a green phosphor is used as the second phosphor, any green phosphor can be used as long as the effects of the present invention are not significantly impaired. At this time, the emission peak wavelength of the green phosphor is usually more than 490 nm, preferably 500 nm or more, and usually 570 nm or less, especially 550 nm or less, and more preferably 540 nm or less. If this emission peak wavelength λ _p is too short, it tends to be bluish, while if it is too long, it tends to be yellowish, and the characteristics as green light may deteriorate. As such a blue phosphor, the green phosphor described in the section of the first phosphor can be used.

(Combination of second phosphors)
As said 2nd fluorescent substance, 1 type of fluorescent substance may be used independently, and 2 or more types of fluorescent substance may be used together by arbitrary combinations and a ratio. Further, the ratio between the first phosphor and the second phosphor is also arbitrary as long as the effects of the present invention are not significantly impaired. Therefore, the usage amount of the second phosphor, the combination and ratio of the phosphors used as the second phosphor, and the like may be arbitrarily set according to the use of the light emitting device.

  In the light emitting device of the present invention, the presence / absence and type of the second phosphor (orange to red phosphor, blue phosphor, etc.) described above may be appropriately selected according to the use of the light emitting device. For example, when the light emitting device of the present invention is configured as a green light emitting device, only the green phosphor of the present invention may be used as the first phosphor, and the second phosphor is usually used. It is unnecessary.

  On the other hand, when the light-emitting device of the present invention is configured as a light-emitting device that emits white light, the first light-emitting body and the second light-emitting body (the first phosphor and the first phosphor) can be used so as to obtain desired white light. 2 phosphors) may be combined appropriately. Specifically, examples of preferable combinations of the first light emitter, the first phosphor, and the second phosphor in the case where the light emitting device of the present invention is configured as a white light emitting device include the following: (I) to (iii) are included.

(I) A near ultraviolet light emitter (near ultraviolet LED or the like) is used as the first light emitter, the green phosphor of the present invention is used as the first phosphor, and a blue phosphor and a red light are used as the second phosphor. Use phosphor together. In this case, the blue phosphor is selected from the group consisting of (Ba, Sr, Ca) MgAl ₁₀ O ₁₇ : Eu and (Mg, Ca, Sr, Ba) ₅ (PO ₄ ) ₃ (Cl, F): Eu. One or more blue phosphors are preferred. The red phosphor is preferably one or two or more red phosphors selected from the group consisting of (Sr, Ca) AlSiN ₃ : Eu and La ₂ O ₂ S: Eu. Among them, it is preferable to use a near ultraviolet LED, the phosphor of the present invention, BaMgAl ₁₀ O ₁₇ : Eu as a blue phosphor, and (Sr, Ca) AlSiN ₃ : Eu as a red phosphor.

(Ii) A near ultraviolet light emitter (near ultraviolet LED or the like) is used as the first light emitter, a blue phosphor (such as the phosphor of the present invention) is used as the first phosphor, and the second phosphor is used. Orange to red phosphors and green phosphors are used.
The phosphors described above can be preferably used as the phosphors of the respective colors. In particular, in the case of the combination (ii), as the red phosphor, one or more red phosphors selected from the group consisting of (Sr, Ca) AlSiN ₃ : Eu and La ₂ O ₂ S: Eu are particularly used. The orange phosphor is preferably (Sr, Ba) ₃ SiO ₅ : Eu. In particular, one or more red phosphors selected from the group consisting of (Sr, Ca) AlSiN ₃ : Eu and La ₂ O ₂ S: Eu are more preferable.
In addition, as the green phosphor, BaMgAl ₁₀ O ₁₇ : Eu, Mn, (Ba, Sr, Ca) ₂ SiO ₄ : Eu, Eu-activated β sialon, and (Ba, Sr, Ca) ₃ Si ₆ O ₁₂ One or more green phosphors selected from the group consisting of N ₂ : Eu are particularly preferred.

(Iii) A near ultraviolet light emitter (near ultraviolet LED or the like) is used as the first light emitter, a blue phosphor (such as the phosphor of the present invention) is used as the first phosphor, and the second phosphor is used as the second phosphor. A yellow phosphor is used.
The phosphors described above can be preferably used as the phosphors of the respective colors. In particular, in the case of the combination (iii), the yellow phosphor includes (Y, Gd, Tb) ₃ (Al, Ga) ₅ O ₁₂ : Ce, (Ba, Sr, Ca) ₂ SiO ₄ : Eu, Eu. One or more green phosphors selected from the group consisting of active α sialon and (Ba, Sr, Ca) Si ₂ O ₂ N ₂ : Eu are particularly preferred.

  In addition, the phosphor of the present invention is mixed with other phosphors (here, mixing does not necessarily mean that the phosphors need to be mixed with each other, but means that different types of phosphors are combined). ) Can be used. In particular, when phosphors are mixed in the combination described above, a preferable phosphor mixture is obtained. In addition, there is no restriction | limiting in particular in the kind and the ratio of the fluorescent substance to mix.

(Sealing material)
In the light emitting device of the present invention, the first and / or second phosphors are usually used by being dispersed in a liquid medium that is a sealing material.
Examples of the liquid medium include [4. Examples thereof are the same as those described in the section “Fluorescent substance-containing composition”.

  The liquid medium can contain a metal element that can be a metal oxide having a high refractive index in order to adjust the refractive index of the sealing member. Examples of metal elements that give a metal oxide having a high refractive index include Si, Al, Zr, Ti, Y, Nb, and B. These metal elements may be used alone or in combination of two or more in any combination and ratio.

The presence form of such a metal element is not particularly limited as long as the transparency of the sealing member is not impaired. For example, even if a uniform glass layer is formed as a metalloxane bond, the metal element is present in a particulate form in the sealing member. It may be. When present in the form of particles, the structure inside the particles may be either amorphous or crystalline, but is preferably a crystalline structure in order to provide a high refractive index. Further, the particle diameter is usually not more than the emission wavelength of the semiconductor light emitting device, preferably not more than 100 nm, more preferably not more than 50 nm, particularly preferably not more than 30 nm so as not to impair the transparency of the sealing member. For example, by mixing particles of silicon oxide, aluminum oxide, zirconium oxide, titanium oxide, yttrium oxide, niobium oxide, etc. with a silicone-based material, the metal element can be present in the sealing member in the form of particles. .
The liquid medium may further contain known additives such as a diffusing agent, a filler, a viscosity modifier, and an ultraviolet absorber.

[5-2. Configuration of light emitting device (others)]
The other configurations of the light emitting device of the present invention are not particularly limited as long as the first light emitting body and the second light emitting body described above are provided. Usually, the first light emitting body described above is formed on an appropriate frame. And a second light emitter. At this time, the second light emitter is excited by the light emission of the first light emitter (that is, the first and second phosphors are excited) to emit light, and the first light emitter emits light. And / or it arrange | positions so that light emission of a 2nd light-emitting body may be taken out outside. In this case, the first phosphor and the second phosphor are not necessarily mixed in the same layer. For example, the second phosphor is contained on the layer containing the first phosphor. For example, the phosphor may be contained in a separate layer for each color development of the phosphor, such as by stacking layers.

  In the light emitting device of the present invention, members other than the above-described excitation light source (first light emitter), phosphor (second light emitter), and frame may be used. Examples thereof include the aforementioned sealing materials. In addition to the purpose of dispersing the phosphor (second light emitter) in the light emitting device, the sealing material is provided between the excitation light source (first light emitter), the phosphor (second light emitter), and the frame. It can be used for the purpose of bonding.

[5-3. Embodiment of Light Emitting Device]
Hereinafter, the light-emitting device of the present invention will be described in more detail with reference to specific embodiments. However, the present invention is not limited to the following embodiments, and does not depart from the gist of the present invention. It can be implemented with arbitrary modifications.

  FIG. 1 is a schematic perspective view showing a positional relationship between a first light emitter serving as an excitation light source and a second light emitter configured as a phosphor containing portion having a phosphor in an example of the light emitting device of the present invention. Shown in In FIG. 1, reference numeral 1 denotes a phosphor-containing portion (second light emitter), reference numeral 2 denotes a surface-emitting GaN-based LD as an excitation light source (first light emitter), and reference numeral 3 denotes a substrate. In order to create a state in which they are in contact with each other, LD (2) and phosphor-containing portion (second light emitter) (1) are produced separately, and their surfaces are brought into contact with each other by an adhesive or other means. Alternatively, the phosphor-containing portion (second light emitter) may be formed (molded) on the light emitting surface of the LD (2). As a result, the LD (2) and the phosphor-containing portion (second light emitter) (1) can be brought into contact with each other.

  When such an apparatus configuration is employed, the light loss is such that light from the excitation light source (first light emitter) is reflected by the film surface of the phosphor-containing portion (second light emitter) and oozes out. Therefore, the light emission efficiency of the entire device can be improved.

  FIG. 2A is a typical example of a light emitting device of a form generally referred to as a shell type, and has a light emission having an excitation light source (first light emitter) and a phosphor-containing portion (second light emitter). It is typical sectional drawing which shows one Example of an apparatus. In the light emitting device (4), reference numeral 5 is a mount lead, reference numeral 6 is an inner lead, reference numeral 7 is an excitation light source (first light emitter), reference numeral 8 is a phosphor-containing resin portion, reference numeral 9 is a conductive wire, reference numeral Reference numeral 10 denotes a mold member.

  FIG. 2B is a typical example of a light-emitting device of a form called a surface-mount type, and has light emission having an excitation light source (first light emitter) and a phosphor-containing portion (second light emitter). It is typical sectional drawing which shows one Example of an apparatus. In the figure, reference numeral 22 is an excitation light source (first light emitter), reference numeral 23 is a phosphor-containing resin portion as a phosphor-containing portion (second light emitter), reference numeral 24 is a frame, reference numeral 25 is a conductive wire, Reference numerals 26 and 27 indicate electrodes.

[5-4. Application of light emitting device]
The application of the light-emitting device of the present invention is not particularly limited and can be used in various fields where ordinary light-emitting devices are used. However, since the color reproduction range is wide and the color rendering property is high, illumination is particularly important. It is particularly preferably used as a light source for a device or an image display device.

[5-4-1. Lighting device]
When the light-emitting device of the present invention is applied to a lighting device, the above-described light-emitting device may be appropriately incorporated into a known lighting device. For example, a surface emitting illumination device (11) incorporating the above-described light emitting device (4) as shown in FIG. 3 can be mentioned.

  FIG. 3 is a cross-sectional view schematically showing one embodiment of the illumination device of the present invention. As shown in FIG. 3, the surface-emitting illumination device has a number of light-emitting devices (13) (described above) on the bottom surface of a rectangular holding case (12) whose inner surface is light-opaque such as a white smooth surface. The light emitting device (4)) is disposed with a power supply and a circuit (not shown) for driving the light emitting device (13) provided outside thereof, and corresponds to the lid portion of the holding case (12). Further, a diffusion plate (14) such as an acrylic plate made of milky white is fixed for uniform light emission.

  Then, the surface emitting illumination device (11) is driven to apply light to the excitation light source (first light emitter) of the light emitting device (13) to emit light, and part of the light emission is converted into the phosphor. The phosphor in the phosphor-containing resin part as the containing part (second light emitter) absorbs and emits visible light, while having high color rendering due to color mixing with blue light or the like that is not absorbed by the phosphor. Luminescence is obtained, and this light is transmitted through the diffusion plate (14) and emitted upward in the drawing, so that illumination light with uniform brightness can be obtained within the surface of the diffusion plate (14) of the holding case (12). Become.

[5-4-2. Image display device]
When the light emitting device of the present invention is used as a light source of an image display device, the specific configuration of the image display device is not limited, but it is preferably used with a color filter. For example, when the image display device is a color image display device using color liquid crystal display elements, the light emitting device is used as a backlight, a light shutter using liquid crystal, and a color filter having red, green, and blue pixels; By combining these, an image display device can be formed.

  EXAMPLES Hereinafter, although this invention is demonstrated further in detail using an Example, this invention is not limited by a following example, unless it deviates from the summary. In the following description, the description of “parts” means “parts by weight”.

[Measurement and evaluation method]
<Powder X-ray diffraction measurement method>
Powder X-ray diffraction was precisely measured with a powder X-ray diffractometer X'Pert made by PANalytical. The measurement conditions are as follows.
Using CuKα tube X-ray output = 45 KV, 40 mA
Divergence slit = 1/4 °, X-ray mirror detector = semiconductor array detector X 'Celerator used, Ni filter used Scanning range 2θ = 10 to 65 degrees Reading width = 0.05 degrees Counting time = 33 seconds

<Measurement method of emission spectrum>
The emission spectrum was measured using a 150 W xenon lamp as an excitation light source and a fluorescence measuring apparatus (manufactured by JASCO Corporation) equipped with a multi-channel CCD detector C7041 (manufactured by Hamamatsu Photonics) as a spectrum measuring apparatus. The light from the excitation light source was passed through a diffraction grating spectrometer having a focal length of 10 cm, and only the excitation light having a wavelength of 395 nm was irradiated to the phosphor through the optical fiber. The light generated from the phosphor by the irradiation of excitation light is dispersed by a diffraction grating spectroscope having a focal length of 25 cm, the emission intensity of each wavelength is measured by a spectrum measuring device in a wavelength range of 300 nm to 800 nm, and a personal computer is used. An emission spectrum was obtained through signal processing such as sensitivity correction. During the measurement, the slit width of the light-receiving side spectroscope was set to 1 nm and the measurement was performed.

<Peak emission wavelength / half width>
The emission peak wavelength and the half width were read from the emission spectrum obtained by the above method.

<Measurement method of chromaticity coordinates>
From data in the wavelength region of 380 nm to 800 nm (excitation wavelength 340 nm), 430 nm to 800 nm (excitation wavelength 400 nm), or 480 nm to 800 nm (excitation wavelength 455 nm) of the emission spectrum, in a method according to JIS Z8724. The chromaticity coordinates CIEx and CIEy in the XYZ color system defined by JIS Z8701 were calculated.

<Ra measurement method>
According to the method described in JIS Z8726, the color system XYZ value obtained from the emission spectrum was used.

[Example 1]
Barium carbonate (Rare Metallic Co., Ltd., BaCO ₃ ), Magnesium Carbonate (Shirakaba Chemical Co., Ltd., MgCO ₃ ), Silicon Oxide (Tatsumori Co., Ltd., SiO ₂ ), Silicon Nitride (Ube Co., Ltd.) , Si ₃ N ₄ ), europium oxide (manufactured by Shin-Etsu Chemical Co., Ltd., Eu ₂ O ₃ ), and lutetium oxide (manufactured by Shin-Etsu Chemical Co., Ltd., Lu ₂ O ₃ ) as raw materials, BaCO ₃ : MgCO ₃ : Weigh and mix so that the molar ratio of SiO ₂ : Si ₃ N ₄ : Eu ₂ O ₃ : Lu ₂ O ₃ is 2.97: 0.9: 2: 0.05: 0.015: 0.1 did.

Next, it was calcined in nitrogen of 0.92 MPa at 1200 ° C. for 2 hours and then at 1400 ° C. for 2 hours. The obtained fired powder was pulverized on an alumina mortar using an alumina pestle, and (Ba, Eu) ₃ (Mg, Lu) Si ₂ (O, N) ₈ (charge composition Ba _2.97 Eu _0.03 Mg _0.82 Lu _0.18 Si _A phosphor having a compound represented by ₂ O _7.82 N _0.18 ) was obtained.

  The obtained phosphor was subjected to powder X-ray diffraction measurement. The diffraction pattern is shown in FIG. In addition, the emission spectrum was measured when the obtained phosphor was excited with 395 nm light. The emission spectrum is shown in [FIG. 5], and the results of evaluating the characteristics are shown in [Table 4].

[Examples 2 to 4]
As indicated in (Ba, Eu) ₃ (Mg, Lu) Si ₂ (O, N) ₈ in the same manner as in Example 1 except that the molar mixing ratio of the raw materials was changed to the ratio described in [Table 3] below. A phosphor comprising the compound obtained was obtained.
The obtained phosphor was subjected to powder X-ray diffraction measurement and emission spectrum measurement. The results are shown in [FIG. 4], [FIG. 5] and [Table 4].

Moreover, the lattice constant calculated | required from the result of powder X-ray diffraction measurement was applied to the hexagonal unit cell, and the volume per unit cell of each Example was also compared. The results are shown in [FIG. 6].
Note that have similar crystal structure, Mg all correspond to those substituted in Lu, volume per unit lattice of Ba ₉ Lu ₂ Si ₆ O ₂₄ was 211Å ^3. For comparison with the example demonstrates the 211A ³ in FIG. 6.

[Comparative Example 1]
The compound shown by (Ba, Eu) ₃ MgSi ₂ O ₈ is included in the same manner as in [Example 1] except that the molar mixing ratio of the raw materials is set to the ratio described in [Table 3] below. A phosphor was obtained.
The obtained phosphor was subjected to powder X-ray diffraction measurement and emission spectrum measurement. The results are shown in [FIG. 4], [FIG. 5] and [Table 4].

[Results and discussion]
From these results, although the phosphor of the present invention shows the same diffraction peak pattern as the phosphor of the comparative example using Ba ₃ MgSi ₂ O ₈ as a crystal matrix, the diffraction peak decreases as the addition amount of Lu increases. It was shifted to the angle side, and it was found that the lattice constant was increased by replacing a part of Mg with Lu.

Also, from the results of the volume comparison of the unit cells, [Example 4] has a smaller value than the volume per unit cell of Ba ₉ Lu ₂ Si ₆ O ₂₄ , so that not all Mg is replaced with Lu. It was confirmed.

  Here, in [Example 3] and [Example 4], the charged composition of the raw materials was the same, but the Lu content in the finished phosphor was different. This is presumably because a slight difference in the firing atmosphere affected the amount of substitution of Lu.

[Example 5]
A surface-mounted white light-emitting device having the configuration shown in FIG. 2 (b) was produced by the following procedure, and its chromaticity was evaluated by CIE chromaticity coordinate values (CIEx, CIEy). Of the constituent elements of [Embodiment 5], the constituent elements corresponding to those in [FIG. 2 (b)] are depicted in parentheses where appropriate.

  As the first illuminant (22), C395EZ290 (manufactured by Cree) BR0428-03A, which is a near-ultraviolet light-emitting diode (hereinafter referred to as “near-ultraviolet LED” as appropriate) having an emission peak at a wavelength of 390 to 400 nm, was used. This near-ultraviolet LED (22) was die-bonded to the electrode (27) at the bottom of the recess of the frame (24) using a silver paste as an adhesive. At this time, the silver paste as the adhesive was applied thinly and uniformly in consideration of the heat dissipation of the heat generated in the near ultraviolet LED (22). After heating at 150 ° C. for 2 hours to cure the silver paste, the near-ultraviolet LED (22) and the electrode (26) of the frame (24) were wire-bonded. As the wire (25), a gold wire having a diameter of 25 μm was used.

  In the phosphor-containing resin part (23), the phosphor-containing part (23) luminescent material (the phosphor of [Example 3] which is a green phosphor) and a silicone resin (Shin-Etsu Chemical Co., Ltd. 6101UP) , Aerosil (registered trademark) (RY-200S), and cured under the curing conditions by heating at 70 ° C. for 1 hour and further at 150 ° C. for 2 hours to form the phosphor-containing part (23), surface mount type A light emitting device was manufactured.

At room temperature (25 ± 1 ° C.), the near-ultraviolet LED (22) of the obtained surface-mounted light-emitting device was driven by applying a current of 20 mA to emit light.
All the light emission from the light emitting device was received by an integrating sphere, and further introduced into a spectroscope by an optical fiber, and the emission spectrum was measured. The emission spectrum is shown in FIG.

[Example 6]
In the phosphor-containing resin part (23), the phosphor of the phosphor-containing part (23) is a phosphor of the above [Example 4] that is a green phosphor, and a red phosphor that emits light having a wavelength of 520 nm to 760 nm. _{Except for using a} certain Sr _0.792 Ca _0.2 AlSiN ₃ : Eu _0.008 (hereinafter sometimes abbreviated as “SCASN”) and using only a silicone resin (6101UP manufactured by Shin-Etsu Chemical Co., Ltd.), the same as in [Example 5]. Thus, a surface mount type white light emitting device was manufactured.
Note that the composition ratio of the light-emitting substance is shown in [Table 5].

At room temperature (25 ± 1 ° C.), the near-ultraviolet LED (22) of the obtained surface-mounted white light-emitting device was driven by applying a current of 20 mA to emit light.
All the light emission from the white light emitting device was received by an integrating sphere, and further introduced into a spectroscope by an optical fiber, the emission spectrum was measured, and the white chromaticity coordinates and Ra were further measured.
The emission spectrum is shown in [FIG. 8], and other results are shown in [Table 6].

[Comparative Example 2]
Instead of the phosphor of the present invention in [Example 4], a blue phosphor Ba _0.7 MgAl ₁₀ O ₁₇ : Eu _0.3 (hereinafter sometimes abbreviated as “BAM”) and a green phosphor Ba _1.39 Sr _0.46 A surface-mounted white light-emitting device was produced in the same manner as in [Example 5] except that SiO ₄ : Eu _0.15 (hereinafter sometimes abbreviated as “BSS”) was used.
Note that the composition ratio of the light-emitting substance is shown in [Table 5].

With respect to the obtained surface-mounted white light-emitting device, an emission spectrum was measured under the same conditions as in [Example 6], and white chromaticity coordinates and Ra were further measured.
The emission spectrum is shown in [FIG. 8], and other results are shown in [Table 6].

  The present invention can be used in any field where light is used. For example, in addition to indoor and outdoor lighting, the present invention is used for image display devices of various electronic devices such as mobile phones, household appliances, and outdoor displays. It is preferable.

It is a typical perspective view which shows the positional relationship of an excitation light source (1st light emission body) and a fluorescent substance containing part (2nd light emission body) in an example of the light-emitting device of this invention. (A) And (b) is typical sectional drawing which shows one Example of the light-emitting device which has both an excitation light source (1st light-emitting body) and a fluorescent substance containing part (2nd light-emitting body). . It is sectional drawing which shows typically one Embodiment of the illuminating device of this invention. It is a figure which shows the result of the powder X-ray-diffraction measurement measured about Example 1-4 of this invention, and the comparative example 1. FIG. It is a figure which shows the result of the emission spectrum measurement measured about Example 1-4 of this invention, and the comparative example 1. FIG. Example 1 is represented by a solid line (thick line), Example 2 is represented by a one-dot chain line, Example 3 is represented by a two-dot chain line, Example 4 is represented by a solid line (thin line), and Comparative Example 1 is represented by a broken line. It is a figure showing the volume per lattice calculated by applying the lattice constant calculated | required from the result of a powder X-ray-diffraction measurement to the hexagonal unit cell about Example 1-Example 4 of this invention. Incidentally, the volume per unit lattice of _{Ba 9 Lu 2 Si 6 O 24} , demonstrating a straight line in the figure 211Å ^3. It is a figure showing the emission spectrum of the surface mounted light-emitting device manufactured in Example 5 of this invention. It is a figure showing the emission spectrum of the surface mount-type white light-emitting device manufactured in Example 6 and Comparative Example 2 of this invention.

Explanation of symbols

1: Second light emitter 2: Surface-emitting GaN-based LD
3: Substrate 4: Light-emitting device 5: Mount lead 6: Inner lead 7: First light-emitting body 8: Phosphor-containing resin portion 9: Conductive wire 10: Mold member 11: Surface-emitting illumination device 12: Holding case 13: Light emitting device 14: Diffuser 22: First light emitter 23: Phosphor-containing resin part 24: Frame 25: Conductive wire 26: Electrode 27: Electrode

Claims (12)

A phosphor having a chemical composition represented by the following formula (1):

(In the above formula (1),
M ¹ is, Ba, represents one or more elements selected from the group consisting of Sr and Ca,
M ² represents one or more elements selected from the group consisting of Mg and Zn,
Ln represents one or more elements selected from the group consisting of La, Lu, Y, Sc and Gd,
x, y and z are each
0 <x <1,
0.05 ≦ y <1,
0 ≦ z <1
Indicates a positive number satisfying. ) 2. The phosphor according to claim 1, having a peak wavelength of an emission spectrum in a wavelength range of 420 nm or more and 550 nm or less when excited with light having a wavelength of 395 nm. The phosphor according to claim 2, wherein a half width of a peak of the emission spectrum is 60 nm or more. When excited with light in a wavelength range of 250 nm to 480 nm, it has an emission spectrum having one peak wavelength in the wavelength range of 420 nm to 550 nm,
A phosphor having a full width at half maximum of a peak of the emission spectrum of 145 nm or more. The phosphor according to claim 4, which has a chemical composition represented by the following formula (2).

(In the above formula (2),
M ³ and M ⁴ each independently represent one or more elements selected from the group consisting of alkali metal elements, alkaline earth metal elements, and divalent transition elements,
M ⁵ represents one or more elements selected from the group consisting of B, Al, Si, Ge, P, As, and Sb;
M ⁶ represents one or more elements selected from the group consisting of O, N, S, and halogen;
L ¹ represents one or more elements selected from the group consisting of Sm, Eu, Tm and Yb;
L ² represents a rare earth element other than L ¹ .
The ion radius of M ³ is greater than the ionic radius of M ^4, the ionic radius of L ² is in the range of less 1.3 times 0.7 times the ionic radius of M ^4. ) A phosphor-containing composition comprising the phosphor according to any one of claims 1 to 5 and a liquid medium. A first light emitter, and a second light emitter that emits visible light when irradiated with light from the first light emitter,
The light emitting device, wherein the second light emitter contains one or more of the phosphors according to any one of claims 1 to 5 as a first phosphor. The light emitting device according to claim 7, wherein the second phosphor includes at least one phosphor having a different emission peak wavelength from the first phosphor as the second phosphor. . The first light emitter has a light emission peak in a wavelength range of 300 nm or more and 420 nm or less;
The second phosphor, as the second phosphor, has at least one phosphor having an emission peak in a wavelength range of more than 490 nm and less than or equal to 570 nm, and an emission peak in a wavelength range of more than 570 nm and less than or equal to 780 nm. The light emitting device according to claim 8, comprising at least one phosphor. The first light emitter has a light emission peak in a wavelength range of 300 nm or more and 420 nm or less;
The second phosphor, as the second phosphor, has at least one phosphor having an emission peak in a wavelength range of 420 nm or more and 490 nm or less, and at least an emission peak in a wavelength range of more than 570 nm and 780 nm or less. The light emitting device according to claim 8, comprising one kind of phosphor. An illumination device comprising the light emitting device according to any one of claims 7 to 10. An image display device comprising the light emitting device according to claim 7.

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