JP2017210529A - Phosphor, production method thereof, light-emitting device, image display device, pigment, and, uv-absorber - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a phosphor that has a high emission intensity even when combined with an LED of 470 nm or shorter and is chemically and thermally stable.SOLUTION: A phosphor of the present invention includes an inorganic compound in which an M element (here, M represents one or more elements selected from Mn, Ce, Pr, Nd, Sm, Eu, Tb, Dy and Yb) is dissolved in a crystal represented by A(D,E)X(here, 0≤x<14) containing at least an A element, a D element, an E element and an X element (here, the A represents one or more elements selected from Mg, Ca, Sr and Ba, the D element represents one or more elements selected from Si, Ge, Sn, Ti, Zr and Hf, the E represents one or more elements selected from B, Al, Ga, In, Sc, Y and La, and the X represents one or more elements selected from O, N and F), an inorganic crystal having the same crystal structure as the crystal represented by A(D,E)X, or a solid solution crystal thereof.SELECTED DRAWING: Figure 1

Description

The present invention includes at least A element, D element, E element, and X element, A _{1 + x} (D, E) ₃₀ X ₄₀ (where 0 ≦ x <14, A is Mg, Ca, Sr, Ba) One or more elements selected, D is one or more elements selected from Si, Ge, Sn, Ti, Zr, and Hf, E is B, Al, Ga, In, Sc, 1 or 2 or more elements selected from Y and La, X is a crystal represented by 1 or 2 or more elements selected from O, N and F), A _{1 + x} (D, E) ₃₀ X ₄₀ An inorganic crystal having the same crystal structure as that shown by the above, or a solid solution crystal thereof, M element (where M is selected from Mn, Ce, Pr, Nd, Sm, Eu, Tb, Dy, Yb) A phosphor containing an inorganic compound in which a seed or two or more elements are dissolved, Manufacturing methods, and, for that purpose.

  The phosphor is a fluorescent display tube (VFD (Vacuum-Fluorescent Display)), a field emission display (FED (Field Emission Display)) or a SED (Surface-Condition Electron-Emitter Display (P panel)). ), Cathode ray tube (CRT (Cathode-Ray Tube)), liquid crystal display backlight (Liquid-Crystal Display Backlight), white light emitting diode (LED (Light-Emitting Diode)), and the like. In any of these applications, in order to make the phosphor emit light, it is necessary to supply the phosphor with energy for exciting the phosphor, and the phosphor is not limited to vacuum ultraviolet rays, ultraviolet rays, electron beams, blue light, etc. When excited by an excitation source having high energy, visible light such as blue light, green light, yellow light, orange light, and red light is emitted. However, as a result of exposure of the phosphor to the excitation source as described above, there is a demand for a phosphor that is liable to lower the luminance of the phosphor and has no luminance reduction. Therefore, instead of conventional phosphors such as silicate phosphors, phosphate phosphors, aluminate phosphors and sulfide phosphors, sialon phosphors can be used as phosphors with little reduction in luminance even when excited with high energy. There have been proposed phosphors based on inorganic crystals containing nitrogen in the crystal structure, such as oxynitride phosphors and nitride phosphors.

An example of this sialon phosphor is manufactured by a manufacturing process generally described below. First, silicon nitride (Si ₃ N ₄ ), aluminum nitride (AlN), and europium oxide (Eu ₂ O ₃ ) are mixed at a predetermined molar ratio, and the temperature is 1700 ° C. in nitrogen at 1 atm (0.1 MPa). It is manufactured by holding for 1 hour and firing by a hot press method (see, for example, Patent Document 1). It has been reported that α sialon activated by Eu ²⁺ ions obtained by this process becomes a phosphor that emits yellow light of 550 to 600 nm when excited by blue light of 450 to 500 nm. Further, it is known that the emission wavelength changes by changing the ratio of Si and Al and the ratio of oxygen and nitrogen while maintaining the crystal structure of α sialon (see, for example, Patent Document 2 and Patent Document 3). ).

As another example of the sialon phosphor, a green phosphor obtained by activating Eu ²⁺ to a β-type sialon is known (see Patent Document 4). In this phosphor, it is known that the emission wavelength changes to a short wavelength by changing the oxygen content while maintaining the crystal structure (see, for example, Patent Document 5). Further, it is known that when Ce ³⁺ is activated, a blue phosphor is obtained (for example, see Patent Document 6).

An example of an oxynitride phosphor, JEM phase _{(LaAl (Si 6-z Al} z) N 10-z O z) blue phosphor were activated with Ce as host crystals (see Patent Document 7) are known ing. In this phosphor, it is known that by exchanging a part of La with Ca while maintaining the crystal structure, the excitation wavelength becomes longer and the emission wavelength becomes longer.

As another example of the oxynitride phosphor, a blue phosphor in which Ce is activated using a La—N crystal La ₃ Si ₈ N ₁₁ O ₄ as a base crystal (see Patent Document 8) is known.

As an example of a nitride phosphor, a red phosphor in which Eu ²⁺ is activated using CaAlSiN ₃ as a base crystal (see Patent Document 9) is known. By using this phosphor, there is an effect of improving the color rendering properties of the white LED. A phosphor added with Ce as an optically active element has been reported as an orange phosphor.

  As described above, the emission color of the phosphor is determined by a combination of a crystal serving as a base and a metal ion (activated ion) to be dissolved therein. Furthermore, the combination of the base crystal and the activated ion determines the emission characteristics such as emission spectrum and excitation spectrum, chemical stability, and thermal stability, so when the base crystal is different or the activated ion is different, Considered as a different phosphor. In addition, even if the chemical composition is the same, materials having different crystal structures are regarded as different phosphors because their emission characteristics and stability differ due to different host crystals.

Furthermore, in many phosphors, it is possible to replace the type of constituent elements while maintaining the crystal structure of the host crystal, thereby changing the emission color. For example, a phosphor obtained by adding Ce to YAG emits green light, but a phosphor obtained by substituting a part of Y in the YAG crystal with Gd and a part of Al with Ga exhibits yellow light emission. Furthermore, it is known that in a phosphor obtained by adding Eu to CaAlSiN ₃ , the composition changes while maintaining a crystal structure by substituting part of Ca with Sr, and the emission wavelength is shortened. In this way, the phosphors that have undergone element substitution while maintaining the crystal structure are regarded as the same group of materials.

  For these reasons, in the development of new phosphors, it is important to find a host crystal having a new crystal structure, and activate the metal ions responsible for light emission in such a host crystal to express fluorescence characteristics. Thus, a novel phosphor can be proposed.

Japanese Patent No. 3668770 Japanese Patent No. 3837551 Japanese Patent No. 4524368 Japanese Patent No. 3921545 International Publication No. 2007/066673 International Publication No. 2006/101096 International Publication No. 2005/019376 JP 2005-112922 A Japanese Patent No. 3837588

  The present invention is intended to meet such a demand, and one of the objects is an LED having emission characteristics (emission color, excitation characteristics, emission spectrum) different from those of conventional phosphors and having a wavelength of 470 nm or less. It is an object to provide an inorganic phosphor having high emission intensity even when combined with the above and chemically and thermally stable. Another object of the present invention is to provide a light emitting device with excellent durability and an image display device with excellent durability using such a phosphor. A further object of the present invention is to provide a pigment and an ultraviolet absorber using such a phosphor.

Under these circumstances, the present inventors have conducted detailed research on a new crystal containing nitrogen and a phosphor based on a crystal obtained by substituting a metal element or N in the crystal structure with another element. A _{1 + x} (D, E) ₃₀ X ₄₀ (where 0 ≦ x <14), A _{1 + x} (D, E) ₃₀ X ₄₀ , including A element, D element, E element, and X element It has been found that inorganic crystals having the same crystal structure as the crystals shown, or inorganic compounds in which luminescent ions are dissolved in inorganic crystals based on these solid solution crystals, become new phosphors and emit high-intensity fluorescence. It was. Further, it has been found that by controlling the composition, yellow to red, particularly, a specific composition exhibits yellow light emission.

  Furthermore, by using this phosphor, it is possible to obtain a white light emitting diode (light emitting device) having high luminous efficiency and small temperature fluctuation, a lighting fixture using the same, or a vivid color image display device. I found.

  As a result of intensive studies in view of the above circumstances, the present inventor has succeeded in providing a phosphor exhibiting a high luminance light emission phenomenon in a specific wavelength region by adopting the configuration described below. Moreover, it succeeded in manufacturing the fluorescent substance with the outstanding luminescent property using the following method. Furthermore, by using this phosphor, it has succeeded in providing a light emitting device, a lighting apparatus, an image display device, a pigment, and an ultraviolet absorber having excellent characteristics by adopting the configuration described below. The configuration is as described below.

The phosphor of the present invention includes at least an A element, a D element, an E element, and an X element (where A is one or more elements selected from Mg, Ca, Sr, and Ba, and D is Si, Ge. , Sn, Ti, Zr, Hf, one or more elements selected from E, E is one, two or more elements selected from B, Al, Ga, In, Sc, Y, La, X is A _{1 + x} (D, E) ₃₀ X ₄₀ (where 0 ≦ x <14), A _{1 + x} (D , E) An inorganic crystal having the same crystal structure as the crystal represented by ₃₀ X ₄₀ , or a solid solution crystal thereof, M element (where M is Mn, Ce, Pr, Nd, Sm, Eu, Tb, Dy) , One or more elements selected from Yb) It includes things, thereby solving the above problems.
The element A includes at least one element selected from the group consisting of Mg, Ca, Sr, and Ba, the element D includes Si, the element E includes Al, and the element X includes N And the X element may contain O if necessary.
Inorganic crystals having the same crystal structure as the crystal represented by A _{1 + x} (D, E) ₃₀ X ₄₀ are Mg _{1 + x} (Si, Al) ₃₀ N ₄₀ , Ca _{1 + x} (Si, Al) ₃₀ N ₄₀ , Sr _{1 + x.} (Si, Al) ₃₀ N ₄₀ , Ba _{1 + x} (Si, Al) ₃₀ N ₄₀ , Mg _{1 + x} (Si, Al) ₃₀ (O, N) ₄₀ , Ca _{1 + x} (Si, Al) ₃₀ (O, N) ₄₀ , Sr _{1 + x} (Si, Al) ₃₀ (O, N) ₄₀ , Ba _{1 + x} (Si, Al) ₃₀ (O, N) ₄₀ , (Mg, Ca) _{1 + x} (Si, Al) ₃₀ N ₄₀ , (Mg, Sr) _{1 + x} (Si, Al) ₃₀ N ₄₀ , (Mg, Ba) _{1 + x} (Si, Al) ₃₀ N ₄₀ , (Ca, Sr) _{1 + x} (Si, Al) ₃₀ N ₄₀ , (Ca, Ba) _{1 + x} (Si, Al) ₃₀ N ₄₀ , (Sr, Ba) _{1 + x} (Si, Al) ₃₀ N ₄₀ , (Mg, Ca) _{1 + x} (Si, Al) ₃₀ (O, N) ₄₀ , (Mg, Sr) _{1 + x} (Si, Al ) ₃₀ (O, N) ₄₀ , (Mg, Ba) _{1 + x} (Si, Al) ₃₀ (O, N) ₄₀ , (Ca, Sr) _{1 + x} (Si, Al) ₃₀ (O, N) ₄₀ , (Ca, It may be Ba) _{1 + x} (Si, Al) ₃₀ (O, N) ₄₀ or (Sr, Ba) _{1 + x} (Si, Al) ₃₀ (O, N) ₄₀ .
Inorganic crystals having the same crystal structure as the crystal represented by A _{1 + x} (D, E) ₃₀ X ₄₀ are Mg _{1 + x} Si _28-2x-z Al _{2 + 2x + z} O _z N _40-z , Ca _{1 + x} Si _{28-2x- z Al 2 + 2x + z O} z N 40-z, Sr 1 + x Si 28-2x-z Al 2 + 2x + z O z N 40-z, Ba 1 + x Si 28-2x-z Al 2 + 2x + z O z N 40-z, (Mg, Ca) 1 + x Si _28-2x-z Al _{2 + 2x + z} O _z N _40-z , (Mg, Sr) _{1 + x} Si _28-2x-z Al _{2 + 2x + z} O _z N _40-z , (Mg, Ba) _{1 + x} Si _28-2x-z Al _{2 + 2x + z O z N 40-z, (} Ca, Sr) 1 + x Si 28-2x-z Al 2 + 2x + z O z N 40-z, (Ca, Ba) _{1 + x} Si _28-2x-z Al _{2 + 2x + z} O _z N _40-z or (Sr, Ba) _{1 + x} Si _28-2x-z Al _{2 + 2x + z} O _z N _40-z (where 0 ≦ x <14, It may be represented by a composition formula of 0 ≦ z ≦ 20).
The M element may be Eu.
Wherein _{A 1 + x (D, E} ) 30 X 40 crystal represented by the _{A 1 + x (D, E} ) 30 inorganic crystals having the same crystal structure as the crystal represented by _{X 40,} or the solid solution crystals, hexagonal It may be a system crystal.
Wherein _{A 1 + x (D, E} ) crystal represented by 30 _{X 40,} wherein _{A 1 + x (D, E} ) inorganic crystals having the same crystal structure as the crystal represented by 30 _{X 40,} or the solid solution crystals, hexagonal A crystal of the system, with symmetry of the space group P-6,
Lattice constants a, b, c are
a = 0.79395 ± 0.05 nm
b = 0.79395 ± 0.05 nm
c = 1.43822 ± 0.05 nm
It may be a value in the range.
The inorganic compound has a composition formula M _d A _e D _f E _g X _h (where d + e + f + g + h = 1, and M is selected from Mn, Ce, Pr, Nd, Sm, Eu, Tb, Dy, Yb) One or more elements selected, A is one or more elements selected from Mg, Ca, Sr, Ba, D is selected from Si, Ge, Sn, Ti, Zr, Hf 1 Species or two or more elements, E is one or more elements selected from B, Al, Ga, In, Sc, Y, and La, X is one or more elements selected from O, N, and F Parameters d, e, f, g, h are
0.00001 ≤ d ≤ 0.3
0.01 ≤ e ≤ 0.3
0.05 ≤ f ≤ 0.5
0.01 ≦ g ≦ 0.4
0.2 ≦ h ≦ 0.7
All of the conditions may be satisfied.
The parameters d, e, f, g, h are
d + e = ((1 + x) / (71 + x)) ± 0.05
f + g = (30 / (71 + x)) ± 0.05
h = (40 / (71 + x)) ± 0.05
(However, 0 ≤ x <14)
All of the conditions may be satisfied.
The parameters f and g are
8/30 ≦ f / (f + g) ≦ 28/30
This condition may be satisfied.
The element X includes O and N, and the inorganic compound is represented by a composition formula M _d A _e D _f E _g O _h1 N _h2 (where d + e + f + g + h1 + h2 = 1 and h1 + h2 = h) ,
0/40 ≦ h1 / (h1 + h2) ≦ 20/40
This condition may be satisfied.
The M element may contain at least Eu.
The element A may include at least Sr, the element D may include at least Si, the element E may include at least Al, and the element X may include at least N.
The composition formula of the inorganic compound is Eu _y Mg _{1 + xy} Si _28-2x-z Al _{2 + 2x + z} O _z N _40-z , Eu _y Ca _{1 + xy} Si _28-2x-z using parameters x, y and _z. Al _{2 + 2x + z} O _z N _40-z , Eu _y Sr _{1 + xy} Si _28-2x-z Al _{2 + 2x + z} O _z N _40-z , Eu _y Ba _{1 + xy} Si _28-2x-z Al _{2 + 2x + z} O _z N _40-z Eu _y (Mg, Ca) _{1 + xy} Si _28-2x-z Al _{2 + 2x + z} O _z N _40-z Eu _y (Mg, Sr) _{1 + xy} Si _28-2x-z Al _{2 + 2x + z} O _z N _40-z , Eu _y (Mg, Ba) _{1 + xy} Si _28-2x-z Al _{2 + 2x + z} O _z N _40-z , Eu _y (Ca, Sr) _{1 + xy} Si _28-2x-z Al _{2 + 2x + z} O _z N _40-z , Eu _y (Ca, Ba) _{1 + x-y} Si _28-2x-z Al _{2 + 2x + z} O _z N _40-z , or Eu _y (Sr, Ba) _{1 + x -y Si 28-2x-z Al 2 +} 2x + z O z N 40-z,
However,
0 ≦ x <14
0.0001 ≤ y ≤ 2
0 ≤ z ≤ 20
May be indicated.
The inorganic compound may be a single crystal particle having an average particle size of 0.1 μm or more and 20 μm or less, or a single crystal aggregate.
The total of Fe, Co and Ni impurity elements contained in the inorganic compound may be 500 ppm or less.
In addition to the inorganic compound, it may further include another crystal phase or an amorphous phase different from the inorganic compound, and the content of the inorganic compound may be 20% by mass or more.
The other crystalline phase or amorphous phase may be an inorganic substance having conductivity.
The conductive inorganic substance may be an oxide, oxynitride, nitride, or a mixture thereof containing one or more elements selected from Zn, Al, Ga, In, and Sn. .
The other crystal phase or amorphous phase may be an inorganic phosphor different from the inorganic compound.
Fluorescence having a peak at a wavelength in the range of 500 nm to 650 nm may be emitted by irradiating the excitation source.
The excitation source may be vacuum ultraviolet ray, ultraviolet ray, visible light, electron beam or X-ray having a wavelength of 100 nm to 500 nm.
Wherein _{A 1 + x (D, E} ) 30 X 40 crystal represented by the _{A 1 + x (D, E} ) 30 inorganic crystals having the same crystal structure as the crystal represented by _{X 40,} or, Eu is solid to the solid solution crystals When dissolved and irradiated with light of 300 nm to 500 nm, yellow to red fluorescence having a peak in a wavelength range of 550 nm to 650 nm may be emitted.
The color emitted when the excitation source is irradiated is the value of (x, y) on the CIE 1931 chromaticity coordinates,
0.2 ≤ x ≤ 0.7
0.2 ≤ y ≤ 0.8
This condition may be satisfied.
In the method for producing a phosphor of the present invention, a mixture of metal compounds that can constitute the above-described inorganic compound by firing is fired in a temperature range of 1200 ° C. or more and 2200 ° C. or less in an inert atmosphere containing nitrogen. This solves the above problem.
The light-emitting device of the present invention includes at least a light-emitting body or a light-emitting light source and a phosphor, and the phosphor includes at least the above-described phosphor, thereby solving the above-described problem.
The light emitting body or light emitting light source may be a light emitting diode (LED), a laser diode (LD), a semiconductor laser, or an organic EL light emitting body (OLED) that emits light having a wavelength of 330 to 500 nm.
The light emitting device may be a white light emitting diode, a lighting fixture including a plurality of the white light emitting diodes, or a backlight for a liquid crystal panel.
The light emitting body or light emitting light source emits ultraviolet or visible light having a peak wavelength of 300 to 500 nm, and mixes yellow light emitted from the above-described phosphor with light having a wavelength of 500 nm or more emitted from another phosphor. Alternatively, light other than white light may be emitted.
The phosphor may further include a blue phosphor that emits light having a peak wavelength of 420 nm to 500 nm or less from the light emitter or the light source.
The blue phosphor is selected from AlN: (Eu, Si), BaMgAl ₁₀ O ₁₇ : Eu, SrSi ₉ Al ₁₉ ON ₃₁ : Eu, LaSi ₉ Al ₁₉ N ₃₂ : Eu, α-sialon: Ce, JEM: Ce May be.
The phosphor may further include a green phosphor that emits light having a peak wavelength of 500 nm or more and 550 nm or less by the light emitter or the light source.
The green phosphor may be selected from β-sialon: Eu, (Ba, Sr, Ca, Mg) ₂ SiO ₄ : Eu, (Ca, Sr, Ba) Si ₂ O ₂ N ₂ : Eu.
The phosphor may further include a yellow phosphor that emits light having a peak wavelength of 550 nm or more and 600 nm or less by the light emitter or the light source.
The yellow phosphor may be selected from YAG: Ce, α-sialon: Eu, CaAlSiN ₃ : Ce, and La ₃ Si ₆ N ₁₁ : Ce.
The phosphor may further include a red phosphor that emits light having a peak wavelength of 600 nm or more and 700 nm or less by the light emitter or the light source.
The red phosphor may be selected from CaAlSiN ₃ : Eu, (Ca, Sr) AlSiN ₃ : Eu, Ca ₂ Si ₅ N ₈ : Eu, and Sr ₂ Si ₅ N ₈ : Eu.
The light emitting body or the light emitting light source may be an LED that emits light having a wavelength of 280 to 500 nm.
The image display apparatus of the present invention includes at least an excitation source and a phosphor, and the phosphor includes at least the above-described phosphor, thereby solving the above-described problem.
The image display device may be any one of a fluorescent display tube (VFD), a field emission display (FED), a plasma display panel (PDP), a cathode ray tube (CRT), or a liquid crystal display (LCD).
The pigment of the present invention comprises the above-described inorganic compound, thereby solving the above-mentioned problems.
The ultraviolet absorber of the present invention comprises the above-described inorganic compound, thereby solving the above-described problems.

The phosphor of the present invention is a multi-element nitride or multi-element oxynitride containing a divalent element, a trivalent element, and a tetravalent element, and a crystal represented by A _{1 + x} (D, E) ₃₀ X ₄₀ , A By containing an inorganic crystal having the same crystal structure as the crystal represented by _{1 + x} (D, E) ₃₀ X ₄₀ or a solid solution crystal thereof as a base crystal, a conventional oxide phosphor or oxynitride By emitting light with higher luminance than phosphors and controlling the composition, it is excellent as a yellow phosphor from yellow to red, and in particular, a specific composition. Even when exposed to an excitation source, this phosphor does not decrease in luminance, so it is suitably used for light emitting devices such as white light emitting diodes, lighting fixtures, backlight sources for liquid crystals, VFD, FED, PDP, CRT, etc. The present invention provides a useful phosphor. Moreover, since this fluorescent substance absorbs an ultraviolet-ray, it is suitable for a pigment and a ultraviolet absorber.

_{A 1 + x (D, E} ) 30 X 40 [Sr 3 (Si, Al) 30 N 40] shows a crystal structure of the crystal. _{A 1 + x (D, E} ) 30 X 40 [Sr 3 (Si, Al) 30 N 40] shows a powder X-ray diffraction using a CuKα ray calculated from the crystal structure of the crystal. The figure which shows the powder X-ray-diffraction result of the compound synthesize | combined in Example 5. FIG. FIG. 6 shows an excitation spectrum and an emission spectrum of a synthesized product synthesized in Example 5. Schematic which shows the lighting fixture (bullet type LED lighting fixture) by this invention. Schematic which shows the lighting fixture (board-mounting type LED lighting fixture) by this invention. Schematic which shows the image display apparatus (plasma display panel) by this invention. Schematic which shows the image display apparatus (field emission display panel) by this invention.

Hereinafter, the phosphor of the present invention will be described in detail with reference to the drawings.
The phosphor of the present invention includes at least an A element, a D element, an E element, and an X element (where A is one or more elements selected from Mg, Ca, Sr, and Ba, and D is Si, Ge. , Sn, Ti, Zr, Hf, one or more elements selected from E, E is one, two or more elements selected from B, Al, Ga, In, Sc, Y, La, X is 1 or 2 or more elements selected from O, N, and F), and a crystal represented by A _{1 + x} (D, E) ₃₀ X ₄₀ (where 0 ≦ x <14), and the same crystal An inorganic crystal having a structure, or an inorganic crystal that is a solid solution thereof, and M element (where M is one or more selected from Mn, Ce, Pr, Nd, Sm, Eu, Tb, Dy, and Yb) By containing an inorganic compound as a main component. It shows high brightness. Note that in this specification, an inorganic crystal having the same crystal structure as a crystal represented by A _{1 + x} (D, E) ₃₀ X ₄₀ , a crystal represented by A _{1 + x} (D, E) ₃₀ X ₄₀ , or a For the sake of simplicity, solid solution crystals of crystals may be collectively referred to as A _{1 + x} (D, E) ₃₀ X ₄₀ series crystals.

_{A 1 + x (D, E} ) for simplicity of the 30 _{X 40} crystal represented by (hereinafter _referred to as A 1 + x _(D, a crystal represented by _{E) 30 X 40 A 1 +} x (D, E) and 30 _{X 40} crystals. ) Is a crystal that has not been reported before the present invention, which was newly synthesized by the present inventor and confirmed to be a new crystal by crystal structure analysis.

FIG. 1 is a diagram showing a crystal structure of Sr ₃ (Si, Al) ₃₀ N ₄₀ crystal.

The Sr ₃ Si ₂₄ Al ₆ N ₄₀ crystal synthesized by the present inventor is _one of A _{1 + x} (D, E) ₃₀ X ₄₀ crystals and is represented as Sr ₃ (Si, Al) ₃₀ N ₄₀ . According to the single crystal structure analysis performed on the Sr ₃ (Si, Al) ₃₀ N ₄₀ crystal (corresponding to the case of x = 2 in the above composition formula), the Sr ₃ (Si, Al) ₃₀ N ₄₀ crystal is hexagonal. It belongs to the crystal system, belongs to the P-6 space group (the 174th space group of International Tables for Crystallography), and occupies the crystal parameters and atomic coordinate positions shown in Table 1.

  In Table 1, lattice constants a, b, and c indicate the lengths of the unit cell axes, and α, β, and γ indicate the angles between the unit cell axes. The atomic coordinates indicate the position of each atom in the unit cell as a value between 0 and 1 with the unit cell as a unit. In this crystal, each atom of Sr, Si, Al, and N exists, and Sr exists in three types of seats (Sr (1), Sr (2), and Sr (3)). Si and Al are the same seven types of seats (Si, Al (1), Si, Al (2), Si, Al (3a), Si, Al (3b), Si, Al (4), Si, Al (5), Si, Al (6)). Further, N exists in 12 types of the same seat (N (1) to N (12)).

As a result of analysis using the data in Table 1, the structure of the Sr ₃ (Si, Al) ₃₀ N ₄₀ crystal is the structure shown in FIG. 1, and a tetrahedron composed of a combination of Si or Al and N is connected. It was found that the skeleton had a structure containing Sr element. In this crystal, the M element that becomes an activating ion such as Eu is incorporated into the crystal in a form that replaces a part of the Sr element.

As crystals having the same crystal structure as the synthesized and structurally analyzed Sr ₃ (Si, Al) ₃₀ N ₄₀ crystal, A _{1 + x} (D, E) ₃₀ X ₄₀ crystal and A _{1 + x} (Si, Al) ₃₀ (O, N ₄₀ crystals may be included. Typical A elements are Sr, Ca, Ba, Mg, Sr and Ca mixed, Sr and Ba mixed, Sr and Mg mixed, Ca and Ba mixed, Ca and Mg mixed, or Ba and Mg mixed. It may be a mixture. Alternatively, the element A may be a mixture of any three of these or all of them.

In the A _{1 + x} (D, E) ₃₀ X ₄₀ crystal, in the Sr ₃ (Si, Al) ₃₀ N ₄₀ crystal, the A element is in the seat where Sr enters, and the D element and the E element are in the seat where Si and Al enter. And X element can enter the seat where N enters. Thus, while maintaining the crystal structure, the ratio of the number of atoms in which the A element is 1 + x (where 0 ≦ x <14), the D element and the E element are 30 in total, and the X element is 40 in total. can do. However, it is desirable that the ratio of the cation of the A element, the D element, and the E element to the anion of the X element satisfies the condition that the electrical neutrality in the crystal is maintained.

In the A _{1 + x} (Si, Al) ₃₀ (O, N) ₄₀ crystal, in the Sr ₃ (Si, Al) ₃₀ N ₄₀ crystal, the A element is in the seat where Sr enters, and the Si in the seat where Si and Al enter. O and N can enter the seat where N enters and N enters. Thus, while maintaining the crystal structure, the ratio of the number of atoms in which the element A is 1 + x (where 0 ≦ x <14) is 30 in total for Si and Al and 40 for O and N in total. can do. However, it is desirable that the Si / Al ratio and the O / N ratio satisfy the conditions for maintaining electrical neutrality in the crystal.

The A _{1 + x} (D, E) ₃₀ X _40- based crystal of the present invention can be identified by X-ray diffraction or neutron diffraction. As a substance showing the same diffraction as the X-ray diffraction result of the Sr ₃ (Si, Al) ₃₀ N ₄₀ crystal shown in the present invention, for example, there is a crystal represented by A _{1 + x} (D, E) ₃₀ X ₄₀ . Further, in the Sr ₃ (Si, Al) ₃₀ N ₄₀ crystal, there is a crystal in which the lattice constant or the atomic position is changed by replacing the constituent element with another element. Here, the constituent element is replaced by another element, for example, a part or all of Sr in Sr ₃ (Si, Al) ₃₀ N ₄₀ crystal is replaced with an A element other than Sr (where A is Mg , Ca, Sr, Ba or one or more elements selected from M) (where M is one selected from Mn, Ce, Pr, Nd, Sm, Eu, Tb, Dy, Yb or There are those substituted with two or more elements. Further, a part or all of Si in the crystal was replaced with a D element other than Si (where D is one or more elements selected from Si, Ge, Sn, Ti, Zr, and Hf). There is something. Furthermore, a part or all of Al in the crystal is replaced with E element other than Al (where E is one or more elements selected from B, Al, Ga, In, Sc, Y, La). There is a replacement. Further, there are those in which part or all of N in the crystal is substituted with O or F. These substitutions are made so that the overall charge in the crystal is neutral. Those whose crystal structure does not change as a result of these element substitutions are A _{1 + x} (D, E) ₃₀ X _40- based crystals. Substitution of the element changes the light emission characteristics, chemical stability, and thermal stability of the phosphor. Therefore, it is preferable to select the phosphor in a timely manner according to the application within the range in which the crystal structure is maintained.

The lattice constant of A _{1 + x} (D, E) ₃₀ X _40- based crystals changes when the constituent components are replaced with other elements, or when an activating element such as Eu is dissolved, but the crystal structure and atoms are The occupied site and the atomic position given by the coordinates do not change so much that the chemical bond between the skeletal atoms is broken. In the present invention, the length of chemical bonds of Al—N and Si—N calculated from the lattice constant and atomic coordinates obtained by Rietveld analysis of the X-ray diffraction or neutron diffraction results in the P-6 space group. Same (distance between adjacent atoms) is within ± 5% of the chemical bond length calculated from the lattice constant and atomic coordinates of the Sr ₃ (Si, Al) ₃₀ N ₄₀ crystal shown in Table 1. It is determined that the crystal structure is A _{1 + x} (D, E) ₃₀ X _40- based crystal. This is because, in the A _{1 + x} (D, E) ₃₀ X ₄₀ series crystal, it was confirmed that when the length of the chemical bond changes beyond ± 5%, the chemical bond is broken and another crystal is formed.

Furthermore, when the solid solution amount is small, there is the following method as a simple determination method for the A _{1 + x} (D, E) ₃₀ X _40- based crystal. The crystal structure is the same when the lattice constant calculated from the X-ray diffraction results measured for the new substance and the diffraction peak position (2θ) calculated using the crystal structure data in Table 1 match for the main peak. Can be identified.

FIG. 2 is a diagram showing powder X-ray diffraction using CuKα rays calculated from the crystal structure of Sr ₃ (Si, Al) ₃₀ N ₄₀ crystal.

By comparing FIG. 2 with a substance to be compared, it is possible to easily determine whether the crystal is an A _{1 + x} (D, E) ₃₀ X _40- based crystal. The main peak of the A _{1 + x} (D, E) ₃₀ X _40- based crystal may be determined by about 10 having strong diffraction intensity. Table 1 is important because it serves as a reference in specifying A _{1 + x} (D, E) ₃₀ X _40- based crystals. An approximate structure can also be defined by using another hexagonal crystal system as the crystal structure of the A _{1 + x} (D, E) ₃₀ X _40- based crystal. In that case, the representation is made using different space groups, lattice constants, and plane indices, but the X-ray diffraction results (for example, FIG. 2) and the crystal structure (for example, FIG. 1) are not changed. The result is the same. For this reason, in the present invention, X-ray diffraction analysis is performed as a hexagonal system. The substance identification method based on Table 1 will be specifically described in the examples described later, and is only a brief description here.

In the A _{1 + x} (D, E) ₃₀ X _40- based crystal, one or more selected from Mn, Ce, Pr, Nd, Sm, Eu, Tb, Dy, Ho, Er, Tm, and Yb as the M element When the element is activated, a phosphor is obtained. Since emission characteristics such as excitation wavelength, emission wavelength, and emission intensity vary depending on the composition of the A _{1 + x} (D, E) ₃₀ X _40- based crystal and the type and amount of the activating element, it may be selected according to the application.

In the crystal represented by A _{1 + x} (D, E) ₃₀ X ₄₀ , the A element includes at least one element selected from the group consisting of Mg, Ca, Sr, and Ba, the D element includes Si, and the E element includes A composition containing Al, containing N in the X element, and optionally containing O has high emission intensity.

An inorganic crystal having the same crystal structure as the crystal represented by A _{1 + x} (D, E) ₃₀ X ₄₀ is
Mg _{1 + x} (Si, Al) ₃₀ N ₄₀ , Ca _{1 + x} (Si, Al) ₃₀ N ₄₀ , Sr _{1 + x} (Si, Al) ₃₀ N ₄₀ , Ba _{1 + x} (Si, Al) ₃₀ N ₄₀ , Mg _{1 + x} (Si, Al ) ₃₀ (O, N) ₄₀ , Ca _{1 + x} (Si, Al) ₃₀ (O, N) ₄₀ , Sr _{1 + x} (Si, Al) ₃₀ (O, N) ₄₀ , Ba _{1 + x} (Si, Al) ₃₀ (O, N) ₄₀ , (Mg, Ca) _{1 + x} (Si, Al) ₃₀ N ₄₀ , (Mg, Sr) _{1 + x} (Si, Al) ₃₀ N ₄₀ , (Mg, Ba) _{1 + x} (Si, Al) ₃₀ N ₄₀ , ( Ca, Sr) _{1 + x} (Si, Al) ₃₀ N ₄₀ , (Ca, Ba) _{1 + x} (Si, Al) ₃₀ N ₄₀ , (Sr, Ba) _{1 + x} (Si, Al) ₃₀ N ₄₀ , (Mg, Ca) _{1 + x} (Si, Al) ₃₀ (O, N) ₄₀ , (Mg, Sr) _{1 + x} (Si, Al) ₃₀ (O, N) ₄₀ , (Mg, Ba) _{1 + x} (Si, Al) ₃₀ (O, N) ₄₀ , (Ca, Sr) _{1 + x} (Si, Al) ₃₀ (O, N) ₄₀ , (Ca, Ba) _{1 + x} (Si, Al) ₃₀ (O, N) ₄₀ , or (Sr, Ba) _{1 + x} (Si , Al) ₃₀ (O, N) ₄₀ has a stable crystal and high emission intensity.

An inorganic crystal having the same crystal structure as the crystal represented by A _{1 + x} (D, E) ₃₀ X ₄₀ is
Mg _{1 + x} Si _28-2x-z Al _{2 + 2x + z} O _z N _40-z , Ca _{1 + x} Si _28-2x-z Al _{2 + 2x + z} O _z N _40-z , Sr _{1 + x} Si _28-2x-z Al _{2 + 2x + z} O _z N _40-z , Ba _{1 + x} Si _28-2x-z Al _{2 + 2x + z} O _z N _40-z , (Mg, Ca) _{1 + x} Si _28-2x-z Al _{2 + 2x + z} O _z N _40-z , (Mg, Sr) _{1 + x} Si _{28-2x- z Al 2 + 2x + z O} z N 40-z, (Mg, Ba) 1 + x Si 28-2x-z Al 2 + 2x + z O z N 40-z, (Ca, Sr) 1 + x Si 28-2x-z Al 2 + 2x + z O z N 40- _{z, (Ca, Ba) 1} + x Si 28-2x-z Al 2 + 2x + z O z N 40-z, or, (Sr, _{a) 1 + x Si 28-2x-} z Al 2 + 2x + z O z N 40-z, ( provided that phosphor crystals and host crystals represented by 0 ≦ x <compositional formula of 14,0 ≦ z ≦ 20), the light emitting It is a phosphor that has high intensity and can control the change in color tone by changing the composition.

  Preferably, the crystal in which the value of x is 0 ≦ x ≦ 6 has high emission intensity. More preferably, the crystal in which the value of x is 0 ≦ x ≦ 3 has a stable crystal structure and particularly high emission intensity. Preferably, the crystal in which the value of x is 1.6 ≦ x ≦ 2.5 has a stable crystal structure and higher emission intensity.

  The phosphor with the activation element M being Eu has particularly high emission intensity.

_{A 1 + x (D, E} ) crystal represented by 30 _{X 40,} inorganic crystals having _{A 1 + x (D, E} ) the same crystal structure and crystal represented by 30 _{X 40,} or, these solid solution crystal, hexagonal Are particularly stable, and phosphors using these as host crystals have high emission intensity.

_{Furthermore, A 1 + x (D, E} ) crystal represented by 30 _{X 40,} inorganic crystals having _{A 1 + x (D, E} ) the same crystal structure and crystal represented by 30 _{X 40,} or, these solid solution crystal, hexagonal A crystal of the crystal system, having symmetry of the space group P-6,
Lattice constants a, b, c are
a = 0.79395 ± 0.05 nm
b = 0.79395 ± 0.05 nm
c = 1.43822 ± 0.05 nm
Crystals that are in this range are particularly stable, and phosphors using these as host crystals have high emission intensity. Outside this range, the crystal becomes unstable and the light emission intensity may decrease.

Such an inorganic compound has a composition formula M _d A _e D _f E _g X _h (where d + e + f + g + h = 1, and M is Mn, Ce, Pr, Nd, Sm, Eu, Tb, Dy, Yb One or two or more elements selected from: A is one or more elements selected from Mg, Ca, Sr, Ba; D is selected from Si, Ge, Sn, Ti, Zr, Hf 1 or 2 or more elements, E is one or more elements selected from B, Al, Ga, In, Sc, Y, La, X is 1 selected from O, N, and F Species or two or more elements) and the parameters d, e, f, g, h are
0.00001 ≤ d ≤ 0.3
0.01 ≤ e ≤ 0.3
0.05 ≤ f ≤ 0.5
0.01 ≦ g ≦ 0.4
0.2 ≦ h ≦ 0.7
A phosphor expressed by a composition in a range that satisfies all of the above conditions has particularly high emission intensity.

  The parameter d is the addition amount of the activation element M, and if it is less than 0.00001, the amount of luminescent ions is insufficient and the luminance is lowered. If it exceeds 0.3, the emission intensity may decrease due to concentration quenching due to the interaction between the luminescent ions. The parameter e is a parameter representing the composition of an A element such as Ca. When the parameter e is less than 0.01 or higher than 0.3, the crystal structure becomes unstable and the emission intensity decreases. The parameter f is a parameter representing the composition of the D element such as Si, and if it is less than 0.05 or higher than 0.5, the crystal structure becomes unstable and the emission intensity decreases. The parameter g is a parameter representing the composition of the E element such as Al, and if it is less than 0.01 or higher than 0.4, the crystal structure becomes unstable and the light emission intensity decreases. The parameter h is a parameter representing the composition of the X element such as O, N, F, etc. If it is less than 0.2 or higher than 0.7, the crystal structure becomes unstable and the emission intensity decreases. The X element is an anion, and the composition of the O, N, and F ratio is determined so that the cation of the A, M, D, and E elements and the neutral charge are maintained.

Preferably, the parameters d, e, f, g, h are
0.00001 ≤ d ≤ 0.3
0.012 ≦ e ≦ 0.17
0.05 ≤ f ≤ 0.4
0.028 ≦ g ≦ 0.36
0.48 ≤ h ≤ 0.57
A crystal having a value in a range that satisfies all of the above conditions has a stable crystal structure and high emission intensity.

More preferably, the parameters d, e, f, g, h are
0.0001 ≦ d ≦ 0.015
0.012 ≦ e ≦ 0.1
0.18 ≦ f ≦ 0.4
0.028 ≤ g ≤ 0.22
0.51 ≤ h ≤ 0.57
A crystal having a value in a range that satisfies all of the above conditions has a stable crystal structure and particularly high emission intensity.

Preferably, the parameters d, e, f, g, h are
0.0005 ≤ d ≤ 0.007
0.03 ≤ e ≤ 0.05
0.31 ≦ f ≦ 0.35
0.06 ≦ g ≦ 0.1
0.542 ≤ h ≤ 0.553
A crystal having a value in a range that satisfies all of the above conditions has a stable crystal structure and a high emission intensity.

Preferably, the parameters d, e, f, g, h are
0.0001 ≦ d ≦ 0.007
0.01 ≦ e ≦ 0.06
0.25 ≤ f ≤ 0.4
0.02 ≦ g ≦ 0.12
0.54 ≤ h ≤ 0.57
A crystal having a value in a range that satisfies all of the above conditions can emit yellow light having a peak in a wavelength range of 550 nm to 600 nm.

Furthermore, the parameters d, e, f, g, h are
d + e = ((1 + x) / (71 + x)) ± 0.05
f + g = (30 / (71 + x)) ± 0.05
h = (40 / (71 + x)) ± 0.05
(However, 0 ≤ x <14)
A crystal having a value in a range that satisfies all of the above conditions has a stable crystal structure and particularly high emission intensity. Above all,
d + e = (1 + x) / (71 + x)
f + g = 30 / (71 + x)
h = 40 / (71 + x)
A crystal having a value satisfying all of the above conditions, that is, a crystal having a composition of (M, A) _{1 + x} (D, E) ₃₀ X ₄₀ (where 0 ≦ x <14) has a particularly stable crystal structure and particularly emits light. High strength.

Furthermore, parameters f and g are
8/30 ≦ f / (f + g) ≦ 28/30
A composition satisfying the above condition has a stable crystal structure and high emission intensity.

Such an inorganic compound in which the X element includes N and O is represented by the composition formula M _d A _e D _f E _g O _h1 N _h2 (where d + e + f + g + h1 + h2 = 1 and h1 + h2 = h) ,
0/40 ≦ h1 / (h1 + h2) ≦ 20/40
A composition satisfying the above condition has a stable crystal structure and high emission intensity.

Preferably,
0/40 ≦ h1 / (h1 + h2) ≦ 10/40
The composition satisfying the above condition has a stable crystal structure and particularly high emission intensity.

  In the above compositional formula, the phosphor containing at least Eu as the M element as the activator is a phosphor having a high emission intensity in the present invention. By controlling the composition, the phosphor is selected from yellow to red. In composition, a yellow phosphor is obtained.

  In the above composition formula, the element A includes at least Sr, the element D includes at least Si, the element E includes at least Al, and the element X includes at least N, and the crystal structure is stable. Is expensive.

The composition formula of such an inorganic compound uses the parameters x, y, and z,
Eu _y Mg _{1 + xy} Si _28-2x-z Al _{2 + 2x + z} O _z N _40-z , Eu _y Ca _{1 + xy} Si _28-2x-z Al _{2 + 2x + z} O _z N _40-z , Eu _y Sr _{1 + xy} Si _{28 -2x-z Al 2 + 2x +} z O z N 40-z, Eu y Ba 1 + x-y Si 28-2x-z Al 2 + 2x + z O z N 40-z, Eu y (Mg, Ca) 1 + x-y Si 28-2x-z Al _{2 + 2x + z} O _z N _40-z , Eu _y (Mg, Sr) _{1 + xy} Si _28-2x-z Al _{2 + 2x + z} O _z N _40-z , Eu _y (Mg, Ba) _{1 + xy} Si _{28-2x-z Al 2 + 2x + z O z} N 40-z, Eu y (Ca, Sr) 1 + x-y Si 28-2x-z Al 2 + 2x + z O z N 40-z, E _{y (Ca, Ba) 1 +} x-y Si 28-2x-z Al 2 + 2x + z O z N 40-z, Eu y (Sr, Ba) 1 + x-y Si 28-2x-z Al 2 + 2x + z O z N 40-z,
However,
0 ≦ x <14
0.0001 ≤ y ≤ 2
0 ≤ z ≤ 20
In the composition range obtained by changing the parameters of x, y, and z while maintaining a stable crystal structure, the phosphor represented by the formula: Eu / Mg ratio, Eu / Ca ratio, Eu / Sr ratio, Eu / Ba ratio Eu / (Mg + Ca) ratio, Eu / (Mg + Sr) ratio, Eu / (Mg + Ba) ratio, Eu / (Ca + Sr) ratio, Eu / (Ca + Ba) ratio, Eu / (Sr + Ba) ratio, Si / Al ratio, N / The O ratio can be changed. Thereby, since the excitation wavelength or the emission wavelength can be continuously changed, the phosphor is easy to design a material. For example, when the inorganic compound satisfies 0 ≦ x ≦ 3, 0.05 ≦ y ≦ 0.4, and 0 ≦ z ≦ 1, yellow fluorescence having a peak at a wavelength in the range of 550 nm to 600 nm can be emitted.

  A phosphor containing an inorganic compound which is a single crystal particle having an average particle size of 0.1 μm or more and 20 μm or less or an aggregate of single crystals has high luminous efficiency and good operability when mounted on an LED. It is better to control the diameter.

  Impurity elements such as Fe, Co, and Ni contained in the inorganic compound may cause a decrease in emission intensity. When the total of these elements in the phosphor is 500 ppm or less, the influence of the decrease in emission intensity is reduced.

As one of the embodiments of the present invention, a phosphor composed of an inorganic compound in which A _{1 + x} (D, E) ₃₀ X _40- based crystal is used as a base and light-emitting ions are dissolved therein, and other crystal phase or amorphous phase A phosphor having a phosphor content of 20% by mass or more. The present embodiment may be used when a desired characteristic cannot be obtained with a single phosphor of A _{1 + x} (D, E) ₃₀ X ₄₀ series crystal, or when a function such as conductivity is added. The content of the A _{1 + x} (D, E) ₃₀ X _40- based crystal may be adjusted according to the intended characteristics, but if it is 20% by mass or less, the emission intensity may be lowered. For this reason, it is preferable that the quantity made into a main component is 20 mass% or more.

  When the phosphor is required to have conductivity such as for electron beam excitation, an inorganic substance having conductivity as another crystal phase or amorphous phase may be added.

Examples of the inorganic substance having conductivity include an oxide, an oxynitride, a nitride, or a mixture thereof containing one or more elements selected from Zn, Al, Ga, In, and Sn. Examples thereof include zinc oxide, aluminum nitride, indium nitride, and tin oxide.

When a target emission spectrum cannot be obtained with a single phosphor of A _{1 + x} (D, E) ₃₀ X ₄₀ series crystal, a second other phosphor may be added. Other phosphors include BAM phosphor, β-sialon phosphor, α-sialon phosphor, (Sr, Ba) ₂ Si ₅ N ₈ phosphor, CaAlSiN ₃ phosphor, (Ca, Sr) AlSiN ₃ phosphor Etc. As described above, an inorganic phosphor different from the above-described inorganic compound of the present invention may be used as the other crystal phase or amorphous phase.

As one embodiment of the present invention, there is a phosphor having a peak at a wavelength in the range of 500 nm to 650 nm when irradiated with an excitation source. For example, an A _{1 + x} (D, E) ₃₀ X _40- based crystal phosphor activated with Eu emits yellow to red fluorescence having an emission peak in this range by adjusting the composition. Further, for example, an A _{1 + x} (D, E) ₃₀ X _40- based crystal phosphor activated with Ce emits green fluorescence having an emission peak in this range by adjusting the composition.

  As one embodiment of the present invention, there is a phosphor that emits light using vacuum ultraviolet rays, ultraviolet rays, visible light, electron beams, or X-rays having an excitation source with a wavelength of 100 nm to 500 nm. By using these excitation sources, light can be emitted efficiently.

One embodiment of the present invention is a phosphor in which Eu is dissolved in an inorganic crystal having the same crystal structure as that represented by A _{1 + x} (D, E) ₃₀ X ₄₀ . By adjusting the composition, it emits yellow to red fluorescence having an emission peak at a wavelength in the range of 550 nm to 650 nm when irradiated with light of 300 nm to 500 nm. good.

As one embodiment of the present invention, the color emitted when the excitation source is irradiated is a value of (x, y) on the CIE1931 chromaticity coordinates,
0.2 ≦ x ≦ 0.7
0.2 ≦ y ≦ 0.8
There is a range of phosphors. For example,
Eu _y Sr _{1 + xy} Si _28-2x-z Al _{2 + 2x + z} O _z N _40-z
However,
0 ≦ x <14
0.0001 ≤ y ≤ 2
0 ≤ z ≤ 20
By adjusting to the composition represented by the formula (1), a phosphor that develops a color having a chromaticity coordinate in this range is obtained. It may be used for yellow to red light emission such as a white LED. Alternatively, even when an element other than Eu (Mn, Ce, Pr, Nd, Sm, Tb, Dy, Ho, Er, Tm, Yb) is used as the activation element M, the color of the chromaticity coordinates in the above range is developed. A phosphor is obtained. Since the emission characteristics such as the emission wavelength vary depending on the type of the activation element, for example, when Ce is used, it may be used for green light emission such as a white LED.

  As described above, the phosphor of the present invention has a broad excitation range of electron beam, X-ray, and ultraviolet to visible light, and is 500 nm or more and 650 nm or less, compared with normal oxide phosphors and existing sialon phosphors. It is characterized in that it emits light from green to red, particularly in a specific composition, which exhibits yellow to red from 550 nm to 650 nm, and the emission wavelength and emission peak width can be adjusted. Due to such light emission characteristics, the phosphor of the present invention is suitable for lighting fixtures, image display devices, pigments, and ultraviolet absorbers. The phosphor of the present invention is superior in heat resistance because it does not deteriorate even when exposed to high temperatures, and also has the advantage of excellent long-term stability in an oxidizing atmosphere and moisture environment, and is durable. Can provide excellent products.

The method for producing the phosphor of the present invention is not particularly defined. For example, it is a mixture of metal compounds, and is fired to form an A _{1 + x} (D, E) ₃₀ X _40- based crystal phosphor. The obtained raw material mixture can be obtained by firing in a temperature range of 1200 ° C. or higher and 2200 ° C. or lower in an inert atmosphere containing nitrogen. Although the main crystal of the present invention is hexagonal and belongs to the space group P-6, crystals having a different crystal system or space group may be mixed depending on the synthesis conditions such as the firing temperature. However, since the change in the light emission characteristics is slight, it can be used as a high-luminance phosphor.

  As a starting material, for example, a mixture of metal compounds is a compound containing M, a compound containing A, a compound containing D, a compound containing E, and a compound containing X (however, M Is one or more elements selected from Mn, Ce, Pr, Nd, Sm, Eu, Tb, Dy, Yb, and A is one or more elements selected from Mg, Ca, Sr, Ba Element, D is one or more elements selected from Si, Ge, Sn, Ti, Zr, and Hf, E is one element selected from B, Al, Ga, In, Sc, Y, and La Alternatively, two or more elements and X may be one or more elements selected from O, N, and F).

  As a starting material, the compound containing M is a simple substance or two kinds selected from metals containing M, silicides, oxides, carbonates, nitrides, oxynitrides, chlorides, fluorides, or oxyfluorides A mixture of the above, wherein the compound containing A is a simple substance selected from metals containing A, silicides, oxides, carbonates, nitrides, oxynitrides, chlorides, fluorides, or oxyfluorides, or A compound containing two or more kinds and containing D is selected from metals containing D, silicides, oxides, carbonates, nitrides, oxynitrides, chlorides, fluorides, or oxyfluorides A simple substance or a mixture of two or more, and a compound containing E is selected from a metal, silicide, oxide, carbonate, nitride, oxynitride, chloride, fluoride, or oxyfluoride containing E With a simple substance or a mixture of two or more It shall is preferred because the raw material is excellent in stability easily available. The compound containing X is preferably a simple substance or a mixture of two or more selected from oxides, nitrides, oxynitrides, fluorides, and oxyfluorides, since the raw materials are easily available and excellent in stability.

In a phosphor of A _{1 + x} (D, E) ₃₀ X ₄₀ series crystal activated with Eu, when producing a phosphor in which the element A is Sr, at least a europium nitride or oxide and a strontium nitride Alternatively, it is preferable to use a starting material containing an oxide, an aluminum nitride or oxide, and silicon oxide or silicon nitride because the reaction easily proceeds during firing.

  The furnace used for firing has a high firing temperature, and the firing atmosphere is an inert atmosphere containing nitrogen. Therefore, carbon is used as a material for the high-temperature part of the furnace in a metal resistance heating method or a graphite resistance heating method. A suitable electric furnace is preferred. From such a viewpoint, it is preferable to use graphite for the heating element, heat insulator, or sample container of the baking furnace.

  The inert atmosphere containing nitrogen is preferably in the pressure range of 0.1 MPa or more and 100 MPa or less because thermal decomposition of nitrides and oxynitrides which are starting materials and products is suppressed. The oxygen partial pressure in the firing atmosphere is preferably 0.0001% or less in order to suppress the oxidation reaction of nitrides and oxynitrides as starting materials and products.

  In addition, although baking time changes also with baking temperatures, it is about 1 to 10 hours normally.

  In order to manufacture the phosphor in the form of powder or agglomerate, it is preferable to take a method in which the raw material is filled in a container in a state where the bulk density is kept at 40% or less and then fired. By setting the bulk density to 40% or less, it is possible to avoid strong adhesion between particles. Here, the relative bulk density is a ratio of a value (bulk density) obtained by dividing the mass of the powder filled in the container by the volume of the container and the true density of the substance of the powder. Unless otherwise specified, in this specification, the relative bulk density is simply referred to as bulk density.

  In the firing of the raw material mixture, various heat-resistant materials can be used as a container for holding the raw material compound. However, since the adverse effect of material deterioration on the metal nitride used in the present invention is low, the academic journal Journal of the. American Ceramic Society 2002 Vol. 85, No. 5, p. 1229 to p. 1234, as shown in the boron crucible-coated graphite crucible used for the synthesis of α-sialon, or a boron nitride-coated container, or boron nitride A sintered body is suitable. When calcination is performed under such conditions, boron or boron nitride components are mixed from the container into the product, but if the amount is small, the light emission characteristics are not deteriorated, so the influence is small. Furthermore, the addition of a small amount of boron nitride may improve the durability of the product, which is preferable in some cases.

  In order to manufacture the phosphor in the form of powder or aggregate, the shape of the mixture of the metal compound as the raw material is powder or aggregate, and when the average particle diameter is 500 μm or less, the reactivity and operability are achieved. It is preferable because it is excellent.

  Use of a spray dryer, sieving, or air classification as a method for setting the particle size of the particles or aggregates to 500 μm or less is preferable because of excellent work efficiency and operability.

  The firing method is not a hot press, but a sintering method that does not apply mechanical pressure from the outside, such as an atmospheric pressure sintering method or a gas pressure sintering method, is a method for obtaining a powder or aggregate product. preferable.

  The average particle diameter of the phosphor powder is preferably 50 nm or more and 200 μm or less in terms of volume-based median diameter (d50) because the emission intensity is high. The volume-based average particle diameter can be measured by, for example, a microtrack or a laser scattering method. By using one or more methods selected from pulverization, classification, and acid treatment, the average particle size of the phosphor powder synthesized by firing may be adjusted to 50 nm to 200 μm.

  Defects in the powder or damage due to pulverization by heat-treating the phosphor powder after firing, phosphor powder after pulverization treatment, or phosphor powder after particle size adjustment at a temperature of 1000 ° C. or more and below the firing temperature May recover. Defects and damage may cause a decrease in emission intensity. In this case, the emission intensity is recovered by heat treatment.

  At the time of firing for phosphor synthesis, an inorganic compound that generates a liquid phase at a temperature lower than the firing temperature is added and fired, which acts as a flux and promotes reaction and grain growth to obtain stable crystals. This may improve the emission intensity.

  Fluoride, chloride, iodide, bromide of one or more elements selected from Li, Na, K, Mg, Ca, Sr, Ba as an inorganic compound that generates a liquid phase at a temperature lower than the firing temperature Or a mixture of one or more phosphates. Since these inorganic compounds have different melting points, they may be used properly depending on the synthesis temperature.

  Furthermore, by washing with a solvent after firing, the emission intensity of the phosphor may be increased by reducing the content of an inorganic compound that generates a liquid phase at a temperature lower than the firing temperature.

  When the phosphor of the present invention is used for a light emitting device or the like, it is preferable to use the phosphor in a form dispersed in a liquid medium. Moreover, it can also be used as a phosphor mixture containing the phosphor of the present invention. The phosphor of the present invention dispersed in a liquid medium is called a phosphor-containing composition.

  The liquid medium that can be used in the phosphor-containing composition of the present invention is a liquid medium that exhibits liquid properties under the desired use conditions, suitably disperses the phosphor of the present invention, and does not cause undesirable reactions. If there is, it is possible to select an arbitrary one according to the purpose. Examples of the liquid medium include addition-reactive silicone resins, condensation-reactive silicone resins, modified silicone resins, epoxy resins, polyvinyl resins, polyethylene resins, polypropylene resins, and polyester resins before curing. These liquid media may be used individually by 1 type, and may use 2 or more types together by arbitrary combinations and a ratio.

  The amount of the liquid medium used may be appropriately adjusted according to the application, etc., but generally, the weight ratio of the liquid medium to the phosphor of the present invention is usually 3% by weight or more, preferably 5% by weight or more, Moreover, it is 30 weight% or less normally, Preferably it is the range of 15 weight% or less.

  In addition to the phosphor and liquid medium of the present invention, the phosphor-containing composition of the present invention may contain other optional components depending on its use and the like. Examples of other components include a diffusing agent, a thickener, a bulking agent, and an interference agent. Specifically, silica-based fine powder such as Aerosil, alumina and the like can be mentioned.

  The light emitting device of the present invention is configured using at least a light emitter or a light emitting light source and the phosphor of the present invention.

  Examples of the light emitter or the light source include an LED light emitting device, a laser diode light emitting device, a semiconductor laser, an organic EL light emitting device, and a fluorescent lamp. The LED light emitting device can be manufactured by using the phosphor of the present invention by a known method as described in JP-A-5-152609, JP-A-7-99345, JP-A-2927279, and the like. In this case, it is desirable that the light emitter or the light source emits light having a wavelength of 330 to 500 nm, and among them, an ultraviolet (or purple) LED light emitting element of 330 to 420 nm or a blue LED light emitting element of 420 to 500 nm is preferable. Some of these LED light-emitting elements are made of a nitride semiconductor such as GaN or InGaN. By adjusting the composition, the LED light-emitting element can be a light-emitting light source that emits light of a predetermined wavelength.

  Examples of the light emitting device of the present invention include a white light emitting diode including the phosphor of the present invention, a lighting fixture including a plurality of white light emitting diodes, and a backlight for a liquid crystal panel.

In such a light emitting device, in addition to the phosphor of the present invention, Eu-activated β-sialon green phosphor, Eu-activated α-sialon yellow phosphor, Eu-activated Sr ₂ Si ₅ N _It may further include one or more phosphors selected from ₈ orange phosphors, Eu-activated (Ca, Sr) AlSiN ₃ orange phosphors, and Eu-activated CaAlSiN ₃ red phosphors . As yellow phosphors other than the above, for example, YAG: Ce, (Ca, Sr, Ba) Si ₂ O ₂ N ₂ : Eu, or the like may be used.

  As one form of the light emitting device of the present invention, the light emitting body or light emitting light source emits ultraviolet or visible light having a peak wavelength of 300 to 500 nm, the yellow light emitted by the phosphor of the present invention, and 500 nm emitted by the other phosphor of the present invention. There is a light-emitting device that emits white light or light other than white light by mixing light of the above wavelengths.

As one form of the light-emitting device of the present invention, in addition to the phosphor of the present invention, a blue phosphor that emits light having a peak wavelength of 420 nm to 500 nm or less by a light emitter or a light source can be included. As such a blue phosphor, AlN: (Eu, Si), BaMgAl ₁₀ O ₁₇ : Eu, SrSi ₉ Al ₁₉ ON ₃₁ : Eu, LaSi ₉ Al ₁₉ N ₃₂ : Eu, α-sialon: Ce, JEM : Ce and the like.

As one form of the light emitting device of the present invention, in addition to the phosphor of the present invention, a green phosphor that emits light having a peak wavelength of 500 nm or more and 550 nm or less by a light emitting body or a light emitting light source can be included. Examples of such green phosphors include β-sialon: Eu, (Ba, Sr, Ca, Mg) ₂ SiO ₄ : Eu, (Ca, Sr, Ba) Si ₂ O ₂ N ₂ : Eu, and the like. is there.

As one form of the light emitting device of the present invention, in addition to the phosphor of the present invention, a yellow phosphor that emits light having a peak wavelength of 550 nm or more and 600 nm or less by a light emitter or a light source can be included. Examples of such a yellow phosphor include YAG: Ce, α-sialon: Eu, CaAlSiN ₃ : Ce, La ₃ Si ₆ N ₁₁ : Ce.

As one form of the light emitting device of the present invention, in addition to the phosphor of the present invention, a red phosphor that emits light having a peak wavelength of 600 nm or more and 700 nm or less by a light emitter or a light source can be included. Examples of such red phosphor include CaAlSiN ₃ : Eu, (Ca, Sr) AlSiN ₃ : Eu, Ca ₂ Si ₅ N ₈ : Eu, and Sr ₂ Si ₅ N ₈ : Eu.

  As an embodiment of the light-emitting device of the present invention, when an LED that emits light having a wavelength of 280 to 500 nm is used as a light emitter or a light-emitting light source, the light-emitting efficiency is high, so that a highly efficient light-emitting device can be configured.

  The image display device of the present invention is composed of at least an excitation source and the phosphor of the present invention, and is a fluorescent display tube (VFD), a field emission display (FED), a plasma display panel (PDP), a cathode ray tube (CRT), a liquid crystal. There is a display (LCD). The phosphor of the present invention has been confirmed to emit light by excitation of vacuum ultraviolet rays of 100 to 190 nm, ultraviolet rays of 190 to 380 nm, electron beams, etc., and in combination of these excitation sources and the phosphor of the present invention, An image display apparatus as described above can be configured.

  Since the phosphor of the present invention mainly composed of an inorganic compound having a specific chemical composition has a yellow object color, it can be used as a pigment or a fluorescent pigment. That is, when the phosphor of the present invention is irradiated with illumination such as sunlight or a fluorescent lamp, a yellow object color is observed, but since the color is good and it does not deteriorate for a long time, the phosphor of the present invention Is suitable for inorganic pigments. For this reason, when used for paints, inks, paints, glazes, colorants added to plastic products, etc., good color development can be maintained high over a long period of time.

  Since the phosphor of the present invention absorbs ultraviolet rays, it is also suitable as an ultraviolet absorber. For this reason, when used as a paint, applied to the surface of a plastic product, or kneaded into a plastic product, the effect of blocking ultraviolet rays is high, and the product can be effectively protected from ultraviolet degradation.

  The present invention will be described in more detail with reference to the following examples, which are disclosed only as an aid for easily understanding the present invention, and the present invention is not limited to these examples. Absent.

[Raw materials used for synthesis]
The raw material powder used for the synthesis was a silicon nitride powder having a specific surface area of 11.2 m ² / g, an oxygen content of 1.29 wt%, and an α-type content of 95% (SN-E10 manufactured by Ube Industries, Ltd.). Grade), an aluminum nitride powder having a specific surface area of 3.3 m ² / g and an oxygen content of 0.82 wt% (E grade manufactured by Tokuyama Corporation), and a specific surface area of 13.2 m ² / g Aluminum oxide powder (Taimicron manufactured by Daimei Chemical Industries), 99.5% pure calcium nitride (Ca ₃ N ₂ ; manufactured by High Purity Chemical Laboratory), and 99.5% pure strontium nitride (Sr ₃ N ₂₎ ; and shellac Ltd.), 99.7% purity barium nitride _(Ba 3 _{N 2,} made of shellac), europium nitride (EuN; by metal europium is heated 10 hours at 800 ° C. in an ammonia gas stream, Genus as those obtained by nitriding), cerium nitride (CeN; and metal cerium those nitrided by heating at 600 ° C. in a nitrogen stream), terbium oxide _(Tb 4 _{O 7;} 99.9% purity by Shin-Etsu Chemical Manufactured by Kogyo Co., Ltd.), ytterbium oxide (Yb ₂ O ₃ ; purity 99.9% manufactured by Shin-Etsu Chemical Co., Ltd.), and manganese carbonate (MnCO ₃ ; purity 99.9%) Manufactured), praseodymium oxide (Pr ₆ O ₁₁ ; purity 99.9% manufactured by Shin-Etsu Chemical Co., Ltd.), neodymium oxide (Nd ₂ O ₃ ; purity 99.9% manufactured by Shin-Etsu Chemical Co., Ltd.), _{They were} samarium oxide (Sm ₂ O ₃ ; purity 99.9% manufactured by Shin-Etsu Chemical Co., Ltd.) and dysprosium oxide (Dy ₂ O ₃ ; purity 99.9% manufactured by Shin-Etsu Chemical Co., Ltd.).

[Synthesis and Structural Analysis of Crystalline Sr ₃ (Si, Al) ₃₀ N ₄₀ ]
The mixture composition of strontium nitride (Sr ₃ N ₂ ), silicon nitride (Si ₃ N ₄ ), and aluminum nitride (AlN) was designed in such a ratio that the cation ratio was Sr: Si: Al = 3: 24: 6. . These raw material powders were weighed so as to have the above mixed composition and mixed for 5 minutes using a silicon nitride sintered pestle and mortar in a glove box in a nitrogen atmosphere having an oxygen content of 1 ppm. Next, the obtained mixed powder was put into a crucible made of a boron nitride sintered body. The bulk density of the mixed powder (powder) was about 30%.

The crucible containing the mixed powder was set in a graphite resistance heating type electric furnace. The firing operation is as follows. First, the firing atmosphere is evacuated at a pressure of 1 × 10 ⁻¹ Pa or less by a diffusion pump, heated from room temperature to 800 ° C. at a rate of 500 ° C. per hour, and the purity at 800 ° C. is 99.999% by volume. Nitrogen was introduced to bring the pressure in the furnace to 1 MPa, and the temperature was raised to 1800 ° C. at 500 ° C. per hour and held at that temperature for 2 hours.

  The synthesized product was observed with an optical microscope, and crystal particles having a diameter of 30 to 50 μm were collected from the synthesized product. The particles were analyzed using a scanning electron microscope (SEM; SU1510 manufactured by Hitachi High-Technologies Corporation) equipped with an energy dispersive element analyzer (EDS; QUANTAX manufactured by Bruker AXS). Analysis was carried out. As a result, the presence of Sr, Si, Al, and N elements was confirmed, and the ratio of the number of atoms contained in Sr, Si: Al was measured to be 3: 24: 6.

  Next, the crystal particles were fixed to the tip of the glass fiber with an organic adhesive. This was measured using a single crystal X-ray diffractometer with a rotating counter cathode of MoKα rays (SMART APEX II Ultra manufactured by Bruker AXS) under the condition that the output of the X-ray source was 50 kV 50 mA. . As a result, it was confirmed that the crystal particles were a single crystal.

  Next, the crystal structure was obtained from the X-ray diffraction measurement result using single crystal structure analysis software (APEX2 manufactured by Bruker AXS). The obtained crystal structure data is shown in Table 1, and the crystal structure is shown in FIG. Table 1 describes the crystal system, space group, lattice constant, atom type, and atom position, and this data is used to determine the shape, size, and arrangement of atoms in the unit cell. be able to. Si and Al enter at the same atomic position, and oxygen and nitrogen enter at the same atomic position, and when they are averaged as a whole, the composition ratio of the crystal is obtained.

This crystal belongs to the hexagonal system (Hexagonal), belongs to the space group P-6, (International Tables for Crystallography No. 174 space group), and the lattice constants a, b, c are a = 0.79395 nm, b = 0.79395 nm, c = 1.43822 nm, and the angles α, β, and γ were α = 90 °, β = 90 °, and γ = 120 °. The atomic positions were as shown in Table 1. In the table, Si and Al are present at a certain ratio determined by the composition at the same atomic position. In general, in a sialon-based crystal, oxygen and nitrogen can enter in the seat where X enters, but since Sr is +2, Al is +3, and Si is +4, the atomic position and Sr If the ratio between Si and Al is known, the ratio of O (-2 valence) to N (-3 valence) occupying the (O, N) position can be determined from the electrical neutrality condition of the crystal. The composition of this crystal obtained from the Sr: Si: Al ratio of the measured value of EDS and the single crystal X-ray structure analysis was Sr ₃ Si ₂₄ Al ₆ N ₄₀ . In some cases, the starting material composition and the crystal composition are different, because a composition other than Sr ₃ Si ₂₄ Al ₆ N ₄₀ is produced as a small amount of the second phase. Even in this case, since this measurement uses a single crystal, the analysis result shows a pure Sr ₃ Si ₂₄ Al ₆ N ₄₀ structure.

When the similar composition was examined, the Sr ₃ Si ₂₄ Al ₆ N ₄₀ crystal had a part or all of Sr while maintaining the crystal structure, where A was selected from Mg, Ca, Sr, and Ba. 1 or 2 or more elements). That is, the A _{1 + x} (Si, Al) ₃₀ X _40- based crystal has the same crystal structure as the Sr ₃ Si ₂₄ Al ₆ N ₄₀ crystal. Among them, Sr can provide stable crystals with a wide range of substitution ratios. Further, a part of Si can be replaced with Al, a part of Al can be replaced with Si, and a part of N can be replaced with oxygen. This crystal has the same crystal structure as Sr ₃ Si ₂₄ Al ₆ N ₄₀ It was confirmed to be one composition of the crystal group. Further, the electrical neutrality _{condition, A 1 + x Si 28-2x-} z Al 2 + 2x + z O z N 40-z ( however, 0 ≦ x <14,0 ≦ z ≦ 20) can be described as a composition represented by.

From the crystal structure data, it was confirmed that this crystal was a novel substance that had not been reported so far. A powder X-ray diffraction pattern was calculated from the crystal structure data. The results are shown in FIG. In the future, if powder X-ray diffraction measurement of the synthesized product is performed and the measured powder X-ray diffraction pattern is the same as FIG. 2, the A _{1 + x} (D, E) ₃₀ X _40- based crystal of FIG. 1 is generated. Can be judged. In addition, the crystal constant data obtained by powder X-ray diffraction measurement and the crystal structure data in Table 1 are those in which the lattice constant and the like are changed while maintaining the crystal structure as an A _{1 + x} (D, E) ₃₀ X ₄₀ series crystal. Therefore, it can be determined that an A _{1 + x} (D, E) ₃₀ X _40- based crystal is generated by comparing with the calculated pattern.

[Phosphor Examples and Comparative Examples; Examples 1 to 18]
According to the design composition shown in Table 2 and Table 3, the raw material powder was weighed so as to have the mixed composition (mass ratio) shown in Table 4. In the composition formula A _{1 + x} (D, E) ₃₀ X ₄₀ , the A element is Sr, the D element is Si, the E element is Al, the X element is N, the activated element is Eu, and the parameter x is 0 to 0. The range was 14. In addition, in the composition formula Eu _y Sr _{1 + xy} Si _28-2x-z Al _{2 + 2x + z} O _z N _40-z , the parameter y representing the Eu amount is in the range of _{0.05 to 1.5} , and the parameter z representing the O amount is 0. Depending on the type of raw material powder used, there may be cases where the composition differs between the design composition in Tables 2 and 3 and the mixed composition in Table 4. In this case, the mixed composition was determined so that the amount of metal ions matched. . The component of the composition deviation is mixed in the product as a second phase, but its amount is small, so that the influence on the performance is small. The weighed raw material powders were mixed for 5 minutes using a silicon nitride sintered pestle and mortar. Thereafter, the mixed powder was put into a crucible made of a boron nitride sintered body. The bulk density of the mixed powder was about 20% to 30%.

The crucible containing the mixed powder was set in a graphite resistance heating type electric furnace. The firing operation is as follows. First, the firing atmosphere is evacuated at a pressure of 1 × 10 ⁻¹ Pa or less by a diffusion pump, heated from room temperature to 800 ° C. at a rate of 500 ° C. per hour, and the purity at 800 ° C. is 99.999% by volume. Nitrogen was introduced to bring the pressure in the furnace to 1 MPa, the temperature was raised to 500 ° C. per hour to the set temperature shown in Table 5, and the temperature was maintained for a predetermined time shown in Table 5.

Next, the synthesized compound was pulverized using an agate mortar, and powder X-ray diffraction measurement was performed using Cu _Kα rays. As a result, it was confirmed that the crystal phase having the same crystal structure as that of the Sr ₃ (Si, Al) ₃₀ N ₄₀ crystal was the main product phase. Moreover, it was confirmed from the measurement of EDS that the composite contains Eu, Sr, Si, Al, and N. That is, it was confirmed that the synthesized product was an inorganic compound in which Eu, which is a luminescent ion, was dissolved in an A _{1 + x} (D, E) ₃₀ X ₄₀ series crystal. In particular, when x is in the range of 1.6 to 3, A _{1 + x} (D, E) ₃₀ X _40- based crystals occupy about 60% or more of the generated phase, and further in the range of x of 1.8 to 2.2. It was confirmed that it accounts for about 90% or more of the produced phase. However, in x = 14 (Comparative Example 13), almost no formation of A _{1 + x} (D, E) ₃₀ X _40- based crystals could be confirmed.

  After firing, the obtained fired body was coarsely pulverized and then ground by hand using a crucible made of a silicon nitride sintered body and a mortar, and passed through a 30 μm sieve. When the particle size distribution was measured, the average particle size was 3 to 8 μm.

  As a result of irradiating these powders with a lamp emitting light having a wavelength of 365 nm, it was confirmed that light was emitted from yellow to red. The emission spectrum and excitation spectrum of this powder were measured using a fluorescence spectrophotometer. Table 6 shows the peak wavelength of the excitation spectrum and the peak wavelength of the emission spectrum. This phosphor can be excited by ultraviolet rays of 300 nm to 380 nm, violet or blue light of 380 nm to 500 nm, and was confirmed to be a phosphor emitting from yellow to red. In particular, when the parameter x is constant, the emission peak wavelength shifts to a long wavelength when the Eu / Sr ratio increases, and when the Eu / Sr ratio decreases when the parameter y is constant, the emission peak wavelength becomes a long wavelength. It was confirmed to shift to.

  In the present specification, for the sake of simplicity, the emission color of the phosphor of this example is defined as follows by the wavelength range having the emission peak wavelength. The blue wavelength range is 420 to 500 nm, the green wavelength range is 500 to 550 nm, the yellow wavelength range is 550 to 600 nm, and the red wavelength range is 600 to 650 nm. The wavelength range to be used is the emission color of the phosphor.

  According to Table 2, Table 3, and Table 6, it can be seen that a phosphor that emits light from yellow to red can be obtained by controlling the specific composition with the parameter x and the parameter y. For example, as shown in the composites of Examples 1 to 12 and 14 to 18, the element A is Sr, the element D is Si, the element E is Al, and the element X is N. A phosphor containing an inorganic compound in which Eu is dissolved as an M element emits light from yellow to red having a peak at a wavelength in the range of 550 to 650 nm. Particularly preferably, as shown in the composites of Examples 1 to 9, as shown in the phosphor in which the parameter x is 0 ≦ x ≦ 3, and the composites of Examples 5, 6, and 14-16. The phosphor whose parameter y is 0.05 ≦ y ≦ 0.4 has a particularly high emission intensity and emits yellow light having a peak at a wavelength in the range of 550 to 600 nm.

  In addition, it is thought that the part in which the chemical composition of a mixed raw material composition and a synthetic | combination compound differs in a small amount in a synthetic | combination as an impurity 2nd phase.

FIG. 3 is a graph showing the result of powder X-ray diffraction of the phosphor synthesized in Example 5.
FIG. 4 is a diagram showing an excitation spectrum and an emission spectrum of the phosphor synthesized in Example 5.

The powder X-ray diffraction result (FIG. 3) of the synthesized phosphor is in good agreement with the structure analysis result (FIG. 2). In Example 5, the Sr ₃ (Si, Al) ₃₀ N ₄₀ crystal and the X-ray diffraction pattern are It was confirmed that the main component was a crystal having the same crystal structure as that of the Sr ₃ (Si, Al) ₃₀ N ₄₀ crystal. In Example 5, it was found that excitation was most efficient at 442 nm, and the emission spectrum when excited at 442 nm showed emission having a peak at 585 nm. In addition, it was confirmed that the emission color of the phosphor of Example 5 was within the range of 0.2 ≦ x ≦ 0.7 and 0.2 ≦ y ≦ 0.8 in the CIE1931 chromaticity coordinates.

[Phosphor Examples; Examples 19 to 24]
According to the design composition shown in Table 7 and Table 8, the raw material powder was weighed so as to have the mixed composition (mass ratio) shown in Table 9. In the composition formula A _{1 + x} (D, E) ₃₀ X ₄₀ , the A element is Sr, Ca, and Ba, the D element is Si, the E element is Al, the X element is N, and the M element that is an activated ion is Eu. The parameter x was 2. Depending on the type of raw material powder used, there may occur a case where the composition differs between the designed composition of Table 7 and Table 8 and the mixed composition of Table 9. In this case, the mixed composition was determined so that the amount of metal ions matched. . The component of the composition deviation is mixed in the product as a second phase, but its amount is small, so that the influence on the performance is small. The weighed raw material powders were mixed for 5 minutes using a silicon nitride sintered pestle and mortar. Thereafter, the mixed powder was put into a crucible made of a boron nitride sintered body. The bulk density of the mixed powder was about 20% to 30%.

The crucible containing the mixed powder was set in a graphite resistance heating type electric furnace. The firing operation is as follows. First, the firing atmosphere is evacuated at a pressure of 1 × 10 ⁻¹ Pa or less by a diffusion pump, heated from room temperature to 800 ° C. at a rate of 500 ° C. per hour, and the purity at 800 ° C. is 99.999% by volume. Nitrogen was introduced to bring the pressure in the furnace to 1 MPa, the temperature was raised to 500 ° C. per hour to a set temperature of 2000 ° C., and the temperature was maintained for 4 hours.

Next, the synthesized compound was pulverized using an agate mortar, and powder X-ray diffraction measurement was performed using Cu _Kα rays. As a result, it was confirmed that the crystal phase having the same crystal structure as that of the Sr ₃ (Si, Al) ₃₀ N ₄₀ crystal was the main product phase. Moreover, it was confirmed from the measurement of EDS that the composite contains Eu, Sr, Ca, Ba, Si, Al, and N. (However, the element A differs depending on the design composition.) That is, the synthesized product was confirmed to be an inorganic compound in which Eu, which is a luminescent ion, was dissolved in an A _{1 + x} (D, E) ₃₀ X ₄₀ series crystal. .

  After firing, the obtained fired body was coarsely pulverized and then ground by hand using a crucible made of a silicon nitride sintered body and a mortar, and passed through a 30 μm sieve. When the particle size distribution was measured, the average particle size was 3 to 8 μm.

  As a result of irradiating these powders with a lamp emitting light having a wavelength of 365 nm, it was confirmed that light was emitted from yellow to red or blue. The emission spectrum and excitation spectrum of this powder were measured using a fluorescence spectrophotometer. Table 10 shows the peak wavelength of the excitation spectrum and the peak wavelength of the emission spectrum. This phosphor can be excited by ultraviolet rays of 300 nm to 380 nm, violet or blue light of 380 nm to 500 nm, and was confirmed to be a phosphor that emits yellow to red light or blue light.

  According to Table 7, Table 8, and Table 10, it can be seen that a phosphor that emits light from yellow to red or blue can be obtained by changing the combination of the A elements to a specific composition.

For example, as shown in the composite of Example 19 and Example 5 described above, a crystal in which the A element is Sr, the D element is Si, the E element is Al, and the X element is N. A phosphor containing an inorganic compound in which Eu is solid-solved as the M element is most preferable from the viewpoint of the generation ratio of A _{1 + x} (D, E) ₃₀ X _40- based crystals and emission intensity, and peaks at a wavelength in the range of 550 to 600 nm. It emits yellow light.

  For example, as shown in the composites of Examples 20, 22 to 23, the A element is Ca, a combination of Sr and Ca, or a combination of Ca and Ba, the D element is Si, and the E element is Al. The phosphor containing an inorganic compound in which Eu as a M element is dissolved in a crystal in which the X element is N is next preferred, and emits yellow light having a peak at a wavelength in the range of 550 to 600 nm.

  For example, as shown in the composite of Example 24, in a crystal in which the A element is a combination of Sr and Ba, the D element is Si, the E element is Al, and the X element is N, the M element A phosphor containing an inorganic compound in which Eu is dissolved as a light source emits red light having a peak at a wavelength in the range of 600 nm to 650 nm.

  Further, for example, as shown in the composite of Example 21, in the crystal in which the A element is Ba, the D element is Si, the E element is Al, and the X element is N, Eu is used as the M element. A phosphor containing an inorganic compound in which is dissolved, emits blue light having a peak at a wavelength in the range of 420 to 500 nm.

  In addition, it is thought that the part in which the chemical composition of a mixed raw material composition and a synthetic | combination compound differs is contained in a trace amount in a synthetic | combination as an impurity 2nd phase.

[Phosphor Examples: Examples 25 to 33]
According to the design composition shown in Table 11 and Table 12, the raw material powder was weighed so as to have the mixed composition (mass ratio) shown in Table 13. In the composition formula A _{1 + x} (D, E) ₃₀ X ₄₀ , the element A is Sr, the element D is Si, the element E is Al, the element X is N and O, and the element M is Eu, and the parameter x 2, the parameter z representing the amount of O in the composition formula A _{1 + x} Si _28-2x-z Al _{2 + 2x + z} O _z N _{40-z was} in the range of 0-20. Depending on the type of raw material powder used, there may occur a case where the composition differs between the design composition of Tables 11 and 12 and the mixed composition of Table 13, but in this case, the mixed composition was determined so that the amount of metal ions matched. . The component of the composition deviation is mixed in the product as a second phase, but its amount is small, so that the influence on the performance is small. The weighed raw material powders were mixed for 5 minutes using a silicon nitride sintered pestle and mortar. Thereafter, the mixed powder was put into a crucible made of a boron nitride sintered body. The bulk density of the mixed powder was about 20% to 30%.

The crucible containing the mixed powder was set in a graphite resistance heating type electric furnace. The firing operation is as follows. First, the firing atmosphere is evacuated at a pressure of 1 × 10 ⁻¹ Pa or less by a diffusion pump, heated from room temperature to 800 ° C. at a rate of 500 ° C. per hour, and the purity at 800 ° C. is 99.999% by volume. Nitrogen was introduced to bring the pressure in the furnace to 1 MPa, the temperature was raised to 500 ° C. per hour to a set temperature of 2000 ° C., and the temperature was maintained for 4 hours.

Next, the synthesized compound was pulverized using an agate mortar, and powder X-ray diffraction measurement was performed using Cu _Kα rays. As a result, it was confirmed that the crystal phase having the same crystal structure as that of the Sr ₃ (Si, Al) ₃₀ N ₄₀ crystal was the main product phase. Moreover, it was confirmed from the measurement of EDS that the composite contains Eu, Sr, Si, Al, N, and O. That is, it was confirmed that the synthesized product was an inorganic compound in which Eu, which is a luminescent ion, was dissolved in an A _{1 + x} (D, E) ₃₀ X ₄₀ series crystal.

  After firing, the obtained fired body was coarsely pulverized and then ground by hand using a crucible made of a silicon nitride sintered body and a mortar, and passed through a 30 μm sieve. When the particle size distribution was measured, the average particle size was 3 to 8 μm.

  As a result of irradiating these powders with a lamp emitting light having a wavelength of 365 nm, it was confirmed that light was emitted from yellow or blue to green. The emission spectrum and excitation spectrum of this powder were measured using a fluorescence spectrophotometer. Table 14 shows the peak wavelength of the excitation spectrum and the peak wavelength of the emission spectrum. This phosphor can be excited by ultraviolet rays of 300 nm to 380 nm, violet or blue light of 380 nm to 500 nm, and was confirmed to be a phosphor emitting light from yellow or blue to green.

  According to Table 11, Table 12, and Table 14, it can be seen that a phosphor emitting light from yellow or blue to green can be obtained by changing the parameter z representing the amount of O and controlling it to a specific composition.

For example, as shown in the composites of Examples 25 to 28, the A element is Sr, the D element is Si, the E element is Al, and the X element is N or a combination of N and O (however, parameters A phosphor containing an inorganic compound in which Eu is solid-solved as an M element in a crystal where z is 0 ≦ z ≦ 1) emits yellow light having a peak in a wavelength range of 550 to 600 nm. The parameter z is preferably in the above range from the viewpoint of the generation ratio of A _{1 + x} (D, E) ₃₀ X _40- based crystal and the emission intensity.

  Further, as shown in the composites of Examples 29 to 33, the A element is Sr, the D element is Si, the E element is Al, and the X element is a combination of N and O (however, the parameter z is A phosphor containing an inorganic compound in which Eu as a M element is dissolved in a crystal of 1 <z) emits light from blue to green having a peak at a wavelength in the range of 420 to 550 nm.

  In addition, it is thought that the part in which the chemical composition of a mixed raw material composition and a synthetic | combination compound differs is contained in a trace amount in a synthetic | combination as an impurity 2nd phase.

[Phosphor Examples: Examples 34 to 41]
According to the design composition shown in Table 15 and Table 16, the raw material powder was weighed so as to have the mixed composition (mass ratio) shown in Table 17. In the composition formula A _{1 + x} (D, E) ₃₀ X ₄₀ , the element A is Sr, the element D is Si, the element E is Al, the element X is N, and the element M is a rare earth element other than Eu. x was 2. Depending on the type of raw material powder used, there may occur a case where the composition differs between the designed composition of Table 15 and Table 16 and the mixed composition of Table 17. In this case, the mixed composition was determined so that the amount of metal ions matched. . The component of the composition deviation is mixed in the product as a second phase, but its amount is small, so that the influence on the performance is small. The weighed raw material powders were mixed for 5 minutes using a silicon nitride sintered pestle and mortar. Thereafter, the mixed powder was put into a crucible made of a boron nitride sintered body. The bulk density of the mixed powder was about 20% to 30%.

The crucible containing the mixed powder was set in a graphite resistance heating type electric furnace. The firing operation is as follows. First, the firing atmosphere is set to a vacuum of 1 × 10 ⁻¹ Pa or less with a diffusion pump, heated from room temperature to 800 ° C. at a rate of 500 ° C. per hour, and the purity is 800.degree. Nitrogen was introduced to bring the pressure in the furnace to 1 MPa, the temperature was raised to 500 ° C. per hour to a set temperature of 2000 ° C., and the temperature was maintained for 4 hours.

Next, the synthesized compound was pulverized using an agate mortar, and powder X-ray diffraction measurement was performed using Cu _Kα rays. As a result, it was confirmed that the crystal phase having the same crystal structure as that of the Sr ₃ (Si, Al) ₃₀ N ₄₀ crystal was the main product phase. In particular, when the M element was Mn or Ce, the generation ratio was high, which was about 80% and about 40%, respectively. From the EDS measurement, it was confirmed that the composite contained Ce, Mn, Pr, Nd, Sm, Tb, Dy, or Yb, and Sr, Si, Al, and N. That is, it was confirmed that the synthesized product was an inorganic compound in which M element as a luminescent ion was dissolved in the A _{1 + x} (D, E) ₃₀ X ₄₀ series crystal.

  After firing, the obtained fired body was coarsely pulverized and then ground by hand using a crucible made of a silicon nitride sintered body and a mortar, and passed through a 30 μm sieve. When the particle size distribution was measured, the average particle size was 3 to 8 μm.

  As a result of irradiating these powders with a lamp emitting light having a wavelength of 365 nm, it was confirmed that light was emitted from green to red. Even if Ce, Mn, Pr, Nd, Sm, Tb, Dy, or Yb is used as the M element which is a luminescent ion, these inorganic compounds are irradiated with ultraviolet rays of 300 nm to 380 nm, violet or blue light of 380 nm to 500 nm. It was confirmed that the phosphor was capable of being excited and emitted green to red light.

According to Tables 15, 16, and 18, for example, as shown in the composites of Examples 34 and 39, the A element is Sr, the D element is Si, the E element is Al, and X A phosphor containing an inorganic compound in which Ce or Tb as a M element is dissolved in a crystal whose element is N emits green light having a peak in a wavelength range of 500 to 550 nm. From the viewpoint of easy generation of A _{1 + x} (D, E) ₃₀ X _40- based crystals, the M element is preferably Ce.

  Further, as shown in the composites of Examples 35, 37, 40, and 41, a phosphor containing an inorganic compound in which M element, Md, Nd, Dy, or Yb as a M element is in the range of 550 to 600 nm. It emits yellow light with a peak at the wavelength of. In addition, as shown in the composites of Examples 36 and 38, the phosphor containing an inorganic compound in which Pr or Sm is dissolved as the M element emits red light having a peak at a wavelength in the range of 600 to 650 nm. .

[Examples of Light Emitting Device and Image Display Device; Examples 42 to 45]
Next, a light emitting device using the phosphor of the present invention will be described.

[Example 42]
FIG. 5 is a schematic view showing a lighting fixture (bullet type LED lighting fixture) according to the present invention.

  A so-called bullet-type white light-emitting diode lamp (1) shown in FIG. 5 was produced. There are two lead wires (2, 3), and one of them (2) has a concave portion, and a blue-violet light emitting diode element (4) having an emission peak at 405 nm is placed thereon. The lower electrode of the blue-violet light emitting diode element (4) and the bottom surface of the recess are electrically connected by a conductive paste, and the upper electrode and the other lead wire (3) are electrically connected by a gold wire (5). It is connected to the. The phosphor (7) is dispersed in the resin and mounted in the vicinity of the light emitting diode element (4). The first resin (6) in which the phosphor is dispersed is transparent and covers the entire blue-violet light emitting diode element (4). The tip of the lead wire including the recess, the blue-violet light emitting diode element, and the first resin in which the phosphor is dispersed are sealed with a transparent second resin (8). The transparent second resin (8) has a substantially cylindrical shape as a whole, and has a lens-shaped curved surface at the tip, which is commonly called a shell type.

  In this example, the phosphor powder prepared by mixing the yellow phosphor prepared in Example 5 and the JEM: Ce blue phosphor at a mass ratio of 7: 3 was mixed with a silicone resin at a concentration of 35% by weight. The first resin (6) in which the appropriate amount (7) mixed with the phosphor was dispersed was formed by dropping an appropriate amount. The color of the obtained light emitting device was x = 0.33, y = 0.33, and was white.

[Example 43]
FIG. 6 is a schematic view showing a lighting fixture (substrate mounted LED lighting fixture) according to the present invention.

  A chip-type white light emitting diode lamp (11) for board mounting shown in FIG. 6 was produced. Two lead wires (12, 13) are fixed to a white alumina ceramic substrate (19) having a high visible light reflectivity, and one end of each of these wires is located at a substantially central portion of the substrate, and the other end is external. It is an electrode that is soldered when mounted on an electric board. One of the lead wires (12) has a blue light emitting diode element (14) having an emission peak wavelength of 450 nm mounted and fixed at one end of the lead wire so as to be in the center of the substrate. The lower electrode of the blue light emitting diode element (14) and the lower lead wire are electrically connected by a conductive paste, and the upper electrode and the other lead wire (13) are electrically connected by a gold thin wire (15). Connected.

A mixture of the first resin (16), the phosphor prepared in Example 5 and the phosphor (17) in which the CaAlSiN ₃ : Eu red phosphor is mixed at a mass ratio of 9: 1 is in the vicinity of the light emitting diode element. Has been implemented. The first resin in which the phosphor is dispersed is transparent and covers the entire blue light emitting diode element (14). A wall surface member (20) having a shape with a hole in the center is fixed on the ceramic substrate. The wall member (20) has a central portion serving as a hole for holding the resin (16) in which the blue light emitting diode element (14) and the phosphor (17) are dispersed, and the portion facing the center is a slope. It has become. This slope is a reflection surface for extracting light forward, and the curved surface shape of the slope is determined in consideration of the light reflection direction. Further, at least the surface constituting the reflecting surface is a surface having a high visible light reflectance having white or metallic luster. In the present embodiment, the wall member (20) is made of a white silicone resin. The hole at the center of the wall member forms a recess as the final shape of the chip-type light-emitting diode lamp. Here, the first resin in which the blue light-emitting diode element (14) and the phosphor (17) are dispersed ( A transparent second resin (18) is filled so as to seal all of 16). In this example, the same silicone resin was used for the first resin (16) and the second resin (18). The addition ratio of the phosphor, the achieved chromaticity, and the like are substantially the same as in Example 42.

  Next, a design example of an image display device using the phosphor of the present invention will be described.

[Example 44]
FIG. 7 is a schematic view showing an image display device (plasma display panel) according to the present invention.

The red phosphor (31), the green phosphor (β-sialon: Eu ²⁺ ) (32) and the blue phosphor (BAM: Eu ²⁺ ) (33) of Example 24 of the present invention are formed on the glass substrate (44). It is apply | coated to the inner surface of each cell (34, 35, 36) arrange | positioned through an electrode (37, 38, 39) and a dielectric material layer (41). When the electrodes (37, 38, 39, 40) are energized, vacuum ultraviolet rays are generated by Xe discharge in the cell, which excites the phosphor and emits red, green, and blue visible light, which is the protective layer. (43), observed from the outside through the dielectric layer (42) and the glass substrate (45), and functions as an image display device.

[Example 45]
FIG. 8 is a schematic view showing an image display device (field emission display panel) according to the present invention.

  The red phosphor (56) of Example 24 of the present invention is applied to the inner surface of the anode (53). By applying a voltage between the cathode (52) and the gate (54), electrons (57) are emitted from the emitter (55). The electrons are accelerated by the voltage of the anode (53) and the cathode, collide with the red phosphor (56), and the phosphor emits light. The whole is protected by glass (51). The figure shows one light-emitting cell consisting of one emitter and one phosphor, but in fact, a display that can produce a variety of colors is constructed by arranging a large number of blue and green cells in addition to red. The Although it does not specify in particular about the fluorescent substance used for a blue or green cell, what emits high brightness | luminance with a low-speed electron beam is good to use.

  The nitride phosphor of the present invention has emission characteristics (emission color, excitation characteristics, emission spectrum) different from those of conventional phosphors, and has high emission intensity even when combined with an LED of 470 nm or less. It is a nitride phosphor that is suitably used for VFD, FED, PDP, CRT, white LED, etc. because it is thermally stable and has little decrease in phosphor brightness when exposed to an excitation source. . In the future, it can be expected to contribute greatly to the development of the industry in material design for various display devices.

1. Cannonball type light emitting diode lamp.
2,3. Lead wire.
4). Light emitting diode element.
5. Gold thin wire.
6,8. resin.
7). Phosphor.
11. Chip-type white light-emitting diode lamp for board mounting.
12,13. Lead wire.
14 Light emitting diode element.
15. Gold thin wire.
16, 18. resin.
17. Phosphor.
19. Alumina ceramic substrate.
20. Side member.
31. Red phosphor.
32. Green phosphor.
33. Blue phosphor.
34, 35, 36. UV light emitting cell.
37, 38, 39, 40. electrode.
41, 42. Dielectric layer.
43. Protective layer.
44, 45. Glass substrate.
51. Glass.
52. cathode.
53. anode.
54. Gate.
55. Emitter.
56. Phosphor.
57. Electronic.

Claims (42)

At least A element, D element, E element, and X element (where A is one or more elements selected from Mg, Ca, Sr, and Ba, and D is Si, Ge, Sn, Ti, Zr, One or more elements selected from Hf, E is one or more elements selected from B, Al, Ga, In, Sc, Y, La, X is O, N, F A _{1 + x} (D, E) ₃₀ X ₄₀ (where 0 ≦ x <14), A _{1 + x} (D, E) ₃₀ X ₄₀ Inorganic crystals having the same crystal structure as the crystals shown, or solid solution crystals thereof, M element (where M is one selected from Mn, Ce, Pr, Nd, Sm, Eu, Tb, Dy, Yb) Or a phosphor containing an inorganic compound in which two or more elements are dissolved The element A includes at least one element selected from the group consisting of Mg, Ca, Sr and Ba,
The element D includes Si,
The E element includes Al,
The X element includes N;
The phosphor according to claim 1, wherein the X element includes O as necessary. Inorganic crystals having the same crystal structure as the crystal represented by A _{1 + x} (D, E) ₃₀ X ₄₀ are Mg _{1 + x} (Si, Al) ₃₀ N ₄₀ , Ca _{1 + x} (Si, Al) ₃₀ N ₄₀ , Sr _{1 + x.} (Si, Al) ₃₀ N ₄₀ , Ba _{1 + x} (Si, Al) ₃₀ N ₄₀ , Mg _{1 + x} (Si, Al) ₃₀ (O, N) ₄₀ , Ca _{1 + x} (Si, Al) ₃₀ (O, N) ₄₀ , Sr _{1 + x} (Si, Al) ₃₀ (O, N) ₄₀ , Ba _{1 + x} (Si, Al) ₃₀ (O, N) ₄₀ , (Mg, Ca) _{1 + x} (Si, Al) ₃₀ N ₄₀ , (Mg, Sr) _{1 + x} (Si, Al) ₃₀ N ₄₀ , (Mg, Ba) _{1 + x} (Si, Al) ₃₀ N ₄₀ , (Ca, Sr) _{1 + x} (Si, Al) ₃₀ N ₄₀ , (Ca, Ba) _{1 + x} (Si, Al) ₃₀ N ₄₀ , (Sr, Ba) _{1 + x} (Si, Al) ₃₀ N ₄₀ , (Mg, Ca) _{1 + x} (Si, Al) ₃₀ (O, N) ₄₀ , (Mg, Sr) _{1 + x} (Si, Al ) ₃₀ (O, N) ₄₀ , (Mg, Ba) _{1 + x} (Si, Al) ₃₀ (O, N) ₄₀ , (Ca, Sr) _{1 + x} (Si, Al) ₃₀ (O, N) ₄₀ , (Ca, The phosphor according to claim 1, which is Ba) _{1 + x} (Si, Al) ₃₀ (O, N) ₄₀ or (Sr, Ba) _{1 + x} (Si, Al) ₃₀ (O, N) ₄₀ . An inorganic crystal having the same crystal structure as the crystal represented by A _{1 + x} (D, E) ₃₀ X ₄₀ ,
Mg _{1 + x} Si _28-2x-z Al _{2 + 2x + z} O _z N _40-z , Ca _{1 + x} Si _28-2x-z Al _{2 + 2x + z} O _z N _40-z , Sr _{1 + x} Si _28-2x-z Al _{2 + 2x + z} O _z N _40-z , Ba _{1 + x} Si _28-2x-z Al _{2 + 2x + z} O _z N _40-z , (Mg, Ca) _{1 + x} Si _28-2x-z Al _{2 + 2x + z} O _z N _40-z , (Mg, Sr) _{1 + x} Si _{28-2x- z Al 2 + 2x + z O} z N 40-z, (Mg, Ba) 1 + x Si 28-2x-z Al 2 + 2x + z O z N 40-z, (Ca, Sr) 1 + x Si 28-2x-z Al 2 + 2x + z O z N 40- _{z, (Ca, Ba) 1} + x Si 28-2x-z Al 2 + 2x + z O z N 40-z, or, (Sr, _{a) 1 + x Si 28-2x-} z Al 2 + 2x + z O z N 40-z, ( provided that, 0 ≦ x <represented by a composition formula of 14,0 ≦ z ≦ 20), phosphor according to claim 1.   The phosphor according to claim 1, wherein the M element is Eu. Wherein _{A 1 + x (D, E} ) 30 X 40 crystal represented by the _{A 1 + x (D, E} ) 30 inorganic crystals having the same crystal structure as the crystal represented by _{X 40,} or the solid solution crystals, hexagonal The phosphor according to claim 1, which is a system crystal. Wherein _{A 1 + x (D, E} ) crystal represented by 30 _{X 40,} wherein _{A 1 + x (D, E} ) inorganic crystals having the same crystal structure as the crystal represented by 30 _{X 40,} or the solid solution crystals, hexagonal A crystal of the system, with symmetry of the space group P-6,
Lattice constants a, b, c are
a = 0.79395 ± 0.05 nm
b = 0.79395 ± 0.05 nm
c = 1.43822 ± 0.05 nm
The phosphor according to claim 1, wherein the phosphor has a value in the range. The inorganic compound has a composition formula M _d A _e D _f E _g X _h (where d + e + f + g + h = 1, and M is selected from Mn, Ce, Pr, Nd, Sm, Eu, Tb, Dy, Yb) One or more elements selected, A is one or more elements selected from Mg, Ca, Sr, Ba, D is selected from Si, Ge, Sn, Ti, Zr, Hf 1 Species or two or more elements, E is one or more elements selected from B, Al, Ga, In, Sc, Y, and La, X is one or more elements selected from O, N, and F Parameters d, e, f, g, h are
0.00001 ≤ d ≤ 0.3
0.01 ≤ e ≤ 0.3
0.05 ≤ f ≤ 0.5
0.01 ≦ g ≦ 0.4
0.2 ≦ h ≦ 0.7
The phosphor according to claim 1, wherein all of the conditions are satisfied. The parameters d, e, f, g, h are
d + e = ((1 + x) / (71 + x)) ± 0.05
f + g = (30 / (71 + x)) ± 0.05
h = (40 / (71 + x)) ± 0.05
(However, 0 ≤ x <14)
The phosphor according to claim 8, wherein all of the conditions are satisfied. The parameters f and g are
8/30 ≦ f / (f + g) ≦ 28/30
The phosphor according to claim 8, which satisfies the following condition. The element X includes O and N, and the inorganic compound is represented by a composition formula M _d A _e D _f E _g O _h1 N _h2 (where d + e + f + g + h1 + h2 = 1 and h1 + h2 = h) ,
0/40 ≦ h1 / (h1 + h2) ≦ 20/40
The phosphor according to claim 8, which satisfies the following condition.   The phosphor according to claim 8, comprising at least Eu as the M element.   The phosphor according to claim 8, wherein the A element includes at least Sr, the D element includes at least Si, the E element includes at least Al, and the X element includes at least N. The composition formula of the inorganic compound is Eu _y Mg _{1 + xy} Si _28-2x-z Al _{2 + 2x + z} O _z N _40-z , Eu _y Ca _{1 + xy} Si _28-2x-z using parameters x, y and _z. Al _{2 + 2x + z} O _z N _40-z , Eu _y Sr _{1 + xy} Si _28-2x-z Al _{2 + 2x + z} O _z N _40-z , Eu _y Ba _{1 + xy} Si _28-2x-z Al _{2 + 2x + z} O _z N _40-z Eu _y (Mg, Ca) _{1 + xy} Si _28-2x-z Al _{2 + 2x + z} O _z N _40-z Eu _y (Mg, Sr) _{1 + xy} Si _28-2x-z Al _{2 + 2x + z} O _z N _40-z , Eu _y (Mg, Ba) _{1 + xy} Si _28-2x-z Al _{2 + 2x + z} O _z N _40-z , Eu _y (Ca, Sr) _{1 + xy} Si _28-2x-z Al _{2 + 2x + z} O _z N _40-z , Eu _y (Ca, Ba) _{1 + x-y} Si _28-2x-z Al _{2 + 2x + z} O _z N _40-z , or Eu _y (Sr, Ba) _{1 + x -y Si 28-2x-z Al 2 +} 2x + z O z N 40-z,
However,
0 ≦ x <14
0.0001 ≤ y ≤ 2
0 ≤ z ≤ 20
The phosphor according to claim 1, which is represented by:   The phosphor according to claim 1, wherein the inorganic compound is a single crystal particle or an aggregate of single crystals having an average particle size of 0.1 μm to 20 μm.   The phosphor according to claim 1, wherein a total of impurity elements of Fe, Co, and Ni contained in the inorganic compound is 500 ppm or less.   The phosphor according to claim 1, further comprising another crystal phase or an amorphous phase different from the inorganic compound in addition to the inorganic compound, wherein the content of the inorganic compound is 20% by mass or more.   The phosphor according to claim 17, wherein the other crystal phase or amorphous phase is a conductive inorganic substance.   The conductive inorganic substance is an oxide, oxynitride, nitride, or a mixture thereof containing one or more elements selected from Zn, Al, Ga, In, and Sn. 18. The phosphor according to 18.   The phosphor according to claim 17, wherein the other crystal phase or amorphous phase is an inorganic phosphor different from the inorganic compound.   The phosphor according to claim 1, which emits fluorescence having a peak in a wavelength range of 500 nm to 650 nm by irradiating an excitation source.   The phosphor according to claim 21, wherein the excitation source is a vacuum ultraviolet ray, an ultraviolet ray, a visible light, an electron beam or an X-ray having a wavelength of 100 nm to 500 nm. Wherein _{A 1 + x (D, E} ) 30 X 40 crystal represented by the _{A 1 + x (D, E} ) 30 inorganic crystals having the same crystal structure as the crystal represented by _{X 40,} or, Eu is solid to the solid solution crystals The phosphor according to claim 1, which melts and emits yellow to red fluorescence having a peak at a wavelength in the range of 550 nm to 650 nm when irradiated with light of 300 nm to 500 nm. The color emitted when the excitation source is irradiated is the value of (x, y) on the CIE 1931 chromaticity coordinates,
0.2 ≤ x ≤ 0.7
0.2 ≤ y ≤ 0.8
The phosphor according to claim 1, which satisfies the following condition.   The mixture of metal compounds capable of constituting the inorganic compound according to claim 1 by firing is fired in a temperature range of 1200 ° C to 2200 ° C in an inert atmosphere containing nitrogen. A method for producing a phosphor.   A light-emitting device including at least a light-emitting body or a light-emitting light source and a phosphor, wherein the phosphor includes at least the phosphor according to claim 1.   27. The light-emitting body or light-emitting light source is a light-emitting diode (LED), a laser diode (LD), a semiconductor laser, or an organic EL light-emitting body (OLED) that emits light having a wavelength of 330 to 500 nm. Light emitting device.   27. The light emitting device according to claim 26, wherein the light emitting device is a white light emitting diode, a lighting fixture including a plurality of the white light emitting diodes, or a backlight for a liquid crystal panel.   The phosphor or emission light source emits ultraviolet or visible light having a peak wavelength of 300 to 500 nm, and mixes yellow light emitted from the phosphor according to claim 1 with light having a wavelength of 500 nm or more emitted from another phosphor. 27. The light emitting device according to claim 26, which emits white light or light other than white light.   27. The light emitting device according to claim 26, wherein the phosphor further includes a blue phosphor that emits light having a peak wavelength of 420 nm to 500 nm or less by the light emitter or the light source. The blue phosphor is selected from AlN: (Eu, Si), BaMgAl ₁₀ O ₁₇ : Eu, SrSi ₉ Al ₁₉ ON ₃₁ : Eu, LaSi ₉ Al ₁₉ N ₃₂ : Eu, α-sialon: Ce, JEM: Ce The light-emitting device according to claim 30.   27. The light emitting device according to claim 26, wherein the phosphor further includes a green phosphor that emits light having a peak wavelength of 500 nm or more and 550 nm or less by the light emitter or the light source. The green phosphor is selected from β-sialon: Eu, (Ba, Sr, Ca, Mg) ₂ SiO ₄ : Eu, (Ca, Sr, Ba) Si ₂ O ₂ N ₂ : Eu. The light-emitting device of description.   27. The light emitting device according to claim 26, wherein the phosphor further includes a yellow phosphor that emits light having a peak wavelength of 550 nm or more and 600 nm or less by the light emitter or the light source. The light emitting device according to claim 34, wherein the yellow phosphor is selected from YAG: Ce, α-sialon: Eu, CaAlSiN ₃ : Ce, and La ₃ Si ₆ N ₁₁ : Ce.   27. The light emitting device according to claim 26, wherein the phosphor further includes a red phosphor that emits light having a peak wavelength of not less than 600 nm and not more than 700 nm by the light emitter or the light source. The light emitting device according to claim 36, wherein the red phosphor is selected from CaAlSiN ₃ : Eu, (Ca, Sr) AlSiN ₃ : Eu, Ca ₂ Si ₅ N ₈ : Eu, and Sr ₂ Si ₅ N ₈ : Eu. .   27. The light emitting device according to claim 26, wherein the light emitting body or light emitting light source is an LED that emits light having a wavelength of 280 to 500 nm.   An image display apparatus comprising at least an excitation source and a phosphor, wherein the phosphor includes at least the phosphor according to claim 1.   40. The image display device according to claim 39, wherein the image display device is any one of a fluorescent display tube (VFD), a field emission display (FED), a plasma display panel (PDP), a cathode ray tube (CRT), or a liquid crystal display (LCD). The image display device described.   A pigment comprising the inorganic compound according to claim 1. An ultraviolet absorber comprising the inorganic compound according to claim 1.