JP5515143B2 - Phosphor, phosphor manufacturing method, and light emitting device - Google Patents

Description

  The present invention relates to a phosphor, a method for manufacturing the same, and a light-emitting device using the phosphor. In particular, the present invention relates to a phosphor containing a chalcopyrite compound, manganese and silicon, a method for producing the same, and a light emitting device using the phosphor.

  First, as a result of the research by the inventors of the present application, the inventors have found that when a predetermined amount of silicon is added to a phosphor obtained by adding a manganese atom as a light emission center to a chalcopyrite compound, the emission intensity is remarkably improved. Therefore, the applicant of the present application has filed a patent application for the invention completed based on such knowledge, and the patent application has already been published (Patent Document 1).

Patent Document 1 contains manganese and silicon, and has a composition formula Cu (Al _1-x Ga _x ) (S _1-y Se _y ) ₂ : Mn, Si (where 0 ≦ x ≦ 0.4, 0 ≦ y ≦ It is disclosed that when the content of silicon in the phosphor represented by 0.4) is in a predetermined range, the emission intensity of the phosphor is remarkably improved.

  Further, the content of silicon in the phosphor is preferably in the range of 2 mol% to 50 mol%, and more preferably in the range of 5 mol% to 30 mol% of the silicon in the phosphor. It is also disclosed in Patent Document 1 that the optimum value of the silicon content in the phosphor is around 20 mol%.

In addition, a mixture obtained by mixing Cu ₂ S, Al ₂ S ₃ , Ga ₂ S ₃ , Al ₂ Se ₃ , Ga ₂ Se ₃ , MnS, MnSe, Si, Se and S at a predetermined ratio, Ar It is also disclosed in Patent Document 1 that the phosphor can be obtained by firing in an atmosphere.

JP 2008-239699 A

  As described above, the phosphor described in Patent Document 1 has a significantly higher emission intensity than conventional phosphors that do not contain silicon, but depending on the application, a higher emission intensity may be required. In some cases, the emission intensity was still insufficient.

  The present invention has been made under such a background, and an object thereof is to provide a chalcopyrite phosphor having an even higher emission intensity by improving the phosphor described in Patent Document 1. Another object is to provide a method for producing the phosphor and a light-emitting device using the phosphor.

The phosphor according to the present invention contains manganese and silicon, and has the composition formula Cu (Al _1−x Ga _x ) (S _1−y Se _y ) ₂ : Mn, Si (where 0 ≦ x ≦ 0.4,0 in the phosphor represented by ≦ y ≦ 0.4), containing the aluminum sulfide as the starting material and the metal aluminum, the ratio occupied by the metal aluminum relative to the total amount of aluminum sulfide and metallic aluminum in molar ratio 0 .. in the range of 2 to 0.5 .

Production method of the phosphor according to the present invention, Cu ₂ S, phosphor Al ₂ S _3, MnS, Si, a mixture obtained by mixing the S and metal Al in a predetermined ratio is fired in an Ar atmosphere In this production method, the ratio of metal Al to the total amount of Al ₂ S ₃ and metal Al in the mixture is in the range of 0.2 to 0.5 in terms of molar ratio .

  A light-emitting device according to the present invention includes the phosphor described above.

According to the present invention, the composition formula Cu (Al _1-x Ga _x ) (S _1-y Se _y ) containing manganese as a luminescent center atom and containing silicon in the range of 0.01 mol to 0.5 mol. ) ₂ : By adding metallic aluminum to the starting material of the phosphor represented by Mn, Si (where 0 ≦ x ≦ 0.4, 0 ≦ y ≦ 0.4), the emission intensity of the phosphor is remarkably increased. Can be improved.

Further, according to the present invention, the emission intensity is increased by firing a mixture obtained by mixing Cu ₂ S, Al ₂ S ₃ , MnS, Si, S and metallic aluminum in a predetermined ratio in an Ar atmosphere. An extremely high phosphor can be obtained.

It is a conceptual diagram of the light emitting diode which shows embodiment of this invention. It is a conceptual diagram of the cold cathode fluorescent lamp which shows embodiment of this invention. It is a conceptual diagram of a field emission display (FED) device showing an embodiment of the present invention. It is a conceptual diagram of the vacuum fluorescent display (VFD) apparatus which shows embodiment of this invention. It is a X-ray diffraction pattern figure of the fluorescent substance of the Example and comparative example of this invention. It is a graph which shows PL intensity | strength of the fluorescent substance of the Example of this invention. It is a graph which shows the light emission peak wavelength of the fluorescent substance of the Example of this invention. It is a graph which shows the light emission luminance of the fluorescent substance of the Example of this invention. It is a graph which shows the CIE-x coordinate of light emission of the fluorescent substance of the Example of this invention. It is a graph which shows the CIE-y coordinate of light emission of the fluorescent substance of the Example of this invention. It is a graph which shows the PLE intensity | strength of the fluorescent substance of the Example of this invention.

The phosphor of the present invention is represented by the following composition formula.
Cu (Al _1-x Ga _x ) (S _1-y Se _y ) ₂ : Mn, Si
In the above formula, x represents a number satisfying 0 ≦ x ≦ 0.4, and y represents a number satisfying 0 ≦ y ≦ 0.4.

The phosphor of the present invention contains a chalcopyrite compound represented by the composition formula Cu (Al _1-x Ga _x ) (S _1-y Se _y ) ₂ . These chalcopyrite compounds particularly have a wide band gap, and have an action of shifting the emission wavelength of the emission center atom to the longer wavelength side. Of the chalcopyrite compounds represented by the composition formula, CuAlS ₂ , CuAlSe _{2, and the} like are particularly preferable because they significantly increase the fluorescence emission intensity.

The phosphor of the present invention contains a manganese atom as an emission center atom that activates the chalcopyrite compound represented by the composition formula. Manganese atoms are present in the phosphor as a complex, but when manganese atoms are added to the chalcopyrite compound, it is thought to be caused by 3d-3d transition of Mn2 + by excitation light having a wavelength of 250 to 450 nm. Broad red fluorescence in the 750 nm range is obtained. In addition, when the content of manganese atoms in the phosphor of the present invention is increased, the emission intensity increases and the emission peak wavelength also shifts to the longer wavelength side. For example, when an excitation light having a wavelength of 365 nm is irradiated to a phosphor obtained by adding manganese atoms as emission center atoms to CuAlS ₂ , the content of manganese atoms in the phosphor is from 0.1 mol% to 5 mol%. Increasing the light emission intensity increases. The emission peak wavelength when the manganese atom content is 0.1 mol% is 595 nm, and the emission peak wavelength when the manganese atom content is 5 mol% is 629 nm. That is, when the manganese atom content is increased, the emission peak wavelength is shifted to the longer wavelength side. The content of manganese atoms in the phosphor of the present invention is preferably 0.1 mol% to 20 mol%, but the content of manganese atoms is particularly preferably about 10 mol%.

Since the phosphor of the present invention contains silicon and selenium, it has a flux effect. The flux effect affects the emission intensity and emission wavelength of the phosphor of the present invention. In addition, the flux effect promotes the fusion of manganese atoms and chalcopyrite compounds, reduces defects in the crystal lattice structure, and suppresses the generation of phonons by excitation light, thereby promoting the emission of manganese atoms. When the phosphor of the present invention contains silicon and selenium, the emission of broad red fluorescence in the range of 550 to 750 nm, which is considered to be caused by the 3d-3d transition of Mn2 +, is promoted. For example, when a phosphor obtained by adding silicon to CuAlS ₂ is irradiated with excitation light having a wavelength of 365 nm, when the silicon content is low, the emission intensity is lower than when silicon is not added, but the silicon content When the amount is in the range of 1 mol% to 10 mol%, the emission intensity increases with an increase in the silicon content, and the emission intensity becomes maximum near 10 mol%. When the silicon content exceeds about 10 mol%, the emission intensity decreases. Further, the emission peak wavelength shifts to the longer wavelength side as the silicon content increases until the silicon content approaches 10 mol%, and the emission peak gradually increases when the silicon content approaches 20 mol%. There is a tendency to shift to the short wavelength side. The silicon content in the phosphor of the present invention is preferably 2 mol% to 50 mol%, more preferably 5 mol% to 30 mol%. It is particularly preferable that the silicon content is around 10 mol% because the emission intensity increases.

  Note that the phosphors of the present invention have the same emission characteristics (emission intensity, emission color) whether or not selenium is added to the phosphor of the present invention. Confirmed by these experiments. Although the reason why the powder color is whitened by the addition of selenium is not known, generally, in the lighting device market, a white powder-colored phosphor is preferred, so it is preferable to add selenium.

  The phosphor of the present invention contains metallic aluminum as a starting material. By containing metallic aluminum as a starting material, the phosphor of the present invention has a significantly improved emission intensity. The specific effect will be described later.

The phosphor of the present invention is such that Cu ₂ S, Al ₂ S ₃ , MnS, Si and metallic aluminum have a molar ratio corresponding to the composition formula of the phosphor that Cu, Al, Mn, Si is to produce. It can be obtained by firing the raw material mixed by adding sulfur to the material mixed at a ratio at a firing temperature of 1000 ° C. and a firing temperature of 1 hour.

Alternatively, the phosphor of the present invention includes Cu ₂ S, Al ₂ S ₃ , Ga ₂ S ₃ , Al ₂ Se ₃ , Ga ₂ Se ₃ , MnS, MnSe, Si, Se and metallic aluminum, Cu, Al, Ga , Mn, Si, and Se are mixed at a ratio corresponding to the molar ratio corresponding to the composition formula of the phosphor to be manufactured, and sulfur is further added to the raw material mixed to obtain a firing temperature of 1000 ° C. and a firing temperature of 1 Obtained by baking in time.

The light emitting device of the present invention is a light emitting device comprising the phosphor according to the present invention as described above, for example, a light emitting element such as a light emitting diode, an electroluminescent element, a fluorescent lamp such as a cold cathode fluorescent lamp or a hot cathode fluorescent lamp, Various light-emitting devices such as emission display (FED) devices, vacuum fluorescent display (VFD) devices, and the like. That is, it contains manganese as a luminescent center atom and contains silicon in a range of 0.01 mol to 0.5 mol, and the composition formula Cu (Al _1-x Ga _x ) (S _1-y Se _y ) ₂ : Mn , Si (where 0 ≦ x ≦ 0.4, 0 ≦ y ≦ 0.4), and a light-emitting device including a phosphor containing metallic aluminum as a starting material has any type or type Regardless, all are included in the light emitting device of the present invention.

  For example, a light emitting diode 1 as shown in FIG. 1 can be given as an example of a light emitting device according to the present invention. In the light emitting diode 1, an ultraviolet diode 4 that emits ultraviolet rays is sealed in a transparent resin 3 raised on a transparent substrate 2, and a phosphor 5 is supported in the transparent resin 3. Note that the outer surface of the transparent resin 3 may be mirrored so that the outer surface acts as a mirror.

  The ultraviolet diode 4 is an element that emits ultraviolet light when a voltage is applied, for example, a GaN-based near ultraviolet light emitting diode. A wiring (not shown) is connected to the ultraviolet diode 4, and a voltage is applied through the wiring to emit ultraviolet light having a wavelength of 250 to 450 nm. Upon receiving this ultraviolet light, the phosphor 5 emits red fluorescence of 550 to 750 nm.

  In addition to the phosphor 5 that emits red fluorescence, the light emitting diode 1 emits white light by supporting the green light emitting phosphor and the blue light emitting phosphor that emit green and blue fluorescence in the transparent resin 3. You can also do it.

Needless to say, the green light-emitting phosphor and the blue light-emitting phosphor are phosphors excited by ultraviolet rays emitted from the ultraviolet diode 4, that is, ultraviolet rays having a wavelength of 250 to 450 nm. Specific examples of the blue light emitting phosphor include (Ba, Sr, Ca, Mg) ₁₀ (PO ₄ ) ₅ Cl ₂ : Eu ²⁺ , BaMgAl ₁₀ O ₁₇ : Eu ²⁺ , and the specific examples of the green light emitting phosphor. Examples include ZnS: Cu, Al, BaMgAl ₁₀ O ₁₇ : Eu, Mn, and the like.

  Further, the cold cathode fluorescent lamp 11 as shown in FIG. 2 is used for a backlight of a liquid crystal panel, and this cold cathode fluorescent lamp 11 can also be cited as an example of the light emitting device of the present invention. As shown in FIG. 2, the cold cathode fluorescent lamp 11 includes a transparent tube 12 made of glass or the like. Both ends of the transparent tube 12 are hermetically sealed with a sealing member 13 such as bead glass, the pressure is reduced to several tenths of the atmospheric pressure, and a predetermined amount of rare gas and mercury are introduced. Further, the phosphor layer 14 is formed on the inner wall surface of the transparent tube 12 over almost the entire length, and the phosphor according to the present invention as described above is carried on the phosphor layer 14. Moreover, the cup-shaped electrode 15 is arrange | positioned at the both ends of the transparent tube 12, and the opening part 16 of this pair of cup-shaped electrode 15 has faced mutually. In addition, lead wires 17 are connected to the cup-shaped electrodes 15, respectively, and the lead wires 17 pass through the sealing member 13 and are drawn out of the transparent tube 12. In addition, the outer diameter of the transparent tube 12 is in the range of 1.5 to 6.0 mm, preferably in the range of 1.5 to 5.0 mm.

  When a voltage is applied between the two cup-shaped electrodes 15, the rare gas is ionized by the electrons that are slightly present in the transparent tube 12, and the ionized rare gas collides with the cup-shaped electrode 15. Since secondary electrons are emitted, glow discharge is generated between the cup-shaped electrodes 15. By this glow discharge, mercury in the transparent tube 12 is excited and emits ultraviolet rays having a wavelength of 253.7 nm, 360 nm, and the like. When this ultraviolet light hits the phosphor layer 14, red fluorescence is emitted from the phosphor in the phosphor layer 14. Note that, as described for the light emitting diode 1, a green light emitting phosphor and a blue light emitting phosphor can be added to the phosphor layer 14 so that the cold cathode fluorescent lamp 11 emits white light.

  Further, a field emission display (Field Emission Display: FED) device 21 as shown in FIG. 3 can be cited as an example of the light emitting device of the present invention. The FED device 21 includes an anode substrate 22 and a cathode substrate 23 made of glass or the like. The anode substrate 22 and the cathode substrate 23 are supported by a support frame (not shown), and are arranged in parallel with an interval of several mm or less. In addition, the space between the anode substrate 22 and the cathode substrate 23 is isolated from the atmosphere by the above-described support frame and kept in a vacuum.

  A transparent anode electrode 22a is disposed on the inner surface of the anode substrate 22. On the anode electrode 22a, a pixel 22b containing a red light emitting phosphor (a phosphor according to the present invention) and a blue light emitting phosphor are contained. A large number of pixels 22c and a pixel 22d containing a green light emitting phosphor are formed. The pixels 22b, 22c, and 22d are arranged with a gap therebetween, and a light absorber made of a black conductive material is arranged in the gap so as to isolate the pixels 22b, 22c, and 22d from each other. Also good.

A large number of cathode electrodes 23a are arranged on the inner surface of the cathode substrate 23 so as to face the pixels 22b, 22c, and 22d of the anode substrate 22, and an electron-emitting device (such as a carbon film) (on the cathode electrode 23a). Emitter) 23b is arranged. The emitter 23b is connected to a signal input terminal (not shown) provided on the support frame by a wiring (not shown) formed on the cathode substrate 23, and a voltage is applied through the wiring. .

  When a voltage is applied between the cathode electrode 23a and the anode electrode 22a, electrons are emitted from the emitter 23b, and the emitted electrons are attracted to the anode electrode 22a as indicated by an arrow A, and are applied to the pixels 22b, 22c, and 22d. Collide and generate fluorescence. As shown by the arrow B, the generated fluorescence is emitted from the anode substrate 22 to the outside.

  Since the FED device 21 contains the phosphor according to the present invention in the pixel 22b, high luminance can be obtained. In addition, since the phosphor according to the present invention has conductivity, charging caused by excessive collision of electrons emitted from the emitter 23b with the phosphor is suppressed. Therefore, it is possible to avoid a situation in which the collision between the phosphor and the electrons is hindered by the charge on the phosphor surface, and it is possible to suppress abnormal discharge between the electrons that have lost the escape field and the emitter 23b.

  A vacuum fluorescent display (vacuum fluorocent display: VFD) device 31 as shown in FIG. 4 can also be cited as an example of the light emitting device of the present invention. In the VFD device 31, a wiring 33 is disposed on a substrate 32 made of glass or the like, the wiring 33 is covered with an insulator layer 34, and an anode 35 is further provided thereon. The anode 35 is electrically connected to the wiring 33 through a through hole 36 drilled in the insulator layer 34. On the anode 35, phosphor layers 35a, 35b, and 35c are formed. The phosphor layer 35a contains a red light emitting phosphor (the phosphor according to the present invention), the phosphor layer 35b contains a blue light emitting phosphor, and the phosphor layer 35c contains a green light emitting phosphor.

  Further, a grid 37 is disposed above the anode 35 and covers the phosphor layers 35a, 35b, and 35c. The grid 37 is electrically connected to a terminal (not shown) provided on the substrate 32. A filament-shaped cathode 38 is disposed above the grid 37. The cathode 38 is stretched on a support (not shown) provided at both ends of the substrate 32. Further, the substrate 32 or the cathode 38 is isolated from the atmosphere by the container 39, and the space inside the container 39 is kept in a vacuum.

  The VFD device 31 applies electrons emitted from the cathode 38 to the phosphors in the phosphor layers 35a, 35b, and 35c, and performs display by light emission from the phosphors. In addition, the VFD device 31 has little variation in emission intensity due to environmental temperature, particularly low temperature, and since the phosphor according to the present invention is contained in the phosphor layer 35a, high luminance can be obtained. Further, as described for the FED device 21, the phosphor according to the present invention has conductivity and suppresses abnormal discharge, so that the VFD device 31 can continuously generate constant fluorescence.

  Hereinafter, the phosphor according to the present invention will be described in more detail with reference to specific examples.

[Example]
Cu ₂ S, Al ₂ S ₃ , MnS, Si, S, and metal Al are mixed, and the resulting mixture is fired in an Ar atmosphere at a firing temperature of 1000 ° C. and a firing time of 1 hour. A phosphor represented by CuAlS ₂ : Mn, Si was prepared.

The phosphor was produced by changing the mixing ratio of Al ₂ S ₃ and metal Al. That is, the mixing ratio (molar ratio) of Al ₂ S ₃ and metal Al was 0.9: 0.1 (Example 1), 0.8: 0.2 (Example 2), 0.7: 0.3 (Example 3), 0.5: 0.5 (Example 4), 0.3: 0.7 (Example 5), 0. The samples having a ratio of 1: 0.9 (Example 6) were prepared. In all of Examples 1 to 6, the manganese content was 5 mol% and the silicon content was 10 mol%.

[Comparative example]
A phosphor (comparative example) represented by the composition formula CuAlS ₂ : Mn, Si was produced using the same materials, procedures and firing conditions as in Examples 1 to 6 except that the raw material did not contain any metallic Al.

  X-ray diffraction (XRD) measurement, photoluminescence (PL) measurement, PL excitation luminescence (Example 1 to Example 6 phosphor samples obtained in the above procedure, and comparative example phosphor sample) Photoluminescence Excitation (PLE) measurement was performed.

[X-ray diffraction measurement]
X-ray diffraction measurement was performed in the atmosphere at room temperature. The X-ray diffraction pattern of the obtained sample is shown in FIG. In FIG. 5, (Comparative Example) shows the X-ray diffraction measurement results for the phosphor sample of the comparative example, and (Example 1) to (Example 4) are the phosphor samples of Example 1 to Example 4. The X-ray-diffraction measurement result with respect to is shown. (A) and (B) show the X-ray diffraction measurement results of Cu ₅ AlS ₈ and CuAlS ₂ described in ICSD (Inorganic Crystal Structure Database). Since the patterns of Examples 1 to 4 coincide with the pattern of (B), the phosphors of the comparative example and Examples 1 to 4 are represented by the composition formula CuAlS ₂ : Mn, Si. It was confirmed that it was a phosphor.

[PL measurement]
The PL measurement was performed in the air at room temperature using excitation light having a wavelength of 365 nm. The PL intensity of the obtained sample is shown in FIG. In addition, I-IV in a figure has shown that the curve is a PL intensity | strength curve of the sample of the fluorescent substance of Example 1- Example 4, respectively (it displays similarly also in FIGS. 7-11). ). In FIG. 6, in all of Examples 1 to 4, a broad red light emission, which seems to be caused by the 3d-3d transition of Mn2 +, was confirmed.

  In addition, the charge ratio of metal Al at this time (number of moles of metal Al in the raw material / (number of moles of all Al atoms in the raw material)), peak wavelength, peak intensity, luminance, and CIE coordinates are shown in Table 1. Show.

  As is clear from Table 1, when the raw material does not contain metallic Al (comparative example), the peak wavelength is 638 nm. However, as the charging ratio of metallic Al in the raw material is increased, the peak wavelength decreases and the charging ratio is 0. In the case of .5 (Example 4), it becomes 609 nm, and when the preparation ratio of metal Al is further increased, the peak wavelength increases again. This is also clear from FIG.

  Further, when the peak intensity when the raw material does not contain metallic Al (comparative example) is 100, the peak intensity is reduced to 95 when the charging ratio is 0.1 (Example 1). As the ratio is increased, the peak intensity increases, reaches the maximum (160) when the charging ratio is 0.3 (Example 3), and decreases when the charging ratio is 0.5 (Example 4). Luminance also increases monotonously as the charge ratio of metal Al increases, reaches a maximum when the charge ratio is 0.3 (Example 3), and then decreases. This is also clear from FIG.

  FIG. 9 shows the relationship between the preparation ratio of metal Al and CIE-x coordinates, and FIG. 10 shows the relationship between the preparation ratio and CIE-y coordinates. As is apparent from FIGS. 9 and 10, red light emission can be obtained regardless of the preparation ratio of metal Al. Further, the CIE-x coordinate is minimized and the CIE-y coordinate is maximized in the range of the preparation ratio 0.6 to the preparation ratio 0.7.

[PLE measurement]
The PLE measurement was performed by changing the excitation light wavelength and monitoring the fluorescence of the wavelength of 625 nm emitted from the sample in the atmosphere at room temperature. FIG. 11 shows the PLE intensity with respect to the excitation light wavelength.

  As is clear from FIG. 11, when the raw material does not contain metallic Al (comparative example), the peak wavelength is about 370 nm, and the peak wavelength hardly changes even if the preparation ratio of metallic Al in the raw material is increased. The emission intensity is maximized when the charging ratio is 0.3 (Example 3).

As described above, according to the present invention, the composition formula Cu (Al _1−x Ga _x ) (S _1−y Se _y ) ₂ : Mn, Si (where 0 ≦ x ≦ 0.4, 0 ≦ y By adding metallic aluminum to the starting material of the phosphor represented by ≦ 0.4), the emission peak intensity of the phosphor is increased up to about 1.6 times and the luminance is increased up to about 2.5 times. be able to. That is, according to the present invention, a phosphor having high emission intensity can be obtained. In addition, a light emitting device having high emission intensity can be obtained.

  The present invention is useful as a light emitting device such as a light emitting diode, a phosphor used in the light emitting device, and a method for producing the phosphor.

1: Light-emitting diode 2: Transparent substrate 3: Transparent resin 4: Ultraviolet diode 5: Phosphor 11: Cold cathode fluorescent lamp 12: Transparent tube 13: Sealing member 14: Phosphor layer 15: Cup-shaped electrode 16: Opening 17 : Lead wire 21: FED device 22: Anode substrate 22a: Anode electrode 22b-22d: Pixel 23: Cathode substrate 23a: Cathode electrode 23b: Electron emitting element (emitter)
31: Vacuum fluorescent display (VFD) device 32: Substrate 33: Wiring 34: Insulator layer 35: Anode 35a to 35c: Phosphor layer 36: Through hole 37: Grid 38: Cathode 39: Container

Claims (6)

It contains manganese and silicon, and has the composition formula Cu (Al _1−x Ga _x ) (S _1−y Se _y ) ₂ : Mn, Si (where 0 ≦ x ≦ 0.4, 0 ≦ y ≦ 0.4) In the phosphor represented,
Its contain aluminum and metallic aluminum sulfide as a starting material, the ratio occupied by the metal aluminum relative to the total amount of aluminum sulfide and metallic aluminum, characterized in that from 0.2 molar ratio in the range of 0.5 Phosphor. The phosphor of claim 1, wherein the phosphor is represented by the composition formula CuAlS ₂ : Mn, Si. A light-emitting device using the phosphor according to claim 1. In a method for producing a phosphor, in which Cu ₂ S, Al ₂ S ₃ , MnS, Si, S and metal Al are mixed, and the resulting mixture is baked in an Ar atmosphere .
The method for producing a phosphor , wherein a ratio of metal Al to a total amount of Al ₂ S ₃ and metal Al in the mixture is in a range of 0.2 to 0.5 in terms of mole ratio . Cu ₂ S, Al ₂ S ₃ , MnS, Si, S and metal Al are further mixed with Ga ₂ S ₃ , Al ₂ Se ₃ , Ga ₂ Se ₃ , MnSe, Se, and the resulting mixture is mixed. The method for producing a phosphor according to claim 4, wherein firing is performed in an Ar atmosphere. A light-emitting device using the phosphor manufactured by the method according to claim 4.

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