KR20080101752A - Phosphor, Manufacturing Method and Light-Emitting Device - Google Patents

Abstract

By having a sufficient band gap and emitting red fluorescence from yellow and changing the molar ratio of the element contained therein, the hue of fluorescence to be emitted can be modulated sequentially from yellow to red, and the desired hue of yellow to red The present invention provides a method for producing a phosphor that can be easily obtained, and furthermore, a phosphor having good luminous efficiency due to a blue LED or a blue LD can be produced, and this can be easily and efficiently produced.

Formula (1)

Y _{3 -a- b} Ce _a L _b Al _{5 - c} Si _c O _{12 - d} N _d (1)

(Wherein L represents any one or two or more elements of Gd, La, Tb, Lu, or Sc, a is 0.01 <a <0.50, b is 0.0≤b <2.5, c is 0.0 <c <2.0) , Represents a value satisfying 0.01 <d <2.67).

Description

Phosphor, manufacturing method and light emitting device therefor {FLUORESCENT SUBSTANCE, MANUFACTURING METHOD THEREOF AND LUMINOUS DEVICE}

The present invention relates to a phosphor, a manufacturing method thereof, and a light emitting device using the same, and more particularly, to a yellow-based phosphor and a light emitting device using the same.

A light emitting device in which a blue light emitting diode (LED), a blue laser (LD), or the like is used as an excitation source, receives light from the excitation source, emits fluorescence in a yellow region, and improves color rendering by mixing these lights. Compared to the above, it is used in various ways because of its low power consumption and long life. Moreover, since the light emitting device using these LEDs can easily obtain the light which does not contain unnecessary ultraviolet-rays or infrared rays, it is suitable also for various illuminations, such as a cultural property, a work of art, and the article which should avoid heat irradiation. As a phosphor of such a light emitting device, the luminous efficiency by LED is good and the degradation by LED is low (Y, Gd) ₃ (Al, Ga) ₅ O ₁₂ : Ce-based phosphors have been used: the so-called YAG such as Ce ^{+ 3.} As this type of white LED device, specifically, for example, (RE _{1 -x} Sm _x ) ₃ (Al _y Ga _1-y ) ₅ O ₁₂ : Ce (wherein RE is at least selected from Y, Gd) Light emitting diodes (Patent Documents 1 to 3) and the like, which have been molded with a phosphor which is excited by a blue LED and is excited by a blue LED and emit yellowish green, have been reported. However, since light emitted from these light emitting devices is white by a combination of blue and yellow complementary colors, there is a problem that sufficient color rendering cannot be obtained.

In such a light emitting device, in order to improve the color rendering property by using a combination of phosphors, phosphors for emitting fluorescence in the red region from yellow near the long wavelength by the emission of blue LEDs have been developed. As such a phosphor, for example, the content of metal impurities other than the constituent components is reduced, and an oxynitride phosphor (Patent Document 4) mainly composed of α-sialon (Si), or a lanthanide metal or the like is dissolved in a CaAlSiN ₃ crystal phase. (Patent Document 5), a phosphor made of an α sialon compound containing a lanthanide metal and the like (Patent Document 6) and the like have been reported. In addition, LED (patent document 7) etc. which formed the non-particle type phosphor layer on the blue LED are reported.

In a white LED device using this kind of sialon-based phosphor, there is a tendency that white with a warm feeling having a low color temperature is obtained as compared with a white LED device using a YAG: Ce phosphor. However, in the above-mentioned phosphor, there is a deviation between the excitation energy and the light emission energy from the blue LED, and there is a demand for a phosphor that efficiently emits fluorescence by light emission from a blue LED or the like.

In addition, a white LED (Patent Document 8) combining an ultraviolet light emitting diode (UV-LED) and blue, green, and red phosphors has been developed, but emits fluorescence in a red region from yellow by light emitted from a blue LED. The phosphor which has the excitation energy approximated by the luminous energy of the blue LED and which can aim at the improvement of luminous efficiency is calculated | required.

<Patent Document 1> Japanese Patent No. 2900928

<Patent Document 2> Japanese Patent No. 2998696

<Patent Document 3> Japanese Patent No. 2927279

<Patent Document 4> Japanese Patent Laid-Open No. 2004-238506

<Patent Document 5> Japanese Patent Laid-Open No. 2005-235934

<Patent Document 6> Japanese Patent Laid-Open No. 2006-265506

<Patent Document 7> Japanese Patent Laid-Open No. 11-046015

Patent Document 8: Japanese Patent Application No. 2000-509912

An object of the present invention is to have a sufficient band gap, to emit red fluorescence from yellow and to change the molar ratio of the elements contained therein so that the color tone of the fluorescence emitted can be sequentially modulated from yellow to red. It is easy to obtain a red color tone from yellow, and also provides the fluorescent substance which is excellent in luminous efficiency by blue LED and blue LD, and provides the manufacturing method of the fluorescent substance which can manufacture this easily easily. Moreover, the subject of this invention makes it possible to adjust to a desired color tone by changing the molar ratio of the element which comprises a fluorescent substance, and does not select fluorescent substance of the other color tone to combine, and it is excellent in color rendering property, and is excellent in color tone. The present invention provides a light emitting device that can emit light, has good light emission efficiency, has sufficient light emission intensity, can reduce power consumption, and is suitable for lighting.

The inventors of the present invention have found that a fluorescent material whose energy of emission from a blue LED or the like and its excitation energy are approximated, has a sufficient band gap, and in addition, the fluorescent wavelength which is excited and emits light by changing the composition shifts from yellow to the long wavelength side of red. An earnest study was conducted. As a result, the fluorescent substance of a specific element composition changed the composition, and the knowledge of changing fluorescence with high emission peak intensity from yellow to red region by light emission from a blue LED was acquired. Based on these findings, the present invention has been completed.

That is, the present invention, the composition formula (1)

Y _{3 -a- b} Ce _a L _b Al _{5 - c} Si _c O _{12 - d} N _d

(Wherein L represents any one or two or more elements of Gd, La, Tb, Lu, or Sc, a is 0.01 <a <0.50, b is 0.0≤b <2.5, c is 0.0 <c <2.0) And a numerical value satisfying 0.01 < d < 2.7).

Moreover, this invention relates to the manufacturing method of the fluorescent substance as a manufacturing method of the said fluorescent substance, The compound containing the element which comprises composition formula (1) is baked under positive pressure.

Moreover, this invention relates to the light-emitting device characterized by using the said fluorescent substance.

The phosphor of the present invention has a sufficient band gap, emits red fluorescence from yellow, and changes the molar ratio of the elements contained therein so that the hue of fluorescence emitted can be sequentially modulated from yellow to red. It is easy to obtain a red color tone from yellow, and the luminous efficiency by blue LED and blue LD is good.

Moreover, the manufacturing method of the fluorescent substance of this invention can manufacture the said fluorescent substance easily and efficiently.

In addition, the light emitting device of the present invention makes it possible to adjust to a desired color tone by changing the molar ratio of the elements constituting the phosphor, so that white light having excellent color rendering properties and excellent color tone without selecting phosphors of different color tones to be combined. Can emit light, has good light emission efficiency, has sufficient light emission intensity, can reduce power consumption, and is suitable for lighting.

The phosphor of the present invention is formula (1)

Y _{3 -a- b} Ce _a L _b Al _{5 - c} Si _c O _{12 - d} N _d

It is expressed as In the formula, L represents any one or two or more of Gd, La, Tb, Lu, or Sc, a is 0.01 <a <0.50, b is 0.0≤b <2.5, c is 0.0 <c <2.0, 0.01 The numerical value which satisfy | fills <d <2.7 is shown.

The fluorescent substance of this invention contains Y, Ce, Al, Si, O, N, and contains any 1 type, or 2 or more types of Gd, La, Tb, Lu, or Sc as needed. Of these phosphors, the molar ratio of Y and Ce and L, Al and Si, O and N is 3: 5: 12. When the number of moles of all the phosphors is 20, the molar ratio of Y is larger than 0.00 and smaller than 2.99, and the molar ratio of Ce is larger than 0.01 and smaller than 0.50. Preferably, the molar ratio of Y is larger than 0.5 and the molar ratio of Ce is larger than 0.02 and smaller than 0.3. When the number of moles of all the phosphors is 20, the molar ratio of Al is larger than 3.0 and smaller than 5.0, and the molar ratio of Si is larger than 0.0 and smaller than 2.0. Preferably, the molar ratio of Al is larger than 4.0 and smaller than 4.99, and the molar ratio of Si is larger than 0.01 and smaller than 1.0. When the number of moles of all the phosphors is 20, the molar ratio of O is larger than 9.33 and smaller than 11.99, and the molar ratio of N is larger than 0.01 and smaller than 2.67. Preferably, the molar ratio of O is greater than 10.0 and less than 11.95, and the molar ratio of N is greater than 0.05 and less than 2.00.

It is preferable that these elements comprise a crystal. In a phosphor excellent in crystallinity, excitation light is consumed for generation of phonon due to crystal lattice defects, whereby the emission of fluorescence can be suppressed from being lowered.

The phosphor represented by the composition formula (1) has a broadband gap excited by light of wavelength 400 to 520 nm. As an excitation source which emits light of wavelength 400-520 nm which has such an excitation energy, a blue laser, a blue LED, etc. can be mentioned. As a blue LED of the said excitation source, InGaN etc. are mentioned specifically ,.

The phosphor is excited by the blue LED to emit fluorescence in the red region. YAG: fluorescence in the red region of 560 nm to 700 nm shifted from Ce fluorescence to long wavelength is emitted. Si and N are considered as an element which participates in red light emission, and the emission peak wavelength can be changed from yellow to red region by changing the element of composition formula (1) in the range of this composition, and the target yellow to red light system It is easy to get a tint of.

In order to manufacture the above-mentioned phosphors, a method may be employed in which compounds containing respective elements are adjusted and combined so as to correspond to the desired elemental composition except for combination, oxygen and nitrogen, and fired under positive pressure. As a compound to combine, the oxide and nitride of the element contained in composition formula (1) can be used. Specifically, yttrium oxide (Y ₂ O ₃ ), aluminum oxide (Al ₂ O ₃ ), aluminum nitride (AlN), silicon oxide (SiO ₂ ), silicon nitride (Si ₃ N ₄ ), cerium oxide (CeO ₂ ), and the like. Can be used. Moreover, in order to form the fluorescent substance of the structure excellent in crystallinity, it is preferable to use a flux material in order to reduce the defect in a crystal structure. The flux material promotes the fusion of these elements upon melting of each oxide or the like by firing described later, reduces crystal lattice defects, and enables formation of a phosphor having excellent crystallinity. As the flux material, halides such as aluminum fluoride (AlF ₃ ) and ammonium chloride (NH ₄ Cl) can be used. As usage-amount of a flux material, 1-5 mol% is mentioned with respect to fluorescent substance.

Each of these compounds is weighed and collected according to the intended compositional formula, and thoroughly mixed in a dry or wet manner. In the case of wet mixing, it is preferable to use organic solvents, such as alcohol, such as ethanol and isopropyl alcohol, and acetone. These organic solvents and the weighed compound can be put in a ball mill made of ceramics together with balls made of alumina or zirconia, and mixed for 1 hour to 24 hours. Thereafter, the organic solvent can be dried and removed to obtain a mixed raw powder.

The obtained mixed raw material powder is filled into heat-resistant containers, such as a carbon crucible, a carbon tray, a boron nitride crucible, and a boron nitride tray, and is baked. As for baking temperature, 1300-1800 degreeC is preferable, for example, More preferably, it is 1350-1750 degreeC, More preferably, it is 1400-1700 degreeC. The firing time can be, for example, 3 to 10 hours. As the atmosphere at the time of baking, a reducing atmosphere such as a mixed gas of nitrogen and hydrogen, ammonia and nitrogen gas is preferable. As a mixed gas of nitrogen and hydrogen, it is preferable that they are 10-90: 90-10 in a capacity ratio of nitrogen and hydrogen, and it is more preferable that nitrogen: hydrogen is 1: 3.

The baking atmosphere of the said mixed raw material powder is made into positive pressure. By firing under positive pressure, it is possible to suppress decomposition of nitrides such as Si ₃ N ₄ and to obtain a phosphor having a desired composition. As pressure of such a baking atmosphere, 1.00-1.50 atmospheres are preferable, More preferably, they are 1.02-1.3 atmospheres, More preferably, they are 1.05-1.2 atmospheres. When the pressure at the time of firing is 1.50 atm or less, it is possible to suppress the sintering of the phosphor as the target product completely, avoiding the destruction of crystals by applying a strong grinding force during the pulverization of the obtained sintered product, and the luminous efficiency of the phosphor The fall can be suppressed. The firing may be repeated after firing, followed by cooling and refiring a plurality of times. The resulting fired product is pulverized, washed, dried, sifted, or the like, and is suitable for an LED element or the like if it is a powder-shaped phosphor.

The light emitting device of the present invention may be anything as long as the above phosphor is used. For example, as a light emitting device of the present invention, an LED element such as a light emitting diode having a semiconductor emitting light having a wavelength of 400 to 520 nm, an electroluminescent element, and an electric field which emits light by directly colliding electrons from a cathode with a phosphor Examples thereof include electron-emitting devices such as emission type display (FED), vacuum fluorescent display (VFD), and other fluorescent lamps such as cold cathode fluorescent lamps and hot cathode fluorescent lamps.

As an example of the light emitting device of the present invention, a white LED device shown in the schematic configuration diagram of FIG. The white LED device shown in FIG. 1 includes a housing 12 having a function of a reflector, an LED chip 13 fixed on a submount (not shown) fixed to the housing, and the LED chip 13. The transparent resin body 14 which surrounds and the fluorescent substance containing glass sheet 11 are provided so that the transparent resin body may be covered. LED chips 13 preferably has a laminated such as the above-mentioned LED light-emitting layer that emits blue light of 400 to 520㎚ of GaN or the like onto the Al ₂ O ₃ or the SIO substrate. The LED of the LED chip is wire-bonded by the wiring L5 to be electrically connected to a power supply (not shown).

The transparent resin body is provided for the protection of the LED chip, and for example, an epoxy resin, a free-form resin, a silicone resin, etc., which are excellent in transmittance of light emission from the LED and have resistance to the energy, are suitably used. The phosphor 11a is contained in the phosphor-containing glass sheet 11 provided on the upper surface of the transparent resin body. It is preferable that the glass sheet 11 contains red fluorescent substance, green fluorescent substance, etc. which emit green or red, using the said LED as an excitation source. Examples of the red phosphor used herein include SrS: Eu, CaS: Eu, CaAlSiN ₃ : Eu, and the like. Examples of the green phosphor include (Ba, Sr) ₂ SiO ₄ : Eu, SrGa. ₂ S ₄ : Eu, (Ba, Sr, Ca) Si ₂ O ₂ N ₂ : Eu, β-sialon: Eu and the like.

Such a glass sheet can be formed by melting the glass component which comprises glass, and making the mixture which mixed the fluorescent substance in this thin film form. Moreover, fluorescent substance can also be contained in a transparent resin body.

In the white LED device, when blue light is emitted from the LED, the phosphor contained in the glass sheet is excited, and the fluorescence of the red region, the red region wave, and the green region is emitted from yellow. These fluorescence and blue light from LED are diffused and mixed in the glass sheet, and white light excellent in color tone is emitted from the glass sheet surface.

As an example of the light emitting device of the present invention, a field emission display (field emission display: FED) device can be exemplified. As this kind of FED apparatus, what is shown, for example in partial sectional drawing of FIG. 2 is mentioned. The FED apparatus shown in FIG. 2 includes an anode substrate 31 and a cathode substrate 32, such as a pair of glasses, and are arranged in parallel at intervals of several mm or less by a support frame (not shown). The inside is kept in a vacuum. A phosphor 31b is provided on the anode substrate 31 via an anode electrode 31a transparent to the inner surface, and phosphors are alternately used for each pixel from yellow to red phosphors, red phosphors, green phosphors, and blue phosphors. do. The same phosphor as the above-mentioned phosphor can be specifically exemplified as the red phosphor and the green phosphor, wherein the above phosphor is used as a yellow to red phosphor, and is selected in combination with this. The light absorber which consists of a black electrically conductive material which isolate | separates these may be provided between each pixel of each fluorescent substance. On the other hand, the electron emission element (emitter) 32b which consists of a carbon film etc. is provided in the inner surface of the cathode board | substrate 32 corresponding to the pixel of each fluorescent substance. Each electron-emitting device is connected to a signal input terminal (not shown) provided in the support frame so that a voltage is applied to each of the electron-emitting devices by an unillustrated wiring formed on the cathode substrate. In addition, in order to suppress the charging of the surface of the phosphor due to the collision of excess electrons emitted from the emitter, and to prevent the surface of the phosphor from charging and the collision of the appropriate phosphor with the electrons is prevented, a conductive layer is provided on the surface of the phosphor, and the phosphor The abnormal discharge between the electrons and the emitter accumulated on the surface may be suppressed. The conductive layer can be formed by coating a conductive material on the surface of the phosphor.

In such an FED device, when a voltage is applied between the cathode electrode 32a and the anode electrode 31a, electrons are emitted from the electron emission element 32b, and the emitted electrons are represented by the anode electrode (as shown by arrow A). It is attracted to 31a), impinges on the phosphor 31b to generate fluorescence, and the generated fluorescence becomes white light and is emitted from the anode substrate 31 to the outside as indicated by arrow B. FIG. By using the above-mentioned phosphor, the FED device can emit white light having excellent color tone.

As an example of the light emitting device of the present invention, a vacuum fluorescent display (Vaccum Fluorocent Display: VFD) device can be exemplified. As this kind of VFD apparatus, what is shown to partial sectional drawing of FIG. 3 is mentioned, for example. The VFD apparatus shown in FIG. 3 has an anode 45 which is provided by filling through-holes 44 formed in the insulator layer 43 in each wiring 42 provided on a substrate 41 made of glass or the like. Phosphor layers 46a, 46b, 46c are formed on each anode. The phosphor layers 46a, 46b, 46c are alternately provided from the yellow, containing a red phosphor, a red phosphor, a green phosphor, and the like. As said yellow fluorescent substance, the said fluorescent substance is used, The thing similar to the fluorescent substance mentioned above can be illustrated specifically as a red fluorescent substance and a green fluorescent substance selected from the combination with this. The grid 47 is disposed above the phosphor layer so as to cover the phosphor layer, and the grid 47 is provided so as to conduct to a terminal (not shown) provided on the substrate. In addition, a filament-shaped cathode 48 is tightly provided on a support provided at both ends of the substrate above the grid, and they are disposed in a container 49 which forms a vacuum space. In addition, a conductive layer may be provided on the surface of the phosphor to suppress charging of the surface of the phosphor to suppress abnormal discharge. The conductive layer can be formed similarly to the conductive layer in the FED device.

In such a vacuum fluorescent display device, electrons from the cathode collide with the phosphor, and display is performed by light emission from the phosphor. The light emission from the phosphor has little variation in the light emission intensity due to the environmental temperature, in particular the low temperature, so that the vacuum fluorescent display device can develop the color rendering property by containing the above phosphor and can continuously generate a constant fluorescence.

<Example>

Hereinafter, the phosphor of the present invention will be described in more detail with reference to Examples.

Example 1

As a powder raw material, Y ₂ O ₃ 19.53 g, Al ₂ O ₃ 13.95 g, Si ₃ N ₄ 0.96 g, CeO ₂ Using 0.61 g, these were put together with acetone and a zirconia ball in the ceramic ball mill, and it mixed for 12 hours. After the zirconia ball was removed from the mixed raw material solution by a sieve and acetone was removed, the mixture was charged into a boron nitride crucible, set in an electric furnace, and calcined at 1400 ° C. for 3 hours in a 1.1 atmosphere of nitrogen reduction. After baking, slow cooling was performed, and the resulting fired product was pulverized and mixed. After that, refiring was performed at 1450 ° C. for 3 hours. Pulverizing the fired product mixture and washed to a desired _{Y 2 .94 Ce 0 .06 Al 4} .95 Si 0 .05 O 11 .9 N to obtain a phosphor of _{0 0.1.}

About the obtained fluorescent substance, the excitation light (Photo lumisescence Excitation: PLE) measurement and the photo luminescence (PL) measurement were performed as follows.

[PL measurement]

About the obtained fluorescent substance, it carried out in air | atmosphere room temperature atmosphere by the fluorescent spectrophotometer (RF-5300PC: Shimadzu Corporation) using 450 nm as excitation light. The PL intensity emission spectrum of the obtained phosphor is shown in FIG.

[PLE Measure]

About the obtained fluorescent substance, the excitation light wavelength was changed in the room temperature atmosphere in air | atmosphere, and the emission peak wavelength of the fluorescent substance was monitored and measured. PLE intensity (excitation spectrum) with respect to the excitation light wavelength is shown in FIG. 5.

[White Chromaticity]

6 and Table 1 show CIE chromaticity coordinates of the fluorescence emitted from the obtained phosphor. White light determined as the intersection of a black line radiation and a straight line connecting the coordinates of fluorescence and blue light in the same chromaticity diagram by setting the CIE chromaticity coordinates of blue light corresponding to the excitation light of the blue LED to (0.130, O.075). Table 2 shows the chromaticity coordinates of. The color temperature and average color rendering index of this white light were calculated | required by the following method. The results are shown in Table 2.

[White LED Device]

The light emission intensity in the white LED device using the obtained phosphor and blue LED was measured. The results are shown in FIG.

[Examples 2 to 5]

A phosphor was produced in the same manner as in Example 1 except that the amount of powder raw material was changed so that a phosphor having a desired composition was obtained, and the obtained phosphor was subjected to PL measurement and PLE measurement to obtain chromaticity coordinates and colors of white light obtained in the future. Temperature and average color rendering index were calculated | required. The results are shown in FIGS. 4 to 6, Table 1 and Table 2.

[Comparative Example]

As a fluorescent substance, PL measurement and PLE measurement were performed similarly to Example 1 using YAG: Ce, and the chromaticity coordinates, color temperature, and average color rendering index number of the white light obtained in the future were calculated | required. The results are shown in FIGS. 4 to 6, Table 1 and Table 2. In addition, the light emission intensity in the white LED device was measured in the same manner as in Example 1 except that the used phosphor was changed. The results are shown in FIG.

In both Examples and Comparative Examples, the peak wavelength of the excitation light was 450 to 480 nm. In the comparative example, the emission peak wavelength in the PL measurement was around 550 nm, and in the example, the emission peak was shifted to the long wavelength side. On the CIE chromaticity diagram, the blue light corresponding to the blue LED and the white light obtained from the phosphor have a high color temperature and an average color rendering index in the comparative example, and the blue color tone is strong. The average color rendering index all approximates those of electric bulb color or sunlight, and it is shown that it is a hue of natural light. The actual light emission of the white LED coincided with the chromaticity of the white light obtained from the black radiation on the chromaticity diagram.

From the results, the phosphor represented by the composition formula (1) has good luminous efficiency with respect to the excitation source, emits red fluorescence from yellow, and is a color tone that approximates natural light together with blue LElD or the like even when used alone without using another phosphor. It is clear that the white light of is obtained.

This invention is an application based on Japanese Patent Application No. 2007-133076 (application date May 18, 2007), and includes all the contents disclosed in this basic application.

The phosphor of the present invention has a sufficient band gap excited by blue light from an LED or an LD, emits red fluorescence from yellow, and changes the molar ratio of the elements to contain the color tone of the fluorescence emitted from yellow to red. It is possible to modulate sequentially, so that it is easy to obtain a red color tone from the desired yellow color. For this reason, by applying this fluorescent substance to the light emitting device using a blue LED or a blue LD, a light emitting device can emit white light which is excellent in color rendering property, and is excellent in color tone, and has sufficient light emission intensity with good light emission efficiency, and consumes it. The electric power can be reduced and it is useful for various illuminations.

1 is a diagram showing a schematic configuration diagram of an LED element as an example of a light emitting device of the present invention.

Fig. 2 is a diagram showing a schematic sectional view of an FED device as an example of the light emitting device of the present invention.

Fig. 3 is a schematic structural diagram of a VFD device as an example of the light emitting device of the present invention.

4 is a diagram showing a PL intensity emission spectrum of one example of the phosphor of the present invention.

Fig. 5 shows the PLE intensity excitation spectrum of an example of the phosphor of the present invention.

Fig. 6 is a diagram showing a CIE chromaticity diagram of an example of the phosphor of the present invention.

Fig. 7 is a diagram showing the light emission intensity of a white LED device of one example of the fluorescent device of the present invention.

<Explanation of symbols for the main parts of the drawings>

46a, 46b, 46c: phosphor layer

11a, 31b: phosphor

Claims (6)

Formula (1) Y _{3 -a- b} Ce _a L _b Al _{5 - c} Si _c O _{12 - d} N _d (Wherein L represents any one or two or more elements of Gd, La, Tb, Lu, or Sc, a is 0.01 <a <0.50, b is 0.0≤b <2.5, c is 0.0 <c <2.0) , Represents a value satisfying 0.01 <d <2.7. The phosphor according to claim 1, which is excited by light of 400 to 520 nm wavelength and emits red fluorescence from yellow. A method for producing a phosphor according to claim 1 or 2, wherein the compound containing the element constituting the composition formula (1) is calcined under a positive pressure. The fluorescent substance of Claim 1 or 2 was used. The light-emitting device characterized by the above-mentioned. The light emitting device according to claim 4, which is a white diode device having any one or two or more phosphors selected from green phosphors and red phosphors. The light emitting device according to claim 4, which is an electron beam light emitting device having any one or two or more phosphors selected from green phosphors and red phosphors.

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