KR101376334B1 - Transition metal nitride phosphors and its manufacturing method and light emitting device comprising such a phosphor - Google Patents

Abstract

The present invention relates to a transition metal nitride phosphor and a manufacturing method thereof and more specifically, to a transition metal nitride phosphor which exhibits a wide light emission region from green to red, is able to control the particle size of phosphor powders with a self-propagating high-temperature synthesis, has high purity, simplifies processes, is able to reduce process time and is able to reduce manufacturing costs by exhibiting excellent thermal efficiency and productivity, and a manufacturing method thereof.

Description

Transition metal nitride phosphors and its manufacturing method and light emitting device comprising such a phosphor

The present invention relates to a transition metal nitride phosphor and a method for producing the same.

The phosphor is used for a fluorescent display tube (VFD), a field emission display (FED), a plasma display panel (PDP), a cathode ray tube (CRT), a white light emitting diode (LED), and the like. Such phosphors are excited by a high energy excitation source such as vacuum ultraviolet ray, ultraviolet ray, electron beam, blue light and the like to emit visible light.

On the other hand, among the various lighting elements, the light emitting conversion light emitting diode (LED) emitting white light emits a blue Ga (In) N light emitting diode having a wavelength of approximately 450 nm and yellow light as proposed in US Patent No. 5,998,925. YAG that: Ce ^{+ 3} made of a combination of phosphors.

However, white light emitting diodes are used only for general purpose lighting because color rendering is degraded due to the absence of color components (mainly red light components).

In order to overcome this problem, WO98 / 39805 discloses a method of mixing white, red, green, and blue colors to produce white light, and a method of mixing white and green phosphors on a blue LED to produce white light, and a yellow phosphor-blue LED on green. And a method of mixing the red phosphor little by little.

As such, the demand for phosphors absorbing light in the visible region (450 to 470 nm) and emitting photons in the green, yellow and red regions (490 to 540 nm) is rapidly increasing worldwide. Accordingly, development of highly efficient phosphors is also increasing. .

On the other hand, nitride and oxynitride-based phosphors, which are one of the phosphors, have a high degree of covalent bonding of the crystals surrounding the active ions, and thus the excitation and emission spectra are shifted toward the red-shift, thus producing a solid light emitting device. Can contribute significantly. At this time, since the emission spectrum depends on the concentration of the active agent used, the application of color reproduction is excellent.

Japanese Laid-Open Patent Publication No. 2003-515665 discloses a M _x Si _y N _z: Eu a phosphor having a composition of ^{2 +} (M is Ca, Sr, and Ba, alkaline earth metal, z = 2 / 3x + 4 / 3y selected from a) It is starting. The nitride phosphor of red light is prepared by nitriding an alkali earth metal and mixing it with silicon nitride, or by heating under nitrogen or argon atmosphere using alkaline earth metal imide and silicon imide as raw materials. It is starting.

US Patent Publication No. 2007/0040152 discloses a phosphor having a composition of M ₂ Si ₅ N ₈ , MSi ₇ N ₁₀ , MSiN _2, and MeAlSiN ₃ , where M is Mg, Ca, Sr, Ba, etc., and which is substantially free of oxygen. Is described. This method uses nitrides of alkaline earth metals and rare earth metals as starting materials, and has disadvantages such as difficulty in manufacturing the nitride, expensive manufacturing cost, and difficulty in handling.

In addition, currently developed oxynitride-based phosphors include silicon oxynitride-based phosphors in which rare earth metal is added as a luminescent activator to the basic structure of MSi ₂ O ₂ N ₂ (M = Ca, Sr, Ba, Zn) (YQ Li, ACA Delsing, G. de with, and HT Hintzen, Chem. Mater. 2005, 17, 3242-3248) in general, an oxynitride and a nitride phosphor is prepared by the solid phase reaction method is a solid phase reaction method, first, a silicon nitride (Si ₃ N ₄ ), Silicon oxide (SiO ₂ ), calcium carbonate (CaCO ₃ ), calcium nitride (Ca ₃ N ₂ ) europium oxide (europium) (Eu ₂ O ₃ ), etc., are mixed at a predetermined molar ratio to obtain 1 atmosphere (0.1 MPa). In the above nitrogen and hydrogen atmosphere, it is maintained at a high temperature for a long time and manufactured by firing by hot press method.

However, the solid-state reaction method has a high manufacturing cost due to the disadvantage of having to react for a long time at high temperature, and the manufactured phosphor is a spherical powder, there is a problem that the light efficiency compared to the weight in the LED package and settle well.

Therefore, the purity is higher, the light efficiency can be increased, and research to overcome the shortcomings in the process is required.

US Patent No. 5,998,925 (1999.12.07) United States Patent Publication No. 7,537,710 (2009.05.26) Japanese Laid-Open Patent No. 2003-515665 (2003.05.07)

The present invention can exhibit a wide light emitting region from green to red depending on the type and concentration of transition metals, rare earth metals and alkaline earth metals, and can control the particle size of the phosphor powder from submicrons to micro units by a rotating combustion reaction. It is an object to provide a transition metal nitride phosphor that can be.

In addition, an object of the present invention is to provide a transition metal nitride phosphor and a method for producing the same, which has a high purity, a simple manufacturing process, a short process time, excellent productivity, and a low manufacturing cost.

In addition, an object of the present invention is to provide a light emitting device or a LED package with a light emitting area is distributed from green to red and high luminous efficiency.

The present invention can provide a transition metal nitride phosphor represented by the following formula (1).

[Formula 1]

M _2-x R _x T _y S _5-y N _8-y D _2y

(In Formula 1, M is alkaline earth metal, R is rare earth metal, T is transition metal, S is metalloid, N is nitrogen, D is halogen element, x and y are 0 <x≤2 and 0≤y≤ It's a mistake that satisfies 5.)

In the transition metal nitride phosphor according to an embodiment of the present invention, x may be 0 <x <2.

In the transition metal nitride phosphor according to an embodiment of the present invention, y may be 0 <y≤4.

The present invention (a) alkaline earth metal halides; Rare earth metal oxides; Transition metal halides; Metalloids and metalloids; Mixing a reducing agent; to provide a reaction mixture;

(b) rotating the reaction mixture in a high pressure reactor under an inert gas atmosphere; And

It may provide a method for producing a transition metal nitride phosphor comprising a; (c) washing and leaching the product of step (b).

In the method for producing a transition metal nitride phosphor according to an embodiment of the present invention, the phosphor to be prepared may be represented by the following formula (1).

[Formula 1]

M _{2 -x} R _x T _y S _{5 -y} N _{8 -y} D _2y

(In Formula 1, M is alkaline earth metal, R is rare earth metal, T is transition metal, S is metalloid, N is nitrogen, D is halogen element, x and y are 0 <x≤2 and 0≤y≤ It's a mistake that satisfies 5.)

In the method for preparing a transition metal nitride phosphor according to an embodiment of the present invention, the alkaline earth metal halide is MgF ₂ , CaF ₂ , SrF ₂ , BaF ₂ , MgCl ₂ , CaCl ₂ , SrCl ₂ , BaCl ₂ , MgBr ₂ , It may be any one or a mixture of two or more selected from CaBr ₂ , SrBr ₂ , BaBr ₂ , MgI ₂ , CaI ₂ , SrI ₂ and BaI ₂ .

In the method for preparing a transition metal nitride phosphor according to an embodiment of the present invention, the rare earth metal oxide is La ₂ O ₃ , CeO ₂ , Pr ₂ O ₃ , Nd ₂ O ₃ , Sm ₂ O ₃ , Eu ₂ O ₃ , Gd ₂ O ₃ , Tb ₂ O ₃ , Dy ₂ O ₃ , Ho ₂ O ₃ , Er ₂ O ₃ , Tm ₂ O ₃ , Yb ₂ O ₃ and Lu ₂ O ₃ It may be any one or a mixture of two or more selected from.

In the method for producing a transition metal nitride phosphor according to an embodiment of the present invention, the transition metal halide is ScF ₃ , YF ₃ , ZrF ₄ , VF ₃ , ScCl ₃ , YCl ₃ , ZrCl ₄ , and VCl ₃ It may be any one or a mixture of two or more selected from.

In the method for producing a transition metal nitride phosphor according to an embodiment of the present invention, the metalloid and metalloid compound are any one selected from silicon (Si), germanium (Ge) and sodium silicon fluoride (Na ₂ SiF ₄ ) or It may comprise two or more mixtures.

In the method for producing a transition metal nitride phosphor according to an embodiment of the present invention, the reducing agent is any one selected from lithium azide (LiN ₃ ), sodium azide (NaN ₃ ) and potassium azide (KN ₃ ) It may be one or a mixture of two or more.

In the method for preparing a transition metal nitride phosphor according to an embodiment of the present invention, the reducing agent may be included in 1 to 20 moles with respect to 1 mole of alkaline earth metal halides.

The present invention can provide a light emitting device comprising the transition metal nitride phosphor.

The present invention can provide an LED package including the transition metal nitride phosphor.

The transition metal nitride phosphor according to the present invention has an advantage of showing a wide light emitting area from green to red depending on the type and concentration of the transition metal, the rare earth metal and the alkaline earth metal. In addition, the present invention can provide a transition metal nitride phosphor that can be produced by the autogenous combustion reaction to control the particle size of the phosphor powder in submicrons to micro units.

In addition, the manufacturing method of the transition metal nitride phosphor according to the present invention has the advantage of very high purity, simple process, shorten the processing time, excellent thermal efficiency and productivity can reduce the manufacturing cost.

In addition, the present invention can provide a light emitting device and an LED package including a transition metal nitride phosphor having a light emitting area is distributed from green to red and excellent in luminous efficiency.

1 is a scanning electron micrograph of the transition metal nitride phosphor powder prepared in Example 1 of the present invention,
Figure 2 is a scanning electron micrograph of the transition metal nitride phosphor powder prepared in Example 2 of the present invention,
3 is a scanning electron micrograph of the transition metal nitride phosphor powder prepared in Example 3 of the present invention,
Figure 4 shows the results of the X-ray diffraction analysis of the oxynitride phosphor powder prepared in Examples 1 to 4 of the present invention,
Figure 5 shows the emission spectrum of the transition metal nitride phosphor powder prepared in Example 1 of the present invention,
Figure 6 shows the emission spectrum of the transition metal nitride phosphor powder prepared in Example 2 of the present invention,
7 is a view showing an emission spectrum of the transition metal nitride phosphor powder prepared in Example 3 of the present invention.

The present invention can provide a transition metal nitride phosphor represented by the following formula (1).

[Formula 1]

M _2-x R _x T _y S _5-y N _8-y D _2y

At this time, in Formula 1, M is an alkaline earth metal, R is a rare earth metal, T is a transition metal, S is a metalloid, N is nitrogen, D is a halogen element, and x and y are 0 <x≤2 and 0≤y≤ 5 is a mistake.

The transition metal nitride phosphor contains a transition metal and can maximize the purity and luminous efficiency of the phosphor while distributing a light emitting region from green to red according to the transition metal, alkaline earth metal and rare earth metal.

The M may be any one or more elements selected from alkaline earth metals including magnesium (Ma), calcium (Ca), strontium (Sr), and barium (Ba).

The R is lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), samarium (Sm), europium (Eu), gadolinium (Gd) which can enter the activator to the transition metal nitride crystal structure ), At least one selected from the group consisting of terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb) and lutetium (Lu) It can be an element.

The S may be any one or more elements selected from metalloids (Si) and germanium (Ge), N is selected from halogen elements including nitrogen (N), D is fluorine (F) and chlorine (Cl) It may be any one or more elements.

In the transition metal nitride phosphor according to an embodiment of the present invention, x may be 0 <x <2. Alkaline earth metal is preferably included to prepare the phosphor according to the present invention by a self-burning synthesis method, it is possible to maximize the luminous efficiency by including the alkaline earth metal. In this case, if the method of synthesizing the phosphor is a conventional method other than the autocombustion synthesis method, the alkaline earth metal is not necessarily included.

In the transition metal nitride phosphor according to an embodiment of the present invention, y may be 0 <y≤4. According to one embodiment of the present invention, the metalloid and metalloid compound may participate in the self-burning synthesis to increase reactivity, but may not be included. However, it is preferable to have the above range in order to express luminous efficiency and a wide luminous area.

In the transition metal nitride phosphor according to the embodiment of the present invention, x and y may be 0 <x <2 and 0 <y ≦ 4, respectively. The transition metal nitride phosphor according to the above range is more chemically stable and may exhibit excellent luminous efficiency.

In the transition metal nitride phosphor according to an embodiment of the present invention, the powder particle size of the phosphor may be 20 μm or less, and more preferably 12 μm or less.

The transition metal nitride phosphor according to the present invention has an excellent luminous efficiency, has a long excitation wavelength region, and has a light emission wavelength of several regions, which is advantageous in that it can be applied to LED devices emitting various kinds of wavelengths.

The present invention can provide a method for producing a transition metal nitride phosphor having high purity, excellent light efficiency, simple manufacturing process, and low mass production.

Method for producing a transition metal nitride phosphor of the present invention,

(a) alkaline earth metal halides; Rare earth metal oxides; Transition metal halides; Metalloids and metalloids; Mixing a reducing agent; to provide a reaction mixture;

(b) rotating the reaction mixture in a high pressure reactor under an inert gas atmosphere; And

(c) washing and leaching the product of step (b).

In the method for producing a transition metal nitride phosphor according to an embodiment of the present invention, the phosphor to be prepared may be represented by the following formula (1).

[Formula 1]

M _{2 -x} R _x T _y S _{5 -y} N _{8 -y} D _2y

In Formula 1, M is an alkaline earth metal, R is a rare earth metal, T is a transition metal, S is a metalloid, N is nitrogen, D is a halogen element, and x and y are 0 <x≤2 and 0≤y≤5 It is a mistake to satisfy.

At this time, x and y in the general formula (1) is preferably a chemically stable compound 0 <x <2, 0 <y ≤ 4 in order to have excellent light efficiency.

The transition metal nitride phosphor according to the present invention satisfies the above formula (1) and is preferably 20 μm or less, more preferably 12 μm or less in powder form.

In the method for preparing a transition metal nitride phosphor according to an embodiment of the present invention, the alkaline earth metal halide may be any one or more selected from magnesium halide, calcium halide, strontium halide and barium halide, and specifically, _{MgF 2, CaF 2, SrF 2} , BaF 2, MgCl 2, CaCl 2, SrCl 2, BaCl 2, MgBr 2, CaBr 2, SrBr 2, BaBr 2, MgI 2, CaI 2, SrI 2 , and BaI ₂ It may be any one or a mixture of two or more selected from.

The alkaline earth metal halide reacts with the reducing agent in step (b) to cause an exothermic reaction and to form a transition metal nitride phosphor due to the heat generated during the reduction nitridation reaction.

In the method for preparing a transition metal nitride phosphor according to an embodiment of the present invention, the rare earth metal oxide is La ₂ O ₃ , CeO ₂ , Pr ₂ O ₃ , Nd ₂ O ₃ , Sm ₂ O ₃ , Eu ₂ O ₃ , Gd ₂ O ₃ , Tb ₂ O ₃ , Dy ₂ O ₃ , Ho ₂ O ₃ , Er ₂ O ₃ , Tm ₂ O ₃ , Yb ₂ O ₃ and Lu ₂ O ₃ It may be any one or a mixture of two or more selected from. The rare earth metal oxide is selected from La ₂ O ₃ , CeO ₂ , Nd ₂ O ₃ , Sm ₂ O ₃ , Eu ₂ O ₃ , Gd ₂ O ₃ , Tb ₂ O ₃ , Er ₂ O ₃ and Yb ₂ O ₃ Any one or more may be more preferable.

The rare earth metal oxide is added to the transition metal nitride phosphor as an activator so that when the transition metal nitride phosphor receives energy from the outside, it can be excited and emit light.

In the method for producing a transition metal nitride phosphor according to an embodiment of the present invention, the transition metal halide is ScF ₃ , YF ₃ , ZrF ₄ , VF ₃ , ScCl ₃ , YCl ₃ , ZrCl ₄ , and VCl ₃ It may be any one or a mixture of two or more selected from.

The transition metal halide reacts with a reducing agent such as an alkaline earth metal halide in step (b) to cause an exothermic reaction and to form a transition metal nitride phosphor due to heat generated during the reduction nitridation reaction. At this time, by being located in the metalloid position in the transition metal nitride lattice it is involved in the energy transfer to change the excitation and emission wavelength and to reduce the energy loss to increase the luminous efficiency.

In the method for producing a transition metal nitride phosphor according to an embodiment of the present invention, the metalloid and metalloid compound are any one selected from silicon (Si), germanium (Ge) and sodium silicon fluoride (Na ₂ SiF ₄ ) or It may comprise two or more mixtures.

The metalloid and metalloid compound are intended to cause an exothermic reaction required in the autogenous combustion reaction, and the metalloid may have a particle size of 0.1 to 15 μm in powder form in order to cause an active combustion reaction. In addition, the number of moles of the entire metalloid in the general formula (1) may be 1 to 5.

In the method for producing a transition metal nitride phosphor according to an embodiment of the present invention, the reducing agent is any one selected from lithium azide (LiN ₃ ), sodium azide (NaN ₃ ) and potassium azide (KN ₃ ) It may be one or a mixture of two or more. The reducing agent may reduce alkaline earth metal halides, rare earth metal oxides and transition metal halides, and are converted to LiF, LiCl, NaF, NaCl, KF, KCl after the autogenous combustion reaction, which is removed by leaching in step (c). Can be.

In the method for preparing a transition metal nitride phosphor according to an embodiment of the present invention, the reducing agent may be included in 1 to 20 moles with respect to 1 mole of alkaline earth metal halides. Outside the above range, the reduction reaction or leaching may not be made well.

In the method for producing a transition metal nitride phosphor according to an embodiment of the present invention, it may be made by mixing alkaline earth metal halides, rare earth metal oxides, transition metal halides, metalloids and metalloids, reducing agents, The method is not limited, but mixing by ball mill may be preferred for rapid processing and uniform mixing.

The reaction mixture obtained by the mixing can be filled into a container to form pellets, the container can be a cup, and the cup can be cylindrical or cuboid.

The cup can be made from various kinds of components such as paper, metal or quartz, and the density of the obtained pellets has a density of 0.7 to 2.0 g / cm ³ , preferably 0.9 to 1.2 g / cm ³ during the autogenous combustion reaction. The ignition and combustion reaction may be made smoothly, but is not necessarily limited thereto.

The pelletized reaction mixture may be complexed from a heat source to initiate a combustion reaction, and the heat source may use a heat source due to metal wire resistance.

The combustion process used in the present invention is preferably carried out under high pressure conditions, it can be carried out in a high pressure reactor under a nitrogen atmosphere. At this time, the reaction pressure of nitrogen may be 0.5 to 5MPa, preferably 1 to 3MPa.

The self-sustaining reaction is a self-sustaining reaction, and when the reaction is initiated by the ignition reaction, there is no need for supplying an external heat source thereafter. have.

The transition metal nitride phosphor of the present invention can be obtained by washing and leaching the product after the autogenous combustion reaction.

The washing may use a conventional method, it is preferred to use distilled water, it can be washed one or more times.

The leaching may use a conventional method, it is preferable to use a hydrochloric acid solution or sulfuric acid solution in order to prevent the light efficiency of the transition metal nitride phosphor prepared due to impurities.

The present invention can provide a light emitting device or LED package including the transition metal nitride phosphor described above.

Hereinafter, it will be described in detail based on the embodiment according to the present invention.

Example 1

Strontium chloride (SrCl ₂ , large gold), urobium oxide (Eu ₂ O ₃ , Alfa Aesar), yttrium chloride (YCl ₃ , KANTO, Y0030), silicon (Si, trielectric chemistry, S2381), sodium azide ( NaN ₃ , large purified gold, 255S0074) powders were weighed in a molar ratio of 1.97: 0.03: 1.0: 4.0: 7.0, and zirconia balls were mixed at a 1/2 weight ratio of the raw materials and mixed with a ball mill for 24 hours. The mixture was placed in a high-purity alumina refractory container, laminated at 5 Mpa, pressurized to 5 Mpa, and then placed in a reactor, followed by a purge process of charging and evacuating nitrogen gas three times, followed by maintaining the inside of the reactor by filling with 50 atm of nitrogen gas. . The laminated raw materials were synthesized by ignition using a hot wire to cause the autogenous combustion reaction to occur. The synthesized powder was washed twice, mixed with HCl solution at pH 1, stirred for 2 hours, and then separated and recovered to wash the powder. The recovered powder was dried at 100 ° C. for 2 hours to prepare a transition metal nitride phosphor powder.

The obtained transition metal nitride phosphor powder was evaluated for chemical composition analysis by X-ray diffraction analysis, particle shape and size by electron microscope.

In addition, in order to evaluate the optical properties of the obtained transition metal nitride phosphor powder, an excitation spectrum at a detection wavelength of 470 to 700 nm and a light emission spectrum at an excitation wavelength of 450 nm using a fluorescence measuring apparatus (FP-6500 manufactured by JASCO Corporation). Was measured.

A scanning electron microscope photograph is shown in FIG. 1, and as shown in FIG. 1, it can be seen that the average particle size of the powder is 10.0 μm or less, and the aggregation between particles is small and well dispersed.

4 shows that the X-ray diffraction results of the transition metal nitride phosphor powder prepared in Example 1 were prepared as pure crystalline transition metal nitride phosphors containing no other impurities.

Figure 5 shows the emission spectrum of the transition metal nitride phosphor powder prepared in Example 1, it can be seen that the emission spectrum of 550 to 800nm with 631nm as a peak.

[Example 2]

Strontium chloride (SrCl ₂ , large gold), urobium oxide (Eu ₂ O ₃ , Alfa Aesar), yttrium chloride (YCl ₃ , KANTO, Y0030), silicon (Si, trielectric chemistry, S2381), sodium azide ( A transition metal nitride phosphor powder was prepared in the same manner as in Example 1, except that NaN ₃ , large purified gold, and 255S0074) powder were weighed and mixed in a molar ratio of 1.97: 0.03: 0.5: 4.5: 5.5.

The particle shape, size and emission spectrum of the transition metal nitride phosphor powder obtained in the above process were measured and observed in the same manner as in Example 1.

Figure 2 shows a scanning electron micrograph of the phosphor according to Example 2, as can be seen that the average particle size of the powder is less than 10.0㎛, it was confirmed that the aggregation between the particles is small and well achieved.

Figure 4 shows the X-ray diffraction results of the transition metal nitride phosphor powder prepared in Example 2, it can be seen that a pure crystalline transition metal nitride phosphor containing no other impurities as shown.

Figure 6 shows the emission spectrum of the transition metal nitride phosphor powder prepared in Example 2, it was confirmed that the emission spectrum of 530 to 800nm with a peak of 630nm.

[Example 3]

Strontium chloride (SrCl ₂ , large gold), cerium oxide (CeO ₂ , Alfa Aesar), scandium chloride (ScCl ₃ , ALDRICH, 451274), silicon (Si, trielectric chemistry, S2381), sodium azide (NaN ₃ , Large crystal gold, 255S0074) The transition metal nitride phosphor powder was prepared in the same manner as in Example 1 except that the powder was weighed and mixed at a molar ratio of 1.97: 0.03: 0.5: 4.5: 5.5.

The particle shape, size and emission spectrum of the obtained transition metal nitride phosphor powder were measured and observed in the same manner as in Example 1.

3 shows a scanning electron micrograph of the phosphor according to Example 3, and as shown, the average particle size of the powder was 10.0 μm or less, and it was confirmed that the aggregation between the particles was small and well achieved.

Figure 4 shows the X-ray diffraction results of the transition metal nitride phosphor powder prepared in Example 3, it can be seen that a pure crystalline transition metal nitride phosphor containing no other impurities as shown.

Figure 7 shows the emission spectrum of the transition metal nitride phosphor powder prepared in Example 3, it was confirmed that the emission spectrum of 470 to 700nm with a peak of 489nm and 530nm.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed embodiments, but, on the contrary, Various modifications and variations are possible in light of the above teachings.

Accordingly, the spirit of the present invention should not be construed as being limited to the embodiments described, and all of the equivalents or equivalents of the claims, as well as the following claims, belong to the scope of the present invention .

Claims (8)

(a) alkaline earth metal halides; La ₂ O ₃ , CeO ₂ , Pr ₂ O ₃ , Nd ₂ O ₃ , Sm ₂ O ₃ , Eu ₂ O ₃ , Gd ₂ O ₃ , Tb ₂ O ₃ , Dy ₂ O ₃ , Ho ₂ O ₃ , Er ₂ Rare earth metal oxides which are any one or a mixture of two or more selected from O ₃ , Tm ₂ O ₃ , Yb ₂ O ₃ and Lu ₂ O ₃ ; Transition metal halides which are any one or a mixture of two or more selected from ScF ₃ , YF ₃ , ZrF ₄ , VF ₃ , ScCl ₃ , YCl ₃ , ZrCl ₄ , and VCl ₃ ; A metalloid which is at least one element selected from silicon and germanium; Mixing a reducing agent of any one or two or more selected from lithium azide, sodium azide and potassium azide; providing a reaction mixture;
(b) rotating the reaction mixture in a high pressure reactor under an inert gas atmosphere;
(c) washing and leaching the product of step (b). The method of claim 1,
The phosphor is a method for producing a transition metal nitride phosphor represented by the following formula (1).
[Chemical Formula 1]
M _{2 -x} R _x T _y S _{5 -y} N _{8 -y} D _2y
(In Formula 1, M is alkaline earth metal, R is rare earth metal, T is transition metal, S is metalloid, N is nitrogen, D is halogen element, x and y are 0 <x≤2 and 0≤y≤ It's a mistake that satisfies 5.) The method of claim 1,
The alkaline earth metal halide is _{MgF 2, CaF 2, SrF 2} , BaF 2, MgCl 2, CaCl 2, SrCl 2, BaCl 2, MgBr 2, CaBr 2, SrBr 2, BaBr 2, MgI 2, CaI 2, SrI 2 And BaI ₂ Method of producing a transition metal nitride phosphor which is any one or a mixture of two or more selected from. delete delete delete delete The method of claim 1,
The reducing agent is a method for producing a transition metal nitride phosphor containing 1 to 20 moles per 1 mole of alkaline earth metal halide.

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