KR102415650B1 - Oxy-nitride phosphor and light emitting device package - Google Patents

Abstract

The present invention relates to a phosphor, and more particularly, to an oxynitride phosphor and a light emitting device package using the same. According to the present invention, in the oxynitride phosphor, diffraction angles 2θ by X-ray diffraction are 10.7 to 11.7°, 14.2 to 15.2°, 16.3 to 17.3°, 21.6 to 22.6°, 23.2 to 24.2°, 27.4 to 28.4°, 30.3 to 30.8 °, 30.8 to 31.8 °, 31.0 to 32.0 °, 31.4 to 32.4 °, 31.7 to 32.7 °, 32.6 to 33.6 °, 33.1 to 34.1 °, 33.3 to 34.3 °, 33.7 to 34.7 °, 36.8 to 37.8 °, It is possible to provide an oxynitride phosphor having clear peaks in the respective ranges of 37.0 to 38.0°, 37.7 to 38.7°, 38.4 to 39.4° and 38.8 to 39.8°.

Description

Oxynitride phosphor and light emitting device package using same {Oxy-nitride phosphor and light emitting device package}

The present invention relates to a phosphor, and more particularly, to an oxynitride phosphor and a light emitting device package using the same.

A light emitting diode (LED) is one of the next-generation light emitting device candidates that can replace a fluorescent lamp, which can be said to be the most representative of existing general lighting.

LED consumes less power than conventional light sources, and unlike fluorescent lamps, it does not contain mercury, so it can be said to be eco-friendly. In addition, compared to the conventional light source, it has a long lifespan and a fast response speed.

Such an LED may be used together with a phosphor that absorbs light emitted from the LED and emits light of various colors. Such phosphors are usually capable of emitting yellow, green and red light.

LED lighting using such a phosphor and a blue light emitting LED is being expanded and applied very quickly in real life.

As described above, although the spread of LED lighting is progressing very rapidly, high quality of the light is required accordingly. Specifically, white LED lighting with high color rendering is required, and white LED lighting produced from phosphors currently in practical use lacks color rendering.

In order to improve color rendering, it is necessary to adjust the emission spectrum close to a continuous spectrum such as sunlight.

Various phosphors have been developed so far, but among them, oxynitride appears to be a promising host crystal due to its chemical stability.

Prior Patent Document 1 proposes a phosphor having a MSi ₂ O ₂ N ₂ composition (M is Ca, Sr, Ba), and it is possible to obtain light emission in a green to yellow wavelength region using Eu as an activator. have.

Prior Patent Document 2 proposes a phosphor using a rare earth element as an activator in MSi ₃ O4N ₂ crystals (M is Ca, Sr, Ba), and also reports green to yellow light emission.

Prior Patent Document 3 proposes a phosphor using Eu as an activator in Ba ₂ Si ₇ O ₁₀ N ₄ crystals as a representative composition, and green light emission is reported.

In Prior Patent Document 4, Sr ₂ Si ₄ ON ₆ :Eu, Sr ₃ Si ₇ ON ₁₀ :Eu, Sr ₃ Si ₈ ON ₁₂ :Eu, Sr ₃ Si ₈ ON ₁₂ :Eu, Sr ₄ Si ₇ O ₃ N ₁₀ : Eu, Sr ₂ Si _{3 O 2} N ₄ :Eu, Sr _{2 .6} Ba _0.2 Si _{6 O 3} N ₈ :Eu _{0.2 , Sr 1.5 Ba 1.5 Si 7 ON 10 :} Eu, _{SrBa 2} Many phosphors of the MSiON family, such as Si ₇ ON ₁₀ :Eu, have been proposed, and all of them emit green light.

However, the half width at half maximum of luminescence of the phosphors disclosed in these prior patent documents is 100 nm or less, and sufficient peak diffusion is not shown to obtain high color rendering properties.

Accordingly, it is required to implement a phosphor having a wide half maximum width of an emission spectrum capable of realizing high color rendering properties.

1. International Patent Application (PCT) Publication No. WO2004/030109 2. Japanese Patent Laid-Open No. 2007-223864 2. Japanese Patent Laid-Open No. 2008-138156 4. US Patent Publication No. 2011/0163322

An object of the present invention is to provide an oxynitride phosphor capable of realizing a phosphor having a wide half maximum width of an emission spectrum in the oxynitride phosphor, and a light emitting device package using the same.

In order to achieve the above technical object, the present invention, in the oxynitride phosphor, the diffraction angle 2θ by X-ray diffraction is 10.7 to 11.7 °, 14.2 to 15.2 °, 16.3 to 17.3 °, 21.6 to 22.6 °, 23.2 to 24.2 ° , 27.4 to 28.4 °, 30.3 to 30.8 °, 30.8 to 31.8 °, 31.0 to 32.0 °, 31.4 to 32.4 °, 31.7 to 32.7 °, 32.6 to 33.6 °, 33.1 to 34.1 °, 33.3 to 34.3 °, 33.7 to 34.7 ° , 36.8 to 37.8 °, 37.0 to 38.0 °, 37.7 to 38.7 °, 38.4 to 39.4 °, and 38.8 to 39.8 °, it is possible to provide an oxynitride phosphor having clear peaks.

Here, the oxynitride phosphor is a composition containing at least an M element, an A element, an N element, an O element, and an R element and is expressed by the general formula MaAbOcNd:Re, wherein M is Mg, Ca, Sr, Ba, Zn and One or more elements selected from divalent rare earth elements other than R, A is one or more elements selected from the group consisting of tetravalent metal elements, O is oxygen, N is nitrogen, and R is one or more elements selected from Mn, Ce, Pr, Nd, Sm, Eu, Tb, Dy, Ho, Er, Tm, and Yb, and the M element, A element, N element, and O The element R is: 2.5 ≤ (a + e) ≤ 3.5, 7.5 ≤ b ≤ 8.5, 3 ≤ c ≤ 5, 9 ≤ d ≤ 11, 13 ≤ (c + d) ≤ 15, and 0.0001 ≤ e ≤ 0.2 may have a composition of

Here, each parameter of the general formula may satisfy at least one of (a + e) = 3, b = 8, c = 4, and d = 10.

Here, the M element may be Sr.

Here, the M element is a mixture of Sr and Ca, and may be Ca/(Sr + Ca) < 0.40 when calculated by the number of atoms included.

Here, the element A may be Si.

Here, the R element may be Eu.

Here, the oxynitride phosphor is a composition containing at least an element M, element A, element B, element C, element N, element O, and element R, and is expressed by the general formula MaBfAbCgOcNd:Re, wherein M is Mg, Ca, One or more elements selected from divalent rare earth elements other than Sr, Ba, Zn and R elements, wherein A is one or more elements selected from the group consisting of tetravalent metal elements, and B is 3 Sc, Y, La, Ce, Pr, Nd, Sm, Gd, Tb, Dy, Ho, Er, Tm, Yb, one or more elements selected from Lu, wherein C is selected from Al, Ga, In One or more elements selected from the group consisting of O is oxygen, N is nitrogen, R is Mn, Ce, Pr, Nd, Sm, Eu, Tb, Dy, Ho, Er, Tm, Yb species or two or more elements, wherein the M element, A element, B element, C element, N element, O element, and R element are 2.5 ≤ (a + e + f) ≤ 3.5, 7.5 ≤ (b + g) ≤ 8.5, 3 ≤ c ≤ 5, 9 ≤ d ≤ 11, 13 ≤ (c + d) ≤ 15, 0.0001 ≤ e ≤ 0.2, and f = g.

Here, each parameter of the general formula may satisfy at least one of (a + e + f) = 3, (b + g) = 8, c = 4, and d = 10.

Here, the M element may be Sr.

Here, the element A may be Si.

Here, the B element may be La.

Here, the C element may be Al.

Here, the R element may be Eu.

Here, the peak points of the emission spectrum excited by blue light may be 560 nm or more and 640 nm or less.

Here, the half width of the emission spectrum excited by the blue light may be 110 nm or more and 130 nm or less.

According to the present invention, as an oxynitride phosphor having a novel crystal structure, there is an effect that a phosphor emitting light having a wide emission spectrum half maximum width can be obtained.

1 is a diagram showing simulated XRD patterns for the crystal structures of Example 1 and Comparative Example 1 of the present invention.
FIG. 2 is a diagram showing emission spectra by 450 nm excitation light of Example 1 and Comparative Example 1 of the present invention.
3 is a view showing emission spectra of Examples 1 to 4 and Comparative Example 3 of the present invention.
4 is a diagram showing emission spectra by excitation light at 450 nm in Examples 1 and 5 to 10 of the present invention in which the amount of Eu is changed.
5 is a diagram showing emission spectra by 450 nm excitation light of Example 11 and Comparative Example 4 of the present invention to which La is added.
6 is a cross-sectional view showing an example of a light emitting device package in which the oxynitride phosphor of the present invention is used.
7 is a cross-sectional view showing another example of a light emitting device package in which the oxynitride phosphor of the present invention is used.

Hereinafter, embodiments according to the present invention will be described in detail with reference to the accompanying drawings.

While the invention is susceptible to various modifications and variations, specific embodiments thereof are illustrated and illustrated in the drawings and will be described in detail hereinafter. However, it is not intended to limit the invention to the particular form disclosed, but rather the invention includes all modifications, equivalents and substitutions consistent with the spirit of the invention as defined by the claims.

It will be understood that when an element, such as a layer, region, or substrate, is referred to as being “on” another component, it may be directly on the other element or intervening elements in between. .

Although the terms first, second, etc. may be used to describe various elements, components, regions, layers and/or regions, such elements, components, regions, layers and/or regions are not It will be understood that they should not be limited by these terms.

According to the present invention, in the oxynitride phosphor, the diffraction angle 2θ by X-ray diffraction is 10.7 to 11.7 °, 14.2 to 15.2 °, 16.3 to 17.3 °, 21.6 to 22.6 °, 23.2 to 24.2 °, 27.4 to 28.4 °, 30.3 to 30.8 °, 30.8 to 31.8 °, 31.0 to 32.0 °, 31.4 to 32.4 °, 31.7 to 32.7 °, 32.6 to 33.6 °, 33.1 to 34.1 °, 33.3 to 34.3 °, 33.7 to 34.7 °, 36.8 to 37.8 °, It is possible to provide an oxynitride phosphor having clear peaks in the respective ranges of 37.0 to 38.0°, 37.7 to 38.7°, 38.4 to 39.4° and 38.8 to 39.8°.

As a means for obtaining such an X-ray diffraction pattern, a composition containing at least M element, A element, N element, O element, and R element is expressed by the general formula (1) MaAbOcNd:Re, and M is Mg, Ca, Sr , Ba, Zn, and one or more elements selected from divalent rare earth elements other than R elements, A is one or more elements selected from the group consisting of tetravalent metal elements, O is oxygen, and N is Nitrogen and R are one or more elements selected from Mn, Ce, Pr, Nd, Sm, Eu, Tb, Dy, Ho, Er, Tm, and Yb, and M element, A element, N element, O The element R is: 2.5 ≤ (a + e) ≤ 3.5, 7.5 ≤ b ≤ 8.5, 3 ≤ c ≤ 5, 9 ≤ d ≤ 11, 13 ≤ (c + d) ≤ 15, and 0.0001 ≤ e ≤ 0.2 The above X-ray diffraction pattern can be obtained by synthesizing a phosphor having a composition of .

Here, each parameter of the general formula (1) may satisfy at least one of (a + e) = 3, b = 8, c = 4, and d = 10.

Here, the M element may be Sr.

In addition, element M is a mixture of Sr and Ca, and may be Ca/(Sr + Ca) < 0.40 when calculated by the number of atoms included.

Here, element A may be Si. In addition, the R element may be Eu.

On the other hand, as a means for obtaining such an X-ray diffraction pattern, a composition containing at least an M element, A element, B element, C element, N element, O element, and R element is represented by the general formula (2) MaBfAbCgOcNd:Re, , M is one or more elements selected from divalent rare earth elements other than Mg, Ca, Sr, Ba, Zn and R elements, and A is one or more selected from the group consisting of tetravalent metal elements Element, B is trivalent Sc, Y, La, Ce, Pr, Nd, Sm, Gd , Tb, Dy, Ho, Er, Tm, Yb, Lu, one or two or more elements selected from, wherein C is Al , Ga, In one or two or more elements selected from, O is oxygen, N is nitrogen, R is Mn, Ce, Pr, Nd, Sm, Eu, Tb, Dy, Ho, Er, Tm, Yb selected from one or two or more elements, and the M element, A element, B element, C element, N element, O element, and R element are 2.5 ≤ (a + e + f) ≤ 3.5, 7.5 ≤ (b + g ) ≤ 8.5, 3 ≤ c ≤ 5, 9 ≤ d ≤ 11, 13 ≤ (c + d) ≤ 15, 0.0001 ≤ e ≤ 0.2, f = g. can

Here, each parameter of the general formula (2) may satisfy at least one of (a + e + f) = 3, (b + g) = 8, c = 4, and d = 10.

Here, the M element may be Sr. In addition, element A may be Si. In addition, element B may be La. In addition, the C element may be Al. In addition, the R element may be Eu.

Here, the peak point of the emission spectrum excited by blue light may be 560 nm or more and 640 nm or less for the phosphor expressed by the general formula (1) or (2) and having the composition described above.

Here, the fluorescent substance represented by the general formula (1) or (2) and having the composition described above may have a half maximum width of an emission spectrum excited by blue light of 110 nm or more and 130 nm or less.

<Example>

Hereinafter, a method for synthesizing the oxynitride phosphor of the present invention will be described. However, the present invention is not limited to this synthesis method.

First, as a raw material for oxynitride, a carbonate or oxide of element M, an oxide of element A, nitride of element A, oxide of element B, nitride of element C, and oxide of element R are mixed until a predetermined non-uniformity is obtained. As the M element raw material, a metal nitride, a hydride, or the like may be used. As element A, element B, and element C, respective oxides, nitrides, and single substances may be used. In addition, an alloy of some constituent elements of the material and oxides and nitrides of the alloy may be used. However, a nitrogen feedstock is always included in the composition.

Hereinafter, it is possible to have sufficient properties to withstand even the approximate compositional values of the raw materials (or the values before and after such compositions) shown in Examples.

Meanwhile, a material acting as a flux, for example, CaF ₂ , SrF ₂ , NaCl, KCl, CaCl ₂ , SrCl ₂ and the like may be mixed at the same time.

These raw material mixtures are placed in a boron nitride crucible or the like and calcined in a reducing atmosphere or inert atmosphere at 1500 to 1900°C. In addition to boron nitride crucibles, molybdenum crucibles and tungsten crucibles may be used.

The calcination temperature is more preferably a calcination temperature of 1600 to 1800°C. The calcination time is 3 hours or longer, more preferably 6 hours or longer.

The reducing atmosphere is a nitrogen-hydrogen atmosphere, an ammonia atmosphere and a nitrogen-ammonia atmosphere. The inert atmosphere is a nitrogen atmosphere.

In addition, a desired phosphor could be obtained by further mixing and firing the remaining materials in one fired product obtained by mixing and firing some of these materials.

The calcined product thus obtained is pulverized and washed with water from which impurities such as distilled water or purified water have been removed, or with a strong acid such as nitric acid, hydrochloric acid or sulfuric acid.

The oxynitride of this embodiment is not limited by such a manufacturing method. It can be prepared according to the gas phase reaction liquid phase reaction as well as the solid phase reaction described above.

Table 1 below shows the composition of each Example described below.

composition (g) SrCO ₃ CaCO ₃ Si ₃ N ₄ SiO ₂ Eu ₂ O ₃ La ₂ O ₃ AlN Example 1 1.1133 0.9596 0.0271 Example 2 0.8777 0.1520 0.9467 0.0267 Example 3 0.7289 0.1901 0.9472 0.1336 Example 4 0.6790 0.2301 0.9559 0.1348 Example 5 1.0484 0.9129 0.0386 Example 6 1.0365 0.9120 0.0514 Example 7 1.0128 0.9101 0.0771 Example 8 0.9892 0.9082 0.1025 Example 9 0.9657 0.9063 0.1279 Example 10 0.9074 0.9017 0.1909 Example 11 0.8555 0.8694 0.1275 0.1180 0.0297 Comparative Example 1 1.1514 0.6166 0.2039 0.0280 Comparative Example 2 1.1044 0.8923 0.0764 0.0269 Comparative Example 3 0.6745 0.3153 0.9823 0.0277 Comparative Example 4 0.8537 0.9014 0.1272 0.1178

<Example 1>

After weighing the raw materials SrCO ₃ , Si ₃ N ₄ , and Eu ₂ O ₃ of the values shown in Table 1, mix them for 30 minutes or more using a bowl to form pellets, and then put them in a boron nitride crucible for N ₂ Firing is performed for about 4 hours at about 1700°C and about 0.9 MPa in a pressurized inert atmosphere using gas.

After calcination, pulverize in a bowl, wash with 1 N aqueous nitric acid solution at room temperature for 15 minutes, and collect sedimentation. Thereafter, the phosphor can be obtained by washing twice to remove the acid.

<Example 2> (Ca employment 20%)

After weighing the raw materials CaCO ₃ , SrCO ₃ , Si ₃ N ₄ , and Eu ₂ O ₃ of the values shown in Table 1, use a bowl to mix the resulting mixture for at least 30 minutes, and then form a pellet into a boron nitride crucible In a pressurized inert atmosphere using N ₂ gas, calcination is carried out for about 4 hours at about 1700 ° C. and about 0.9 MPa.

After calcination, pulverize in a bowl, wash with 1 N aqueous nitric acid solution at room temperature for 15 minutes, and collect sedimentation. Thereafter, the phosphor can be obtained by washing twice to remove the acid.

<Example 3> (Ca employment 25%)

After weighing the raw materials CaCO ₃ , SrCO ₃ , Si ₃ N ₄ , and Eu ₂ O ₃ of the values shown in Table 1, use a bowl to mix the resulting mixture for at least 30 minutes, and then form a pellet into a boron nitride crucible In a pressurized inert atmosphere using N ₂ gas, calcination is carried out for about 4 hours at about 1700 ° C. and about 0.9 MPa.

After calcination, pulverize in a bowl, wash with 1 N aqueous nitric acid solution at room temperature for 15 minutes, and collect sedimentation. Thereafter, the phosphor can be obtained by washing twice to remove the acid.

<Example 4> (Ca employment 30%)

After weighing the raw materials CaCO ₃ , SrCO ₃ , Si ₃ N ₄ , and Eu ₂ O ₃ of the values shown in Table 1, use a bowl to mix the resulting mixture for at least 30 minutes, and then form a pellet into a boron nitride crucible In a pressurized inert atmosphere using N ₂ gas, calcination is carried out for about 4 hours at about 1700 ° C. and about 0.9 MPa.

After calcination, pulverize in a bowl, wash with 1 N aqueous nitric acid solution at room temperature for 15 minutes, and collect sedimentation. Thereafter, the phosphor can be obtained by washing twice to remove the acid.

<Example 5> (Composition of Eu 0.03)

After weighing the raw materials SrCO ₃ , Si ₃ N ₄ , and Eu ₂ O ₃ of the values shown in Table 1, mix them for 30 minutes or more using a bowl to form pellets, and then put them in a boron nitride crucible for N ₂ Firing is performed for about 4 hours at about 1700°C and about 0.9 MPa in a pressurized inert atmosphere using gas.

After calcination, pulverize in a bowl, wash with 1 N aqueous nitric acid solution at room temperature for 15 minutes, and collect sedimentation. Thereafter, the phosphor can be obtained by washing twice to remove the acid.

<Example 6> (Composition of Eu 0.04)

After weighing the raw materials SrCO ₃ , Si ₃ N ₄ , and Eu ₂ O ₃ of the values shown in Table 1, mix them for 30 minutes or more using a bowl to form pellets, and then put them in a boron nitride crucible for N ₂ Firing is performed for about 4 hours at about 1700°C and about 0.9 MPa in a pressurized inert atmosphere using gas.

After calcination, pulverize in a bowl, wash with 1 N aqueous nitric acid solution at room temperature for 15 minutes, and collect sedimentation. Thereafter, the phosphor can be obtained by washing twice to remove the acid.

<Example 7> (Composition of Eu 0.06)

After weighing the raw materials SrCO ₃ , Si ₃ N ₄ , and Eu ₂ O ₃ of the values shown in Table 1, mix them for 30 minutes or more using a bowl to form pellets, and then put them in a boron nitride crucible for N ₂ Firing is performed for about 4 hours at about 1700°C and about 0.9 MPa in a pressurized inert atmosphere using gas.

After calcination, pulverize in a bowl, wash with 1 N aqueous nitric acid solution at room temperature for 15 minutes, and collect sedimentation. Thereafter, the phosphor can be obtained by washing twice to remove the acid.

<Example 8> (Composition of Eu 0.08)

After weighing the raw materials SrCO ₃ , Si ₃ N ₄ , and Eu ₂ O ₃ of the values shown in Table 1, mix them for 30 minutes or more using a bowl to form pellets, and then put them in a boron nitride crucible for N ₂ Firing is performed for about 4 hours at about 1700°C and about 0.9 MPa in a pressurized inert atmosphere using gas.

After calcination, pulverize in a bowl, wash with 1 N aqueous nitric acid solution at room temperature for 15 minutes, and collect sedimentation. Thereafter, the phosphor can be obtained by washing twice to remove the acid.

<Example 9> (Composition of Eu 0.10)

After weighing the raw materials SrCO ₃ , Si ₃ N ₄ , and Eu ₂ O ₃ of the values shown in Table 1, mix them for 30 minutes or more using a bowl to form pellets, and then put them in a boron nitride crucible for N ₂ Firing is performed for about 4 hours at about 1700°C and about 0.9 MPa in a pressurized inert atmosphere using gas.

After calcination, pulverize in a bowl, wash with 1 N aqueous nitric acid solution at room temperature for 15 minutes, and collect sedimentation. Thereafter, the phosphor can be obtained by washing twice to remove the acid.

<Example 10> (Composition of Eu 0.15)

After weighing the raw materials SrCO ₃ , Si ₃ N ₄ , and Eu ₂ O ₃ of the values shown in Table 1, mix them for 30 minutes or more using a bowl to form pellets, and then put them in a boron nitride crucible for N ₂ Firing is performed for about 4 hours at about 1700°C and about 0.9 MPa in a pressurized inert atmosphere using gas.

After calcination, pulverize in a bowl, wash with 1 N aqueous nitric acid solution at room temperature for 15 minutes, and collect sedimentation. Thereafter, the phosphor can be obtained by washing twice to remove the acid.

<Example 11> (La 10%, Al addition)

After weighing the raw materials SrCO ₃ , La ₂ O ₃ , Si ₃ N ₄ , AlN and Eu ₂ O ₃ as shown in Table 1, use a bowl to mix the resulting mixture for at least 30 minutes. It is placed in a boron crucible and calcined for about 4 hours at about 1700° C. and about 0.9 MPa in a pressurized inert atmosphere using N ₂ gas.

After calcination, pulverize in a bowl, wash with 1 N aqueous nitric acid solution at room temperature for 15 minutes, and collect sedimentation. Thereafter, the phosphor can be obtained by washing twice to remove the acid.

<Comparative Example ₁ > (Sr _1.02 Si ₂ O ₂ N ₂ phase)

After weighing the raw materials SrCO ₃ , Si ₃ N ₄ , SiO ₂ and Eu ₂ O ₃ of the figures shown in Table 1, use a bowl to mix the resulting mixture for 30 minutes or more to form a pellet, and then put it in a boron nitride crucible In a reducing atmosphere using N ₂ 4% H ₂ gas, calcination is performed at about 1500° C. for about 4 hours.

After calcination, pulverize in a bowl, wash with 1 N aqueous nitric acid solution at room temperature for 15 minutes, and collect sedimentation. Thereafter, the phosphor can be obtained by washing twice to remove the acid.

<Comparative Example 2> (A large amount of O input)

After weighing the raw materials SrCO ₃ , Si ₃ N ₄ , SiO ₂ and Eu ₂ O ₃ of the figures shown in Table 1, use a bowl to mix the resulting mixture for 30 minutes or more to form a pellet, and then put it in a boron nitride crucible Firing is performed for about 4 hours at about 1700° C. and about 0.9 MPa in a pressurized inert atmosphere using N ₂ gas.

After calcination, pulverize in a bowl, wash with 1 N aqueous nitric acid solution at room temperature for 15 minutes, and collect sedimentation. Thereafter, the phosphor can be obtained by washing twice to remove the acid.

<Comparative Example 3> (Ca 40% replacement)

After weighing the raw materials SrCO ₃ , CaCO ₃ , Si ₃ N ₄ , and Eu ₂ O ₃ of the values shown in Table 1, use a bowl to mix the resulting mixture for 30 minutes or more to form a pellet, and put it in a boron nitride crucible Firing is performed for about 4 hours at about 1700° C. and about 0.9 MPa in a pressurized inert atmosphere using N ₂ gas.

After calcination, pulverize in a bowl, wash with 1 N aqueous nitric acid solution at room temperature for 15 minutes, and collect sedimentation. Thereafter, the phosphor can be obtained by washing twice to remove the acid.

<Comparative Example 4> (La 10%, Al free)

After weighing the raw materials SrCO ₃ , La ₂ O ₃ , Si ₃ N ₄ , and Eu ₂ O ₃ as shown in Table 1, use a bowl to mix the resulting mixture for at least 30 minutes, and then form a pellet into a boron nitride crucible In a pressurized inert atmosphere using N ₂ gas, calcination is performed for about 4 hours at about 1700 ° C. and about 0.9 MPa.

After calcination, pulverize in a bowl, wash with 1 N aqueous nitric acid solution at room temperature for 15 minutes, and collect sedimentation. Thereafter, the phosphor can be obtained by washing twice to remove the acid.

The crystal phase was evaluated for each Example and Comparative Example. The crystal phase was evaluated using an X-ray diffraction apparatus (XRD) ("SmartLab" manufactured by RIGAKU Co., Ltd.). Measurement was carried out in the range of 2θ = 10 to 40° using CuKa rays as X-rays.

As a result of analyzing the obtained XRD pattern, Comparative Example 1 is ICDD database No. It was attributed to the Sr _1.02 Si ₂ O ₂ N ₂ phase described in _01-076-3141 . In Example 1, there is no crystalline phase corresponding to the ICDD database.

The results of analyzing the XRD results of Example 1 in detail and assigning an index to the patterns are shown in Table 3 below. As such, the space group P 1 21 / n 1 (No.14 setting 2) shown in Table 2 a = 4.8259 Å, b = 24.2157 Å, c = 10.566 Å, β = monoclinic ( monoclinic) for each index.

space group P 1 2 ₁ /n 1 (No.14 setting 2) a (Å) 4.8259 b (Å) 24.2157 c (Å) 10.566 β (°) 90.634

Peak No. 2θ(deg) d(Å) h k l One 11.13 7.944 0 2 One 2 14.66 6.036 0 4 0 3 16.81 5.271 0 0 2 4 17.20 5.150 0 One 2 5 18.36 4.827 0 2 2 6 22.04 4.029 0 6 0 7 22.38 3.969 0 4 2 8 23.61 3.765 One 4 0 9 25.55 3.483 0 One 3 10 26.36 3.378 One 5 0 11 27.11 3.286 0 7 One 12 27.82 3.204 0 6 2 13 28.96 3.080 One 6 0 14 29.28 3.047 0 4 3 15 30.72 2.907 0 8 One 16 31.27 2.858 One 0 -3 17 31.41 2.846 0 5 3 18 31.83 2.809 One 7 0 19 32.15 2.782 One 2 -3 20 33.03 2.710 One 7 One 21 33.54 2.670 One 6 -2 22 33.78 2.651 0 6 3 23 34.13 2.624 0 8 2 24 34.39 2.605 0 9 One 25 34.68 2.584 One 4 -3 26 36.01 2.492 One 8 -One 27 37.13 2.419 0 10 0 28 37.48 2.398 2 One 0 29 38.10 2.360 2 2 0 30 38.83 2.317 0 5 4 31 39.22 2.295 One 8 2 32 39.78 2.264 One 2 4

Table 4 below shows the crystal structure parameters obtained by performing structural analysis of the crystal obtained in Example 1 by single crystal X-ray scattering. It was found that this crystal is represented by the compositional formula Sr ₃ Si ₈ O ₄ N ₁₀ . The crystalline phase obtained from this ingredient is an unknown crystal and was first discovered in this review. This crystal has a structure in which Sr penetrates between layers in which Si(N, O) 4 tetrahedra are connected through vertex sharing of N atoms.

In addition, a portion of Sr exhibits an irregular (disorder) distribution. When the R element is dissolved in the Sr site of the crystal structure, light is emitted as a phosphor. Hereinafter, this crystal composition is called Sr ₃ Si ₈ O ₄ N ₁₀ phase.

atom x y z B g Site Sr 0.08338 (16) 0.22423(3) 0.20577(6) 0.01325(17) One 4d Sr 0.1415(3) -0.01311(6) 0.18329(13) 0.0197(3) 0.5 4d Sr 0.3671(3) -0.02538(6) 0.06245(13) 0.0195(3) 0.5 4d Sr 0.3821(3) -0.00383(7) 0.56614(15) 0.0251(4) 0.5 4d Sr -0.1180(3) -0.04302(6) 0.31478(17) 0.0255(4) 0.5 4d Si -0.4112(4) 0.30656(8) 0.06614(17) 0.0087(4) One 4d Si -0.4096(4) 0.09469(7) 0.20266(18) 0.0088(4) One 4d Si -0.4146(4) 0.30277(8) 0.34107 (16) 0.0091(4) One 4d Si 0.0869(4) 0.11075(8) 0.04956 (17) 0.0096(4) One 4d Si -0.4162(4) 0.17629(8) 0.42119(17) 0.0094(4) One 4d Si -0.4112(4) 0.18045(8) -0.01428(17) 0.0091(4) One 4d Si 0.0854(4) 0.10419(8) 0.35594(17) 0.0094(4) One 4d Si -0.4175(4) 0.14422(8) 0.70270(18) 0.0098(4) One 4d O -0.3523(12) 0.0299(2) 0.1971(5) 0.0183(12) One 4d O -0.3930(13) 0.0783(2) 0.6977(5) 0.0234(12) One 4d O 0.1370(12) 0.0545(2) -0.0237(5) 0.0223(12) One 4d O 0.1270(11) 0.0433(2) 0.4118(5) 0.0199(12) One 4d N -0.3727(12) 0.2342(2) 0.3387(5) 0.0097(12) One 4d N -0.3414(13) 0.2398(2) 0.0544(5) 0.0124(12) One 4d N -0.2603(13) 0.1256(2) 0.0709(5) 0.0110(12) One 4d N -0.2607(12) 0.1205(2) 0.3401(5) 0.0113(12) One 4d N -0.7629(12) 0.1575(2) 0.4407(5) 0.0122(13) One 4d N -0.7623(12) 0.1095(2) 0.2028(5) 0.0111(12) One 4d N -0.2640(12) 0.1779(2) 0.5735(5) 0.0114(12) One 4d N -0.7621(12) 0.1682(2) 0.7063(5) 0.0117(12) One 4d N -0.7620(12) 0.3234(2) 0.3350(5) 0.0110(12) One 4d N 0.2347(12) 0.1666(2) -0.0250(5) 0.0100(12) One 4d

1 is a diagram showing simulated XRD patterns for the crystal structures of Example 1 and Comparative Example 1 of the present invention. As described above, Sr _{1.02 Si 2} O ₂ N ₂ :Eu, which is a known phosphor, clearly shows a different XRD pattern.

As a result of comparing the XRD pattern simulated by the crystal structure of Example 1 with the XRD pattern of each example, the peak positions are exactly the same, and the XRD pattern of each example is attributed to the Sr ₃ Si ₈ O ₄ N ₁₀ phase. No peaks were reported. Accordingly, each example can be regarded as a single compound.

The list of XRD peaks extracted from the XRD patterns of each example is shown in Table 5 below. A slight variation is seen due to the different proportions of constituent elements in each embodiment. This is because the constituent elements have different ionic radii. For example, if the solid solution of Ca having a small atomic radius in Sr increases, the crystal lattice becomes smaller, and as a result, the XRD peak shifts to a wide angle. The position of the peak for each plane index is in the range of ±0.5 ° from the average value of each example. Therefore, when the XRD peak of the present invention is present in the range of ±0.5 ° from the average value of each peak position, it can be determined that it is a Sr ₃ Si ₈ O ₄ N ₁₀ crystal phase.

No. Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 Example 10 Example 11 h k l One 11.13 11.19 11.19 11.20 11.15 11.17 11.17 11.17 11.15 11.20 11.15 0 2 One 2 14.66 14.74 14.75 14.77 14.66 14.70 14.69 14.71 14.69 14.70 14.68 0 4 0 3 16.81 16.83 16.83 16.80 16.81 16.83 16.83 16.85 16.83 16.85 16.79 0 0 2 4 17.20 17.24 17.23 17.26 17.21 17.22 17.20 17.25 17.20 17.24 17.20 0 One 2 5 18.36 18.40 18.42 18.42 18.36 18.35 18.39 18.40 18.37 18.40 18.32 0 2 2 6 22.04 22.15 22.17 22.19 22.05 22.08 22.06 22.09 22.07 22.09 22.06 0 6 0 7 22.38 22.43 22.41 22.48 22.38 22.38 22.40 22.38 22.37 22.40 22.34 0 4 2 8 23.61 23.73 23.75 23.76 23.61 23.64 23.63 23.65 23.63 23.65 23.63 One 4 0 9 25.55 25.63 25.57 25.56 25.57 25.59 25.62 25.61 25.60 25.62 25.62 0 One 3 10 26.36 26.43 26.42 26.46 26.35 26.39 26.36 26.41 26.40 26.40 26.20 One 5 0 11 27.11 27.27 27.30 27.16 27.11 27.16 27.13 27.17 27.15 27.20 26.95 0 7 One 12 27.82 27.94 27.96 27.98 27.83 27.85 27.84 27.86 27.84 27.86 27.82 0 6 2 13 28.96 29.04 29.07 29.07 28.98 28.98 29.03 29.00 29.04 29.06 28.99 One 6 0 14 29.28 29.42 29.46 29.46 29.35 29.35 29.40 29.40 29.40 29.40 29.32 0 4 3 15 30.72 30.88 30.90 30.93 30.73 30.76 30.74 30.77 30.75 30.77 30.73 0 8 One 16 31.27 31.39 31.41 31.42 31.28 31.31 31.30 31.33 31.29 31.33 31.26 One 0 -3 17 31.41 31.51 31.53 31.53 31.42 31.44 31.44 31.45 31.43 31.45 31.39 0 5 3 18 31.83 31.94 31.95 31.96 31.84 31.86 31.85 31.87 31.86 31.87 31.82 One 7 0 19 32.15 32.22 32.23 32.19 32.17 32.19 32.21 32.21 32.19 32.22 32.16 One 2 -3 20 33.03 33.16 33.18 33.18 33.04 33.06 33.03 33.07 33.07 33.06 33.03 One 7 One 21 33.54 33.65 33.64 33.66 33.56 33.56 33.56 33.56 33.57 33.59 33.51 One 6 -2

In order to evaluate the phosphor properties of each Example and Comparative Example, photo-excitation luminescence properties were measured. An emission spectrum obtained when blue light of 450 nm monochromatized by a diffraction grating was incident using an Xe lamp as an excitation light source was measured. At this time, stimulation by a blue LED excited with blue light is assumed.

Table 6 below shows a list of emission peak wavelengths and half-width relative intensities of each Example. In addition, the phases identified as a result of XRD measurement are also listed. The relative intensity is a certain intensity based on the integrated intensity of the emission peak of Example 1, and is not an absolute value.

In the Sr ₃ Si ₈ O ₄ N ₁₀ phase, the emission spectrum changes depending on the composition, and the emission peak wavelength is 589 to 620 nm, and the half width is 120 to 127 nm. In Comparative Examples 3 and 4, the full width at half maximum is increased to 132 and 135 nm, but this is not essential because several steps are included in the obtained phosphor, and the light emission at various steps overlaps, and the half maximum width is large, which is not essential. The Sr _{1.02 Si 2} O ₂ N ₂ phosphor of Comparative Example 1 has a full width at half maximum of 74 nm, and it is a phosphor capable of improving color rendering with a greater width at half maximum.

Emission peak wavelength (nm) Full width at half maximum (nm) Luminescence Relative Intensity Phase identified by XRD Example 1 602 120 1.00 Sr ₃ Si ₈ O ₄ N ₁₀ Example 2 589 120 0.76 Sr ₃ Si ₈ O ₄ N ₁₀ Example 3 608 125 1.03 Sr ₃ Si ₈ O ₄ N ₁₀ Example 4 620 142 0.92 Sr ₃ Si ₈ O ₄ N ₁₀ Example 5 601 121 0.95 Sr ₃ Si ₈ O ₄ N ₁₀ Example 6 605 121 1.00 Sr ₃ Si ₈ O ₄ N ₁₀ Example 7 608 123 0.97 Sr ₃ Si ₈ O ₄ N ₁₀ Example 8 609 123 1.12 Sr ₃ Si ₈ O ₄ N ₁₀ Example 9 613 124 1.15 Sr ₃ Si ₈ O ₄ N ₁₀ Example 10 618 127 1.08 Sr ₃ Si ₈ O ₄ N ₁₀ Example 11 619 135 0.59 Sr ₃ Si ₈ O ₄ N ₁₀ Comparative Example 1 537 74 1.12 Sr _{1.02 Si 2} O ₂ N ₂ Comparative Example 2 545 111 0.75 Sr ₃ Si ₈ O ₄ N ₁₀ +Sr ₂ Si ₂ O ₂ N ₂ Comparative Example 3 648 132 0.20 unknown (plural phases) Comparative Example 4 554 135 0.46 Sr ₃ Si ₈ O ₄ N ₁₀ +Sr ₂ Si ₂ O ₂ N ₂ +LaSi ₃ N ₅

FIG. 2 is a diagram showing emission spectra by 450 nm excitation light of Example 1 and Comparative Example 1 of the present invention. In order to compare the spectral shapes, normalization is performed with the maximum value of the emission intensity. As described above, the phosphor of the present invention is characterized in that it exhibits an emission spectrum having a very wide full width at half maximum with a peak in the vicinity of 600 nm. Comparative Example ₁ is an Sr _1.02 Si ₂ O ₂ N ₂ phase, and shows light emission with a peak around 540 nm.

3 is a road showing the emission spectra of Examples 1 to 4 and Comparative Example 3 of the present invention, Example 1 of 0% Ca, Examples 2 to 4 with Ca added, and 450 nm of Comparative Example 3 The emission spectrum by excitation light is shown. In Examples 1 to 4, it was confirmed that all Sr ₃ Si ₈ O ₄ N ₁₀ crystal phases.

Incidentally, the emission peak wavelength is 589 to 620 nm. It can be seen that the emission wavelength can be controlled according to the composition. In Comparative Example 3, which became another crystalline phase, it can be seen that the luminescence intensity was greatly reduced.

4 is a diagram showing emission spectra by excitation light at 450 nm in Examples 1 and 5 to 10 of the present invention in which the amount of Eu is changed. In all of these examples of FIG. 4, it was confirmed that Sr ₃ Si ₈ O ₄ N ₁₀ was present. As the amount of Eu added increases, the emission peak shifts to a longer wavelength, indicating light emission with a peak wavelength of 600 to 615 nm.

5 is a diagram showing emission spectra by 450 nm excitation light of Example 11 and Comparative Example 4 of the present invention to which La is added. As shown in Table 4 above, the single addition of La in Comparative Example 4 does not solid-solve in the Sr ₃ Si ₈ O ₄ N ₁₀ phase, and La forms a LaSi ₃ N ₅ phase, showing significantly different emission spectra.

La is a rare earth element, and it is expected to be able to replace Sr, an alkaline earth metal element with similar properties, but La, which becomes a trivalent ion, has 3 at the Si site to compensate for the charge to replace Sr, a divalent ion. It is necessary to simultaneously add a valent metal, and as in Example 11, by adding Al, Sr and La having a different valency are dissolved in a solid solution to obtain light emission on Sr ₃ Si ₈ O ₄ N ₁₀ .

In Example 1, the case of M = Sr, A = Si, R = Eu, a = 2.94, b = 8, c = 4, d = 10, e = 0.06 in the formula MaAbOcNd:Re was described. However, it may be basically an oxynitride, characterized in that the compound represented by the compositional formula M3A8O4N10 is the main component, and the parameters of the constituent elements of M, A, and R are not particularly limited within the scope not departing from the description.

Although the parameters in Example 1 of the general formula represent a configuration derived from the crystal structure, it is common that the actual crystal contains lattice defects such as void alternating stacking defects. It can be predicted that the parameters will have a certain range in the range that maintains the crystal structure as such defects are included.

M element is one or more elements selected from divalent rare earth elements other than Mg, Ca, Sr, Ba, Zn and R elements, and even when the M element is an element other than Sr, alkaline earth metal elements, rare earth elements It can be predicted that the same phosphor as in Example 1 is constituted from the similarity of chemical properties.

In addition, although Zn is a Group 12 element, it can be predicted that the same phosphor as in Example 1 is constituted from the fact that the electron configuration is similar to that of the Group 2 alkaline earth metal element.

In addition, element A is one or more elements selected from the group consisting of tetravalent metal elements, and even when element A is a tetravalent element other than Si, the same phosphor as in Example 1 in terms of scientific properties What constitutes is predictable.

In addition, the R element is one or two or more elements selected from Mn, Ce, Pr, Nd, Sm, Eu, Tb, Dy, Ho, Er, Tm, and Yb acting as a luminescence center. Thus, it is clear that elements of this group act as luminescent centers, and it can be predicted that they act as phosphors as in Example 1 even if they are dissolved in a solid solution instead of Eu.

Similarly, in Example 11, in the formula MaBfAbCgOcNd: Re, M = Sr, A = Si, B = La, C = Al, R = Eu, a = 2.4, b = 7.7, c = 4, d = 10, e = 0.3 , f = 0.3, g = 0.3 has been described, but basically, if it is an oxynitride characterized by a compound represented by the composition formula (M + B) ₃ (A + C) ₈ O ₄ N ₁₀ as a main component The characteristics of the present invention can be exhibited, and the parameters of the constituent elements of M, A, B, C, and R are not particularly limited within the range not departing from the description.

Although the parameters of Example 11 indicate a configuration derived from the crystal structure, it is common that actual crystals contain lattice defects such as vacant hole alternating stacking defects. As such defects are included, it can be predicted that the parameters have a certain range in the range that maintains the crystal structure.

M element is one or two or more elements selected from divalent rare earth elements other than Mg, Ca, Sr, Ba, Zn and R elements, and even when M element is an element other than Sr, alkaline earth metal elements, rare earth elements, etc. From the similarity of chemical properties of

Further, although Zn is a Group 12 element, it can be predicted that the same phosphor as in Example 11 is constituted from the fact that the electron configuration is similar to that of the Group 2 alkaline earth metal element.

In addition, element A is one or two or more elements selected from the group consisting of tetravalent metal elements, and when element A is a tetravalent element other than Si, the tetravalent element is group 14 and the scientific properties of the element of the same group It can be predicted that the same phosphor as in Example 11 is constituted by the similarity.

Further, the B element is one or two or more elements selected from trivalent Sc, Y, La, Ce, Pr, Nd, Sm, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu. All of these elements are group III elements, and even when element B is a trivalent element other than La, it can be predicted that the same phosphor as in Example 11 will be constituted by the chemical similarity of the elements of the same group.

In addition, the C element is one or two or more elements selected from Al, Ga, and In, all of which are Group 13 elements, and even when the C element is Ga or In other than Al, by the chemical similarity of these Group 13 elements It is predictable to constitute the same phosphor as in Example 11.

In addition, the R element is one or two or more elements selected from Mn, Ce, Pr, Nd, Sm, Eu, Tb, Dy, Ho, Er, Tm, and Yb acting as a luminescence center. Thus, it is clear that elements of these groups act as luminescence centers, and it can be predicted that they act as phosphors as in Example 11 even if they are dissolved in a solid solution instead of Eu.

<Light-emitting device>

6 is a cross-sectional view showing an example of a light emitting device package in which the oxynitride phosphor of the present invention is used. 6 shows a surface mount type light emitting device package.

As shown in FIG. 6 , the surface mount type light emitting device package 100 according to an embodiment of the present invention is provided with a lead frame 110 of an anode and a cathode, and among the lead frames 110 of the anode and the cathode It includes a light emitting device 120 that is positioned on any one and generates light according to the application of a voltage. The light emitting device 120 may use a light emitting diode or a laser diode.

The light-emitting device 120 is electrically connected to the lead frame 110 and the wire 130 , and the light-transmitting resin 140 is molded on the light-emitting device 120 .

In addition, it is configured to include a phosphor 141 dispersed in the light-transmitting resin 140 .

The phosphor 141 used herein may include other phosphors in addition to the above-described oxynitride phosphor dispersed therein. For example, it may be dispersed with other phosphors such as YAG and β-SiAlON. In this case, two or more types of these different dispersed phosphors may be used.

The light emitting device 120 may use a near ultraviolet or blue light emitting device that generates light having a main peak of an emission spectrum in a wavelength region of 400 to 480 nm when a voltage is applied.

In addition, as a light emitting device having a main emission peak in the same wavelength region instead of the near ultraviolet light emitting device, a laser diode, a surface light emitting laser diode, an inorganic electroluminescent device, an organic electroluminescent device, or the like may be used. In the present invention, an example in which a nitride semiconductor light emitting diode is used is shown as a preferable application example.

As the light transmitting resin 140 used as the molding member, a light transmitting epoxy resin, a silicone resin, a polyimide resin, a urea resin, an acrylic resin, or the like may be used. Preferably, a light-transmitting epoxy resin or a light-transmitting silicone resin may be used.

The light-transparent resin 140 may be entirely molded around the light emitting device 120 , but it is also possible to partially mold the light emitting part if necessary. That is, in the case of a small-capacity light emitting device, it is preferable to mold the whole, but in the case of a high power light emitting device, when the light emitting device 120 is molded as a whole due to the enlargement of the size, the uniform dispersion of the phosphor 141 dispersed in the light transmitting resin 140 because it can be detrimental to In this case, it is preferable to partially mold the light emitting part.

7 is a cross-sectional view showing another example of a light emitting device package in which the oxynitride phosphor of the present invention is used. 7 shows an example of a lamp-type light emitting device package 200 according to another embodiment of the present invention.

The lamp-type light emitting device package 200 includes a pair of lead frames 210 and a light emitting device 220 that generates light according to the application of voltage.

The light-emitting device 220 is electrically connected to the lead frame 210 by a wire 230 , and a light-transmitting resin 240 is molded on the light-emitting device 220 .

A phosphor 241 may be dispersedly provided in the light-transmitting resin 240 , and an exterior material 250 for closing the entire external space of the device may be provided on the light-transmitting resin 240 .

The phosphor 241 used herein may be dispersedly provided with phosphors other than the oxynitride phosphors described above, for example, phosphors such as YAG and β-SiAlON. Two or more types of the dispersed phosphor 241 may be provided.

The light-transmitting resin 240 of the present embodiment may also be molded entirely around the light-emitting device 220 , but may also be partially molded to the light-emitting portion if necessary. The reason for this is as mentioned above.

The surface mount type light emitting device package 100 or the lamp type light emitting device package 200 according to the present invention described in detail above may be implemented as a white light emitting package. A process for implementing such white light will be described as follows.

Blue light in a wavelength region of 400 to 480 nm corresponding to near ultraviolet emitted from the light emitting devices 120 and 220 passes through the phosphors 141 and 241 . Here, some light drives the phosphors 141 and 241 to generate light having a main peak in the range of 500 to 600 nm at the center of the emission wavelength, and the remaining light is transmitted as blue light as it is.

As a result, white light having a broad wavelength spectrum of 400 to 700 nm is emitted.

The phosphors 141 and 241 may include other phosphors in addition to the above-described oxynitride phosphors dispersed therein.

For example, these phosphors 141 and 241 may be used together by mixing the above-described oxynitride phosphor (hereinafter, referred to as a first phosphor) and a second phosphor having a different emission peak.

The light emitting device packages 100 and 200 may have an emission spectrum having one or more emission peaks in at least one of at least 430 to 500 nm and 500 to 730 nm wavelength bands.

On the other hand, the embodiments of the present invention disclosed in the present specification and drawings are merely presented as specific examples to aid understanding, and are not intended to limit the scope of the present invention. It will be apparent to those of ordinary skill in the art to which the present invention pertains that other modifications based on the technical spirit of the present invention can be implemented in addition to the embodiments disclosed herein.

100, 200: light emitting device package 110, 210: lead frame
120, 220: light emitting element 130, 230: wire
140, 240: light transmitting resin 141, 241: phosphor

Claims (18)

delete delete delete delete delete delete delete In the oxynitride phosphor,
Diffraction angle 2θ by X-ray diffraction is 10.7 to 11.7 °, 14.2 to 15.2 °, 16.3 to 17.3 °, 21.6 to 22.6 °, 23.2 to 24.2 °, 27.4 to 28.4 °, 30.3 to 30.8 °, 30.8 to 31.8 °, 31.0 ~32.0°, 31.4~32.4°, 31.7~32.7°, 32.6~33.6°, 33.1~34.1°, 33.3~34.3°, 33.7~34.7°, 36.8~37.8°, 37.0~38.0°, 37.7~38.7°, 38.4 with distinct peaks in the respective ranges of ∼39.4° and 38.8∼39.8°,
The oxynitride phosphor is a composition containing at least element M, element A, element B, element C, element N, element O, and element R, and is expressed by the general formula MaBfAbCgOcNd:Re;
M is one or two or more elements selected from divalent rare earth elements other than Mg, Ca, Sr, Ba, Zn and R, and A is one or two selected from the group consisting of tetravalent metal elements. or more elements, wherein B is one or two or more elements selected from trivalent Sc, Y, La, Ce, Pr, Nd, Sm, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu, the C is one or more elements selected from Al, Ga, In, O is oxygen, N is nitrogen, R is Mn, Ce, Pr, Nd, Sm, Eu, Tb, Dy, Ho, Er, One or two or more elements selected from Tm and Yb,
The M element, A element, B element, C element, N element, O element, and R element are 2.5 ≤ (a + e + f) ≤ 3.5, 7.5 ≤ (b + g) ≤ 8.5, 3 ≤ c ≤ 5 , 9 ≤ d ≤ 11, 13 ≤ (c + d) ≤ 15, 0.0001 ≤ e ≤ 0.2, f = g,
The B element replaces the M element, the C element simultaneously replaces the A element,
The B element is La, and the C element is Al. The method of claim 8, wherein each parameter of the general formula satisfies at least one of (a + e + f) = 3, (b + g) = 8, c = 4, and d = 10 oxynitride phosphor. The oxynitride phosphor according to claim 8, wherein the M element is Sr. The oxynitride phosphor according to claim 8, wherein the element A is Si. delete delete The oxynitride phosphor according to claim 8, wherein the R element is Eu. The oxynitride phosphor according to claim 8, wherein the peak points of the emission spectrum excited by blue light are 560 nm or more and 640 nm or less. The oxynitride phosphor according to claim 8, wherein the full width at half maximum of the emission spectrum excited by blue light is 110 nm or more and 130 nm or less. The oxynitride phosphor according to claim 8, wherein the B element substitutes the M element, and the C element simultaneously substitutes the A element. In the oxynitride phosphor,
Diffraction angle 2θ by X-ray diffraction is 10.7 to 11.7 °, 14.2 to 15.2 °, 16.3 to 17.3 °, 21.6 to 22.6 °, 23.2 to 24.2 °, 27.4 to 28.4 °, 30.3 to 30.8 °, 30.8 to 31.8 °, 31.0 ~32.0°, 31.4~32.4°, 31.7~32.7°, 32.6~33.6°, 33.1~34.1°, 33.3~34.3°, 33.7~34.7°, 36.8~37.8°, 37.0~38.0°, 37.7~38.7°, 38.4 with distinct peaks in the respective ranges of ∼39.4° and 38.8∼39.8°,
The oxynitride phosphor is a composition comprising at least element M, element A, element B, element C, element N, element O, and element R, and is expressed by the general formula MaBfAbCgOcNd:Re;
wherein M is Sr, A is Si, B is La, C is Al, and R is an element Eu, in the general formula a = 2.4, b = 7.7, c = 4, d = 10, having a composition of e = 0.3 , f = 0.3 and g = 0.3,
The oxynitride phosphor, characterized in that the B element substitutes the M element, and the C element simultaneously substitutes the A element.

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