KR20170125218A - Garnet phosphor and light emitting diodes comprising the garnet phosphor for solid-state lighting applications - Google Patents

Abstract

The present invention relates to a phosphor capable of being used for an LED lamp. More specifically, the present invention relates to a garnet-based phosphor having a new composition with improved light-emitting properties while having a reduced rare earth element content, and to a light-emitting device to which the phosphor is applied. The garnet-based phosphor has chemical formula 1, (A_(3-y-x)B_x)(C_(2-2x)D_(2x))(E_(3-3x)F_(3x))O_(12):Ce_y^(3+).

Description

[0001] The present invention relates to a garnet phosphor and a light emitting element using the phosphor,

The present invention relates to a phosphor that can be used for LED illumination, and more specifically, to a garnet fluorescent material having a novel composition with improved light emission characteristics while reducing rare earth content and a light emitting device using the phosphor.

BACKGROUND ART Globally known phosphors are widely used in vacuum fluorescent display (VFD), electroluminescence display (FED), plasma display panel (PDP), cathode ray tube (CRT), white light emitting diode (WLED) and the like in vacuum ultraviolet, And blue light and emits visible light by receiving energy from an excitation source having high energy. Among these applications, researches on light emitting diodes (LEDs) having high efficiency and environment-friendly advantages compared with the existing methods are being actively pursued with a worldwide interest in environment such as recent global energy crisis and global warming.

In order to use a LED having excellent advantages as a solid light source to replace an existing light source, it is most important to realize a high-quality white light, and a phosphor having good characteristics is required in this respect. There are three main ways to implement white light using LEDs and phosphors. First, it is a method of realizing white color by exciting a yellow phosphor as a light source of a blue LED. This method has a simple structure of one chip and two terminals, so it can reduce manufacturing cost and has excellent luminous efficiency. However, it has a limitation that it is difficult to apply it as a high quality solid light source because of low color rendering index due to insufficient light emission in the red region. Second, white light is realized by mixing two or more kinds of inorganic luminescent materials such as green and red phosphors with a blue LED as a light source and exciting them. In this method, a high quality solid light source having a high color rendering index can be produced by mixing two or more kinds of phosphors with a wide emission spectrum, but there is a problem of cost increase as the number of kinds of phosphors applied increases. Third, white light is realized by mixing near-UV LEDs with blue, green or yellow and red phosphors as a light source. This method is very similar to the method of embodying a fluorescent lamp with ultraviolet rays. It has a wide wavelength spectrum such as an incandescent lamp, has excellent color stability, and has a merit that it is easy to control correlated color temperature and color rendering index, There is a problem that the efficiency of the ultraviolet LED is increased and the efficiency of the solid-state lighting is decreased due to the phosphor blending.

The most popular method is the first method, but it is difficult to develop and utilize the technology because of the patent of nichia Japan. In the third method, it is difficult that the efficiency of the near ultraviolet LED does not reach the blue LED. Therefore, a second method of mixing a blue LED with a green phosphor and a red phosphor is now widely used for solid state lighting using LEDs. The luminescent efficiency of Lu ₃ Al ₅ O ₁₂ : Ce ³⁺ green phosphor used at this time is good, but the unit price of Lu ₂ O ₃ entering the matrix is very high, which makes it difficult to raise the cost of solid-state lighting. Therefore, it is necessary to develop a green phosphor having good luminescence efficiency and thermal stability while reducing the amount of lutetium. In addition, in order to secure competitiveness of the LED business, it is essential to develop a new phosphor having a good optical characteristic and a composition based on a low cost material.

The inventors of the present invention have found that Lu ₂ CaMg ₂ Si ₃ O ₁₂ : Ce ^{3+ is added} to Lu ₃ Al ₅ O ₁₂ : Ce ³⁺ The ruthenium content is reduced and the luminescent efficiency is improved. The present invention has been completed based on this finding.

Accordingly, it is an object of the present invention to provide a garnet fluorescent material having a new composition which is cost-reduced by changing the composition of the phosphor so that the amount of rare earth metals used is reduced as much as possible by using a solid solution method.

Another object of the present invention is to provide a garnet fluorescent material having a high efficiency by controlling the emission characteristics of phosphors by changing the environment of a site where an active agent is substituted using a solid solution method, and a method for producing the same.

It is still another object of the present invention to provide a light emitting device which not only increases emission brightness but also exhibits excellent power consumption by applying a garnet fluorescent material having a novel composition.

The objects of the present invention are not limited to the above-mentioned objects, and other objects not mentioned can be clearly understood by those skilled in the art from the following description.

In order to achieve the object of the present invention described above, the present invention provides a garnet fluorescent material having the following general formula (1).

[Chemical Formula 1]

(A _{3-y x} B _x ) (C _2-2x D _2x ) (E _3-3x F _3x ) O ₁₂ : Ce _y ³⁺

Wherein A is an element selected from the group consisting of Lu, Y, La and Tb and B is an element selected from the group consisting of Ca, Ba, Sr and Mg, C is an element selected from the group consisting of Al, Sc, Ga and Gd; D is an element selected from divalent alkali metal groups including Ca, Ba, Sr and Mg; E is one kind of element selected from the group consisting of ternary metal ions including Al, Sc, Ga and Gd, and F is one kind of element selected from the group consisting of Si, Ge, Zr and Ti. 0 < x < 1, 0 < y < 0.3.

In a preferred embodiment, Formula 1 has the same composition as the solid solution of A ₃ C ₅ O ₁₂ and A ₂ BD ₂ F ₃ O ₁₂ .

In a preferred embodiment, x and y in formula (1) are determined according to the ratio of A ₃ C ₅ O ₁₂ and A ₂ BD ₂ F ₃ O ₁₂ solubilized.

In a preferred embodiment, the emission wavelength and the emission luminance of the phosphor vary according to the compositional change according to the x value and the y value in the formula (1).

In a preferred embodiment, the environment of the site where the activator is substituted by at least one of B and D in the formula (1) is changed to control the luminescent properties of the phosphor.

According to another aspect of the present invention, there is provided a method for preparing a phosphor according to the present invention, Weighing the raw materials at a phosphor composition ratio of Formula 1 and uniformly mixing them; And firing the uniformly mixed raw material in a reducing atmosphere.

In a preferred embodiment, the firing is performed by heat-treating at a temperature of 1000 to 1600 ° C for 1 to 12 hours under a gas atmosphere in which nitrogen and hydrogen are mixed at a volume percentage of 75 to 95: 25 to 5 at a volume ratio.

The present invention also provides a light emitting device comprising a luminescent light source and a phosphor, wherein the phosphor comprises the garnet fluorescent material of claim 1.

In a preferred embodiment, when the luminescent light source is an ultraviolet ray, a visible ray or an electron ray having a wavelength in the range of 100 nm to 470 nm, the phosphor exhibits fluorescence characteristic of emitting green or yellow light having a wavelength in the range of 500 nm to 600 nm.

In a preferred embodiment, if the luminescent light source is an excitation light source of 450 to 470 nm, the luminescent element is a white luminescent element.

In a preferred embodiment, the phosphor is mixed with silicone resin in a weight ratio of 1: 5 to 15.

In a preferred embodiment, the light emitting device includes a light emitting diode, a laser diode, a surface emitting laser diode, an inorganic electroluminescence device, or an organic electroluminescence device.

The present invention has the following effects.

First, the garnet fluorescent material of the present invention has a new composition in which the cost is reduced by changing the composition of the phosphor so that the amount of rare earth metal used is reduced as much as possible by using a solid solution method.

In addition, the garnet fluorescent material of the present invention has high efficiency by controlling the luminescent property of the phosphor by changing the environment of the site where the activator is substituted using a solid solution method.

Further, the light emitting device of the present invention not only increases emission luminance but also exhibits excellent power consumption by applying a garnet fluorescent material having a novel composition.

These technical advantages of the present invention are not limited to the above-mentioned technical scope, and even if not explicitly mentioned, the effect of the invention which can be recognized by a person skilled in the art from the description of the concrete contents for carrying out the invention Of course.

1 is a crystal structure of (a) Lu ₃ Al ₅ O ₁₂ and (b) Lu ₂ CaMg ₂ Si ₃ O ₁₂ phosphors.
2 is an X-ray diffraction pattern graph of a garnet fluorescent material according to an embodiment of the present invention.
3 shows excitation and emission spectra of a garnet fluorescent material according to an embodiment of the present invention.
FIG. 4 shows a spectrum of an LED lighting apparatus including a garnet fluorescent material according to another embodiment of the present invention.
FIG. 5 shows CIE coordinates of an LED lighting fixture including a garnet fluorescent material according to another embodiment of the present invention.
6 is an X-ray diffraction pattern graph of a garnet fluorescent material according to another embodiment of the present invention.
FIG. 7 shows emission spectra of a garnet fluorescent material according to another embodiment of the present invention.
8 is an X-ray diffraction pattern of a garnet fluorescent material according to another embodiment of the present invention.
FIG. 9 shows the emission spectrum of a garnet fluorescent material according to another embodiment of the present invention.

Although the terms used in the present invention have been selected as general terms that are widely used at present, there are some terms selected arbitrarily by the applicant in a specific case. In this case, the meaning described or used in the detailed description part of the invention The meaning must be grasped.

Hereinafter, the technical structure of the present invention will be described in detail with reference to the accompanying drawings and preferred embodiments.

However, the present invention is not limited to the embodiments described herein but may be embodied in other forms. Like reference numerals used to describe the present invention throughout the specification denote like elements.

A technical feature of the present invention is to provide a solid solution of A ₃ C ₅ O ₁₂ and A ₂ BD ₂ F ₃ O ₁₂ having a garnet structure, wherein A is selected from the group consisting of Lu, Y, La, Tb B is an element selected from a divalent alkali metal group including Ca, Ba, Sr and Mg, and C is an element selected from the group consisting of Al, Sc, Ga, Gd, D is an element selected from divalent alkali metal groups including Ca, Ba, Sr and Mg, and F is an element selected from a tetravalent metal ion group including Si, Ge, Zr and Ti. ) Can reduce the amount of rare earth metal A to lower the cost, A new phosphor having high efficiency can be developed by controlling the luminescence characteristic of the phosphor, and the environment of the site where the activator is substituted is changed according to the newly introduced element when the phosphor is employed. have.

That is, as shown in FIG. 1, (a) Lu ₃ Al ₅ O ₁₂ (b) As to the crystal structure of Lu ₂ CaMg ₂ Si ₃ O ₁₂ , since the two materials have very similar crystal structures, complete solid solution can be formed. In one embodiment, Lu ₃ Al ₅ O ₁₂ matrix Lu ₂ CaMg ₂ Si ₃ O ₁₂ to form Lu ₃ Al ₅ O ₁₂ ?? The solid solution of Lu ₂ CaMg ₂ Si ₃ O ₁₂ can reduce the amount of lutetium, which is a rare earth metal, to lower the phosphor cost, And is a phosphor of a new composition having a high efficiency by controlling the luminescence characteristics of the phosphor.

Accordingly, the garnet phosphor of the present invention has a composition represented by the following formula (1).

[Chemical Formula 1]

(A _{3-y x} B _x ) (C _2-2x D _2x ) (E _3-3x F _3x ) O ₁₂ : Ce _y ³⁺

Wherein A is an element selected from the group consisting of Lu, Y, La and Tb and B is an element selected from the group consisting of Ca, Ba, Sr and Mg, C is an element selected from the group consisting of Al, Sc, Ga and Gd; D is an element selected from divalent alkali metal groups including Ca, Ba, Sr and Mg; E is one kind of element selected from the group consisting of ternary metal ions including Al, Sc, Ga and Gd, and F is one kind of element selected from the group consisting of Si, Ge, Zr and Ti. 0 < x < 1, 0 < y < 0.3.

In the garnet fluorescent material according to the present invention, the content of Ce is determined experimentally. If it is less than 0.0005, it is not enough to act as an activator. If it is more than 0.3, the concentration quenching effect There is a problem in that the luminance degradation becomes large. Therefore, the amount of Ce as an activator in the formula (1) may be in the range of 0 < y < 0.3.

Since the formula 1 has the same composition as the solid solution of A ₃ C ₅ O ₁₂ and A ₂ BD ₂ F ₃ O ₁₂ , x and y in the formula (1) for producing the garnet fluorescent material of the present invention are A ₃ C ₅ O ₁₂ A ₂ BD ₂ F ₃ O ₁₂ is employed.

In addition, the emission wavelength and the emission luminance of the garnet fluorescent material change according to the compositional change depending on the x value and the y value in the formula (1). As evidenced by experimental examples to be described later, The environment of the site where the active agent is substituted is changed by at least one of the composition and / or one or more of B and D in the formula (1), thereby controlling the luminescence characteristics such as the emission wavelength of the phosphor, thereby increasing the luminescence brightness.

Accordingly, the garnet fluorescent material of the present invention is useful as a material for a light emitting element, particularly a white light emitting element, including a light emitting diode, a laser diode, a surface emitting laser diode, an inorganic electroluminescence element, or an organic electroluminescence element.

Next, a method for manufacturing a garnet fluorescent material according to the present invention comprises the steps of: preparing a raw material of the phosphor of Formula 1 according to the phosphor composition; Uniformly mixing the phosphor powder with the phosphor composition of Formula 1; And firing the uniformly mixed raw material under a reducing atmosphere.

The firing step is preferably performed by heat-treating at 1000-1600 ° C for 1 to 12 hours in a gas atmosphere in which nitrogen and hydrogen are mixed at a volume percentage of 75 to 95: 25 to 5. If the calcination temperature is less than 1000 ° C, the single-phase crystals can not be completely formed and unreacted materials and by-products are formed. At 1600 ° C or higher, the grain shape is irregular and the constituent elements constituting the phosphor are volatilized, Is rapidly decreased.

On the other hand, the firing step may be performed one or more times, since the emission intensity of the phosphor may increase when the firing step is repeated several times.

Finally, the light emitting device according to the present invention is a light emitting device including a luminescent light source and a phosphor, and in particular, may include the garnet fluorescent material of claim 1 as the phosphor. When the luminescent light source is an ultraviolet ray, a visible ray or an electron ray having a wavelength in the range of 100 nm to 470 nm, the garnet fluorescent material exhibits fluorescence characteristics of emitting green or yellow light having a wavelength in the range of 500 nm to 600 nm, If it is an excitation light source of 470 nm, the light emitting element may be a white light emitting element. At this time, the garnet fluorescent material can be mixed with the silicone resin in a weight ratio of 1: 5 to 15, and it is possible to exhibit more excellent properties when used in a weight ratio of 1:10.

Example 1

The garnet phosphor was prepared as follows so that the molar composition ratio of each component of the garnet phosphor having the formula (1) had Lu: Ca: Al: Mg: Si: O: Ce = 2.85: Respectively.

That is, Lu ₂ O ₃ (1.3560 g), Al ₂ O ₃ (0.5486 g), CaCO ₃ (0.0239 g), MgO (0.0193 g), SiO ₂ (0.0431 g), CeO ₂ ) Were wet-mixed and pulverized. The mixture was sufficiently dried and heat-treated for 4 hours in a reducing atmosphere of 1600 ° _C. to prepare Lu _2.85 Ca _0.1 Ce _0.05 Al _4.5 Mg _0.2 Si _0.3 O ₁₂ (garnet phosphor 1).

Example 2

The garnet fluorescent material was prepared as follows so that the molar composition ratio of each component of the garnet fluorescent material having the formula 1 was such that Lu: Ca: Al: Mg: Si: O: Ce = 2.65: 0.3: 3.5: 0.6: 0.9: Respectively.

Specifically, Lu ₂ O ₃ (1.3035 g), Al ₂ O ₃ (0.4411 g), CaCO ₃ (0.0742 g), MgO (0.0598 g), SiO ₂ (0.1337 g), CeO ₂ ) Were wet-mixed and pulverized. The mixture was sufficiently dried and heat-treated for 4 hours in a reducing atmosphere of 1600 ° _C. to prepare Lu _2.65 Ca _0.3 Ce _0.05 Al _3.5 Mg _0.6 Si _0.9 O ₁₂ (garnet phosphor 2).

Example 3

The garnet fluorescent material was prepared as follows so that the molar composition ratio of each component of the garnet fluorescent material having the formula 1 was such that Lu: Ca: Al: Mg: Si: O: Ce = 2.45: 0.5: Respectively.

Specifically, Lu ₂ O ₃ (1.2474 g), Al ₂ O ₃ (0.3261 g), CaCO ₃ (0.1281 g), MgO (0.1031 g), SiO ₂ (0.2306 g), CeO ₂ ) Were wet-mixed and pulverized. The mixture was sufficiently dried and then heat-treated for 4 hours in a reducing atmosphere of 1500 degrees to prepare Lu _2.45 Ca _0.5 Ce _0.05 Al _2.5 Mg _1.0 Si _1.5 O ₁₂ (Garnet Phosphor 3).

Example 4

The garnet phosphor was manufactured as follows so that the molar composition ratio of each component of the garnet phosphor having the formula (1) was Lu: Ca: Al: Mg: Si: O: Ce = 2.25: 0.7: 1.5: Respectively.

That is, Lu ₂ O ₃ (1.1871 g), Al ₂ O ₃ (0.2028 g), CaCO ₃ (0.1858 g), MgO (0.1496 g), SiO ₂ (0.3346 g), CeO ₂ ) Were wet-mixed and pulverized. The mixture was sufficiently dried and then heat treated in a 1450 ° C reducing atmosphere for 4 hours to produce Lu _2.25 Ca _0.7 Ce _0.05 Al _1.5 Mg _1.4 Si _2.1 O ₁₂ (Garnet Phosphor 4).

Example 5

The garnet phosphor was prepared as follows so that the molar composition ratio of each component of the garnet phosphor having the formula (1) was Lu: Ba: Al: Si: O: Ce = 2.85: 0.3: 4.5: 0.3: 12:

That is, to have the molar composition ratio of _{Lu 2 O 3 (1.3055g),} Al 2 O 3 (0.5282g), BaCO 3 (0.1363g), SiO 2 (0.0415g), wet mixing and grinding the CeO ₂ (0.0198g) Respectively. The mixture was thoroughly dried and then heat treated in a 1600 degree reduction atmosphere for 4 hours to prepare Lu _2.85 Ba _0.3 Ce _0.05 Al _4.5 Si _0.3 O ₁₂ (garnet phosphor 5).

Example 6

The garnet phosphor was prepared as follows so that the molar composition ratio of each component of the garnet phosphor having the formula (1) was Lu: Ba: Al: Si: O: Ce = 2.65: 0.9: 3.5: 0.9: 12:

Namely, Lu ₂ O ₃ (0.8730 g), Al ₂ O ₃ (0.2954 g), BaCO ₃ (0.2941 g), SiO ₂ (0.0895 g) and CeO ₂ (0.0142 g) were wet-mixed and pulverized Respectively. The mixture was sufficiently dried and heat-treated for 4 hours in a reducing atmosphere of 1600 ° _C. to prepare Lu _2.65 Ba _0.9 Ce _0.05 Al _3.5 Si _0.9 O ₁₂ (garnet phosphor 6).

Comparative Example 1

A commercially available Lu ₃ Al ₅ O ₁₂ : Ce _0.05 ³⁺ (Comparative Example 1) was prepared.

Comparative Example 2

Lu ₂ CaMg ₂ Si ₃ O ₁₂ : Ce _0.05 ³⁺ (Comparative Example 2) was prepared using the method of Example 1.

Experimental Example 1

XRD analyzes of the garnet fluorescent materials 1 to 4 and the comparative fluorescent materials 1 and 2 obtained in Examples 1 to 4 were carried out, and the results are shown in Fig. PL results (luminescent center wavelengths) and quantum efficiencies of Garnet Phosphors 1 to 4 and Comparative Phosphors 1 and 2 are shown in Fig. 3 and Table 1. Fig.

λ _ex (nm) ? _em (nm) Quantum efficiency (%) Comparative Example Phosphor 1 450 526 96 Garnet Phosphor 1 450 521 90 Garnet Phosphor 2 450 530 92 Garnet Phosphor 3 450 541 90 Garnet Phosphor 4 450 553 89 Comparative Example Phosphor 2 450 578 90

It can be seen from FIG. 2 that the garnet fluorescent material 1 to the garnet fluorescent material 4 and the comparative fluorescent materials 1 and 2 have the same crystal structure.

From Table 1, it can be seen that in Lu ₃ Al ₅ O ₁₂ matrix It can be seen that even when the amount of Lu ₂ CaMg ₂ Si ₃ O ₁₂ is increased, a phosphor having a high efficiency of quantum efficiency of 89% or more can be synthesized.

3 shows that the garnet fluorescent material 1 to the garnet fluorescent material 4 obtained in the present invention can control the wavelength within the wavelength range between the fluorescent materials 1 and 2 of the comparative examples.

Example 7

The garnet fluorescent material 1 obtained in Example 1, the comparative fluorescent material 2 obtained in Comparative Example 2, the red fluorescent material and the commercialized red fluorescent material were mixed to prepare a mixture (a). Further, the garnet fluorescent material 1 obtained in Example 1, the comparative fluorescent substance 2 obtained in Comparative Example 2, and the silicone resin were mixed to prepare a mixture (b). These mixtures were injected into surface-mount device (SMD) type blue LEDs and cured at 150 ° C for 1 hour to fabricate LED-based WLEDs with excitation wavelengths of 450 nm.

Experimental Example 2

The emission spectrum when 20 mA was applied to the white LED prepared in Example 7 was observed and the results are shown in FIG.

FIG. 4 shows the applicability of the present invention when the phosphor is applied to the blue LED.

Experimental Example 3

The CIE coordinate change according to 20 mA was measured for the WLED fabricated in Example 7, and the result is shown in FIG. (A) shows the color temperature of CRI of 89, and the color temperature of 3473K (b) of 89 showed the color temperature of CRI of 89 at 6140K. In light of the fact that commercial LED lighting has a CRI of around 85, it shows the possibility of application to WLED.

Experimental Example 4

The Garnet Phosphor 5 obtained in Example 5 was subjected to XRD analysis and the results are shown in Fig. PL results (luminescence center wavelength and relative efficiency) and quantum efficiency obtained by comparing the garnet fluorescent material 5 of Example 5 with the commercial Lu ₃ Al ₅ O ₁₂ : Ce ³⁺ fluorescent material and the garnet fluorescent material 1 obtained in Example 1 are shown in FIG. 7 And Table 2.

λ _ex (nm) ? _em (nm) Relative light emission intensity (%) Quantum efficiency (%) Commercial phosphor 450 513 100 90 Garnet Phosphor 1 450 521 95 90 Garnet Phosphor 5 450 513 107 93

From FIG. 6, it can be seen that Garnet Phosphor 5 has the same crystal structure as Comparative Garnet 1 as Garnet Phosphor 1 to Garnet Phosphor 4.

7 and Table 2, it can be seen that the garnet fluorescent material 5 developed through the present invention has a higher luminescence intensity and quantum efficiency than the commercial fluorescent material by reducing the amount of lutetium through the solid solution method.

Experimental Example 5

The garnet fluorescent material 6 obtained in Example 6 was subjected to XRD analysis and the results are shown in Fig. The PL result (luminescent center wavelength and relative efficiency) of the Garnet Phosphor 6 of Example 6 compared with the Garnet Phosphor 2 obtained in Example 2 is shown in Fig.

It can be seen from FIG. 8 that the garnet fluorescent material 6 has the same crystal structure as the comparative example fluorescent material 1, like the garnet fluorescent material 1 to the garnet fluorescent material 5.

It can be seen from FIG. 9 that the garnet fluorescent material 6 exhibits a better light emission intensity than the garnet fluorescent material 3, and thus it has different light emission characteristics depending on the selected ions even when the same solid solution fluorescent material method is used.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is clearly understood that the same is by way of illustration and example only and is not to be taken by way of limitation, Various changes and modifications will be possible.

Claims (12)

A garnet fluorescent material having the following formula (1).
[Chemical Formula 1]
(A _{3-y x} B _x ) (C _2-2x D _2x ) (E _3-3x F _3x ) O ₁₂ : Ce _y ³⁺
Wherein A is an element selected from the group consisting of Lu, Y, La and Tb and B is an element selected from the group consisting of Ca, Ba, Sr and Mg, C is an element selected from the group consisting of Al, Sc, Ga and Gd; D is an element selected from divalent alkali metal groups including Ca, Ba, Sr and Mg; E is one kind of element selected from the group consisting of ternary metal ions including Al, Sc, Ga and Gd, and F is one kind of element selected from the group consisting of Si, Ge, Zr and Ti. 0 < x < 1, 0 < y < 0.3.
The method according to claim 1,
Wherein the formula (1) has the same composition as the solid solution of A ₃ C ₅ O ₁₂ and A ₂ BD ₂ F ₃ O ₁₂ .
3. The method of claim 2,
Wherein x and y in the formula (1) are determined according to the ratio of A ₃ C ₅ O ₁₂ and A ₂ BD ₂ F ₃ O ₁₂ solubilized.
The method according to claim 1,
Wherein the emission wavelength and the emission luminance of the phosphor are changed according to the compositional change according to x value and y value in the above formula (1).
5. The method according to any one of claims 1 to 4,
Wherein the environment of the site where the activator is substituted by at least one of B and D in the formula (1) is changed to control the luminescence properties of the phosphor.
Preparing a raw material according to the phosphor composition according to claim 1;
Weighing the raw materials at a phosphor composition ratio of Formula 1 and uniformly mixing them; And
And firing the uniformly mixed raw material in a reducing atmosphere.
The method according to claim 6,
Wherein the calcining step is performed by performing a heat treatment at a temperature of 1000 to 1600 캜 for 1 to 12 hours in a gas atmosphere in which nitrogen and hydrogen are mixed at a volume ratio of 75 to 95: 25 to 5 .
In a light-emitting device including a luminescent light source and a phosphor,
Wherein the phosphor comprises the garnet fluorescent material according to any one of claims 1 to 5. The light emitting device according to claim 1,
9. The method of claim 8,
Wherein the phosphor emits green or yellow light having a wavelength in the range of 500 nm to 600 nm when the luminescent light source is an ultraviolet ray, a visible ray or an electron ray having a wavelength in the range of 100 nm to 470 nm.
9. The method of claim 8,
Wherein the light emitting device is a white light emitting device if the light emitting source is an excitation light source of 450 to 470 nm.
9. The method of claim 8,
Wherein the phosphor is mixed with the silicone resin in a weight ratio of 1: 5-15.
9. The method of claim 8,
Wherein the light emitting element comprises a light emitting diode, a laser diode, a surface emitting laser diode, an inorganic electroluminescence element, or an organic electroluminescence element.

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