WO2016114481A1 - Method for manufacturing color conversion material using nano glass powder, and white light-emitting device - Google Patents

Abstract

Disclosed are a method for manufacturing a color conversion material using nano glass powder, and a white light-emitting device. The method for manufacturing a color conversion material using nano glass powder according to the present invention is a method for manufacturing a color conversion material (phosphor-in-glass (PiG)) which is disposed on the front side of an LED and converts colors, the method comprising the steps of: crushing parent glass to form nano glass powder with an average grain size equal to or less than 100 nm; mixing the nano glass powder and phosphors to form a mixture; shaping the mixture to form a compact; and sintering the compact.

Description

Color conversion material manufacturing method and white light emitting device using nano glass powder

The present invention relates to a color conversion glass (Phosphor In Glass (PIG)) manufacturing technology for LEDs, and more particularly to a method for producing a color conversion material and a light emitting device having excellent color conversion efficiency and light transmittance using nano glass powder. will be.

Phosphors are required for white light emission from LEDs emitting monochromatic light such as blue light.

The following three methods are mainly used to implement the phosphor.

The first method is to mold silicon mixed with yellow phosphor on a blue LED chip. In the case of the white LED package manufactured in such a form, there is a problem in that yellowing occurs due to deterioration of the color conversion material at a high temperature, and also serves as a main factor in the deterioration of reliability due to gas and moisture penetration.

The second is a method of dispersing and molding a yellow phosphor in an organic material such as epoxy. In this case, too, there is a problem that the heat resistance is weak by using an organic material.

The third method is to mount a color conversion glass (Phosphor In Glass (PIG)) in which a yellow phosphor is dispersed in the glass in a cover form. In this case, the high temperature deterioration problem can be solved as described above, and the resistance to gas and moisture penetration is also excellent. In this case, firing should be performed at a sufficiently high temperature to increase the light transmittance. However, in the case of high temperature firing, the problem of phosphor degradation often occurs.

Background art related to the present invention is a rare earth ion-containing glass-phosphor composite disclosed in Korea Patent Publication No. 10-2014-0106332 (published on September 3, 2014) and a light emitting diode comprising the same.

One object of the present invention is to provide a method for producing a color conversion material that can reduce the firing temperature using the nano glass powder to suppress the reaction with the phosphor, and also excellent light transmittance.

Another object of the present invention is to provide a white light emitting device having excellent color conversion efficiency and light transmittance even when the temperature of the light emitting device is increased to 200 ° C. or more.

Color conversion material manufacturing method according to an embodiment of the present invention for achieving the above object is a method of manufacturing a color conversion material (Phosphor In Glass (PIG)) is disposed on the front of the LED to convert the color, the average particle diameter of 100nm Forming a nano glass powder which is less than or equal to; Mixing the nano glass powder and the phosphor to form a mixture; Molding the mixture to form a molded body; And firing the molded body.

Color conversion material manufacturing method according to another embodiment of the present invention for achieving the above object is a method for manufacturing a color conversion material to convert the color is disposed on the front surface of the LED, forming a nano glass powder having an average particle diameter of 100nm or less Making; Preparing a paste including the nano glass powder and the phosphor; And baking the paste on the substrate glass and then firing the paste.

At this time, the nano glass powder is made of a weight percent, SiO ₂ 55-70%, Al ₂ O ₃ 10-22%, B ₂ O ₃ 1-15%, CaO 10% or less and SrO 2-10%, R ₂ O (R = Li, Na, K, Rb and Cs), Sb ₂ O ₃ , F, Cl, SO ₃ , P ₂ O ₅ , V ₂ O ₅ , PbO, ZnO and Bi ₂ O ₃ are intentionally It may not be added.

In addition, the nano glass powder is by weight, SiO ₂ 55-70%, Al ₂ O ₃ 10-22%, B ₂ O ₃ 1-15%, CaO 10% or less, SrO 2-10%, MgO 5 weight It consists of one or more of% or less and BaO: 5% by weight or less, R ₂ O (R = Li, Na, K, Rb and Cs), Sb ₂ O ₃ , F, Cl, SO ₃ , P ₂ O ₅ , V ₂ O ₅ , PbO, ZnO and Bi ₂ O ₃ may not be added intentionally.

In addition, the phosphor may be (Lu _x Ce _1-x ) ₃ Al ₅ O ₁₂ (0.75 ≦ _x ≦ 0.95).

A white light emitting device according to an embodiment of the present invention for achieving the other object includes an LED and a color conversion material (Phosphor In Glass (PIG)) disposed on the front of the LED, the LED emits blue light, the color The conversion material is a yellow phosphor is dispersed in the glass, the yellow phosphor is characterized in that (Lu _x Ce _1-x ) ₃ Al ₅ O ₁₂ (0.75≤x≤0.95).

At this time, the glass in weight%, SiO ₂ 55-70%, Al ₂ O ₃ 10-22%, B ₂ O ₃ 1-15%, CaO 10% or less and SrO 2-10%, R ₂ O (R = Li, Na, K, Rb and Cs), Sb ₂ O ₃ , F, Cl, SO ₃ , P ₂ O ₅ , V ₂ O ₅ , PbO, ZnO and Bi ₂ O ₃ are not intentionally added It may not be.

In addition, the glass by weight, SiO ₂ 55-70%, Al ₂ O ₃ 10-22%, B ₂ O ₃ 1-15%, CaO 10% or less, SrO 2-10%, MgO 5% by weight or less And BaO: made of at least one of 5 wt% or less, R ₂ O (R = Li, Na, K, Rb and Cs), Sb ₂ O ₃ , F, Cl, SO ₃ , P ₂ O ₅ , V ₂ O ₅ , PbO, ZnO and Bi ₂ O ₃ may not be intentionally added.

According to the method of manufacturing a color conversion material using the nano glass powder according to the present invention, by using the characteristic that the firing temperature is lowered as the size of the glass powder is nanoscaled, the firing temperature can be lowered without lowering the light transmittance, and thus the phosphor reaction. By suppressing this, the fall of the color conversion efficiency can be prevented.

In addition, (Lu _x Ce _1-x ) ₃ Al ₅ O ₁₂ (0.75≤x≤0.95), which is mainly used as a green phosphor, was calcined together with glass powder to prepare a color conversion material and applied to a white light emitting device. Even if the temperature was increased to 200 ° C. or more during driving of the LED, the deterioration of the phosphor characteristic was not large, and thus the light output characteristic was not deteriorated even at a high temperature.

Figure 1 _{(Lu 0. 9 Ce 0.} 1) shows the characteristics change according to the temperature of ₃ Al ₅ O ₁₂ phosphor.

2 schematically shows an example of a white light emitting device according to the present invention.

[Description of the code]

101: package body 102: LED chip

103: color conversion glass

Advantages and features of the present invention and methods for achieving them will be apparent with reference to the embodiments and drawings described below in detail. However, the present invention is not limited to the embodiments disclosed below, but can be implemented in various different forms, only the embodiments are to make the disclosure of the present invention complete, it is common in the art It is provided to fully inform those skilled in the art of the scope of the invention, which is to be defined only by the scope of the claims.

Hereinafter, with reference to the accompanying drawings, a method for manufacturing a color conversion material and a white light emitting device using nano glass powder according to the present invention will be described in detail.

The method for producing a color conversion material (Phosphor In Glass; PIG) according to the present invention uses a nano glass powder having an average particle diameter of 100 nm or less.

In the case of a glass-based color conversion material, the glass firing temperature must be high enough to suppress the generation of bubbles, thereby obtaining a high light transmittance. However, at such high firing temperatures, color conversion efficiency decreases often due to phosphor deterioration.

As disclosed in the detailed description of Korean Patent Laid-Open Publication No. 10-2009-0032639, in the case of glass powder, the smaller the size thereof, the higher the meltability, and the lower the firing temperature thereof. The present invention provides a method for producing a color conversion material having excellent light transmittance and excellent color conversion efficiency by applying such characteristics.

The color conversion material manufacturing method according to an embodiment of the present invention may use a bulk baking method or a paste baking method.

In the case of the bulk firing method, a nano glass powder having an average particle diameter of 100 nm or less is formed, and mixed with a phosphor to form a mixture, and then molding, and then firing the molded body.

The phosphor may be included in an amount of about 3 to 70 wt% based on the total weight of the nano glass powder and the phosphor. The content of the phosphor may be adjusted by the thickness of the color conversion material, the LED size, the number of LEDs, and the like.

In the case of the paste firing method, a process may include forming a nano glass powder having an average particle diameter of 100 nm or less, preparing a paste including the nano glass powder and the phosphor, applying the paste to the substrate glass, and then firing the paste.

The paste may include an organic solvent, an organic binder, and the like, and these components are removed in a drying process and a firing process after applying the paste.

On the other hand, the nano glass powder is composed of weight%, SiO ₂ 55-70%, Al ₂ O ₃ 10-22%, B ₂ O ₃ 1-15%, CaO 10% or less and SrO 2-10%, R ₂ O (R = Li, Na, K, Rb and Cs), Sb ₂ O ₃ , F, Cl, SO ₃ , P ₂ O ₅ , V ₂ O ₅ , PbO, ZnO and Bi ₂ O ₃ are intentionally added It may not be. Glass Composition 1

In addition, nano glass powder is in weight percent, SiO ₂ 55-70%, Al ₂ O ₃ 10-22%, B ₂ O ₃ 1-15%, CaO 10% or less, SrO 2-10%, MgO 5% by weight It consists of one or more of the following and BaO: 5% by weight or less, R ₂ O (R = Li, Na, K, Rb and Cs), Sb ₂ O ₃ , F, Cl, SO ₃ , P ₂ O ₅ , V ₂ O ₅ , PbO, ZnO and Bi ₂ O ₃ may not be intentionally added. Glass Composition 2

Phosphors can be degraded not only at high temperatures but also by the glass itself.

In the case of the glasses, components capable of exhibiting chemical reactions with phosphors, such as R ₂ O (R = Li, Na, K, Rb and Cs), Sb ₂ O ₃ , F, Cl, SO ₃ , By preventing the use of P ₂ O ₅ , V ₂ O ₅ , PbO, ZnO, and Bi ₂ O ₃ , the color conversion efficiency can be maximized and bubbles can be suppressed by firing for a short time above the softening temperature. As a result, light transmittance and light extraction efficiency can be improved.

Hereinafter, the role of each component and its content will be described.

SiO ₂ contributes to improving the glass stability by forming a three-dimensional network structure. The SiO ₂ is preferably added at 55 to 70% by weight of the total weight of the glass. When the addition amount of SiO ₂ is less than 55% by weight, the addition effect is insufficient. In contrast, if SiO ₂ exceeds 70% by weight, there is a problem in the glass softening temperature is too high.

Al ₂ O ₃ contributes to glass stabilization. The Al ₂ O ₃ is preferably added at 10 to 22% by weight of the total weight of the glass. When the addition amount of Al ₂ O ₃ is less than 10% by weight, the addition effect is insufficient. On the contrary, when the addition amount of Al ₂ O ₃ exceeds 22% by weight, the glass fluidity may be greatly reduced.

B ₂ O ₃ contributes to the formation of mesh, and contributes to lowering the firing temperature through viscosity reduction. The B ₂ O ₃ is preferably added in 1 to 15% by weight of the total weight of the glass. When the amount of B ₂ O ₃ added is less than 1% by weight, the effect of addition is insufficient. In contrast, when the amount of B ₂ O ₃ added exceeds 15% by weight, crystallization of the glass may proceed rapidly.

CaO and SrO lower the softening temperature of the glass, contributing to lowering the firing temperature for producing color converted glass. These components are preferably added in CaO: 10% by weight or less, SrO: 2-10% by weight, and may further include one or more of 5% by weight or less of MgO and 5% by weight or less of BaO. In addition, the total content of CaO, SrO, MgO, BaO is more preferably 10 to 25% by weight of the total weight of the glass. In the above range, the softening temperature may be lowered without reducing the light transmittance, and when any component exceeds the above range, problems such as reduced fluidity and promotion of crystallization may occur.

When the glass having the composition has a micro size of about 100 μm, the glass may be manufactured by baking at about 800 ° C. or more corresponding to a softening temperature or more. In particular, when miniaturized to nano size, the firing temperature may be lowered to about 750 ℃ or more. When firing below the softening temperature of the glass powder, there is a problem that a large amount of bubbles are generated in the fired glass to lower the light transmittance and light extraction efficiency, it is preferable to perform the firing above the softening temperature of the glass. However, when the firing temperature is too high exceeding 980 ℃, phosphor discoloration may occur.

In order to evaluate the effect of the glass composition was carried out the following experiment.

To the glass powder having a glass composition shown in Table 1 and Table 2, the phosphors were mixed in the same amount and molded in a plate form, and then baked at the firing temperature shown in Table 3 for 30 minutes to prepare a color conversion material.

In Table 1 and Table 2, a unit is a weight part, and when a total is 100 weight part, it is the same value as weight%.

TABLE 1

TABLE 2

TABLE 3

(2) Visually evaluating the phosphor reaction with respect to the basic color conversion glass to which glass compositions 1 to 42 were applied, and evaluated according to the following criteria.

O: Excellent (no phosphor discoloration)

(Triangle | delta): Normal (phosphor discolors finely)

X: Not applicable (phosphor discoloration)

Referring to Table 3, in the case of the specimens 38 to 41 satisfying the glass component presented in the present invention, the phosphor discoloration did not occur as a whole, although firing was performed at 800 ° C. or higher. However, in case of specimen 42, the phosphor was slightly discolored when firing was performed at an excessively high temperature of 1000 ° C.

However, in the case of specimens 1 to 37 that did not satisfy the glass component presented in the present invention, phosphor discoloration occurred as a whole.

In the above examples, the glass powder having an average particle diameter of 100 μm is used. When the glass powder is micronized, the firing temperature may be lowered, and thus the effect of preventing phosphor degradation during firing may be further improved.

In addition, the phosphor may be a (Lu _x Ce _1-x ) ₃ Al ₅ O ₁₂ (0.75 ≦ _x ≦ 0.95) phosphor. In general, where yellow and blue light emitting phosphor is a YAG _{phosphor, (Sr 1. 7 Ba 0} . 2 Eu 0. 1) SiO 4 phosphor, a nitride phosphor is used. However, these phosphors have a characteristic in that when the temperature of the light emitting device rises above 200 ° C by driving the LED, the characteristics thereof deteriorate rapidly.

In the case of the (Lu _x Ce _1-x ) ₃ Al ₅ O ₁₂ (0.75 ≦ _x ≦ 0.95) phosphor, it is mainly used as a blue excited green light emitting phosphor. However, when the (Lu _x Ce _1-x ) ₃ Al ₅ O ₁₂ phosphor was fired like glass to prepare a color conversion material, a phenomenon in which white light was output was shown. This is a result of converting the color characteristics from green to yellow when the (Lu _x Ce _{1 -x} ) ₃ Al ₅ O ₁₂ phosphor is fired together with the glass.

In _{addition, (Lu x Ce 1 -x)} 3 Al 5 O ₁₂ phosphor of the _{case, (. Lu 0 9 Ce 0} . 1) and then fired together with the glass ₃ Al ₅ O diagram showing a characteristic variation due to temperature of the first phosphor ₁₂ As shown in the present invention, when the light output characteristics are not significantly reduced at a high temperature of 200 ° C. or higher, when the glass and the phosphor are fired together, the phosphor can be replaced with the conventional yellow phosphor.

2 schematically shows an example of a white light emitting device according to the present invention.

Referring to FIG. 2, the white light emitting device according to the present invention includes an LED chip 102 and a color conversion material 103. The LED chip 102 is mounted on the package body 101 and outputs blue light.

The color conversion material 103 is disposed in front of the LED, the color conversion material is a yellow phosphor dispersed in the glass, the yellow phosphor as described above (Lu _x Ce _{1 -x} ) ₃ Al ₅ O ₁₂ (0.75 ≤ x ≤ 0.95).

At this time, the glass is by weight, SiO ₂ 55-70%, Al ₂ O ₃ 10-22%, B ₂ O ₃ 1-15%, CaO 10% or less and SrO 2-10%, R ₂ O (R = Li, Na, K, Rb and Cs), Sb ₂ O ₃ , F, Cl, SO ₃ , P ₂ O ₅ , V ₂ O ₅ , PbO, ZnO and Bi ₂ O ₃ are not intentionally added It may be.

In addition, the glass is in terms of weight%, 55 to 70% SiO ₂ , 10 to 22% Al ₂ O ₃ , 1 to 15% B ₂ O ₃ , 10% or less CaO, 2 to 10% SrO, 5% to MgO and BaO: made of one or more of 5% by weight or less, R ₂ O (R = Li, Na, K, Rb and Cs), Sb ₂ O ₃ , F, Cl, SO ₃ , P ₂ O ₅ , V ₂ O ₅ , PbO, ZnO and Bi ₂ O ₃ may not be intentionally added.

As described above, according to the method of manufacturing a color conversion material using the nano glass powder according to the present invention, by using the characteristic that the firing temperature is lowered as the size of the glass powder becomes nano, the firing temperature can be lowered without lowering the light transmittance. Therefore, the fall of color conversion efficiency can be prevented by suppressing fluorescent reaction.

In addition, (Lu _x Ce _1-x ) ₃ Al ₅ O ₁₂ (0.75≤x≤0.95), which is mainly used as a green phosphor, was calcined together with glass powder to prepare a color conversion material and applied to a white light emitting device. In addition to exhibiting characteristics, even at a high temperature of 200 ° C. or more, the light output characteristic deterioration can be exhibited with little effect.

Although the embodiments of the present invention have been described above with reference to the accompanying drawings, the present invention is not limited to the above embodiments and can be modified in various forms, and having ordinary skill in the art to which the present invention pertains. It will be understood by those skilled in the art that the present invention may be embodied in other specific forms without changing the technical spirit or essential features of the present invention. Therefore, it should be understood that the embodiments described above are exemplary in all respects and not restrictive.

Claims (8)

1. As a method of manufacturing a color conversion material (Phosphor In Glass (PIG)) is disposed on the front of the LED to convert the color,

   Forming a nano glass powder having an average particle diameter of 100 nm or less;

   Mixing the nano glass powder and the phosphor to form a mixture;

   Molding the mixture to form a molded body; And

   Calcining the molded body; color conversion material manufacturing method comprising a.
2. As a method of manufacturing a color conversion material disposed on the front of the LED to convert the color,

   Forming a nano glass powder having an average particle diameter of 100 nm or less;

   Preparing a paste including the nano glass powder and the phosphor; And

   And applying the paste to the substrate glass and then firing the paste.
3. The method according to claim 1 or 2,

   The nano glass powder

   By weight%, consisting of 55 to 70% SiO ₂ , 10 to 22% Al ₂ O ₃ , 1 to 15% B ₂ O ₃ , CaO 10% or less and SrO 2 to 10%,

   R ₂ O (R = Li, Na, K, Rb and Cs), Sb ₂ O ₃ , F, Cl, SO ₃ , P ₂ O ₅ , V ₂ O ₅ , PbO, ZnO and Bi ₂ O ₃ are intentionally Color conversion material manufacturing method characterized in that it is not added.
4. The method according to claim 1 or 2,

   The nano glass powder

   By weight%, SiO ₂ 55-70%, Al ₂ O ₃ 10-22%, B ₂ O ₃ 1-15%, CaO 10% or less, SrO 2-10%, MgO 5% by weight or BaO: 5 weight It consists of one or more of% or less,

   R ₂ O (R = Li, Na, K, Rb and Cs), Sb ₂ O ₃ , F, Cl, SO ₃ , P ₂ O ₅ , V ₂ O ₅ , PbO, ZnO and Bi ₂ O ₃ are intentionally Color conversion material manufacturing method characterized in that it is not added.
5. The method according to claim 1 or 2,

   The phosphor is a (Lu _x Ce _1-x ) ₃ Al ₅ O ₁₂ (0.75≤x≤0.95) phosphor, characterized in that the color conversion material manufacturing method.
6. An LED and a color conversion material (Phosphor In Glass; PIG) disposed on the front of the LED,

   The LED emits blue light,

   The color conversion material is a white light emitting device, characterized in that the yellow phosphor is dispersed in the glass, the yellow phosphor is (Lu _x Ce _1-x ) ₃ Al ₅ O ₁₂ (0.75≤x≤0.95) phosphor.
7. The method of claim 6,

   The glass is

   By weight%, consisting of 55 to 70% SiO ₂ , 10 to 22% Al ₂ O ₃ , 1 to 15% B ₂ O ₃ , CaO 10% or less and SrO 2 to 10%,

   R ₂ O (R = Li, Na, K, Rb and Cs), Sb ₂ O ₃ , F, Cl, SO ₃ , P ₂ O ₅ , V ₂ O ₅ , PbO, ZnO and Bi ₂ O ₃ are intentionally White light emitting device, characterized in that not added.
8. The method of claim 6,

   The glass is

   By weight%, SiO ₂ 55-70%, Al ₂ O ₃ 10-22%, B ₂ O ₃ 1-15%, CaO 10% or less, SrO 2-10%, MgO 5% by weight or BaO: 5 weight It consists of one or more of% or less,

   R ₂ O (R = Li, Na, K, Rb and Cs), Sb ₂ O ₃ , F, Cl, SO ₃ , P ₂ O ₅ , V ₂ O ₅ , PbO, ZnO and Bi ₂ O ₃ are intentionally White light emitting device, characterized in that not added.

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