JP2009270091A - Fluorescent glass, method of manufacturing fluorescent glass, semiconductor light-emitting device, and method of manufacturing semiconductor light-emitting device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a sealing material excellent in transmittance of light in a wavelength region from the ultraviolet ray to the visible ray (achromatic transparency), light fastness, heat resistance, hydrothermal resistance, resistance to ultraviolet ray, scratch resistance, and chemical resistance. <P>SOLUTION: The fluorescent glass includes glass and a phosphor, and is characterized in that it has an L<SB>*</SB>value of 65 or more in the chromaticity coordinate of an L<SB>*</SB>a<SB>*</SB>b<SB>*</SB>color system, or the fluorescent glass is characterized in that it includes the glass having characteristics described below and the phosphor. [The characteristics of the glass]: the L<SB>*</SB>value in the chromaticity coordinate of the L<SB>*</SB>a<SB>*</SB>b<SB>*</SB>color model is 50 or more when the glass has been pulverized so as to have an average particle size of 60 μm or less and has been sintered at a temperature of (surrender point +50)°C for one hour. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

The present invention relates to a fluorescent glass exhibiting excellent heat resistance and UV resistance. Such fluorescent glass is suitably used, for example, in the field of sealing materials for semiconductor light emitting devices.
The present invention also relates to an efficient method for producing the fluorescent glass.
In this specification, “colorless” means that light in the wavelength range of visible light from near ultraviolet light (350 to 800 nm) is not substantially absorbed. Specifically, in the measured value of a color difference meter This can be confirmed by the fact that the a _* value and b _* value are zero and the L _* value is positive.

Currently, lighting equipment using a white light emitting diode (hereinafter referred to as “LED”) as a light emitting element is being put into practical use. Advantages of using a white LED as a light source for illumination are: 1) lower power consumption and lower running costs compared to incandescent and fluorescent lamps, 2) long life and saves time and effort for replacement 3) small size 4) Do not use harmful substances such as mercury in fluorescent lamps.
A general white LED has a structure in which the LED is sealed (hereinafter referred to as “translucent sealing”) with a transparent resin while maintaining the transparency. For example, in a classic one-chip type white LED, a blue LED, for example, a blue LED having an emission layer of InGaN in which GaN is added with In, a phosphor that emits yellow light by blue light emitted from the LED, For example, it is sealed with a transparent resin containing a YAG phosphor. As a transparent resin used for the sealing, an epoxy resin has been conventionally used. (Patent Documents 1 and 2) When a current is passed through the blue LED, blue light (wavelength 450 to 460 nm) is emitted from the LED. Next, the YAG phosphor is excited by part of the blue light, and yellow light is emitted from the phosphor. Since blue light and yellow light are in a complementary color relationship, when they are mixed, they are recognized as pseudo white light by human eyes.

However, the pseudo white light produced by the combination of the blue LED and the YAG phosphor has low color rendering, and the color of the object illuminated with the pseudo white does not look vivid, and it is illuminated under sunlight, particularly in the red region. There is a problem that a considerable shift occurs between the obtained color tone and the color tone.
Therefore, research has been actively conducted to develop a light source that emits white light using RGB tricolor phosphors by making light emitted from the LED chip shorter near-ultraviolet.
However, since epoxy resins that have been used in the past are extremely inferior in heat resistance and light resistance (particularly, UV resistance), the epoxy resin is subject to thermal degradation or light degradation at the time of use. There has been a problem that light penetration of the light-transmitting sealed portion is reduced due to moisture entering the LED and hindering the operation of the LED, or the resin being discolored by ultraviolet rays emitted from the LED.

  Further, the LED can be used at a higher ambient temperature and a larger input as the heat resistance from the mounting substrate to the light emitting portion is smaller and the heat resistant temperature is higher. Therefore, thermal resistance and heat resistance are key points for increasing the output of the LED. However, since the epoxy resin is inferior in heat resistance, there is a problem that it is not suitable for use at high output. For example, a general epoxy resin is yellowed at a temperature of 130 ° C. or higher.

  In order to solve the above-described problems, it has been disclosed to use a fluorinated cured product for translucent sealing of a light emitting element (Patent Document 3). Fluorine-containing cured products are superior in colorless transparency, light resistance and heat resistance compared to epoxy resins, but are inferior in adhesion to the object to be encapsulated, and therefore easily peel off from the object to be encapsulated. There is. In addition, the material of the LED chip, specifically the material of the light emitting layer of the LED chip, has a refractive index, specifically, the refractive index of light in the visible light region is as high as 2.5 to 3.0, but it contains fluorine. Since the cured product has a low refractive index of light in the same wavelength region, extraction efficiency of light in the same wavelength region is not always sufficient.

On the other hand, LED sealed with the glass produced by the sol-gel method is proposed conventionally (patent document 4). According to this LED, it is possible to reduce the hygroscopicity through the sealing material and the light transmission deterioration due to the discoloration of the sealing material, and it is also possible to improve the heat resistance.
However, since the sol-gel glass easily has pores and cracks are easily generated, there is a problem that the operation of the LED is hindered when moisture enters the pores or cracks. In general, glass is inferior in adhesiveness to a substrate or a wiring metal as compared with a resin, so that there is a problem that moisture enters from an interface between the sealing glass and the substrate or the wiring metal.

  In addition, silicone resins (polyorganosiloxane), which are excellent in heat resistance and ultraviolet light resistance, have been used as substitutes for epoxy resins. However, all of the silicone resins up to now are easily scratched, and adhesion, colorless transparency, heat resistance, hydrothermal resistance, and UV resistance are still insufficient (Patent Documents 5 to 10).

Moreover, although an epoxy resin and a silicone resin are usually mixed with a phosphor as a liquid medium and used as a phosphor paste, there are problems in the following points.
First of all, it was difficult to uniformly disperse micron-sized phosphor particles in a liquid. Secondly, precipitation was often caused by gravity before or during curing, and uniform light emission was often not obtained. Third, when phosphors of a plurality of colors are mixed and used, their precipitation conditions are different from each other, so that the color may be influenced by the difference in the precipitation condition. Fourth, it is difficult to adjust the viscosity by dispersion mixing, and it is difficult to obtain a uniform situation with good reproducibility. Fifth, the liquid paste mixed with the phosphor often thickens in a relatively short time, and it has been pointed out that the pot life is short and the storage stability is not good.

  In addition, hybrid materials of inorganic nanoparticles and silicone have been used recently for the purpose of increasing the refractive index of this sealing glass to increase the light extraction efficiency from the LED and to improve physical properties. Such a system usually prepares an optically transparent formulation by uniformly dispersing nanoparticles with a diameter of 10 nm or less in the silicone before curing, but the evidence that the performance and durability as an LED device has been greatly improved. The reality is that I haven't caught it.

  In response to these problems, it has also been proposed that the low melting point glass is heated and melted to translucently seal the LED (Patent Documents 5 and 10). However, the low-melting glass has a problem that the emission intensity is not sufficient when it is used for a semiconductor light-emitting device because colorless transparency is impaired in the heating and melting step.

US Published Patent US2004 / 0063840 Specification International Publication WO2005 / 085303 Pamphlet Japanese Patent Laid-Open No. 2002-203989 JP 2004-356506 A US Pat. No. 5,648,687 International Publication WO2006 / 055456 Pamphlet US Patent US7160972 US Pat. No. 6,204,523 US Pat. No. 6,590,235 JP 2008-41844 A

  In order to solve the above-mentioned problems in the prior art, the present invention is transparent to light in the wavelength region from ultraviolet light to visible light, that is, colorless transparency, light resistance, heat resistance, hydrothermal resistance, UV resistance, scratch resistance. It aims at providing the sealing material excellent in chemical resistance.

  As a result of intensive studies, the present inventors have found that the low-melting glass causes a color change due to carbonization of a carbon component contained as an impurity by heating and melting and impairs the colorlessness. And it discovered that fluorescent glass fully satisfying colorless transparency was obtained by introducing the process of removing this carbon component beforehand. The gist of the present invention is as follows.

(1) A fluorescent glass containing glass and a phosphor dispersed in the glass, wherein the L _* value in the chromaticity coordinates of the L _* a _* b _* color system is 65 or more .
(2) A fluorescent glass containing a glass having the following characteristics and a phosphor dispersed in the glass.
[Characteristics of glass]
The glass was ground to average particle size of not more than 60 [mu] m, at a temperature of (sag +50) ° C., when 1 hour of sintering, the value of L _* is in the L _* a _* b _* color system chromaticity coordinates 50 or more.
(3) The fluorescent glass according to (1) or (2), wherein a carbon component of the glass is 100 ppm or less.
(4) The fluorescent glass according to any one of (1) to (3), wherein the surface is hydrophobized.
(5) The phosphor is a group consisting of M ₃ SiO ₅ , MS, MGa ₂ S ₄ , MAlSiN ₃ , M ₂ Si ₅ N ₈ , MSi ₂ N ₂ O ₂ as a base crystal (where M is Ca, At least one selected from the group consisting of Sr and Ba, and Cr, Mn, Fe, Bi, Ce, Pr, Nd, Sm, Eu, The fluorescence according to any one of (1) to (4), which is a phosphor containing at least one of Tb, Dy, Ho, Er, Tm, and Yb, or a phosphor containing Mn ⁴⁺ as an activator. Glass.
(6) The fluorescent glass according to any one of (1) to (5), wherein the specific gravity is 4 or less.
(7) The method for producing a fluorescent glass according to any one of (1) to (6), wherein the step of preparing the glass, the glass, and the phosphor or phosphor precursor are mixed. And a method for producing fluorescent glass, comprising a step of sintering and a step of sintering the mixture obtained in the step of mixing.
(8) The method for producing a fluorescent glass according to (7), wherein the step of preparing the glass comprises:
A method for producing fluorescent glass, comprising a step of firing and pulverizing the glass.
(9) The method for producing a fluorescent glass according to (7) or (8), wherein the mixing step includes a step of mixing the glass powder obtained in the crushing step and the phosphor. A method for producing fluorescent glass.
(10) The method for producing a fluorescent glass according to any one of (7) to (9), wherein the phosphor and the sintered body surface of the phosphor and glass obtained in the sintering step are bonded to the phosphor. A process of repeating a step of adhering a small amount of the mixed powder with the glass powder and sintering it at a high temperature so as to be integrated with the sintered body of the base material, and a step of adhering and sintering the mixed powder in a small amount. To produce fluorescent glass.
(11) A semiconductor light-emitting device comprising a sealing member containing the fluorescent glass according to any one of (1) to (6), wherein the semiconductor light-emitting device includes a sealing member for sealing a semiconductor light-emitting element, and the fluorescent glass Is a semiconductor light emitting device arranged on the optical path of the semiconductor light emitting element.
(12) The semiconductor light-emitting device according to (11), wherein the fluorescent glass has a part having a different specific gravity, and a specific gravity at a part far from the semiconductor light-emitting element than a specific gravity at a part near the semiconductor light-emitting element. Semiconductor light-emitting device arranged so that becomes larger.
(13) The semiconductor light-emitting device according to (11) or (12), wherein the fluorescent glass contains bubbles.
(14) A method for manufacturing a semiconductor light-emitting device according to any one of (11) to (13), which is obtained in a step of mixing glass and a phosphor or a phosphor precursor, and the step of mixing. A method of manufacturing a semiconductor light emitting device, comprising: arranging a mixture so as to cover the semiconductor light emitting element, and sintering the mixture together with the semiconductor light emitting element.
(15) The method for manufacturing a semiconductor light emitting device according to (14), wherein the sintering step includes a step of heating in an oxidizing atmosphere.
(16) A method for manufacturing a semiconductor light emitting device according to (11) to (13), wherein a step of placing a semiconductor light emitting element on a base including a wiring portion, and the semiconductor light emitting element on the base A method for manufacturing a semiconductor light emitting device, comprising: a step of arranging fluorescent glass so as to cover the substrate; and a step of hermetically sealing the fluorescent glass and the base via a sealing member.

It is a SEM photograph of the section of fluorescent glass of the present invention. 1 is a schematic cross-sectional view showing a first embodiment. FIG. 6 is a schematic cross-sectional view showing a second embodiment. FIG. 6 is a cross-sectional view of a main part shown in the second embodiment. FIG. 6 is a schematic cross-sectional view showing a third embodiment. FIG. 6 is a cross-sectional view of a main part shown in the third embodiment. FIG. 6 is a schematic cross-sectional view showing a fourth embodiment. FIG. 10 is a cross-sectional view of a main part shown in the fourth embodiment. FIG. 10 is a perspective view of a main part shown in the fourth embodiment. It is a result of the lighting life test of the semiconductor light-emitting device using the fluorescent glass of this invention. It is a result of the weight change test of the semiconductor light-emitting device using the fluorescent glass of this invention. It is the light emission characteristic (light emission spectrum) of the semiconductor light-emitting device using the fluorescent glass of this invention. It is the light emission characteristic (light emission spectrum) of the semiconductor light-emitting device using the fluorescent glass of this invention.

The fluorescent glass of the present invention is a fluorescent glass containing glass and phosphor, and is characterized in that the value of L _* in the chromaticity coordinates of the L _* a _* b _* color system is 65 or more.
The fluorescent glass of the present invention can be prepared by the following production method using the glass and phosphor described below.
By using the fluorescent glass of the present invention (fluorescent glass containing glass or phosphor, and the value of L _* in the chromaticity coordinates of the L _* a _* b _* color system is 65 or more), It can be made colorless and transparent, and the light extraction efficiency is improved. Therefore, it is possible to increase the brightness of the semiconductor light emitting device. In this specification, colorless and transparent includes a state in which only light having a specific emission wavelength can be transmitted.

[1] Glass [1-1] L _* a _* b _* L _* value in chromaticity coordinates in the color system The glass used in the fluorescent glass of the present invention is obtained by pulverizing the glass to an average particle size of 60 μm or less ( When sintered for 1 hour at a temperature of yield point +50) ° C., the value of L _* in the chromaticity coordinates of the L _* a _* b _* color system is 50 or more, preferably 55 or more, more preferably It is 60 or more, and is usually 100 or less, preferably 99.8 or less, more preferably 99.5 or less. As a method for setting the L _* value within the above range, as described later, A) using a glass obtained through firing and pulverizing steps, B) using a glass having less impurities such as a reducing metal component, etc. C) The production process is preferably performed in a clean environment. D) It is preferable to use a glass having a small surface area and low adsorption ability to various substances. Here, A) to D) may be singular or may have a plurality of requirements. As will be described in detail below, by reducing the reducing metal component, the carbon component is easily oxidized and removed when sintered together with the phosphor, preventing the carbon component from remaining, L _* A value becomes low and it becomes possible to suppress that colorless transparency falls.

[1-2] Bending Point The glass used in the present invention has a yield point of 700 ° C. or lower, preferably 600 ° C. or lower, more preferably 500 ° C. or lower, and is usually 200 ° C. or higher, preferably 250 ° C. or higher.

[1-3] Trace component The carbon component of the glass used in the present invention is usually 100 ppm or less, preferably 60 ppm or less, more preferably 30 ppm or less, and particularly preferably 10 ppm or less. The smaller the carbon component, the better. However, if the amount is too large, the L _* value becomes low, and colorless transparency cannot be sufficiently secured. As a method for reducing the carbon component, a method using glass obtained through firing and pulverizing steps is preferable as described later.

  The glass used in the present invention is preferably substantially free of lead. That is, the lead content is usually 0.1% by weight or less, preferably 0.01% by weight or less, and more preferably 0.001% by weight or less. The lead content is preferably as low as possible, and if it is too high, there is a possibility of contamination by harmful elements during disposal.

The glass used in the present invention is preferably one having as little content of the following metal component as possible from the viewpoint of further enhancing colorless transparency.
When the oxygen partial pressure is 5% or less, when heated at a temperature of 800 ° C. or less, a metal component in which 1% by weight or more is reduced and its valence becomes zero in that weight. That is, the content of the metal is The amount is usually 10% by weight or less, preferably 1% by weight or less, and more preferably 0.1% by weight or less. It is preferable that the content of the metal is too small. If the content is too large, the L _* value of the glass component in the fluorescent glass after sintering is lowered. Examples of such a metal component include Ti.

  Furthermore, the content of Zn and Ba is also important from the viewpoint of enhancing colorlessness. Zn and Ba are often essential components in the form of an oxide, for example, for constituting a glass having desired physical properties, and there are cases where it is difficult to reduce the amount, but from the viewpoint of increasing colorlessness. Zn and Ba are each usually 50% by weight or less, preferably 30% by weight or less, more preferably 15% by weight or less. Preferably, the total content is usually 60% by weight or less, preferably 40% by weight or less, more preferably 20% by weight or less.

[1-4] Preferred Glass Mode As the glass used in the present invention, a glass composition containing at least one selected from alkali metals, alkaline earth metals and Zn (hereinafter simply referred to as “glass composition”). .) Is preferred. Preferably, the following compounds (I) and (II) are contained.
(I) Glass formation with Zachariasen comprising one or more selected from SiO ₂ , B ₂ O ₃ , P ₂ O ₅ , GeO ₂ , TeO ₂ , Al ₂ O ₃ , Ga ₂ O ₃ , and Bi ₂ O ₃ Oxide
(II) A network-modified oxide containing one or more selected from alkali metal atoms, alkaline earth metal atoms, and Zn
The “glass-forming oxide by Zachariasen” in the component (I) is a concept proposed in the non-patent document W.H. Zachariasen, J. Am. Chem. Soc., 54, 3841-3851 (1932). The glass-forming oxide which is the basic skeleton of glass. Among _these, preferably glass forming oxides including _{SiO 2, B 2 O 3,} P 2 O 5, Al 2 O 3, Al 2 O 3, glass-forming oxides containing SiO _2, P 2 _{O 5} is Particularly preferred are those containing both Al ₂ O ₃ and P ₂ O ₅ .
The blending amount of the component (I) is usually 20% by weight or more, preferably 30% by weight or more, more preferably 33% by weight or more, and usually 90% by weight or less, preferably 80% with respect to the entire glass composition. % By weight or less, more preferably 70% by weight or less. If the blending amount of the component (I) is too small, the mechanical strength may be lowered or the water resistance may be inferior. If it is too much, the yield point may be increased.

In the present invention, (II) a network-modified oxide containing one or more selected from an alkali metal atom, an alkaline earth metal atom, and Zn serves to lower the yield point or improve the durability. is there. Among these, a network modification oxide containing BaO, SrO, ZnO, Li ₂ O, Na ₂ O, K ₂ O, and MgO is preferable, and a network containing Li ₂ O, Na ₂ O, K ₂ O, ZnO, and CaO is preferable. Modified oxides are particularly preferred.
The amount of the component (II) is usually 10% by weight or more, preferably 20% by weight or more, more preferably 30% by weight or more, and usually 80% by weight or less, preferably 70%, based on the entire glass composition. % By weight or less, more preferably 67% by weight or less. If the amount of the component (II) is too large, the durability may decrease, and if it is too small, the yield point may be increased.

Examples of the combination of (I) and (II), and a combination of network-modifying oxide containing glass-forming oxides and Na ₂ O including, for example, _P 2 _{O 5.}
The weight ratio of (I) and (II) is usually 90:10 to 20:80, preferably 80:20 to 20:80.
Moreover, in the fluorescent glass of this invention, the yield point of a glass composition is 700 degrees C or less, Preferably it is 600 degrees C or less, More preferably, it is 500 degrees C or less. Moreover, it is 200 degreeC or more normally, Preferably it is 250 degreeC or more, More preferably, it is 300 degreeC or more. If the yield point is too large, the temperature becomes too high during sintering, and the phosphor itself may deteriorate or the emission characteristics of the phosphor may deteriorate due to the reaction between the phosphor and the glass composition. If the yield point is too small, the stability of the coating is lowered, and there may be a problem that the product is softened during use.

Also, a low yield point in the fluorescent glass of the present invention, a so-called low-melting glass (containing P ₂ O ₅₎ phosphoric acid is preferably a glass composition.
Further, it is more preferable to contain a fluorine atom for the purpose of reducing the yield point of the glass and improving the durability. Even if the fluorine atom is not contained in the glass, it is AlF ₃ , LiF, NaF, CaF ₂ , SrF ₂ , BaF ₂ , ZnF ₂ , MgF ₂ when the glass composition is coated (at the time of raw material mixing and / or firing). You may add fluorine compounds, such as.

  In addition to the effects of lowering the yield point and improving the durability of the glass composition, the fluorine atom is presumed to have the effect of improving the affinity with the phosphor surface. That is, it is presumed that there is an interface layer forming function for matching expansion coefficients and improving adhesion between the phosphor and the glass. Since adhesion is increased at the interface between the phosphor and the glass layer, it is estimated that at least a part of the glass component penetrates from the interface between the phosphor and the glass. It is speculated that fluoride ions promote this penetration. As long as the affinity with the phosphor surface increases, the type of additive is not limited, and chlorine, iodine, and bromine can be used, but fluorine is preferred from the viewpoint of stability.

  In the glass composition of the fluorescent glass of the present invention, the lead content is usually 0.1% by weight or less, preferably 0.01% by weight or less, and more preferably 0.001% by weight or less. The lead content is preferably as low as possible, and if it is too high, there is a possibility of contamination by harmful elements during disposal.

Preferable specific examples of the glass composition in the fluorescent glass of the present invention include, for example, P ₂ O ₅ of 34 wt% to 50 wt%, Li ₂ O of 2 wt% to 9 wt%, and Na ₂ O of 7 wt%. % To 28% by weight, R ₂ O (where R is an alkali metal) is 17% to 41% by weight, Al ₂ O ₃ is 6.5% to 30% by weight, and ZnO is 0% by weight or more. 22% by weight or less, BaO from 0% by weight to 21% by weight, SrO from 0% by weight to 18% by weight, CaO from 0% by weight to 16% by weight, RO (where R is an alkaline earth metal) A glass composition having a composition of 0% by weight to 34% by weight and F of 0% by weight to 32% by weight can be given. R ₂ O is preferably K ₂ O, and preferably 3 wt% or more and 27 wt% or less. RO is preferably MgO, and preferably 0 wt% or more and 14 wt% or less. F is preferably 1.5-32%.

Known glass compositions can be used for the glass composition used in the present invention. Examples thereof include known glass compositions described in International Publication No. 2003/037813, JP-A No. 2003-26439, and JP-A No. 5-199379.
Moreover, a commercially available glass composition can be used. Specifically, “K-PG325”, “K-PG375” manufactured by Sumita Optical Glass Co., Ltd. described in OPTICAL GLASS DATA BOOK (Version 5.00 issued on April 28, 2005, revised on July 5, 2005), “K-PG395”, “K-PMK10”, “K-PMK10”, “K-PSKn2”, “K-BK7”, “K-BPG2”, “K-SKF6”, “K-LaK7”, “K -CaFK95 "," K-PFK85 "," K-PFK80 "," K-GFK70 "," K-GFK68 "," K-CD45 "," K-CD120 "," K-LaFK55 "," K-LaFK60 " ”,“ K-PSK200 ”,“ K-PSFn1 ”,“ K-PSFn2 ”,“ K-PSFn3 ”,“ K-PSFn4 ”,“ K-PSFn5 ”,“ K-PMK1 ” ”,“ K-PSK100 ”,“ K-VC80 ”,“ K-VC81 ”,“ K-VC82 ”,“ K-VC89 ”,“ P-SK5S ”,“ P-SK12S ”,“ P ”manufactured by Hikari Glass Co., Ltd. -LAK13S "," P-LAF010S "," P-FKH2S "," P-LASF03S "," P-FK01S ", Asahi Fiber Glass" ZP150 ", Asahi Techno Glass" SK-231 "," SK -360 "," K801 "," K805 "," K806 "," K807 "," K808 "," LS-5 "," BS-7 "," FF201 "," FF209 ", 2007 ASF for Asahi Glass Electronics “IWF-7574”, “FF201”, “FF209”, “K301”, “K303”, “K30” manufactured by Asahi Glass Co., Ltd. ”,“ K805 ”,“ K807 ”,“ K808 ”,“ K834 ”,“ K835 ”,“ K836 ”,“ LS-5 ”,“ KF9079 ”,“ ASF1495 ”,“ ASF1560 ”,“ ASF1561 ”,“ ASF1620B ” "," ASF1620M "," ASF1700 "," ASF1702 "," ASF1710 "," ASF1765B "," ASF1768 "," ASF1771 "," ASF1800 "," ASF1891 "," ASF1891F "," ASF1898 "," ASF1939 " “ASF1941”, “ASF1941B”, “developed product 1991” and the like can be mentioned.
Examples of the glass that can be used for the fluorescent glass of the present invention include Bi ₂ O ₃ —SiO ₂ —B ₂ O ₃ glass having a glass softening point of about 550 ° C., and a glass transition point of about 500 to 700. SiO ₂ —B ₂ O ₃ —R ₂ O, SiO ₂ —B ₂ O ₃ —RO—R ₂ O-based glass (wherein R represents an alkali metal or an alkaline earth metal) at a temperature of 0 ° C. was used. Examples include lead-free glass ceramics.

In addition, focusing on the applications that have been used in the past, Bi used as an additive for lowering the sintering temperature of glass, ceramics, powdered glass used for adhesion and sealing, various ceramics, and metal powder. _{2 O 3 -B 2 O 3 -SiO} 2, B 2 O 3 -ZnO, SiO 2 -B 2 O 3 -R 2 O, powdered glass such as SiO ₂ -B ₂ O 3 -RO based (wherein, _{R 2} O represents an alkali metal oxide, and RO represents an alkaline earth metal oxide.).

Hereinafter, further detailed examples will be given focusing on the constituent elements of the glass.
The glass preferably used in the present invention is a non-Pb-containing low-melting glass, and this glass is a conventional Pb-containing low-melting glass. Non-Pb conversion is achieved by changing to salt glass, increasing alkali / boric acid components, or introducing fluoride.

Examples of bismuth (Bi) -introduced glass include Bi ₂ O ₃ —B ₂ O ₃ -based glass compositions. _{Specifically, 37Bi 2 O 3 -39.3B 2 O} 3 -7.2BaO-16.7CuO, 65Bi 2 O 3 -25ZnO-7.5B 2 O 3 -2.0Al 2 O 3, Bi 2 O 3 Bi ₂ O ₃ —ZnO—B ₂ O ₃ -based glass composition containing 27 wt% or more and 55 wt% or less, Bi ₂ O ₃ —SiO ₂ -based crystallized glass powder (Bi ₂ O ₃ content is 50 -62 _{wt%), SiO 2 -B 2 O} 3 -Bi 2 O 3 -ZnO based glass composition, and the like.

As an example of phosphate glass, phosphate glass is preferably used because it has high solubility in other components and has a low firing temperature. _{Examples, P 2 O 5: Na 2} O: CaO: BaO: Al 2 O 3: B 2 O 3 = 30~40: 10~20: 10~20: 10~20: 2~8: 1~5 Can be mentioned.

Addition of alumina is effective in improving chemical durability, but it may negatively affect low melting point. SnO is added based on phosphate glass, and B ₂ O ₃ or SiO ₂ , which is a normal glass forming oxide, may also be added. P ₂ O ₅ -SnO-based glass _{compositions, P 2 O 5 -SnO-B} 2 O 3 based glass _composition, mention may be made of P ₂ O 5 -SnO-SiO ₂ based glass composition. In addition, a CuO—P ₂ O ₅ —RO-based glass composition (where R represents any one of Zn, Ba, Ca, Mg, Sr, Sn, Ni, Fe, and Mn) can be given. In addition, P ₂ O ₅ —ZnO—SnO—R ₂ O—RO (where R ₂ O represents an alkali metal oxide, and RO represents an alkaline earth metal oxide), SrO—ZnO—P ₂ O ₅ , 10SrO-50ZnO-40P ₂ O ₅ glass composition.

Examples of alkali borosilicate glass include R ₂ O—RO—B ₂ O ₃ —SiO ₂ glass composition (where R ₂ O is an alkali metal oxide, RO is an alkaline earth metal oxide) Is shown.). Specifically, B ₂ O ₃ —SiO ₂ —Al ₂ O ₃ —ZrO ₂ glass composition, SiO ₂ —B ₂ O ₃ —ZnO—R ₂ O—RO glass composition (provided that R ₂ O Represents an alkali metal oxide, RO represents an alkaline earth metal oxide), SiO ₂ —B ₂ O ₃ —Al ₂ O ₃ —RO—R ₂ O-based glass composition (where R ₂ O represents , Alkali metal oxides, and RO are alkaline earth metal oxides).

[2] Phosphor The phosphor used in the present invention is not limited, but in particular, (i) phosphor particles having excellent light emission characteristics but low moisture resistance, and (ii) easily deteriorated by exposure to oxygen. Particularly when using the following phosphors: (iii) phosphor particles that are likely to elute ions, (iv) phosphor particles that are easily degraded by electrolysis, and (v) phosphor particles that have an odor. It is valid. In the fluorescent glass of the present invention, gas barrier properties are secured by the glass, and water vapor, oxygen, and odor-causing substances are blocked. Further, deterioration of peripheral members such as a package and a sealing material due to elution of ions derived from the phosphor is suppressed. Moreover, deterioration of the phosphor due to leakage current can be suppressed. Hereinafter, specific examples of the phosphor are illustrated, but in the illustrated general formula, phosphors that are different only in a part of the structure are appropriately omitted. For example, “Y ₂ SiO ₅ : Ce ³⁺ ”, “Y ₂ SiO ₅ : Tb ³⁺ ” and “Y ₂ SiO ₅ : Ce ³⁺ , Tb ³⁺ ” are changed to “Y ₂ SiO ₅ : Ce ³⁺ , Tb ³⁺ ”, “ “La ₂ O ₂ S: Eu”, “Y ₂ O ₂ S: Eu” and “(La, Y) ₂ O ₂ S: Eu” are collectively shown as “(La, Y) ₂ O ₂ S: Eu”. ing. Omitted parts are shown separated by commas (,).

[2-1] Preferred phosphor From the viewpoints of (i) to (v) described above, preferred phosphors include inorganic phosphors and organic phosphors. In the present invention, since there may be a step of sintering together with glass at a relatively high temperature, it is preferable to use an inorganic phosphor from the viewpoint of heat resistance.
As the inorganic phosphor, for example, (a) a group consisting of M ₃ SiO ₅ , MS, MGa ₂ S ₄ , MAlSiN ₃ , M ₂ Si ₅ N ₈ , MSi ₂ N ₂ O _{2 as} a host crystal (where M is At least one selected from the group consisting of Ca, Sr, and Ba), and Cr, Mn, Fe, Bi, Ce, Pr, Nd, Sm, Examples include phosphors containing at least one of Eu, Tb, Dy, Ho, Er, Tm, and Yb, and (b) a phosphor containing Mn ⁴⁺ as an activator.

Specific examples of the phosphor of (a) include, for example, Ba ₃ SiO ₅ : Eu, (Sr _1-a Ba _a ) ₃ SiO ₅ : Eu, Sr ₃ SiO ₅ : Eu, CaS: Eu, SrS: Eu. _{, BaS: Eu, CaS: Ce} , SrS: Ce, BaS: Ce, CaGa 2 S 4: Eu, SrGa 2 S 4: Eu, BaGa 2 S 4: Eu, CaGa 2 S 4: Ce, SrGa 2 S 4: _{Ce, BaGa 2 S 4: Ce} , CaAlSiN 3: Eu, SrAlSiN 3: Eu, (Ca 1-a Sr a) AlSiN 3: Eu, CaAlSiN 3: Ce, SrAlSiN 3: Ce, (Ca 1-a Sr a) _{AlSiN 3: Ce, Ca 2 Si} 5 N 8: Eu, Sr 2 Si 5 N 8: Eu, Ba 2 Si 5 N 8: Eu, (Ca 1-a Sr a) 2 Si 5 N _{8: Eu, Ca 2 Si 5} N 8: Ce, Sr 2 Si 5 N 8: Ce, Ba 2 Si 5 N 8: Ce, (Ca 1-a Sr a) 2 Si 5 N 8: Ce, CaSi 2 N ₂ O ₂ : Eu, SrSi ₂ N ₂ O ₂ : Eu, BaSi ₂ N ₂ O ₂ : Eu, CaSi ₂ N ₂ O ₂ : Ce, SrSi ₂ N ₂ O ₂ : Ce, BaSi ₂ N ₂ O ₂ : Ce (Ba, Sr, Ca) ₂ SiO ₄ : Eu, Ba ₃ Si ₆ O ₉ N ₄ : Eu (in relation to the above, a satisfies 0 ≦ a ≦ 1).

Among them, CaS, CaGa ₂ S ₄ : Eu, SrGa ₂ S ₄ : Eu, (Sr _0.8 Ca _0.2 ) AlSiN ₃ : Eu, (Ba, Sr, Ca) ₂ SiO ₄ : Eu, Ba ₃ Si ₆ Preferred examples include O ₉ N ₄ : Eu and (Sr, Ca) AlSiN ₃ : Eu.

The phosphor of (b) is preferably selected from at least one element selected from alkali metal elements, alkaline earth metal elements and Zn, Si, Ti, Zr, Hf, Sn, Al, Ga, and In. Phosphors containing at least one element selected from halogen elements and at least one element selected from halogen elements. More preferably, phosphors represented by the following formulas (r1) to (r8) are exemplified.
A ₂ [L1F ₅ ]: Mn ⁴⁺ (r1)
A ₃ [L1F ₆ ]: Mn ⁴⁺ (r2)
Zn ₂ [L1F ₇ ]: Mn ⁴⁺ (r3)
A [L1 ₂ F ₇ ]: Mn ⁴⁺ (r4)
A ₂ [L2F ₆ ]: Mn ⁴⁺ (r5)
E [L2F ₆ ]: Mn ⁴⁺ (r6)
Ba _0.65 Zr _0.35 F _2.70 : Mn ⁴⁺ (r7)
A ₃ [L2F ₇ ]: Mn ⁴⁺ (r8)

In the above formulas (r1) to (r8), A represents Li, Na, K, Rb, Cs, NH ₄ and combinations thereof, L1 represents Al, Ga, In, and combinations thereof, and L2 represents Ge, Si, Sn, Ti, Zr and combinations thereof are shown.

Among these, phosphors that can be particularly preferably used in the present invention include K ₂ [AlF ₅ ]: Mn ⁴⁺ , K ₃ [AlF ₆ ]: Mn ⁴⁺ , K ₃ [GaF ₆ ]: Mn ⁴⁺ , Zn ₂ [ AlF ₇ ]: Mn ⁴⁺ , K [In ₂ F ₇ ]: Mn ⁴⁺ , K ₂ [SiF ₆ ]: Mn ⁴⁺ , K ₂ [TiF ₆ ]: Mn ⁴⁺ , K ₃ [ZrF ₇ ]: Mn ⁴⁺ , Ba [ ^{_{TiF 6]: Mn 4+, K}} 2 [SnF 6]: Mn 4+, Na 2 [TiF 6]: Mn 4+, Na 2 [ZrF 5]: Mn 4+, KRb [TiF 6]: Mn 4+, K 2 [Si _0.5 Ge _0.5 F ₆ ]: Mn ⁴⁺ .

[2-2] Other phosphor particles
In addition to the above phosphors, other phosphors can be used depending on the purpose, such as improved durability and improved dispersibility.
The composition of the phosphor is not particularly limited, but a metal oxide represented by Y ₂ O ₃ , Zn ₂ SiO ₄ or the like that is a crystal matrix, a metal nitride represented by Sr ₂ Si ₅ N ₈ or the like, Phosphates represented by Ca ₅ (PO ₄ ) ₃ Cl and the like and sulfides represented by ZnS, SrS, CaS and the like, Ce, Pr, Nd, Pm, Sm, Eu, Tb, Dy, Ho, Er , Ions of rare earth metals such as Tm and Yb, and ions of metals such as Ag, Cu, Au, Al, Mn, and Sb are preferably combined as activators or coactivators.

Preferred examples of the crystal matrix include sulfides such as (Zn, Cd) S, SrGa ₂ S ₄ , SrS, and ZnS, oxysulfides such as Y ₂ O ₂ S, and (Y, Gd) ₃ Al ₅ O. ₁₂ , YAlO ₃ , BaMgAl ₁₀ O ₁₇ , (Ba, Sr) (Mg, Mn) Al ₁₀ O ₁₇ , (Ba, Sr, Ca) (Mg, Zn, Mn) Al ₁₀ O ₁₇ , BaAl ₁₂ O ₁₉ , CeMgAl ₁₁ O ₁₉ , (Ba, Sr, Mg) O.Al ₂ O ₃ , BaAl ₂ Si ₂ O ₈ , SrAl ₂ O ₄ , Sr ₄ Al ₁₄ O ₂₅ , aluminate such as Y ₃ Al ₅ O ₁₂ , Y Silicates such as ₂ SiO ₅ and Zn ₂ SiO ₄ , oxides such as SnO ₂ and Y ₂ O ₃ , borates such as GdMgB ₅ O ₁₀ and (Y, Gd) BO ₃ , Ca ₁₀ (PO ₄ ) ₆ ( _{F, Cl) 2, (Sr} , Ca, Ba, g) ₁₀ (PO ₄₎ such as ₆ Cl _{2 halophosphate,} Sr ₂ P _{2 O 7,} can be cited (La, Ce) phosphate PO _4, etc. and the like.

However, the crystal matrix and the activator element or coactivator element are not particularly limited in element composition, and can be partially replaced with elements of the same family, and the obtained phosphor is light in the near ultraviolet to visible region. Any material that absorbs and emits visible light can be used.
Specifically, the following phosphors can be used, but these are merely examples, and phosphors that can be used in the present invention are not limited to these.

[2-2-1] Orange to red phosphor
Examples of phosphors that emit orange to red fluorescence (hereinafter appropriately referred to as “orange to red phosphors”) include the following. The emission peak wavelength of the orange to red phosphor is preferably in the wavelength range of usually 580 nm or more, preferably 585 nm or more, and usually 780 nm or less, preferably 700 nm or less. Examples of such orange to red phosphors include europium composed of broken particles having a red fracture surface and emitting red region (Mg, Ca, Sr, Ba) ₂ Si ₅ N ₈ : Eu. The activated alkaline earth silicon nitride phosphor is composed of growing particles having a substantially spherical shape as a regular crystal growth shape, and emits light in the red region (Y, La, Gd, Lu) ₂ O ₂ S: Examples include europium activated rare earth oxychalcogenide phosphors represented by Eu.

  Furthermore, the oxynitride and / or acid containing at least one element selected from the group consisting of Ti, Zr, Hf, Nb, Ta, W, and Mo described in JP-A No. 2004-300247 A phosphor containing a sulfide and containing an oxynitride having an alpha sialon structure in which a part or all of the Al element is substituted with a Ga element can also be used in this embodiment. These are phosphors containing oxynitride and / or oxysulfide.

Also, other examples of the red _{phosphor, (La, Y) 2 O} 2 S: Eu Tsukekatsusan sulfide phosphor such as _{Eu, Y (V, P)} O 4: Eu, Y 2 O 3: Eu , etc. Eu-activated oxide _{phosphor, (Ba, Sr, Ca,} Mg) 2 SiO 4: Eu, Mn, (Ba, Mg) 2 SiO 4: Eu, Eu such as Mn, Mn-activated silicate phosphor, Eu-activated tungstate phosphors such as LiW ₂ O ₈ : Eu, LiW ₂ O ₈ : Eu, Sm, Eu ₂ W ₂ O ₉ , Eu ₂ W ₂ O ₉ : Nb, Eu ₂ W ₂ O ₉ : Sm (Ca, Sr) S: Eu-activated sulfide phosphors such as Eu, YAlO ₃ : Eu-activated aluminate phosphors such as Eu, LiY ₉ (SiO ₄ ) ₆ O ₂ : Eu, Ca ₂ Y ₈ (SiO ₄ ) ₆ O ₂ : Eu, (Sr, Ba, Ca) ₃ SiO ₅ : Eu, Sr ₂ Ba-activated silicate phosphors such as BaSiO ₅ : Eu, (Y, Gd) ₃ Al ₅ O ₁₂ : Ce, (Tb, Gd) ₃ Al ₅ O ₁₂ : Ce-activated aluminate phosphors such as Ce, _{(Mg, Ca, Sr, Ba} ) 2 Si 5 N 8: Eu, (Mg, Ca, Sr, Ba) SiN 2: Eu, (Mg, Ca, Sr, Ba) AlSiN 3: Eu -activated nitride such as Eu Phosphors, Ce-activated nitride phosphors such as (Mg, Ca, Sr, Ba) AlSiN ₃ : Ce, (Sr, Ca, Ba, Mg) ₁₀ (PO ₄ ) ₆ Cl ₂ : Eu, Mn, etc. Eu, Mn-activated halophosphate phosphor, Ba ₃ MgSi ₂ O ₈ : Eu, Mn, (Ba, Sr, Ca, Mg) ₃ (Zn, Mg) Si ₂ O ₈ : Eu, Mn, etc. activated silicate phosphor, 3.5MgO · 0.5MgF ₂ · Ge _2: Mn activated germanate salt phosphors such as Mn, Eu Tsukekatsusan nitride phosphor such as Eu-activated _{α-sialon, (Gd, Y, Lu,} La) 2 O 3: Eu, Bi, etc. Eu, Bi-activated oxide phosphor, (Gd, Y, Lu, La) ₂ O ₂ S: Eu, Bi-activated oxysulfide phosphor such as Eu, Bi, (Gd, Y, Lu, La) VO ₄ : Eu, Bi activated vanadate phosphors such as Eu, Bi, etc., SrY ₂ S ₄ : Eu, Ce activated sulfide phosphors such as Eu, Ce, etc., Ce activated sulfide fluorescence such as CaLa ₂ S ₄ : Ce, etc. (Ba, Sr, Ca) MgP ₂ O ₇ : Eu, Mn, (Sr, Ca, Ba, Mg, Zn) ₂ P ₂ O ₇ : Eu, Mn-activated phosphate phosphors such as Eu and Mn , (Y, Lu) ₂ WO ₆ : Eu, Mo-activated tungstate phosphor such as Eu, Mo, (Ba, Sr, Ca) _x Si _y Nz: Eu, Ce (where x, y, z represent an integer of 1 or more. Eu, Ce activated nitride phosphors such as (Ca, Sr, Ba, Mg) ₁₀ (PO ₄ ) ₆ (F, Cl, Br, OH) ₂ : Eu, Mn activated halophosphorus such as Eu, Mn Acid salt phosphor, ((Y, Lu, Gd, Tb) _1-xy Sc _x Ce _y ) ₂ (Ca, Mg) _1-r (Mg, Zn) _{2 + r} Siz _-q Ge _q O _{12 + δ} It is also possible to use a Ce-activated silicate phosphor or the like.

Among the red phosphors, those having a peak wavelength in the range of 580 nm or more, preferably 590 nm or more, and 620 nm or less, preferably 610 nm or less can be suitably used as the orange phosphor. Examples of such orange phosphors include Eu-activated silicate phosphors such as (Sr, Ba, Ca) ₃ SiO ₅ : Eu, Sr ₂ BaSiO ₅ : Eu, (Sr, Mg) ₃ (PO ₄ ). ₂ : Sn-activated phosphate phosphors such as Sn ^{2+ and the} like.

Any one of the red phosphors exemplified above may be used alone, or two or more may be used in any combination and ratio.
Among the above examples, as the red phosphor, (Ca, Sr, Ba) AlSiN ₃ : Eu, (Ca, Sr, Ba) AlSiN ₃ : Ce, (La, Y) ₂ O ₂ S: Eu are preferable, (Sr, Ca) AlSiN ₃ : Eu and (La, Y) ₂ O ₂ S: Eu are particularly preferable.
Moreover, among the above examples, (Sr, Ba) ₃ SiO ₅ : Eu is preferable as the orange phosphor.

[2-2-2] Green phosphor
Examples of phosphors that emit green fluorescence (hereinafter referred to as “green phosphors” as appropriate) include the following. The emission peak wavelength of the green phosphor is usually in the wavelength range of 490 nm or more, preferably 510 nm or more, more preferably 515 nm or more, and usually 560 nm or less, preferably 540 nm or less, more preferably 535 nm or less. .

As such a green phosphor, for example, a europium-activated alkali represented by (Mg, Ca, Sr, Ba) Si ₂ O ₂ N ₂ : Eu that is composed of fractured particles having a fracture surface and emits light in the green region. Europium-activated alkaline earth silicate composed of an earth silicon oxynitride phosphor, broken particles having a fracture surface, and emitting green light (Ba, Ca, Sr, Mg) ₂ SiO ₄ : Eu System phosphors and the like.

Other green phosphors include Eu-activated aluminate phosphors such as Sr ₄ Al ₁₄ O ₂₅ : Eu, (Ba, Sr, Ca) Al ₂ O ₄ : Eu, and (Sr, Ba) Al _2. Si ₂ O ₈ : Eu, (Ba, Mg) ₂ SiO ₄ : Eu, (Ba, Sr, Ca, Mg) ₂ SiO ₄ : Eu, (Ba, Sr, Ca) ₂ (Mg, Zn) Si ₂ O ₇ : Eu, (Ba, Ca, Sr, Mg) ₉ (Sc, Y, Lu, Gd) ₂ (Si, Ge) ₆ O ₂₄ : Eu-activated silicate phosphor such as Eu, Y ₂ SiO ₅ : Ce, Ce, Tb-activated silicate phosphors such as Tb, Sr ₂ P ₂ O ₇ —Sr ₂ B ₂ O ₅ : Eu-activated borate phosphate phosphors such as Eu, Sr ₂ Si ₃ O ₈ -2SrCl ₂ : Eu-activated halo silicate phosphor such as _Eu, Zn 2 _SiO 4: M such as Mn Activated silicate _{phosphors, CeMgAl 11 O 19: Tb,} Y 3 Al 5 O 12: Tb -activated aluminate phosphors such as _{Tb, Ca 2 Y 8 (SiO} 4) 6 O 2: Tb, La 3 Ga ₅ SiO ₁₄ : Tb-activated silicate phosphor such as Tb, (Sr, Ba, Ca) Ga ₂ S ₄ : Eu, Tb, Sm-activated thiogallate phosphor such as Eu, Tb, Sm, Y ₃ (Al, Ga) ₅ O ₁₂ : Ce, (Y, Ga, Tb, La, Sm, Pr, Lu) ₃ (Al, Ga) ₅ O ₁₂ : Ce-activated aluminate phosphor such as Ce, Ca ₃ Sc ₂ Si ₃ O ₁₂ : Ce, Ca ₃ (Sc, Mg, Na, Li) ₂ Si ₃ O ₁₂ : Ce activated silicate phosphor such as Ce, Ce activated oxide phosphor such as CaSc ₂ O ₄ : Ce, _{SrSi 2 O 2 N 2: Eu} , (Mg, Sr, B _{, Ca) Si 2 O 2 N} 2: Eu, Eu Tsukekatsusan nitride phosphor such as Eu-activated _{β-sialon, BaMgAl 10 O 17: Eu,} Eu such as Mn, Mn-activated aluminate phosphor, SrAl ₂ O ₄ : Eu-activated aluminate phosphor such as Eu, (La, Gd, Y) ₂ O ₂ S: Tb-activated oxysulfide phosphor such as Tb, LaPO ₄ : Ce such as Ce, Tb, Tb-activated phosphate phosphor, ZnS: Cu, Al, ZnS : Cu, Au, sulfide phosphor such as Al, (Y, Ga, Lu , Sc, La) BO 3: Ce, Tb, Na 2 Gd ₂ B ₂ O ₇ : Ce, Tb, (Ba, Sr) ₂ (Ca, Mg, Zn) B ₂ O ₆ : Ce, Tb activated borate phosphor such as K, Ce, Tb, Ca ₈ Mg (SiO 2 _{4) 4 Cl 2: Eu,} Eu such as Mn, Mn-activated halo silicate phosphor, ( r, Ca, Ba) (Al , Ga, In) 2 S 4: Eu activated thioaluminate phosphor or thiogallate phosphor such as _{Eu, (Ca, Sr) 8} (Mg, Zn) (SiO 4) 4 Cl ₂ : Eu, Mn activated halosilicate phosphor such as Eu, Mn, etc., MSi ₂ O ₂ N ₂ : Eu, M ₃ Si ₆ O ₉ N ₄ : Eu, M ₂ Si ₇ O ₁₀ N ₄ : Eu , M represents an alkaline earth metal element. It is also possible to use Eu-activated oxynitride phosphors such as

[2-2-3] Blue phosphor
Examples of phosphors emitting blue fluorescence (hereinafter referred to as “blue phosphors” as appropriate) include the following. The emission peak wavelength of the blue phosphor is usually 420 nm or more, preferably 430 nm or more, more preferably 440 nm or more, and usually 490 nm or less, preferably 470 nm or less, more preferably 460 nm or less. .

As such a blue phosphor, a europium-activated barium magnesium aluminate system represented by BaMgAl ₁₀ O ₁₇ : Eu composed of growing particles having a substantially hexagonal shape as a regular crystal growth shape and emitting light in a blue region. Europium activated halo represented by (Ca, Sr, Ba) ₅ (PO ₄ ) ₃ Cl: Eu, which is composed of phosphors and growing particles having a substantially spherical shape as a regular crystal growth shape, and emits light in a blue region. Calcium phosphate phosphor, composed of growing particles having a substantially cubic shape as a regular crystal growth shape, emits light in the blue region, and is activated by europium represented by (Ca, Sr, Ba) ₂ B ₅ O ₉ Cl: Eu Consists of alkaline earth chloroborate phosphors, fractured particles with fractured surfaces, and light emission in the blue-green region And (Sr, Ca, Ba) Al ₂ O ₄ : Eu or (Sr, Ca, Ba) ₄ Al ₁₄ O ₂₅ : Eu are europium activated alkaline earth aluminate phosphors.

Other blue phosphors include Sn-activated phosphate phosphors such as Sr ₂ P ₂ O ₇ : Sn, (Sr, Ca, Ba) Al ₂ O ₄ : Eu or (Sr, Ca, Ba). ₄ Al ₁₄ O ₂₅ : Eu, BaMgAl ₁₀ O ₁₇ : Eu, BaAl ₈ O ₁₃ : Eu-activated aluminate phosphors such as Eu, SrGa ₂ S ₄ : Ce, CaGa ₂ S ₄ : Ce-activated such as Ce Thiogallate phosphor, (Ba, Sr, Ca) MgAl ₁₀ O ₁₇ : Eu, BaMgAl ₁₀ O ₁₇ : Eu-activated aluminate phosphor such as Eu, Tb, Sm, (Ba, Sr, Ca) MgAl ₁₀ O ₁₇ : Eu, Mn activated aluminate phosphor such as Eu, Mn, (Sr, Ca, Ba, Mg) ₁₀ (PO ₄ ) ₆ Cl ₂ : Eu, (Ba, Sr, Ca) ₅ (PO ₄ ) ₃ (Cl, F, Br, OH): Eu , Mn, Eu -activated halophosphate phosphors such as _{Sb, BaAl 2 Si 2 O 8} : Eu, (Sr, Ba) 3 MgSi 2 O 8: Eu -activated silicate such as Eu Salt phosphors, Eu-activated phosphate phosphors such as Sr ₂ P ₂ O ₇ : Eu, sulfide phosphors such as ZnS: Ag, ZnS: Ag, Al, and Ce-activated such as Y ₂ SiO ₅ : Ce Silicate phosphor, tungstate phosphor such as CaWO ₄ , (Ba, Sr, Ca) BPO ₅ : Eu, Mn, (Sr, Ca) ₁₀ (PO ₄ ) ₆ .nB ₂ O ₃ : Eu, 2SrO. 0.84P ₂ O ₅ .0.16B ₂ O ₃ : Eu, Mn-activated borate phosphate phosphor such as Eu, Eu-activated halosilicate phosphor such as Sr ₂ Si ₃ O ₈ · 2SrCl ₂ : Eu Etc. can also be used.

Among the above examples, as the blue phosphor, BaMgAl ₁₀ O ₁₇ : Eu, (Ba, Ca, Mg) ₂ SiO ₄ : Eu, (Sr, Ca, Ba, Mg) ₁₀ (PO ₄ ) ₆ Cl ₂ : Eu is preferred, and BaMgAl ₁₀ O ₁₇ : Eu is particularly preferred.

[2-2-4] Yellow phosphor
Examples of the phosphor that emits yellow fluorescence (hereinafter, appropriately referred to as “yellow phosphor”) include the following. The emission peak wavelength of the yellow phosphor is usually in the wavelength range of 530 nm or more, preferably 540 nm or more, more preferably 550 nm or more, and usually 620 nm or less, preferably 600 nm or less, more preferably 580 nm or less. .

Examples of such yellow phosphors include various oxide-based, nitride-based, oxynitride-based, sulfide-based, and oxysulfide-based phosphors.
In particular, RE ₃ M ₅ O ₁₂ : Ce (where RE represents at least one element selected from the group consisting of Y, Tb, Gd, Lu, and Sm, and M represents Al, Ga, and Sc. And M ^a ₃ M ^b ₂ M ^c ₃ O ₁₂ : Ce (where M ^a is a divalent metal element and M ^b is a trivalent metal element) , ^{M c} represents a tetravalent metal element) garnet phosphor having a garnet structure represented by ^{_{like, AE 2 M d O 4:}} . Eu ( where, AE is, Ba, Sr, Ca, Mg , and An orthosilicate phosphor represented by at least one element selected from the group consisting of Zn, M ^d represents Si and / or Ge, and the like, oxygen of constituent elements of the phosphors of these systems Acid in which a part of Compound phosphor, AEAlSiN _3: Ce (., Where, AE is, Ba, Sr, Ca, represents at least one element selected from the group consisting of Mg and Zn) nitride having CaAlSiN ₃ structures such as system Examples thereof include phosphors activated with Ce such as phosphors.

In addition, as yellow phosphors, sulfide-based fluorescence such as CaGa ₂ S ₄ : Eu, (Ca, Sr) Ga ₂ S ₄ : Eu, (Ca, Sr) (Ga, Al) ₂ S ₄ : Eu, etc. It is also possible to use a phosphor activated by Eu, such as an oxynitride phosphor having a SiAlON structure such as a body, Cax (Si, Al) ₁₂ (O, N) ₁₆ : Eu.

[2-4] Physical properties of phosphor particles
There is no particular limitation on the particle size of the phosphors used in the phosphor of the present invention, the median particle diameter (D ₅₀₎ in a conventional 0.1μm or more, preferably 2μm or more, more preferably 10μm or more. Moreover, it is 100 micrometers or less normally, Preferably it is 50 micrometers or less, More preferably, it is 25 micrometers or less. If D ₅₀ is too small, and the luminance decreases, there is a possibility that phosphor particles tend to aggregate.
The particle size distribution (QD) of the phosphor particles is preferably smaller in order to align the dispersed state of the particles in the phosphor-containing composition, but in order to reduce the particle size, the classification yield is lowered, leading to an increase in cost. Usually, it is 0.03 or more, preferably 0.05 or more, more preferably 0.07 or more. Moreover, it is 0.4 or less normally, Preferably it is 0.3 or less, More preferably, it is 0.2 or less. Further, the shape of the phosphor particles is not particularly limited.

In the present invention, the median particle size (D ₅₀ ) and particle size distribution (QD) can be obtained from a weight-based particle size distribution curve. The weight-based particle size distribution curve is obtained by measuring the particle size distribution by a laser diffraction / scattering method, and specifically, for example, can be measured as follows.
The phosphor is dispersed in a solvent such as ethylene glycol in an environment of a temperature of 25 ° C. and a humidity of 70%.
Measurement is performed with a laser diffraction particle size distribution measuring apparatus (Horiba, Ltd. LA-300) in a particle size range of 0.1 μm to 600 μm.

Integrated value in the weight particle size distribution curve is denoted a particle size value when the 50% and median particle diameter D _50. Further, the particle size values when the integrated values are 25% and 75% are expressed as D ₂₅ and D ₇₅ , respectively, and defined as QD = (D ₇₅ −D ₂₅ ) / (D ₇₅ + D ₂₅ ). A small QD means a narrow particle size distribution.

[2-5] Surface treatment of phosphor
The phosphor particles used in the present invention may be further subjected to a surface treatment for the purpose of improving water resistance.
Examples of such surface treatments include surface treatments using organic materials, inorganic materials, glass materials, and the like described in JP-A No. 2002-223008, and metal phosphates described in JP-A No. 2000-96045. Known surface treatments such as coating treatment, coating treatment with metal oxide, and silica coating can be used. Examples of the silica coat include a method of precipitating SiO ₂ by neutralizing water glass, a method of treating the surface of hydrolyzed alkoxysilane (for example, JP-A-3-231987), and the like. In terms of enhancement, a method of treating the surface of hydrolyzed alkoxysilane is preferred.

Further, for example, a method described in Japanese Patent Application No. 2007-172930 is also preferable in which a glass composition is heated and melted to coat a phosphor. In this case, the glass composition used can be the glass composition used in the above-described present invention.
Further, as described in JP-T-2006-523245, the phosphor particles are subjected to a heat treatment or the like to form a coating by chemically modifying the original components of the phosphor particles. Known surface treatments are also suitable.

  Moreover, the surface treatment which coat | covers a metal phosphate is also suitable. Specifically, for example, a surface treatment method that can be performed by the following procedures (i) to (iii) can be given. (I) A predetermined amount of a water-soluble phosphate such as potassium phosphate and sodium phosphate and at least one of alkaline earth metals such as calcium chloride, strontium sulfate, manganese chloride and zinc nitrate, Zn and Mn A water-soluble metal salt compound is added to the phosphor suspension and stirred. (Ii) A phosphate of at least one metal among alkaline earth metals, Zn and Mn is formed in the suspension, and the generated metal phosphate is deposited on the phosphor surface. (Iii) Remove moisture.

[3] Fluorescent glass [3-1] L _* a _* b _* L _* value in chromaticity coordinates in the color system The fluorescent glass used in the present invention is in chromaticity coordinates in the L _* a _* b _* color system. The value of L _* is 65 or more, preferably 75 or more, more preferably 85 or more, and is usually 100 or less, preferably 99.8 or less, more preferably 99.5 or less. As a method for setting the L _* value within the above range, as described later, a method using a glass obtained through firing and pulverization steps is preferable.

[3-2] Specific gravity The glass used in the present invention can be adjusted, for example, by appropriately mixing bubbles so that the light scattering effect of the phosphor and / or the semiconductor light emitting element can be expected. In such a case, the specific gravity of the fluorescent glass of the present invention is usually 1 or more, preferably 1.3 or more, more preferably 1.5 or more, and usually 4 or less, preferably 3 or less, more preferably 2. 5 or less. If the specific gravity is too large, the scattering effect derived from the bubbles will be low, and if it is too small, there will be too many bubbles, leading to reduced light guiding properties, occurrence of peeling and cracking, reduced strength, and the like. The specific gravity can be measured by, for example, a known method of measuring and calculating the volume and weight of a fluorescent glass sample. When bubbles are mixed, there are usually portions having different specific gravities in the fluorescent glass due to the uneven distribution of bubbles. The generation of bubbles can be adjusted by adjusting the sintering temperature or sintering atmosphere (pressure) and the particle size and shape of the glass before firing.

  When the fluorescent glass obtained by mixing bubbles is used for a semiconductor light emitting device, it is preferable to give a scattering effect to the semiconductor element side and then irradiate the phosphor with light, so that there are few bubbles on the light emitting surface side. It is preferable to take a structure with a lot of bubbles in a portion close to the semiconductor light emitting element. Therefore, in the fluorescent glass of the present invention formed in the semiconductor light emitting device, the specific gravity at the site far from the semiconductor light emitting element is larger than the specific gravity at the site near the semiconductor light emitting element. Since the difference in specific gravity can be visually confirmed by the amount of bubbles H, it can be measured, for example, by cutting the fluorescent glass of the present invention and observing the cross section with a scanning electron microscope or the like as shown in FIG. . Bubbles H in the figure had a diameter of about 100 μm.

  The number average diameter of the formed bubbles is usually 0.1 μm or more, preferably 0.5 μm or more, more preferably 1 μm or more, and usually 2 mm or less, preferably 1 mm or less, more preferably 300 μm or less. When the number average diameter is too small, the scattering effect derived from foaming is lowered, and when the number average diameter is too large, light guideability is reduced, peeling and cracks are generated, and strength is lowered. The number average diameter of the bubbles can be measured, for example, by cutting the fluorescent glass of the present invention and observing the cross section with a scanning electron microscope or the like.

[3-3] Preferred Combination of Phosphor and Glass Composition In order to obtain a homogeneous fluorescent glass with good dispersibility of the phosphor particles, a combination of the phosphor particles and the glass composition is important. That is, it is preferable that the wettability between the phosphor surface and the melt of the glass composition is good. Specifically, it preferably has the following properties.
(I) The contact angle of the glass composition in the molten state on the phosphor particle plane is usually 140 degrees or less, preferably 130 degrees or less, more preferably 120 degrees or less, usually 2 degrees or more, preferably 5 degrees. Above, more preferably 10 degrees or more.
(Ii) A chemical reaction occurs on the surface of the glass composition component and the phosphor particles.
(Iii) The reaction temperature of the chemical reaction does not affect the deterioration of the phosphor particles. That is, the reaction temperature is usually 800 ° C. or lower, preferably 600 ° C. or lower.

A known method can be employed for measuring the contact angle. In measuring the contact angle, it is preferable to measure the average contact angle of the phosphor surface in the coating temperature and the clothing atmosphere. For example, by using “OCA 15 plus” manufactured by Eiko Seiki Co., Ltd., the temperature control mechanism “TEC700” is used to measure the dynamic contact angle in the heated state, and the average value of the advance angle is used to contact the glass melt with the phosphor surface. It can be a corner.
Examples of the combination of the phosphor particles having a good coating property and the glass composition include the following combinations.

Moreover, from the viewpoint of the affinity between the phosphor particles and the glass composition, the zeta potential (mV) of the phosphor particles in water (pH 5.6) is usually −5 or less, preferably −10 or less, more preferably. -20 or less, particularly preferably -21 or less.
On the other hand, the zeta potential (mV) of the glass composition in water (pH 5.6) is usually −50 or less, preferably −60 or less, and more preferably −50 or less. If the zeta potential of the glass composition is too large, the affinity with the phosphor particles may be lowered.

[3-4] Hydrophobization of fluorescent glass surface It is also preferable to extend the function of the fluorescent glass by hydrophobizing the fluorescent glass surface as necessary. The hydrophobic treatment method is preferably carried out by immersing the fluorescent glass in a fluorine compound, or applying or spraying the fluorine compound from above.
Examples of the fluorine compound include heptadecafluoro-1,1,2,2-tetrahydrodecyl) trimethoxysilane, heptadecafluoro-1,1,2,2- Tetrahydrodecyl) triethoxysilane (Heptadecafluoro-1,1,2,2-tetrahydrodecyl) triethoxysilane, heptadecafluoro-1,1,2,2-tetrahydrodecyl) trichlorosilane (Heptadecafluoro-1,1,2,2-tetrahydrodecyl) ) Trichlorosilane, pentafluorophenyltrimethoxysilane, pentafluorophenyltrimethoxysilane, pentafluorophenyltriethoxysilane, pentafluorophenyltrichlorosilane, perfluorododecyl-1H, 1H, 2H, 2H-triethoxysilane perfluorododecyl-1H, 1H, 2H, 2H-triethoxysilane, Tridecafluoro-1,1,2,2-tetrahydrodecyl) trimethoxysilane (Tridecafluoro-1,1,2,2-tetrahydrooctyl) trimethoxysilane, tridecafluoro-1,1,2,2-tetrahydrodecyl) triethoxysilane (tridecafluoro-1,1,2,2-tetrahydrodecyl) A fluorine-based silane coupling agent such as trichlorosilane (Tridecafluoro-1,1,2,2-tetrahydrooctyl) trichlorosilane is particularly preferably used.

[3-4] Manufacturing method [3-4-1] Step of firing and pulverizing glass The fluorescent glass used in the present invention is preferably obtained by firing and pulverizing the glass of the material. This is technically significant in ensuring colorless transparency by removing trace substances that cause blackening, such as carbon in the glass as a raw material.
The firing temperature is usually 500 ° C. or higher, preferably 600 ° C. or higher, more preferably 900 ° C. or higher, and usually 3000 ° C. or lower, preferably 2500 ° C. or lower, more preferably 2000 ° C. or lower.
If the firing temperature is too low, the black matter may not be sufficiently removed, and if it is too high, the energy required for heating increases, which is not economically and environmentally undesirable.

  The firing time is usually 0.05 hours or more, preferably 0.2 hours or more, more preferably 0.4 hours or more, usually 24 hours or less, preferably 12 hours or less, more preferably 8 hours or less. . If the baking time is too short, there is a possibility that the black matter cannot be sufficiently removed, and if it is too long, the productivity is inferior and this is not industrially preferable.

  Examples of the firing atmosphere include a method of carrying out in an air atmosphere containing oxygen from the viewpoint of removing residual carbon by oxidative decomposition to carbon monoxide, carbon dioxide or the like. In addition, a method in which gas molecules are small and helium or the like is performed in an atmosphere is preferable in that it penetrates into the fine structure of the glass and the removal of residual substances is efficient. From the viewpoint of converting a zero-valent metal into an oxide, it is preferably performed in an air atmosphere containing oxygen.

  The curing temperature is not particularly limited as long as it is lower than the yield point, but the cooling rate is preferably as slow as possible in order to suppress the occurrence of cracks and the like due to rapid shrinkage during curing. Although there is no particular limitation on the temperature drop profile related to cooling, for example, when the temperature is lowered to 25 ° C., particularly at the initial temperature drop, usually 50 ° C./min. Or less, preferably 40 ° C./min. Or less, more preferably 30 ° C./min. It is usually 1 ° C./min. Or more, preferably 2 ° C./min. Or more, more preferably 5 ° C./min. Or more.

If the temperature lowering rate is too fast, there is a risk of causing problems such as cracks in the glass, and if it is too slow, the productivity will be inferior, which is not industrially preferable.
In the firing step, the atmosphere related to cooling and curing is not particularly limited, and can be performed, for example, in an air atmosphere.
The pulverization can be performed by a dry pulverization method such as a hammer mill, a ball mill, a jet mill, or a roll mill, or a wet ball mill pulverization method. In such a pulverization step, it is preferable that the particle size of the glass is appropriately adjusted so as to be as equal as possible to the particle size of the phosphor to be mixed in the subsequent step. That is, the average particle size of the glass is 0.1 times or more, preferably 0.2 times or more, more preferably 0.3 times or more, and usually 10 times or less, preferably 8 times the particle size of the phosphor particles. Hereinafter, it is more preferably 5 times or less. Specifically, it is usually 0.5 μm or more, preferably 1 μm or more, more preferably 5 μm or more, and usually 1 mm or less, preferably 300 μm or less, more preferably 100 μm or less.

[3-4-2] Step of Mixing Glass and Phosphor The fluorescent glass used in the present invention preferably has a step of mixing the above-mentioned crushed glass and phosphor. This mixing step is technically significant in the following respects compared to liquid media such as conventional epoxy resins and silicone resins. First of all, the mixing of the powder can be performed with a very uniform mixing and dispersion unlike the case of mixing and dispersing in a liquid having a problem of precipitation. Also, the high viscosity of the glass at temperatures above the yield point and softening point is suitable for avoiding undesirable problems such as aggregation and precipitation of powders. Furthermore, the glass can be quickly adapted to the surface of the phosphor particles by virtue of its good affinity for the metal oxide crystals contained in the glass-containing phosphors containing silicon.

Hereinafter, the mixing process according to the present invention will be described.
The glass obtained in the above process is mixed with the phosphor. The weight ratio of the glass and the phosphor needs to be appropriately selected so that the chromaticity of light obtained when the fluorescent glass mixed and sintered and the semiconductor light emitting element are combined becomes a desired one. The ratio of the glass weight to the phosphor weight (the total weight when a plurality of phosphors are used) is usually 100: 1 to 1: 100, preferably 50: 1 to 1:50, more preferably 20: 1 to 1. : 20. If the glass component is too much, the excitation light from the semiconductor light emitting element is not suitable for leaking, and if the phosphor component is too much, there is a problem that it cannot be sintered beautifully. The mixing is usually carried out uniformly industrially, for example, using a V-type or box-type tumbler. In this case, it is also preferable to increase mixing efficiency by adding beads.

  In the mixing step of the present invention, a phosphor precursor synthesized by, for example, sintering may be mixed. In this case, the phosphor is synthesized at the same time in the sintering step described later, and the fluorescent glass can be manufactured.

  According to the present invention, inorganic phosphors and pigments can be synthesized, fixed and fused in a glassy base material in one step. In fact, phosphors such as YAG and BAM are synthesized by a synthesis method involving sol-gel and subsequent combustion reaction. A gel is made from these water-soluble ions, undergoes auto-oxidation / nucleation at the molecular level, and finally fired to prepare the desired powder. According to this preparation method, a suspending matrix (matrix material) is not required, and micron-sized sintered particles can be obtained and used for subsequent processes.

  In the present embodiment, the surface of a micron-sized glass powder can be used as the nucleus of a sol-gel type phosphor production reaction. The water-soluble precursor is mixed with the glass powder in various proportions and poured into the mold of the desired shape. The mold is set in a furnace and gelled and self-oxidized to uniformly produce an amorphous substance on the glass surface. Further, the temperature of the furnace is raised to fire the inorganic structure. During the firing, the glass powder softens and fuses to uniformly fix the inorganic structure (phosphor).

[3-4-3] Pressure Molding Processing Step When the glass and phosphor mixture obtained in the above-described step is subjected to a pressure molding processing step for the purpose of preforming before the sintering step described later. There is. Pre-molding is an effective means from the viewpoint of obtaining a uniform fluorescent glass molding.

In the pressure molding process, the pressure applied to the glass and phosphor mixture is usually 0.1 t or more, preferably 1 t or more, more preferably 2.5 t or more, usually 50 t or less, preferably 20 t or less, Preferably it is 10 t or less.
If the pressure is too small, the molding becomes insufficient and brittle fluorescent glass is formed. If the pressure is too large, the molding material may be contaminated.

The treatment temperature is usually −10 ° C. or higher, preferably 0 ° C. or higher, more preferably 5 ° C. or higher, usually 250 ° C. or lower, preferably 150 ° C. or lower, more preferably 80 ° C. or lower. If the treatment temperature is too low, the resulting molded body is likely to cause dew condensation and the like, and if it is too high, the phosphor may be decomposed at that temperature and pressure, such being undesirable.
The treatment time is usually 0.5 minutes or more, preferably 1 minute or more, more preferably 1.5 minutes or more, and usually 1 hour or less, preferably 30 minutes or less, more preferably 20 minutes or less. If the treatment time is too short, the molding will be insufficient, and if it is too long, the productivity will deteriorate.
The pressure treatment is preferably performed in an air atmosphere from the viewpoint of ease of processing, but it is also preferable to perform the treatment under vacuum.
The pressure treatment is usually performed using a press.

[3-4-4] Sintering process The mixture of glass and phosphor can be converted into a target fluorescent glass through a sintering process.
The sintering temperature is usually 5 ° C or higher than the yield point of glass, preferably 30 ° C or higher, more preferably 50 ° C or higher, and the temperature difference from the yield point is usually 500 ° C or lower. Preferably, it is 300 degrees C or less, More preferably, it is 200 degrees C or less.
If the sintering temperature is too low, it takes a long time to sinter, and if the sintering is insufficient, it becomes brittle fluorescent glass. is there.

The sintering time is usually 3 minutes or more, preferably 10 minutes or more, more preferably 15 minutes or more, and is usually 24 hours or less, preferably 12 hours or less, more preferably 5 hours or less. If the sintering time is too short, it becomes brittle fluorescent glass even if the sintering is insufficient, and if it is too high, decomposition and segregation of the phosphor may be caused, which is not preferable and economically disadvantageous.
Sintering may be performed in the air or in an inert gas atmosphere. From the viewpoint of preventing an unnecessarily large amount of bubbles from being generated in the fluorescent glass, the pressure may be adjusted, and it is preferably performed under reduced pressure or in a vacuum atmosphere.

As the inert gas, helium, argon or nitrogen is usually used. From the viewpoint of preventing deterioration due to oxidative decomposition of the phosphor, for example, a method using a gas containing a small amount of hydrogen can be mentioned.
In the case of sintering as a fluorescent glass plate, a platinum or boron nitride container, preferably boron nitrite, is preferred from the viewpoint of having no adverse effect on the glass and the phosphor and ease of taking out the product. This should be done in a ride container.

  Fluorescent glass may take a process of sintering and preparing after combining separately from the semiconductor light emitting device. In this case, the temperature and time required for the coalescence process are lower and shorter than those required when sintering in the semiconductor light-emitting device from the beginning, so that the thermal history of the chip and the like is small, which is preferable in preventing deterioration. Is a process.

Although there is no restriction | limiting in particular about the preparation method of fluorescent glass separately sinter-prepared, For example, the following processes are preferable from the surface of simplicity and economical efficiency.
Glass powder and phosphor powder are mixed in advance, and one small glass body is softened at a high temperature. The mixed powder is adhered around the glass body by covering the softened glass body with the mixed powder, or by burying the glass body in the mixed powder or rolling on the powder deposit. By exposing the glass body to high temperature for a short time, the mixed powder adhered to the periphery is fused with the glass body. The mixed powder is applied to the glass body again, or the mixed powder is bonded around the glass body by being buried or rolled on the powder deposit, and then exposed to a high temperature for a short time. Fuse. By repeating these operations, a fluorescent glass sintered body having a desired size can be obtained, and further formed into a desired shape by being softened by being exposed to a high temperature. As a method for increasing the temperature, it is possible to use a firing furnace, and it is also preferable to use an open flame for small scale synthesis. In addition, a system in which a path in which a high temperature part for softening and a low temperature part where mixed powder is installed is alternately arranged is moved to a belt conveyor type is also preferable in production.

  It can also be formed directly on the substrate by coating, potting or the like as a sealing material for a semiconductor light emitting device. In this case, since the sintering process is performed on the semiconductor light emitting device, it is necessary to pay attention to disconnection due to shrinkage accompanying the sintering of the glass powder, deterioration of the chip due to holding at a high temperature for a long time, and the like.

[4] Semiconductor Light-Emitting Device The fluorescent glass of the present invention can form various optical members in combination with a semiconductor light-emitting element, an organic EL, etc. As an example of such an optical member of the present invention, A semiconductor light emitting device including at least a fluorescent glass and a semiconductor light emitting element (hereinafter sometimes referred to as “semiconductor light emitting device of the present invention” as appropriate) will be described as an example. In each of the following embodiments, the semiconductor light emitting device of the present invention may be abbreviated as “light emitting device” as appropriate. Which part is used for the fluorescent glass of the present invention will be described collectively after the description of all the embodiments. However, these embodiments are merely used for convenience of explanation, and examples of the semiconductor light emitting device including at least the fluorescent glass and the semiconductor light emitting element of the present invention are not limited to these embodiments. Absent.

Embodiment 1
In the light emitting device of this embodiment, as shown in FIG. 2, the semiconductor light emitting element 2 is surface-mounted on an insulating substrate 16 provided with a printed wiring 17. Here, the semiconductor light emitting element 2 is formed with an n-type semiconductor layer (not shown) on the lower surface side in FIG. 2 and a p-type semiconductor layer (not shown) on the upper surface side. Since the output is taken out, the upper part of FIG. A light emitting layer portion 21 made of a gallium nitride based semiconductor is formed on the insulating substrate 16. In the semiconductor light emitting device 2, the p-type semiconductor layer (not shown) and the n-type semiconductor layer (not shown) of the light emitting layer portion 21 are electrically connected to the printed wirings 17 and 17 through the conductive wires 15 and 15, respectively. It is connected to the.

Further, a frame-shaped frame member 18 surrounding the semiconductor light emitting element 2 is fixed on the insulating substrate 16, and a sealing portion 19 for sealing and protecting the semiconductor light emitting element 2 is provided inside the frame member 18. is there.
Thus, in the light emitting device of this embodiment, the sealing portion 19 is made of the fluorescent glass 3B of the present invention, so that it is possible to obtain a combined light of the light from the semiconductor light emitting element 2 and the light from the phosphor. . In FIG. 2, the upper surface of the sealing portion 19 is a flat surface, but may have a concave or convex lens shape as appropriate.

  The fluorescent glass of the present invention can be obtained by putting a mixture of glass and phosphor into a portion surrounded by the insulating substrate 16 and the frame member 18 and performing the above-described sintering step. When this method is used, since the sintering process is performed on the semiconductor light emitting device 2 as the semiconductor light emitting device, the disconnection due to the shrinkage accompanying the sintering of the glass powder, the deterioration of the chip due to holding at a high temperature for a long time, etc. It is necessary to keep in mind.

  Here, the semiconductor light emitting element 2 may be installed by so-called flip chip bonding. Hereinafter, an embodiment of installation by flip chip bonding will be described.

[Embodiment 2]
As shown in FIG. 3, the light emitting device of the present embodiment is a sealing portion that seals the semiconductor light emitting element 2 disposed at the bottom of the recess 16 a provided on one surface (the upper surface in FIG. 3) of the insulating substrate 16. 19 and is characterized in that the sealing portion 19 is formed of the fluorescent glass 3B of the present invention. Here, like the first embodiment, the sealing portion 19 can be obtained by putting a mixture of glass and phosphor in the recess 16a and performing the above-described sintering step.

  For the purpose of simplifying the sealing process, as shown in FIG. 4, the semiconductor light emitting element 2 is previously housed in a portion corresponding to the semiconductor light emitting element 2 with an outer peripheral shape corresponding to the recess 16 a. For example, a method of mounting a semiconductor chip that has been processed into a shape having a recess 19c in the recess 16a of the insulating substrate 16 on which the semiconductor light emitting element 2 is mounted can be used.

  Furthermore, as a simple method, there is a method in which a fluorescent glass previously formed into a flat plate shape, a lens shape, or a dome shape is placed on a substrate (package) of a semiconductor light emitting device. Examples of detailed embodiments are shown below.

[Embodiment 3]
As shown in FIG. 5, the light emitting device of the present embodiment includes a dome-shaped sealing portion 19 that seals the semiconductor light emitting element 2 on one surface (upper surface in FIG. 5) side of the insulating substrate 16. The fluorescent glass 3B of the present invention is used as a material used as a feature.

  Therefore, in the light emitting device of the present embodiment, the phosphor that is excited by the light from the semiconductor light emitting element 2 to emit light is dispersed in the sealing portion 19, so the light emitted from the semiconductor light emitting element 2 and the sealing portion A light output composed of the combined light with the light emitted from the phosphor is obtained. For example, a material that emits near-ultraviolet light is selected as the material of the light-emitting layer portion 21 of the semiconductor light-emitting element 2, and a phosphor that emits red, green, or blue light when excited by near-ultraviolet light. In this case, each color phosphor in the sealing portion 19 is excited by the light emitted from the semiconductor light emitting element 2 and each emits unique light, and white light, for example, is obtained as the combined light.

In the present embodiment, as shown in FIG. 6, a plurality of dome-shaped sealing portions 19 may be stacked to form a dome-shaped sealing portion having a laminated structure.
Each dome-shaped sealing part 19a, 19b, 19c in the laminated structure is formed of fluorescent glass containing red, green, and blue phosphors, respectively. Accordingly, each color phosphor in each dome-shaped sealing portion is excited to exhibit its own light emission, and for example, white light is obtained as its combined light.

Here, the order of stacking is not particularly limited, and the layers are appropriately arranged in consideration of the characteristics of the phosphor and other factors. For example, the closer to the semiconductor light emitting element 2 as shown in FIG. 6, the more preferable it is to have a fluorescent color with a short wavelength from the viewpoint of utilization efficiency of excitation light and phosphor emission. It is preferable from the viewpoint of expecting the effect of efficiently scattering the excitation light if the stacking order is closer to the semiconductor light emitting device 2 so that the average particle diameter of the contained phosphor becomes smaller. From the viewpoint of preventing deterioration of the phosphor, the following arrangement is preferable.
(I) A phosphor that is susceptible to photodegradation is disposed on the upper layer so as to be farthest from the semiconductor light emitting element 2;
(Ii) A phosphor that is easily deteriorated by moisture is disposed on the lower layer so as to be closest to the semiconductor light emitting element 2. This keeps the phosphor away from the outside air and suppresses moisture degradation.
(Iii) A phosphor containing a sulfur component is disposed in the middle of the stack. Thereby, moisture deterioration of the outside air is suppressed, and blackening due to the sulfur component of the semiconductor light emitting element 2 is suppressed.

[Embodiment 4]
As shown in FIG. 7, the light emitting device of this embodiment includes a frame-shaped frame member 18 disposed so as to surround the semiconductor light emitting element 2 on one surface (the upper surface in FIG. 7) side of the insulating substrate 16. In addition, a sealing portion 19 is optionally provided inside the frame member 18, and further, oxygen or the outside of the semiconductor light emitting element 2 and the optional sealing portion 19 is formed on the upper surface side of the semiconductor light emitting device 2 and the optional sealing portion 19 by the lid 36 made of the fluorescent glass 3B of the present invention. Shielded from moisture. The lid 36 and the sealing portion 19 may be in direct contact or may have a gap. However, if there is no gap, the light extraction efficiency is higher and a high-luminance semiconductor light-emitting device can be obtained. When it has a space | gap, it is preferable to set it as vacuum sealing or inert gas enclosure.

  Therefore, in this embodiment, since the lid body 36 is formed of the phosphor portion, the combined light of the light emitted from the semiconductor light emitting element 2 and the light emitted from the phosphor contained in the lid body 36. An optical output consisting of For example, a material that emits near-ultraviolet light is selected as the material of the light-emitting layer portion 21 of the semiconductor light-emitting element 2, and a phosphor that emits red, green, or blue light when excited by near-ultraviolet light. In this case, each color phosphor in the lid body 36 is excited by the light emitted from the semiconductor light emitting element 2 and each emits unique light, and for example, white light is obtained as the combined light.

  Further, in this embodiment, the lid 36 suppresses the entry of external factors such as moisture and oxygen that accelerate the deterioration of the phosphor and the sealing resin, and the volatilization of the decomposition gas of the sealing portion 19 due to heat and light. , There is an advantage that luminance reduction and shrinkage and peeling of the sealing portion due to these can be reduced. In FIG. 7, the lid body 36 is on a flat plate, but may have a lens shape in which one side or both sides are concave or convex.

  In the present embodiment, as shown in FIG. 8, a plurality of lid bodies 36 may be stacked to form a lid body having a laminated structure. Each lid 36a, 36b, 36c in the laminated structure is made of fluorescent glass containing red, green and blue phosphors, respectively. Accordingly, the respective color phosphors of the respective lids 36a, 36b, 36c are excited and each emits unique light, and, for example, white light is obtained as the synthesized light.

The order of stacking is the same as in the third embodiment.
Further, in the present embodiment, as shown in FIG. 9, the lid body 36 may be formed so as to form a single plate by arranging a plurality of fluorescent glasses having different fluorescent colors. Each of the arrangement units 36d, 36e, and 36f to be arranged is formed of fluorescent glass containing red, green, and blue phosphors, respectively. Accordingly, the respective color phosphors of the respective array units 36d, 36e, and 36f are excited to each emit unique light, and, for example, white light is obtained as the combined light. In FIG. 8, the lid body 36 is on a flat plate, but may have a lens shape in which one side or both sides are concave or convex.

  Although there is no restriction | limiting in the said semiconductor light-emitting device as a light source, What emits the light which has a peak wavelength in the range of 350 nm or more and 500 nm or less is preferable. The present invention is effective in that a semiconductor light emitting device having a light emission wavelength from the ultraviolet region to the near ultraviolet region can be used because it mainly comprises a glass material that is less deteriorated than ultraviolet rays. As specific values in the ultraviolet to near ultraviolet region, a semiconductor light emitting device having a peak emission wavelength of usually 350 nm or more, preferably 380 nm or more, and usually 430 nm or less, preferably 420 nm or less is used.

Specific examples of such a semiconductor light emitting element include a light emitting diode or a laser diode (hereinafter, abbreviated as “LD” where appropriate). Among these, those using ZnO-based compound semiconductors or GaN-based compound semiconductors are preferable, and GaN-based LEDs and LDs are particularly preferable. This is because GaN-based LEDs and LDs have significantly higher light emission output and external quantum efficiency than SiC-based LEDs that emit light in this region, and are extremely bright with very low power when combined with the phosphor. This is because light emission can be obtained. For example, for a current load of 20 mA, GaN-based LEDs and LDs usually have a light emission intensity 100 times or more that of SiC-based. GaN-based LEDs and LDs preferably have an Al _X Ga _Y N light emitting layer, a GaN light emitting layer, or an In _X Ga _Y N light emitting layer. Among the GaN-based LEDs, those having an In _X Ga _Y N light-emitting layer are particularly preferable because the emission intensity is very strong, and in the GaN-based LD, the multiple quantum of the In _X Ga _Y N layer and the GaN layer is preferable. A well structure is particularly preferable because the emission intensity is very strong.

  In the above, the value of X + Y is usually a value in the range of 0.8 to 1.2. In the GaN-based LED, those in which the light emitting layer is doped with Zn or Si or those without a dopant are preferable for adjusting the light emission characteristics.

A GaN-based LED has these light-emitting layer, p-layer, n-layer, electrode, and substrate as basic components, and the light-emitting layer is an n-type and p-type Al _X Ga _Y N layer, GaN layer, or In _X Those having a heterostructure sandwiched between Ga _Y N layers and the like have high luminous efficiency, and those having a heterostructure having a quantum well structure have higher luminous efficiency and are more preferable.
In addition, it is preferable to appropriately provide various structures (such as an electrode structure, a reflective layer structure, and a flip chip structure that can be mounted upside down) for extracting more light generated in the light emitting layer to the outside.

  When the semiconductor light emitting device of the present invention emits white light, the luminous efficiency of the apparatus is 20 lm / W or more, preferably 22 lm / W or more, more preferably 25 lm / W or more, and particularly preferably 28 lm / W or more. Yes, the average color rendering index Ra is 80 or more, preferably 85 or more, more preferably 88 or more.

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples unless it exceeds the gist.
[1] Kind of glass and physical property values Glasses shown in Table 2 below were subjected to the present invention.

[2] Production of fluorescent glass Fluorescent glass was produced by the following procedure.
[2-1] Mixing of phosphor and glass Blue phosphor (BaMgAl ₁₀ O ₁₇ : Eu, hereinafter sometimes referred to as “BAM”), green phosphor ((Ba _0.75 Sr _0.25 ) ₂ SiO ₄ : Eu, Hereinafter, “BSS” may be referred to as “BSS”), and red phosphor ((Sr, Ca) AlSiN ₃ : Eu, hereinafter also referred to as “CASON”) may be referred to as 82.02%, and 6. Each phosphor was precisely weighed to a ratio of 3% and 11.66% and mixed.
The phosphor mixture obtained above or 0.0185 g (18% by weight) of each desired monochromatic phosphor and 0.1 g of the glass powder are precisely weighed and charged in a 20 ml screw tube to uniformly disperse the glass powder and the phosphor. Until mixed.

[2-2] Pressing / Molding [2-2-1] Pressing Molding While putting 0.1 g of glass powder or fluorescent glass mixed powder into a cylindrical mold with a diameter of 9 mm, maintaining a pressure of 3 t from the top. Pressed for 3 minutes to produce a molded product.

[2-2-2] Atmospheric pressure molding Glass powder or 0.05 g of the above fluorescent glass mixed powder is put into a cylindrical frame made of boronite (diameter 10 mm x depth 2 mm), and the surface is lightly pressed with a SUS flat plate. A cylindrical molded product was produced.

[2-3] Firing / Sintering If the glass molded body or fluorescent glass molded body molded as described above is placed in a quartz beaker if it is a pressure molded body, and boron nitride if it is molded under normal pressure As it was, it was fired at a desired temperature for a desired time (usually 1 hour) using an “Isuzu Muffle Furnace Model ETS-29KS Electric Furnace” manufactured by Isuzu. Temperature reduction started at an initial temperature drop rate of about 20 ° C./second after firing.

[2-4] Crushing and classification of calcined glass The glass calcined in [2-3] is uniformly pulverized with an agate mortar and agate teat, and processed with a 200 mesh (75μ) sieve to remove coarse particles. Cut and aligned to particles having an average diameter of about 60 μm or less as a target size.

[3] Chromaticity evaluation
Using a spectrophotometer “SpectroEyx” manufactured by Gretag Macbeth, the surface of the molded product was measured under the following conditions, L _* a _* b _* was determined from the color difference formula CIE LAB, and the brightness difference of the L _* values was evaluated.
<Measurement conditions>
Measurement wavelength range 380 nm to 730 nm, 10 nm interval ΔE <0.02 (standard deviation value) in reproducible white tile measurement
Light source D65
Measurement area 4.5mm diameter Measurement time 1.5 seconds

[4] SEM Observation Using a scanning electron microscope (SEM) “JEOL JSM-6060” manufactured by JEOL Data Corporation, a cross section of the glass molded body or fluorescent glass molded body was observed. The observation result of the cross section of Example i in Table 4 to be described later is shown in FIG. According to this, foam particles having a diameter of about 100 μm were confirmed on the semiconductor element side.

[5] Lighting life treatment and evaluation of semiconductor light-emitting element sealed with fluorescent glass [5-1] Preparation of glass molded body sealing sample The fluorescent glass molded body prepared in [2] above is formed on the substrate of the semiconductor light-emitting element. A sample of a semiconductor light emitting device was prepared by covering the gap and bonding and sealing the periphery with a silicone resin “LPS-2410” manufactured by Shin-Etsu Chemical.

[5-2] Preparation of silicone resin potting sample A mixture of red, green, and blue phosphors in a silicone resin “LPS-2410” manufactured by Shin-Etsu Chemical Co., Ltd. on a semiconductor light emitting device so as to be 18% by weight. A sample of a semiconductor light emitting device which was potted and cured was prepared. Each sample was processed for a predetermined time under the following lighting life test conditions.
<Lighting life test conditions>
Semiconductor light emitting element: manufactured by Cree, emission wavelength of 405 nm
Energization environment condition: 350 mA continuous energization / 85 ° C x 85% RH
Environmental tester: ESPEC's small environmental tester “SH-221”
Lighting power supply: Asahi Seisakusho <Evaluation conditions>
The optical characteristics (change rate, spectrum, etc. from the initial value of the luminous flux lm value) of the semiconductor light emitting device after the life test for a predetermined time were evaluated using a spectroscopic measuring device manufactured by Opto Sirius Co., Ltd.
Integrating sphere: Sphere Optics 4inchi integrating sphere (10cm)
Detector: Ocean Optics HR200
Temperature controller: CELL TDC-1110 PELTIER CONTROLLER

[6] Evaluation results Table 3 below shows the chromaticity measurement results of the glass fired at various temperatures.

  Table 4 below shows the chromaticity measurement results of the fluorescent glass using LS0500.

In Table 4, “firing conditions only for glass” is (temperature × time), and “sintering conditions for fluorescent glass” is (temperature × time).
From these results, it was found that once the glass was baked at a high temperature, the color of the glass or fluorescent glass became very beautiful.
Furthermore, the result of having performed the lighting life test using the fluorescent glass shown in following Table 5 is shown in FIG.

  In Table 5, “Sintering conditions for glass only” is (temperature × time), and “Sintering conditions for fluorescent glass” is (temperature × time).

  FIG. 10 shows a graph comparing the luminous flux maintenance rates of the fluorescent glass sealing sample (the glass molded body sealing sample of [5-1]) and the silicone resin potting sample of [5-2].

  From the above, it was found that when the phosphor sealed with glass is used, the maintenance rate of the luminous flux is high and the life can be extended.

[7] Effect of surface hydrophobization treatment of orange fluorescent glass [7-1] Weight change From “K-PG375” manufactured by Sumita Optical Glass Co., Ltd. and Sol-Gel method using ammonia catalyst (ethanol solvent) of triethoxysilane on the surface Fluorescent glasses of glass-coated orange phosphor (Sr ₂ BaSiO ₅ : Eu, hereinafter sometimes referred to as “SBS”) and orange phosphor SBS without glass coating were respectively prepared at a temperature of 85 ° C. A change in weight under an environmental condition of 85% humidity was confirmed.

For fluorescent glass using glass-coated SBS, drop two drops of fluorinating agent (Glest Heptadecafluoro-1,1,2,2-Tetra hydrodecyl triethoxysilane) onto the glass surface with a dropper, air-dry overnight, and an explosion-proof furnace. At 100 ° C. for 1 hour.
The weights of glass-coated SBS and non-glass-coated SBS are weighed in advance with a balance, and a sealed sample is prepared according to the procedure for preparing a glass molded body sealed sample described in [5-1]. We compared moisture resistance and durability under the environment.
<Environmental conditions>
Operating environment tester: ESPEC's small environmental tester “SH-221”
Temperature / humidity conditions: 85 ° C / 85% RH × 0 hr to 2000 hr treatment As shown in FIG. 11, the improvement in moisture resistance is confirmed particularly in the combination of the glass-coated phosphor treated with the fluorination treatment agent. It was.

[7-2] Optical characteristics The optical characteristics (maintenance ratio) of the semiconductor light emitting device using the SBS fluorescent glass sample subjected to the high temperature and humidity treatment were also evaluated. The light emission characteristics of glass-coated SBS are shown in FIG. 12, and the light emission characteristics of SBS without glass coating are shown in FIG.
<Semiconductor light emitting device>
LED package: Cree's emission wavelength 405nm
Integrating sphere: Sphere Optics 4inchi integrating sphere (10cm)
Detector: Ocean Optics HR200
Temperature controller: CELL TDC-1110 PELTIER CONTROLLER
As a result, in terms of light emission characteristics, it was confirmed that the moisture resistance was improved by combining a glass-coated phosphor treated with a fluorination treatment agent.

  The use of the fluorescent glass of the present invention is not particularly limited, but can be suitably used as a sealing material in the semiconductor field, particularly in the semiconductor light-emitting device field. For example, a light source for a liquid crystal backlight such as a lighting device, an image display device, and a thin television. It can be suitably used in a wide range of fields. In particular, in the fields of semiconductor light emitting devices that emit near-ultraviolet light and ultraviolet light that did not have an appropriate sealing material, as well as lighting devices and image display devices to which the light-emitting devices can be applied. Industrial applicability is extremely high.

  Furthermore, it is possible to select a wider range of phosphors than blue excitation by using as a binder for holding phosphors excited by near-ultraviolet / ultraviolet light, and provide a semiconductor light emitting device with high color rendering properties and high brightness. It becomes possible. Such white light source using ultraviolet light-excited red, green, and blue phosphors has high color rendering and excellent color reproducibility, and the fluorescent glass of the present invention is used for backlights for liquid crystal displays, lighting for homes and stores, physics and chemistry, and medical use. -By using the illumination for photographic imaging for process inspections, etc., it is possible to provide high-quality illumination that is less likely to cause eye fatigue or illness even when staring for a long time.

  The fluorescent glass of the present invention is not only used in the field of semiconductor light-emitting devices described above, but also has various characteristics such as light transmittance (transparency), light resistance, heat resistance, hydrothermal resistance, and UV resistance. Space industry materials and other materials such as thermal conductive sheets, thermal conductive adhesives, insulating thermal conductive materials, underfill materials, sealants, optical waveguide structures, light guide plates, light guide sheets, reflections High applicability to light control materials, diagnostic microfluid materials, microbial culture media, and nanoimprint materials, so the industrial applicability is extremely high in various fields such as aerospace, optics, electrical electronics, and biotechnology. .

1B light emitting device (semiconductor light emitting device)
2 Semiconductor light-emitting element 3B phosphor part (member for semiconductor light-emitting device)
15 Conductive wire 16 Insulating substrate 16a Recess 17 Printed wiring 18 Frame material 19 Sealing portions 19a, 19b, 19c Domed sealing portion (laminated structure)
19d Concave part 21 Light emitting layer part 24 Bump 36 Cover body 36a, 36b, 36c Cover body (laminated structure)
36d, 36e, 36f Lid (arrangement unit)

Claims (16)

A fluorescent glass containing glass and a phosphor dispersed in the glass, wherein the L _* value in the chromaticity coordinates of the L _* a _* b _* color system is 65 or more. Fluorescent glass containing glass having the following characteristics and a phosphor dispersed in the glass.
[Characteristics of glass]
The glass was ground to average particle size of not more than 60 [mu] m, at a temperature of (sag +50) ° C., when 1 hour of sintering, the value of L _* is in the L _* a _* b _* color system chromaticity coordinates 50 or more.   The fluorescent glass according to claim 1 or 2, wherein the glass has a carbon component of 100 ppm or less.   The fluorescent glass according to claim 1, wherein the surface is subjected to a hydrophobic treatment. The phosphor is a group consisting of M ₃ SiO ₅ , MS, MGa ₂ S ₄ , MAlSiN ₃ , M ₂ Si ₅ N ₈ , MSi ₂ N ₂ O ₂ as a base crystal (where M is Ca, Sr, Ba) And at least one selected from the group consisting of: Cr, Mn, Fe, Bi, Ce, Pr, Nd, Sm, Eu, Tb, Dy The fluorescent glass according to any one of claims 1 to 4, which is a phosphor containing at least one of, Ho, Er, Tm, and Yb, or a phosphor containing Mn ⁴⁺ as an activator.   Specific gravity is 4 or less, The fluorescent glass of any one of Claims 1-5. It is a manufacturing method of fluorescent glass given in any 1 paragraph of Claims 1-6,
A process of preparing glass;
Mixing the glass and the phosphor or phosphor precursor;
The manufacturing method of the fluorescent glass which has the process of sintering the mixture obtained at the said process to mix. It is a manufacturing method of the fluorescent glass of Claim 7,
The step of preparing the glass includes
A method for producing fluorescent glass, comprising a step of firing and pulverizing the glass. A method for producing a fluorescent glass according to claim 7 or 8,
The said mixing process is a manufacturing method of fluorescent glass which has the process of mixing the glass powder obtained by the said process to grind | pulverize, and the said fluorescent substance. It is a manufacturing method of fluorescent glass given in any 1 paragraph of Claims 7-9,
A small amount of the mixed powder of the phosphor and the glass powder is attached to the surface of the sintered body of the phosphor and glass obtained in the sintering step, and sintered at a high temperature to form a sintered body of the base. A method for producing fluorescent glass, characterized by having a process of repeating a process of integrating and sintering a mixed powder in a small amount. A sealing member comprising the fluorescent glass according to any one of claims 1 to 6, wherein the semiconductor light emitting device comprises a sealing member for sealing a semiconductor light emitting element,
A semiconductor light emitting device in which the fluorescent glass is disposed on an optical path of the semiconductor light emitting element. The semiconductor light-emitting device according to claim 11,
A semiconductor light emitting device in which the fluorescent glass has a part having a different specific gravity, and is arranged such that the specific gravity of a part far from the semiconductor light emitting element is larger than the specific gravity of a part close to the semiconductor light emitting element. The semiconductor light-emitting device according to claim 11 or 12,
A semiconductor light emitting device in which the fluorescent glass contains bubbles. A method for manufacturing a semiconductor light-emitting device according to claim 11,
Mixing glass with a phosphor or phosphor precursor;
The mixture obtained in the mixing step is arranged so as to cover the semiconductor light emitting device,
And a step of sintering the mixture together with a semiconductor light emitting element. A method of manufacturing a semiconductor light emitting device according to claim 14,
The sintering step is a method for manufacturing a semiconductor light emitting device, including a step of heating in an oxidizing atmosphere. A method for manufacturing a semiconductor light-emitting device according to claim 11,
Placing the semiconductor light emitting element on the base including the wiring portion;
Arranging fluorescent glass so as to cover the semiconductor light emitting element on the base;
The manufacturing method of the semiconductor light-emitting device including the process of airtightly sealing the said fluorescent glass and the said base via a sealing member.