JP2007016171A - Wavelength-transforming material, light-emitting device and method for producing the wavelength-transforming material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a wavelength-transforming material presenting more efficient fluorescence than that of conventional ones by combining an oxynitride phosphor or a nitride phosphor with a material dispersing the same, a method for producing the wavelength-transforming material and a light emitting device using the same. <P>SOLUTION: In the wavelength-transforming material, oxynitride phosphor particles or nitride phosphor particles are dispersed in glass having ≥700°C softening point. By the aforesaid combination, rare earth elements in the phosphor do not dissolve in the glass even in a process for dispersing the phosphor particles in the glass, the wavelength-transforming efficiency is enhanced and is not deteriorated by excited lights ranging from violet to ultraviolet. The wavelength-transforming material has high light emission efficiency from the phosphor and stable without influenced by environmental atmosphere such as water and the like. The light-emitting device small and having long life is provided by combining the wavelength-transforming material with a nitride semiconductor light-emitting device or the like. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a wavelength conversion member using a phosphor, and a light emitting device using a semiconductor light emitting element and the phosphor.

A light-emitting device that converts the wavelength of light from a semiconductor light-emitting element such as a light-emitting diode (LED) with a phosphor is small in size and consumes less power than an incandescent bulb. In order to promote practical use as a light source, developments are being made to further improve efficiency and reliability. Patent Document 1 discloses a light emitting device that obtains pseudo white light by combining a blue light emitting diode (LED) and a phosphor that is excited by light of the blue light emitting diode and emits yellow light. As materials for dispersing the phosphor particles, three types of materials such as epoxy resin, acrylic resin, and water glass are disclosed. Patent Document 2 discloses a luminescent color in which a blue LED and a Y ₃ Al ₅ O ₁₂ (garnet) phosphor that emits yellow fluorescence when excited by light from the blue LED are dispersed in glass having a softening point of 500 ° C. or higher. A white illumination light source combined with a conversion member is disclosed.

  In the future, it is considered to use an excitation light source having a wavelength shorter than that of a blue light emitting diode in order to improve efficiency and stabilize chromaticity in a light emitting device in which a semiconductor light emitting element such as a light emitting diode or a semiconductor laser is combined with a phosphor. It has been. At this time, a major problem is that the resin, which is a material for dispersing the phosphor, is deteriorated by light having a wavelength from purple to ultraviolet. In order to solve this problem, a technique using glass as a material for dispersing a phosphor is disclosed.

Patent Document 3 discloses an oxynitride glass (oxynitride glass) phosphor composed of CaCO ₃ , Al ₂ O ₃ , SiO ₂ , AlN, and rare earth oxide or transition metal oxide components. . The glass is doped with rare earth elements Eu ²⁺ , Eu ³⁺ , Ce ³⁺ , Tb ³⁺ , or the like, or transition metal elements Cr ³⁺ , Mn ^2+, etc., which act as the luminescence center, to give strong emission intensity. It is said that an oxynitride glass having the same was obtained. The production method is to mix CaCO ₃ , Al ₂ O ₃ , SiO ₂ , AlN, Eu ₂ O ₃ at a ratio of 24.0: 3.3: 33.4: 33.3: 6.0 Is heated and melted at 1700 ° C. for 2 hours in a nitrogen atmosphere, and further rapidly cooled to obtain fluorescent glass. This fluorescent glass emits red fluorescence at an excitation wavelength of about 500 nm. It is said that it was done.

  In this example, the oxynitride glass itself functions as a phosphor, but the glass is amorphous and does not have a certain atomic arrangement. Therefore, since the atomic arrangement of the glass component around the rare earth atom that is the emission center changes due to changes in manufacturing conditions such as the raw material ratio and processing temperature, it is difficult to obtain a certain wavelength conversion efficiency. Further, since the emission color changes depending on the manufacturing conditions, the reproducibility is poor, and there is a problem that the rare earth element emission intensity and the chromaticity (emission spectrum) of the emission color change. Further, the wavelength conversion efficiency is low as compared with an oxynitride phosphor described later.

Patent Document 4 discloses an example in which α sialon, which is an oxynitride phosphor having high wavelength conversion efficiency and excellent heat resistance, is dispersed in a low melting glass having a melting point of 500 ° C. for evaluation. Using a UV LED having an emission peak wavelength of 350 to 380 nm, light emitted from the UV LED is incident on a low-melting glass molded body containing α sialon, and a light emitting device that performs wavelength conversion with a phosphor is obtained.
Japanese Patent Laid-Open No. 10-163535 JP 2003-258308 A JP 2001-214162 A JP 2004-238506 A

  When a rare earth element acting as a light emission center is added as a component of the amorphous glass itself as in Patent Document 3, the atomic arrangement around the rare earth atoms is not constant unlike the case of the crystal structure. For this reason, it is difficult to obtain good wavelength conversion efficiency, and the luminescent color varies depending on the manufacturing conditions, so that the chromaticity reproducibility of the light emitting device is not sufficient.

  On the other hand, when the oxynitride phosphor particles are dispersed in the low-melting glass as in Patent Document 4, a component for lowering the melting point in the low-melting glass (for example, lead glass) causes violet to ultraviolet light to be emitted. There was a problem that the transmittance was not sufficient.

  The present invention relates to a wavelength conversion member capable of obtaining fluorescence with higher efficiency than before by a combination of an oxynitride phosphor or a nitride phosphor and a material in which they are dispersed, a manufacturing method thereof, and a light emitting device using the same. The purpose is to obtain.

  (1) The present invention is a wavelength conversion member in which oxynitride phosphor particles or nitride phosphor particles are dispersed in a glass having a softening point of 700 ° C. or higher.

  As a result of various studies on the combination of phosphor and glass in order to solve the problem, the present inventor has simply dispersed oxynitride phosphor particles or nitride phosphor particles in silicone resin or low-melting glass. In comparison with the above, it has been found that the wavelength conversion efficiency is increased by dispersing oxynitride phosphor particles or nitride phosphor particles in glass having a softening point of 700 ° C. or higher. The reason for this is that these phosphors have excellent heat resistance, so even in the step of melting the glass above the softening point and dispersing in the glass, the particles of the phosphor do not mix with the glass. It is possible to keep it. In addition, since these phosphors are nitrides or nitride-based oxynitrides and are not oxides, it is assumed that there is little reaction with glass, particularly with respect to crystals. On the other hand, it is estimated that the amorphous substance existing on the surface of the particles may be diffused and removed in the molten high melting point glass. Furthermore, depending on the composition ratio of the oxynitride phosphor particles or the nitride phosphor particles, the wavelength conversion efficiency may increase due to the annealing effect that stabilizes the crystal structure.

(2) The present invention is a wavelength conversion member characterized in that the oxynitride phosphor particles or the nitride phosphor particles contain 50% or more by mole ratio of a combination of Si and N. While the melting point of silicon oxide (SiO ₂ ) is 1710 ° C., the melting point of silicon nitride is as high as 1900 ° C., and silicon nitride does not soften like silicon oxide. Therefore, phosphor particles containing 50% or more of the combined components of Si and N can be combined with glass having a high softening point because the phosphor can maintain a particle state even in a high-temperature melting step. Suitable for

  (3) The wavelength conversion member according to the present invention is characterized in that 50% or more of oxynitride phosphor particles or nitride phosphor particles are crystalline. The atomic arrangement structure of the phosphor particles may be a crystalline body or an amorphous body, but the wavelength conversion efficiency of the crystalline body is generally larger by one digit or more. Therefore, the wavelength conversion member with higher wavelength conversion efficiency is obtained by containing many crystal bodies.

  (4) The wavelength conversion member according to the present invention is characterized in that the oxynitride phosphor particles are phosphor particles made of Si, Al, O, N and one or more lanthanoid rare earth elements. It is. A material system composed of Si, Al, O, and N is sometimes called Sialon, and is a material having excellent heat resistance. Therefore, even when dispersed in glass at a temperature higher than the softening point of glass, the phosphor It exists as a particle and does not melt. This material is a mixture of one or more of the lanthanoid rare earths (La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb) that become the emission center. Therefore, it becomes a stable wavelength conversion member having excellent wavelength conversion efficiency.

  (5) The wavelength conversion member according to the present invention is characterized in that the nitride phosphor particles are phosphor particles composed of Ca, Si, Al, N, and one or more lanthanoid rare earth elements. is there. Since the material system composed of Ca, Si, Al, and N is a material excellent in heat resistance, even if dispersed in glass at a temperature equal to or higher than the softening point of glass, it exists as phosphor particles and does not melt. This material is a mixture of one or more of the lanthanoid rare earths (La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb) that become the emission center. Therefore, the wavelength conversion efficiency is excellent and a stable wavelength conversion member is obtained.

  (6) The wavelength conversion member according to the present invention is characterized in that the glass having a softening point of 700 ° C. or higher is oxynitride glass.

  As a result of various studies on combinations of phosphors and glasses in order to solve the problems, the present inventor has found that oxynitride phosphors or combinations of nitride phosphors and oxynitride glasses are particularly suitable. Since these phosphors are excellent in heat resistance, the phosphor component does not mix with the oxynitride glass even in the step of dispersing in the oxynitride glass and maintains the particle state. Therefore, stable chromaticity and wavelength conversion efficiency can be obtained regardless of manufacturing conditions. In addition, by using these phosphors and oxynitride glass, a wavelength conversion member that is not deteriorated even by irradiation with excitation light particularly from purple to ultraviolet can be obtained. Furthermore, oxynitride glass has a higher refractive index than oxide glass, as will be described later, and is close to the refractive index of oxynitride phosphors and nitride phosphors, so that light extraction efficiency from phosphor particles is high. improves.

  (7) The present invention relates to a first oxynitride phosphor particle or nitride phosphor particle having an emission peak wavelength of 460 nm to 510 nm, and a second oxynitride having an emission peak wavelength of 510 nm to 550 nm. A wavelength conversion member comprising phosphor particles or nitride phosphor particles and third oxynitride phosphor particles or nitride phosphor particles having an emission peak wavelength of 600 nm to 670 nm. is there. Thereby, since the color which mixed three primary colors of blue, green, and red is obtained, the wavelength conversion member excellent in color rendition and the reproducibility of chromaticity is obtained.

  (8) In the light emitting device of the present invention, the emission peak wavelength of the semiconductor light emitting element which is a phosphor excitation light source is 300 nm or more and 500 nm or less. If it is 300 nm or more, good transmittance can be obtained in the oxynitride glass, and if it is a wavelength of 500 nm or less, highly efficient light emission can be obtained particularly in a nitride semiconductor light emitting device in which the light emitting layer is made of InGaN.

  (9) In the light emitting device of the present invention, the emission peak wavelength of the semiconductor light emitting element which is a phosphor excitation light source is 350 nm or more and 420 nm or less. This wavelength range is particularly effective in a nitride semiconductor light emitting device having a light emitting layer made of InGaN. In addition, since the luminous sensitivity is low, chromaticity (light emission color) due to variation in emission peak wavelength of the semiconductor light emitting device. This has the advantage that almost no fluctuation occurs.

(10) In the present invention, the chromaticity coordinate x of the emission color of the light emitting device is 0.22 to 0.44 and the chromaticity coordinate y is 0.22 to 0.44, or the light emission of the light emitting device. The light emitting device is characterized in that the chromaticity coordinate x of the color is 0.36 or more and 0.5 or less and the chromaticity coordinate y is 0.33 or more and 0.46 or less. Since the chromaticity is white and light bulb color (warm white), it is suitable for wide use as illumination.

  (11) The present invention provides an oxynitride phosphor particle by heating oxynitride phosphor particles or nitride phosphor particles and glass or a glass raw material to a softening point of glass or higher and 1600 ° C. or lower. Or it is the manufacturing method of the wavelength conversion member characterized by having the process of disperse | distributing the particle | grains of nitride fluorescent substance in glass. Oxynitride phosphor particles or nitride phosphor particles are less likely to mix in the glass at 1600 ° C. or lower and maintain a particle state, so that stable fluorescence can be obtained regardless of the conditions of this step. Can do.

  (12) In the present invention, the oxynitride phosphor or the nitride phosphor raw material is fired at a first temperature of 1600 ° C. or higher to produce oxynitride phosphor particles or nitride phosphor particles. A second temperature that is 50 ° C. or more lower than the first temperature by mixing the oxynitride phosphor particles or nitride phosphor particles obtained in the first step and the glass raw material; It is a manufacturing method of the wavelength conversion member characterized by having the 2nd process of disperse | distributing the particle | grains of the said oxynitride fluorescent substance or the particle | grains of nitride fluorescent substance in the said glass by heating by. In this manufacturing method, the oxynitride phosphor particles or the nitride phosphor particles can be dispersed in the glass at a temperature lower than the firing temperature by 50 ° C. or more, and under such conditions, the oxynitride phosphor particles do not mix with the glass. Since the particle state is maintained, stable fluorescence can be obtained regardless of the conditions of this step.

  (13) In the present invention, the oxynitride phosphor or the nitride phosphor raw material is fired at a first temperature of 1600 ° C. or higher to produce oxynitride phosphor particles or nitride phosphor particles. A first step, a second step of melting and mixing glass raw materials to produce a glass, an oxynitride phosphor particle or a nitride phosphor particle obtained by the first step, and a second step The glass obtained by the step is mixed and heated at a second temperature that is 50 ° C. or more lower than the first temperature, whereby the oxynitride phosphor particles or the nitride phosphor particles are contained in the glass. It has the 3rd process made to disperse | distribute to a wavelength conversion member manufacturing method characterized by the above-mentioned. In this manufacturing method, it is not necessary to consider the influence of the oxynitride phosphor particles or the nitride phosphor particles on the temperature at which the glass is produced from the glass raw material. Oxynitride phosphor particles or nitride phosphor particles can be dispersed in glass at a temperature of 50 ° C. or more lower than the firing temperature, and under these conditions, the particles are not mixed and maintained in a particle state. Stable fluorescence can be obtained regardless of the conditions of this step.

  (14) The present invention is a method for producing a wavelength conversion member, wherein the glass is oxynitride glass.

  As a result of studying various combinations of phosphors and glasses in order to solve the problems, the present inventors have found that oxynitride phosphors or combinations of nitride phosphors and oxynitride glasses are particularly suitable for this production method. I found out. Since these phosphors are excellent in heat resistance, the phosphor component does not mix with the oxynitride glass even in the step of dispersing in the oxynitride glass and maintains the particle state. Therefore, stable chromaticity and wavelength conversion efficiency can be obtained regardless of manufacturing conditions. In addition, by using these phosphors and oxynitride glass, a wavelength conversion member that is not deteriorated even by irradiation with excitation light particularly from purple to ultraviolet can be obtained. Furthermore, oxynitride glass has a higher refractive index than oxide glass, as will be described later, and is close to the refractive index of oxynitride phosphors and nitride phosphors, so that light extraction efficiency from phosphor particles is high. improves.

  In the wavelength conversion member of the present invention, the oxynitride phosphor particles or the nitride phosphor particles are dispersed in glass having a softening point of 700 ° C. or higher. Is not absorbed. Further, since the refractive index of glass having a softening point of 700 ° C. or higher is close to the refractive indexes of oxynitride phosphors and nitride phosphors, the light extraction efficiency from the phosphors to the outside is high. Accordingly, high wavelength conversion efficiency can be obtained without deterioration even when excited at a wavelength from purple to ultraviolet.

  In addition, according to the method for manufacturing a wavelength conversion member of the present invention, the oxynitride phosphor or the nitride phosphor can be dispersed in the glass while maintaining its particle state, so that high wavelength conversion efficiency can be maintained.

  The light-emitting device of the present invention is a long-life and high-efficiency light-emitting device by combining a semiconductor light-emitting element that emits light with a wavelength from violet to ultraviolet and the wavelength conversion member.

  Below, the wavelength conversion member of this invention, its manufacturing method, and embodiment of the light-emitting device which combined the wavelength conversion member and the semiconductor light-emitting element are shown.

  Regarding glass, temperatures such as a transition point, a softening point, and a melting point are defined, but in this embodiment, a softening point that is a lower limit temperature when particles are dispersed in glass is mainly used. The softening point is defined as the temperature at which the viscosity of the glass corresponds to 1E + 7.6 dPa · s.

(Embodiment 1)
The wavelength conversion member which is Embodiment 1 of this invention is shown in FIG. The wavelength conversion member 21 is obtained by dispersing three types of phosphor particles 11, 12, and 13 in the oxynitride glass 10. Phosphor particles 11 were Ce-activated α sialon, phosphor particles 12 were Eu-activated β sialon, and phosphor particles 13 were Eu-activated CaAlSiN ₃ . Each of these phosphor particles contains 50% or more of a combined ratio of Si and N in a molar ratio, that is, a crystal of oxynitride phosphor and nitride phosphor based on silicon nitride. Excellent heat resistance and stability against atmospheric gases such as moisture. By irradiating the phosphor particles 11, 12, and 13 with light having a wavelength of 405 nm, very strong visible light fluorescence having emission peak wavelengths of 480 nm, 540 nm, and 660 nm is emitted. By adjusting the mixing ratio of the phosphor particles 11, 12, and 13, the overall emission color changes. In this embodiment, the phosphor is set so that the entire emission color has chromaticity corresponding to white light. The mixing ratio of the particles 11, 12, and 13 was adjusted to 4: 4: 2.

A method for manufacturing the wavelength conversion member 21 in the first embodiment will be described below.
(Phosphor particles)
The phosphor particles 11 are α sialon represented by the composition formula Ce _0.5 (Si, Al) ₁₂ (O, N) ₁₆ and are produced as follows. As raw materials, silicon nitride, aluminum nitride, and cerium oxide powder are weighed so as to obtain the above composition, and pulverized and mixed by a ball mill. The obtained mixture was molded by applying a pressure of 20 MPa using a mold to obtain a molded body 11A having a diameter of 12 mm and a thickness of 5 mm. As shown in FIG. 2, the molded body 11 </ b> A is set in the electric furnace 50. In the firing operation, first, the gas introduction port 53 is closed and exhausted from the exhaust port 54 to evacuate the inside of the electric furnace 50, the molded body 11A is heated to 800 ° C., and then the exhaust port 54 is closed to introduce the gas. Nitrogen having a purity of 99.9% by volume is introduced from the port 53 to a pressure of 30 MPa, the temperature is raised to 2200 ° C. at 500 ° C. per hour, and held at 2200 ° C. for 2 hours. Thereby, the molded body 11A is fired to become α sialon. The sintered compact 11A is pulverized in a ball mill to produce α sialon phosphor particles 11 that emit blue light.
About the fluorescent substance particle 11, it confirmed that the ratio of the crystal body was 50% or more.

  The phosphor particles 12 are produced as follows. Β sialon fluorescence in which Eu that emits green light is activated by mixing silicon nitride, aluminum nitride, and europium oxide powder, then putting it in a boron nitride crucible, reacting in nitrogen at 1 MPa and 1900 ° C., and then grinding. Body particles 12 are produced.

The phosphor particles 13 are produced as follows. Silicon nitride, aluminum nitride, calcium nitride, and europium nitride powder are mixed in a glove box where moisture and air are blocked, then placed in a boron nitride crucible, reacted at 1 MPa in nitrogen at 1800 ° C., and then pulverized As a result, CaAlSiN ₃ phosphor particles 13 activated with Eu emitting red light are produced.

(Wavelength conversion member)
A mixed powder 55 is prepared by mixing fine powders of CaCO ₃ , Al ₂ O ₃ , SiO ₂ , and AlN, which are raw materials for oxynitride glass, in a weight ratio of 29: 3: 34: 34, and mixed powder 55, The phosphor particles 11, 12 and 13 are mixed and molded by a hot press method to obtain a molded body 19. As shown in FIG. 3, the compact 19 is placed in an electric furnace 50, heated to 1500 ° C. in dry nitrogen and normal pressure, held for 2 hours, and rapidly cooled to obtain an oxynitride as shown in FIG. The wavelength conversion member 21 in which the phosphor particles 11, 12, 13 were dispersed almost uniformly in the nitride glass 10 was formed.

  Although the temperature for forming the wavelength conversion member 21 is 1500 ° C., it is necessary to suppress the reaction with the oxynitride phosphor particles or the nitride phosphor particles to prevent melting. A temperature that is 50 ° C. or more lower than the temperature (in this case, a temperature that is 50 ° C. lower than the firing temperature of the lowest phosphor particle 13, that is, 1750 ° C. or less) is desirable. A temperature lower by 200 ° C. or more than the firing temperature of the phosphor is more desirable.

  In addition, although the Ca-Si-Al-ON-type oxynitride glass of the said composition was used as the oxynitride glass 10, in addition to this, Ca-Mg-Si-Al-ON, La-Si -O-N, Mg-Si-ON, Y-Al-Si-ON, Mg-Si-Al-ON, Na-Si-ON, Na-Ca-Si-ON , Li-K-Al-Si-ON, Na-B-Si-ON, Ba-Al-Si-ON, Na-BO-N, Li-P-O-N, Na An oxynitride glass having a composition such as —P—O—N can be used.

Generally, a metal oxide such as SiO ₂ is used as a raw material for oxynitride glass, and a metal nitride or metal oxynitride is used as a nitrogen supply source.

Here, as the metal oxide, in addition to _{SiO 2, Al 2 O 3,} BaO, Sb 2 O 3, SrO, Na 2 O, Na 2 O 3, CaO, MgO, K 2 O, La 2 O 3 , CeO ₂ , Y ₂ O ₃ , ZrO ₂ , ZnO ₂ , As ₂ O ₃ , TiO ₂ , B ₂ O ₃ , Cr ₂ O ₃ , PbO, V ₂ O ₅ , SnO _{2 and the} like. Further, carbonates, hydroxides, and oxalates that become these metal oxides by thermal decomposition may be blended as raw materials.

Examples of the metal nitride include Si ₃ N ₄ , AlN, Al ₂ N ₂ , Mg ₂ N ₂ , and Li ₃ N.

Examples of the metal oxynitride include Si ₂ N ₂ O and Si ₅ N ₆ O.
Moreover, although the softening point of oxynitride glass is based also on a composition, generally it is 850-100.
It is about 0 ° C.

(Comparative example)
For comparison with the present embodiment, the following comparative wavelength conversion member 21B was also produced. Fine powder of low melting point glass and phosphor particles 11, 12, 13 are mixed and put in a crucible, the crucible is put in an electric furnace 50, heated to 500 ° C. in dry nitrogen at normal pressure and held for 30 minutes, By rapidly cooling, the wavelength conversion member 21B in which the phosphor particles 11, 12, and 13 were dispersed almost uniformly in the low melting point glass was formed.

(Characteristic)
As described above, the wavelength conversion member according to the present embodiment undergoes a high-temperature process in the manufacturing process. However, since the heat-resistant oxynitride phosphor or nitride phosphor is used, the wavelength conversion member has a high wavelength after the glass melting step. Conversion efficiency could be obtained. That is, compared with the wavelength conversion member 21B as the comparative example, the intensity of the emission spectrum is increased as a whole, and when the emission spectrum is analyzed, the wavelength conversion efficiency of the phosphor particles 11 is 1.3 times that of the phosphor particles 12. The wavelength conversion efficiency of the phosphor particles 13 increased 1.1 times, and the wavelength conversion efficiency of the phosphor particles 13 increased 1.15 times. The reason for the increase in wavelength conversion efficiency is that these phosphors are nitrides or nitride-based oxynitrides and are not oxides, and therefore, especially for crystals, there is little reaction with glass, but on the surface of the particles. It is presumed that the non-crystalline substance having low luminous efficiency is diffused into the molten high melting point glass and may be removed. Furthermore, depending on the composition ratio of the oxynitride phosphor particles or the nitride phosphor particles, the wavelength conversion efficiency may increase due to the annealing effect that stabilizes the crystal structure.

  In this embodiment, since the oxynitride phosphor particles or the nitride phosphor particles are dispersed in the oxynitride glass while maintaining the particle state, the electronic state of the rare earth element serving as the luminescence center is Unaffected by external conditions. Therefore, the reproducible excitation spectrum (depending on the excitation wavelength dependence of the wavelength conversion efficiency), regardless of the dispersion process and composition of the glass, compared with the case where the rare earth element serving as the luminescent center is directly melted and dispersed so as to become a glass component. ) And the chromaticity (emission spectrum) of the emission color.

  Since the oxynitride glass used in the present embodiment has higher hardness and elastic modulus than ordinary oxide glass, it is easy to reduce the thickness and weight. Oxynitride glass has a glass softening point higher by 100 ° C. or more than oxide glass. This contributes to increasing the degree of freedom of the process after glass formation. In the present embodiment, since the oxynitride phosphor or nitride phosphor excellent in high-temperature stability is used as the phosphor particles, the particle state is maintained even when dispersed in the oxynitride glass. Can do. A stable wavelength conversion member that does not change with time in emission intensity and emission color by combining oxynitride glass excellent in moisture barrier properties and oxynitride phosphor or nitride phosphor excellent in high temperature stability Is obtained.

  Moreover, the refractive index of oxynitride glass is 1.6 to 1.9, which is higher than the refractive index (1.5 to 1.8) of oxide glass, and is an oxynitride phosphor or nitride fluorescence. Since it is close to the refractive index of the body (about 2.0), the light extraction efficiency from the phosphor is high.

(Embodiment 2)
In Embodiment 2, an oxynitride glass is once produced, and the wavelength conversion member is produced by mixing and melting the powder and oxynitride phosphor particles or nitride phosphor particles. .

_SiO 2 as a raw material for oxynitride glass (35 _{mol%), Al 2 O 3 (} 2 _{mol%), Al 2 N 2 (} 4 _{mol%), Si 3 N 4 (} 13 mol%), CaO (43 mol %) And MgO (5 mol%) powder were mixed in a crucible 66 shown in FIG. The temperature was raised to 1600 ° C. in an electric furnace 50 filled with dry nitrogen and melted for 2 hours (glass melting step), and then cooled to obtain oxynitride glass 67.

  The melting of the oxynitride glass raw material is preferably performed, for example, at 1400 to 1900 ° C. for 3 to 100 hours in an inert gas atmosphere not containing oxygen such as nitrogen and argon.

  Next, the oxynitride glass 67 is pulverized into a fine powder, and the same phosphor particles 11, 12, and 13 as used in the first embodiment are mixed and molded by a hot press method. It was set as the body 68. This molded body 68 is heated in an electric furnace 50 shown in FIG. 5 at 1200 ° C. in a dry atmosphere and at normal pressure, held for 2 hours, and rapidly cooled, whereby phosphor particles are contained in the oxynitride glass 67. A wavelength conversion member 69 in which 11, 12, and 13 were dispersed almost uniformly was formed.

  Although the temperature at which the wavelength conversion member 69 is formed is 1200 ° C., the phosphor particles can be dispersed in the glass if the heating is at or above the glass softening point. However, in order to disperse the phosphor particles at a temperature near the softening point, firing at about 900 ° C. requires about 24 hours. Therefore, in order to shorten the working time, 900 ° C. or higher is preferable, and oxynitride fluorescence 1600 ° C. or lower, which is the temperature at which the body particles or nitride phosphor particles maintain the particle state, is desirable. Further, unlike the first embodiment, since the oxynitride glass is once formed, the temperature of the wavelength conversion member manufacturing process can be lowered, and the phosphor particles can be melted and the significant reaction with the glass is suppressed. Is convenient. Therefore, it can suppress that a part of fluorescent substance particles 11, 12, and 13 melt in oxynitride glass.

(Embodiment 3)
In the present embodiment, commercially available non-alkali glass AF45 (manufactured by SiO ₂ , BaO, Al ₂ O _3, etc., softening point 883 ° C.) is used as the glass. This glass has good transmittance from purple to ultraviolet wavelengths.

  The purchased AF45 is made into powdery glass 75 with a mixer. Powdered glass 75 and the same phosphor particles 11, 12, and 13 as used in Embodiment 1 are mixed and placed in platinum crucible 76, placed in electric furnace 50 shown in FIG. 6, and heated to 1100 ° C. And melt by holding for 2 hours. As shown in FIG. 7, the molten raw material 79 was poured out on a carbon plate 77 and formed into a wavelength conversion member sheet 80. In addition, in order to shape | mold into a sheet form, you may use the float method which pours and casts glass on molten Sn, and the fusion method which hangs down molten glass from an elongate slit, and shape | molds.

  The wavelength conversion member sheet 80 was cut by a dicing method to obtain a wavelength conversion member 81 having a 10 cm square both in length and width and a thickness of 0.5 mm.

  In the present embodiment, since the glass melting temperature is lowered as compared with the case of using oxynitride glass, it is possible to suppress melting of oxynitride phosphor particles or nitride phosphor particles and significant reaction with glass. Is convenient. In addition, unlike oxynitride glass, it can be manufactured in an atmosphere containing oxygen, and thus is easy to manufacture.

(Embodiment 4)
In this embodiment, borosilicate glass is used as the glass. Borosilicate glass has good transmittance from purple to ultraviolet wavelengths.

BK7 glass which is a typical borosilicate glass (estimated raw material composition: SiO ₂ = 70 wt%, B ₂ O ₃ = 10 wt%, BaO = 3 wt%, K ₂ O = 8 wt%, Na ₂ O = 8 % By weight, softening point 718 ° C.). These glass powders and phosphor particles 11, 12, and 13 obtained in the first embodiment are mixed and heated to 1000 ° C. using the same electric furnace 50 used in the third embodiment. Melts by holding for 2 hours. This raw material is formed into a sheet glass by a float process. The plate glass is cut into a 10 cm square and a thickness of 0.5 mm both vertically and horizontally by a dicing method, and the oxynitride phosphor particles or the nitride phosphor particles 11, 12, and 13 are almost contained in the glass body 10. The wavelength conversion member 82 was uniformly dispersed.

  In the present embodiment, since the glass melting temperature is lowered as compared with the case of using oxynitride glass, it is possible to suppress melting of oxynitride phosphor particles or nitride phosphor particles and significant reaction with glass. Is convenient. In addition, unlike oxynitride glass, it can be manufactured in an atmosphere containing oxygen, and thus is easy to manufacture.

(Embodiment 5)
Next, the light-emitting device 20 using the wavelength conversion member of Embodiment 1 is demonstrated using FIG. 8 which is sectional drawing. A nitride LED 23 made of InGaAlN-based crystal is installed on the base 22. The n-type electrode 23A of the nitride LED 23 is electrically connected to the electrode 24 on the base 22, and the p-type electrode 23B of the nitride LED 23 is electrically connected to the electrode 25 on the base 22. The wavelength conversion member 21 made of the oxynitride glass 10 in which the phosphor particles 11, 12, and 13 are dispersed is bonded onto the support portion 22 </ b> B that is a part of the substrate 22. Yes.

  The nitride LED 23 made of an InGaAlN-based crystal can change the emission peak wavelength from 300 nm to 500 nm by changing the composition of the constituent material such as the light emitting layer. Here, the excitation light 27 having the emission peak wavelength of 390 nm is changed. Emitting nitride LED 23 was used. Excitation light 27 emitted from the nitride LED 23 enters the wavelength conversion member 21, excites the phosphor particles 11, 12, and 13 dispersed in the wavelength conversion member 21, and fluorescence 28 having a wavelength longer than that of the excitation light. Is converted to

  By changing the mixing ratio of the phosphor particles 11, 12, 13, light emitting devices with various chromaticities can be manufactured. In particular, a light emitting device having a white color obtained by combining the emission colors emitted from the respective phosphors can be suitably used as an illumination light emitting device. For use in such a white light emitting device, the dispersion composition of each phosphor is adjusted to, for example, 4: 4: 2, and the chromaticity coordinate x of the emission color is 0.22 to 0.44, and the chromaticity coordinate y. Was set to 0.22 or more and 0.44 or less. For example, by setting the dispersion composition of each phosphor to 2: 4: 6, the chromaticity coordinate x is set to 0.36 or more and 0.5 or less, and the chromaticity coordinate y is set to 0.33 or more and 0.46 or less. It is also possible to produce a warm-colored light-emitting device for illumination that is close to the light-emitting color of a light bulb. The mixing ratio of the phosphors needs to be adjusted as appropriate because the luminous efficiency of each phosphor may vary depending on the production lot.

  The emission peak wavelength of the nitride LED 23 may be 300 nm or more and 500 nm, but is more preferably 350 nm or more and 420 nm or less. This wavelength region almost corresponds to the peak of the excitation spectrum (excitation wavelength dependence of wavelength conversion efficiency) of the oxynitride phosphor or nitride phosphor, so that high efficiency is obtained and the visibility is low. This is because there is almost no variation in emission color due to variations in emission peak wavelength.

Conventionally, when such short-wavelength excitation light is used, there has been a problem of ultraviolet degradation of the phosphor itself or a resin in which the phosphor is dispersed. Uses chemically stable oxynitride glass that does not absorb wavelengths and oxynitride phosphors or nitride phosphors with excellent stability, resulting in a 3% change in luminous intensity even when operated for 3000 hours or more. An unprecedented long-life light-emitting device was obtained.

(Embodiment 6)
The present embodiment is a light emitting device using a plate-like wavelength conversion member.

  In FIG. 9, which is a perspective view showing a cross section of a light emitting device 90 using the wavelength conversion member 81 obtained in the third embodiment, p electrode wiring and n electrode wiring (both not shown) are formed. A plurality of nitride LEDs 93 are installed on the base 92. At that time, the p-electrode and the n-electrode formed on one surface of the nitride LED 93 are connected so as to be connected to the p-electrode wiring and the n-electrode wiring on the base 92, respectively. A spacer 94 is formed on the base 92, and a plate-like wavelength conversion member 81 is bonded onto the spacer 94.

  The nitride LED 93 emits excitation light 97 having an emission peak wavelength of 410 nm by flowing current, and this is converted into fluorescence 98 by the wavelength conversion member 81.

(Embodiment 7)
Next, another light-emitting device 130 using the wavelength conversion member of Embodiment 1 will be described with reference to FIG. A wavelength conversion member 69 having a diameter of 0.5 mm and a length of 20 mm produced in the second embodiment in which the phosphor particles 11, 12, and 13 are dispersed in the oxynitride glass 67 is fixed on the substrate 131. . A submount 132 is disposed on the base 131, and a nitride semiconductor laser 133 made of InGaAlN-based crystal is mounted on the submount 132. A lead wire 136 is connected to the nitride semiconductor laser 133 so that a current can be supplied. The nitride semiconductor laser 133 can change the emission peak wavelength from 300 nm to 500 nm by changing the composition of the constituent materials. Here, the nitride semiconductor laser 133 that emits the excitation light 137 having the emission peak wavelength of 405 nm is used. Using. Excitation light 137 emitted from the nitride semiconductor laser 133 is converted into substantially parallel light by the lens 134, enters the wavelength conversion member 69, and excites the phosphor particles 11, 12, 13 dispersed therein. , Converted into fluorescence 138 having a longer wavelength than the excitation light 137. The nitride semiconductor laser 133 is superior in current / light conversion efficiency compared to the LED. In addition, since the directivity of the excitation light 137 emitted from the nitride semiconductor laser 133 is strong, it is easy to adopt a configuration in which the incident direction of the excitation light 137 and the emission direction of the fluorescence 138 are different directions. For this reason, it is easy to separate and shield the short-wavelength excitation light 137 that adversely affects the human body from the fluorescence 138.

  The emission peak wavelength of the nitride semiconductor laser 133 is more preferably 350 nm or more and 420 nm or less. This wavelength region almost corresponds to the peak of the excitation spectrum (excitation wavelength dependence of wavelength conversion efficiency) of the oxynitride phosphor or nitride phosphor, so that high efficiency is obtained and the visibility is low. This is because there is almost no variation in emission color due to variations in emission peak wavelength. Conventionally, when such short-wavelength excitation light is used, there has been a problem of ultraviolet degradation of the phosphor itself and the resin in which the phosphor is dispersed. In this embodiment, the crystal structure is very Since stable oxynitride phosphor particles or nitride phosphor particles and oxynitride glass are used, an unprecedented long-life light-emitting device was obtained. Although the wavelength conversion member 69 has a rod shape, an optical fiber in which the diameter of the wavelength conversion member 69 is further reduced and the length is increased by utilizing the characteristics that the strength of the oxynitride glass is very high and the elastic modulus is high. It is also possible to form a light emitting device in the form of a ring.

(Other possible embodiments)
As the wavelength conversion member used in each embodiment, a material in which three types of phosphor particles are dispersed is disclosed. However, one type, two types, or four types or more of oxynitride phosphors or nitride phosphor particles are made of glass. The oxide phosphor or sulfide phosphor may be added if necessary. For example, a single color can be obtained by using a wavelength conversion member using one type of phosphor, and white or pseudo white can be obtained by combining them.

  Since the light emitting device using the wavelength conversion member of the present invention is small and consumes less power and can stably emit light with high luminance, the light source for backlight of a liquid crystal display, a mobile phone or a personal digital assistant, It can be widely used as a display device for advertisements, indicators for various portable devices, lighting switches or various display devices for OA (office automation) devices, or a light source for lighting devices.

  The embodiment disclosed this time should be considered as illustrative in all points and not restrictive. The scope of the present invention is defined by the terms of the claims, rather than the description above, and is intended to include any modifications within the scope and meaning equivalent to the terms of the claims.

2 is a structural diagram of a wavelength conversion member according to Embodiment 1. FIG. FIG. 3 is an explanatory diagram of a phosphor firing step in the first embodiment. FIG. 5 is an explanatory diagram of a manufacturing process of the wavelength conversion member in the first embodiment. FIG. 5 is an explanatory diagram of a production process for the oxynitride glass in the first embodiment. 10 is an explanatory diagram of a manufacturing process of a wavelength conversion member in Embodiment 2. FIG. FIG. 10 is an explanatory diagram of a manufacturing process of a wavelength conversion member in Embodiment 3. FIG. 10 is an explanatory diagram of a manufacturing process of a wavelength conversion member in Embodiment 3. FIG. 6 is a cross-sectional view of a light emitting device according to a fifth embodiment. FIG. 10 is a perspective view showing a cross section of a light emitting device according to a sixth embodiment. FIG. 10 is a structural diagram of a light emitting device according to a seventh embodiment.

Explanation of symbols

10, 67 Oxynitride glass 11, 12, 13 Phosphor particle 11A Molded body 19 Molded body 20, 90, 100, 130 Light emitting device 21, 21B, 69, 81 Wavelength converting member 22, 92, 131 Base body 22B Support portion 23 , 93 Nitride LED
23A n-type electrode 23B p-type electrode 24, 25 electrode 27, 97, 137 excitation light 28, 98, 138 fluorescence 50 electric furnace 53 gas introduction port 54 exhaust port 55 mixed powder 65 mixed powder 66 crucible 68 compact 75 glass 76 platinum Crucible 77 Carbon plate 79 Molten raw material 80 Wavelength conversion member sheet 94 Spacer 132 Submount 133 Nitride semiconductor laser 134 Lens 136 Lead wire

Claims (14)

  A wavelength conversion member comprising a glass having a softening point of 700 ° C. or higher and oxynitride phosphor particles or nitride phosphor particles dispersed in the glass.   2. The wavelength conversion member according to claim 1, wherein the particles of the oxynitride phosphor or the particles of the nitride phosphor contain a component in which Si and N are combined in a molar ratio of 50% or more.   3. The wavelength conversion member according to claim 1, wherein the oxynitride phosphor particles or the nitride phosphor particles contain 50% or more of a crystal.   The wavelength conversion member according to any one of claims 1 to 3, wherein the particles of the oxynitride phosphor are composed of Si, Al, O, and N, and one or more lanthanoid rare earth elements. .   The wavelength conversion member according to any one of claims 1 to 3, wherein the nitride phosphor particles are made of Ca, Si, Al, and N, and one or more lanthanoid rare earth elements.   The wavelength conversion member according to claim 1, wherein the glass is oxynitride glass.   First oxynitride phosphor particles or nitride phosphor particles having an emission peak wavelength of 460 nm to 510 nm, and second oxynitride phosphor particles or nitride of an emission peak wavelength of 510 nm to 550 nm 7. The phosphor according to claim 1, comprising phosphor particles and third oxynitride phosphor particles or nitride phosphor particles having an emission peak wavelength of 600 nm to 670 nm. Wavelength conversion member.   A semiconductor light emitting device that emits light having an emission peak wavelength of 300 nm or more and 500 nm or less, and a wavelength conversion member according to any one of claims 1 to 7 disposed so that light emitted from the semiconductor light emitting device is incident thereon. A light emitting device characterized.   The light emitting device according to claim 8, wherein the emission peak wavelength is 350 nm or more and 420 nm or less.   The chromaticity coordinate x of the luminescent color of the light emitting device is 0.22 to 0.44 and the chromaticity coordinate y is 0.22 to 0.44, or the chromaticity coordinate x of the luminescent color of the light emitting device. The light emitting device according to claim 8, wherein the chromaticity coordinate y is 0.33 or more and 0.46 or less.   The oxynitride phosphor particles are heated by heating the oxynitride phosphor particles or the nitride phosphor particles and the glass or the glass raw material to a softening point of the glass or higher and 1600 ° C. or lower. The method for producing a wavelength conversion member according to claim 1, further comprising a step of dispersing particles of the nitride phosphor in the glass. First, the oxynitride phosphor material or the nitride phosphor material is fired at a first temperature of 1600 ° C. or higher to produce the oxynitride phosphor particles or the nitride phosphor particles. And the process of
The oxynitride phosphor particles obtained by the first step or the nitride phosphor particles are mixed with the glass raw material and heated at a second temperature that is 50 ° C. or more lower than the first temperature. The method according to claim 11, further comprising a second step of dispersing the particles of the oxynitride phosphor or the particles of the nitride phosphor in the glass. . First, the oxynitride phosphor material or the nitride phosphor material is fired at a first temperature of 1600 ° C. or higher to produce the oxynitride phosphor particles or the nitride phosphor particles. And the process of
A second step of producing the glass by melting and mixing the raw materials of the glass;
Mixing the oxynitride phosphor particles or nitride phosphor particles obtained in the first step with the glass obtained in the second step, the second temperature lower than the first temperature by 50 ° C. or more. The wavelength conversion member according to claim 11, further comprising a third step of dispersing the oxynitride phosphor particles or the nitride phosphor particles in the glass by heating at a temperature. Manufacturing method.   The said glass is oxynitride glass, The manufacturing method of the wavelength conversion member in any one of Claim 11 to 13 characterized by the above-mentioned.

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