JP2022007638A - Molding, light emitting device and method for producing molding - Google Patents

Abstract

To provide a molding having excellent color rendering and heat resisting properties, a light emitting device and a method for producing the molding.SOLUTION: A molding 31 has: a translucent substrate 101 composed of an inorganic material containing first phosphor particles 101a; second phosphor particles 102a disposed on the substrate 101; and translucent second ceramic 102b for fixing the second phosphor particles 102a to the substrate 101. A surface of the molding 31 is provided with irregularities resulting from the second phosphor particles 102a.SELECTED DRAWING: Figure 1

Description

The present invention relates to a molded body, a light emitting device, and a method for manufacturing the molded body.

A light emitting device that combines a light emitting element such as a light emitting diode (LED) or a semiconductor laser (LD) chip with a phosphor is used as a lighting, a backlight of a liquid crystal display device, an in-vehicle light, a light source for a projector, and the like. The light emitting device is required to be miniaturized according to the application and location. Further, for example, in a projector light source using an LD as a light emitting element, high energy light is locally emitted from the light emitting element, so that a member containing a phosphor whose wavelength is converted by the light emitted from the light emitting element has high heat resistance. It is required to have sex.

For example, in Patent Document 1, a wavelength conversion member made of an inorganic material such as glass or sapphire having good thermal conductivity and having a phosphor layer composed of a phosphor and translucent ceramics on a base material that transmits light. Is disclosed.

International Release 2017/12640

One aspect of the present invention is to provide a molded body, a light emitting device, and a method for manufacturing the molded body, which are excellent in color rendering and heat resistance.

The present invention includes the following aspects.
In the first aspect of the present invention, a translucent substrate made of an inorganic material containing the first phosphor particles, a second fluorescent particle arranged on the substrate, and the second fluorescent particle on the substrate. It is a molded body containing a translucent second ceramics to be fixed, and is a molded body in which irregularities due to the second phosphor particles are formed on the surface of the molded body.

A second aspect of the present invention is a light emitting device including the molded body and an excitation light source.

A third aspect of the present invention is to prepare a translucent substrate made of an inorganic material containing the first fluorescent substance particles, and a fluorescent substance-containing composition containing the second fluorescent substance particles and the second inorganic binder. A second heat-transmitting property derived from the second inorganic binder is obtained by preparing a substance, applying the fluorescent substance-containing composition to the substrate, and first heat-treating the substrate and the fluorescent substance-containing composition. A method for manufacturing a molded body, which comprises fixing the second fluorescent substance particles to the surface of the substrate via ceramics to obtain a molded body having irregularities due to the second fluorescent substance particles formed on the surface. be.

According to one aspect of the present invention, it is possible to provide a molded body, a light emitting device, and a method for manufacturing the molded body, which are excellent in color rendering and heat resistance.

It is a schematic cross-sectional view which shows the molded body which concerns on 1st Embodiment. It is a schematic cross-sectional view which shows the molded body which concerns on 2nd Embodiment. It is a schematic cross-sectional view which shows the molded body which concerns on 3rd Embodiment. It is a schematic cross-sectional view which shows the molded body which concerns on 4th Embodiment. It is a schematic cross-sectional view which shows the molded body which concerns on 5th Embodiment. It is a schematic perspective view which shows the light emitting module which is an example of a light emitting device. It is a schematic plan view which shows the light emitting module which is an example of a light emitting device. 6 is a cross-sectional view taken along the line VIC-VIC of FIG. 6B. 6 is a cross-sectional view taken along the line VID-VID of FIG. 6B. It is a schematic cross-sectional view which shows the light emitting device which provided the molded body as a light transmissive member. It is a schematic bottom view of a light emitting device. It is a flowchart which shows an example of the manufacturing method. It is a flowchart which shows an example of the manufacturing method. It is a schematic side view which shows the outline of the light source apparatus for a projector. It is a schematic plan view which shows one side of the phosphor wheel seen from the arrow A of FIG. It is a schematic plan view which shows one side of the phosphor wheel seen from the arrow B of FIG. It is a schematic plan view which shows one side of the phosphor wheel seen from the arrow C of FIG. It is a schematic diagram which shows the structure of the projector provided with the light source device. FIG. 11 is a planar SEM photograph of the substrate on the side where the second phosphor particles are present before forming the third ceramics and the fourth ceramics according to the eleventh embodiment. FIG. 3 is a diagram showing a state in which a planar SEM photograph of a substrate on the side where the second phosphor particles exist before forming the third ceramics and the fourth ceramics is binarized according to the eleventh embodiment. FIG. 11 is a partial cross-sectional SEM photograph of the molded body before forming the third ceramics and the fourth ceramics according to the eleventh embodiment. 11 is an SEM-EDS element mapping diagram in a partial cross-sectional SEM photograph of a molded body before forming the third ceramics and the fourth ceramics according to the eleventh embodiment. FIG. 11 is an SEM-EDS element mapping diagram showing a portion where Si is present in a partial cross-sectional SEM photograph of a molded body before forming the third ceramics and the fourth ceramics according to the eleventh embodiment. FIG. 11 is an SEM-EDS element mapping diagram showing a portion where Sr is present in a partial cross-sectional SEM photograph of a molded body before forming the third ceramics and the fourth ceramics according to the eleventh embodiment. FIG. 11 is an SEM-EDS element mapping diagram showing a location where Ca is present in a partial cross-sectional SEM photograph of a molded body before forming the third ceramics and the fourth ceramics according to the eleventh embodiment.

Hereinafter, a molded body, a light emitting device, and a method for manufacturing the molded body according to the present invention will be described based on one embodiment. However, the embodiments shown below are examples for embodying the technical idea of the present invention, and the present invention is not limited to the following molded body, light emitting device, and method for manufacturing the molded body. The relationship between the color name and the chromaticity coordinates is in accordance with JIS Z8110.
The above-mentioned Patent Document 1 describes that glass or sapphire having high thermal conductivity is used as a base material, but does not describe that fluorescent particles are used as a base material. The fluorophore layer is formed on the substrate. If the film thickness of the phosphor layer becomes excessively thin with respect to the particle size of the phosphor particles, the excitation light is transmitted without being wavelength-converted by the phosphor, and the performance of wavelength-converting the excitation light may not be sufficiently exhibited. Are listed. Further, it is disclosed that depending on the size of the particle size of the phosphor, a film thickness of 1.5 or more is required for the particle size 1 of the phosphor, and depending on the particle size of the phosphor. , It may not be possible to meet the demand for thinning. Further, by using a base material having high thermal conductivity, heat storage of the phosphor layer is suppressed, and when the film thickness of the phosphor layer exceeds a predetermined time with respect to the particle size of the phosphor, the thermal resistance of the grain boundaries increases. It is described that the temperature increases, the temperature of the phosphor layer rises, and the emission intensity decreases. Depending on the particle size of the fluorophore particles, it may not be possible to contain the desired fluorophore in the fluorophore layer, and the desired emission color may not be obtained.
On the other hand, according to the molded body and the light emitting device according to the present embodiment, it is possible to provide a molded body having excellent color rendering properties and heat resistance. That is, by using the first phosphor particles having a predetermined thickness on the substrate and arranging the second phosphor particles so as to supplement the portion having poor color rendering property, the color rendering property can be improved as a whole. Further, in a substrate in which only the first phosphor particles or the first phosphor particles are mainly used and the first ceramics or glass is used as a sub, the heat generated by the first phosphor particles is transferred to the adjacent first phosphor particles. Therefore, it is possible to efficiently release heat to the outside, so that it is possible to provide a molded body having excellent heat resistance. Further, the heat generated by the second phosphor particles is also transferred to the first phosphor particles, and the heat can be efficiently released to the outside, so that it is possible to provide a molded product having excellent heat resistance. Since the second phosphor particles use only the second ceramics having irregularities, they have excellent heat resistance. A substrate in which the first phosphor particles are mainly used and the first ceramics or glass is used as a secondary is a substrate in which the content of the first phosphor particles in the substrate is higher than the content of the first ceramics or glass.

Molded body The molded body is a translucent substrate made of an inorganic material containing the first phosphor particles, a second phosphor particle arranged on the substrate, and a translucent substrate that immobilizes the second phosphor particles on the substrate. Includes second ceramics. Concavities and convexities due to the second phosphor particles are formed on the surface of the molded body. The substrate may further contain at least one of the first ceramics and glass in addition to the first phosphor particles. As used herein, ceramics means an inorganic non-metallic material at a temperature of 1000 ° C. or lower. The molded body contains a substrate made of an inorganic material containing the first phosphor particles and the first ceramics, and the second phosphor particles fixed with the second ceramics, and is made of the inorganic material, and therefore has excellent heat resistance. .. Further, even when the molded product contains the third phosphor particles, the third ceramics, and the fourth ceramics, which will be described later, it is made of an inorganic material and therefore has excellent heat resistance.
In the present specification, the fact that the unevenness caused by the second phosphor particles is formed on the surface of the molded body means that the state before a plurality of layers such as the third ceramics and the fourth ceramics are arranged, that is, , Refers to the surface of a molded product formed of a substrate, second phosphor particles, and second ceramics.

FIG. 1 is a schematic cross-sectional view showing a molded product according to the first embodiment. The molded body 31 is a translucent substrate 101 made of an inorganic material containing the first phosphor particles 101a and the first ceramics 101b, a second phosphor particles 102a arranged on the substrate 101, and a second substrate 101. Includes a translucent second ceramic 102b that immobilizes the phosphor particles 102a. Concavities and convexities due to the second phosphor particles 102a are formed on the surface of the molded body 31. The second phosphor particles 102a are intermittently present on the surface of the substrate 101 in the horizontal direction. The second ceramic 102b is a ceramic derived from the second inorganic binder, and the second phosphor particles 102a are fixed to the substrate 101. The unevenness caused by the second phosphor particles 102a is formed on the surface of the molded body 31, for example, the second phosphor particles 102a having a large particle size are present in the horizontal direction along the surface of the substrate 101. The second phosphor particles 102a having a small particle size and the portion may be present, or the height of the second phosphor particles 102a may differ due to the difference in particle size, the stacking method of the particles, or the like. This is because there is a portion where the second phosphor particles 102a are present and a portion where the second phosphor particles 102a are not present. The portion where the second phosphor particles 102a do not exist means that there is a portion on the surface of the substrate 101 where the second phosphor particles 102a do not exist. In the present specification, even if there is a portion where the second phosphor particles 102a do not exist in the horizontal direction along the surface of the substrate 101, the substrate 101 has no voids and is covered with the second ceramics 102b. Further, the materials such as the first ceramics and the second ceramics using the inorganic binder may be the same or different unless otherwise specified.

The second phosphor particles 102a and the second ceramics 102b, which are intermittently present in the horizontal direction along the surface of the substrate 101, do not form a layer having a uniform thickness. The surface of the substrate 101 has a portion E in which the second phosphor particles 102a are intermittently present and a portion N in which the second phosphor particles 102a are not present. On the surface of the substrate 101, the portion N in which the second phosphor particles 102a do not exist may have only the second ceramic 102b or may not have the second ceramic 102b. The portion where the second phosphor particles 102a are present is convex, and the portion where the second phosphor particles 102a are not present, that is, the portion where only the second ceramics 102b is present is present with the second phosphor particles 102a. It becomes concave compared to the part. As a result, irregularities due to the second phosphor particles 102a are formed on the surface of the molded body 31.
Concavities and convexities due to the second phosphor particles 102a are formed on the surface of the molded body 31, and the surface roughness Ra of the irregularities is preferably 10 μm or less, more preferably 8 μm or less, further preferably 7 μm or less, and further preferably 6.6 μm or less. Is particularly preferable. Further, the surface roughness Ra of the unevenness is preferably 2 μm or more, more preferably 3 μm or more, further preferably 4 μm or more, and particularly preferably 5 μm or more. However, the surface roughness Ra varies depending on the size of the second phosphor particles 102a, and is not limited thereto.

From the molded body 31, the light wavelength-converted by the second phosphor particles 102a fixed so that the surface of the substrate 101 has irregularities and the portion where the second phosphor particles 102a do not exist are translucent. A mixed color light of the light from the excitation light source transmitted through the substrate 101 and the light wavelength-converted by the first phosphor particles 101a contained in the substrate 101 is emitted, and the light from the excitation light source and the first phosphor particles are emitted. The light wavelength-converted by 101a and the light wavelength-converted by the second phosphor particles 102a can emit mixed-color light having excellent color revelation. Further, the molded body 31 diffusely reflects the light emitted by the unevenness caused by the second phosphor particles 102a on the surface thereof, and can reduce the color unevenness. Further, since the second phosphor particles 102a existing so as to form irregularities on the surface of the molded body 31 are fixed by the second ceramics 102b, the layer formed by stacking the second phosphor particles 102a. The thickness of the second phosphor particles 102a and the second ceramics 102b can be reduced as compared with the above, and the demand for thinning can be satisfied. This is because the thickness of the molded body 31 can be reduced by reducing the amount of the second ceramics 102b.

When the unit area of the surface of the substrate 101 is 100% in the plan view of the molded body 31, the total surface area where the second phosphor particles 102a are present is preferably 97% or less, more preferably 90% or less. It is more preferably 80% or less, further preferably 78% or less, and particularly preferably 72% or less. Further, when the unit area of the surface of the substrate 101 is 100%, the total surface area where the second phosphor particles 102a are present is preferably 10% or more, more preferably 20% or more, still more preferably. It is 25% or more, more preferably 30% or more, and particularly preferably 35% or more. In a plan view of the molded body 31, the total surface area where the second phosphor particles 102a are present with respect to 100% of the unit area of the surface of the substrate 101 is also referred to as a coverage. In a plan view, if the total surface area of the second phosphor particles 102a on the surface of the substrate 101 is 97% or less with respect to 100% of the unit area of the surface of the substrate 101, the second phosphor particles 102a are present. The light from the portion that is not wavelength-converted by the first phosphor particles 101a in the substrate 101 and the light from the excitation light source that has passed through the translucent substrate 101 without being wavelength-converted by the first phosphor particles 101a. With these lights and the light wavelength-converted by the second phosphor particles 102a, mixed-color light having a desired chromaticity can be obtained from the molded body 31, and the demand for thinning can be satisfied. Can be done. In the plan view of the molded body, when the unit area of the surface of the substrate is 100%, the total area (coverage) in which the second phosphor particles are present is, for example, in the molded body, the second phosphor particles are present. An SEM image is obtained from the plane of the molded body on the side using a scanning electron microscope (SEM), and image analysis is performed using, for example, the image analysis software used in the examples described later, and the second fluorescence is performed. The body particles are binarized, the area of the SEM image to be measured is 100%, and the total area of the binarized second phosphor particles is calculated as the coverage of the second phosphor particles. Can be done.

FIG. 2 is a schematic cross-sectional view showing a molded product according to the second embodiment. The molded body 32 according to the second embodiment is different from the molded body 31 according to the first embodiment in that the substrate 101 is composed of only the first phosphor particles 101a. First phosphor particles 101a having a predetermined size are sintered and hardened at a predetermined temperature. Since the substrate 101 can be formed only by the first phosphor particles 101a, it has excellent heat resistance. The first phosphor particles 101a may have a part or all of the surface of at least a part of the particles melted to fix the first phosphor particles 101a to each other.

FIG. 3 is a schematic cross-sectional view showing a molded product according to the third embodiment. Compared to the molded body 31 according to the first embodiment, the molded body 33 according to the third embodiment has a fluorescent substance arranged on the surface of the substrate 101 in addition to the second fluorescent body particles 102a and the third fluorescent body particles 102c. Is different in that is arranged. This makes it possible to obtain mixed color light having a desired chromaticity from the molded product. The molded body 33 further includes a third phosphor particle 102c that emits light in a wavelength range different from that of the second phosphor particle 102a, which is fixed by the second ceramic 102b in the horizontal direction along the surface of the substrate 101. .. The third phosphor particles 102c may be arranged adjacent to the second phosphor particles 102a in the horizontal direction along the surface of the substrate 101, and may be arranged apart from the second phosphor particles 102a. You may. The third phosphor particles 102c may be arranged at a portion where the second phosphor particles 102a are not arranged on the surface of the substrate 101. Further, the third phosphor particles 102c may be arranged in the concave portion in the unevenness of the second phosphor particles 102a. As a result, the thickness of the second phosphor particles 102a and the third phosphor particles 102c can be reduced while correcting the color tone.

FIG. 4 is a schematic cross-sectional view showing a molded product according to the fourth embodiment. The molded body 34 according to the fourth embodiment is different from the molded body 31 according to the first embodiment in that the translucent third ceramics 103 is fixed on the second phosphor particles 102a. This makes it possible to prevent the second phosphor particles 102a from falling off or peeling off. Further, the unevenness on the surface of the molded body 34 can be eliminated or reduced. Further, it is possible to improve the efficiency of extracting the light emitted from the molded body 34.

FIG. 5 is a schematic cross-sectional view showing a molded product according to the fifth embodiment. The molded body 35 according to the fifth embodiment is on the second phosphor particles 102a as compared with the molded body 34 according to the fourth embodiment, and the fourth ceramics 104 is fixed on the third ceramics 103. It differs in that it is. In the molded body 35, the third ceramics 103 are fixed on the second ceramic particles 102a on which the irregularities caused by the second phosphor particles 102a are formed, and the fourth ceramics 104 are fixed on the third ceramics 103. ing. As a result, the second phosphor particles 102a fixed to the substrate 101 by the second ceramics 102b can be prevented from falling off or peeling off, and the adhesion between the second phosphor particles 102a and the substrate 101 can be further improved. Further, the difference in unevenness on the surface of the fourth ceramics 104 can be reduced or eliminated. Here, since the unevenness caused by the second phosphor particles is formed on the surface of the molded body and coated with the third ceramics and the fourth ceramics, the unevenness caused by the second phosphor particles is present on the surface. It may become smaller, or the unevenness caused by the second phosphor particles may disappear.
Hereinafter, the constituent members will be described in detail.

Substrate The substrate is composed of an inorganic material containing at least the first phosphor particles. As the substrate, only the first phosphor particles may be fixed by sintering, pressure welding, or the like. Since the substrate can be composed of only the first phosphor particles, the wavelength conversion efficiency can be increased. Further, since the substrate can be composed of only the first phosphor particles, it is not necessary to consider the deterioration of other members and the difference in linear expansion coefficient from other members. On the other hand, the substrate is not only the first phosphor particles, but also an inorganic material containing the first phosphor particles and glass, an inorganic material containing the first phosphor particles and the first ceramics, and the first phosphor particles. Inorganic materials including first ceramics and glass can be used. Since it is composed of only an inorganic material regardless of whether the first phosphor particles are used alone or in any combination, they are excellent in heat resistance and light resistance. In the present specification, the translucency means that the light transmittance at the emission peak wavelength of the excitation light is 60% or more, and the light transmittance at the emission peak wavelength of the excitation light is preferably 70% or more. More preferably, it is 80% or more.

In addition to the first phosphor particles, the substrate may contain at least one inorganic material selected from the first ceramics and glass that do not wavelength-convert the excitation light. The first ceramic is preferably at least one selected from the group consisting of aluminum oxide, aluminum nitride, mullite, and silicon nitride. If the first ceramic is at least one selected from the group consisting of aluminum oxide, aluminum nitride, mullite, and silicon nitride, a substrate having translucency and excellent heat resistance can be obtained. The first ceramic is more preferably at least one selected from the group consisting of aluminum oxide, aluminum nitride and silicon nitride. When the first ceramic is at least one selected from the group consisting of aluminum oxide, aluminum nitride and silicon nitride as the inorganic material contained in the substrate, it has translucency and heat resistance and is excellent in thermal conductivity. A substrate is obtained.

Examples of the glass include borosilicate glass. Examples of the borosilicate glass include barium borosilicate glass and aluminoborosilicate glass. The glass may have a softening point of 500 ° C. or higher, a softening point of 600 ° C. or higher, or a softening point of 700 ° C. or higher.

The thickness of the substrate is not particularly limited. In consideration of mechanical strength and wavelength conversion efficiency, the thickness of the substrate may be in the range of 1 μm or more and 1 mm or less, may be in the range of 10 μm or more and 800 μm or less, may be in the range of 50 μm or more and 500 μm or less, and may be 100 μm or more. It may be within the range of 300 μm or less.
The surface roughness Ra of the substrate is preferably 1.5 μm or less, more preferably 1 μm or less, and particularly preferably 0.9 μm or less in order to facilitate fixing of the second phosphor particles to the substrate via the second ceramics.

First Fluorescent Material Particle The first fluorescent material particle may be a fluorescent material particle having an emission peak wavelength in the range of 530 nm or more and 590 nm or less due to light from an excitation light source, and may have an emission peak in the range of 490 nm or more and 555 nm or less. It may be a fluorescent substance particle having a wavelength.

When the first phosphor particles are phosphor particles having an emission peak wavelength in the range of 530 nm or more and 590 nm or less due to the light from the excitation light source, the first phosphor particles are at least one kind of aluminate. It is preferable to include a fluorescent substance.

Examples of the aluminate phosphor include an aluminate phosphor having a composition represented by the following formula (1A).
M ¹ ₃ (Al, Ga) ₅ O ₁₂ : Ce (1A)
In formula (1A), M ¹ is at least one selected from the group consisting of Y, Lu, Gd and Tb.
In the present specification, the plurality of elements described separated by commas (,) in the composition formula means that at least one element among these plurality of elements is contained in the composition. The plurality of elements described separated by commas (,) in the composition formula include at least one element selected from the plurality of elements separated by commas in the composition, and two kinds from the plurality of elements. The above may be included in combination. In the present specification, in the formula expressing the composition of the phosphor, the element before the colon (:) represents the element constituting the parent crystal and its molar ratio, and after the colon (:), the activating element is represented.

When the first phosphor particles are phosphor particles having an emission peak wavelength in the range of 530 nm or more and 590 nm or less due to the light from the excitation light source, the first phosphor particles are Y ₃ Al ₅ O ₁₂ : Ce, Y ₃ (Al, Ga) ₅ O ₁₂ : Ce, (Y, Gd) ₃ Al ₅ O ₁₂ : Ce, Lu ₃ A _l5 O ₁₂ : Ce, or Lu ₃ (Al, Ga) ₅ O ₁₂ : Ce. Be done.

As described above, or in place of the above, when the first phosphor particle is a phosphor particle having an emission peak wavelength in the range of 490 nm or more and 555 nm or less due to the light from the excitation light source, the first fluorescence The body particle is at least one fluorescent substance selected from the group consisting of an alkaline earth metal silicate phosphor, an alkaline earth metal aluminate fluorescent substance, an alkaline earth metal halosilicate fluorescent substance, and a β-sialon fluorescent substance. May be. For example, an alkaline earth metal silicate phosphor having a composition represented by the following formula (1B), an alkaline earth metal aluminate phosphor having a composition represented by the following formula (1C), and the following formula (1D). ), And at least one selected from the group consisting of an alkaline earth metal halosilicate phosphor having a composition represented by the following formula (1E) and a β-sialon phosphor having a composition represented by the following formula (1E).

BaSi ₂ O ₂ N ₂ : Eu (1B)
Sr ₄ Al ₁₄ O ₂₅ : Eu (1C)
(Ca, Sr, Ba) ₈ MgSi ₄ O ₁₆ (F, Cl, Br) ₂ : Eu (1D)
Si _6-a Al _a O _a N _8-a : Eu (1E)
In equation (1E), a is a number satisfying 0 <a <4.2.

When the first phosphor particles are phosphor particles having an emission peak wavelength in the range of 490 nm or more and 555 nm or less due to the light from the excitation light source, the first phosphor particles are specifically Ca ₈ MgSi ₄ . O ₁₆ Cl ₂ : Eu and the like can be mentioned.

The content of the first phosphor particles in the substrate depends on the desired chromaticity. As described above, the substrate may be one obtained by sintering the first phosphor particles, and the content of the first phosphor particles in the substrate may be 100%. When the substrate contains at least one inorganic material selected from the first ceramics and glass that do not wavelength-convert the excitation light in addition to the first phosphor particles, the inorganic material constituting the substrate and the first phosphor particles The content of the first phosphor particles may be in the range of 0.1% by mass or more and 99.9% by mass or less with respect to the total amount of the above. The content of the first phosphor particles is more preferably 0.5% by mass or more, more preferably 1% by mass or more, still more preferably 3% by mass or more, and particularly preferably 5% by mass or more. The content of the first phosphor particles is more preferably 95% by mass or less, more preferably 80% by mass or less, still more preferably 70% by mass or less, and particularly preferably 50% by mass or less. When the substrate contains at least one inorganic material selected from the first phosphor particles and the first ceramics and glass that do not wavelength-convert the excitation light, with respect to the total amount of the first phosphor particles and the inorganic material. When the content of the first phosphor particles is in the range of 0.1% by mass or more and 99.9% by mass or less, the substrate containing the first phosphor particles and the substrate containing the first phosphor particles are intermittently arranged in the horizontal direction along the surface of the substrate. The second phosphor particles containing the particles present in the above can be used for wavelength conversion of the excitation light to obtain mixed color light having a desired chromaticity.

The average particle size of the first phosphor particles is preferably in the range of 1 μm or more and 50 μm or less. The average particle size of the first phosphor particles is more preferably 2 μm or more, and more preferably 5 μm or more. The average particle size of the first phosphor particles is more preferably 40 μm or less, further preferably 20 μm or less, and particularly preferably 15 μm or less. When the average particle size of the first phosphor particles is 1 μm or more, the first phosphor particles can be dispersed substantially uniformly on the substrate. When the average particle size of the first phosphor particles is 50 μm or less, the voids in the substrate are reduced, so that the wavelength conversion efficiency of the excitation light can be increased. In the present specification, the average particle size of the phosphor particles is the average particle size (Fisher Sub-Sieve Sizar's) measured by the Fisher Sub-Sieve Sizar method (hereinafter, also referred to as “FSSS method”). Number).

Second Fluorescent Particle The second phosphor particle emits light having a wavelength range different from that of the first phosphor particle by the light from the excitation light source. The second phosphor particles preferably emit light having an emission peak wavelength in the range of 600 nm or more and 690 nm or less. The second phosphor particles are preferably at least one phosphor selected from the group consisting of fluoride phosphors, alkaline earth metal silicon nitride phosphors and α-sialone phosphors.

In the molded product, when the first phosphor particles have an emission peak wavelength in the range of 530 nm or more and 590 nm or less, the second phosphor particles have an emission peak wavelength in the range of 600 nm or more and 670 nm or less. Is preferable.

In the molded product, when the first phosphor particles have an emission peak wavelength in the range of 490 nm or more and 555 nm or less, the second phosphor particles have an emission peak wavelength in the range of 600 nm or more and 690 nm or less. Is preferable.

When the second phosphor particles are phosphor particles having an emission peak wavelength in the range of 600 nm or more and 690 nm or less due to the light from the excitation light source, a fluoride having a composition represented by the following formula (2A). A fluorescent substance, a fluorogermanate (hereinafter, also referred to as “MGF”) phosphor contained in a fluoride phosphor having a composition represented by the following formula (2B), and a composition represented by the following formula (2C). Alkaline earth metal silicon nitride phosphor, alkaline earth metal silicon nitride phosphor having a composition represented by the following formula (2D), α-sialon phosphor having a composition represented by the following formula (2E), And at least one fluorescent substance selected from the group consisting of nitride phosphors having a composition represented by the following formula (2F) is preferable.

A ₂ [M ²¹ _1-b Mn ^{4 +} _b F ₆ ] (2A)
In formula (2A), A is at least one selected from the group consisting of alkali metal elements and NH ₄₊ , and M ² is at least selected from the group consisting of Group ⁴ elements and Group 14 elements. It is one kind of element, and b is a number satisfying 0 <b <0.2.

(I-j) MgO · (j / 2) M ³ ₂ O ₃ · kmgF ₂ · mCaF ₂ · (1-n) GeO ₂ · (n / 2) M ⁴ ₂ O ₃ : zMn ⁴⁺ (2B)
In formula (2B), M ³ is derived from Li, Na, K, Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu. M4 is at least one element selected from the group consisting of Al, Ga and ^In , and i, j, k, m, n and z are at least one element selected from the group consisting of Al, Ga and In. Satisfy 2≤i≤4, 0≤j <0.5, 0 <k <1.5, 0≤m <1.5, 0 <n <0.5, and 0 <z <0.05, respectively. It is a number.

(Ca _1-p Sr _p ) AlSiN ₃ : Eu (2C)
In the formula (2C), p is a number satisfying 0 ≦ p ≦ 1.0.

(Ca _{1-q-r Sr q} Bar) ₂ Si ₅ N ₈ : Eu (2D)
In the formula (2D), q and r are numbers satisfying 0 ≦ q ≦ 1.0, 0 ≦ r ≦ 1.0, and q + r ≦ 1.0, respectively.

M ⁵ _c Si _{12- (d + e)} Al _{d + e Oe} N _16-e : Eu (2E)
In formula (2E), M ⁵ is at least one element selected from the group consisting of Li, Mg, Ca, Sr, Y and lanthanoid elements (excluding La and Ce), and c, d and e is a number satisfying 0 <c ≦ 2.0, 2.0 ≦ d ≦ 6.0, and 0 ≦ e ≦ 1.0, respectively.

M ⁶ _f M ⁷ _g M ⁸ _h Al _3-i Si _i N _j (2F)
In formula (2F), M ⁶ is at least one element selected from the group consisting of Sr, Ca, Ba and Mg, and M ⁷ is at least 1 selected from the group consisting of Li, Na and K. M 8 is an element of the species, M ⁸ is at least one element selected from the group consisting of Eu, Ce, Tb and Mn, and f, g, h, j and j are 0.80 ≦ f ≦, respectively. It is a number satisfying 1.05, 0.80 ≦ g ≦ 1.05, 0.001 <h ≦ 0.1, 0 ≦ i ≦ 0.5, 3.0 ≦ j ≦ 5.0.

When the second phosphor particles are phosphor particles having an emission peak wavelength in the range of 600 nm or more and 670 nm or less due to the light from the excitation light source, the second phosphor particles are specifically K ₂ SiF ₆ . : Mn, MGF: Mn, Ca ₂ Si ₅ N ₈ : Eu, (Ba, Sr) ₂ Si ₅ N ₈ : Eu, (Sr, Ca) AlSiN ₃ : Eu, CaAlSiN ₃ : Eu, Sr _0.9925 Li _{1 .0000} Eu _0.0075 Al ₃ N ₄ and the like can be mentioned.

The average particle size of the second phosphor particles may be in the range of 1 μm or more and 50 μm or less. The average particle size of the second phosphor particles is preferably 2 μm or more, more preferably 5 μm or more. The average particle size of the second phosphor particles is preferably 40 μm or less, more preferably 20 μm or less, and further preferably 15 μm or less. When the average particle size of the second phosphor particles is within the range of 1 μm or more and 50 μm or less, the second ceramics derived from the second inorganic binder are used to include particles that are intermittently present in the horizontal direction along the surface of the substrate. In addition, the second phosphor particles fixed to the substrate by the second ceramics, the first phosphor particles in the substrate, and the light from the excitation light source provide mixed color light with improved color playability.

The second phosphor particles are fixed by the second ceramics so that irregularities due to the second phosphor particles are formed on the surface of the substrate. The second phosphor particles are fixed to the surface of the substrate by the translucent second ceramics derived from the second inorganic binder described later. As will be described later, the second inorganic binder contains a second ceramic precursor to be the second ceramic and a solvent. The second fluorescent substance particles are mixed with the second inorganic binder to form a fluorescent substance-containing composition, and the fluorescent substance-containing composition is applied to the surface of the substrate by a method described later. The second phosphor particles tend to be easily aggregated by the solvent contained in the second inorganic binder in the phosphor-containing composition. When the solvent volatilizes, the agglomerated second phosphor particles and the second ceramic precursor contained in the second inorganic binder are likely to exist between the second phosphor particles and the substrate due to a capillary phenomenon or surface tension. Become. Therefore, the second phosphor particles are arranged on the surface of the substrate so as to include particles that are intermittently present in the horizontal direction along the surface of the substrate. Then, by the subsequent heat treatment, the second phosphor particles are translucent second ceramics derived from the second inorganic binder on the surface of the substrate so as to include particles that are intermittently present in the horizontal direction along the surface of the substrate. Is fixed by, and irregularities due to the second phosphor particles are formed on the surface.

The second ceramics derived from the second inorganic binder The translucent second ceramics derived from the second inorganic binder is obtained by heat-treating the second ceramic precursor contained in the inorganic binder. The second ceramic precursor is preferably a silica precursor. The silica precursor is preferably polysilanol or polysilazane. The second ceramic is preferably silicon dioxide (SiO ₂ ), but alumina (Al ₂ O ₃ ) can also be used. Polysilanol is a compound containing a siloxane (Si—O—Si) bond, and the hydroxyl group and alkoxy group bonded to Si are removed by heat treatment to form translucent silicon dioxide (SiO ₂ ). 2 Fix the substrate to each other or to the second phosphor particles. In addition, polysilazane is a compound containing a SiH2 _- NH bond, and when heat-treated in the air or in a water vapor-containing atmosphere, it reacts with water and oxygen to become translucent silicon dioxide (SiO ₂ ). The second phosphor particles are fixed to each other or the second phosphor particles and the substrate are fixed.

The second ceramics for fixing the second phosphor particles arranged so as to form irregularities due to the second phosphor particles on the surface form a layered material on the surface of the substrate. The layered material may not be a layer of uniform thickness. The thickness of the layered material containing the second phosphor particles and the second ceramics may be in the range of 1 μm or more and 180 μm or less, may be in the range of 1 μm or more and 150 μm or less, and may be 2 μm or more and 120 μm or less. It may be within a range, or may be within a range of 2 μm or more and 100 μm or less. In the present specification, the thickness of the layered material can also be measured by a contact type thickness measuring machine, and more accurately, it can be confirmed by observing the cross section by SEM.

The third fluorescent particle molded body may further contain the third fluorescent particle that emits light in a wavelength range different from that of the second fluorescent particle on the surface of the substrate. When the molded body contains the third phosphor particles on the surface of the substrate, the excitation light transmitted through the substrate without being wavelength-converted by the first phosphor particles is further wavelengthd by the third phosphor particles on the surface of the substrate. It can be converted and mixed-color light having a desired chromaticity can be obtained from the molded body. The third phosphor particles may be fixed with the third ceramics described later.

The third phosphor particles may be those that wavelength-convert the light from the first phosphor particles or the second phosphor particles, but are preferably those that wavelength-convert the light from the excitation light source. The excitation light transmitted through the substrate without being wavelength-converted by the first phosphor particles contained in the substrate can be wavelength-converted by the third phosphor particles, and the wavelengths of the excitation light transmitted through the substrate and the first phosphor particles can be converted. The converted light, the light wavelength-converted by the second phosphor particles, and the wavelength-converted light by the third phosphor particles can be used to obtain mixed-color light having a desired chromaticity from the molded body. The emission color from the third phosphor particles is the same as or close to the emission color of the first phosphor particles to supplement the emission color of the first phosphor particles, and the light emitted from the light emitting device is the first phosphor particles. The color can be shifted to the emission color side of.

The third phosphor particle may be a phosphor particle having an emission peak wavelength in the range of 530 nm or more and 590 nm or less due to light from an excitation light source, or a phosphor having an emission peak wavelength in the range of 490 nm or more and 555 nm or less. It may be a particle.

When the third phosphor particle is a phosphor particle having an emission peak wavelength in the range of 530 nm or more and 590 nm or less due to the light from the excitation light source, the third phosphor particle is at least one kind of aluminate. It may be a phosphor. Examples of the aluminate phosphor include an aluminate phosphor having a composition represented by the above formula (1A). When the third phosphor particle is a phosphor particle having an emission peak wavelength in the range of 530 nm or more and 590 nm or less due to the light from the excitation light source, the _third phosphor particle is Y3 Al ₅ O ₁₂ : Ce, Y ₃ (Al, Ga) ₅ O ₁₂ : Ce, (Y, Gd) ₃ Al ₅ O ₁₂ : Ce, Lu ₃ A _l5 O ₁₂ : Ce, or Lu ₃ (Al, Ga) ₅ O ₁₂ : Ce. Be done.

When the third phosphor particle is a phosphor particle having an emission peak wavelength in the range of 490 nm or more and 555 nm or less due to the light from the excitation light source, the alkaline earth metal silicate phosphor and the alkaline earth metal It is preferably at least one fluorophore selected from the group consisting of an aluminate fluorophore, an alkaline earth metal halosilicate fluorophore, and a β-sialon fluorophore. When the third phosphor particle is a phosphor particle having an emission peak wavelength in the range of 490 nm or more and 555 nm or less due to the light from the excitation light source, the alkaline soil having the composition represented by the above formula (1B). Metal silicate phosphor, alkaline earth metal aluminate phosphor having the composition represented by the above formula (1C), alkaline earth metal halosilicate fluorescent material having the composition represented by the above formula (1D). , And at least one selected from the group consisting of β-sialon fluorescent substances having the composition represented by the above formula (1E). When the third phosphor particle is a phosphor particle having an emission peak wavelength in the range of 490 nm or more and 555 nm or less due to the light from the excitation light source, the third phosphor particle is specifically BaSi ₂ O ₂ N. ₂ : Eu, Sr ₄ Al ₁₄ O ₂₅ : Eu, Ca ₈ MgSi ₄ O ₁₆ Cl ₂ : Eu, Si _6-a Al _a O _a N _8-a : Eu (in the formula, a is 0 <a <4. It is a number that satisfies 2.).

In a plan view, when the unit area of the surface of the substrate is 100%, the total surface area where the second phosphor particles and the third phosphor particles are present is preferably 97% or less, more preferably 90% or less. It is more preferably 80% or less, further preferably 78% or less, and particularly preferably 72% or less. Further, when the unit area of the surface of the substrate is 100%, the total surface area where the second phosphor particles and the third phosphor particles are present is preferably 10% or more, more preferably 20% or more. , More preferably 25% or more, even more preferably 30% or more, and particularly preferably 35% or more. In the plan view of the molded body, the total surface area where the second fluorescent substance particles and the third fluorescent substance particles are present with respect to 100% of the unit area of the surface of the substrate is also referred to as a coverage ratio. In a plan view, if the total surface area of the second phosphor particles and the third phosphor particles present on the surface of the substrate is 97% or less with respect to 100% of the unit area of the surface of the substrate, the second phosphor particles And the light wavelength-converted by the first phosphor particles in the substrate from the portion where the third phosphor particles do not exist, and the excitation light source transmitted through the translucent substrate without being wavelength-converted by the first phosphor particles. Light can be extracted, and by using these lights and the light wavelength-converted by the second phosphor particles and the third phosphor particles, it is possible to obtain mixed-color light having a desired chromaticity from the molded body, and the thickness is reduced. Can meet the demands of.

The second phosphor particles and the third phosphor particles that are intermittently present along the surface of the substrate and the second ceramics form a layered substance on the surface of the substrate. The layered material may not be a layer of uniform thickness. The thickness of the layered material containing the second phosphor particles and the third phosphor particles and the second ceramics may be in the range of 1 μm or more and 180 μm or less, or may be in the range of 1 μm or more and 150 μm or less. It may be in the range of 2 μm or more and 120 μm or less, or may be in the range of 2 μm or more and 100 μm or less. The maximum height of the second phosphor particles and the second ceramics is preferably in the range of 1 μm or more and 150 μm or less.

Third Ceramic The third ceramic is preferably a translucent member derived from the third inorganic binder, and is preferably obtained by heat-treating the third ceramic precursor contained in the third inorganic binder. The third inorganic binder is preferably the same as the first inorganic binder or the second inorganic binder, but may be different. The third ceramics precursor is preferably a silica precursor. The third ceramic is preferably silicon dioxide (SiO ₂ ) derived from the silica precursor contained in the third inorganic binder, but alumina (Al ₂ O ₃ ) can also be used. In the third ceramics, the third inorganic binder is placed on the second phosphor particles and the second ceramics, or the second phosphor particles, the third phosphor particles and the second ceramics are coated with the third inorganic binder by the spin coating method. It is preferably made of a third ceramic formed by coating and heat treatment.

The thickness of the third ceramics is not particularly limited, but the substrate is used to emit light transmitted through the substrate, light wavelength-converted by the first phosphor particles, the second phosphor particles, or the third phosphor particles. 3 The thickness to the upper surface of the ceramics is preferably in the range of 2 μm or more and 100 μm or less. The thickness from the substrate to the upper surface of the third ceramics may be in the range of 3 μm or more and 70 μm or less, or may be in the range of 5 μm or more and 50 μm or less.

Fourth Ceramic The fourth ceramic is preferably a translucent fourth ceramic formed by an atomic layer deposition method (hereinafter, also referred to as “ALD method”). The fourth ceramic is preferably aluminum oxide (Al ₂ O ₃ ). When the fourth ceramics are formed by the ALD method, they have a uniform thickness and can form a dense film, so that the adhesion between the second phosphor particles or the third phosphor particles and the substrate is enhanced, and the second fluorescence It is possible to suppress the shedding and peeling of the body particles or the third phosphor particles. The thickness of the fourth ceramics may be, for example, in the range of 0.5 nm or more and 100 nm or less, or in the range of 1 nm or more and 50 nm or less.

Light emitting device The light emitting device includes the molded body and an excitation light source. The light emitting device can be used as a light source for a projector, a lighting device, a marking device, or the like.

The excitation light source is preferably a light emitting device composed of a light emitting diode (LED) or a semiconductor laser (LD) chip, and is a nitride-based semiconductor (In _X Al _Y Ga _1-XY N, 0 ≦ X, 0 ≦ Y. , X + Y ≦ 1) can be used as a semiconductor light emitting device. By using a semiconductor light emitting device as an excitation light source, it is possible to obtain a stable light emitting device having high efficiency, high output linearity with respect to input, and resistance to mechanical impact.

The excitation light source is more preferably a semiconductor laser. The excitation light emitted from the semiconductor laser, which is the excitation light source, is incident on the molded body, and the light whose wavelength is converted by the molded body is condensed to cause a plurality of lens arrays, polarization conversion elements, color separation optical systems, and the like. It may be separated into red light, green light, and blue light by an optical system and modulated according to image information to form color image light. The excitation light emitted from the semiconductor laser as the excitation light source may be incident on the molded body through an optical system such as a dichromic mirror or a collimating optical system.

The light emitting device preferably has an average color rendering index Ra of 70 or more. The average color rendering index Ra of the light emitting device is more preferably 71 or more, still more preferably 72 or more. The average color rendering index Ra of the light emitting device can be measured according to JIS Z8726. The closer the value of the average color rendering index Ra of the light emitting device is to 100, the closer the color rendering property is to the reference light source. When the average color rendering index Ra is 70 or more, it is possible to provide a light emitting device that emits light suitable for lighting applications for performing general work such as offices and schools.

Light emitting device (light emitting module)
A light emitting device provided with a molded body and an excitation light source, and a light emitting module provided with the light emitting device will be described. The light emitting device is not limited to the following light emitting modules. Unless otherwise specified, the dimensions, materials, shapes, relative arrangements, etc. of the components of the light emitting device and the light emitting module described below are not intended to be limited to the following descriptions, but are merely examples. .. In addition, the size and positional relationship of the members shown in each drawing may be exaggerated in order to clarify the explanation. Further, the number of light emitting elements shown in each figure is set as an example so that the configuration can be easily understood.

FIG. 6A is a schematic perspective view showing the configuration of a light emitting module which is an example of a light emitting device, which includes a light emitting device including a molded body and an excitation light source. FIG. 6B is a schematic plan view showing the configuration of a light emitting module which is an example of a light emitting device, which includes a light emitting device including a molded body and an excitation light source. FIG. 6C is a cross-sectional view taken along the line VIC-VIC of FIG. 6B. FIG. 6D is a cross-sectional view taken along the line VID-VID of FIG. 6B. FIG. 6E is a schematic cross-sectional view showing the configuration of an example light emitting device. FIG. 6F is a schematic bottom view showing the configuration of an example light emitting device.

The light emitting module 200, which is an example of the light emitting device, includes a light emitting device 100 and a module substrate 80 on which the light emitting device 100 is mounted.

Light emitting device The light emitting device 100 will be described.
The light emitting device 100 includes a plurality of light emitting surfaces on the upper surface as a light extraction region of the light emitting device 100.
The light emitting device 100 includes a submount substrate 10, a light emitting element 20 provided on the submount substrate 10, a light transmitting member 30 made of the above-mentioned molded body provided on the light emitting element 20, and a light transmitting member. An element structure 15 and an element structure 15 including a light guide member 40 arranged between the light emitting element 30 and the light emitting element 20, and a first covering member 50 that covers the side surface of the light emitting element 20 on the submount substrate 10. A second covering member 60, which covers the side surface of the device and holds a plurality of element structures 15, is provided. The upper surface of the light transmissive member 30 is exposed from the second covering member 60, and constitutes a plurality of light emitting surfaces included in the light emitting device 100.
In the light emitting device 100, a plurality of element structures 15 each having a light emitting surface are held by a second covering member 60. Since each element structure 15 can be held in a desired arrangement by the second covering member 60, a plurality of light emitting surfaces can be arranged at a higher density at a narrower distance.
The light emitting device 100 may directly join the light transmitting member 30 and the light emitting element 20 without using the light guide member 40.

Hereinafter, each configuration of the light emitting device 100 will be described.
The submount substrate 10 is a member on which the light emitting element 20 and the protective element 25 are placed. The submount substrate 10 is formed, for example, in a substantially rectangular shape in a plan view.
As the submount substrate 10, it is preferable to use an insulating material, and it is preferable to use a material that does not easily transmit light emitted from the light emitting element 20, external light, or the like. For example, ceramics such as alumina, aluminum nitride, and murite, thermoplastic resins such as polyamide, polyphthalamide, polyphenylene sulfide, or liquid crystal polymers, epoxy resins, silicone resins, modified epoxy resins, urethane resins, phenol resins, and the like. Resin can be used. Above all, it is preferable to use ceramics having excellent heat dissipation.

The submount substrate 10 includes wiring on the upper surface, the lower surface, and the inside for electrically connecting to the light emitting element 20 and an external power source. The wiring can be formed by using, for example, a metal such as Fe, Cu, Ni, Al, Ag, Au, Al, Pt, Ti, W, Pd, or an alloy containing at least one of these.
For example, the submount substrate 10 includes a top surface wiring 2 connected to the light emitting element 20 on the upper surface on which the light emitting element 20 is mounted, and an external power supply and electricity on the lower surface opposite to the upper surface on which the light emitting element 20 is mounted. Examples include those provided with an external connection electrode 3 (for example, an anode electrode 3a and a cathode electrode 3b) to be specifically connected. In this case, the upper surface wiring 2 and the external connection electrode 3 may be formed with vias 4 extending over both the upper surface and the lower surface, that is, penetrating the submount substrate 10. As a result, the top surface wiring 2 and the external connection electrode 3 are electrically connected.

In the light emitting device 100, the distance L1 between the adjacent submount substrates 10 may be, for example, 0.05 mm or more and 0.2 mm or less. As a result, the thickness of the second covering member 60 arranged between the submount substrates 10 is 0.05 mm or more and 0.2 mm or less, so that the adjacent submount substrates 10 can be closely joined to each other. Further, in the light emitting device 100 including the plurality of element structures 15, each of the plurality of element structures 15 includes the submount substrate 10, and the second covering member 60 can be arranged between the submount substrates 10. As a result, it is possible to suppress the influence of thermal stress due to expansion or contraction of the submount substrate 10 due to heat generated in each element structure 15 and heat history at the time of mounting the light emitting device.

The light emitting element 20 is a semiconductor element that emits light by itself when a voltage is applied. Any shape, size, etc. of the light emitting element 20 can be selected. As the emission color of the light emitting element 20, one having an arbitrary wavelength can be selected depending on the intended use. For example, as the blue-based (light with a wavelength of 430 nm to 500 nm) and green-based (light with a wavelength of 500 nm to 570 nm) light emitting device 20, the above-mentioned nitride-based semiconductor (In _X Al _Y Ga _1-XY N, 0) Those using ≦ X, 0 ≦ Y, X + Y ≦ 1), GaP and the like can be used. As the red light emitting device 20 (light having a wavelength of 610 nm to 700 nm), GaAlAs, AlInGaP, or the like can be used in addition to the nitride semiconductor device. The excitation light source is preferably a semiconductor laser among the semiconductor light emitting devices, but a light emitting diode can also be used.

As the light emitting element 20, it is preferable to use one having positive and negative element electrodes on one surface, whereby the conductive adhesive material 8 can be flip-chip mounted on the wiring on the submount substrate 10. As the conductive adhesive material 8, for example, eutectic solder, conductive paste, bumps, or the like may be used.

The protection element 25 is, for example, a Zener diode. The protective element 25 is provided with positive and negative element electrodes on one surface, and is flip-chip mounted on the wiring on the submount substrate 10 by the conductive adhesive material 8. The light emitting device may not be provided with the protective element 25.

As the light transmissive member 30, the above-mentioned molded body can be used. The light transmissive member 30 is a flat plate-shaped member having an upper surface serving as a main light emitting surface of each element structure 15 and a light emitting device 100, and a lower surface facing the upper surface. The light transmissive member 30 is arranged on the light emitting element 20. The light transmissive member 30 preferably has a wider upper surface than the upper surface of the light emitting element 20, and is preferably arranged so as to include the light emitting element 20 in a plan view.
In the light emitting device 100, the distance L2 between the light transmitting members 30 exposed on the upper surface of the light emitting device 100 may be, for example, 0.2 mm or less. When the distance L2 between the adjacent light transmitting members 30 is 0.2 mm or less, the light source can be reduced. The distance L2 between the adjacent light transmitting members 30 may be 0.1 mm or less, or may be 0.05 mm or less. The distance L2 between the light transmitting members 30 may be 0.03 mm or more from the viewpoint of ease of manufacturing the light emitting device 100.

The planar shape of the light transmissive member 30 can be various, such as a circular shape, an elliptical shape, a polygonal shape such as a square or a hexagonal shape, and the like. Among them, from the viewpoint of arranging a plurality of light emitting surfaces in close proximity to each other, a rectangle such as a square or a rectangle is preferable, and a shape similar to the planar shape of the light emitting element 20 is more preferable.

The light guide member 40 is a member that is arranged between the light transmitting member 30 and the light emitting element 20 and joins the light emitting element 20 and the light transmitting member 30. Further, the light guide member 40 is a member that facilitates light extraction from the light emitting element 20 and guides the light from the light emitting element 20 to the light transmissive member 30. The light guide member 40 can improve the efficiency of extracting light flux and light. It is preferable that the light guide member 40 is also provided on the side surface of the light emitting element 20.
The light guide member 40 that covers the side surface of the light emitting element 20 can be formed by the adhesive member that joins the light transmitting member 30 and the light emitting element 20 to wet and spread on the side surface of the light emitting element 20.

The light guide member 40 is formed in a triangular shape so that the width of the member widens from the lower surface of the light emitting element 20 (on the side of the submount substrate 10) toward the light transmitting member 30 in a cross-sectional view. With such a form, the light traveling laterally from the light emitting element 20 is easily reflected upward, so that the light flux and the light extraction efficiency are further improved. However, the cross-sectional shape of the outer surface of the light guide member 40 is not limited to a linear shape, but may be a curved shape. For example, the curved shape of the light guide member 40 may be a curved shape that swells toward the first covering member 50 or a curved shape that dents toward the light emitting element 20 side.

The light guide member 40 may cover the region including the light emitting portion on the side surface of the light emitting element 20, but covers substantially the entire side surface of the light emitting element 20 from the viewpoint of improving the light flux and the light extraction efficiency. Is more preferable.
As the light guide member 40, for example, a translucent resin material, glass, or ceramics can be used. Further, the light guide member 40 may contain a diffusing material. As a result, the light can be more evenly incident on the light transmissive member 30, and the color unevenness of the light emitting device 100 can be suppressed.

The first covering member 50 is provided on the submount substrate 10 and covers the side surface of the light emitting element 20. The first covering member 50 can increase the adhesive force between the submount substrate 10 and the light emitting element 20. The first covering member 50 covers the side surface of the light emitting element 20 via the light guide member 40.
The first covering member 50 is formed, for example, in a triangular shape in cross-sectional view so that the width of the member widens from the light transmissive member 30 side toward the submount substrate 10 in cross-sectional view. The cross-sectional shape of the outer surface of the first covering member 50 is not limited to a linear shape, but may be a curved shape. For example, the curved shape of the first covering member 50 may be a curved shape that swells toward the second covering member 60 or a curved shape that dents toward the light emitting element 20 side.

As the first covering member 50, for example, a translucent resin material containing a reflective material can be used. Examples of the resin material used for the first covering member 50 include silicone resin, epoxy resin, urea resin and the like. In particular, it is preferable to use a silicone resin having excellent light resistance and heat resistance. Examples of the reflective material include titanium oxide, silica, silicon oxide, aluminum oxide, zirconium oxide, magnesium oxide, potassium titanate, zinc oxide, silicon nitride, boron nitride and the like. Above all, from the viewpoint of light reflection, it is preferable to use titanium oxide having a relatively high refractive index.

The first covering member 50 may cover at least a part of the side surface of the light emitting element 20. Preferably, the first covering member 50 covers the entire side surface of the light emitting element 20. More preferably, it may extend from the side surface of the light emitting element 20 to cover at least a part of the side surface of the light transmitting member 30. Thereby, in each element structure 15, it is possible to suppress the light emitted from the side surface of the light emitting element 20 directly to the outside. As a result, in the light emitting device 100 provided with the plurality of element structures 15, light leakage to the adjacent element structures 15 is suppressed, and the light emitting device 100 with less light emission unevenness can be obtained. Further, as will be described later, it becomes easier to grasp the chromaticity coordinates of the element structure 15 when the sorting step is performed after the element structure 15 is separated into individual pieces.
Further, it is preferable that the first covering member 50 covers the lower surface of the light emitting element 20. As a result, the light traveling downward of the light emitting element 20 is irradiated to the reflective material contained in the first covering member 50 and reflected, so that the light flux of the light emitting device 100 can be further increased. Further, the adhesive force between the submount substrate 10 and the light emitting element 20 can be further enhanced.

The second covering member 60 is a member provided around the plurality of element structures 15. It is preferable to use a resin material for the second covering member 60, but glass or ceramics can also be used. The second covering member 60 is formed by covering the side surface of the element structure 15 with, for example, a white resin containing a reflective material in a translucent resin material. That is, the second covering member 60 covers the side surface of the submount substrate 10, the side surface of the first covering member 50, and the side surface of the light transmitting member 30. The second covering member 60 is also provided between the adjacent element structures 15, and the upper surface of the light transmissive member 30 is exposed to cover the outer peripheral side surfaces of each of the plurality of element structures 15.

Examples of the resin material used for the second covering member 60 include those exemplified as the resin material used for the first covering member 50. Examples of the reflective material contained in the resin used for the second covering member 60 include those exemplified as the reflective material used for the first covering member 50.

Since the light emitting device 100 includes a plurality of element structures 15, and each of the plurality of element structures 15 includes a first covering member 50 that covers the side surface of the light emitting element 20, the light emitted from the light emitting element 20 in the lateral direction. It is possible to suppress light leakage to. This makes it possible to arrange the plurality of element structures 15 closer to each other without lowering the light extraction efficiency of the individual element structures 15.
Here, as an example, in the light emitting device 100, four element structures 15 arranged in a matrix of 2 rows and 2 columns are held by a second covering member 60. The element structure 15 is arranged so that the protective element 25 is located on the outside. As a result, the four light transmissive members 30 can be arranged in a matrix at narrower intervals. The light emitting device may include three or less element structures 15, or may include five or more element structures 15.

Manufacturing method of light emitting device The manufacturing method of the light emitting device 100 is as follows: a submount substrate 10, a light emitting element 20 provided on the submount substrate 10, a light transmitting member 30 provided on the light emitting element 20, and a light emitting element. An element structure that is a step of preparing a plurality of element structures 15 including a light guide member 40 provided on the side surface of the 20 and a first covering member 50 that covers the side surface of the light emitting element 20 on the submount substrate 10. A preparatory step, an element structure mounting step of mounting a plurality of element structures 15 on the sheet member so that the submount substrate 10 of the element structure 15 faces the sheet member, and a plurality of element structures. A second covering member forming step, which is a step of forming a second covering member 60 on the sheet member, which covers the side surface of the 15 and holds the plurality of element structures 15, and a sheet member removal step, which is a step of removing the sheet member. The process and may be included. As a method for manufacturing the light emitting device, in addition to using the above-mentioned molded body as the light transmissive member 30, the manufacturing method described in Japanese Patent Application No. 2020-006262 can be referred to.

Light-emitting module Next, the light-emitting module 200, which is a light-emitting device, will be described.
The light emitting module 200 includes a light emitting device 100 having a configuration already described above, and a module board 80 on which the light emitting device 100 is mounted so that the submount board 10 of the light emitting device 100 faces each other.
When the light emitting device 100 is not provided with the protective element 25, the protective element 25 may be provided on the module substrate 80 side. Further, the module substrate 80 may be configured to include electronic components other than the protective element 25.

The light emitting device 100 has the configuration as described above.
The module substrate 80 is a member on which the light emitting device 100 is placed, and electrically connects the light emitting device 100 to the outside. The module substrate 80 is formed, for example, in a substantially rectangular shape in a plan view.
Examples of the material of the module substrate 80 include those exemplified as the material used for the submount substrate 10.
The module substrate 80 has a wiring on the upper surface for electrically connecting to the light emitting device 100. Examples of the wiring material of the module substrate 80 include those exemplified as the material used for the wiring of the submount substrate 10. Further, a composite material of an insulating material and a metal member may be used.

The light emitting device 100 is mounted on the upper surface of the module substrate 80 so that the wiring of the submount substrate 10 and the wiring of the module substrate 80 are joined via a conductive adhesive material. As the conductive adhesive, for example, eutectic solder, conductive paste, bumps, metal sintered bodies and the like may be used. It is possible to firmly fix a metal sintered body, for example, a metal powder such as silver particles, which is sintered at 160 ° C. or higher, preferably 180 ° C. or higher, 400 ° C. or lower, preferably 280 ° C. or lower. can.

When the light emitting module 200 is driven, a current is supplied to the light emitting element 20 from an external power source, and the light emitting element 20 emits light. As for the light emitted by the light emitting element 20, the light traveling upward is taken out to the outside above the light emitting device 100 via the light transmitting member 30. Further, the light traveling downward is reflected by the submount substrate 10 and is taken out to the outside of the light emitting device 100 via the light transmissive member 30. Further, the light traveling in the lateral direction is reflected by the first covering member 50 and / or the second covering member 60, and is taken out to the outside of the light emitting device 100 via the light transmitting member 30.

Manufacturing method of the light emitting module The manufacturing method of the light emitting module 200 includes a light emitting device preparation step which is a step of preparing the light emitting device 100 by using the manufacturing method of the light emitting device 100, and a submount substrate 10 of the light emitting device 100 on the module board 80. It may include a light emitting device mounting step, which is a step of mounting so as to face each other. As a method for manufacturing a light emitting module as a light emitting device, the manufacturing method described in Japanese Patent Application No. 2020-006262 can be referred to.

Method for manufacturing a molded product An example of a method for manufacturing a molded product according to an embodiment of the present invention will be described with reference to the drawings. FIG. 7 is a flowchart showing an example of a method for manufacturing a molded product. The method for producing the molded product is derived from the step S101 for preparing the substrate, the step S102 for preparing the phosphor-containing composition, the step S103 for applying the phosphor-containing composition to the substrate, and the second phosphor particles on the surface. Includes step S104 of obtaining a molded product having irregularities formed therein. This step involves preparing a translucent substrate made of an inorganic material selected from the first ceramics, glass, and first fluorophore particles and containing at least one that requires the first fluorophore particles. A fluorescent substance-containing composition containing the fluorescent substance particles and the second inorganic binder is prepared, the fluorescent substance-containing composition is applied to the substrate, and the substrate and the fluorescent substance-containing composition are first heat-treated. The second fluorescent substance particles are fixed on the surface of the substrate via the translucent second ceramics derived from the second inorganic binder, and a molded body having irregularities due to the second fluorescent substance particles formed on the surface is obtained. ,including.

FIG. 8 is a flowchart showing another example of a method for manufacturing a molded product. The method for producing the molded product is derived from the step S201 for preparing the substrate, the step S202 for preparing the phosphor-containing composition, the step S203 for applying the phosphor-containing composition to the substrate, and the second phosphor particles on the surface. A step S204 for obtaining a molded product having irregularities formed therein, a step S205 for applying a third inorganic binder, a step S206 for fixing the second phosphor particles via the third ceramics, and a step for fixing the fourth ceramics. S207 and may be included. Further, after the step S204 of obtaining the molded product, the second phosphor particles are fixed via the step S205 of applying the third inorganic binder onto the second phosphor particles and the third ceramics derived from the third inorganic binder. Step S206 may be included. The method for producing the molded product is as follows: after the step of obtaining the molded product, a third inorganic binder is applied onto the second phosphor particles by a spin coating method, and the third inorganic binder is subjected to a second heat treatment to obtain the third inorganic binder. It may include fixing the second phosphor particles via a translucent third ceramic derived from an inorganic binder. The method for producing the molded product may include fixing the second phosphor particles via the third ceramics and then fixing the translucent fourth ceramics by the ALD method. Further, the method for producing a molded product may include a step of cutting the obtained molded product into a desired size or thickness and processing the molded product, if necessary.

Step of preparing a substrate S101 (S201)
The substrate preparation step prepares a translucent substrate made of an inorganic material containing the first phosphor particles. As the substrate, a commercially available product may be used. The substrate may be a substrate composed of first phosphor particles having a content of 100% by mass of the first phosphor particles obtained by sintering the first phosphor particles, and the content of the first phosphor particles in the substrate is 0. The substrate may be in the range of 1% by mass or more and 99.9% by mass or less. The substrate used for the molded body may contain at least one inorganic material selected from the first ceramics and glass that do not wavelength-convert the excitation light, in addition to the first phosphor particles. Specifically, the above-mentioned substrate can be used. As the first fluorescent particle, the same first fluorescent particle as the first fluorescent particle used for the above-mentioned molded product can be used. As the substrate, a transparent substrate containing the first phosphor particles and the first ceramics may be produced by curing or firing a substrate containing the first phosphor particles in a first inorganic binder. Since the same material as the second inorganic binder and the third inorganic binder may be used as the material of the first inorganic binder, they will be described together. When the first inorganic binder, the second inorganic binder, and the third inorganic binder are collectively described, they may be referred to as "inorganic binder".

Step of preparing a fluorescent substance-containing composition S102 (S202)
The fluorescent substance-containing composition contains a second fluorescent substance particle and a second inorganic binder. As the second fluorescent particle, the same second fluorescent particle as the second fluorescent particle used in the above-mentioned molded product can be used. Further, a third inorganic binder to be the third ceramic may be prepared.

Inorganic Binder At least one inorganic binder of the first inorganic binder to be the first ceramic, the second inorganic binder to be the second ceramic, and the third inorganic binder to be the third ceramic contains a ceramic precursor, and the ceramic precursor is. It is preferably at least one silica precursor selected from polysilanol and polysilazane. Polysilanol is a compound containing a siloxane (Si—O—Si) bond. Polysilazane is a compound containing a SiH2 _- NH bond. The polysilazane is preferably perhydropolysilazane in which all hydrogen is bonded to Si or N. The silica precursor contained in the inorganic binder becomes silicon dioxide (SiO ₂ ) having translucency by heat treatment. The second inorganic binder fixes the substrate to each other or to the second phosphor particles. When the phosphor-containing composition contains the third phosphor particles, the second phosphor particles, the third phosphor particles, and the substrate may be fixed by the second ceramics derived from the second inorganic binder.

In the step of preparing the fluorescent substance-containing composition, when the fluorescent substance-containing composition is 100% by mass, the content of the ceramic precursor in the fluorescent substance-containing composition is 0.5% by mass or more and 70% by mass or less. It is preferably within the range of. When the content of the ceramic precursor in the phosphor-containing composition is within the range of 0.5% by mass or more and 70% by mass or less, it is easy to mix the inorganic binder containing the ceramic precursor and the phosphor particles, and the particles are intermittent. The second phosphor particles containing the particles present in the above or the second phosphor particles and the substrate are easily fixed by the second ceramics derived from the second inorganic binder.

The inorganic binder contains a solvent. The amount of the solvent contained in the inorganic binder is the balance obtained by subtracting the amount of the ceramic precursor in the inorganic binder. By heat treatment after applying the inorganic binder, the second fluorescent particle or the third fluorescent particle is added to the surface of the substrate so as to contain particles that are intermittently present in the horizontal direction along the surface of the substrate. It is fixed by a translucent second ceramic derived from it, or fixed by a translucent third ceramic derived from a third inorganic binder.

Examples of the solvent contained in the inorganic binder include acetone, ethanol, isopropyl alcohol (IPA), propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether acetate (PGMEA), tridecane, and triethylene glycol. The solvent contained in the inorganic binder preferably has a relatively high boiling point, and has a boiling point of 80 ° C. or higher at room temperature in the range of 10 ° C. or higher and 40 ° C. or lower in an atmospheric pressure (101.325 kPa) atmosphere. Is more preferable. When the boiling point of the solvent is relatively high, the volatilization of the solvent can be suppressed when the fluorescent substance-containing composition is applied to the substrate, and the fluorescent substance-containing composition is evenly applied to the surface of the substrate. Can be done. If the volatilization of the solvent contained in the inorganic binder can be suppressed, the second phosphor particles flow and easily aggregate in the phosphor-containing composition, and intermittently in the horizontal direction along the surface of the substrate. It becomes easy to arrange the second phosphor particles on the surface of the substrate so as to include the existing particles. Further, the solvent contained in the inorganic binder is preferably hydrophilic. When the solvent is hydrophilic, the second phosphor particles aggregate in the phosphor-containing composition and include the particles that are intermittently present in the horizontal direction along the surface of the substrate. Even when the particles are arranged on the surface of the substrate, the ceramic precursor contained in the inorganic binder, together with the hydrophilic solvent, is formed between the second phosphor particles by the action of the capillary phenomenon or the surface tension, or between the second phosphor particles. It becomes easy to be sucked between the second phosphor particles and the substrate, and after the solvent is volatilized by drying, the ceramic precursor becomes the first ceramics by the heat treatment, and the second phosphor particles can be fixed to the substrate.

The content of the second phosphor particles in 100% by mass of the phosphor-containing composition is preferably in the range of 20% by mass or more and 99.5% by mass or less, and more preferably 25% by mass or more and 98% by mass or less. It is within the following range, more preferably within the range of 30% by mass or more and 95% by mass or less, and particularly preferably within the range of 40% by mass or more and 90% by mass or less. If the content of the second phosphor particles in the phosphor-containing composition is within the range of 20% by mass or more and 99.5% by mass or less with respect to the total amount of the phosphor-containing composition, the inorganic binder and the second By applying the fluorophore-containing composition containing the two fluorophore particles to the substrate by the method described later, the second phosphor particles are applied to the substrate so as to contain the particles that are intermittently present in the horizontal direction along the surface of the substrate. It becomes easy to place on the surface of.

In the step of preparing the fluorescent substance-containing composition, the fluorescent substance-containing composition may further contain a third phosphor particle that emits light in a wavelength range different from that of the second phosphor particle. As the third fluorescent particle, the same third fluorescent particle as the third fluorescent particle used for the above-mentioned molded product can be used.

When the phosphor-containing composition contains the third phosphor particles, the total content of the second phosphor particles and the third phosphor particles in 100% by mass of the phosphor-containing composition is preferably 20% by mass or more. It is in the range of 99.5% by mass or less, more preferably in the range of 25% by mass or more and 98% by mass or less, further preferably in the range of 30% by mass or more and 95% by mass or less, and particularly preferably 40. The third phosphor particles are contained so as to be in the range of mass% or more and 90 mass% or less. When the third fluorescent substance particles are contained in the fluorescent substance-containing composition, a molded product that emits mixed color light having a desired chromaticity can be obtained.

The mass ratio of the second phosphor particles to the third phosphor particles (second phosphor particles: third phosphor particles) in the phosphor-containing composition is preferably in the range of 1:99 or more and 99: 1 or less. be. When the mass ratio of the second phosphor particles to the third phosphor particles in the phosphor-containing composition is in the range of 1:99 or more and 99: 1 or less, a molded product that emits light of a desired chromaticity can be obtained. Can be done.

Step of applying the fluorescent substance-containing composition to the substrate S103 (S203)
In the step of applying the fluorescent substance-containing composition to the substrate, the fluorescent substance-containing composition is applied to the substrate by spray spraying, potting, or printing. Examples of the method for applying the fluorescent substance-containing composition include spray spraying, potting, and printing. Spraying Even if the fluorescent substance-containing composition is a combination in which particles are likely to settle, the fluorescent substance-containing composition can be applied to the substrate with a stable thickness due to the structure for circulating the slurry. In potting, the fluorescent substance-containing composition is applied to the substrate by ejection from a syringe, so that the amount of the fluorescent substance-containing composition applied can be reduced. Printing has a limitation that it can be applied only to a planar structure, but the processing speed is fast and it is suitable for mass production. The fluorescent substance-containing composition can be appropriately selected from these coating methods and coated on the substrate.

In the step of applying the fluorescent substance-containing composition to the substrate, the thickness of the fluorescent substance-containing composition applied is preferably in the range of 20 μm or more and 150 μm or less. The thickness at which the phosphor-containing composition is arranged on the surface of the substrate is not particularly limited by the desired chromaticity, but can be arranged, for example, in the range of 20 μm or more and 150 μm or less, and in the range of 30 μm or more and 140 μm or less. It may be arranged in the inner thickness, or may be arranged in the range of 40 μm or more and 120 μm or less. The thickness at which the phosphor-containing composition is arranged on the surface of the substrate can be adjusted by, for example, the thickness of the printing mask when printing is performed. The fluorescent substance-containing composition may be applied to the substrate once or may be repeatedly applied a plurality of times. After being applied, the fluorescent substance-containing composition may be subjected to a drying step described later to be dried and then applied again, or the application and the drying may be alternately and repeatedly applied. Further, the fluorescent substance-containing composition may be subjected to at least one drying step during the coating step repeated a plurality of times.

Step S104 (S204) for obtaining a molded product having irregularities formed on the surface due to the second phosphor particles.
In the step of obtaining a molded body having irregularities caused by the second phosphor particles on the surface, the substrate and the fluorescent substance-containing composition are first heat-treated, and the translucent second ceramics derived from the second inorganic binder are used. The second phosphor particles are fixed on the surface of the substrate, and a molded body having irregularities due to the second phosphor particles formed on the surface is obtained.
After applying the fluorophore-containing composition to the surface of the substrate and arranging the second phosphor particles on the surface of the substrate so as to contain the particles that are intermittently present in the horizontal direction along the surface of the substrate, the first 2 In order to remove the solvent contained in the inorganic binder, a first drying step may be included. In the first drying step, it is preferable to dry for 10 minutes or more and 60 minutes or less in a temperature range of, for example, 50 ° C. or higher and 100 ° C. or lower. The first drying step may be repeated a plurality of times. Even if the temperature in the first drying step is lower than the boiling point of the solvent contained in the second inorganic binder, the solvent may be removed.

The temperature of the first heat treatment is preferably in the range of 150 ° C. or higher and 500 ° C. or lower, more preferably in the range of 180 ° C. or higher and 400 ° C. or lower, and further preferably in the range of 200 ° C. or higher and 350 ° C. or lower. .. The higher the temperature, the higher the purity of the ceramic precursor, but if the temperature is 350 ° C. or lower, the ceramic precursor can be used for a fluorescent material having slightly inferior heat resistance.

The first heat treatment step is preferably performed in an oxygen-containing atmosphere. The oxygen content in the atmosphere is preferably 5% by volume or more, more preferably 10% by volume or more, still more preferably 15% by volume or more, even in an atmosphere (oxygen content is 20% by volume or more). good. In an atmosphere containing less than 1% by volume of oxygen in the atmosphere, the ceramic precursor contained in the inorganic binder may be difficult to react. The amount of oxygen in the atmosphere may be measured by, for example, the amount of oxygen flowing into the firing apparatus, or may be measured at a temperature of 20 ° C. and a pressure of atmospheric pressure (101.325 kPa). The heat treatment may be performed under a slight reduced pressure of about 100 kPa, which is slightly lower than the atmospheric pressure, or may be performed under the atmospheric pressure.

Step of applying the third inorganic binder S205
After obtaining a molded body in which the second fluorescent particles, and in some cases, the third fluorescent particles are fixed to the surface of the substrate with the second ceramics, the third inorganic binder is spin-coated to the second fluorescent particles or the third fluorescence. Apply on top of body particles. As the third inorganic binder, the same as the first inorganic binder or the second inorganic binder can be used. The conditions for applying the third inorganic binder onto the second phosphor particles of the molded product by the spin coating method are not particularly limited, but the molded product is coated at 500 rpm (rpm) or more and 3000 rpm (rpm) or less. The third inorganic binder can be applied onto the second phosphor particles or the third phosphor particles by rotating at a speed of 30 seconds or more and 5 minutes or less. After applying the third inorganic binder on the second phosphor particles, a second heat treatment step may be included in order to remove the solvent contained in the third inorganic binder. The step of the second heat treatment can be performed at the same temperature and time as the second inorganic binder. Further, the second heat treatment step may be repeated a plurality of times.

Step S206 for fixing the second phosphor particles via the third ceramics
This includes the second heat treatment of the applied third inorganic binder to fix the second fluorescent particles, and in some cases, the third fluorescent particles, via the translucent third ceramics derived from the third inorganic binder. You may go out. The second phosphor particles and the like are fixed via the third ceramics. In order to remove the solvent contained in the third inorganic binder, a second drying step having the same temperature range and drying time as the first drying step may be included.

The second heat treatment can be performed in the same temperature range and atmosphere as the first heat treatment. The second heat treatment may be performed at the same temperature as the first heat treatment or at a temperature different from that of the first heat treatment as long as it is in the same temperature range as the first heat treatment. The second heat treatment may be performed in the same atmosphere as the first heat treatment or may be heat-treated in an atmosphere different from that of the first heat treatment, as long as the atmosphere is the same as that of the first heat treatment.

Step of fixing the fourth ceramics S207
It is preferable that the method for producing the molded product includes fixing the second phosphor particles via the third ceramics and then fixing the translucent fourth ceramics by the ALD method. The fourth ceramic is preferably formed on the third ceramic. In the method for producing a molded body, the second is including particles that are intermittently present in the horizontal direction along the surface of the substrate by fixing the fourth ceramics on the third ceramics to which the second phosphor particles are fixed. It is possible to further enhance the adhesion between the phosphor particles or the third phosphor particles and the substrate, and prevent the second phosphor particles or the third phosphor particles from falling off or peeling off. By the ALD method, uniform and dense fourth ceramics can be fixed. When the fourth ceramics are fixed by the ALD method, it is preferable that the material contains the fourth ceramics precursor to be the fourth ceramics, and examples of the fourth ceramics precursor to be the fourth ceramics include trimethylaluminum. Be done. In the ALD method, for example, trimethylaluminum is introduced into the apparatus together with the carrier gas, a trimethylaluminum layer is deposited on the third ceramics, and then the trimethylaluminum in the gas phase is removed by purging, and then in the apparatus. By introducing water vapor (H ₂ O) into the water, trimethylaluminum reacts with water vapor to fix the fourth ceramics made of aluminum oxide (Al ₂ O ₃ ) as the fourth ceramics.

Processing Step The obtained molded product may be processed to be cut into a desired size or thickness. As a cutting method, a known method can be used, and examples thereof include a method of cutting using blade dicing, laser dicing, and a wire saw. Of these, blade dicing is preferable because of its high dimensional accuracy and no debris generation.

Light source device for a projector The molded body and a light emitting device including an excitation light source can be used as a light source for a projector. An example of the projector will be described with reference to FIGS. 9 and 10A to 10C. FIG. 9 is a schematic side view showing an outline of the light source device 300 for a projector.

As shown in FIG. 9, the light source device 300 includes a light source 310, a condenser lens 320 to which the light emitted from the light source 310 is incident, a phosphor wheel 330 to which the emitted light of the condenser lens 320 is incident, and a phosphor wheel. It includes a light receiving lens 340 to which the emitted light of 330 is incident. The phosphor wheel 330 is a disk-shaped phosphor wheel that transmits light from a light source, and is rotated by a drive motor 350 via a drive shaft 352. In FIG. 9, the light source 310, the condenser lens 320, the phosphor wheel 330, and the light receiving lens 340 are included as the light source device 300, but the light source device 300 does not include the light receiving lens 340, and the light source 310. The light source device 300 may be configured by the condenser lens 320 and the phosphor wheel 330.

Next, an outline of the light source device 300 will be described along with the flow of light emitted from the light source 310. In the present embodiment, a case where a semiconductor laser that emits blue light is used as the light source 310 will be described as an example. Blue light is emitted from the light source 310, and the emitted blue light is incident on the condenser lens 320, is condensed by the condenser lens 320, and is incident on the phosphor wheel 330 rotated by the drive motor 350. The phosphor wheel 330 is made of a material that allows light to pass through, and a molded body 33 containing the phosphor is provided in at least a part of the region. Not limited to the molded body 33, any of the molded bodies 31, 32, 34, and 35 can be used. The phosphor wheel 330 may be divided into a region in which the molded body 33 is provided and a region in which the molded body 33 is not provided. If the region is divided into a region provided with the molded body 33 and a region not provided with the molded body 33, when blue light is incident on the phosphor wheel 330 from the condenser lens 320, the first phosphor particles are formed from the phosphor wheel 330. Green light, red light of the second phosphor particles, yellow light of the third phosphor particles, and blue light of the light source 310 are emitted and incident on the light receiving lens 340. Then, it is made into parallel light by the light receiving lens 340 and emitted from the light source device 300. It should be noted that the light receiving lens 340 can not only emit parallel light but also emit light in a direction in which the light spreads, or can condense the light at a predetermined position.

Explanation of Phosphor Wheel Next, the structure of the phosphor wheel 330 used in the light source device 300 for a projector will be described with reference to FIGS. 9 and 10A to 10C. As the phosphor provided on the phosphor wheel 330, the above-mentioned molded product can be used, and for example, the molded product 33 can be used.
The phosphor wheel 330 is a transmissive phosphor wheel that transmits light from the light source 310, and includes a first substrate 332 and a second substrate 334 in order from the light source 310 side. The first substrate 332 and the second substrate 334 are fixed to the drive shaft 352 of the drive motor 350, and are rotated around the drive shaft 352 by the drive force of the drive motor 350. That is, the positions of the first substrate 332 and the second substrate 334 are fixed to each other by the drive shaft 352. However, the method of fixing the relative positions of the first substrate 332 and the second substrate 334 is not limited to the case where the drive shaft 352 is used, and for example, the first substrate 332 and the second substrate 334 are fixed. It can be fixed by any other means such as inserting a spacer between the two.
The phosphor wheel 330 includes, for example, a molded body 33 between the first substrate 332 and the second substrate 334. In the molded body 33 seen from the arrow B in FIG. 9, it is preferable that the substrate containing the first phosphor particles is arranged on the side of the first substrate 332. Further, it is preferable that the second phosphor particles 102a and the third phosphor particles 102c of the molded body 33 are arranged on the second substrate 334 side.

The phosphor wheel 330 transmits light in the wavelength range of the light from the light source 310 to the light source 310 side, and has a wavelength due to the first phosphor particles, the second phosphor particles, or the third phosphor particles contained in the molded body 33. It includes a filter 360 that reflects light in the wavelength range of the converted light. In the embodiment shown in FIG. 9, the filter 360 is provided on the light source side of the first substrate 332. Specifically, as the filter 360, a short-pass filter that transmits light in the wavelength range of blue light and reflects light in the wavelength range of green light, yellow light, and red light can be used.

The phosphor wheel 330 transmits light in the wavelength range of the light wavelength-converted by the first phosphor particles, the second phosphor particles, and the third phosphor particles on the opposite side of the light source 310, and the light from the light source 310. It is provided with a filter 362 that reflects light in the wavelength range of. In the embodiment shown in FIG. 9, the second substrate 334 is provided with a filter 362 on the surface opposite to the light source 310 at a position corresponding to the molded body 33 in the rotation direction. Specifically, as the filter 362, a long-pass filter that transmits light in the wavelength range of green light, yellow light, and red light and reflects light of blue light can be used. For light in the wavelength range between blue light and red light, for example, light in the wavelength range of yellow light or green light, the filter 362 may be made to transmit light in a specific wavelength range. It can also be reflected, and the optimum transmission wavelength range of the filter can be determined according to the application.

Here, the arrangement of the first substrate 332 and the second substrate 334 on each surface will be described with reference to FIGS. 10A to 10C. FIG. 10A is a diagram showing a surface of the phosphor wheel 330 on the light source side of the first substrate 332 as seen from the arrow A in FIG. The first substrate 332 includes a filter 360 in a region where the molded body 33 is provided on the back surface side.

FIG. 10B is a view showing a surface of the phosphor wheel 330 on the light source side of the second substrate 334 as seen from the arrow B in FIG. The second substrate 334 is provided with a region SP in which the molded body 33 is provided in the rotation direction and a blue emission region SB in which the phosphor is not provided.

FIG. 10C is a view showing a surface of the phosphor wheel 330 on the opposite side of the second substrate 334 as seen from the arrow C in FIG. 9 with respect to the light source. The second substrate 334 is provided with a filter 362 on the surface opposite to the surface on the light source side so as to correspond to the region SP provided with the molded body 33 on the surface on the light source side. Further, the blue emission region SB does not have a phosphor. However, it is also possible to deposit a dielectric multilayer film on the blue emission region SB, form an antireflection film, or form a layer containing a scatterer.

In the phosphor wheel 330 shown in FIGS. 9A to 10C, the substrate of the molded body 33 is arranged on the surface of the first substrate 332 opposite to the light source 310, and the substrate of the second substrate 334 is on the light source 310 side. The second phosphor particles 102a and the third phosphor particles 102c of the molded body are arranged on the surface.

Explanation of Projector Next, a case where the above-mentioned light source device 300 is used as a light source device in a so-called one-chip type DLP projector will be described with reference to FIG. Note that FIG. 11 is a schematic diagram for showing the configuration of the projector 400 according to one embodiment provided with the above-mentioned light source device 300, and is a schematic plan view of the light source device 300 and the projector 400 as viewed from above. Is.
In FIG. 11, the light emitted from the light source device 300 is incident on the DMD (Digital Micromirror Device) element (optical modulation means) 470, which is an optical space modulator, via the optical system. Then, it is reflected by the DMD element 470, condensed by the projection lens 480 which is a projection means, and projected on the screen 490. The DMD element 470 is a matrix of fine mirrors corresponding to each pixel of the image projected on the screen 490, and the light emitted to the screen by changing the angle of each mirror is emitted in microsecond units. Can be turned on / off. In addition, by changing the gradation of the light incident on the projection lens according to the ratio of the time when each mirror is on and the time when it is off, it is possible to display the gradation based on the image data of the projected image. Become.

In the present embodiment, the DMD element is used as the light modulation means, but the present invention is not limited to this, and any other light modulation element can be used depending on the application. Further, the light source device 300 according to the present invention and the projector 400 using the light source device 300 are not limited to the above-described embodiment, and various other embodiments are included in the present invention.
Further, in the present embodiment, the light receiving lens 340 is included in the light source device 300, but the present invention is not limited to this. For example, the light receiving lens 340 may not be included in the light source device 300 but may be included in a part of the optical system.

As described above, the projector 400 in the present embodiment is a DMD element that sequentially modulates the light of a plurality of wavelength bands emitted from the light source device 300 based on the above-mentioned light source device 300 and the image data to form an image. It includes a 470 and a projection lens 480 that magnifies and projects an image.
By the above steps, it is possible to easily manufacture a molded body and a light emitting device having excellent color rendering properties and heat resistance.

Hereinafter, this embodiment will be specifically described with reference to Examples. The present embodiment is not limited to these examples.

First phosphor particle a
The first phosphor particles a have a composition represented by Y _2.955 Ce _0.045 Al ₅ O ₁₂ (hereinafter, also referred to as “YAG”), and the average particle size measured by the FSSS method is 14. 9 μm rare earth aluminate phosphor particles were used. The first phosphor particles a had an emission peak wavelength in the range of 530 nm or more and 590 nm or less. The true density of the YAG first phosphor particles b was 4.60 g / cm ³ .

First phosphor particle b
The first phosphor particles b have a composition represented by Lu _2.984 Ce _0.016 Al ₅ O ₁₂ (hereinafter, also referred to as “LAG”), and the average particle size measured by the FSSS method is 21. 5 μm rare earth aluminate phosphor particles were used. The first phosphor particles b had an emission peak wavelength in the range of 490 nm or more and 555 nm or less. The true density of the LAG first phosphor particles a was 6.69 g / cm ³ .

Second Fluorescent Particle The second fluorescent particle has a composition represented by (Sr, Ca) AlSiN ₃ : Eu (hereinafter, also referred to as “SCASSN”) and has an average particle size of 12 as measured by the FSSS method. .5 μm nitride fluorophore particles were used. The second phosphor particles had an emission peak wavelength in the range of 600 nm or more and 670 nm or less.

Inorganic binder An inorganic binder containing polysilanol in the range of 1% by mass or more and 10% by mass or less and containing isopropyl alcohol as a solvent was used.

Third Fluorescent Particle As the third fluorescent particle, the same as the first fluorescent particle was used as the third fluorescent particle.

Example 1: Step of preparing a substrate A substrate containing 13% by mass of YAG first phosphor particles a and 87% by mass of aluminum oxide as the first ceramics, having a relative density of 99.7% and a thickness of 0.18 mm. Prepared. In Examples and Reference Examples, the relative density of the substrate can be calculated based on the following formulas (1) to (3).

Example 1: Step of preparing a fluorescent substance-containing composition 50% by mass of the second fluorescent substance particles and 50% by mass of the second inorganic binder with respect to 100% by mass of the total amount of the second fluorescent substance particles and the second inorganic binder. % Was mixed to produce a fluorescent substance-containing composition. The second inorganic binder contains a silica precursor composed of polysilanol as a second ceramic precursor.

Example 1: Step of applying the fluorescent substance-containing composition to the substrate The fluorescent substance-containing composition was applied to the surface of the substrate by printing using a mask. The thickness of the mask used was 58 μm. By applying the fluorescent substance-containing composition, the second fluorescent substance particles were arranged on the surface of the substrate.
The substrate coated with the fluorescent substance-containing composition was placed on a hot plate and dried at 80 ° C. for 3 minutes in a first drying step to remove the solvent contained in the second inorganic binder.

Example 1: Step of obtaining a molded product A substrate coated with a dried phosphor-containing composition is placed on a hot plate and placed in an atmospheric atmosphere (oxygen content of 20% by volume or more, atmospheric pressure 101.325 kPa), 150. After 5 minutes at ° C, 5 minutes at 200 ° C, and 5 minutes at 250 ° C, the temperature is gradually raised, and after the temperature is raised, heat treatment is performed at 300 ° C for 30 minutes. The second phosphor particles containing the particles that are intermittently present in the horizontal direction along the surface of the substrate are fixed to the surface of the substrate through the second ceramics of the substrate, and the unevenness caused by the second phosphor particles is formed on the surface. Was obtained.

Example 2
A phosphor-containing composition was produced by mixing 55% by mass of the second phosphor particles and 45% by mass of the inorganic binder with respect to 100% by mass of the total amount of the second phosphor particles and the inorganic binder. A molded product having the second phosphor particles fixed to the substrate via the second ceramics was obtained in the same manner as in Example 1 except that this fluorescent substance-containing composition was used.

Example 3
A phosphor-containing composition was produced by mixing 60% by mass of the second phosphor particles and 40% by mass of the inorganic binder with respect to 100% by mass of the total amount of the second phosphor particles and the inorganic binder. A molded product having the second phosphor particles fixed to the substrate via the second ceramics was obtained in the same manner as in Example 1 except that this fluorescent substance-containing composition was used.

Example 4
A phosphor-containing composition was produced by mixing 70% by mass of the second phosphor particles and 30% by mass of the inorganic binder with respect to 100% by mass of the total amount of the second phosphor particles and the inorganic binder. A molded product having the second phosphor particles fixed to the substrate via the second ceramics was obtained in the same manner as in Example 1 except that this fluorescent substance-containing composition was used.

Example 5
Using the same substrate as in Example 1, the mask was fixed to the substrate via the second ceramics in the same manner as in Example 1 except that the thickness of the mask for printing was 116 μm (two masks). A molded product having the second phosphor particles was obtained.

Reference example 1
Using the same substrate as in Example 1, the mask was fixed to the substrate via the second ceramics in the same manner as in Example 1 except that the thickness of the mask for printing was 174 μm (three masks). A molded product having the second phosphor particles was obtained.

Example 6
After obtaining a molded product having the second phosphor particles fixed to the substrate via the second ceramics in the same manner as in Example 1, the following step of applying the third inorganic binder and the second via the third ceramics. A step of fixing the phosphor particles was carried out. Hereinafter, the step of applying the third inorganic binder and the step of fixing the second phosphor particles via the third ceramics are also referred to as a third ceramics forming step.

Example 6: Third Ceramics Forming Step A third inorganic binder similar to the second inorganic binder was spin-coated (1000 rpm (rpm), 30 seconds) on the second phosphor particles and applied. After applying the third inorganic binder, dry it once on a hot plate at 80 ° C. for 3 minutes, and then leave it at 150 ° C. for 5 minutes, 200 ° C. for 5 minutes, and 250 ° C. for 5 minutes to gradually ascend. After warming and heat-treating at 300 ° C. for 30 minutes, a third ceramic is formed, and the second phosphor particles fixed to the substrate with the second ceramic are fixed to the substrate via the third ceramic. Got

Example 7
The second phosphor particles fixed to the substrate with the second ceramics in the same manner as in Example 6 except that the step of applying the third inorganic binder and the drying step of the third ceramics forming step were repeated three times in this order. Was fixed to the substrate via the third ceramics to obtain a molded product.

Example 8
Similar to Example 7, the second phosphor particles fixed to the substrate via the second ceramics are fixed to the substrate via the third ceramics to obtain a molded body, and then magnetron sputtering is performed on the third ceramics. By the method, SiO ₂ is formed into a film having a thickness of 400.0 nm to form a translucent fourth ceramic made of silicon dioxide, and the second phosphor particles fixed to the substrate via the second ceramic and the second one. 2 A molded body having a third ceramic on which phosphor particles were fixed and a fourth ceramic on the third ceramic was obtained.

Example 9
Example 8 and Example 8 except that SiO ₂ was formed to a thickness of 1200.0 nm from the top of the third ceramic by a CVD (Chemical Vapor Deposition) method and a translucent fourth ceramic made of silicon dioxide was fixed. Similarly, a molded body having the second ceramic particles fixed to the substrate via the second ceramics, the third ceramics to which the second ceramic particles are fixed, and the fourth ceramics on the third ceramics is obtained. rice field. The step of fixing the fourth ceramic on the third ceramic is also referred to as a fourth ceramic forming step.

Example 10
Using the ALD method from above the third ceramic, trimethylaluminum and steam were used as the fourth ceramic precursor, which is the raw material of the fourth ceramic, and aluminum oxide (Al ₂ O ₃ ) was used as the fourth ceramic at 100 ° C. of substrate heating. Second phosphor particles fixed to the substrate via the second ceramic in the same manner as in Example 8 except that a film was formed with a thickness of 5 nm and a translucent fourth ceramic made of aluminum oxide was fixed. A molded body having the third ceramics to which the second phosphor particles were fixed and the fourth ceramics on the third ceramics was obtained.

Example 11
A substrate having 26.7% by mass of LAG first phosphor particles b, 73.3% by mass of aluminum oxide as the first ceramics, a relative density of 98.8%, and a thickness of 0.17 mm was prepared. Except for the fact that this substrate was used, the second ceramics particles fixed to the substrate via the second ceramics, the third ceramics to which the second ceramic particles were fixed, and the second ceramics were obtained in the same manner as in Example 10. A molded body having the fourth ceramic on the three ceramics was obtained.

SEM Photographs Using a scanning electron microscope (product name: JSM-IT200, manufactured by JEOL Ltd.), SEM photographs of planes or cross sections of the molded bodies of each Example and Reference Example were obtained. FIG. 12 is a planar SEM photograph of the substrate on the side where the second phosphor particles are present before forming the third ceramics and the fourth ceramics according to the eleventh embodiment. FIG. 13 is a flat surface SEM photograph in which the flat surface of the substrate on the side where the second phosphor particles are present before forming the third ceramics and the fourth ceramics is binarized according to the eleventh embodiment. FIG. 14 is a partial cross-sectional SEM photograph showing the state of the substrate, the second phosphor particles, and the second ceramics before forming the third ceramics and the fourth ceramics according to the eleventh embodiment.

SEM-EDS element mapping Elements (Lu, Al, Element mapping of O), elements contained in the first ceramics (Si, O), elements contained in the second phosphor particles (Ca, Sr, Al, Si), and elements contained in the second ceramics (Si, O). Was produced. The measurement conditions in the SEM-EDS were an acceleration voltage of 20 kV, a focal length of 11.7 mm, and a sample tilt angle of 0 °. FIG. 15 is a diagram showing a cross-sectional SEM-EDS mapping showing the states of the substrate, the second phosphor particles, and the second ceramics before forming the third ceramics and the fourth ceramics according to the eleventh embodiment. FIG. 16 is an SEM-EDS element mapping diagram showing a portion where Si is present in a partial cross-sectional SEM photograph of a molded body before forming the third ceramics and the fourth ceramics according to the eleventh embodiment. FIG. 17 is an SEM-EDS element mapping diagram showing a portion where Sr is present in a partial cross-sectional SEM photograph of a molded body before forming the third ceramics and the fourth ceramics according to the eleventh embodiment. FIG. 18 is an SEM-EDS element mapping diagram showing a portion where Ca is present in a partial cross-sectional SEM photograph of a molded body before forming the third ceramics and the fourth ceramics according to the eleventh embodiment.

Surface roughness Ra
In each of the molded bodies of Examples and Reference Examples, the plane of the molded body on the side where the second phosphor particles are present is measured using a stylus type profiler (trade name: Alpha Step IQ3, manufactured by KLA-Tencor). The surface roughness Ra was measured under the conditions of 2 mm, a measuring speed of 50 μm / sec, and the use of a Gaussian filter.

Coverage rate In each of the molded bodies of Examples and Reference Examples, image analysis software (trade name: GIMP2, free software) is used for the SEM image (photographing magnification 700 times) of the plane of the molded body on the side where the second phosphor particles are present. Image analysis was performed using the image, the second phosphor particles were binarized, the area of the SEM image to be measured was set to 100%, and the total area of the binarized second phosphor particles was the first. 2 Calculated as the coverage of phosphor particles.

Chromaticity x, y and color rendering index Ra by LED irradiation
Each of the molded bodies of Examples and Reference Examples is irradiated with blue light having a wavelength of 455 nm from a bullet-shaped LED, and is used at room temperature using a handy LED spectral radiation measuring instrument (product: MK-350, manufactured by UPRtek). The transmitted light emitted from the side where the second phosphor particles of each molded body are present is measured, and from this measured value, the chromaticity in the CIE (Commission Internationale de l'eclarrage) 1931 color system. The x and y chromaticity coordinates in the figure were obtained. The average color rendering index Ra was measured according to JIS Z8726. The input current at the time of measuring the color rendering index Ra was 20 mA for the rated forward current, and the forward voltage at that time was 3 V. The results are shown in Table 1.

Peeling test For each molded product of Examples and Reference Examples, polyimide tape (trade name: Nо360A, manufactured by Nitto Denko Co., Ltd., adhesive strength 408 g / 19 mm) or dicing tape (trade name: D-510T, Lintec Corporation) A tape was attached to the side of the second phosphor particles fixed to the substrate via the second ceramics using an adhesive force of 2200 g / 25 mm), and a peeling test of the second phosphor particles was performed. The results are shown in Table 2. When the tape was peeled off from the molded body, if there was no peeling of the second phosphor particles, it was defined as "no peeling". When a large amount of the second phosphor particles were peeled off, it was regarded as "large peeling".

The molded products according to Examples 1 to 5 had a color rendering index of more than 70 and were excellent in color rendering properties. The molded body according to Examples 1 to 5 has a total surface area (coverage) of 97% or less in which the second phosphor particles are present with respect to 100% of the unit area of the surface of the substrate, and the first fluorescence in the substrate. Mixed color light of light wavelength-converted by body particles, light from an excitation light source that has passed through a translucent substrate without wavelength conversion by the first phosphor particles, and light wavelength-converted by the second phosphor particles. Was obtained, and the desired mixed-color light could be extracted from the molded body, and the demand for thinning could be satisfied.

The molded body of Reference Example 1 had a mask thickness of 174 μm, and the fluorescent substance-containing composition was applied by printing to fix the second phosphor particles to the substrate with the second ceramics, so that the molded body was intermittent in the horizontal direction along the surface of the substrate. The second fluorescent particles were not contained, the second fluorescent particles were present on the entire surface of the substrate, and the unevenness caused by the second fluorescent particles was not formed on the surface. Therefore, the light emitted from the substrate 101 was wavelength-converted by the second phosphor particles, the light emitted from the molded body was shifted to the long wavelength side, and the color rendering index became 0.

According to Table 2, the molded product according to Example 1 in which the third ceramics and the fourth ceramics are not formed has a large peeling in the tape peeling test. On the other hand, the third ceramics forming step was carried out, and the molded products according to Examples 6 and 7 having the third ceramics did not have the second phosphor particles peeled off even in the peeling test of the polyimide tape. In particular, the molded product according to Example 7 in which the coating and drying step was performed three times in the third ceramics forming step was more resistant to peeling of the dicing tape than the molded product according to Example 6 in which the coating and drying step was performed once. As a result, the peeling of the second phosphor particles was reduced, and improvement was observed. Further, the molded bodies according to Examples 8 to 11 in which the fourth ceramics forming step was carried out showed improvement in the molded bodies according to Examples 9 to 11 with respect to the peeling of the dicing tape, and the molded bodies according to Example 9 showed improvement. Further improvement was observed, and the second phosphor particles did not peel off in the molded products according to Examples 10 and 11. It is said that the molded bodies according to Examples 10 and 11 could form the fourth ceramics in a form that follows the unevenness of the second phosphor particles, probably by the ALD method, and the fixing strength of the second phosphor particles was improved. Guessed. Whether or not the durability of the tape peeling test is necessary when the molded product is actually used depends on the mode of use, but if necessary, the molded product is made of the third ceramics by the third ceramics and the fourth ceramics forming step. And it is desirable to have a fourth ceramic.

Chromaticity x, y and color rendering index Ra due to LD irradiation
The molded body of Example 11 was pulsed with blue light having a wavelength of 453 nm from the LD (0.05 ms / 5 ms, 3A, LD output 35 W), and using an integrating sphere measuring instrument, the molded body of Example 11 was subjected to the pulse of the example 11 at room temperature. The transmitted light emitted from the side where the second phosphor particles of the molded body are present is measured, and the x and y chromaticity coordinates of the chromaticity diagram in the CIE) 1931 color system are obtained from this measured value, and further, JIS Z8726. The average color development evaluation number Ra was measured according to the above. As a result, the chromaticity x = 0.40, the chromaticity y = 0.45, the average color rendering index Ra = 72.9, and the luminous flux = 4508 lm.

FIG. 12 is a planar SEM photograph of the substrate on the side where the second phosphor particles are present before forming the third ceramics and the fourth ceramics according to the eleventh embodiment. On the surface of the substrate according to Example 11, the second phosphor particles fixed with the second ceramics are intermittently present on the surface of the molded body, and the surface of the molded body has irregularities due to the second phosphor particles. It was formed. Therefore, in the molded body according to the eleventh embodiment, the light transmitted through the substrate is wavelength-converted at the portion where the second phosphor particles are present, and a part of the light transmitted from the substrate and the first fluorescence of the substrate are formed. A part of the light wavelength-converted by the body particles is emitted to the outside of the molded body as it is without being wavelength-converted by the second phosphor particles. Therefore, it is possible to obtain a mixed color light of the light wavelength-converted by the second phosphor particles, the light transmitted through the substrate as it is by the excitation light, and the light wavelength-converted by the first phosphor particles from the molded body. did it. In addition, the molded product according to Example 11 had an excellent color rendering property with a color rendering index Ra of more than 70 by irradiation with LED or LD.

FIG. 13 is a diagram showing a state in which a planar SEM photograph of the substrate on the side where the second phosphor particles exist before forming the third ceramics and the fourth ceramics is binarized according to the eleventh embodiment. The coverage of the second phosphor particles was 66.9%, which is the total area of the binarized second phosphor particles with the area of the SEM image to be measured as 100%. In the horizontal direction along the surface of the molded body, the portion where the second phosphor particles 102a are present and the portion where the second phosphor particles are not present and the surface of the substrate 101 can be confirmed can be binarized. rice field. Since the surface of the substrate 101 can be confirmed in the portion of the molded body where the second phosphor particles do not exist, the second phosphor particles do not exist with the voids interposed in the horizontal direction along the surface of the substrate, and the second phosphor particles do not exist. The two fluorescent particles were not in a state where the second fluorescent particles were present with the voids interposed therebetween. Therefore, in the molded body, the light transmitted through the substrate is wavelength-converted at the portion where the second phosphor particles are present, and the wavelength is converted between a part of the light transmitted from the substrate and the first phosphor particles of the substrate. A part of the generated light was emitted to the outside of the molded body as it was without being wavelength-converted by the second phosphor particles. Therefore, it is possible to obtain a mixed color light of the light wavelength-converted by the second phosphor particles, the light transmitted through the substrate as it is by the excitation light, and the light wavelength-converted by the first phosphor particles from the molded body. did it.

FIG. 14 is a partial cross-sectional SEM photograph of the molded body before forming the third ceramics and the fourth ceramics according to the eleventh embodiment. According to the eleventh embodiment, the molded body before forming the third ceramics and the fourth ceramics has a portion E in which the second phosphor particles 102a are intermittently present in the horizontal direction along the surface of the substrate 101 and a second portion E. The portion N in which the 2 phosphor particles did not exist could be confirmed, and irregularities due to the 2nd phosphor particles 102a were formed on the surface. Further, it was confirmed that the substrate 101 contained the first phosphor particles 101a and the first ceramics 101b.

FIG. 15 is an SEM-EDS element mapping diagram in a partial cross-sectional SEM photograph of a molded body before forming the third ceramics and the fourth ceramics according to the eleventh embodiment. On the surface of the substrate 101, Sr and Ca, which are the elements constituting the second phosphor particles 102a, are detected in the portion where the second phosphor particles 102a are present, and the second phosphor particles 102a are surrounded by the second element. Si contained in the second ceramics for fixing the phosphor particles 102a and the substrate 101 or the second phosphor particles 102a was detected. Sr and Ca constituting the second phosphor particles 102a were not detected in the portion N in which the second phosphor particles 102a did not exist along the horizontal direction of the surface of the substrate 101. Further, Si contained in the second ceramics 102b was hardly detected in the portion N in which the second phosphor particles 102a did not exist along the horizontal direction of the surface of the substrate 101. Lu constituting the first phosphor particles 101a was detected in the portion of the substrate 101 where the first phosphor particles 101a existed. Further, Si constituting silicon dioxide (SiO ₂ ), which is the second ceramic 102b, was detected in the portion of the substrate 101 where the second ceramic 102b exists.

FIG. 16 is an SEM-EDS element mapping diagram showing a portion where Si is present in a partial cross-sectional SEM photograph of a molded body before forming the third ceramics and the fourth ceramics according to the eleventh embodiment. FIG. 17 is an SEM-EDS element mapping diagram showing a portion where Sr is present in a partial cross-sectional SEM photograph of a molded body before forming the third ceramics and the fourth ceramics according to the eleventh embodiment. FIG. 18 is an SEM-EDS element mapping diagram showing a portion where Ca is present in a partial cross-sectional SEM photograph of a molded body before forming the third ceramics and the fourth ceramics according to the eleventh embodiment. Comparing FIGS. 16 to 18, the presence of Si contained in the second ceramic 102b (SiO ₂ ) and the presence of Sr and Ca contained in the second phosphor particles ((Sr, Ca) AlSiN ₃ : Eu). The locations were almost the same, and it was confirmed that the second phosphor particles 102a were fixed by the second ceramics 102b.

All of the molded products according to the examples and the reference examples showed a large value of surface surface Ra exceeding 5 μm. From this result, it was confirmed that the molded bodies according to the examples and the reference examples had irregularities formed on the surface due to the second phosphor particles. The surface of the translucent substrate made of an inorganic material containing general first phosphor particles having no irregularities due to the second phosphor particles on the surface has a surface roughness Ra even on a roughly polished polished surface. Is 1 μm or less, and even if particles are applied to the polished surface using a resin binder, the surface roughness Ra is 2 μm or less. The second ceramics derived from the second inorganic binder fixing the second phosphor particles have a very thin thickness as shown in the SEM image of FIG. 12, and the second ceramic particles are fixed by the second ceramics. Since the resulting unevenness is formed, the surface roughness Ra of the molded body becomes large. If the light extraction surface is uneven, the light extraction efficiency is improved, and such an effect can be expected.
Compared to using an organic material for fixing the second phosphor particles, the second ceramics are used for fixing the second phosphor particles, so that the heat resistance is excellent.

In one aspect of the present invention, the molded body is used as a wavelength conversion member of a lighting device for in-vehicle or general lighting, a backlight of a liquid crystal display device, and a light emitting device used as a light source for a projector in combination with an excitation light source of an LED or LD. can do.

2: Top wiring, 3: External connection electrode, 3a: Anode electrode, 3b: Cathode electrode, 4: Via 8: Conductive adhesive, 10: Submount substrate, 15: Element structure, 20: Light source element, 25: Protective element, 30: light transmissive member (molded body), 31, 32, 33, 34, 35: molded body, 40: light source member, 50: first covering member, 60: second covering member, 80: module Substrate, 100: Light source, 101: Substrate, 101a: First phosphor particles, 101b: First ceramics, 102a: Second phosphor particles, 102b: Second ceramics, 102c: Third phosphor particles, 103: First 3 ceramics, 104: 4th ceramics, 200: light emitting module, 300: light source device, 310: light source, 320: condenser lens, 330: phosphor wheel, 332: first substrate, 334: second substrate, 340 : Light receiving lens, 350: Drive motor, 352: Drive shaft, 360: Filter, 362: Filter, 400: Projector, 470: DMD element, 480: Projection lens, 490: Screen, L1: Distance between adjacent submount substrates , L2: Distance between adjacent light transmissive members

Claims (29)

A translucent substrate made of an inorganic material containing the first phosphor particles,
The second phosphor particles arranged on the substrate and
A molded product containing the translucent second ceramics for fixing the second phosphor particles to the substrate.
A molded product having irregularities formed on the surface of the molded product due to the second phosphor particles. The molded product according to claim 1, wherein the substrate further contains at least one of the first ceramics and glass. The molded product according to claim 1 or 2, wherein the total surface area of the second phosphor particles is 50% or more and 97% or less when the unit area of the surface of the substrate is 100% in a plan view. The molded product according to claim 2 or 3, wherein the first ceramic is at least one selected from the group consisting of aluminum oxide, aluminum nitride, mullite, and silicon nitride. The molded product according to any one of claims 1 to 4, wherein the translucent third ceramics is fixed on the second phosphor particles. The molded product according to any one of claims 1 to 5, wherein the maximum heights of the second phosphor particles and the second ceramics are within the range of 1 μm or more and 150 μm or less. Claims 1 to 6 further include a third phosphor particle that is fixed by the second ceramic and emits light in a wavelength range different from that of the second phosphor particle in the horizontal direction along the surface of the substrate. The molded body according to any one of the above items. The molded product according to claim 7, wherein the third phosphor particles are wavelength-converted from the light from the excitation light source. The first phosphor particles have an emission peak wavelength in the range of 530 nm or more and 590 nm or less.
The molded product according to any one of claims 1 to 8, wherein the second phosphor particles have an emission peak wavelength in the range of 600 nm or more and 670 nm or less. The first phosphor particles are at least one kind of aluminate phosphor, and the first phosphor particles are
Any of claims 1 to 9, wherein the second phosphor particles are at least one selected from the group consisting of fluoride phosphors, alkaline earth metal silicon nitride phosphors, and α-sialone phosphors. The molded body according to item 1. The molded product according to any one of claims 7 to 10, wherein the third phosphor particles are at least one aluminate phosphor having an emission peak wavelength in the range of 530 nm or more and 590 nm or less. The first phosphor particles have an emission peak wavelength in the range of 490 nm or more and 555 nm or less.
The molded product according to any one of claims 1 to 8, wherein the second phosphor particles have an emission peak wavelength in the range of 600 nm or more and 690 nm or less. The molded product according to any one of claims 5 to 11, wherein the translucent fourth ceramics is fixed on the second phosphor particles. The molded product according to any one of claims 1 to 13, wherein the second ceramic is silicon dioxide. The molded product according to any one of claims 5 to 14, wherein the third ceramic is silicon dioxide. The molded product according to any one of claims 13 to 15, wherein the fourth ceramic is aluminum oxide. A light emitting device comprising the molded body according to any one of claims 1 to 16 and an excitation light source. The light emitting device according to claim 17, wherein the excitation light source is a semiconductor laser. The light emitting device according to claim 17 or 18, wherein the average color rendering index Ra is 70 or more. Preparing a translucent substrate made of an inorganic material containing the first phosphor particles, and
To prepare a phosphor-containing composition containing the second phosphor particles and the second inorganic binder,
By applying the fluorescent substance-containing composition to the substrate,
The substrate and the fluorescent substance-containing composition are first heat-treated, and the second phosphor particles are fixed on the surface of the substrate via the translucent second ceramics derived from the second inorganic binder, and the surface is covered with the second phosphor particles. A method for producing a molded body, which comprises obtaining a molded body having irregularities formed by the second phosphor particles. The method for producing a molded product according to claim 20, wherein in the step of preparing the substrate, the substrate further comprises at least one of the first ceramics and glass. After the step of obtaining the molded product, a third inorganic binder is applied onto the second phosphor particles by a spin coating method.
The 20 or 21 according to claim 20, wherein the third inorganic binder is subjected to a second heat treatment to fix the second phosphor particles via a translucent third ceramic derived from the third inorganic binder. How to manufacture a molded product. The method for producing a molded body according to claim 22, wherein the second phosphor particles are fixed via the third ceramics, and then the translucent fourth ceramics are fixed by an atomic layer deposition method. .. At least one of the first inorganic binder, the second inorganic binder and the third inorganic binder contains a ceramic precursor, and the ceramic precursor is at least one silica precursor selected from polysilanol and polysilazane. , The method for producing a molded product according to any one of claims 20 to 23. In the step of preparing the fluorescent substance-containing composition, when the fluorescent substance-containing composition is 100% by mass, the content of the ceramic precursor in the fluorescent substance-containing composition is 0.5% by mass or more and 70. The method for producing a molded product according to any one of claims 20 to 24, which is within the range of mass% or less. In the step of preparing the fluorescent substance-containing composition, claims 20 to 25 further include the third fluorescent substance particles that emit light in a wavelength range different from that of the second fluorescent substance particles. The method for producing a molded product according to any one of the above items. The invention according to any one of claims 20 to 26, wherein in the step of applying the fluorescent substance-containing composition to the substrate, the fluorescent substance-containing composition is applied to the substrate by spray spraying, potting, or printing. Manufacturing method of the molded product. The method for producing a molded product according to any one of claims 20 to 27, wherein the temperatures of the first heat treatment and the second heat treatment are in the range of 150 ° C. or higher and 500 ° C. or lower. The invention according to any one of claims 20 to 28, wherein in the step of applying the fluorescent substance-containing composition to the substrate, the thickness of the fluorescent substance-containing composition applied is within the range of 20 μm or more and 150 μm or less. The method for manufacturing a molded product according to the description.

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