TW201517329A - Light emitting element, light emitting device and manufacturing methods thereof - Google Patents

Abstract

The invention provides a light emitting element, a light emitting device and manufacturing methods thereof, which can increase heat tolerance and achieve miniaturization. A plurality of semiconductor light emitting chips 12 composed of LEDs are carried on a substrate 11. On the semiconductor light emitting chips 12, there is a wavelength conversion member 14 connected with the semiconductor light emitting chips 12. The wavelength conversion member 14 is formed by means of coating phosphor film raw material on one surface formed as base material 14A and proceeding with a reaction at the room temperature or a thermal treatment at a temperature less than 500 DEG C. The phosphor film raw material includes phosphor material and adhesive raw material. The adhesive raw material includes at least one selected from the group consisting of silicon oxide precursor, silicic acid compound, silica and amorphous silica that can be converted into silicon oxide via hydrolysis or oxidization.

Description

Light-emitting element, light-emitting device and manufacturing method thereof

The present invention relates to a light-emitting element using a phosphor material, a light-emitting device, and a method of manufacturing the same.

For example, Patent Document 1 or Patent Document 2 is known in which a phosphor is dispersed in an epoxy resin or an oxime resin. However, in the light-emitting device, as the LED is increased in output or the LED is heated, the epoxy resin or the fluorene ketone resin is deteriorated, deformed, and peeled off, and there is a problem that it is difficult to increase the output. As a countermeasure against this, for example, a light-emitting device in which a phosphor is dispersed in a glass in which an epoxy resin or an oxime resin is substituted has been developed (for example, refer to Patent Document 3 to Patent Document 5). According to this light-emitting device, the heat resistance of the structure can be improved by using an inorganic material in the dispersion medium.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent No. 3364229

[Patent Document 2] Japanese Patent No. 3824917

[Patent Document 3] Japanese Patent Laid-Open Publication No. 2009-91546

[Patent Document 4] Japanese Patent Laid-Open Publication No. 2008-143978

[Patent Document 5] Japanese Patent Laid-Open Publication No. 2008-115223

However, when the general low-melting glass is not heated to substantially 500 ° C or more, it is difficult to soften it to such an extent that the phosphor can be dispersed (refer to the cited example 4). For example, it is possible to lower the melting point by adding a heavy metal such as lead, but from the viewpoint of the influence on the environment or the human body, the use of those elements is now extremely rare. Therefore, the use of the phosphor has a problem that the performance is deteriorated due to the influence of heat.

Further, when the phosphor is dispersed in the glass, the filling rate of the phosphor cannot be increased in order to maintain the strength of the glass to be the base material, and the excitation light is transmitted in excess of the high luminance of the LED. problem. In order to suppress this transmission, it is necessary to thicken the thickness of the glass in which the phosphor has been dispersed. As a result, the thickness of the light-emitting device cannot be reduced, and the light transmittance is lowered by the increase in the thickness of the glass, and there is also a problem that the heat radiation is hindered.

The present invention has been made in view of such a problem, and an object thereof is to provide a light-emitting element, a light-emitting device, and a method of manufacturing the same that can improve heat resistance and can be downsized.

The light-emitting device according to claim 1 includes a semiconductor light-emitting wafer and a wavelength conversion member disposed in contact with the semiconductor light-emitting wafer; the wavelength conversion member has a base material and a phosphor film; and the phosphor film is formed therein. At least one surface of the substrate includes a particulate phosphor material and a binder; the phosphor film is formed by coating a phosphor film material on at least one side of the substrate to react at a normal temperature or 500 ° C Formed by heat treatment at a temperature comprising a phosphor material and a binder raw material, the binder raw material comprising a cerium oxide precursor comprising a cerium oxide by hydrolysis or oxidation, a ceric acid compound, At least one of a group of vermiculite and amorphous vermiculite.

The method for producing a light-emitting device according to claim 7 is a method of manufacturing a light-emitting device including a semiconductor light-emitting chip and a wavelength conversion member disposed in contact with the semiconductor light-emitting wafer, wherein the wavelength conversion member has a substrate and a phosphor. a film, wherein the phosphor film is formed on at least one surface of the substrate, and comprises a particulate phosphor material and a binder; and the phosphor film is coated with fluorescent light on at least one side of the substrate by a printing method. The bulk film material is formed by reacting at room temperature or heat-treating at a temperature of 500 ° C or lower, the phosphor film material comprising a phosphor material and a binder material, the binder material comprising comprising by hydrolysis or oxidation Further, it is at least one selected from the group consisting of cerium oxide precursors of cerium oxide, ceric acid compounds, vermiculite, and amorphous vermiculite.

The light-emitting element according to claim 8 is characterized in that the wavelength conversion member is disposed on the semiconductor light-emitting chip by an adhesive, and the wavelength conversion member has a base material and a phosphor film formed thereon, and the phosphor film is formed thereon. At least one side includes a particulate phosphor material and a binder: the phosphor film is formed by coating a phosphor film material on at least one side of the substrate to be reacted at a normal temperature or at a temperature of 500 ° C or lower. Formed by heat treatment, the phosphor film raw material comprises a phosphor material and a binder raw material, and the binder raw material comprises a cerium oxide precursor including a cerium oxide by hydrolysis or oxidation, a ceric acid compound, vermiculite, and non- At least one of the group of crystalline vermiculite; the binder is reacted at room temperature by using the binder raw material Or heat-treating at a temperature of 500 ° C or lower, the binder raw material comprising a cerium oxide precursor comprising cerium oxide by hydrolysis or oxidation, a ceric acid compound, a phosphoric acid compound, and at least a part of carbon detachment by heating At least one of the group of inorganic resins bonded to the inorganic bond.

The light-emitting device described in claim 14 is provided with the light-emitting element described in claim 8.

The method for producing a light-emitting device according to claim 15 is a method for producing a light-emitting device in which a wavelength conversion member is disposed on a semiconductor light-emitting wafer by an adhesive, and the wavelength conversion member has at least a substrate and a substrate formed thereon. a phosphor film on one side, the phosphor film includes a particulate phosphor material and a binder; and the phosphor film is coated on the at least one side of the substrate by a printing method to coat the phosphor film material Formed at room temperature or heat treated at a temperature below 500 ° C. The phosphor film material comprises a phosphor material and a binder material, the binder material comprising a cerium oxide precursor comprising cerium oxide by hydrolysis or oxidation. At least one of a group of a substance, a phthalic acid compound, a vermiculite, and an amorphous vermiculite, the semiconductor light-emitting chip and the wavelength conversion member are carried by an adhesive agent by using the adhesive raw material at a normal temperature The lower reaction is obtained by heat treatment at a temperature of 500 ° C or lower, and the binder raw material includes a cerium oxide precursor including cerium oxide by hydrolysis or oxidation, and ceric acidification Thereof, phosphoric acid compounds, and by heating at least a portion of at least one carbon to become disengaged inorganic group bonded to silicon resin.

According to the light-emitting device of claim 1, the use of a binder composed mainly of an inorganic material is used depending on the wavelength conversion member. Since the heat resistance of the heat generated from the semiconductor light-emitting wafer is improved, it is possible to achieve high output and high luminance. In addition, since the wavelength conversion member is formed by applying a phosphor film material to at least one surface of the substrate, the filling rate of the phosphor material in the phosphor film can be increased, and the phosphor can be thinned. a thickness of the film, wherein the phosphor film raw material comprises a phosphor material and a binder raw material, the binder raw material comprising a cerium oxide precursor comprising a cerium oxide by hydrolysis or oxidation, a ceric acid compound, vermiculite, and At least one of the group of amorphous vermiculite. As a result, the size can be reduced, and the heat release efficiency can be improved, and the degree of freedom in design can be improved. Further, since the phosphor film is obtained by a reaction at a normal temperature or a heat treatment at a temperature of 500 ° C or lower, it can be formed at a low temperature and can suppress deterioration of characteristics of the phosphor material.

In addition, when the average particle diameter of the primary particles of the phosphor material is 1 μm or more and 20 μm or less, the film thickness distribution of the phosphor film is set to within ±10%. In addition, when the surface roughness of the phosphor film is set to 10 μm or less in terms of arithmetic mean roughness Ra, color unevenness can be suppressed, uniformity can be suppressed, and performance can be stabilized. In addition, when the thickness of the base material to be formed is set to 0.05 mm or more and 3 mm or less, the shape can be maintained and the size can be further reduced.

According to the method for producing a light-emitting device according to the seventh aspect of the invention, since the phosphor film material is applied to at least one surface of the substrate by the printing method, the in-plane film thickness distribution of the phosphor film can be uniform. Sexual improvement. Thereby, color unevenness and uniformity can be suppressed, and performance can be stabilized.

The light-emitting device according to claim 8 or the light-emitting device described in claim 14 is formed by using a binder composed mainly of an inorganic material depending on the wavelength conversion member, so that it can be generated from the semiconductor light-emitting wafer. The heat resistance of the heat is improved, and high output and high luminance can be achieved. Further, since the wavelength conversion member is formed by applying a phosphor film material to at least one surface of the substrate, the filling rate of the phosphor material in the phosphor film can be increased and the phosphor film can be thinned. The thickness of the phosphor film material comprising a phosphor material and a binder material, the binder material comprising a cerium oxide precursor comprising a cerium oxide by hydrolysis or oxidation, a ceric acid compound, a vermiculite, and a non- At least one of the group of crystalline vermiculite. As a result, the size can be reduced, and the heat release efficiency can be improved, and the degree of freedom in design can be improved. Further, since the phosphor film is obtained by a reaction at a normal temperature or a heat treatment at a temperature of 500 ° C or lower, it can be formed at a low temperature and can suppress deterioration of characteristics of the phosphor material.

Further, since it is carried out in such a manner that a majority of the inorganic material of the main component is used as the adhesive or at least a part of the material which is inorganically bonded, heat resistance can be further improved. Further, since the thermal conductivity can be improved compared to the resin, the heat generated in the wavelength conversion member can be transmitted to the side of the semiconductor light-emitting chip, and the heat-dissipating property can be improved by the semiconductor light-emitting chip. In addition, since the periphery of the light-emitting element can be packaged without the resin, the heat dissipation property can be further improved. Thereby, deterioration of the phosphor material can be suppressed.

In addition, if the average particle diameter of the primary particles of the phosphor material is 1 μm or more and 20 μm or less, or When the film thickness distribution of the phosphor film is set to within ±10%, the surface roughness of the phosphor film is set to 10 μm or less in terms of arithmetic mean roughness Ra. , can suppress color unevenness, homogenization, and stabilize performance. In addition, when the thickness of the base material to be formed is set to 0.05 mm or more and 3 mm or less, the shape can be maintained and the size can be further reduced.

According to the method for producing a light-emitting device according to the fifteenth aspect of the invention, since the phosphor film material is applied to at least one surface of the substrate by the printing method, the in-plane film thickness distribution of the phosphor film can be improved. Sex. Thereby, color unevenness and uniformity can be suppressed, and performance can be stabilized.

10‧‧‧Lighting device

11‧‧‧Substrate

12‧‧‧Semiconductor light-emitting chip

13‧‧‧ reflector frame

14‧‧‧wavelength conversion member

14A‧‧‧ Forming the substrate

14B‧‧‧Fluorescent film

20‧‧‧Lighting elements

21‧‧‧Semiconductor light-emitting chip

22‧‧‧Adhesive

23‧‧‧ Wavelength conversion member

23A‧‧‧Forming a substrate

23B‧‧‧Fluorescent film

30‧‧‧Lighting device

31‧‧‧Substrate

32‧‧‧ reflector frame

Fig. 1 is a view showing the configuration of a light-emitting device according to a first embodiment of the present invention.

Fig. 2 is a view showing the configuration of a light-emitting element according to a second embodiment of the present invention.

Fig. 3 is a view showing a configuration of a light-emitting device using the light-emitting element of Fig. 2.

Fig. 4 is a characteristic diagram showing changes in luminance with time in an exposure test at a high temperature and high humidity environment of 85 ° C and 85% RH.

Fig. 5 is a characteristic diagram showing changes in luminance with time in an exposure test in a dry high temperature environment at 150 °C.

Fig. 6 is a characteristic diagram showing changes in luminance with time in an exposure test in a dry high temperature environment at 200 °C.

Fig. 7 is a characteristic diagram showing the relationship between the exposure temperature in the exposure test in a dry high-temperature environment and the luminance after 24 hours.

[Formation of the Invention]

Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings.

(First embodiment)

Fig. 1 is a view showing a constituent of a light-emitting device 10 according to a first embodiment of the present invention. In the light-emitting device 10, for example, a plurality of semiconductor light-emitting chips 12 composed of LEDs are mounted on a substrate 11. In the semiconductor light-emitting chip 12, for example, ultraviolet light, blue light, or green light which emits excitation light is used, and among them, blue light is preferably emitted. This is because the white color can be easily obtained, and the influence of the surrounding member is deteriorated with respect to the ultraviolet light, and the influence of the blue light is small. The semiconductor light-emitting chip 12 is electrically connected to each other by, for example, a wiring formed on the substrate 11 and a bump, although not shown. The reflector frame 13 is formed around the semiconductor light-emitting wafer 12, for example, so as to surround the entirety.

On the semiconductor light-emitting wafer 12, for example, the wavelength conversion member 14 is placed in contact with the semiconductor light-emitting wafer 12. The wavelength conversion member 14 has, for example, a phosphor film 14B formed by forming at least one surface of the substrate 14A and the substrate 14A. Between the LEDs, that is, between the substrate 11 and the wavelength conversion member 14, although not shown, an adhesive or a package member may be disposed to fill the space. The adhesive or the encapsulating member is preferably made of an inorganic material and has high heat resistance. For example, the same adhesive as that used in the phosphor film 14B to be described later can be used. again In the first embodiment, for example, the case where the phosphor film 14B is disposed on the side of the semiconductor light-emitting wafer 12 is disposed, but the substrate 14A may be disposed so as to be disposed on the semiconductor light-emitting chip 12 side.

The base material 14A is preferably made of, for example, glass or quartz, or sapphire or the like, and is particularly optically transparent like glass, if it is made of sapphire. Further, even if it is compared with glass, the heat dissipation property can be greatly improved, and deterioration of the phosphor material can be suppressed, which is more preferable. Further, the formation of the base material 14A may be carried out by using a high-purity polycrystalline alumina. This is because it is less expensive than sapphire, has less light absorption, and the thermal conductivity is equal to sapphire. As a characteristic of forming the substrate 14A, for example, it is preferable that the light transmittance is 90% or more in a wavelength region of 400 nm to 800 nm. Further, in the case where the substrate 14A is formed, for example, when glass or sapphire is used, the surface may be roughened into a ground glass shape in order to scatter light. In the case of using polycrystalline alumina, since light is scattered by internal grain boundaries, scattered light can be obtained without applying a treatment to the surface.

The thickness of the formed base material 14A is, for example, preferably 0.05 mm or more and 3 mm or less. This is because the thickness can be reduced to 3 mm or less, and if it is thicker than 3 mm, it is thicker than necessary, and the heat dissipation property and light transmittance are also lowered. In addition, when it is thinner than 0.05 mm, it is difficult to maintain its own shape, and there is a possibility that flatness cannot be maintained due to the influence of a fixing jig used for printing or the like. The base material 14A is formed, and when the phosphor film 14B is formed, the wavelength conversion member 14 may be formed by using such a thickness, or After the phosphor film 14B is formed to be thicker than this, the thickness of the formed substrate 14A is reduced by polishing or the like. However, in the case where the shape of the wavelength conversion member 14 is large and the substrate 14A itself is to be subjected to the task for holding the structure, the thickness of the formed substrate 14A can be made thicker than 3 mm. Further, the base material 14A may be formed in any shape, and may have a circular plate shape or a square plate shape. Further, although the case of the flat shape is shown in Fig. 1, it may be a concave shape, a convex shape, or an electric bulb shape.

The phosphor film 14B is, for example, a particulate phosphor material and a binder attached to the phosphor material, and may contain a filler as needed. The thickness of the phosphor film 14B is preferably, for example, 30 μm or more and 1 mm or less, and more preferably 50 μm or more and 500 μm or less. This is because if the amount of the phosphor material is too small, the amount of the phosphor material becomes small, and the adjustment of the color becomes difficult. When the thickness is too large, the scattering of light is excessively increased, and the absorption of light becomes remarkable, and the light is hard to be exported to the outside. The surface roughness of the phosphor film 14B (that is, the surface roughness of the surface of the phosphor film 14B opposite to the substrate 14A) is preferably 10 μm or less in terms of the arithmetic mean roughness Ra. The film thickness distribution of the phosphor film 14B is preferably set to within ±10%. This is because it is possible to suppress color unevenness, homogenize, and stabilize the performance. The surface roughness of the phosphor film 14B or the film thickness distribution of the phosphor film 14B can be adjusted, for example, by polishing or grinding after the phosphor film 14B is formed.

The phosphor material may include, for example, phosphor particles, or a coating layer may be formed on the surface of the phosphor particles. Examples of the phosphor particles include BaMgAl ₁₀ O ₁₇ :Eu, ZnS:Ag, Cl, BaAl ₂ S ₄ :Eu or a blue-based phosphor such as CaMgSi ₂ O ₆ :Eu, and Zn ₂ SiO _{4 .} : Mn, (Y, Gd) BO ₃ : Tb, ZnS: Cu, Al, (M1) ₂ SiO ₄ : Eu, (M1) (M2) ₂ S: Eu, (M3) ₃ Al ₅ O ₁₂ : Ce, SiAlON: Eu, CaSiAlON: Eu, (M1)Si ₂ O ₂ N: Eu or (Ba, Sr, Mg) ₂ SiO ₄ : Eu, Mn or the like yellow or green phosphor, (M1) ₃ SiO ₅ : Eu or a yellow, orange or red phosphor such as (M1)S:Eu, (Y, Gd) BO ₃ :Eu, Y ₂ O ₂ S:Eu, (M1) ₂ Si ₅ N ₈ :Eu,( M1) AlSiN ₃ : Eu or a red-based phosphor such as YPVO ₄ :Eu. Further, in the above chemical formula, M1 includes at least one of the group consisting of Ba, Ca, Sr, and Mg, M2 includes at least one of Ga and Al, and M3 includes at least one of the group including Y, Gd, Lu, and Te.

When the heat resistance of the wavelength conversion member 14 is considered, the phosphor particles are preferably (M3) ₃ Al ₅ O ₁₂ :Ce, SiAlON:Eu, CaSiAlON:Eu, (M1)Si ₂ O ₂ N:Eu (M1) ₂ Si ₅ N ₈ :Eu or (M1)AlSiN ₃ :Eu. M1 and M3 are as described above. The phosphor particles are selected in accordance with the type of the semiconductor light-emitting chip 12 and the like. One or two or more kinds of phosphor particles are used for the phosphor material, and when a plurality of types are used, they may be used in combination, or may be divided into a plurality of layers to be laminated.

The coating layer of the phosphor particles preferably contains, for example, a composite oxide including lanthanum and aluminum such as a rare earth oxide, zirconium oxide, titanium oxide, zinc oxide, aluminum oxide, lanthanum-garnet-garnet, or magnesium oxide. At least one metal oxide of a group of composite oxides of aluminum and magnesium such as MgAl ₂ O _{4 is} used as a main component. This is because the characteristics such as water resistance and ultraviolet light resistance can be improved. Among them, a rare earth oxide or zirconium oxide is preferred. As the rare earth oxide, it is more preferable to include at least one element selected from the group consisting of ruthenium, osmium, iridium and osmium, and it is more preferable to use zirconia. This is because higher effects can be obtained or costs can be suppressed.

The average particle diameter of the primary particles of the phosphor material is, for example, preferably 1 μm or more and 20 μm or less. This is because the reduction in the average particle diameter can suppress color unevenness and uniformity. However, if the shrinkage is too small, the optical properties of the phosphor material itself are often lowered, and since the particles smaller than 1 μm are agglomerated twice and the effect of miniaturization is lost, it is preferably set. 1 μm or more.

The binder is obtained by reacting a binder raw material at a normal temperature or heat-treating at a temperature of 500 ° C or lower, and the binder raw material includes a cerium oxide precursor including a cerium oxide by hydrolysis or oxidation, and a ceric acid compound. At least one of the group of vermiculite, and amorphous vermiculite. As the cerium oxide precursor, for example, perhydropolysilazane, ethyl decanoate or methyl decanoate is preferably used as a main component. This is because these cerium oxide precursors are easily oxidized by cerium oxide such as cerium oxide by hydrolysis or oxidation at normal temperature or heat treatment, and can function as a binder. Further, as the binder, the cerium oxide precursor reaction is not required to completely become cerium oxide, and may include an unreacted portion or an incompletely reacted portion.

Further, as the citric acid compound, for example, sodium citrate is preferably mentioned. As the citric acid compound, a dehydrated state can be used, and a hydrate can also be used. As the vermiculite or the amorphous vermiculite, for example, a nano-sized ultrafine particle powder is used, and for example, an ultrafine particle powder having an average particle diameter of 5 nm or more and 100 nm or less as a primary particle diameter is used, and 5 nm or more and 50 nm are used. The following ultrafine particle powder is more preferable. These phthalic acid compounds, vermiculite, or amorphous vermiculite are dissolved or dispersed by The solvent is heat-treated and dried to be solidified, so that it can function as a binder.

The heat treatment temperature of the binder raw material is preferably 500 ° C or less in order to reduce the heat influence on the formation of the base material 14A and the phosphor material, and when it is necessary to further reduce the heat influence, if it is 300 ° C or less, Preferably, it is better if it is set to 200 ° C or less. Further, if the binder raw material is reacted at a normal temperature, it is preferred because it has no heat influence. Preferably, the type of the binder raw material is selected in accordance with the heat resistance characteristics of the formed substrate 14A and the phosphor material to be used, and the binder raw material is reacted at room temperature according to the adjustment, or the binder raw material is heat-treated at several degrees. Further, in the gas atmosphere during heat treatment, when the phosphor material is easily oxidized and deteriorated by heat, it is preferably a non-oxidizing gas atmosphere such as a nitrogen atmosphere.

For example, the filler is preferably used to adjust the filling ratio of the phosphor material, and is preferably composed of a light-transmitting inorganic material, and examples thereof include cerium oxide particles, alumina particles, or zirconia particles. More preferably, the cerium oxide particles may be in the form of crystals or glass. The average particle diameter of the filler is preferably, for example, about 1 μm to 20 μm which is the same as the phosphor material.

The wavelength conversion member 14 is formed by applying a phosphor film material containing a phosphor material and a binder raw material to at least one surface of the formation substrate 14A, and reacting it at room temperature or heat treatment at a temperature of 500 ° C or lower. By. The coating method may, for example, be a printing method, a spray method, a drawing method using a dispenser, or an inkjet method. Among them, if the printing method or the spraying method is used, the phosphor film 14B can be improved. The uniformity of the in-plane thickness distribution is preferred, and the printing method is the best. The coating can be repeated until the desired film thickness is reached.

For example, in the case of using a printing method, one or two or more kinds of phosphor materials, a binder raw material, a diluting solvent, and a filler-like phosphor film material are prepared by mixing the filler. At least one side of the base material 14A is formed and applied by a printing method (for example, screen printing). The printing method (for example, screen printing) is preferable because the uniformity of the in-plane film thickness distribution of the phosphor film 14B can be improved. In addition, for example, when a spray method is used, one or two or more types of phosphor materials, a binder raw material, a diluted solvent, and a slurry in the form of a slurry are prepared in accordance with a desired filler. The film raw material is coated on at least one side of the substrate 14A with a spray gun using a spray gun. Preferably, the spray path of the spray and the spray gun are uniformly moved while moving back and forth at a fixed speed.

After the phosphor substrate material is applied to the substrate 14A, the applied phosphor film material is dried, for example, to remove the diluted solvent. In this case, it is also possible to heat at 500 ° C or lower, preferably 300 ° C or lower, more preferably 200 ° C or lower, as needed. Thereby, the binder raw material is reacted at room temperature or by heat treatment, or is solidified by heat treatment.

Further, when the area of the phosphor film 14B is extremely small, a plurality of phosphor films 14B may be formed on the same surface on which the substrate 14A is formed, and then cut by dicing or the like. get on. The phosphor film 14B may be formed on the entire surface of the substrate 14A or may be patterned. If the plurality of wavelength conversion members 14 are once applied in this way In the case of the sexual treatment, it is preferable because it can reduce the cost, shorten the time, and improve the efficiency. Further, even if a part of the phosphor film 14B is variated in thickness, it can be selected by slicing, and therefore it is preferable to stabilize the quality. Further, in the case where a fine pattern is required, if screen printing is used, it is preferable to be able to print a large number of patterns at a time on one sheet forming substrate 14A.

According to this embodiment, since the wavelength conversion member 14 is formed by using a binder mainly composed of an inorganic material, heat resistance to heat generated from the semiconductor light-emitting wafer 12 can be improved, and the heat resistance can be improved. High output and high brightness. Further, the wavelength conversion member 14 is formed by applying a phosphor film material to at least one surface of the formation substrate 14A, and the phosphor film material contains a phosphor material and a binder material, and the binder material is used. At least one of the group consisting of a cerium oxide precursor, a ceric acid compound, vermiculite, and an amorphous vermiculite which becomes cerium oxide by hydrolysis or oxidation, thereby improving the phosphor in the phosphor film 14B The filling rate of the material can reduce the thickness of the phosphor film 14B. As a result, the size can be reduced, and the heat release efficiency can be improved, and the degree of freedom in design can be improved. Further, since the phosphor film 14B is obtained by a reaction at a normal temperature or a heat treatment at a temperature of 500 ° C or lower, it can be formed at a low temperature, and deterioration of characteristics of the phosphor material can be suppressed.

In addition, when the average particle diameter of the primary particles of the phosphor material is 1 μm or more and 20 μm or less, the film thickness distribution of the phosphor film 14B is set to within ±10%. In addition, if the surface roughness of the phosphor film 14B is set to 10 μm or less in terms of the arithmetic mean roughness Ra, it can be suppressed. The color is uneven and uniform, and the performance is stabilized.

In addition, when the base material 14A is formed by sapphire or polycrystalline alumina, since the thermal conductivity is higher than that of the glass, the heat dissipation property can be improved, and the heat-resistant temperature is also drastically improved, so that deterioration can be suppressed.

In addition, when the thickness of the base material 14A is set to 0.05 mm or more and 3 mm or less, the shape can be maintained and the size can be further reduced.

Further, if the phosphor film material is applied by at least one surface of the formed substrate 14A by printing, the uniformity of the in-plane film thickness distribution of the phosphor film 14B can be improved. Thereby, color unevenness and uniformity can be suppressed, and performance can be stabilized.

(Second embodiment)

Fig. 2 is a view showing a constituent of a light-emitting element 20 according to a second embodiment of the present invention. The light-emitting element 20 includes, for example, a semiconductor light-emitting chip 21 and a wavelength conversion member 23, and the wavelength conversion member 23 is disposed on the semiconductor light-emitting wafer 21 by an adhesive 22. The semiconductor light-emitting chip 21 has a structure in which a plurality of semiconductor layers including a light-emitting layer are laminated, for example, although not shown, and a pair of electrodes are disposed. As the semiconductor light-emitting wafer 21, for example, an LED chip is used, and ultraviolet light, blue light, or green light is used as the excitation light. Among them, as the semiconductor light-emitting chip 21, it is preferable to emit blue light. This is because the white color can be easily obtained, and the influence of the surrounding member is deteriorated with respect to the ultraviolet light, and the influence of the blue light is small. The semiconductor light-emitting chip 21 may be a face-up type in which the light-emitting layer is disposed on the upper side, or may be A face-down type in which the light-emitting layer is disposed on the lower side.

The wavelength conversion member 23 is directly disposed on the light-emitting surface of the semiconductor light-emitting chip 21 through the adhesive 22, for example. The wavelength conversion member 23 has, for example, a phosphor film 23B formed by forming at least one surface of the base material 23A and the base material 23A. In addition, in the second drawing, the phosphor film 23B is formed on one of the front surface and the back surface of the base material 23A, but it may be formed on both surfaces, or may be replaced by a surface. The back surface is formed on the side surface or formed on the side surface in addition to at least one of the front surface and the back surface. The wavelength conversion member 23 may be disposed such that the base material 23A is formed on the side of the semiconductor light-emitting wafer 21, or the phosphor film 23B may be disposed on the side of the semiconductor light-emitting wafer 21.

The structure in which the base material 23A and the phosphor film 23B are formed is the same as that of the base material 14A and the phosphor film 14B which have been described in the first embodiment. Further, the wavelength conversion member 23 can be manufactured in the same manner as the wavelength conversion member 14 described in the first embodiment.

The adhesive agent 22 is obtained by reacting an adhesive raw material at a normal temperature or heat-treating at a temperature of 500 ° C or lower, and the adhesive raw material includes a cerium oxide precursor including a cerium oxide by hydrolysis or oxidation to form cerium oxide. At least one of a group of phosphoric acid compounds and at least a part of carbon which is desorbed by heating to form an inorganic bond. These materials are light-transmissive, and most of the inorganic components of the main component or at least a part of the inorganic bonding materials have a small influence on the light-emitting characteristics and are excellent in heat resistance.

As the cerium oxide precursor, for example, it is preferably exemplified All-hydrogen polyazane, ethyl decanoate, and methyl decanoate are the main components. These cerium oxide precursors are easily oxidized by cerium oxide such as cerium oxide by hydrolysis or oxidation at normal temperature or heat treatment, and can function as a binder 22. Further, as the adhesive 22, the cerium oxide precursor reaction is not required to completely become cerium oxide, and may include an unreacted portion or an incompletely reacted portion.

As the citric acid compound, for example, sodium citrate is preferably mentioned. As the citric acid compound, a dehydrated state can be used, and a hydrate can also be used. As the phosphoric acid compound, for example, aluminum phosphate is preferable. The citric acid compound and the phosphoric acid compound can be solidified by heat treatment and drying by dissolving or dispersing them in a solvent to produce a function as the adhesive 22 . An example of a ruthenium resin which is at least a part of carbon by heating and is inorganically bonded is, for example, an organopolysiloxane. Since the organic resin is desorbed by heating and the organic component is reduced by heating, the resin is high in heat resistance and can be used as a function of the adhesive 22 .

The heat treatment temperature of the binder raw material is preferably 500 ° C or less in order to reduce the thermal influence on the formation of the base material 23A and the phosphor material, and when it is necessary to further reduce the heat influence, if it is 300 ° C or less, Preferably, it is better if it is set to 200 ° C or less. Further, if the binder raw material is reacted at a normal temperature, it is preferred because it has no heat influence. It is preferable to select the type of the binder raw material in accordance with the heat resistance characteristics of the formed base material 23A and the phosphor material to be used, and to adjust the binder raw material to react at normal temperature or to heat the binder raw material to several degrees. Also, the gas environment during heat treatment, in the phosphor material or semi-conductive When the bulk light-emitting wafer 21 is easily oxidized and deteriorated by heat, it is preferably a non-oxidizing gas atmosphere such as a nitrogen atmosphere.

When it is desired to form the adhesive 22 in a thick manner or when it is desired to increase the viscosity of the adhesive raw material, the filler may be added to the adhesive raw material, and the adhesive 22 may be added to the adhesive. The filler is preferably composed of an inorganic material having light transmissivity, and examples thereof include cerium oxide particles, alumina particles, or zirconia particles.

Fig. 3 is a view showing a configuration example of the light-emitting device 30 using the light-emitting element 20. In the light-emitting device 30, the light-emitting element 20 is mounted on the substrate 31. A reflector frame 32 is formed around the light emitting element 20, for example. An encapsulant may not be disposed around the light-emitting element 20. This is because the heat release property can be improved compared to the case of covering with a resin encapsulant. Further, although not shown, it may be carried out by arranging an encapsulant on the side of the light-emitting element 20 to protect the circuit on the substrate 31. Further, although not shown, the encapsulant may be disposed so as to cover the upper surface of the light-emitting element 20. This is because it can alleviate the influence caused by direct contact with moisture or harmful gases from the outside.

According to the present embodiment, the wavelength conversion member 23 is made of a binder mainly composed of an inorganic material, so that heat resistance to heat generated from the semiconductor light-emitting chip 21 can be improved, and high output and high can be achieved. Brightness. Further, the wavelength conversion member 23 is formed by applying a phosphor film material to at least one surface of the formation substrate 23A, and the phosphor film material includes a phosphor material and a binder material, and the binder material contains Including oxidation by hydrolysis or oxidation At least one of the group of cerium oxide precursor, ceric acid compound, vermiculite, and amorphous vermiculite can increase the filling rate of the phosphor material in the phosphor film 23B, and can reduce the phosphor film The thickness of 23B. As a result, the size can be reduced, and the heat release efficiency can be improved, and the degree of freedom in design can be improved. Further, since the phosphor film 23B is obtained by a reaction at a normal temperature or a heat treatment at a temperature of 500 ° C or lower, it can be formed at a low temperature, and deterioration of characteristics of the phosphor material can be suppressed.

Further, since the binder 22 is made of a material having a light-transmitting and main component of a majority of inorganic materials or at least a part of inorganic bonding, heat resistance can be further improved. In addition, since the heat conductivity is improved as compared with the resin, the heat generated in the wavelength conversion member 23 can be transmitted to the semiconductor light-emitting chip 21 side, and the semiconductor light-emitting chip 21 can be transmitted to improve the heat dissipation property. In addition, since the periphery of the light-emitting element 20 can be packaged without resin, the heat dissipation property can be further improved. Thereby, deterioration of the phosphor material can be suppressed.

In addition, when the average particle diameter of the primary particles of the phosphor material is 1 μm or more and 20 μm or less, or if the film thickness distribution of the phosphor film 23B is within ±10%, When the surface roughness (in terms of arithmetic mean roughness Ra) of the phosphor film 23B is 10 μm or less, color unevenness can be suppressed, uniformity can be achieved, and performance can be stabilized.

In addition, when the base material 23A is formed by sapphire or polycrystalline alumina, since the thermal conductivity is higher than that of the glass, the heat dissipation property can be improved, and the heat-resistant temperature is also drastically improved, so that deterioration can be suppressed.

Further, if the thickness of the substrate 23A to be formed is set When it is carried out in a manner of 0.05 mm or more and 3 mm or less, the shape can be maintained and the size can be further reduced.

[Examples] (Examples 1-1 to 1-4)

First, a phosphor film material, a binder raw material, a filler, and a diluent solvent are mixed to prepare a phosphor film material. As the phosphor material, phosphor particles composed of Y ₃ Al ₅ O ₁₂ :Ce having an average particle diameter of primary particles of about 15 μm and phosphor particles composed of CaAlSiN ₃ :Eu are used. As a binder raw material, ethyl decanoate was used in Example 1-1, perhydropolyazoxide was used in Example 1-2, and hydrate of sodium citrate was used in Example 1-3, and further, in Examples 1-4 is a suspension of ultrafine particle powder of vermiculite or amorphous vermiculite in a solvent. As the filler, cerium oxide particles having an average particle diameter of about 15 μm were used. As a diluent solvent, terpineol was used.

Next, the produced phosphor film material was printed on the side of the substrate 14A formed of a transparent glass plate having a thickness of 1 mm, and applied to have a desired thickness. Thereafter, the diluted solvent was removed by drying it at 150 °C. Thus, for each of the examples, the wavelength conversion member 14 having the phosphor film 14B having a thickness of about 80 μm formed on one surface of the substrate 14A was obtained. The surface roughness of the obtained phosphor film 14B was measured, and as a result, the arithmetic mean roughness Ra was 10 μm or less. The film thickness distribution of the phosphor film 14B was also measured and found to be within ±10%. The light-emitting device 10 shown in Fig. 1 was produced using each of the obtained wavelength conversion members 14. In the semiconductor light-emitting chip 12, a blue LED is used to form a light-emitting device 10 that emits white light.

The light-emitting device 10 of each of the examples was energized, and as a result of the luminescence test, good white light emission was obtained in either case. That is, it is understood that even if the thickness of the phosphor film 14B is reduced, good white color can be obtained and the size can be reduced.

(Examples 2-1 to 2-4)

First, in the same manner as in Examples 1-1 to 1-4, a phosphor material, a binder raw material, a filler, and a diluent solvent were mixed to prepare a phosphor film material. As a binder raw material, ethyl citrate was used in Example 2-1, perhydropolyazoxide was used in Example 2-2, hydrate of sodium citrate was used in Example 2-3, or in Examples 2-4. The ultrafine particle powder of vermiculite or amorphous vermiculite is suspended in a solvent. Next, a formed substrate 14A having a thickness of 1 mm and having a size of a plurality of wavelength conversion members 14 was prepared.

Then, on one side of the substrate 14A, the prepared phosphor film material is printed, applied to a desired thickness, and dried at 150 ° C to remove the diluted solvent to form a plurality of thicknesses of about 80 μm. Part of the phosphor film 14B. Thereafter, the formation base material 14A on which the phosphor film 14B has been formed is cut into a plurality of pieces by slicing or the like to obtain the respective wavelength conversion members 14. The light-emitting device 10 shown in Fig. 1 was produced using each of the obtained wavelength conversion members 14. In the semiconductor light-emitting chip 12, a blue LED is used to form a light-emitting device 10 that emits white light. The light-emitting device 10 of each of the examples was energized, and as a result of the luminescence test, good white light emission was obtained in either case.

(Examples 3-1 to 3-33, Comparative Examples 3-1 to 3-4)

First, mix phosphor materials, binder materials, as appropriate A solvent film and a filler as appropriate are prepared to prepare a phosphor film material. The material of the phosphor particles of the phosphor material in each of the examples and the comparative examples - the average particle diameter (particle diameter) of the phosphor particles - the amount of addition, the material of the filler - the average particle diameter (particle diameter) - The amount of addition and the material of the binder raw material-added amount are shown in Tables 1 to 4. Further, as the phosphor material, either or both of the phosphor material A and the phosphor material B are used. As the diluent solvent, α-terpineol was used.

Next, the produced phosphor film material is applied onto one surface of the substrate 14A formed of a glass plate of 100 mm square, heat-treated or treated at room temperature to obtain a phosphor film 14B having a predetermined thickness. Wavelength conversion member 14. Using the obtained wavelength conversion member 14, the light-emitting device 10 shown in Fig. 1 is formed. The coating method of the phosphor film raw material in each of the examples and the comparative examples, the heat treatment temperature, the average film thickness of the phosphor film 14B, the film thickness distribution of the phosphor film 14B, and the arithmetic of the phosphor film 14B. The average roughness Ra is shown in Tables 2 and 4.

Further, the film thickness measurement of the phosphor film 14B is performed in advance to measure the thickness of the substrate 14A, and the thickness of the wavelength conversion member 14 after the phosphor film 14B has been formed is measured, and the difference is regarded as the film thickness. The average film thickness was measured for 5 points in the vertical direction and 25 lines in the horizontal direction of the substrate 14A of 100 mm square, and the average value of the film thickness was taken as the average film thickness. Moreover, the film thickness distribution of the phosphor film 14B is calculated according to the following calculation formula. Further, the maximum film thickness is the maximum of the 25-point film thickness measured, and the minimum film thickness is the minimum of the 25-point film thickness measured.

Film thickness distribution (%) = {(maximum film thickness - minimum film thickness) / (maximum film thickness + minimum film thickness)} × 100

The arithmetic mean roughness Ra of the phosphor film 14B is measured by a stylus type surface roughness measuring instrument.

As shown in Tables 1 and 2, the film thickness distribution of the phosphor film 14B can be set to ±10 according to Examples 3-1 to 3-33 in which the average particle diameter of the phosphor particles and the filler is 20 μm or less. Within the %, the arithmetic mean roughness Ra is set to 10 μm or less.

For the wavelength conversion member 14 produced in each of the examples and the comparative examples, the initial luminance of the initial characteristics was examined. Further, as a high-temperature and high-humidity test, an exposure test in a high-temperature and high-humidity environment of 85 ° C and 85% RH was performed, and the rate of decrease in luminance after 2000 hours passed was examined. Further, as a dry high temperature test, an exposure test was performed in a dry high temperature environment of 150 ° C or 200 ° C, and the rate of decrease in luminance after 2000 hours passed was examined. The results obtained are shown in Tables 5 and 6. In Tables 5 and 6, the luminescent luminance of the initial characteristics is the relative luminescent luminance when the luminescent luminance of Example 3-27 is 100. The rate of decrease in luminance in the high-temperature and high-humidity test and the dry high-temperature test is the rate of decrease from the luminance of the initial characteristics in each of the examples and the comparative examples.

Further, the results of Example 3-1 and Comparative Example 3-1 among the obtained results are shown in Figs. 4 to 6. Figure 4 shows the results of the exposure test in a high temperature and high humidity environment of 85 ° C and 85% RH. Figure 5 is at 150 ° C. The results of the exposure test in a dry high temperature environment, Fig. 6 are the results of an exposure test in a dry high temperature environment at 200 °C. In the fourth to sixth figures, the vertical axis is a relative luminance value when each initial luminance is set to 100.

Further, the wavelength conversion members 14 of Examples 3-1 to 3-4 and Comparative Example 3-1 were heated in an air oven, and subjected to a dry high-temperature environment exposure test at 100 ° C to 500 ° C to investigate changes in luminance with time. Moreover, since the wavelength conversion member 14 may be damaged in a high temperature region exceeding 200 ° C, it is also confirmed by visual appearance. The exposure time of each temperature was set to 24 hours. The results of Example 3-1 and Comparative Example 3-1 among the obtained results are shown in Fig. 7. In Fig. 7, the vertical axis is a relative luminance value when each initial luminance is set to 100. Further, although not shown, the same results as in Example 3-1 were obtained also in Examples 3-2 to 3-4.

As shown in Tables 5 and 6, according to the present embodiment, the relative luminance of the initial characteristics is 80% or more, but the comparative examples 3-2 to 3-4 which have been heat-treated at 550 ° C or higher are as low as 70% or less.

Further, as shown in Tables 5, 6 and 4 to 6, in Comparative Example 3-1 using an anthrone resin, the luminance reduction rate in the high-temperature and high-humidity test was 15%, and in the high-temperature drying test at 150 °C. The luminance reduction rate was 12%, and the wavelength conversion member was peeled off after 1200 hours in a dry high temperature test at 200 ° C, and the luminance reduction rate after 1000 hours was 33%. On the other hand, according to the present embodiment, the luminance reduction rate can be greatly improved to 7% or less regardless of the high temperature and high humidity test, the high temperature drying test at 150 ° C, and the dry high temperature test at 200 ° C.

Further, as shown in Fig. 7, in Comparative Example 3-1 using an fluorenone resin, the luminance maintenance ratio was lowered as the temperature became higher, and the phosphor film was powdered at 300 ° C or higher due to chemical changes caused by heat. Stripping. On the other hand, in Examples 3-1 to 3-4, there was no change in appearance, and no decrease in the luminance maintenance ratio was observed.

Further, as shown in Tables 1, 2 and 5, the average particle diameter of the phosphor particles is larger than 20 μm, the film thickness distribution of the phosphor film 14B is larger than ±10%, and the arithmetic mean roughness Ra ratio is larger. Example 10-34 to 3-36, which is also larger than 10 μm, is set according to the average particle diameter of the phosphor particles and the filler. When the film thickness distribution of the phosphor film 14B is within ±10% and the arithmetic mean roughness Ra is 10 μm or less, the relative luminance of the initial luminance can be improved by 20 μm or less. .

(Examples 4-1, 4-2)

First, a phosphor film material, a binder raw material, a filler, and a diluent solvent are mixed to prepare a phosphor film material. The material of the phosphor particles of the phosphor material in each of the examples - the average particle diameter (particle diameter) of the phosphor particles - the amount of the filler, the material of the filler - the average particle diameter (particle diameter) - the amount of addition, and the bonding The material-addition amount of the raw material of the agent is shown in Tables 7 and 8. As the diluent solvent, α-terpineol was used. Next, the produced phosphor film material is applied onto one surface of the substrate 14A formed of a glass plate of 100 mm square by a spray method or a brush, and subjected to heat treatment or treatment at room temperature to obtain a predetermined thickness. The wavelength conversion member 14 of the phosphor film 14B. Using the obtained wavelength conversion member 14, the light-emitting device 10 shown in Fig. 1 is formed. The coating method of the phosphor film material in each of the examples, the heat treatment temperature, the average film thickness of the phosphor film 14B, the film thickness distribution of the phosphor film 14B, and the arithmetic mean roughness Ra of the phosphor film 14B. Shown in Table 8. Further, in Tables 7 and 8, the values of Example 3-1 are also shown.

As shown in Tables 7 and 8, the film thickness distribution of the phosphor film 14B was compared with Examples 4-1 and 4-2 coated by a spray method or a brush as compared with Example 3-1 coated by a printing method. The arithmetic mean roughness Ra is increased, and the relative luminance of the initial characteristics is lowered. That is, it is understood that it is preferable to carry out the method of applying the phosphor film 14B by a printing method.

(Examples 5-1 to 5-4)

As an adhesive raw material, ethyl ruthenate (Example 5-1) and aluminum phosphate (Example 5-2) were prepared, and at least a part of carbon was removed by heating to become an inorganic bonded oxime resin (organic polyoxyl (Alkyl) (Example 5-3) and sodium citrate (Example 5-4), an adhesive raw material was applied between two glass plates, and heat treatment was performed, whereby two glass plates were adhered by the adhesive 22. The liquid is used for each of the adhesive materials. In either embodiment, two sheets of glass can be brought together. Thereafter, for each of the examples, a heat resistance test was performed from 100 ° C to 300 ° C. The results are shown in Table 9. In Table 9, ○ indicates no peeling, and × indicates peeling.

As shown in Table 9, good heat resistance was obtained regardless of the one, and in particular, the aluminum phosphate of Example 5-2 and the heat of at least a part of the heat of Example 5-3 were detached to become inorganic bonds. The enamel resin and the sodium citrate of Example 5-4 can achieve high effects. That is, it is understood that any one of them is effective as the adhesive 22.

(Examples 6-1 to 6-4)

The heat resistance test was carried out in the same manner as in Examples 5-1 to 5-4 except that the glass plate and the ceramic plate were adhered by the adhesive 22. The following raw material, Example 6-1 is ethyl decanoate, and Example 6-2 is aluminum phosphate. Example 6-3 is an inorganically bonded oxime resin which is detached by heating to at least a part of carbon (organic polymerization) Hexane), Example 6-4 is sodium citrate. The results obtained are shown in Table 10. In Table 10, ○ indicates no peeling, and × indicates peeling.

As shown in Table 10, good heat resistance was obtained regardless of the one, and in particular, the indole resin which was inorganically bonded by heating at least a part of carbon of Example 6-3, and Example 6- 4 sodium citrate can achieve high effect. That is, it is understood that any one of them is effective as the adhesive 22.

(Examples 7-1 to 7-4)

In addition to the filler which adds cerium oxide particles to the binder raw material, The heat resistance test was carried out in the same manner as in Examples 6-1 to 6-4. Regarding the binder raw material, Example 7-1 is ethyl decanoate, and Example 7-2 is aluminum phosphate, and Example 7-3 is an inorganically bonded oxime resin by heating at least a part of carbon detached (organic Polyoxyalkylene), Example 7-4 is sodium citrate. The results obtained are shown in Table 11. In Table 11, ○ indicates no peeling, and × indicates peeling.

As shown in Table 11, a high effect was obtained in the case of the enamel resin in which at least a part of the carbon was removed by heating and the inorganic bond was bonded by heating, and the sodium citrate of Example 7-4. That is, it is understood that good adhesion can be obtained even if a filler is added.

(Production of Light Emitting Devices of Examples 8-1 to 8-4)

First, a phosphor film material, a binder raw material, a filler, and a diluent solvent are mixed to prepare a phosphor film material. As the phosphor material, phosphor particles composed of Y ₃ Al ₅ O ₁₂ :Ce having an average particle diameter of primary particles of about 15 μm and phosphor particles composed of CaAlSiN ₃ :Eu are used. As a binder raw material, ethyl decanoate was used in Example 8-1, perhydropolyazoxide was used in Example 8-2, hydrate of sodium citrate was used in Example 8-3, or Example 8 was used. -4 A suspension of ultrafine particle powder of vermiculite or amorphous vermiculite in a solvent is used. As the filler, cerium oxide particles having an average particle diameter of about 15 μm were used. As a diluent solvent, terpineol was used.

Next, the produced phosphor film material was printed on the side of the substrate 23A formed of a transparent glass plate having a thickness of 1 mm, and applied to have a desired thickness. Thereafter, the diluted solvent was removed by drying it at 150 °C. Thus, for each of the examples, the wavelength conversion member 23 in which the phosphor film 23B having a thickness of about 80 μm was formed on one surface of the substrate 23A was obtained. The surface roughness of the obtained phosphor film 23B was measured, and as a result, the arithmetic mean roughness Ra was 10 μm or less. The film thickness distribution of the phosphor film 23B was also measured and found to be within ±10%.

Each of the obtained wavelength conversion members 23 and the separately prepared semiconductor light-emitting wafer 21 are subsequently formed by the adhesive 22, and the light-emitting elements 20 as shown in Fig. 2 are produced. As an adhesive material, for each of the examples, ethyl ruthenate, aluminum phosphate, and at least a part of carbon which is desorbed by heating to form an inorganic bond (an organic polysiloxane) or sodium citrate will be used. After the material of the material is applied between the semiconductor light-emitting chip 21 and the wavelength conversion member 23, it is followed by heating. Further, in the semiconductor light-emitting chip 21, a blue LED chip is used to form a light-emitting element 20 that emits white light.

The light-emitting element 20 of each of the examples was energized, and as a result of the luminescence test, good white light emission was obtained in either case.

The present invention has been described above by way of embodiments, but the invention is not limited by the embodiments described above, and various modifications are possible. For example, in the above embodiment, the structure of the light-emitting element 20 and the light-emitting devices 10 and 30 is specifically described, but other structures may be used. The way it is composed. Further, in the above embodiment, the wavelength conversion members 14 and 23 are specifically described, but other components may be separately provided.

Further, in the above-described first embodiment, the wavelength conversion members 14 and 23 which form the phosphor films 14B and 23B including one or two or more kinds of phosphor materials on at least one surface of the base materials 14A and 23A are formed. Although it is not necessary to use two kinds of phosphor materials, it is also possible to form a phosphor film 14B or 23B containing different phosphor materials in accordance with at least one surface of the base materials 14A and 23A. Alternatively, the phosphor films 14B and 23B containing different phosphor materials may be formed on the both surfaces of the base materials 14A and 23A.

Further, in the above-described embodiment, the case where the LEDs are used as the semiconductor light-emitting chips 12 and 21 may be described as follows. However, other semiconductor light-emitting chips such as laser light-emitting diodes may be used. In particular, according to the present invention, since it is possible to increase the output, it can be suitably used for applications requiring high output, for example, a laser projector, an LED headlight, or a laser headlight.

[Industrial availability]

It can be used for a light-emitting element and a light-emitting device using a semiconductor light-emitting chip such as an LED or a laser diode.

10‧‧‧Lighting device

11‧‧‧Substrate

12‧‧‧Semiconductor light-emitting chip

13‧‧‧ reflector frame

14‧‧‧wavelength conversion member

14A‧‧‧ Forming the substrate

14B‧‧‧Fluorescent film

Claims (15)

A light-emitting device comprising a semiconductor light-emitting chip and a wavelength conversion member disposed in contact with the semiconductor light-emitting wafer, wherein the wavelength conversion member has a base material and a phosphor film, and the phosphor film is formed thereon Forming at least one surface of the substrate, comprising a particulate phosphor material and a binder, wherein the phosphor film is coated on at least one surface of the substrate to be reacted at room temperature or Formed by heat treatment at a temperature of 500 ° C or less, the phosphor film raw material comprising the phosphor material and a binder raw material, the binder raw material comprising a cerium oxide precursor comprising cerium oxide by hydrolysis or oxidation, cerium At least one of the group consisting of an acid compound, vermiculite, and amorphous vermiculite. The light-emitting device of claim 1, wherein the primary particles of the phosphor material have an average particle diameter of 1 μm or more and 20 μm or less. The light-emitting device of claim 1, wherein the film thickness distribution of the phosphor film is within ±10%. The light-emitting device of claim 1, wherein the surface roughness of the phosphor film is 10 μm or less in terms of arithmetic mean roughness Ra. The light-emitting device of claim 1, wherein the forming substrate is composed of glass, quartz, sapphire or polycrystalline alumina. The light-emitting device of claim 1, wherein the thickness of the formed substrate is 0.05 mm or more and 3 mm or less. A method of manufacturing a light-emitting device, comprising: a semiconductor light-emitting chip; and a wavelength conversion member disposed in contact with the semiconductor light-emitting wafer, the wavelength conversion member having a substrate and a phosphor a film, wherein the phosphor film is formed on at least one side of the substrate, comprising a particulate phosphor material and a binder; and the method of manufacturing is characterized in that the phosphor film is produced by using a printing method. The phosphor film material is coated on at least one side of the substrate, and is formed by reacting at room temperature or heat-treating at a temperature of 500 ° C or lower, and the phosphor film material contains the phosphor material and the binder material. The binder raw material includes at least one of the group consisting of a cerium oxide precursor, a ceric acid compound, vermiculite, and an amorphous vermiculite which become cerium oxide by hydrolysis or oxidation. A light-emitting element which is a light-emitting element in which a wavelength conversion member is disposed on a semiconductor light-emitting chip by an adhesive, wherein the wavelength conversion member has a substrate and a phosphor film formed thereon, and the phosphor film is formed therein. At least one surface of the substrate comprises a particulate phosphor material and a binder, wherein the phosphor film is coated on at least one side of the substrate to be reacted at room temperature or Formed by heat treatment at a temperature of 500 ° C or less, the phosphor film raw material comprising the phosphor material and a binder raw material, the binder raw material comprising a cerium oxide precursor comprising cerium oxide by hydrolysis or oxidation, and ceric acid At least one of the group consisting of a compound, vermiculite, and an amorphous vermiculite obtained by reacting an adhesive raw material at a normal temperature or a heat treatment at a temperature of 500 ° C or lower, the adhesive raw material including a cerium oxide precursor which becomes cerium oxide by hydrolysis or oxidation, a ceric acid compound, a phosphoric acid compound, and at least a part of carbon which is detached by heating to become an inorganic bonded cerium resin At least one group. The light-emitting element of claim 8, wherein the primary particles of the phosphor material have an average particle diameter of 1 μm or more and 20 μm or less. The light-emitting element of claim 8, wherein the film thickness distribution of the phosphor film is within ±10%. The light-emitting element of claim 8, wherein the surface roughness of the phosphor film is 10 μm or less in terms of arithmetic mean roughness Ra. The light-emitting element of claim 8, wherein the forming substrate is composed of glass, quartz, sapphire or polycrystalline alumina. The light-emitting element of claim 8, wherein the thickness of the formed substrate is 0.05 mm or more and 3 mm or less. A light-emitting device characterized by comprising the light-emitting element of claim 8. A method of manufacturing a light-emitting element, wherein the light-emitting element is provided with a wavelength conversion member on a semiconductor light-emitting chip by using an adhesive, the wavelength conversion member having a base material and a phosphor film formed on at least one side of the substrate; The phosphor film includes a particulate phosphor material and a binder. The method of manufacturing the film is characterized in that the phosphor film is coated with a phosphor film material on at least one side of the substrate by a printing method. And forming the reaction at normal temperature or by heat treatment at a temperature of 500 ° C or lower, the phosphor film raw material comprising the phosphor material and a binder raw material, the binder raw material comprising including oxidation or oxidation to become an oxidation At least one of the group consisting of cerium oxide precursor, ceric acid compound, vermiculite, and amorphous vermiculite, the semiconductor light-emitting chip and the wavelength conversion member are followed by an adhesive, the adhesive being The adhesive raw material is reacted at a normal temperature or heat-treated at a temperature of 500 ° C or lower, and the adhesive is obtained. The material includes at least one of the group consisting of a cerium oxide precursor which is hydrolyzed or oxidized to form cerium oxide, a ceric acid compound, a phosphoric acid compound, and at least a part of carbon which is detached by heating to be inorganically bonded.