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  • H01L2224/42—Wire connectors; Manufacturing methods related thereto
  • H01L2224/47—Structure, shape, material or disposition of the wire connectors after the connecting process
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  • H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
  • H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
  • H01L33/50—Wavelength conversion elements
  • H01L33/501—Wavelength conversion elements characterised by the materials, e.g. binder
  • H01L33/502—Wavelength conversion materials

Definitions

• the present invention relates to a light-emitting device such as a light-emitting diode that can be used for a display, illumination, backlight light source, and the like. More specifically, the light-conversion composite that is a light-conversion member that obtains fluorescence using irradiated light, The present invention relates to a light emitting device using a conversion complex and a color tone control method. Background
• white light-emitting diodes using blue light-emitting diodes are light weight, do not use mercury, and have a long service life. Therefore, demand is expected to increase rapidly in the future.
• the most commonly used method for converting blue light of a blue light emitting element into white light is to obtain a pseudo white color by mixing yellow that is complementary to blue. For example, as described in Japanese Patent Application Laid-Open No. 2 0 0 0-2 0 8 8 1 5, fluorescence that emits yellow light by absorbing part of blue light is emitted on the front surface of a light emitting diode that emits blue light.
• the coating layer containing the body is provided, and the blue light from the light source and the yellow light from the phosphor are mixed before that.
• a white light emitting diode can be formed by providing a mold layer or the like.
• As the phosphor YAG (Y 3 A 15 10 12 ) powder activated with cerium is used.
• Japanese Patent Application Laid-Open No. 2000-059-1 9 1 1 9 7 In a light-emitting device in which a light-transmitting member is formed so as to cover a light-emitting element formed on a substrate, and further, a phosphor layer made of a phosphor powder-containing resin is formed so as to cover the light-transmitting member. It has been proposed that the upper surfaces of the conductive member and the phosphor layer have an arithmetic average roughness of 0.1 to 0.8 / xm.
• the present inventors emit fluorescence (Y, C e) 3 A 1 5 0 12 phase and a plurality of oxide phases including A 1 2 0 3 phase are continuously and three-dimensionally entangled with each other.
• a white light-emitting device composed of a light-conversion composite formed of a solidified body and a blue light-emitting element has been proposed (International Publication WO 2 0 0 4 Z 0 6 5 3 2 4).
• This composite for light conversion can stably obtain homogeneous yellow fluorescence because the phosphor phase is uniformly distributed, and is excellent in heat resistance because it is a ceramic.
• the ratio of blue light to yellow fluorescence can be controlled by changing the thickness of the light conversion composite. For this reason, by suppressing variations in thickness, it is possible to easily suppress variations in color tone of the white light emitting device, which is a great advantage in the manufacturing process compared to a configuration using a conventional phosphor powder.
• the composite for light conversion uses a eutectic reaction between oxide phases that are constituent phases in the production process, the ratio of each phase is limited to some extent, and the amount of the phosphor phase cannot be changed greatly. Have difficulty. Therefore, when it is necessary to increase the amount of yellow component light when adjusting the color tone of the light emitting device, the required thickness of the light conversion complex increases, and the material cost of the spectral conversion complex increases. There is a problem that it ends up. In addition, although the loss of light inside the light conversion composite is small, it increases as the thickness increases, which is not preferable in terms of improving the light emission efficiency of the light emitting device.
• An object of the present invention is to provide a complex for light conversion that can obtain necessary fluorescence with a thinner thickness, has a low cost, and suppresses light loss in the complex.
• Another object of the present invention is to provide a light-emitting device that uses a light-emitting element and the composite for light conversion and that is highly efficient, easy to adjust color, has little variation, and is extremely suitable for high output. Disclosure of the invention
• the present invention is a light conversion composite comprising a plurality of oxide phases including an oxide crystal phase that emits at least one fluorescence, and a light emitting surface opposite to the light incident surface of the light conversion composite
• the surface roughness of at least one surface The present invention relates to a composite for light conversion characterized by having an arithmetic average roughness (R a) of not less than 0.05 m.
• the composite for light conversion according to the present invention is an integral body (a lump) of an oxide composite, and is different from a conventional light converter in which particulates are dispersed in a resin.
• the composite for light conversion has a structure in which at least two or more oxide phases are continuously and three-dimensionally entangled with each other, and the oxide phase At least one of them relates to a composite for light conversion comprising a solidified body that is a crystalline phase that emits fluorescence.
• the light emitting surface of the composite for light conversion is an uneven surface having a different height for each oxide phase.
• the composite for light conversion relates to a composite for light conversion containing at least Y element, A1 element and Ce element as composition components.
• the present invention also relates to a light emitting device comprising the light conversion composite and a light emitting element.
• the complex for light conversion emits fluorescence having a peak at a wavelength of 530 to 5800 nm, and the light emitting element has a light having a peak at a wavelength of 400 to 500 nm.
• this invention relates to the color tone adjustment method which adjusts the color tone of the said light-emitting device by changing the surface roughness of the said composite for light conversion.
• the composite for light conversion of the present invention fluorescence stronger than before can be obtained with the same incident light.
• the necessary fluorescence intensity can be obtained with a thinner light-conversion complex, so that it is possible to provide a light-conversion complex with low cost and reduced light loss in the complex.
• the fluorescence intensity can be controlled without changing the thickness of the composite for light conversion, the light emitting element and the composite for light conversion can be easily adjusted in color. It is possible to provide a white light-emitting device that is highly efficient and highly suitable for high output.
• FIG. 1 is a schematic cross-sectional view showing an embodiment of a light-emitting device of the present invention.
• FIG. 2 is a photomicrograph of Example 1 showing an example of a tissue structure of a composite for light conversion of the present invention.
• FIG. 3 is a fluorescence spectrum diagram of Example 1 showing an example of the fluorescence characteristics of the complex for light conversion of the present invention.
• FIG. 4 is a light emission spectrum diagram of Example 8 showing an example of the light emitting device of the present invention.
• FIG. 5 is a chromaticity diagram of Examples 9, 10 and 11 showing an example of the color tone adjustment method of the light emitting device of the present invention.
• FIG. 6 is a photomicrograph showing the cross section of the surface of the composite for light conversion produced in Example 13.
• FIG. 7 is a photomicrograph showing a cross section of the surface of the composite for light conversion produced in Example 19.
• FIG. 8 is a laser micrograph of the surface of the light conversion composite prepared in Example 20.
• FIG. 9 is a light emission spectrum diagram of Example 21 showing an example of the light emitting device of the present invention.
• the composite for light conversion of the present invention is a composite for light conversion comprising a plurality of oxide phases including an oxide crystal phase emitting at least one fluorescence, Light characterized in that the surface roughness of at least one surface of the light emitting surface opposite to the light incident surface of the composite for light conversion is not less than 0.05 xim in terms of arithmetic mean roughness (Ra) It is a complex for conversion.
• the composite for light transmission conversion is plate-shaped, and has an incident surface on which light before conversion is incident and a radiation surface from which the converted light exits.
• the surface roughness (R a) of the incident surface or radiation surface is 0.05 m or more.
• the composite for light conversion of the present invention comprises a plurality of oxide phases including an oxide crystal phase that emits at least one fluorescence, and the constituent oxide phases other than the oxide crystal phase that emits fluorescence include glass or molten It may be a solidified body and is not particularly limited.
• a preferred form of the composite for light conversion is a solidified body having a structure in which at least two or more oxide phases are continuously and three-dimensionally entangled with each other. At least one of them is a light conversion complex, which is a crystalline phase that emits fluorescence.
• Fluorescence can be emitted by entering excitation light into the light conversion complex.
• At least one surface of the composite for light conversion has a surface roughness of not less than 0.05 m in terms of arithmetic average roughness (hereinafter referred to as R a) as described in JISB 0 6 0.0 5 — 1 9 94 Has been processed.
• the surface of the composite for light conversion has a surface roughness of R a ⁇ 0. 0 5; a rough surface of tim, R a ⁇ 0. 0 5; for light conversion of the same thickness compared to the surface close to the mirror surface of m. Since stronger fluorescence can be obtained from the complex, the surface roughness Ra is limited to the above range. The fluorescence intensity obtained increases as the surface roughness Ra increases, and the surface roughness Ra ⁇ 0.1 m is more preferred.
• Light conversion composites with a surface roughness R a ⁇ 0.1 m are compared to light conversion composites of the same material and thickness that have a surface close to a mirror with a surface roughness R a ⁇ 0. 0 5.
• the upper limit of the surface roughness Ra is not particularly limited, but if the surface roughness Ra is too large relative to the thickness of the composite for light conversion, it is difficult to maintain the shape and the handling property is also deteriorated.
• the surface roughness Ra is preferably 1/2 or less of the thickness of the composite for light conversion. Further, it is more preferably 50 zm or less, and further preferably 30 m or less, from the viewpoint of easy formation of surface roughness.
• the composite for light conversion of the present invention if the light transmission surface is a rough surface with a surface roughness R a ⁇ 0.05 zm, light is scattered on the light output surface, but finally light conversion is performed.
• the relative amount of the total radiant flux passing through the composite for the total incident flux is not necessarily reduced, but can be increased.
• the light extraction efficiency is remarkably improved, and the fluorescence intensity can be further improved.
• the rough surface of the composite for light conversion with a surface roughness of R 8 ⁇ 0.05 5 111 is located across the path of the incident light, the incident light is scattered and efficiently absorbed by the crystalline phase that emits fluorescence. This is preferable because stronger fluorescence can be obtained.
• the light conversion composite is plate-shaped and light travels in the thickness direction, either the light incident surface (incident surface) or the light exiting surface (radiation surface) is rough. If so, strong fluorescence can be obtained due to the above effects. Furthermore, it is more preferable that both the incident surface and the emitting surface are rough because the scattering effect increases and stronger fluorescence is obtained. That's right.
• oxide phase is not particularly limited constant varies with the production conditions of the composition components and solidified body, in which Y element at least as a composition component, comprising the A 1 element and C e elements, A 1 2 0 3 (sapphire) phase, (Y, C e) 3 A 15 0 12 equality may be mentioned, include two or more phases at least the oxide phase was doing. At least two phases of each oxide phase have a structure that is continuously and three-dimensionally entangled with each other. Some oxide phases may be present in granular form in an intertwined structure formed by other oxide phases. In any case, there is no boundary layer such as amorphous at the boundary of each phase, and the oxide phases are in direct contact with each other. For this reason, there is little light loss in the light conversion complex, and the light transmittance is high.
• the crystalline phase that emits fluorescence also varies depending on the compositional components and the manufacturing conditions of the solidified body, and is not particularly limited. However, if the compositional components include at least Y, A1 and Ce, (Y, Ce) 3 ⁇ 1 5 ⁇ ⁇ 2 phases are included, and at least one crystal phase that emits such fluorescence is included. These oxide phases, including crystalline phases that emit fluorescence, have a structure in which they are continuously and three-dimensionally entangled with each other, and as a whole, each oxide phase is evenly distributed in the light conversion complex. It is possible to obtain uniform fluorescence with no bias.
• the combination of the Al 2 O 3 phase and the (Y, Ce) 3 A 1 5 0 12 phase makes it easy to obtain a structure in which both are continuously and three-dimensionally entangled with each other.
• the (Y, C e) is 3 A 1 5 0 12 phase, 4 0 0 ⁇ 5 0 0 nm violet to blue excitation light, since it emits fluorescence having a peak wavelength of 5 3 0 ⁇ 5 6 0 nm, white It is suitable as a light conversion member for a light emitting device. Therefore, it is preferable that the composition component contains at least Y element, A 1 element and Ce element.
• a (Y, Gd, Ce) 3 A 1 5 ⁇ 12 phase is generated as a crystalline phase that emits fluorescence. It can emit fluorescence having a wavelength of 5400 to 5800 nm.
• the solidified body constituting the composite for light conversion of the present invention is produced by solidifying the raw material oxide after melting.
• a solidified body by a simple method of cooling and condensing a melt charged in a loop kept at a predetermined temperature while controlling the cooling temperature, but most preferably, it is produced by a unidirectional solidification method. It is a thing. This is because the unidirectional solidification causes the contained crystal phase to continuously grow in a single crystal state, reducing the attenuation of light within the member.
• the solidified body constituting the composite for light conversion of the present invention is the one in which the applicant of the present application has already been disclosed in Japanese Patent Application Laid-Open No. Hei 7-1 4 9 5 9 Japanese Patent Laid-Open No. 7-1 8 7 8 93, Japanese Patent Laid-Open No. 8-8 1 2 5 7, Japanese Patent Laid-Open No. 8-2 5 3 3 8 9, Japanese Patent Laid-Open No. 8-2 5 3 3 9 No. 0 and Japanese Patent Laid-Open No. 9 6 7 1 94 and U.S. applications corresponding thereto (US Pat. Nos. 5, 5 6 9 and 5 4 7, 5, 4 8 4 and 7 5 2, No. 5, 90, 96, etc.) and the like, and can be manufactured by the manufacturing method disclosed in these applications (patents). The disclosures of these applications or patents are hereby incorporated by reference.
• the composite for light conversion of the present invention can be obtained by processing the solidified body obtained by the above method into a predetermined shape and adjusting the surface to a predetermined surface roughness.
• the method used for adjusting the surface roughness is not particularly limited, but a physical method such as grinding / polishing with a grindstone / abrasive grain is easy and suitable.
• the surface roughness of the composite for light conversion of the present invention is adjusted by performing a surface treatment so that the surface oxide phases each have a predetermined height, and forming uneven surfaces having different heights for each oxide. But it can be done.
• the surface treatment method is not particularly limited, but chemical treatment in an acid solution (wet etching) ), Heat treatment under various gas atmospheres (dry etching), and the like are preferable.
• This is a so-called selective etching method, that is, an etching method in which the etching selectivity varies depending on the type of oxide.
• the etching agent may be appropriately selected according to the type of the complex oxide.
• a sulfuric acid / phosphoric acid mixed solution a gas containing an element capable of reducing oxides such as C, and the like can be used.
• the surface roughness of the composite for light conversion can be achieved without destroying the surface texture. Fluorescence intensity can be realized, and it is also preferable for forming a larger surface roughness Ra.
• the adjustment of the surface roughness of the composite for light conversion of the present invention is carried out by a physical method such as grinding / polishing with the above-mentioned grindstone-abrasive grains, chemical treatment in an acid solution, under various gas atmospheres A combination of methods such as heat treatment may be used. In this case, an uneven surface having a different height is formed for each oxide, and the uneven surface having a step is further roughened.
• the fluorescence intensity is improved by having a surface roughness of 0.05 m / m or more.
• a surface roughness of 0.05 m / m or more.
• the ratio of total reflection at the light exit surface is probably lower, so more light can be extracted from the light conversion complex. It can greatly contribute to the improvement of strength. It is more preferable that uneven surfaces having different heights are formed for each oxide and that the surface roughness is 0.1 m or more.
• each oxide phase including a crystal phase that emits fluorescence exists continuously and three-dimensionally intertwined with each other, so that uniform fluorescence can be obtained.
• the surface of the composite for light conversion has a surface roughness R a ⁇ 0.05 m. Since incident light can be absorbed more efficiently in the crystalline phase that emits fluorescence than in the case of coalescence, stronger fluorescence can be obtained. Moreover, the fluorescence intensity obtained can be controlled by changing the surface roughness Ra. As a result, the required fluorescence intensity can be obtained with a thinner thickness, and the volume of the required light conversion complex can be reduced. Therefore, the cost of light loss in the complex can be reduced.
• a composite for light conversion can be provided.
• the light-emitting device of the present invention is a device comprising the light-conversion composite of the present invention and a light-emitting element, and irradiates the light-conversion complex with light from the light-emitting element and transmits the light-converted composite Further, the present invention is characterized in that the light from the light emitting element uses fluorescence whose wavelength is converted by the complex for light conversion.
• FIG. 1 is a schematic cross-sectional view showing an embodiment of a light emitting device of the present invention.
• 1 is a composite for light conversion
• 2 is a light emitting element (light emitting diode element)
• 3 is a lead wire
• 4 is a lead electrode
• 5 is a member for holding the composite 1 for light conversion of a fixed member.
• the side surface of the composite 1 for light conversion is held and covered by the member 5, the surface 2 a on which the light from the light emitting element 2 is incident, and the light that passes through the composite 1 for light conversion (some light is converted)
• the surface 2 b which emits (which is mixed with transmitted light).
• a white light-emitting device that is an embodiment of the light-emitting device of the present invention includes a violet to blue light-emitting element that emits light having a peak at a wavelength of 400 nm to 500 nm, and a peak generated by light emitted from the light-emitting element. It consists of the said composite for light conversion which emits yellow fluorescence with a wavelength of 530-058 nm. Violet-blue light emitted from the violet-blue light-emitting element is incident on the light conversion complex whose fluorescence peak wavelength is adjusted so that white is obtained in accordance with the wavelength.
• the composite for light conversion used in the light emitting device of the present invention is produced in an appropriate shape such as a plate shape by the above method.
• the color tone of the light emitting device can be easily controlled by changing the surface roughness of the surface of the light conversion composite as well as changing the thickness of the light conversion composite. By optimizing the thickness and surface roughness of the composite for light conversion, it is possible to obtain a highly efficient light-emitting device that suppresses light loss inside the composite for light conversion.
• the variation in color tone of the light emitting device can be easily reduced by maintaining the accuracy of the thickness of the composite for light conversion, and can be further reduced by finely adjusting the surface roughness later. .
• This composite for light conversion can be used as a component as it is, no encapsulating resin is required, and there is no deterioration due to heat and light, so it can be used in combination with high-power purple to blue light-emitting elements. High output of the light emitting device is possible.
• Examples of the light-emitting element used in the light-emitting device of the present invention include a light-emitting diode element and an element that generates laser light, but the light-emitting diode element is preferable because it is small and inexpensive.
• the color tone can be easily adjusted by the surface roughness of the light conversion composite, and the optical loss inside the light conversion composite is suppressed by optimizing the thickness and the surface roughness.
• a highly efficient light-emitting device can be provided.
• this light-emitting device is not deteriorated by heat or light, and is extremely suitable for high output.
• Facial -1 2 ⁇ 3 powder (purity 9 9. 99%) 0 with A 1 0 3/2 terms. 8 2 mol, Y 2 0 3 powder (purity 9 9. 9%) 0.13 5 mol in terms of 3/2 , and € 0 2 powder (purity 9 9, 9) 0. 0 0 5 mol Weighed so that These powders were wet mixed in ethanol for 16 hours with a pole mill, and then ethanol was removed using an evaporator to obtain a raw material powder. The raw material powder was pre-melted in a vacuum furnace and used as a raw material for unidirectional solidification.
• this raw material was charged into a molypden crucible as it was, set in a unidirectional solidification device, and the raw material was melted under a pressure of 1. 3 3 X 1 0— 3 Pa (1 0 " 5 Torr).
• the rusppo is lowered at a speed of 5 mm Z time, A 1 2 0 3 (sapphire) phase, (Y, C e) 3 A 1 5 ⁇ 12 phase, C e A 1 0 18 phase
• a solidified body consisting of three oxide phases was obtained.
• Figure 2 shows the cross-sectional structure perpendicular to the solidification direction of the solidified body.
• the black part of A is the A 1 2 0 3 (sapphire) phase
• the white part of B is (Y, C e) 3 A 1 5 O!
• Two phases, the slightly gray part of C present is CeA 1 j, ⁇ , 8 phases.
• Each oxide phase has a structure that is continuously and highly entangled with each other, and the main phosphor phases (Y, Ce) 3 A 1 5 ⁇ 12 phases are uniformly distributed I understand that. For this reason, homogeneous fluorescence can be obtained.
• a disc-shaped sample (i 16 mm x 0.2 mm) was cut out from the obtained solidified body, and the fluorescence characteristics were evaluated with a solid-state quantum efficiency measurement device manufactured by JASCO. Correction was performed using a sub-standard light source to determine the true spectrum
• the fluorescence spectrum is shown in Fig. 3. Peak wavelength at 5 47 nm with excitation light at wavelength 4 6 O nm
• a professional fluorescent spectrum with the following characteristics was obtained.
• the resulting solidified body has a plate shape of 2 mmX 2 mmX 0.15 mm.
• the upper surface is ground with # 3 00 0 (JISR 6 0 0 1) abrasive grains, and the lower surface is adjusted to the desired surface roughness by polishing with a polishing paste.
• a composite sample for light conversion having a plate shape of 2 mmX 2 mmX 0.15 mm and a surface roughness of 2 mmX 2 mm as shown in Table 1 was prepared from the solidified body prepared in Example 1. Excitation light was incident from the lower surface side, and the fluorescence intensity emitted from the upper surface side was measured in the same manner as in Example 1. To adjust the surface roughness, use the count of the grindstone (JISR 6 0 0 1) of the grindstone used for grinding. This was done by setting 1 0 0 0 to # 2 0 0. Table 1 shows the relative fluorescence intensity of each example.
• Examples 2, 3, and 4 the relative fluorescence intensity increased as the surface roughness Ra of the upper surface increased, and the relative fluorescence intensity of 10 5 or more was obtained in all cases, and the surface roughness Ra ⁇ 0. It can be seen that strong fluorescence can be obtained by setting 1 m to 5% or more, and Ra Ra 0.25 m to 10% or more. In Examples 4 and 5, a strong relative fluorescence intensity can be obtained in the same manner regardless of whether the surface having a surface roughness Ra of 0.05 Xm or more is the lower surface that is the incident surface or the upper surface that is the radiation surface. I understand that. In Examples 4, 6, and 7, it can be seen that the relative fluorescence intensity is further increased by increasing the surface roughness Ra on both the upper and lower surfaces.
• the 2 mmX 2 mmX 0.0 7 mm plate shape from the solidified body prepared in Example 1, and the surface roughness of the 2 mmX 2 mm surface is R a 1.6 nm for both the upper and lower surfaces.
• Figure 5 shows the CIE chromaticity in combination with Comparative Example 2 when a white light-emitting device is configured in combination with light-emitting diode elements.
• the thickness of the composite for light conversion is 0.15 mm and is the same.
• the color tone of the light emitting device can be controlled by the surface roughness Ra of the surface of the composite for light conversion.
• the composite sample for light conversion with 1.6 m was able to obtain approximately 15% stronger fluorescence.
• Sulfuric acid: Phosphoric acid 200 in a mixed acid of 1: 1 (volume ratio).
• a CX 2 h heat treatment was performed to obtain a ceramic composite for light conversion in which the (Y, Ce) 3 A 1 5 0 12 phase was an uneven surface about 7 zm lower than the A 1 2 0 3 phase.
• Figure 6 shows the cross section of the surface of the resulting ceramic composite for light conversion.
• the black part of A is the Al 2 0 3 (sapphire) phase
• the white part of B is the (Y, C e) 3 A 1 5 0 12 phase
• the (Y, C e) 3 A 1 5 0 12 phase is An uneven surface that is approximately 7 m lower than the A 1 2 0 3 phase is formed.
• the light emitted from the upper surface was collected using an integrating sphere, and the integrated value (total radiant flux) of the total emitted light was determined. Assuming that Comparative Example 1 is 1 0 0, the relative total radiant flux is 1 0 9, indicating that the total radiant flux is significantly increased.
• the fluorescence intensity was measured in the same manner as in Example 13 and the obtained fluorescence intensity is shown in Table 2.
• the fluorescence intensity increases as the height difference and the accompanying surface roughness Ra increase, and the surface roughness Ra ⁇ 0.1 m. It can be seen that strong fluorescence is obtained by 5% or more, and further by Ra ⁇ 0.25m, 10% or more. At the same time, the total radiant flux increases.
• heat treatment is not performed at 1.400 ° CX for 1 h in a carbon container under the pressure of 1. 3 3 X 1 0— 3 Pa (1 0— 5 Torr)
• a ceramic composite for light conversion having uneven surfaces with different heights was obtained.
• Figure 7 shows a cross section of the surface of the resulting ceramic composite for light conversion.
• the black part of A is the A 1 2 0 3 (safia) phase
• the white part of B is the (Y, Ce) 3 A 1 5 0 12 phase.
• An uneven surface having an A 1 5 0 1 2 phase approximately 5-IO m lower than the A 1 2 0 3 phase was obtained.
• a 1 2 ⁇ The surface of the three phases remains rough
• phase 12 is a surface whose roughness has been reduced by the treatment.

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