JP2013229438A - Light-emitting device, and method of manufacturing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a light-emitting device having a color conversion compact with reduced restrictions of a thickness, a shape, and an inorganic phosphor to be used, and to provide a method of manufacturing the same.SOLUTION: A light-emitting device 1 comprises: a semiconductor light-emitting element 2; and a phosphor layer 3 containing granular inorganic phosphor 31 provided at least on an upper surface of the semiconductor light-emitting element 2. In addition, the granular inorganic phosphor 31 is coated by a coating layer 32 made of ceramics for coating particles of the inorganic phosphor 31 and adhering the particles to each other. Further, air gaps 33 are formed inside the phosphor layer 3, and an unevenness shape caused by a particle diameter of particles of the inorganic phosphor 31 is formed on a surface of the phosphor layer 3.

Description

  The present invention relates to a light emitting device including a color conversion molded body made of an inorganic material containing a granular inorganic phosphor and a method for manufacturing the same.

  In a semiconductor light emitting device such as a light emitting diode or a semiconductor laser, part or all of the light color emitted from the semiconductor light emitting device is color-converted using a color conversion molding containing a phosphor, and the emission color is converted. There are light emitting devices that output. Such light emitting devices are also used for applications that require high output such as headlights and projectors.

  Conventionally, as a color conversion molded body used in such a light-emitting device, a color conversion molded body in which a phosphor is dispersed in a silicone resin having relatively good heat resistance and light resistance has been used. However, in recent severe applications corresponding to higher output and higher load of light sources using semiconductor light emitting devices such as LEDs (light emitting diodes) and LD (laser diodes), they are used for molded products for color conversion. It is conceivable that the resin deteriorated.

Therefore, ceramic conversion body for color conversion, which does not contain resin or organic matter, and only inorganic phosphor, or inorganic phosphor and transparent inorganic material are molded into a plate shape, has high output and high load. LEDs and LDs used as color conversion moldings have been put to practical use.
In addition, various methods have been proposed for manufacturing a ceramic molded body for color conversion made of only an inorganic material.

  For example, Patent Document 1 describes an inorganic oxide rare earth garnet-based compound, particularly a YAG (yttrium, aluminum, garnet) -based phosphor as an example of a durable light-emitting converter. Although the manufacturing method is not described in detail, it is assumed that a light emitting conversion body is manufactured by a method of manufacturing a polycrystalline ceramic body from a ceramic base material and then doping an activator serving as a light emission center. Thereafter, a method of using the polycrystalline ceramic body, which is the luminescence conversion body, in combination with a semiconductor light emitting element is described.

Patent Document 2 describes the configuration and manufacturing method of glass containing an inorganic phosphor as a luminescent color conversion member. Here again, YAG phosphors of oxide phosphors are cited as examples.
Patent Document 3 describes a method of obtaining a luminescent ceramic as a color converter by sintering an inorganic phosphor at high temperature and pressure.

Patent Document 4 discloses a method of producing an inorganic color conversion glass sheet by producing a sheet from phosphor powder and glass powder and introducing the sheet into a high-temperature furnace. Here, a method of using a low-melting glass having a melting point of 400 ° C. or lower is described as a method of making phosphors of various compounds into inorganic color conversion glass sheets.
Furthermore, Patent Document 5 describes a method for depositing and growing a YAG phosphor from a melt such as alumina as a method for producing a ceramic composite for light conversion.

JP 2004-146835 A JP 2003-258308 A JP 2006-5367 A JP 2006-37097 A JP 2006-169422 A

  However, the ceramic molded bodies described in Patent Document 1 to Patent Document 5 are all manufactured by sintering or melting an inorganic material. A ceramic molded body produced by sintering or melting is generally molded into a desired shape by processing such as slicing and polishing from a bulk ceramic. For this reason, for example, when forming into a plate shape, there was a limit to reducing the thickness.

  Furthermore, when a ceramic body is formed by sintering a phosphor and an inorganic material other than the phosphor, the phosphor content in the produced ceramic body is low, so that sufficient color conversion can be performed. A considerable thickness was necessary.

  Moreover, since the conventional ceramic molded body needs to be cut out from a bulk ceramic and molded into a desired shape, there is a restriction on the shape of the molded body that can be processed.

Further, as inorganic red phosphors, for example, nitride phosphors such as CASN having a basic composition of CaSiAlN ₃ : Eu and SCASN containing a large amount of Sr are known. The shape is not made. In addition, many of the nitride phosphors are vulnerable to heat, and the phosphors are deactivated by the heat during sintering. Therefore, it has been impossible to produce a molded body containing these phosphors by sintering.

  This invention makes it a subject to provide the light-emitting device provided with the molded object for color conversion with few restrictions of the thickness, shape, and inorganic fluorescent substance to be used, and its manufacturing method in view of this problem.

The present invention has been devised to solve the above-described problems, and a light-emitting device according to a first invention includes a semiconductor light-emitting element, an inorganic particle layer containing particles of a color conversion member made of an inorganic material, The inorganic particle layer has an aggregate, a coating layer, and voids.
Note that the “light emitting device” in the present invention is a device in which a color conversion member is mounted on a semiconductor light emitting element and emits a target emission color by electrical connection.

  According to this configuration, the light of the first color emitted from the semiconductor light emitting element and incident on the inorganic particle layer is absorbed by the color conversion member, and is converted into light of the second color different from the first color. Is emitted. At this time, the incident light to the inorganic particle layer is scattered by the voids existing in the inorganic particle layer, and is efficiently irradiated to the color conversion member in the inorganic particle layer. As a result, the incident light is efficiently absorbed by the particles of the color conversion member, and is converted into light of the second color.

  The color conversion member absorbs light of the first color and emits light of a second color different from the first color. For example, a nitride phosphor, a fluoride phosphor, or the like is used. It is an inorganic phosphor. Moreover, in the inorganic particle layer, the particles of the color conversion member become aggregates continuously connected by contacting the particles or the semiconductor light emitting element. And the surface of a semiconductor light-emitting device and the surface of the particle | grains of a color conversion member are continuously coat | covered with the coating layer which consists of inorganic materials. That is, the thickness and shape of the inorganic particle layer, which is a layer that performs color conversion, are determined by the thickness and shape of the aggregate of particles of the color conversion member. In addition, a void surrounded by any of the semiconductor light emitting element, the color conversion member particles, and the coating layer is formed inside the inorganic particle layer.

  In the light emitting device according to the second invention, the voids in the inorganic particle layer preferably have a porosity of 1 to 50%.

  According to such a configuration, the light-emitting device contains the color conversion member with a high content rate by the voids in this range, and scatters incident light well and irradiates the color conversion member in the inorganic particle layer. Efficient color conversion of incident light. In addition, the voids with a porosity in this range allow the light-emitting device to absorb strain due to thermal expansion during heat generation even when there is a difference between the linear expansion coefficient of the light-emitting device and the linear expansion coefficient of the inorganic particle layer. Prevents the generation of cracks.

  In the light emitting device according to the third invention, the average particle diameter of the particles of the color conversion member may be 0.1 to 100 μm, and the average thickness of the coating layer may be 10 nm to 50 μm.

  By using a color conversion member having an average particle diameter in this range, a thin color conversion inorganic conversion member can be obtained. Moreover, the particle | grains of a color conversion member can be coat | covered favorably by making the average thickness of a coating layer into this range.

  In the light emitting device according to the fourth aspect of the invention, it is preferable that a concavo-convex shape resulting from the particle size of the color conversion member particles is formed on the surface of the inorganic particle layer.

  According to such a configuration, the light emitting device can reduce total reflection at the interface of light propagating in the inorganic particle layer, and can be efficiently taken out from the surface on which the uneven shape is formed.

  In the light emitting device according to the fifth invention, the covering layer is preferably formed by an atomic layer deposition method.

  According to such a configuration, in the light emitting device, the particles contained in the inorganic particle layer are covered with the uniform and dense coating layer formed by the atomic layer deposition method, and the voids are favorably formed in the gaps between the particles. Is done.

In the light-emitting device according to a sixth aspect of the invention, the coating layer has Al ₂ O ₃ , SiO ₂ , ZrO ₂ , HfO ₂ , TiO ₂ , ZnO, Ta ₂ O ₅ , Nb ₂ O ₅ , In ₂ O ₃ , It is preferable to contain at least one compound selected from the group consisting of SnO ₂ , TiN, and AlN.

  According to such a configuration, the light emitting device satisfactorily coats the particles of the color conversion member with the coating layer made of a suitable material.

  In the light emitting device according to the seventh invention, the color conversion member is selected from the group consisting of sulfide phosphors, halogen silicate phosphors, nitride phosphors, and oxynitride phosphors. At least one compound can be contained.

  According to this configuration, the light-emitting device can perform color conversion using these inorganic phosphors that are easily deactivated by heat.

  In the light emitting device according to the eighth invention, the color conversion member can contain at least a fluoride fluorescent material.

  According to such a configuration, the light emitting device can perform color conversion using the fluoride phosphor that is easily deteriorated by moisture.

  In the light emitting device according to the ninth invention, it is preferable that the particles of the color conversion member are bound to each other and to the semiconductor light emitting element by an inorganic binder.

  According to such a configuration, the inorganic particle layer of the light emitting device is formed without dissipating the aggregates of the particles of the color conversion member due to the inorganic binder.

  A method for manufacturing a light emitting device according to a tenth invention includes a semiconductor light emitting element manufacturing process, an inorganic particle layer forming process, and a coating layer forming process, and is performed in this order.

  According to this procedure, first, a semiconductor light emitting device is manufactured in a semiconductor light emitting device manufacturing process. Next, in the inorganic particle layer forming step, the surface of the semiconductor light emitting element absorbs the first color light emitted from the semiconductor light emitting element and emits the second color light different from the first color. Aggregates containing particles of the color conversion member made of the material are formed. That is, the thickness and shape of the inorganic particle layer, which is a layer that performs color conversion, are determined by the thickness and shape of the aggregate of particles of the color conversion member.

  Next, in the coating layer forming step, a coating layer made of an inorganic material that continuously covers the surface of the semiconductor light emitting element and the surface of the color conversion member particles is formed. That is, the above-described aggregate is a light-emitting device integrated with the semiconductor light-emitting element by the coating layer while maintaining this shape.

  According to an eleventh aspect of the present invention, there is provided a method for manufacturing a light emitting device, wherein in the inorganic particle layer forming step, the aggregate is obtained by electrodeposition, electrostatic coating, pulse spraying or centrifugal sedimentation, or a combination of these methods. It is preferable to form on the surface of the semiconductor light emitting device.

  According to such a procedure, in the inorganic particle layer forming step, the aggregate containing the particles of the color conversion member is formed without becoming high temperature.

A method for manufacturing a light emitting device according to a twelfth aspect of the invention performs a conductor layer forming step before the inorganic particle layer forming step, and after the inorganic particle layer forming step and before the coating layer forming step. It is preferable to perform a conductor layer transparentizing step.
According to this procedure, first, in the conductor layer forming step, a conductor layer made of metal is formed on the surface of the semiconductor light emitting element. Next, in the inorganic particle layer forming step, the aggregate containing the inorganic phosphor via the conductor layer on the surface of the semiconductor light emitting element by the electro-deposition method or the electrostatic coating method using the conductor layer as one electrode Form. Next, in the conductor layer transparentizing step, the conductor layer made of metal is made transparent by oxidizing, for example, using hot water. In the coating layer forming step, a coating layer made of an inorganic material that continuously covers the surface of the transparent conductor layer and the surface of the color conversion member particles is formed.

In the light emitting device manufacturing method according to a thirteenth aspect of the invention, the transparent conductor layer is preferably made of the same material as the coating layer.
According to such a procedure, in the coating layer forming step, the particle layer of the color conversion member formed on the surface of the semiconductor light emitting element via the transparent conductor layer is coated with the same material as the transparent conductor layer. Cover with.

In the method for manufacturing a light emitting device according to the fourteenth invention, it is preferable to perform a conductor layer forming step before the inorganic particle layer forming step.
According to this procedure, first, in the conductor layer forming step, a conductor layer made of a light-transmitting conductive material is formed on the surface of the semiconductor light emitting element. Next, in the inorganic particle layer forming step, the aggregate containing the inorganic phosphor via the conductor layer on the surface of the semiconductor light emitting element by the electro-deposition method or the electrostatic coating method using the conductor layer as one electrode Form. In the coating layer forming step, a coating layer made of an inorganic material that continuously covers the surface of the transparent conductor layer and the surface of the color conversion member particles is formed.

  In the method for manufacturing a light emitting device according to a fifteenth aspect of the present invention, it is preferable that the coating layer is formed by an atomic layer deposition method in the coating layer forming step.

  According to such a procedure, in the coating layer forming step, a dense and uniform thickness coating layer is formed by the atomic layer deposition method, and the color conversion member particles are satisfactorily covered and the gaps between the particles are crushed. It is well formed as a void.

  In the method for manufacturing a light emitting device according to a sixteenth aspect, in the inorganic particle layer forming step, a compound containing at least an alkaline earth metal element as a component is used as an inorganic binder when forming the aggregate. Is preferred.

  According to such a procedure, the aggregate formed in the inorganic particle layer forming step is bound by the inorganic binder. This prevents the particles constituting the aggregate from escaping until the coating layer is formed in the subsequent coating layer forming step and the aggregate is firmly fixed.

  In the manufacturing method of the light emitting device according to the seventeenth aspect, the color conversion member may have an average particle size of 0.1 to 100 μm, and the coating layer may have an average thickness of 10 nm to 50 μm.

  According to this procedure, a color conversion inorganic conversion member having a small thickness is formed by using a color conversion member having an average particle diameter in this range. Moreover, the particle | grains of a color conversion member are coat | covered favorably by making the average thickness of a coating layer into this range.

In the method for manufacturing a light emitting device according to an eighteenth aspect of the invention, the coating layer is made of Al ₂ O ₃ , SiO ₂ , ZrO ₂ , HfO ₂ , TiO ₂ , ZnO, Ta ₂ O ₅ , and Nb ₂ O ₅ , In _2. It is preferable to contain at least one compound selected from the group consisting of O ₃ , SnO ₂ , TiN, and AlN.

  According to such a procedure, in the coating layer forming step, the particles of the color conversion member are satisfactorily coated with the coating layer made of a suitable material.

  According to the first invention, the thickness and shape of the inorganic particle layer, which is a layer that performs color conversion, can be determined by covering the aggregates of the particles of the color conversion member with the coating layer and providing voids therein. Since the shape can be determined, the thickness and shape can be freely determined. In addition, with this configuration, the inorganic particle layer can increase the content of the color conversion member in the inorganic particle layer, and has high color conversion efficiency due to the light scattering effect of the voids provided therein. Therefore, the thickness of the inorganic particle layer for obtaining a certain color conversion rate can be reduced. In addition, since the inorganic particle layer is made of an inorganic material without using an organic material such as a resin, a light-emitting device with little deterioration over time can be obtained even when exposed to high-luminance light irradiation or high temperatures. .

  According to the second aspect of the invention, by providing a void having an appropriate porosity, a good color conversion efficiency can be obtained, so that the thickness of the inorganic particle layer can be reduced. Moreover, since generation | occurrence | production of a crack can be prevented, the yield at the time of manufacture and the reliability at the time of use can be improved.

  According to 3rd invention, the thickness of an inorganic particle layer can be made thin by comprising with the color conversion member of a moderate average particle diameter, and the coating layer of moderate thickness.

  According to the fourth aspect of the invention, the light extraction efficiency to the outside can be improved by the uneven shape on the surface of the inorganic particle layer.

  According to the fifth invention, since the color conversion member is covered with a dense and uniform coating layer formed by atomic layer deposition, a highly reliable light-emitting device even when using a phosphor that easily deteriorates in an atmosphere such as moisture. It can be. Further, since the coating layer is formed at a relatively low temperature by the atomic layer deposition method, a light emitting device using a phosphor that is easily deteriorated by heat can be formed. Further, since the voids are favorably formed in the gaps between the particles of the inorganic particle layer, the color conversion efficiency can be improved.

  According to the sixth aspect, since the color conversion member is protected from the atmosphere by the coating layer using a suitable material, the reliability is improved.

  According to the seventh invention or the eighth invention, since the phosphor that can be easily deactivated by heat or the atmosphere can be used as the color conversion member, various colors, for example, color conversion inorganic that converts color to red A phosphor can be constructed.

  According to the ninth aspect, since the light emitting device is formed without dissipating the aggregate of the particles of the color conversion member by the inorganic binder, the shape of the inorganic particle layer is stabilized.

  According to the tenth invention, the thickness and shape of the inorganic particle layer, which is a layer that performs color conversion, are determined as the thickness and shape of the aggregates of the particles of the color conversion member. Therefore, the thickness and shape can be freely determined. it can. Further, since the shape of the inorganic particle layer is fixed by covering the aggregate of the particles of the color conversion member with the coating layer, the content of the color conversion member in the inorganic particle layer can be increased and provided inside. High color conversion efficiency can be obtained due to the light scattering effect of the voids. For this reason, the thickness of the inorganic particle layer for obtaining a constant color conversion rate can be reduced. In addition, since the inorganic particle layer is formed of an inorganic material without using an organic material such as a resin, a light-emitting device with little deterioration over time can be manufactured even when exposed to high-intensity light irradiation or high temperatures. it can.

  According to the eleventh aspect, since the aggregate containing the particles of the color conversion member can be formed without increasing the temperature, a light emitting device can be manufactured using a phosphor that is easily deteriorated by heat. .

  According to the twelfth aspect of the present invention, the metal provided for imparting the conductivity necessary for forming the aggregate containing the inorganic phosphor on the surface of the semiconductor light emitting device by the electrodeposition method or the electrostatic coating method. In order to make the conductor layer made of the material transparent thereafter, a light emitting device in which an inorganic particle layer is provided on the surface of the semiconductor light emitting element can be manufactured.

  According to the thirteenth invention, the particle layer of the color conversion member formed on the surface of the semiconductor light-emitting element via the transparent conductor layer is covered with the coating layer made of the same material as the transparent conductor layer. In addition, a light emitting device in which the color conversion member is better protected from an atmosphere such as moisture can be manufactured.

  According to the fourteenth aspect of the present invention, in order to impart the conductivity necessary for forming the aggregate containing the inorganic phosphor on the surface of the semiconductor light emitting device by the electrodeposition method or the electrostatic coating method, Since the conductive layer having the property is provided, a light-emitting device in which an inorganic particle layer is provided on the surface of a light-transmitting semiconductor light-emitting element made of insulating glass or ceramics can be manufactured. Moreover, since a conductor layer has translucency, the process for transparentizing a conductor layer is unnecessary after an inorganic particle layer formation process.

  According to the fifteenth aspect of the invention, since the color conversion member is covered with a dense and uniform covering layer formed by the atomic layer deposition method, a highly reliable light-emitting device using a phosphor that is easily deteriorated by an atmosphere such as moisture. Can be manufactured. Further, since the coating layer is formed at a relatively low temperature by the atomic layer deposition method, a light emitting device can be manufactured using a phosphor that is easily deteriorated by heat. Furthermore, since a space | gap is favorably formed in the space | gap between the particle | grains of an inorganic particle layer, a light-emitting device with high color conversion efficiency can be manufactured.

  According to the sixteenth invention, since the aggregate is bound by the inorganic binder, it is possible to manufacture a light emitting device in which the shape of the inorganic particle layer is stable without causing particles to dissipate from the aggregate during the manufacturing. .

  According to the seventeenth aspect, the thickness of the inorganic particle layer can be reduced by using the color conversion member having an appropriate average particle diameter and forming the cover layer having an appropriate thickness.

  According to the eighteenth aspect, since the color conversion member is protected from the atmosphere by the coating layer using a suitable material, a highly reliable light-emitting device can be manufactured.

It is typical sectional drawing which shows the structure of the light-emitting device concerning this invention, (a) is a general view, (b) is the elements on larger scale of (a). 2A and 2B are schematic cross-sectional views showing the configuration of a semiconductor light emitting device, where FIG. 1A is a face-down mounting type or face-up mounting type device, and FIG. 2B is a vertical structure type device. It is typical sectional drawing which shows the structure of the light-emitting device provided with the translucent layer. It is a flowchart which shows the flow of the manufacturing method of the 1st light-emitting device which concerns on this invention. (A)-(h) is typical sectional drawing for demonstrating the manufacturing process of the 1st light-emitting device based on this invention. 4 is a flowchart showing a detailed processing flow of a coating layer forming step in the method for manufacturing a light emitting device according to the present invention. It is a flowchart which shows the flow of the manufacturing method of the 2nd light-emitting device which concerns on this invention. (A)-(h) is typical sectional drawing for demonstrating the manufacturing process of the 2nd light-emitting device which concerns on this invention. It is a flowchart which shows the flow of the manufacturing method of the 3rd light-emitting device which concerns on this invention. (A)-(f) is typical sectional drawing for demonstrating the manufacturing process of the 3rd light-emitting device which concerns on this invention. (A) is typical sectional drawing which shows the structure of the light-emitting device provided with the protective layer, (b) is typical sectional drawing which shows the structure of the light-emitting device provided with the filler particle. It is the photograph image which image | photographed the cross section of the fluorescent substance layer of the light-emitting device based on the Example of this invention with the electron microscope. FIG. 13 is an image in which a coating layer is filled in a region A of FIG. FIG. 13 is an image in which a coating layer and a phosphor are filled in a region A in FIG. 12.

  Hereinafter, a light emitting device according to the present invention and a method for manufacturing the light emitting device will be described.

<Light emitting device>
[Configuration of light emitting device]
A structure of a light emitting device according to an embodiment of the present invention will be described with reference to FIG.
As shown in FIG. 1A, the light emitting device 1 according to the first embodiment is provided with a phosphor layer (inorganic particle layer) 3 on the side surface of the semiconductor light emitting element 2 and the upper surface of the semiconductor light emitting element 2. Yes. The phosphor layer 3 is formed of a granular inorganic phosphor (color conversion member) 31 and a coating layer 32 that covers the inorganic phosphor 31. More specifically, as shown in FIG. 1B, a gap 33 is formed inside the phosphor layer 3.

  Here, for the sake of convenience, the upper side of the paper surface of FIG. The light emitting device 1 only needs to be provided with the phosphor layer 3 on at least the upper surface of the semiconductor light emitting element 2. Here, the “upper surface” is either the substrate side or the semiconductor layer side of the semiconductor light emitting element 2. That is, as will be described later in the method for manufacturing a light emitting device, the surface on which the semiconductor light emitting element 2 is placed on a jig or an insulating substrate is not covered with the phosphor layer 3. The phosphor layer 3 is provided only on one side of the semiconductor layer side.

  Further, “at least the upper surface” means that the phosphor layer 3 only needs to be provided on either the upper surface or the side surface of the semiconductor light emitting element 2. Note that the phosphor layer 3 may not be provided on the side surface of the semiconductor light emitting element 2, but here, the case where the phosphor layer 3 is also provided on the side surface of the semiconductor light emitting element 2 will be described. To do. If the phosphor layer 3 is also provided on the side surface of the semiconductor light emitting element 2, the light from the side surface can be converted to the same color tone as the upper surface, so that the semiconductor light emitting element 2 having a uniform color tone can be obtained.

  When phosphors are provided on the upper and side surfaces of the semiconductor light emitting device 2 using a conventional ceramic molded body containing an inorganic phosphor produced by sintering, the phosphors provided on the respective surfaces are processed into a plate shape. And it is necessary to stick on each side. Here, in the case where a gap is generated at a joint portion between the plates, blue light leaks from the portion, which causes a problem that the uniformity of the emission color is lowered. In addition, when the upper plate or side plate is longer than desired and protrudes laterally or upward at the joint between the plates, and the surplus of the plate occurs at the joint, the emission color uniformity is also the same. This causes a problem of lowering. However, the side surface of the semiconductor light emitting element 2 is a surface generated by dicing, scribing, or breaking, and has poor surface flatness and parallelism. In addition, the semiconductor light emitting element 2 varies in size, and the height of the semiconductor light emitting element 2 is at most several hundred μm, and the size of the plate-like phosphor attached to the side surface is very small. For this reason, there is a problem that it is very difficult to apply without any gap or surplus at the joint, and it is difficult to obtain a uniform color tone.

In addition, there is a method in which a plate-like phosphor is installed only on the upper surface, and the side surface is covered with a reflective material such as a resin containing a light reflecting filler. Since it is returned to the element, there is a problem that light loss increases and it is difficult to obtain a highly efficient semiconductor light emitting device.
If the phosphor layer 3 is also provided on the side surface of the semiconductor light emitting element 2, such a problem can be solved.

The light emitting device 1 according to the present embodiment absorbs a part or all of the light incident on the phosphor layer 3 by the inorganic phosphor 31 of the phosphor layer 3 by the light emission from the semiconductor light emitting element 2, and the incident light is It is a light-emitting device provided with a transmissive color conversion molded body that converts light of different colors and emits it.
Hereinafter, the configuration of each part of the light emitting device 1 will be described in detail.

(Semiconductor light emitting device)
The semiconductor light emitting element 2 may have any structure, and as an example, the face down mounting type or face up mounting type element 2a shown in FIG. 2A or the vertical structure type shown in FIG. The element 2b is mentioned.

  As shown in FIG. 2A, the semiconductor light emitting element 2a includes a substrate (support substrate) 41 and a semiconductor layer 42 stacked on the support substrate 41 (down in the drawing). In this semiconductor layer 42, an n-type semiconductor layer 42a, an active layer 42b, and a p-type semiconductor layer 42c are sequentially stacked, and an n-side electrode 43 is formed on the n-type semiconductor layer 42a. A p-side electrode 44 is formed on the p-type semiconductor layer 42 c via a reflective electrode (or transparent electrode) 45 and a cover electrode 46. Further, the semiconductor layer 42 (and the cover electrode 46) of the semiconductor light emitting element 2a is covered with an insulating protective film 47.

As shown in FIG. 2B, the semiconductor light emitting device 2 b includes a support substrate 41 and a semiconductor layer 42 stacked on the support substrate 41 via a wafer bonding layer (Au—Au bonding layer) 49. Have. In this semiconductor layer 42, a p-type semiconductor layer 42c, an active layer 42b, and an n-type semiconductor layer 42a are sequentially stacked, and an n-side electrode 43 is formed on the n-type semiconductor layer 42a. A reflective electrode (Ag) 45 and a current constriction (dielectric) 48 are provided at predetermined intervals on the back surface of the p-type semiconductor layer 42c. A p-side electrode 44 is formed on the back surface of the support substrate 41. Further, the semiconductor layer 42 of the semiconductor light emitting element 2 b is covered with an insulating protective film 47.
The form of the semiconductor light emitting element 2 is not limited to the form of the semiconductor light emitting element 2 (2a, 2b), and may be a form without the support substrate 41 and the wafer bonding layer 49, for example.
Further, the semiconductor light emitting device 2 (2a, 2b) shown in FIGS. 2A and 2B is further simplified in other drawings.

As the semiconductor light emitting element 2, it is preferable to use a light emitting diode, and a light emitting diode having an arbitrary wavelength can be selected. For example, as the semiconductor light emitting element 2 of blue (light with a wavelength of 430 nm to 490 nm) and green (light with a wavelength of 490 nm to 570 nm), ZnSe, nitride-based semiconductor (In _X Al _Y Ga _1-XY N, 0 ≦ X, 0 ≦ Y, X + Y ≦ 1), GaP, or the like can be used. As the red semiconductor light emitting element 2 (light having a wavelength of 620 nm to 750 nm), GaAlAs, AlInGaP, or the like can be used. In the case of the light emitting device 1 using a fluorescent material as in the present invention, a nitride semiconductor (In _X Al _Y Ga _1-X— capable of emitting light of a short wavelength that can efficiently excite the fluorescent material. _YN , 0 ≦ X, 0 ≦ Y, X + Y ≦ 1) are preferably used. Various emission wavelengths can be selected by adjusting the material of the active layer 42b and the mixed crystal thereof. Furthermore, the semiconductor light emitting element 2 made of a material other than these can also be used. Note that the component composition, emission color, size, and the like of the semiconductor light emitting element 2 to be used can be appropriately selected according to the purpose.
Moreover, it can be set as the semiconductor light emitting element 2 which outputs not only the light of a visible light range but an ultraviolet-ray and infrared rays.

(Phosphor layer (inorganic particle layer))
As shown in FIG. 1, the phosphor layer 3 is an inorganic particle layer in which an aggregate of particles of an inorganic phosphor 31 is coated with a coating layer 32 made of an inorganic material. In the present embodiment, the phosphor layer 3 is provided so as to cover the upper surface and side surfaces of the semiconductor light emitting element 2. The phosphor layer 3 is a layer having a color conversion function that absorbs part or all of the light incident on the phosphor layer 3 by light emission from the semiconductor light emitting element 2 and emits light of a color different from the incident light. It is.

  As shown in FIG. 1B, the phosphor layer 3 is formed by covering particles of the granular inorganic phosphor 31 with a coating layer 32 made of an inorganic material, and the coating layer 32 covers the inorganic phosphor 31. The particles and the semiconductor light-emitting element 2 and the particles are fixed to each other to form a light-emitting device in which the granular inorganic phosphor 31 is integrated. Further, the surface of the phosphor layer 3 is formed with unevenness due to the particle size of the inorganic phosphor 31. Further, voids 33 are formed between the particles of the inorganic phosphor 31 inside the phosphor layer 3.

  The light incident on the phosphor layer 3 is scattered by the gap 33 and is efficiently absorbed by the inorganic phosphor 31 contained in the phosphor layer 3, so that it has a higher color than that without the gap 33. Conversion efficiency can be obtained. For this reason, in order to obtain the same color conversion rate, the thickness of the phosphor layer 3 can be made thinner than when the gap 33 is not provided.

  Further, since the surface of the phosphor layer 3 has irregularities due to the particle size of the inorganic phosphor 31, total reflection at the interface can be reduced and light can be efficiently extracted from the phosphor layer 3. For this reason, this light-emitting device 1 can obtain high luminous efficiency.

  Further, the phosphor layer 3 may include an inorganic binder (not shown) made of a translucent alkaline earth metal salt. The inorganic binder is for binding the inorganic phosphor 31 and the semiconductor light emitting element 2 and / or the inorganic phosphors 31 to each other. This inorganic binder is added in the manufacturing process of laminating the inorganic phosphor 31 on the surface of the semiconductor light emitting element 2, and the particles of the inorganic phosphor 31 and the semiconductor light emitting element are formed by the coating layer 32 made of an inorganic material. 2 and a binder that binds the particles of the inorganic phosphor 31 so that the particles of the inorganic phosphor 31 do not dissipate until a coating layer 32 that firmly binds the particles of the inorganic phosphor 31 is formed.

Moreover, the phosphor layer 3 may include conductor particles such as an inorganic filler and metal powder. For example, by adding an inorganic filler, the light incident on the phosphor layer 3 is scattered and diffused, or heat generated by the Stokes loss is efficiently conducted to the semiconductor light emitting element 2 to improve heat dissipation. (Note that the form including the filler particles will be described later with reference to FIG. 11B). Moreover, the content rate of the inorganic fluorescent substance 31 in the fluorescent substance layer 3 can be adjusted by addition of an inorganic filler. Moreover, the shape of the space | gap 33, the porosity, and the uneven | corrugated shape of the surface of the fluorescent substance layer 3 can be adjusted with the particle size and shape of the inorganic filler to add.
Further, by adding conductive particles, heat generated by the Stokes loss described above can be efficiently conducted to the semiconductor light emitting element 2, thereby improving heat dissipation.

Examples of the inorganic filler include aluminum nitride, barium titanate, titanium oxide, aluminum oxide, silicon oxide, silicon dioxide, heavy calcium carbonate, light calcium carbonate, silver, silica (fume silica, precipitated silica, etc.), titanic acid Examples include potassium, barium silicate, glass fiber, carbon, diamond and the like, and combinations of two or more thereof.
Alternatively, a light-transmitting material that mainly absorbs little light, such as tantalum oxide, niobium oxide, or a rare earth oxide, or an inorganic compound that reflects or absorbs light with a specific wavelength can be used.
In addition, as an inorganic filler, the thing comparable as the particle size of the inorganic fluorescent substance 31 mentioned later, a slightly small thing, or a somewhat large thing can be used.

  The phosphor layer 3 is a layer in which the aggregate of particles of the inorganic phosphor 31 is continuously covered and integrated with the coating layer 32, and a protective layer, an antireflection layer, and the like are further laminated. Also good. In this case, the total film thickness of the phosphor layer 3 that is the film thickness from the surface of the semiconductor light emitting element 2 to the upper surface of the phosphor layer 3 including the protective layer and the reflective layer is about 10 to 300 μm. It is preferable (a mode including a protective layer will be described later with reference to FIG. 11A).

In addition, since the phosphor layer 3 is an aggregate of particles of the inorganic phosphor 31, the film thickness is influenced by the particle size, but the thickness of the phosphor layer 3 that substantially contributes to color conversion is small. 1 to 100 μm, preferably 5 to 70 μm, and more preferably 10 to 50 μm. The “phosphor layer that substantially contributes to color conversion” means that the aggregate of particles of the inorganic phosphor 31 is continuously covered with the coating layer 32 and integrated, except for the protective layer and the reflective layer. Refers to the layer.
The thickness of the phosphor layer 3 (the thickness and total thickness of the phosphor layer that substantially contributes to color conversion) can be measured using a scanning electron microscope.

  In addition, the content of the inorganic phosphor 31 in the phosphor layer 3 is made higher than that of a conventional phosphor molded body made of sintered ceramics, etc. The film thickness of the phosphor layer 3 can be reduced. For this reason, the Stokes heat generated in the inorganic phosphor 31 contained in the phosphor layer 3 can be quickly conducted to the semiconductor light emitting element 2 having a heat radiation function. That is, the light emitting device 1 having excellent heat dissipation can be obtained.

(Inorganic phosphor (color conversion member))
The inorganic phosphor 31 is a phosphor made of an inorganic material that absorbs light incident on the phosphor layer 3 and emits light of a color different from the color of the incident light.
The phosphor material used as the inorganic phosphor 31 may be any material that absorbs incident light that is excitation light and performs color conversion (wavelength conversion) to light of a different color (wavelength). In particular, the inorganic phosphor 31 is preferably a material that absorbs ultraviolet light or blue light and emits blue light or red light.

Moreover, the average particle diameter of the particles of the inorganic phosphor 31 is not particularly limited, but those having a size of about 0.1 to 100 μm can be used. From the viewpoint of ease of handling, it is preferably 1 to 50 μm, more preferably 2 Those having a thickness of ˜30 μm can be used.
In addition, the value of an average particle diameter is the air permeation method or F.I. S. S. S. No (Fisher-SubSieve-Sizers-No.) (A value represented by a so-called D bar (bar above D)).

  Further, the central particle size Dm measured by a laser diffraction type particle size distribution measuring device (for example, SALD series manufactured by Shimadzu Corporation) or an electric resistance type particle size distribution device (for example, Coulter counter manufactured by Coulter COULTER). When the ratio of (Median Diameter) to the above-described average particle diameter D bar is (Dm / D bar) as an index indicating the dispersibility of the particles of the inorganic phosphor 31, the index value is closer to 1 preferable. That is, the closer the index value is to 1, the higher the dispersibility of the particles (the particles do not aggregate), and the phosphor layer 3 with less stress can be formed. Thereby, generation | occurrence | production of the crack in the fluorescent substance layer 3 can be suppressed.

  In addition, the inorganic phosphor 31 may be used by mixing particles of a plurality of types of inorganic phosphors 31 as well as one type. Moreover, you may make it laminate | stack the particle layer of multiple types of inorganic fluorescent substance 31 one by one.

Specific examples of the inorganic phosphor 31 include the following.
For example, nitride phosphors / oxynitride phosphors / sialon phosphors mainly activated by lanthanoid elements such as Eu and Ce, lanthanoid elements such as Eu, and transition metal elements such as Mn. Activated alkaline earth halogen apatite phosphor, alkaline earth metal halogen borate phosphor, alkaline earth metal aluminate phosphor, alkaline earth silicate phosphor, alkaline earth sulfide phosphor Alkaline earth thiogallate phosphor, thiosilicate phosphor, alkaline earth silicon nitride phosphor, germanate phosphor, alkali metal halogen silicate phosphor, alkali metal germanate phosphor, or Ce, etc. It is preferably at least one selected from rare earth aluminate phosphors and rare earth silicate phosphors mainly activated with lanthanoid elements. . As specific examples, the following phosphors can be used, but are not limited thereto.

Nitride-based phosphors mainly activated with lanthanoid elements such as Eu and Ce are M ₂ Si ₅ N ₈ : Eu, MAlSiN ₃ : Eu (M is selected from Sr, Ca, Ba, Mg, Zn) At least one or more). In addition to M ₂ Si ₅ N ₈ : Eu, MSi ₇ N ₁₀ : Eu, M _1.8 Si ₅ O _0.2 N ₈ : Eu, M _0.9 Si ₇ O _0.1 N ₁₀ : Eu (M Is at least one selected from Sr, Ca, Ba, Mg, and Zn.

An oxynitride phosphor mainly activated by a lanthanoid element such as Eu or Ce is MSi ₂ O ₂ N ₂ : Eu (M is at least one selected from Sr, Ca, Ba, Mg, Zn) Etc.).

Eu, sialon phosphors activated mainly with lanthanoid elements such as Ce _{is, M p / 2 Si 12-} p-q Al p + q O q N 16-p: Ce, M-Al-Si-O-N (M is at least one selected from Sr, Ca, Ba, Mg, and Zn. Q is 0 to 2.5, and p is 1.5 to 3).

Alkaline earth halogen apatite phosphors mainly activated by lanthanoid elements such as Eu and transition metal elements such as Mn include M ₅ (PO ₄ ) ₃ X: R (M is Sr, Ca, Ba, At least one selected from Mg and Zn, X is at least one selected from F, Cl, Br and I. R is any one of Eu, Mn, Eu and Mn. )and so on.

In the alkaline earth metal halogen borate phosphor, M ₂ B ₅ O ₉ X: R (M is at least one selected from Sr, Ca, Ba, Mg, Zn. X is F, And at least one selected from Cl, Br, and I. R is Eu, Mn, Eu and Mn.).

Alkaline earth metal aluminate phosphors include SrAl ₂ O ₄ : R, Sr ₄ Al ₁₄ O ₂₅ : R, CaAl ₂ O ₄ : R, BaMg ₂ Al ₁₆ O ₂₇ : R, BaMg ₂ Al ₁₆ O ₁₂ : R, BaMgAl ₁₀ O ₁₇ : R (R is any one of Eu, Mn, Eu and Mn).

Examples of the alkaline earth metal silicate phosphor include M ₂ SiO ₄ : Eu (M is at least one selected from Ca, Sr, Ba, Mg, and Zn).

Examples of the alkaline earth sulfide phosphor include La ₂ O ₂ S: Eu, Y ₂ O ₂ S: Eu, and Gd ₂ O ₂ S: Eu.

The alkali metal halogen silicate phosphor includes MSix ₆ : Mn (M is one or more selected from Li, Na and K, and X is one or more selected from F, Cl, Br and I). In addition, there is a phosphor represented by a composition formula of Li ₂ SiF ₆ : Mn, K ₂ (SiGe) F ₆ : Mn.

Examples of rare earth aluminate phosphors mainly activated with lanthanoid elements such as Ce include Y ₃ Al ₅ O ₁₂ : Ce, (Y _0.8 Gd _0.2 ) ₃ Al ₅ O ₁₂ : Ce, Y ₃ There are YAG phosphors represented by the composition formula of (Al _0.8 Ga _0.2 ) ₅ O ₁₂ : Ce, (Y, Gd) ₃ (Al, Ga) ₅ O ₁₂ : Ce. Further, there are Tb ₃ Al ₅ O ₁₂ : Ce, Lu ₃ Al ₅ O ₁₂ : Ce, etc. in which a part or all of Y is substituted with Tb, Lu or the like.

Other phosphors include MS: Eu, Zn ₂ GeO ₄ : Mn, 0.5MgF ₂ .3.5MgO · GeO ₂ , MGa ₂ S ₄ : Eu (M is Sr, Ca, Ba, Mg, Zn) At least one selected from the above). These phosphors contain at least one selected from Tb, Cu, Ag, Au, Cr, Nd, Dy, Co, Ni, and Ti in place of or in addition to Eu as desired. You can also

  Further, phosphors other than the above-described phosphors and having the same performance and effect can be used.

  These phosphors can be used with those having emission spectra in yellow, red, green, and blue by the excitation light from the light-emitting element, and also have emission spectra in yellow, blue-green, orange, etc., which are intermediate colors of these phosphors. It can also be used. By using these phosphors in various combinations, light emitting devices having various emission colors can be manufactured.

For example, using a GaN-based or InGaN-based compound semiconductor light emitting element that emits blue light as a light source, a phosphor of Y ₃ Al ₅ O ₁₂ : Ce or (Y _0.8 Gd _0.2 ) ₃ Al ₅ O ₁₂ : Ce The light emitting device that emits white light by the mixed color of the light from the light emitting element and the light from the phosphor can be provided.

For example, CaSi ₂ O ₂ N ₂ : Eu or SrSi ₂ O ₂ N ₂ : Eu that emits green to yellow, and blue (Sr, Ca) ₅ (PO ₄ ) ₃ Cl: Eu that emits red By using three kinds of phosphors composed of Ca ₂ Si ₅ N ₈ : Eu or CaAlSiN ₃ : Eu, a light emitting device that emits white light with excellent color rendering can be provided. Since the three primary colors of light, red, blue and green are used, desired white light can be realized only by changing the blending ratio of the phosphors.

  Examples of the inorganic phosphor 31 include phosphors such as sulfide phosphors, halogen silicate phosphors, nitride phosphors, and oxynitrides, which are non-oxide phosphors. Some phosphors, such as phosphors, are easily decomposed by heat or the activator is deactivated. In addition, some fluoride phosphors are deteriorated depending on the atmosphere, such as deliquescence by moisture.

In the present invention, when the light emitting device 1 is formed, since it does not become a high temperature like molding by sintering or glass sealing, it is easily deteriorated by heat, for example, CASN which is a non-oxide phosphor. And nitride phosphors such as SCASN can be used.
In the present invention, the inorganic phosphor 31 is preferably densely covered with a coating layer 32 formed by an atomic layer deposition method to be described later, so that it can be easily deliquescent by moisture, such as LiSiF ₄ : Mn. A fluoride phosphor can be used.
When the inorganic phosphor 31 is directly bonded to the semiconductor light emitting element 2, the above-described YAG, CASN, SCASN, etc. are often used as the inorganic phosphor 31 having good temperature characteristics. In addition, LAG, β sialon, α sialon, or the like may be used.

(Coating layer)
The covering layer 32 is a light-transmitting film that covers the particles of the granular inorganic phosphor 31 and fixes the particles, the semiconductor light emitting element 2, and the particles. That is, the coating layer 32 has a function as a protective layer of the inorganic phosphor 31, a function as a binder, and a function as a heat conduction path.

The coating layer 32 is made of Al ₂ O ₃ , SiO ₂ , ZrO ₂ , HfO ₂ , TiO ₂ , ZnO, Ta ₂ O ₅ , Nb ₂ O ₅ , In ₂ O ₃ , SnO ₂ , TiN, AlN, or the like. At least one compound selected from the group described above can be suitably used. The coating layer 32 is formed by an ALD (Atomic Layer Deposition) method, a MOCVD (Metal Organic Chemical Vapor Deposition) method, or a PECVD (Plasma-Enhanced Chemical Vapor Deposition) method. It can be formed by an atmospheric pressure plasma film formation method or the like.

  In particular, the ALD method is preferable because a film to be formed is dense, a shape having a step (unevenness) is high, and a film with a uniform thickness can be formed. In addition, the coating layer 32 formed by the ALD method can satisfactorily cover the particles of the inorganic phosphor 31 and integrate the aggregates of the particles of the inorganic phosphor 31 even if the film thickness is thin. The thickness of the phosphor layer 3 can be further reduced. For this reason, the Stokes heat generated by the particles of the inorganic phosphor 31 can be quickly conducted to the semiconductor light emitting element 2 having a heat dissipation function through the thin coating layer 32. As a result, the light emitting device 1 having excellent heat dissipation can be formed. In order to obtain good heat dissipation, the thickness of the phosphor layer 3 is preferably set in the above-described range, and the thickness of the coating layer 32 is preferably set in the range described later.

In addition, as a raw material for the coating layer 32 formed by the ALD method, an organometallic material having a vapor pressure from room temperature to 300 ° C., a metal halide, or the like is used. In particular, a film made of Al ₂ O ₃ formed by the ALD method is preferable because it has a high barrier property against an atmosphere such as moisture. TMA (trimethylaluminum) and water are used as raw materials for forming the Al ₂ O ₃ film.

Moreover, the film thickness of the coating layer 32 can be 10 nm-50 micrometers by average thickness, Preferably it is 50 nm-30 micrometers, More preferably, it can be 100 nm-10 micrometers.
The film thickness of the coating layer 32 is the thickness of the portion uniformly covering the particles of the inorganic phosphor 31 (in the case where an inorganic filler or the like is added, particles such as the inorganic phosphor 31 and the inorganic filler). Point to.

  The covering layer 32 can be formed as a single layer made of the above-described compound, or can be formed as a multilayer film made of different materials. In the case of forming with a multilayer film, for example, a dense layer by ALD method is formed as the first layer (layer in contact with the inorganic phosphor 31), and then PECVD method or atmospheric pressure plasma film forming method is used as the second layer. It is also possible to form a film by a method having a high film formation speed.

(Void)
The gap 33 is formed as a gap between particles of the inorganic phosphor 31 laminated on the surface of the semiconductor light emitting element 2. That is, the gap 33 is a space surrounded by any one of the semiconductor light emitting element 2, the inorganic phosphor 31 and the coating layer 32. When the phosphor layer 3 includes particles other than the inorganic phosphor 31 such as an inorganic filler or conductive particles, the void 33 is formed as a gap between these particles including the inorganic phosphor 31. The

  The air gap 33 can scatter light incident on the phosphor layer 3 and efficiently absorb the incident light in the inorganic phosphor 31. The porosity is preferably about 1 to 50%, more preferably 5 to 30%. The optimum value of the porosity depends on the particle diameter of the inorganic phosphor 31 and the film thickness of the coating layer 32. By setting the porosity to 1% or more, incident light can be effectively scattered, By setting it to 50% or less, even when the phosphor layer 3 is thinned, the content of the inorganic phosphor 31 sufficient for color conversion can be obtained.

  Further, by providing the gap 33 within the above-described range of the porosity, even when the difference in the coefficient of linear expansion between the semiconductor light emitting element 2 and the phosphor layer 3 is large, the temperature rise during use in the manufacturing process or after manufacturing. Therefore, the strain applied to the light emitting device can be absorbed and the generation of cracks can be prevented.

  Note that the porosity in the phosphor layer 3 can be controlled by adjusting the average particle diameter of the inorganic phosphor 31 and the film thickness of the coating layer 32 within the above-described ranges. That is, by determining the film thickness of the coating layer 32 according to the average particle diameter of the inorganic phosphor 31, the void 33 having a desired porosity can be formed. In addition, when an inorganic filler is added to the phosphor layer 3, the porosity can be controlled by the average particle diameter of the inorganic phosphor 31 particles and the inorganic filler particles combined with the film thickness of the coating layer 32. it can. In controlling the porosity, it is preferable to further consider the shape of the particles and the dispersibility of the particles.

(Void filling)
Alternatively, the gap 33 may be filled with a filler. As the filler, a gas such as an air layer (mixed gas of N ₂ , O ₂ , CO _2, etc.) is preferable. However, the present invention is not limited thereto, and an inorganic compound (for example, AlOOH, SiOx, etc.), an inorganic raw material (for example, polysilazane, etc.), a solid such as glass or nano-inorganic particles occupies a part or all of the packing. Also good. As a raw material for such a solid filler, a liquid containing an inorganic compound such as a liquid glass material or a sol-gel material can be given. Further, as the liquid solvent containing the inorganic compound as described above, water, an organic solvent, or a resin mainly composed of an inorganic substance such as silicone or a fluororesin can be used.

Note that these solid fillers provided in the gaps 33 may include the same material as that of the coating layer 32. In this case, it is preferable that the coating layer 32 and the filling of the gap 33 have different physical properties such as refractive index and transmittance. For this purpose, for example, the coating layer 32 can be Al ₂ O ₃ formed by the ALD method, and the filling of the gap 33 can be Al ₂ O ₃ formed by the sol-gel method. Thus, by different formation methods, crystallinity and density are different, and the above-described physical properties can be made different.
In this way, by filling the gap 33 with a material having physical properties different from those of the coating layer 32, diffusion and extraction of light incident on the phosphor layer 3 can be controlled.

As another embodiment of the light-emitting device, as shown in FIG. 3, a light-transmitting layer 5 may be provided on at least the upper surface of the semiconductor light-emitting element 2.
That is, as shown in FIG. 3, the light emitting device 1 </ b> A has a light transmissive layer 5 on the side surface and top surface of the semiconductor light emitting element 2, and fluorescent light on the side surface and top surface of the semiconductor light emitting element 2 via the light transmissive layer 5. A body layer 3 is provided.

(Translucent layer)
The translucent layer 5 is formed of an inorganic phosphor by an electrodeposition method or an electrostatic coating method on the surface of the semiconductor light emitting element 2 in phosphor layer forming steps S14, S26, and S33 (see FIGS. 4, 7, and 9) described later. The transparent conductor layer 6 is a transparent conductor layer 6 (see FIG. 5B) formed to be used as an electrode for forming the particle layer 34 of 31. Therefore, the light-transmitting layer 5 can be made of a material that has conductivity in the manufacturing process described later and can be made transparent thereafter, or a light-transmitting material having conductivity.

Examples of the material that has conductivity and can be made transparent later include a metal material containing at least one selected from Al, Si, Zn, Sn, Mg, and In. For example, Al can be oxidized by being exposed to hot water at about 90 ° C., and can be changed to translucent Al ₂ O ₃ . In addition, Al is preferable because it can be oxidized and transparentized at a relatively low temperature. In this case, an Al ₂ O ₃ film is formed as the translucent layer 5. Furthermore, when an Al ₂ O ₃ film is formed as the covering layer 32, since the same material is used, the covering layer 32 and the translucent layer 5 are well adhered. For this reason, the inorganic phosphor 31 is well protected from an atmosphere such as moisture, and the peeling of the phosphor layer 3 from the semiconductor light emitting element 2 is prevented. Also for materials other than Al, it is preferable that the light-transmitting layer 5 and the covering layer 32 be made of the same material so that good adhesion between the light-transmitting layer 5 and the covering layer 32 can be obtained. .

Further, as another method for converting the conductor layer 6 into the translucent layer 5, treatment with ammonia water can be used. For example, when Al or Zn is used as the material of the conductor layer 6, light-transmitting Al (OH) ₃ (aluminum hydroxide) and Zn (OH) ₂ (hydroxylation) are obtained by treating with ammonia water. Zinc). Moreover, since these are produced | generated as a gel-like substance, the effect as a binding material of the particle | grains of the inorganic fluorescent substance 31 can also be anticipated.

In addition, as the translucent material having conductivity, for example, at least one selected from the group consisting of Zn (zinc), In (indium), Sn (tin), Ga (gallium), and Mg (magnesium) And conductive metal oxides containing these elements. Specifically, ZnO, AZO (Al-doped ZnO), IZO (In-doped ZnO), GZO (Ga-doped ZnO), In ₂ O ₃ , ITO (Sn-doped In ₂ O ₃ ), IFO (F-doped In ₂ O ₃ ), conductive metal oxides such as SnO ₂ , ATO (Sb-doped SnO ₂ ), FTO (F-doped SnO ₂ ), CTO (Cd-doped SnO ₂ ), and MgO.
In addition, when the translucent material which has electroconductivity is used, the conductor layer transparency process S15, S27 (refer FIG. 4, 7) can be abbreviate | omitted in the manufacturing method mentioned later.

  The internal structure of the phosphor layer 3 is the same as that of the phosphor layer 3 of the light emitting device 1 according to the embodiment shown in FIG. In FIG. 3, the description of the gap 33 is omitted.

≪Method for manufacturing light emitting device≫
Next, a method for manufacturing a light emitting device according to the present invention will be described with reference to FIGS. Here, three manufacturing methods will be described.

(First manufacturing method)
As shown in FIG. 4, the first manufacturing method is a manufacturing method of the light emitting device 1A shown in FIG. 3, and includes a semiconductor light emitting element manufacturing step S11, an arraying step S12, a conductor layer forming step S13, and a fluorescent light. The body layer forming step S14, the conductor layer transparentizing step S15, the covering layer forming step S16, and the final singulation step S17 are performed in this order.
Here, on the assumption that a plurality of light emitting devices 1A are manufactured, the description will be made assuming that the arrangement step S12 and the final singulation step S17 are included. Moreover, as will be described later, depending on the conditions of the manufacturing method, the conductor layer forming step S13 and the conductor layer transparentizing step S15 may not be included.
Hereinafter, each step will be described in detail with reference to FIG. 5 (refer to FIGS. 1 to 4 as appropriate).

(Semiconductor light emitting device manufacturing process)
The semiconductor light emitting device manufacturing step S11 is a step of manufacturing the semiconductor light emitting device 2 that is singulated. By this step, the semiconductor light emitting device 2a having the structure shown in FIG.

  The semiconductor light emitting device 2a may be manufactured by a conventionally known method. For example, on the support substrate 41 made of sapphire (C-plane), each nitridation constituting the n-type semiconductor layer 42a, the active layer 42b, and the p-type semiconductor layer 42c by a MOVPE (Metal-Organic Vapor Phase Epitaxy) reactor. A semiconductor is sequentially grown (a substrate on which each layer of nitride semiconductor is grown is referred to as a wafer as appropriate). Next, a resist mask is formed and etched to remove the resist, and then a film constituting the reflective electrode (or transparent electrode) 45 and the cover electrode 46 is formed by sputtering. Further, a resist mask is formed and etched to remove the resist, and then the p-side electrode 44 and the n-side electrode 43 are provided by sputtering. Then, a protective film 47 is formed by sputtering, a resist mask is formed, and etching is performed to remove the resist. Further, the p-side electrode 44 and the n-side electrode 43 are exposed by etching. Then, the wafer is separated into pieces by dicing or the like.

(Sequence process)
The arranging step S12 is a step of arranging the semiconductor light emitting elements 2 on a flat jig with a predetermined interval.
In the arranging step S12, as shown in FIG. 5 (a), the semiconductor light emitting device 2 manufactured in the semiconductor light emitting device manufacturing step S11 is bonded to the adhesive sheet (with the electrodes 43 and 44 facing down with a predetermined interval). (Not shown) are arranged on a jig 50 to which is attached. At this time, for example, bumps (not shown) may be provided on the electrodes 43 and 44 to adjust the height. The semiconductor light emitting elements 2 arranged on the jig 50 are attached to the jig 50 by an adhesive sheet, and the position is held.

  In the arranging step S12, the semiconductor light emitting elements 2 can be arranged on the jig 50 by adsorbing the semiconductor light emitting elements 2 one by one using a collet, for example.

  Here, the jig 50 is a plate-like member that holds the arrangement of the semiconductor light emitting elements 2. As the jig 50, a plate-like member such as ceramic, glass, metal, or plastic having rigidity can be used.

(Conductor layer forming process)
The conductor layer forming step S13 is a step of forming the conductor layer 6 made of metal on the surface of the semiconductor light emitting element 2 between the arranging step S12 and the phosphor layer forming step S14.
In the conductor layer forming step S13, as shown in FIG. 5B, the surfaces of the jig 50 and the semiconductor light emitting element 2 are covered so that the upper surface and the side surface of the semiconductor light emitting element 2 disposed on the jig 50 are covered. A conductor layer 6 made of a conductor material (metal material) is formed. As the conductor layer 6, for example, Al can be used as a material that can be made transparent in the conductor layer transparency step S <b> 15, which is a subsequent step. The conductor layer 6 can be formed by, for example, a sputtering method, a vapor deposition method, a plating method, or the like.

Further, using the above-described light-transmitting material such as ITO or ZnO as the conductor material, the conductor layer 6 can be formed by, for example, a physical method such as a sputtering method or a vapor deposition method, a spray method or a CVD (chemical method). It can be formed by a chemical method such as a vapor deposition method. In addition, when the conductor layer 6 is formed using a translucent material, the conductor layer transparency step S15 can be omitted.
In addition, electroconductivity can also be provided with a conductive epitaxial layer by peeling the support substrate 41 of the semiconductor light emitting element 2.

  In the present specification, “having translucency” means light emitted from the semiconductor light emitting element 2 (first color light) and light color-converted by the phosphor layer 3 (second color light). It has translucency with respect to.

(Phosphor layer forming step (inorganic particle layer forming step))
In the phosphor layer forming step S14, the surface of the semiconductor light emitting element 2 absorbs the first color light emitted from the semiconductor light emitting element 2 and emits the second color light different from the first color. This is a step of forming an aggregate (particle layer 34) containing particles of a color conversion member (inorganic phosphor 31) made of a material.
In the phosphor layer forming step S14, as shown in FIG. 5C, the surface (upper surface) of the semiconductor light-emitting element 2 is formed by electro-deposition (electrodeposition) method or electrostatic coating method using the conductor layer 6 as one electrode. And the side surface), the particle layer 34 of the inorganic phosphor 31 is formed via the conductor layer 6.
Even if the semiconductor light emitting element 2 is an insulator, by using a metal as a conductor as the conductor layer 6, using the conductor layer 6 as an electrode, the inorganic phosphor 31 can be formed by an electrodeposition method or an electrostatic coating method. The particle layer 34 can be formed.

  In addition, when adding inorganic particles, such as an inorganic filler and electroconductive particle, to the fluorescent substance layer 3, the particle layer 34 becomes an aggregate of the particles of the inorganic fluorescent substance 31 and these particles.

Here, the phosphor layer forming step S14 in the case of using the electrodeposition method will be described in detail.
According to the electro-deposition method, the semiconductor light-emitting element 2 in which the conductor layer 6 is formed in the electrodeposition tank in which the solution in which the granular inorganic phosphor 31 is suspended is placed at room temperature. Then, a counter electrode serving as the other electrode is immersed, and a voltage is applied between the electrodes. In addition, a voltage having a polarity different from the polarity with which the inorganic phosphor 31 is charged is applied to the semiconductor light emitting element 2 side. Thereby, the particles of the inorganic phosphor 31 are electrophoresed and adhere to the semiconductor light emitting element 2 through the conductor layer 6. The thickness of the particle layer 34 of the inorganic phosphor 31 can be controlled by adjusting the amount of coulomb determined by the current and time passed between the electrodes.

  Although the solvent used for this electrodeposition method is not specifically limited, Alcohol solvents, such as IPA (isopropyl alcohol), can be used conveniently.

  Moreover, it is preferable to add an inorganic binder for binding particles of the inorganic phosphor 31 and the semiconductor light emitting element 2 and particles of the inorganic phosphor 31 to the solution. The inorganic binder is for preventing the particles of the inorganic phosphor 31 laminated by the electro-deposition method from being dissipated until the coating layer 32 is formed in the coating layer forming step S16 as a subsequent step. As the inorganic binder, for example, alkaline earth metal ions such as Mg ions, Ca ions, and Sr ions can be used. The added alkaline earth metal ions are precipitated as hydroxides and carbonates and exhibit binding power. Since these hydroxides and carbonates are colorless and transparent, even if they remain in the phosphor layer 3 after manufacture, the color conversion efficiency does not decrease. Further, since it is an inorganic substance, the color conversion efficiency is not lowered due to a change with time.

  In order to efficiently perform the electrophoresis of the inorganic phosphor 31, it is preferable to add a charge control agent such as a metal salt to the solution. In addition, the charge control agent may be coated on the particles of the inorganic phosphor 31 without being added to the solution.

  In the present embodiment, the particle layer 34 of the inorganic phosphor 31 is formed by the electrodeposition method in the phosphor layer forming step S14. However, the present invention is not limited to this. For example, an electrostatic coating method can be used with the semiconductor light emitting element 2 as one electrode. Further, when the phosphor layer 3 is formed on the upper surface, a centrifugal sedimentation method can also be used. In addition, a pulse spray method can also be used. Moreover, it can also use combining the above-mentioned method.

  In addition, when forming the particle layer 34 of the inorganic fluorescent substance 31 using a centrifugal sedimentation method or a pulse spray method, formation of the conductor layer 6 is unnecessary. In this case, the conductor layer forming step S13 and the conductor layer transparency step S15 can be omitted. In this case, the light emitting device 1 having the configuration in which the phosphor layer 3 is directly provided on the surface of the semiconductor light emitting element 2 having non-conductive translucency without the translucent layer 5 is formed. .

(Conductor layer transparency process)
The conductor layer transparentization step S15 is a step of oxidizing and transparentizing the metal of the conductor layer 6 between the phosphor layer forming step S14 and the coating layer forming step S16.
In the conductor layer transparentization step S <b> 15, as shown in FIG. 5D, the conductor layer 6 is made transparent and changed to the light transmissive layer 5. When the conductor layer 6 is formed of an Al film, for example, the Al can be oxidized by being exposed to hot water at about 90 ° C. to be changed to a light-transmitting Al ₂ O ₃ film.
Further, when the conductor layer 6 is formed of an Al film, it can be treated with ammonia water to change the Al to translucent Al (OH) ₃ .

Further, the metal forming the conductor layer 6 may be dissolved and removed. As a method for removing the conductor layer 6, a dissolution reaction with an acid can be used. As the acid, for example, HCl (hydrochloric acid), H ₂ SO ₄ (sulfuric acid), HNO ₃ (nitric acid), an aqueous solution of other inorganic acids or organic acids can be used. For example, in the case of using Al as the material of the conductor layer 6, by immersion in acid solution, it is removed by dissolving the Al ³⁺ next acid solution.

Further, when an amphoteric metal such as Al, Zn or Sn is used as the material of the conductor layer 6, NaOH (sodium hydroxide), KOH (potassium hydroxide) or other methods can be used as a method of removing the conductor layer 6. A dissolution reaction with an aqueous alkali solution can be used. For example, when Al, Zn, or Sn is used as the material of the conductor layer 6, Na [Al (OH) ₄ ] and Na ₂ [Zn (OH) ₄ ]] are reacted with a sodium hydroxide aqueous solution, respectively. , Na ₂ [Sn (OH) ₄ ] and the like are generated and dissolved in an alkaline aqueous solution to be removed.

  In the case where the conductor layer 6 is removed, the phosphor layer 3 is provided directly on the surface of the non-light-transmitting semiconductor light-emitting element 2 without the light-transmitting layer 5. The light emitting device 1 is formed.

(Coating layer forming process)
The covering layer forming step S16 is a step of forming the covering layer 32 made of an inorganic material that continuously covers the surface of the semiconductor light emitting element 2 and the surface of the particles of the color conversion member (inorganic phosphor 31).
In the coating layer forming step S16, as shown in FIG. 5E, the particle layer 34 of the inorganic phosphor 31 formed in the phosphor layer forming step S14 is coated to form a coating layer 32 for fixing the particles together. In the coating layer forming step S16, the coating layer 32 can be formed by an ALD method, an MOCVD method, or the like. The particles of the inorganic phosphor 31 are covered with the coating layer 32, and the particles of the inorganic phosphor 31 and the translucent layer 5 and the particles of the inorganic phosphor 31 are fixed to each other, thereby obtaining an integrated light emitting device. .

  Further, when the translucent layer 5 and the covering layer 32 are formed of the same material, the adhesion between the phosphor layer 3 and the translucent layer 5 is good, and the inorganic phosphor 31 in contact with the translucent layer 5 is formed. A good barrier property against an atmosphere such as moisture can be obtained, and the phosphor layer 3 can be made difficult to peel from the semiconductor light emitting element 2.

  Moreover, when providing solid as a filler other than an air layer in the space | gap 33, it can carry out as it demonstrates below, following coating layer formation process S16. Note that air is filled in the gap 33 after the coating layer forming step S16.

  The solid packing can be provided by filling a solution (solid-containing liquid) in which a solid is dispersed in a solvent into the gap 33 and volatilizing the solvent, followed by solidification by heating at a low temperature. For example, a solid-containing liquid such as liquid glass or a sol-gel material is provided on the phosphor layer 3 by dropping or coating, and is evacuated. As a result, the air filling the gap 33 can be removed from the gap 33 and the solid-containing liquid can be filled in the gap 33 instead. Then, the solid filling can be provided in the gap 33 by setting the temperature at which the solvent of the solid-containing liquid volatilizes. In addition, it is preferable that the temperature heated in order to volatilize a solvent is a comparatively low temperature of about 300 degrees C or less.

(Coating layer formation process by ALD method)
Here, with reference to FIG. 6, the coating layer forming step S16 when the ALD method is used will be described in detail. As shown in FIG. 6, the coating layer forming step S16 in this embodiment includes a pre-baking step S121, a sample setting step S122, a pre-deposition storage step S123, a first raw material supply step S124, and a first exhaust step S125. The second raw material supply step S126 and the second exhaust step S127, and the first raw material supply step S124 to the second exhaust step S127 are repeated a predetermined number of times.

(Pre-baking process)
First, in the pre-baking step S121, a baking process is performed in which a sample in which the particle layer 34 of the inorganic phosphor 31 is formed on the upper surface and side surfaces of the semiconductor light emitting device 2 is heated using an oven.
In this embodiment, H ₂ O (water) is used as the first raw material, TMA (trimethylaluminum) is used as the second raw material, and the Al ₂ O ₃ film is formed as the coating layer 32. For this reason, in order to form a film satisfactorily, it is preferable to remove as much as possible by evaporating moisture contained in the sample before film formation.

The baking treatment can be performed, for example, by heating the sample in an oven at 120 ° C. for about 2 hours.
(Sample setting process)
Next, in the sample setting step S122, in order to form the coating layer 32, the sample is put into a reaction container (not shown). The reaction vessel is connected to a first raw material supply line, a second raw material supply line, a nitrogen gas supply line, a vacuum line (all not shown), and the like.

(Storage process before film formation)
Next, in the pre-deposition storage step S123, the reaction container in which the sample is stored is brought into a low pressure state through, for example, a vacuum line connected to a rotary pump, and the state in the reaction container is stabilized. At this time, nitrogen gas is introduced into the reaction vessel, and unnecessary substances such as air are exhausted from the reaction vessel.

The pressure in the reaction vessel is, for example, about 0.1 to 10 torr (133 to 13332 Pa), the flow rate of nitrogen gas is about 20 sccm (33 × 10 ⁻³ Pa · m ³ / s), and this state is maintained for stabilization. The maintaining time can be about 10 minutes.
Moreover, although the temperature in reaction container can be about 100 degreeC, for example, the film-forming temperature can be freely set within the range of 50-500 degreeC. During the subsequent film formation, this temperature is generally maintained, but the present invention is not limited to this, and the temperature may be changed midway.

  The temperature during film formation can be set as appropriate, but is preferably set in the range of about 50 to 500 ° C., taking into consideration the heat resistance of the inorganic phosphor 31 to be used, and is set to 100 to 200 ° C. More preferably. Film formation by the ALD method can be performed at a lower temperature than molding by the sintering method or film formation by the MOCVD method. For this reason, the light-emitting device 1 (1A) using the inorganic phosphor 31 that emits red light such as CASN or SCASN having particularly low heat resistance can be manufactured.

(First raw material supply process)
Next, in the first raw material supply step S124, H ₂ O as the first raw material is introduced into the reaction vessel. H ₂ O is introduced as normal temperature steam. After introduction of the H 2 _O, it introduced H _{2 O} is then waits for a predetermined time to spread over the entire surface of the sample, is reacted with the entire surface of the sample. Incidentally, introduction of _{H 2} O, to the duration of the first feed step S124, the vapor of _{H 2} O, for example, be introduced in a short time into the reaction vessel, such as 0.001 seconds.
However, the introduction time of the raw material can be determined according to the surface area of the sample, the volume of the apparatus, and the raw material supply amount per unit time. After introducing the raw material H ₂ O, a sufficient time is required for the reaction of the entire surface of the sample.

(First exhaust process)
Next, in the first evacuation step S125, a vacuum line is connected to the reaction vessel, nitrogen gas is introduced, and excess H ₂ O and by-products that have not contributed to the reaction are exhausted from the reaction vessel. In addition, the by-product in this process is methane gas.

(Second raw material supply process)
Next, in the second raw material supply step S126, TMA as the second raw material is introduced into the reaction vessel. TMA is introduced as normal temperature steam. After introducing the TMA, the system waits for a predetermined time until the introduced TMA reaches the entire surface of the sample. The introduction of TMA can be performed in the same manner as the introduction of H ₂ O described above.
However, the introduction time of the raw material can be determined according to the surface area of the sample, the volume of the apparatus, and the raw material supply amount per unit time. After introducing the raw material TMA, a sufficient time is required for the reaction of the entire surface of the sample.

(Second exhaust process)
Next, in the second evacuation step S127, a vacuum line is connected to the reaction vessel, nitrogen gas is introduced, and excess TMA and by-products that have not contributed to the reaction are exhausted from the reaction vessel.

  The film forming process in the present embodiment is a predetermined number of cycles repeated using the first raw material supply process S124 to the second exhaust process S127 as the basic film forming cycle. Therefore, after the end of the second exhaust process S127, it is determined whether this cycle has been performed a predetermined number of times (step S128). If the predetermined number of times has not been completed (No in step S128), the process returns to the first raw material supply process S124, and Repeat the cycle. On the other hand, when the predetermined number of times has been completed (Yes in step S128), the coating layer forming process is terminated.

According to the ALD method, the coating layer 32 is stacked in units of atomic layer level by performing the basic cycle of film formation once. For this reason, the thickness of the coating layer 32 can be freely controlled according to the number of cycles to be executed.
Further, since the covering layer 32 is laminated in units of atomic layer level, the covering layer 32 has a high step coverage such as a concavo-convex shape, and forms a dense and uniform film with very few pinholes. Can do.
In addition, by forming the covering layer 32 having an appropriate thickness, the gap between the particles of the inorganic phosphor 31 is not completely filled, and the gap 33 (see FIG. 1B) is left in the phosphor layer 3. Can do.

  Moreover, according to the ALD method, since the particles of the inorganic phosphor 31 are densely and uniformly coated, a fluoride phosphor that is easily deteriorated by moisture can be used.

  In addition, when using the fluorescent substance which is easy to deteriorate with moisture like a fluoride fluorescent substance, it is preferable to do as follows. First, the surface of the particles of the inorganic phosphor 31 is water-resistant coated in advance by various coating methods. Next, the particle layer 34 is formed on the surface of the semiconductor light-emitting element 2 by an electro-deposition method, an electrostatic coating method, or the like within a short time using the inorganic phosphor 31 with a water-resistant coating. Then, by forming the coating layer 32 by the ALD method, the semiconductor light emitting element 2 and the particle layer 34 are integrated to form the light emitting device 1A. Thus, the light emitting device 1A can be manufactured while preventing the influence of moisture in the manufacturing process. In addition, the light-emitting device 1A which is protected from the atmosphere such as moisture by the coating layer 32 and hardly deteriorates after the manufacture can be obtained.

(Final singulation process)
The final singulation step S17 is a step of singulating the semiconductor light emitting element 2 on which the coating layer 32 is formed.
As shown in FIG. 5 (f), here, the portion where the semiconductor light emitting element 2 on which the coating layer 32 is formed on the jig 50 is not placed, that is, the coating layer 32 is formed by dicing, polishing, or the like. The translucent layer 5 and the phosphor layer 3 between the semiconductor light emitting elements 2 are removed. Further, the semiconductor light emitting element 2 on which the coating layer 32 is formed is peeled from the jig 50.

In FIG. 5, the phosphor layer 3, the translucent layer 5, and the conductor layer 6 are shown thick for easy understanding, and therefore the covering layer 32 in FIG. It has a shape that covers a part of the side. However, in practice, almost all the side surfaces of the semiconductor light emitting element 2 can be covered with the covering layer 32 by adjusting the film thickness of the phosphor layer 3.
In addition, the translucent layer 5 between the semiconductor light emitting elements 2 is removed before forming the covering layer 32, or the translucent layer 5 between the semiconductor light emitting elements 2 is formed after forming the covering layer 32. After removing the phosphor layer 3, the covering layer 32 may be formed on the entire side surface of the semiconductor light emitting element 2. Therefore, in FIGS. 5F to 5H, for convenience, the state in which the coating layer 32 is formed on the entire side surface of the semiconductor light emitting element 2 is illustrated. Similarly, when the phosphor layer 3 is formed, the conductor layer 6 is removed before the phosphor layer 3 is formed, so that the phosphor layer 3 is formed on the entire side surface of the semiconductor light emitting element 2. Good.

Then, as shown in FIG. 5G, the light emitting device 1 </ b> A manufactured in this way is provided in the recess 15 a of the package 15. The package 15 is a mounting substrate for mounting the light emitting device 1A. The package 15 has a recess 15a for mounting the light emitting device 1A, and the upper portion of the recess 15a is open.
Here, when the semiconductor light emitting element 2 is an FD element to be face-down mounted, the electrodes 43 and 44 are mounted on the conductive members 73 and 74. On the other hand, in the case of a FU element to be face-up mounted, the electrodes 43 and 44 face up and the support substrate 41 side is mounted on the conductive member 73. The electrodes 43 and 44 and the conductive members 73 and 74 are connected by wires 80 and 80.
As a mounting method of the light emitting device 1A, mounting using a solder paste as a bonding member or mounting using a bump using solder or the like is used.

(Second manufacturing method)
As shown in FIG. 7, the second manufacturing method is another manufacturing method of the light emitting device 1A shown in FIG. 3, and includes a semiconductor light emitting element manufacturing step S21, an arraying step S22, and a conductor layer forming step S23. , Including a half-cut individualizing step S24, a preliminary mounting step S25, a phosphor layer forming step S26, a conductor layer transparentizing step S27, a covering layer forming step S28, and a final individualizing step S29, This is done in this order.
Here, on the assumption that a plurality of light emitting devices 1A are manufactured, the description will be made assuming that the arrangement step S22 and the final singulation step S29 are included. Similarly to the first manufacturing method, depending on the conditions of the manufacturing method, the conductor layer forming step S23 and the conductor layer transparentizing step S27 may not be included.
Hereinafter, each step will be described in detail with reference to FIG. 8 (see FIGS. 1 to 3 and FIG. 7 as appropriate).

(Semiconductor light emitting device manufacturing process)
Since the semiconductor light emitting element manufacturing step S21 in the second manufacturing method is the same as the semiconductor light emitting element manufacturing step S11 in the first manufacturing method, detailed description thereof is omitted.

(Sequence process)
As shown in FIG. 8A, since the arrangement step S22 in the second manufacturing method is the same as the arrangement step S12 in the first manufacturing method, detailed description thereof is omitted.

(Conductor layer forming process)
As shown in FIG. 8B, the conductor layer forming step S23 in the second manufacturing method is the same as the conductor layer forming step S13 in the first manufacturing method, and thus detailed description thereof is omitted.

(Individual fragmentation process)
The half-separation step S24 is a step of separating the semiconductor light emitting element 2 on which the conductor layer 6 is formed.
In the mid-sectioning step S24, here, the portion where the semiconductor light emitting element 2 on which the conductor layer 6 is formed on the jig 50 is not placed, that is, the conductor layer 6 is formed by dicing or polishing. The conductor layer 6 between the semiconductor light emitting elements 2 is removed. Further, the semiconductor light emitting element 2 on which the conductor layer 6 is formed is peeled from the jig 50.

(Preliminary mounting process)
The preliminary mounting step S25 is a step of mounting the semiconductor light emitting element 2 on the flat insulating substrate 60 at a predetermined interval.
In the preliminary mounting step S25, as shown in FIG. 8C, the semiconductor light emitting device 2 on which the conductor layer 6 is formed is insulated with a predetermined interval with the electrodes 43 and 44 facing down. It is arranged and mounted on the insulating substrate 60 via the conductive members 71 and 72 attached to the substrate 60. The semiconductor light emitting element 2 mounted on the insulating substrate 60 is placed on the conductive members 71 and 72 and the position thereof is maintained.
As a method for mounting the semiconductor light emitting element 2, mounting using a solder paste as a bonding member or mounting using a bump using solder or the like is used.

  In the preliminary mounting step S25, the semiconductor light emitting elements 2 can be mounted on the insulating substrate 60 by adsorbing the semiconductor light emitting elements 2 one by one using a collet, for example.

  Here, the insulating substrate 60 is a plate-like member for electrically connecting the power source and the electrode after being mounted on the package 15 described later. That is, the insulating substrate 60 is mounted on the package 15 to be described later through the inside, the side surface, and the like, and then the conductive member 73 and the conductive member 71 and the conductive member 74 and the conductive member 72 are made of a conductive member such as a conductive wire. And electrically connect. Alternatively, these may be conducted by wire bonding. However, the conducting method is not limited to these, and any method may be used. The insulating substrate 60 can be a plate-like member such as ceramic.

(Phosphor layer forming step (inorganic particle layer forming step))
As shown in FIG. 8D, the phosphor layer forming step S26 in the second manufacturing method is the same as the phosphor layer forming step S14 in the first manufacturing method, and thus detailed description thereof is omitted.

(Conductor layer transparency process)
As shown in FIG. 8 (e), the conductor layer transparentizing step S27 in the second manufacturing method is the same as the conductor layer transparentizing step S15 in the first manufacturing method, and thus detailed description thereof is omitted. .

(Coating layer forming process)
As shown in FIG. 8F, the covering layer forming step S28 in the second manufacturing method is the same as the covering layer forming step S16 in the first manufacturing method, and thus detailed description thereof is omitted.
Note that the portion of the insulating substrate 60 where the semiconductor light emitting element 2 having the coating layer 32 is not placed, that is, the coating layer 32 between the semiconductor light emitting elements 2 having the coating layer 32 formed thereon is removed by etching or the like. Alternatively, masking may be performed so that the coating layer 32 is not formed.

(Final singulation process)
The final singulation step is a step of singulating the semiconductor light emitting element 2 on which the coating layer 32 is formed.
As shown in FIG. 8G, here, the semiconductor light emitting element 2 on which the covering layer 32 is formed by cutting the insulating substrate 60 by dicing or the like is separated into pieces. Through the above steps, the light emitting device 1A shown in FIG. 3 can be manufactured.

As shown in FIG. 8H, the light emitting device 1 </ b> A manufactured in this way is provided in the recess 15 a of the package 15 together with the conductive members 71 and 72 and the insulating substrate 60. At this time, the light emitting device 1 </ b> A is mounted on the conductive members 73 and 74 provided at the bottom in the recess 15 a of the package 15 via the conductive members 71 and 72 and the insulating substrate 60. Note that the conductive member 73 and the conductive member 71, and the conductive member 74 and the conductive member 72 are electrically connected to each other through the inside of the insulating substrate 60, the side surface, and the like by a conductive member such as a conductive wire. Alternatively, these are made conductive by wire bonding. However, the conducting method is not limited to these, and any method may be used.
As a mounting method of the light emitting device 1A, mounting using a solder paste as a bonding member or mounting using a bump using solder or the like is used.

(Third production method)
As shown in FIG. 9, the third manufacturing method is a method of manufacturing the light emitting device 1 shown in FIG. 1, and includes a semiconductor light emitting element manufacturing step S31, a preliminary mounting step S32, a phosphor layer forming step S33, The coating layer forming step S34 and the final singulation step S35 are performed in this order.
Here, on the assumption that a plurality of light emitting devices 1 are manufactured, the description will be made assuming that the preliminary mounting step S32 and the final singulation step S35 are included.
Hereinafter, each step will be described in detail with reference to FIG. 10 (see FIGS. 1 to 3 and FIG. 9 as appropriate).

(Semiconductor light emitting device manufacturing process)
The semiconductor light emitting element manufacturing step S31 is a process for manufacturing the semiconductor light emitting element 2. By this step, the semiconductor light emitting element 2b having the structure shown in FIG. 2B is manufactured.

  The semiconductor light emitting device 2b may be manufactured by a conventionally known method. For example, each nitride semiconductor constituting the n-type semiconductor layer 42a, the active layer 42b, and the p-type semiconductor layer 42c is sequentially grown on a substrate (not shown) made of sapphire (C-plane) by a MOVPE reactor. . Subsequently, a reflective electrode (Ag) 45 and a current constriction (dielectric) 48 are provided by sputtering. Thereafter, a wafer bonding layer 49 is formed by sputtering and bonded to a support substrate 41 having conductivity such as Si by a method such as thermocompression bonding. Next, the sapphire substrate is peeled off by a laser lift-off (LLO) method in which a laser is applied from the sapphire side. Subsequently, a resist mask is formed and the semiconductor layer is patterned to remove the resist, and then an n-side electrode 43 is provided by sputtering. Then, a protective film 47 is formed by sputtering, a resist mask is formed, etching is performed, the resist is removed, and the n-side electrode 13 is exposed. On the other hand, a p-side electrode 44 is provided on the back surface of the support substrate 41 by sputtering.

(Preliminary mounting process)
The preliminary mounting step S32 is a step of arranging the semiconductor light emitting elements 2 on the flat insulating substrate 60 at a predetermined interval.
In the preliminary mounting step S32, as shown in FIG. 10 (a), the semiconductor light emitting element 2 is bonded to the insulating substrate 60 with a predetermined interval with the p-side electrode 44 face down. Then, they are arranged and mounted on the insulating substrate 60 via 71. The semiconductor light emitting element 2 mounted on the insulating substrate 60 is placed on the conductive member 71 and its position is maintained.
As a method for mounting the semiconductor light emitting element 2, mounting using a solder paste as a bonding member or mounting using a bump using solder or the like is used.
On the other hand, the n-side electrode 43 and the conductive member 72 provided on the insulating substrate 60 are connected by a wire 80.
In such a vertical structure type semiconductor light emitting device 2b, the p-side electrode 44 and the n-side electrode 43 are electrically connected via the wire 80, whereby the side surface and the top surface of the semiconductor light emitting device 2b are electrically connected. Therefore, electrodeposition is possible without providing a conductor layer.

(Phosphor layer forming step (inorganic particle layer forming step))
As shown in FIG. 10B, the phosphor layer forming step S33 in the third manufacturing method is the same as the phosphor layer forming step S14 in the first manufacturing method, and a detailed description thereof will be omitted. Here, the particle layer 34 is also formed on the surface of the wire 80. Further, since the entire semiconductor layer functions as an electrode for electrodeposition or electrostatic coating, the particle layer 34 is formed on the exposed surface of the semiconductor layer.

(Coating layer forming process)
As shown in FIG. 10C, the coating layer forming step S34 in the third manufacturing method is the same as the coating layer forming step S16 in the first manufacturing method, and thus detailed description thereof is omitted. Here, the coating layer 32 is also formed on the surface of the wire 80.

(Final singulation process)
As shown in FIG. 10D, the final singulation step S35 in the third manufacturing method is the same as the final singulation step S29 in the second manufacturing method, and thus detailed description thereof is omitted. In this case, the wires 80 are separated into individual pieces. Through the above steps, the light emitting device 1 shown in FIG. 1 can be manufactured. In FIG. 1, the wires are not shown.

As shown in FIG. 10E, the light emitting device 1 manufactured in this way is provided in the recess 15 a of the package 15 together with the conductive members 71 and 72 and the insulating substrate 60. At this time, the light emitting device 1 is mounted on the conductive members 73 and 74 provided at the bottom in the recess 15 a of the package 15 via the conductive members 71 and 72 and the insulating substrate 60. Note that the conductive member 73 and the conductive member 71, and the conductive member 74 and the conductive member 72 are electrically connected to each other through the inside of the insulating substrate 60, the side surface, and the like by a conductive member such as a conductive wire. Alternatively, these are made conductive by wire bonding. However, the conducting method is not limited to these, and any method may be used.
As a mounting method of the light emitting device 1, mounting using a solder paste as a bonding member or mounting using bumps using solder or the like is used.

  The light emitting device and the method for manufacturing the light emitting device of the present invention have been described above, but the present invention is not limited to this. Hereinafter, other modified examples will be described with reference to FIGS.

As shown in FIG. 11A, in the light emitting device 1 </ b> B, a protective layer 7 is formed so as to cover the phosphor layer 3. The protective layer 7 is a transparent layer and is made of an oxide film such as SiO ₂ .

  With such a configuration, the strength of the phosphor layer 3 and the light extraction can be improved. Moreover, since the final shape is formed by the further fragmentation, the manufactured semiconductor light emitting element 2 needs to have strength enough to withstand the cutting process. Then, the semiconductor light emitting element 2 is used by being joined to another member after the cutting process. At that time, it is predicted that the flatness of the surface affects the bonding, and the formation of the protective layer 7 can achieve the flattening. Further, when further planarization is required, it can be used for a processed layer by polishing, grinding, or CMP.

Next, a protective layer forming process for forming the protective layer 7 will be described.
The protective layer forming step is an inorganic material that continuously covers the surface of the semiconductor light emitting element 2 and the surface of the particles of the color conversion member (inorganic phosphor 31) after the coating layer forming step and before the final singulation step. In this step, the protective layer 7 made of an oxide film is formed on the coating layer 32 made of

In the protective layer forming step, as shown in FIG. 11A, the protective layer is formed so as to cover the inorganic phosphor 31 and the coating layer 32. The protective layer 7 can be formed by a CVD method, an atmospheric pressure plasma deposition method, a sputtering method, or the like. Thereby, the unevenness | corrugation of the fluorescent substance layer 3 can be reduced, and fixation of the formation body which consists of the inorganic fluorescent substance 31 and the coating layer 32 can be improved.
The film formation method described above can be formed with a low coverage of the film formation material. For this reason, not only the unevenness of the outermost surface can be reduced, but also the gap near the outermost surface can be closed. Further, when a flatter surface is required for bonding or the like, the protective layer 7 can be processed by grinding, polishing, CMP, or the like without processing the phosphor layer 3.

(Protective layer formation process by CVD method)
A protective layer forming process when the CVD method is used will be described. The CVD process includes evacuation, plasma treatment, and a purge process. Vacuum exhaust is performed up to about 10 Pa. Then, after reaching the vacuum, it is stored at a high temperature up to 200 ° C. Next, TEOS and oxygen are introduced, plasma is generated in units of 2 μm, and peeling and residual stress are alleviated. The film thickness is formed between 16 μm. Then, return to atmospheric pressure and take out.

Further, as shown in FIG. 11B, a light emitting device 1 </ b> C in which filler particles 8 having a refractive index different from that of the coating layer are formed on the surface of the inorganic phosphor 31, and a coating layer 32 is formed on the surface of the filler particles 8. It is good. Examples of the filler particles 8 include the inorganic fillers described above.
After the inorganic phosphor 31 is formed and before the coating layer 32 is formed, filler particles 8 having a refractive index different from that of the coating layer 32 are disposed on the surface of the inorganic phosphor 31, and then the coating layer 32 is formed. The efficiency of diffusion and extraction can be increased. For example, when the coating layer 32 is Al ₂ O ₃ , SiO ₂ or TiO ₂ particles are arranged on the outermost surface of the inorganic phosphor 31, and then the coating layer 32 is formed. The filler particles 8 can be formed by, for example, the above-described electrodeposition method, electrostatic coating method, pulse spray method or centrifugal sedimentation method, or a combination of these methods.
In these modified examples, the light-transmitting layer 5 (see FIG. 3) may be provided on the surface of the semiconductor light emitting element 2.

[Operation of light emitting device]
Next, the operation of the light-emitting devices 1 and 1A will be described with reference to FIGS.
In the present embodiment, the case where the semiconductor light emitting element 2 that emits blue light is used as the light source will be described. Moreover, the light-emitting device 1 and 1A which have the inorganic fluorescent substance 31 which converts blue light into yellow light shall be used as a color conversion molding.

  Blue light emitted from the semiconductor light emitting element 2 propagates in the phosphor layer 3 while being scattered by the gap 33 (see FIG. 1B) of the phosphor layer 3, and is output as light from the light emitting devices 1 and 1A. Is output.

  A part of the blue light incident on the phosphor layer 3 is absorbed by the inorganic phosphor 31 until it passes through the phosphor layer 3 and is emitted. The inorganic phosphor 31 is excited by the absorbed blue light and emits (emits) yellow light. That is, the inorganic phosphor 31 converts blue light into yellow light.

  The yellow light emitted from the inorganic phosphor 31 and the blue light transmitted through the phosphor layer 3 without being absorbed by the inorganic phosphor 31 are emitted as transmitted light from the side surfaces and the upper surface of the light emitting devices 1 and 1A. . At this time, the transmitted light includes yellow light that has been color-converted by the phosphor layer 3 and blue light that has not been color-converted, and the transmitted light has a mixed color. By adjusting the film thickness of the inorganic phosphor 31 in the phosphor layer 3 and the ratio of the gaps 33 (see FIG. 1B) so that the blue light and the yellow light have an appropriate ratio, the light emitting device 1, The output light of 1A can be white light.

In addition, this invention is not limited to white light, All the light radiate | emitted from the semiconductor light-emitting element 2 can be color-converted into yellow light, and can also be comprised so that it may output as yellow light. Further, for example, an inorganic phosphor 31 that converts color to green or red may be used. Further, by forming a phosphor layer 3 by laminating or mixing a plurality of types of inorganic phosphors 31, it can be configured to be converted into various colors and output.
The light emitting devices 1B and 1C are the same as the light emitting devices 1 and 1A except that the protective layer 7 and the filler particles 8 are present.

Next, examples of the present invention will be described.
<Example 1>
As Example 1, a manufacturing example of the light emitting device 1A according to the embodiment illustrated in FIG. 3 will be described.

(Semiconductor light emitting device manufacturing process and alignment process)
The semiconductor light emitting device having the structure shown in FIG. 2A is manufactured by the method described in the first manufacturing method. The semiconductor light emitting elements are arranged on a flat jig at a predetermined interval.

(Conductor layer forming process)
In order to provide conductivity to the surface of the semiconductor light emitting element, an Al layer having a thickness of about 0.1 μm is formed by sputtering.

(Phosphor layer forming process)
Next, as an inorganic phosphor, F.I. S. S. S. A negative electrode is immersed in an electrodeposition bath of about 25 ° C. in which CASN particles having an average particle diameter of 7 μm are dispersed together with a counter electrode, and an inorganic phosphor is electrodeposited on the exposed portion of the semiconductor light emitting element by electrophoresis. Mg ion is added to the electrodeposition tank as an inorganic binder, and this precipitates as magnesium hydroxide and / or magnesium carbonate, thereby obtaining a binding force. The thickness of the inorganic phosphor particle layer is controlled to a thickness of 30 μm by controlling the amount of coulomb applied between the electrodes.
After washing and drying, a semiconductor light emitting device in which a particle layer of an inorganic phosphor is laminated is obtained.

(Conductor layer transparency process)
After washing and drying, the Al layer is treated with hot water at 90 ° C., and the Al layer as the conductor layer is oxidized to form an Al ₂ O ₃ layer, thereby making the conductor layer transparent.

(Coating layer forming process)
Next, an Al ₂ O ₃ layer is formed by the ALD method as a coating layer that covers the particle layer of the inorganic phosphor laminated on the surface of the semiconductor light emitting device.

A semiconductor light emitting element on which a particle layer of CASN phosphor is laminated is inserted into a reaction vessel of an ALD apparatus which is a film forming apparatus by the ALD method.
Under a temperature condition of about 150 ° C., raw materials H ₂ O and TMA are alternately introduced into the reaction vessel with a vacuum purge interposed therebetween. By repeating the basic cycle of the film forming process in which the raw materials are alternately introduced, the Al ₂ O ₃ layer is deposited monomolecularly, and the Al ₂ O ₃ layer is formed to a thickness of about 1 μm.
Details of the coating layer forming step will be described later.

(Final singulation process)
Next, a portion where the semiconductor light emitting element 2 having the coating layer 32 formed on the jig 50 for separating the semiconductor light emitting element having the coating layer formed thereon is not placed is removed by dicing and polishing, and the semiconductor light emitting element Is peeled off from the jig.

In this light emitting device, the voids in the phosphor layer are 24.0%, and although there is a difference in the linear expansion coefficient between the semiconductor light emitting element and the phosphor layer, the occurrence of cracks and the like is prevented.
This light-emitting device can be used as a light source for a projector or a headlight for an automobile that is excited by an LD light source.

  The light emitting device manufactured in this example has a maximum temperature of 150 ° C. during the process, and even when a CASN phosphor that is a nitride phosphor is used as the inorganic phosphor, the CASN phosphor is not deteriorated. Further, the phosphor layer is formed with a thickness of 30 μm, which is 100 μm or less, which is difficult to process with ordinary sintered ceramics, and is in direct contact with the metal. Therefore, heat generated by Stokes loss generated by excitation of the phosphor can be efficiently radiated, and a decrease in phosphor color conversion efficiency due to temperature rise is suppressed.

  Further, the surface of the phosphor layer has irregularities due to the particle size of the inorganic phosphor particles, and moderate gaps are formed inside the light emitting device. Also, a dense film is formed by the ALD method.

[Coating layer forming step]
The coating layer forming step by the ALD method of Example 1 will be described in more detail.
In the present example, the inner diameter of the reaction vessel of the ALD apparatus is 300 mm, and the thickness of the sample is 6 mm.

(Pre-baking process)
First, a sample having an inorganic phosphor particle layer formed on the surface of a semiconductor light emitting element having a conductor layer is placed in an oven and heated at 120 ° C. for 2 hours to evaporate moisture in the sample.

(Sample setting process)
Next, a sample is placed in the reaction vessel of the ALD apparatus, and the reaction vessel lid is closed.

(Storage process before film formation)
Next, the inside of the reaction vessel is brought into a low pressure state using a rotary pump. The pressure setting in the reaction vessel is 10 torr (13332 Pa). In addition, a nitrogen gas flow is introduced into the reaction vessel. The flow rate of nitrogen gas is 20 sccm (33 × 10 ⁻³ Pa · m ³ / s), and this state is maintained for about 60 minutes for stabilization and final moisture removal.
The temperature of the reaction vessel is 150 ° C., and this temperature is maintained during the subsequent film formation.

(First raw material supply process)
H ₂ O is introduced into the reaction vessel as a first raw material for 0.015 seconds.
In order to react the sample and H ₂ O, a stop valve, which is a valve connecting the reaction vessel and the vacuum line, is closed, and the sample is exposed to H ₂ O for 15 seconds.

(First exhaust process)
The stop valve is opened, and unreacted H ₂ O and by-products are exhausted from the reaction vessel with a nitrogen gas flow for 60 seconds.

(Second raw material supply process)
TMA is introduced into the reaction vessel as the second raw material for 0.015 seconds.
In order to react the sample with TMA, the stop valve of the reaction vessel is closed and the sample is exposed to TMA for 15 seconds.

(Second exhaust process)
The stop valve is opened, and unreacted TMA and by-products are exhausted from the reaction vessel with a nitrogen gas flow for 32 seconds.

The cycle from the first raw material supply process to the second exhaust process is set as one cycle, and this cycle is repeated so as to obtain an Al ₂ O ₃ film having a desired thickness. In this embodiment, an Al ₂ O ₃ film having a thickness of about 1 μm is formed in 6000 cycles.

After the film formation is completed, the stop valve is closed, the flow of nitrogen gas is set to 100 sccm (169 × 10 ⁻³ Pa · m ³ / s), and the pressure in the reaction vessel is brought to normal pressure, and then the sample is taken out.
With the above procedure, an Al ₂ O ₃ film is formed as a coating layer.

<Example 2>
As Example 2, another example of manufacturing the light emitting device 1A according to the embodiment shown in FIG. 3 will be described.

A conductor layer made of ITO is masked on the surface of the semiconductor light emitting element to form a limited number of formation locations. In the same manner as in Example 1, a fluoride phosphor particle layer is laminated on the semiconductor light emitting device after the masking is removed. After washing and drying, an Al ₂ O ₃ layer having a thickness of about 1 μm is formed by ALD.

  Since the conductor layer in this embodiment has a light-transmitting property, a transmissive light-emitting device can be manufactured without performing a conductor layer transparentization step.

<Example 3>
As Example 3, a YAG-based inorganic phosphor was used, and a light emitting device produced by forming an Al ₂ O ₃ layer as a coating layer by the ALD method was analyzed from a photographic image obtained by photographing a cross section of the phosphor layer. The porosity of the phosphor layer was measured by the method. Hereinafter, the procedure for measuring the porosity will be described.

  The average particle size of the inorganic phosphor used in this example is F.R. S. S. S. The measurement by the No method was 3.6 μm. In addition, the center particle size by volume distribution obtained from the particle size distribution measured using a Coulter counter was 6.2 μm.

First, as shown in FIG. 12, the produced light emitting device is divided, and a cross section of the phosphor layer is photographed with a scanning electron microscope. In FIG. 12, the light gray portion of the granular lump is the inorganic phosphor 31, and the dark gray portion at the outer edge of the granular lump is the coating layer 32.
In addition, the scale displayed on the lower right of FIG. 12 indicates 1 μm, and the film thickness of the coating layer 32 is about 300 nm.

  Next, a region A to be measured is cut out from the photographic image shown in FIG. 12, and the covering layer 32 is blacked out as shown in FIG.

  Next, using the particle analysis software, the region surrounded by the coating layer 32 painted black is painted black as shown in FIG. 14, and this black painted region is the phosphor region (31 + 32) including the coating layer 32. ). Here, the void 33 is defined as a region other than the region painted black. Then, the content ratio of the inorganic phosphor (31 + 32) including the coating layer 32 is obtained by dividing the area (number of pixels) of the blacked area by the area (number of pixels) of the area A, and the remaining portion The porosity is required as follows.

  In this example, the content of the inorganic phosphor was 75.4%. Therefore, the porosity was 24.6%.

As described above, the light-emitting device of the present invention can be a light-emitting device with little deterioration even at high current and high temperature by coating the surface of a semiconductor light-emitting element with an inorganic material. In addition, it is possible to select an inorganic phosphor that easily deteriorates under a low current and constant temperature, and it is possible to suppress a change in output. In addition, by directly applying the atomic layer volume method to the semiconductor light emitting device, it is possible to protect the epitaxial layer from damage, the electrode layer in the die section, and the exposed layers.
Furthermore, by coating with an inorganic material, unlike the case where the inorganic phosphors are bonded with resin, the linear expansion coefficient of the material is small, so that the change in emission color of the light-emitting device due to expansion / contraction or adhesion change is suppressed. It is possible.

1, 1A, 1B, 1C Light emitting device 2 Semiconductor light emitting element 3 Phosphor layer (inorganic particle layer)
31 Inorganic phosphor (color conversion member)
32 Coating layer 33 Void 34 Particle layer (aggregate)
5 Translucent Layer 6 Conductor Layer 7 Protective Layer 8 Filler Particle 15 Package 15a Concave

Claims (18)

A semiconductor light emitting device;
A color made of an inorganic material provided on at least the upper surface of the semiconductor light emitting element, which absorbs light of a first color emitted by the semiconductor light emitting element and emits light of a second color different from the first color. An inorganic particle layer containing particles of the conversion member,
The inorganic particle layer is
Aggregates in which the particles are continuously connected by contacting the particles or the semiconductor light emitting element,
A coating layer made of an inorganic material that continuously covers the surface of the semiconductor light emitting element and the surface of the particles;
A void surrounded by any of the semiconductor light emitting device, the particles and the coating layer;
A light emitting device comprising:   The light emitting device according to claim 1, wherein the voids in the inorganic particle layer have a porosity of 1 to 50%. The average particle diameter of the particles of the color conversion member is 0.1 to 100 μm,
3. The light emitting device according to claim 1, wherein an average thickness of the coating layer is 10 nm to 50 μm.   4. The light emitting device according to claim 1, wherein the surface of the inorganic particle layer has a concavo-convex shape due to a particle diameter of the color conversion member. 5.   The light emitting device according to claim 1, wherein the covering layer is formed by an atomic layer deposition method. The coating layer is made of Al ₂ O ₃ , SiO ₂ , ZrO ₂ , HfO ₂ , TiO ₂ , ZnO, Ta ₂ O ₅ , and Nb ₂ O ₅ , In ₂ O ₃ , SnO ₂ , TiN, and AlN. The light-emitting device according to claim 1, comprising at least one compound selected from the group consisting of:   The color conversion member contains at least one compound selected from the group consisting of sulfide phosphors, halogen silicate phosphors, nitride phosphors, and oxynitride phosphors. The light emitting device according to any one of claims 1 to 6.   The light emitting device according to any one of claims 1 to 7, wherein the color conversion member contains at least a fluoride phosphor.   The light emitting device according to claim 1, wherein the particles of the color conversion member are bound to each other and to the semiconductor light emitting element by an inorganic binder. A semiconductor light emitting device manufacturing process for manufacturing a semiconductor light emitting device;
A color conversion member made of an inorganic material that absorbs light of a first color emitted from the semiconductor light emitting element and emits light of a second color different from the first color on the surface of the semiconductor light emitting element. An inorganic particle layer forming step of forming an agglomerate containing particles;
A coating layer forming step of forming a coating layer made of an inorganic material that continuously covers the surface of the semiconductor light emitting element and the surface of the particles;
A method for manufacturing a light-emitting device, comprising:   In the inorganic particle layer forming step, the aggregate is formed on the surface of the semiconductor light emitting element by an electrodeposition method, an electrostatic coating method, a pulse spray method or a centrifugal sedimentation method, or a combination of these methods. A method for manufacturing a light emitting device according to claim 10. Prior to the inorganic particle layer forming step, a conductor layer forming step of forming a conductor layer made of metal on the surface of the semiconductor light emitting element is performed,
After the inorganic particle layer forming step and before the coating layer forming step, perform a conductor layer transparentizing step of oxidizing and transparentizing the conductor layer,
In the inorganic particle layer forming step, the aggregate is formed on the surface of the semiconductor light-emitting element via the conductor layer by an electrodeposition method or an electrostatic coating method using the conductor layer as one electrode. The method for manufacturing a light emitting device according to claim 10.   The method for manufacturing a light-emitting device according to claim 12, wherein the transparent conductor layer is made of the same material as the coating layer. Prior to the inorganic particle layer forming step, a conductor layer forming step of forming a conductive layer made of a light-transmitting conductive material on the surface of the semiconductor light emitting element is performed,
In the inorganic particle layer forming step, the aggregate is formed on the surface of the semiconductor light-emitting element via the conductor layer by an electrodeposition method or an electrostatic coating method using the conductor layer as one electrode. The method for manufacturing a light emitting device according to claim 10.   The method for manufacturing a light emitting device according to claim 10, wherein in the covering layer forming step, the covering layer is formed by an atomic layer deposition method.   16. The method according to claim 10, wherein a compound containing at least an alkaline earth metal element as a component is used as the inorganic binder when forming the aggregate in the inorganic particle layer forming step. A method for manufacturing the light emitting device according to claim 1. The average particle diameter of the color conversion member is 0.1 to 100 μm,
The method for manufacturing a light emitting device according to any one of claims 10 to 16, wherein an average thickness of the coating layer is 10 nm to 50 µm. The coating layer is made of Al ₂ O ₃ , SiO ₂ , ZrO ₂ , HfO ₂ , TiO ₂ , ZnO, Ta ₂ O ₅ , and Nb ₂ O ₅ , In ₂ O ₃ , SnO ₂ , TiN, and AlN. The method for manufacturing a light emitting device according to claim 10, comprising at least one compound selected from the group consisting of: