WO2006057172A1 - 半導体発光装置、照明装置、携帯通信機器、カメラ、及び製造方法 - Google Patents
半導体発光装置、照明装置、携帯通信機器、カメラ、及び製造方法 Download PDFInfo
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- WO2006057172A1 WO2006057172A1 PCT/JP2005/020731 JP2005020731W WO2006057172A1 WO 2006057172 A1 WO2006057172 A1 WO 2006057172A1 JP 2005020731 W JP2005020731 W JP 2005020731W WO 2006057172 A1 WO2006057172 A1 WO 2006057172A1
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- Prior art keywords
- semiconductor light
- light emitting
- electrode
- emitting device
- alloy containing
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Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
- H01L33/58—Optical field-shaping elements
- H01L33/60—Reflective elements
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L2224/42—Wire connectors; Manufacturing methods related thereto
- H01L2224/44—Structure, shape, material or disposition of the wire connectors prior to the connecting process
- H01L2224/45—Structure, shape, material or disposition of the wire connectors prior to the connecting process of an individual wire connector
- H01L2224/45001—Core members of the connector
- H01L2224/45099—Material
- H01L2224/451—Material with a principal constituent of the material being a metal or a metalloid, e.g. boron (B), silicon (Si), germanium (Ge), arsenic (As), antimony (Sb), tellurium (Te) and polonium (Po), and alloys thereof
- H01L2224/45138—Material with a principal constituent of the material being a metal or a metalloid, e.g. boron (B), silicon (Si), germanium (Ge), arsenic (As), antimony (Sb), tellurium (Te) and polonium (Po), and alloys thereof the principal constituent melting at a temperature of greater than or equal to 950°C and less than 1550°C
- H01L2224/45144—Gold (Au) as principal constituent
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L2224/42—Wire connectors; Manufacturing methods related thereto
- H01L2224/47—Structure, shape, material or disposition of the wire connectors after the connecting process
- H01L2224/48—Structure, shape, material or disposition of the wire connectors after the connecting process of an individual wire connector
- H01L2224/4805—Shape
- H01L2224/4809—Loop shape
- H01L2224/48091—Arched
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L2224/42—Wire connectors; Manufacturing methods related thereto
- H01L2224/47—Structure, shape, material or disposition of the wire connectors after the connecting process
- H01L2224/48—Structure, shape, material or disposition of the wire connectors after the connecting process of an individual wire connector
- H01L2224/481—Disposition
- H01L2224/48151—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive
- H01L2224/48221—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked
- H01L2224/48245—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being metallic
- H01L2224/48247—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being metallic connecting the wire to a bond pad of the item
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
- H01L33/483—Containers
Definitions
- the present invention relates to a semiconductor light emitting device that emits light, a lighting device using the semiconductor light emitting device as a light source, a portable communication device, and a camera, and in particular, efficiently outputs output light to the outside.
- the present invention relates to a technique for improving the conversion rate by a fluorescent substance.
- the electrode is preferably formed of a metal having a high light reflectance.
- Patent Document 1 Japanese Patent Laid-Open No. 2000-286457
- the present invention uses output light such as blue light emitted from a semiconductor light-emitting element or yellow-green light converted by a fluorescent material, regardless of whether a material having high reflectance is suitable as an electrode. It is an object of the present invention to provide a semiconductor light emitting device that is well output to the outside, an illumination device equipped with the semiconductor light emitting device, a portable communication device and a camera, and a method for manufacturing the semiconductor light emitting device.
- a semiconductor light emitting device includes a mount member and a semiconductor light emitting element disposed on the mount member, and the mount member includes a substrate, An electrode part disposed on the upper surface of the substrate and in direct contact with the semiconductor light emitting element; and an electrode part disposed on the upper surface of the substrate and directly connected to the semiconductor light emitting element and the electrode part. It is characterized by having a small reflective part in contact with it.
- a reflective portion is provided on the upper surface of the mount member separately from the electrode portion. Nevertheless, this can be used.
- the output light emitted from the semiconductor light emitting element can be output to the outside more effectively than the method in which the electrode has a function as a reflective film.
- the electrode portion includes an electrode formed on the upper surface of the substrate, and a connection portion that electrically connects the semiconductor light emitting element and the electrode. It can be characterized by containing.
- the electrode such as the wiring pattern on the mount member and the semiconductor light emitting element are connected by the connection portion such as a bump or a bonding wire.
- the reflection portion may have a light reflectivity higher than that of the electrode.
- the reflectance of a reflection part is higher than an electrode, it can reflect more light which a semiconductor light-emitting device emits rather than using an electrode as a reflecting film.
- the light emission efficiency of the semiconductor light emitting device can be improved.
- the reflecting portion is formed of metal, and the electrode is less likely to cause electoric port migration than the metal forming the reflecting portion. .
- the electrode is a metal that is less likely to cause electoric port migration than the reflecting part, it is a material more suitable as the electrode than the reflecting part, and the occurrence of short-circuit failure between the electrodes due to electoric port migration can be suppressed.
- the reflective part has a higher reflectance than the electrode and is made of a material, it is possible to easily select a material suitable for each application.
- the reflection portion includes Ag, an alloy containing Ag, an alloy containing Ag, Bi, and Nd, an alloy containing Ag, Au, and Sn, Al, an alloy containing A1, or A1. It may be characterized by being formed of an alloy containing Nd. [0010] Thereby, the reflectance of the reflecting portion can be increased.
- the semiconductor light emitting element when the reflecting portion is formed of Ag or an alloy containing the same, and the electrode is formed of Au or an alloy containing the same as a main component, the semiconductor light emitting element
- the wavelength band of light emitted from is approximately 340 nm or more and approximately 800 ⁇ m or less, and when the electrode is formed of Pt or an alloy containing the same as the main component, the wavelength band is approximately 350 nm.
- the electrode is formed of Cu or an alloy mainly composed of Cu
- the wavelength band is approximately 350 nm or more and approximately 800 nm or less
- the electrode is Ni or
- the wavelength band is approximately 340 nm or more and approximately 800 nm or less.
- Wavelength band is approximately 370nm
- the wavelength band is about 800 nm or less
- the wavelength band is about 460 nm or more and about 800 nm or less.
- the reflectance of the reflecting portion is the electrode in the above wavelength range. It is higher than the reflectivity of.
- the semiconductor light emitting element when the reflective portion is formed of A1 or an alloy containing the same, and the electrode is formed of Au or an alloy containing the same as a main component, the semiconductor light emitting element
- the wavelength band of the light emitted by is about 200 nm or more and about 600 ⁇ m or less, and when the electrode is formed of Pt or an alloy containing this as a main component, the wavelength band is about 200 nm.
- the wavelength band is approximately 200 nm or more and approximately 630 nm or less, and the electrode is Ni or When formed of an alloy containing this as a main component, the wavelength band is approximately 200 nm or more and approximately 800 nm or less, and when formed using the electrode Rh or an alloy containing this as a main component, Wavelength band is approximately 200nm It may be characterized by being about 800 nm or less.
- the substrate may include Si.
- the substrate containing Si generally has a low reflectivity over the entire visible light region, the output light emitted from the semiconductor light emitting element can be efficiently and efficiently externally provided by providing the reflecting portion. Can be output to.
- the reflection portion may have an open portion that is not shielded by the semiconductor light emitting element when viewed from above.
- the reflection part formed in the open part can efficiently reflect the light emitted from the semiconductor light emitting element in the direction opposite to the light emitting direction and direct it in the light emitting direction.
- the light emitted by the element can be used efficiently. Therefore, the light emission efficiency of the semiconductor light emitting device can be improved.
- the reflection portion may be characterized in that a portion far from the semiconductor light emitting element is close and higher in the upward direction than the portion.
- the semiconductor light emitting device is provided with a translucent conversion portion that covers a part or all of the light emitting portion of the semiconductor light emitting element and a part or all of the reflecting portion. It's a monkey.
- the light of the first wavelength band of the blue light emitted from the semiconductor light emitting element and the light of the second wavelength band of the yellow-green light, which is a complementary color of the blue light converted by the fluorescent substance are efficiently used.
- white light mixed color light can be output while suppressing luminance unevenness and color unevenness, and at least in the part where the reflective part is covered with the translucent conversion part Since the light of the first wavelength band is reflected, the conversion rate by the fluorescent substance can be improved.
- the portion far from the semiconductor light emitting element has a higher ratio of reflecting light of the power of the semiconductor light emitting element than the near portion. I'll do it. As a result, the luminance unevenness and the color unevenness can be suppressed by reflecting more light that is attenuated and weakened as the semiconductor light emitting element power becomes farther away.
- the reflection part is characterized in that a part or all of the reflection part has irregularities.
- the surface area is increased by the unevenness, and the light in the first wavelength band can be diffusely reflected, so that the conversion rate by the fluorescent substance can be improved.
- the reflection portion may be characterized in that the portion far from the semiconductor light emitting element has larger irregularities than the near portion.
- the reflecting portion has a spherical surface in part or in whole.
- the surface area is increased by the curved surface, and the light in the first wavelength band can be irregularly reflected, so that the conversion rate by the fluorescent substance can be improved.
- the spherical surface of the reflective portion may be characterized in that a portion far from the semiconductor light emitting element has a smaller curvature than a close portion.
- the light intensity of the semiconductor light emitting element is attenuated and weakened as the distance increases. Color unevenness can be suppressed.
- the semiconductor light emitting device may be characterized in that an insulating part is provided between the reflecting part and the substrate.
- the semiconductor light emitting element is provided with a first element electrode and a second element electrode on one main surface side
- the mount member includes the first substrate as the electrode.
- the second element electrode and the second substrate electrode are one of the connection parts
- the second microelectrode is one of the connection parts. It can also be characterized by being electrically connected by a bump.
- the output light emitted from the semiconductor light emitting element can be output to the outside more effectively, so that high luminance can be obtained.
- an illumination device includes the semiconductor light emitting device and a lens portion arranged in a main light emitting direction of the semiconductor light emitting device.
- indoor lighting such as ceiling lights and downlights using a plurality of the above-mentioned semiconductor light emitting devices
- desktop lighting such as stands
- portable lighting such as flashlights
- photographing lighting such as camera strobes
- Luminous efficiency of various lighting devices is improved.
- high brightness and energy-saving effect can be expected.
- portable lighting high brightness and continuous lighting time can be expected.
- a portable communication device includes the semiconductor light emitting device or the lighting device.
- a camera according to the present invention includes the above semiconductor light emitting device or illumination device.
- the method of manufacturing a semiconductor light emitting device includes the steps of forming the electrode on the upper surface of the substrate, forming a protective film in the electrode portion and a region adjacent to the electrode portion, A step of forming a coating for a reflective portion on substantially the entire upper surface of the substrate, which is composed of a region where the protective film is formed and a region where the reflective portion is to be formed; the protective film; and the protective film Removing the coating for the reflecting portion formed thereon. It is characterized by.
- the protective film is formed in the electrode portion and the separation region around the electrode portion, so that the electrode portion protection and the separation region formation can be performed simultaneously.
- the metal for the reflective part to be deposited is less likely to be coated on the vertical surface compared to the horizontal plane, a film thickness of a certain level or more is formed on the reflective part that requires film thickness, and at the same time, the vertical surface, i. In this case, a reflective part is formed, and a discontinuous thin film can be formed.
- FIG. 1 (a) is a perspective view showing an appearance of a semiconductor light emitting device 100 in an embodiment of the present invention.
- (B) is a plan view of the semiconductor light emitting device 100 shown in (a).
- (C) is the longitudinal cross-sectional view of the semiconductor light-emitting device 100 shown to (a) at the AA 'line.
- FIG. 2 is a bottom view of the semiconductor light emitting device 110 before assembly.
- FIG. 3] (a) is a plan view of the submount 130 before the thread is erected.
- (b) is a longitudinal sectional view taken along line AA ′ of the submount 130 shown in (a).
- FIG. 4 is a diagram showing an appropriate combination of a wavelength range of output light, an electrode material, and a reflective part material.
- FIG. 5 is a diagram showing an outline of a manufacturing method of a submount 130.
- FIG. 6 is a diagram showing an outline of a cross section of a submount 130 in a reflecting portion forming step.
- FIG. 7 is a diagram showing an outline of a manufacturing method of a submount 130.
- FIG. 8 is a diagram showing an outline of a cross section of a submount 130 in the step of forming a reflecting portion.
- FIG. 9 is a diagram schematically showing a method for manufacturing the semiconductor light emitting device 100.
- FIG. 10 (a) is a plan view of the submount 510 before assembly.
- (b) is a vertical cross-sectional view of the semiconductor light emitting device 500 taken along the line AA ′ of the submount 510 shown in (a).
- (c) is a vertical cross-sectional view of the semiconductor light emitting device 500 taken along the line BB ′ of the submount 510 shown in (a).
- FIG. 11 (a) is a plan view of the submount 610 before assembly.
- FIG. 12 (a) is a plan view of the submount 710 before assembly. (b) is a semiconductor light emitting device
- FIG. 700 is a vertical sectional view taken along line AA ′ of the submount 710 shown in FIG.
- FIG. 13 is a diagram showing an illumination device 200 using the semiconductor light emitting device 100 as a light source.
- FIG. 15 A camera 400 equipped with a lighting device 200 as a strobe for taking a picture.
- the upper surface of the mounting member is made slightly larger than the outer shape of the semiconductor light emitting device, and the upper surface is more reflective than the electrodes such as Au (gold) and A1 (aluminum).
- the reflective portion With a high-rate metal such as Ag (silver), regardless of whether or not a material with high reflectivity is suitable as an electrode, the semiconductor light emitting element emits blue light or ultraviolet light. This is a semiconductor light emitting device that efficiently outputs light and output light such as yellowish green light converted by a fluorescent substance to the outside.
- FIG. 1 (a) is a perspective view showing an external appearance of a semiconductor light emitting device 100 in an embodiment of the present invention.
- the X-axis direction shown in FIG. 1 (a) is the front-rear direction of the semiconductor light emitting device 100 (the + side is the front side, the side is the rear side), and the Y-axis direction is the left-right direction (the + side is the left side, The Z axis direction is the vertical direction (the + side is the upper side and the side is the lower side).
- FIG. 1 (b) is a plan view of the semiconductor light emitting device 100 as viewed from the upper side (the Z axis direction + side).
- FIG. 1C is a vertical cross-sectional view taken along the line AA ′ of the semiconductor light emitting device 100 as viewed from the right side (the Y-axis direction side).
- a semiconductor light emitting device 100 is a device that outputs white light, and has a light transmitting property as an example of a semiconductor light emitting element 110 and a light transmitting conversion unit.
- a resin 120 and a submount 130 as a mount member are provided.
- FIG. 2 is a bottom view of the semiconductor light emitting device 110 before standing, as viewed from the lower side (the Z-axis direction side), that is, the main surface side facing the submount 130.
- the semiconductor light emitting device 110 is, for example, a light emitting diode that emits blue light in which a GaN-based compound semiconductor layer is formed on a light-transmitting substrate, and has a negative electrode 111 and a positive electrode on one main surface facing the submount 130. 112 and a main light emitting portion that mainly emits light on the other main surface.
- the external shape of the semiconductor light emitting device 110 is a rectangular parallelepiped shape with a main surface of a square of 0.3 mm square and a thickness of about 0.1 mm, and is arranged on the submount 130 as shown in FIG. And
- the translucent resin 120 is a resin material that includes a fluorescent material (not shown) that converts blue light emitted from the semiconductor light emitting element 110 into yellow-green light, which is a complementary color thereof. Transmits blue light that is not converted by the quality and yellow-green light that is converted by the fluorescent material.
- the translucent resin 120 is disposed on the submount 130 so as to cover the entire semiconductor light emitting device 110 and its periphery.
- the translucent resin 120 is disposed so as to cover a part of the reflecting portion 132.
- the translucent resin 120 may cover at least a part of the light-emitting portion, which does not necessarily cover the entire force of covering the entire semiconductor light-emitting element 110. Further, although the translucent resin 120 covers a part of the reflection part 132, it may cover the whole.
- FIG. 3 (a) is a plan view of the submount 130 before assembly, as viewed from the upper side (the Z-axis direction + side), that is, from the upper surface side where the semiconductor light emitting device 110 is disposed
- FIG. FIG. 4 is a vertical cross-sectional view taken along the line AA ′ of the submount 130 shown in FIG. 3A as viewed from the right side (the Y axis direction-side).
- the submount 130 includes the semiconductor light emitting device 110 and the light transmitting device. It is arranged on the lower side (the Z-axis direction side) of the synthetic resin 120.
- the submount 130 includes a silicon substrate 131 as an example of a substrate, an electrode portion and a reflection portion 132 provided on the upper surface of the silicon substrate 131, and a back electrode 133 provided on the lower surface of the silicon substrate 131. ing.
- the silicon substrate 131 is a substrate containing Si, and specifically, is a protective diode such as a Zener diode based on silicon.
- the electrode portion includes a positive electrode 134, a negative electrode 135, and microbumps 140 to 144 as an example of the connection portion.
- the positive electrode 134 is disposed on the upper surface of the p-type semiconductor region of the submount 130, and the negative electrode 135 and the reflecting portion 132 are disposed on the upper surface of the n-type semiconductor region of the submount.
- the reflecting portion 132 may be disposed on the upper surface of the p-type semiconductor region of the submount.
- the material of the back electrode 133 is, for example, any one of Au, Pt (platinum), Cu (copper), Ni (nickel), Rh (mouth dome), Al, and Ag, a combination of a plurality, Or an alloy containing these.
- the submount 130 has a rectangular parallelepiped shape with a main surface of a rectangle of 0.5 ⁇ 0.8 mm and a thickness of about 0.2 mm. Therefore, as shown in FIG. 1 (b), V and the submount 130 are slightly larger than the semiconductor light emitting device 110 in plan view.
- the submount 130 has at least a positive electrode 134 disposed in a portion of the open portion larger than the translucent resin 120 that is not covered with the translucent resin 120, and If the positive electrode 134 is covered with the translucent resin 120, a part of the portion becomes a bonding pad 136.
- various diodes such as a Zener diode, a pn diode, a pin diode, a Schottky key diode, a tunnel diode, and a Gunn diode can be used.
- the submount 130 that is a protective diode and the semiconductor light emitting element 110 that is a light emitting diode are connected by electrodes having opposite polarities. Since the protective diode is connected to the light emitting diode in this way, even if an attempt is made to apply a reverse voltage to the light emitting diode, the current flows in the forward direction to the protective diode, so the light emitting diode is almost reverse Even if no forward voltage is applied and an excessive forward voltage is applied to the light emitting diode, a forward voltage higher than the reverse breakdown voltage (Zener voltage) of the protective diode is not applied.
- Zener voltage reverse breakdown voltage
- the forward voltage is usually about 0.9 V, so that the reverse breakdown voltage can be set to about 10 V.
- the forward breakdown voltage of the GaN-based light emitting diode is about 100V and the reverse breakdown voltage is about 30V, so the light emitting diode is destroyed by an excessive voltage due to static electricity, etc. The situation can be prevented.
- light emitting diodes that emit blue light are mainly GaN-based, and are less susceptible to static electricity than other Balta compound semiconductors (GaP, GaAlAs, etc.). The effect of comprising is great. However, when other measures against static electricity from the outside are taken, or strong against static electricity like other Balta compound semiconductors! When using a semiconductor light emitting device, the submount 130 is not necessarily a diode.
- the positive electrode 134 is an electrode and is electrically connected to the negative electrode 111 of the semiconductor light emitting device 110 by the microbump 140.
- the negative electrode 135 is an electrode and the positive electrode of the semiconductor light emitting device 110.
- the semiconductor light emitting element 110 emits light by being electrically connected to the micro bumps 141 to 144 and applying a voltage between the positive electrode 134 and the negative electrode 135.
- Each of the micro bumps 140 to 144 is a conductor that electrically connects the semiconductor light emitting element and the electrode.
- the material of the positive electrode 134 and the negative electrode 135 is a metal having a characteristic suitable for an electrode such that the electoric port migration hardly occurs.
- a metal having a characteristic suitable for an electrode such that the electoric port migration hardly occurs for example, as shown in the leftmost column of the table shown in FIG.
- Elect port migration is a phenomenon in which a metal component moves across or inside a non-metallic medium due to the influence of an electric field, and the insulation resistance value between electrodes increases with the passage of time of use. Decreases to short circuit failure. Elect port migration does not occur if there is no electric field.
- the reflectance is compared when the wavelength of light is 340 nm or more and 800 nm or less.
- Ag which is particularly high, is a metal that is particularly prone to electoric migration, and is unsuitable for use as an electrode.
- the reflecting portion 132 is formed on an open portion of the upper surface of the silicon substrate 131 that is not shielded by the semiconductor light emitting device 110 except for the positive electrode 134 and the negative electrode 135. It is arranged over the entire surface. Also, an insulating part (not shown) may be provided between the reflecting part 132 and the silicon substrate 131.
- the reflector 132 is provided so as not to be in direct contact with any of the positive electrode 134, the negative electrode 135, and the semiconductor light emitting device 110.
- the term “not in direct contact” refers to a state in which no physical contact is made, and it may be connected via another object or may be electrically connected.
- the reflection unit 132 is smaller in voltage application than the electrode unit during light emission. Therefore, electo-site migration with little influence of the electric field is unlikely to occur. For this reason, the material of the reflecting portion 132 may be a metal having a habit characteristic that is not suitable as an electrode, for example, that is likely to cause electoric port migration.
- the material of the reflecting portion 132 for example, as shown in the uppermost column of the table shown in FIG. 4, in addition to Au, Pt, Cu, Ni, Rh, and Al, Ag that easily causes electoric port migration is also considered. Furthermore, it may be a combination of them, or an alloy containing them. Depending on the wavelength of light emitted from the semiconductor light emitting element 110, Ag or an alloy containing Ag (Ag—Bi, Ag—Bi—Nd), Al, an alloy containing Al, or the like may be used.
- the reflection unit 132 has a reflectance with respect to the light in the wavelength band emitted by the semiconductor light emitting device 110 and the light in the wavelength band converted by the fluorescent substance in the translucent resin 120. Higher than 135.
- the semiconductor light emitting device that outputs white light that is a mixed color of blue light and yellow-green light for illumination has been described as an example. Even a semiconductor light emitting device that outputs light other than white light can be similarly realized. Various effects can be expected.
- FIG. 4 is a diagram showing an appropriate combination of the wavelength range of the output light, the electrode material, and the reflective portion material.
- each element symbol described in the column of the electrode and the reflection part means a metal indicated by the element symbol.
- the wave length is only shown for 200 nm or more and 800 nm or less. The present invention is not limited to this.
- FIG. 4 it is possible to reflect more light in the wavelength range described in the figure emitted by the semiconductor light emitting element than using an electrode having a higher reflectivity of the reflecting part than the electrode as the reflecting film.
- the electrode is a metal that is less likely to cause electoric port migration.
- the light emitted from the semiconductor light emitting element is preferably about 340 nm to about 800 nm.
- the reflective part is made of Ag or an alloy containing this, and the electrode is made of Pt or an alloy containing this as a main component
- the light emitted from the semiconductor light emitting element is preferably from about 350 nm to about 800 nm.
- the light emitted from the semiconductor light-emitting element is desired to be approximately 350 nm or more and approximately 800 nm or less.
- the electrode is Ni or an alloy containing the same as the main component, the light emitted from the semiconductor light emitting device is desired to be approximately 340 nm or more and approximately 800 nm or less.
- the electrode is Rh or an alloy mainly composed of Rh The light emitted from the semiconductor light emitting device is approximately 370 nm or more and approximately 800 nm or less.
- the semiconductor light emitting The light emitted from the device is preferably about 460 ⁇ m or more and about 800 nm or less.
- the main component of the alloy means a metal that occupies 50% or more of the composition of the alloy.
- the reflective portion is A1 or an alloy containing the same, and the electrode is Au or an alloy containing this as a main component
- the light emitted from the semiconductor light emitting element is approximately 200 nm or more and approximately 600 nm.
- the desired reflective part is Al or an alloy containing this
- the electrode is Pt or an alloy mainly composed of Pt
- the light emitted from the semiconductor light emitting element is approximately 200 nm to approximately 800 nm.
- the desired reflection part is A1 or an alloy containing this, and the electrode force SCu or an alloy containing this as a main component
- the light emitted from the semiconductor light emitting element is preferably approximately 200 nm or more and approximately 630 nm or less.
- the light emitted from the semiconductor light emitting element is preferably approximately 200 nm or more and approximately 800 nm or less.
- the electrode is made of Rh or an alloy containing this as a main component, the light emitted from the semiconductor light emitting element is preferably about 200 nm or more and about 800 nm or less.
- Ag and A1 have the property that the reflectance decreases due to the generation of crystal grains by heat and the aggregation of halogens even if there is no influence of the electric field.
- the reflective portion be formed of an alloy containing Ag, Bi, and Nd, or an alloy containing Ag, Au, and Sn, rather than being formed of Ag alone.
- the weight ratio of these alloys is about Ag—Bi (0. 35%) -Nd (0.2%), Ag—Au (10%) — Sn (10%), Al—Nd (2%). Is desirable.
- the reflecting portion and the insulating portion are caused by generation of crystal grains or aggregation of halogen due to the heat of Ag or A1.
- the semiconductor light emitting element of the present invention is not limited to an element that emits blue light.
- an element that emits ultraviolet light may be used. It contains a fluorescent material that excites blue light, red light, and green light from the ultraviolet light generated, and it is a resin material that transmits blue light, red light, and green light excited by this fluorescent material. It becomes a fluorescent substance with translucency.
- FIG. 5 is a diagram showing an outline of a method for manufacturing the submount 130.
- Steps S1 to S7 and S12 to S15 are the same as the manufacturing method of the conventional submount not including the reflecting portion, and steps S8 to S11 are different from the manufacturing method of the conventional submount.
- Step S1 In the oxidation process, the wafer surface of the substrate 131 containing n-type Si before processing is oxidized.
- Step S 2 In the resist process, a PN junction forming window is formed by forming a resist film in addition to the portion where the positive electrode 134 is to be formed on the wafer surface and the adjacent portion.
- Step S3 In the diffusion step, a PN junction is formed by selectively diffusing p-type impurities into the PN junction formation window on the wafer surface.
- a passivation film (silicon oxide film) as an example of the insulating portion is formed on the wafer surface by using a plasma CVD apparatus or the like after the insulating portion generating process. Or a silicon nitride film) is formed to a thickness of 5000 to 6000 A (angstrom aperture).
- Step S5 An electrode contact window is formed by removing a part or all of the insulating portion on the wafer surface where the positive electrode 134 and the negative electrode 135 are to be formed.
- Step S6 Electrode metal is deposited on the wafer surface.
- A2 with a thickness of 2 to 6 ⁇ m is deposited.
- Step S7 By removing unnecessary portions of the deposited A1, patterns of the positive electrode 134 and the negative electrode 135 are formed.
- FIG. 6 is a diagram showing an outline of a cross section of the submount 130 in the reflecting portion forming step.
- Reference numeral 801 shown in FIG. 6 shows a cross-sectional state of the submount 130 before the reflection part forming step is entered.
- Step S8 In order to prevent adverse effects on the electrodes when forming the reflective portion 132, a silicon nitride film is formed on the wafer surface by using a plasma CVD apparatus or the like to a thickness of 4000 to 5000 A )Form. Use a silicon oxide film instead of a silicon nitride film.
- Reference numeral 802 shown in FIG. 6 shows a state where processing is performed in the process of step S8.
- the silicon nitride film is formed by plasma CVD at a relatively low temperature of 250 to 400 ° C, the surfaces of the positive electrode 134 and the negative electrode 135 that do not cause changes such as aggregation on the surface of the A1 electrode are made glossy. Can be maintained. In particular, the silicon nitride film has excellent moisture resistance.
- Step S9 Reflector metal is deposited on the wafer surface by 1000A (angstrom aperture) or more.
- Ag alloy is deposited.
- methods for depositing the Ag alloy include an electron beam method, a resistance heating method, and a sputtering method.
- Reference numeral 803 shown in FIG. 6 shows a state in which processing is performed in the step S9.
- the pattern of the reflective portion 132 is formed by removing the region for separating the reflective portion 132 and the electrode and the unnecessary portion of the electrode surface of the metal for the reflective portion.
- the Ag alloy is removed by wet etching, and the silicon nitride film is removed by dry etching using plasma to form a pattern of the reflecting portion 132.
- the silicon nitride film is removed by dry etching, so that it can be performed at a relatively low temperature (100 to 200 ° C). Can be prevented.
- the interface between the electrode and the insulating portion is protected, and the electrode having a weak adhesive force is peeled off from the insulating portion. To prevent it from happening.
- Reference numeral 804 shown in FIG. 6 shows a state in which processing is performed in the step S10.
- Step S11 The silicon nitride film of the positive electrode 134 and the microbumps 140 to 144 on the negative electrode 135 and the silicon nitride film in the periphery thereof are removed by dry etching, etc. Form a pattern.
- Step S12 The rear surface of the wafer is shaved and the thickness is adjusted to 100 to 200 ⁇ m.
- a back electrode 133 is formed by depositing a metal such as Au or Ag for the back electrode on the wafer surface by an evaporation method such as electron beam, sputtering, or resistance heating.
- Step S14 Characteristic inspection is performed, and the position information of defective elements is stored if the specifications are not met.
- the position information of the defective element stored here is used to discard the defective element at the time of die bonding.
- Step S15 The wafer is attached to a dicing tape and diced into chips.
- the submount 130 can be manufactured by the above method.
- step S8 to step S11 unnecessary portions such as wet etching used for removing unnecessary reflecting portions and dry etching used for removing unnecessary silicon nitride films are removed. It is necessary to go through complicated steps. Therefore, it is possible to replace the process (step S8 to step S11) for removing unnecessary portions with the following simplified process (step S21 to step S23).
- FIG. 7 is a diagram showing an outline of a method for manufacturing the submount 130.
- FIG. 8 is a diagram showing an outline of the cross section of the submount 130 in the reflecting portion forming step. 901 shown in FIG. 8 shows the state of the cross section of the submount 130 before entering the reflecting portion forming step.
- Step S21 In order to prevent an adverse effect on the electrode when forming the reflecting portion 132, the area where the positive electrode 134 and the negative electrode 135 are arranged on the wafer surface using a spin coater, and its A resist film as an example of a protective film is selectively formed in a peripheral area adjacent to the area by 2 to 3 ⁇ m.
- the protective film has a side surface extending in the vertical direction, and the film thickness is preferably about 10 times that of a reflection portion to be formed later. This utilizes the property that the vapor deposition speed for forming the reflecting portion is slower as the angle of the deposition target surface is closer to the vertical, and the lift-off of the protective film can be ensured.
- FIG. 8 shows a state where processing is performed in the process of step S21.
- Step S22 The metal for the reflective portion is formed into the region where the protective film is formed and the reflective portion 132. Vapor deposition is performed on the entire wafer surface (on the upper surface of the substrate) consisting of the region to be formed as a coating for the reflecting portion.
- the metal to be deposited is preferably formed in the range of 1000 to 4000 A (angstrom). This is because if the film thickness is 1000 A (angstrom aperture) or less, it cannot function as a reflective film. If it is 4000 A or less, an opening is formed in a part of the side surface extending in the vertical direction of the protective film. Thus, the protective film can be easily removed by the lift-off action of the protective film. Furthermore, if an organic resist is used, the protective film can be removed with an organic solvent in a relatively short time, so that it is not necessary to use an acid that affects the gloss of the electrode surface.
- metal when metal is vapor-deposited, first, a metal such as titanium that does not easily react with the wafer surface is vapor-deposited, and a metal with high reflectivity such as Ag or Ag alloy is vapor-deposited thereon.
- a metal with high reflectivity such as Ag or Ag alloy is vapor-deposited thereon.
- a double structure may be used.
- Step S23 By removing the protective film together with the reflective part coating formed on the protective film by a solvent dipping method or the like, the positive electrode 134 and the negative electrode 135 are exposed, and at the same time, for the reflective part
- the reflective part pattern is formed by leaving the film only in the area apart from each electrode.
- FIG. 8 shows a state in which processing is performed in the process of step S23.
- the reflective part metal to be deposited is less likely to be coated on the vertical surface compared to the horizontal plane. If the reflection part 132 is formed, a discontinuous thin film can be formed.
- FIG. 9 is a diagram showing an outline of a method for manufacturing the semiconductor light emitting device 100.
- a method for manufacturing the semiconductor light emitting device 100 will be described below with reference to FIG.
- Step S31 The submount 130 is fixed to a predetermined position of the die bonding machine.
- Step S32 The semiconductor light emitting device 110 is fixed at a predetermined position of the die bonding machine.
- Step S 33 Micro bumps 140 to 144 are generated on the submount 130 at positions where the semiconductor light emitting device 110 should be bump-connected.
- Step S34 The semiconductor light emitting elements 110 are picked up one chip at a time, and the semiconductor light emitting elements 110 are bump-connected to the submount 130.
- Step S35 When the semiconductor light emitting device 110 is bump-connected to the submount 130, it is transferred to a phosphor printing machine using a metal plate.
- Step S36 In the phosphor printing machine, the phosphor is printed at a position to be printed covering the semiconductor light emitting element 110 on the submount 130 and its periphery.
- Step S37 the semiconductor light emitting device 100 is completed.
- the reflective portion by providing the reflective portion with a material having high reflectivity so as not to be affected by the electric field separately from the electrodes, the material having high reflectivity can be electrified. Regardless of whether or not the light is likely to occur, output light such as blue light and ultraviolet light emitted from the semiconductor light emitting device and yellow-green light converted by the fluorescent material is efficiently output to the outside. The excellent effect of being able to be obtained is obtained.
- Modification 1 of the present invention is an improvement of the semiconductor light emitting device of the embodiment, so that the shape of the reflection portion and the like is higher with respect to the light emitting direction side than the portion where the semiconductor light emitting element force is near.
- This is a semiconductor light emitting device that suppresses uneven brightness and color unevenness by efficiently collecting light that is attenuated and weakens as the distance increases.
- the semiconductor light emitting device 500 in Modification 1 of the present invention is a device that outputs white light in the same manner as the semiconductor light emitting device 100 of the embodiment, and includes a semiconductor light emitting element 110, a translucent resin 120, And a submount 510 as a mount member, and the submount 130 is replaced with the submount 510.
- FIG. 10 (a) is a plan view of the submount 510 before assembly
- Fig. 10 (b) shows the semiconductor light-emitting device 500 along the AA 'line of the submount 510 shown in Fig. 10 (a).
- FIG. 10 (c) is a cross-sectional view of the semiconductor light emitting device 500 taken along the line B-B 'of the submount 510 shown in FIG. 10 (a).
- the submount 510 in Modification 1 of the present invention is similar to the submount 510 of the embodiment: Protection of, for example, a Zener diode based on silicon, as with L30 Including a silicon substrate 513 that is a diode for a semiconductor, disposed below the semiconductor light emitting device 110 and the translucent resin 120, on the main surface on the front side of the silicon substrate 513 on which these are disposed, that is, on the upper surface, The positive electrode 511, the negative electrode 135, the reflection part 512, and the micro bumps 140 to 144 are provided, and the back side electrode 133 is provided on the back main surface, that is, the lower surface, the positive electrode 134 is reflected on the positive electrode 511, and the reflection part 132 is reflected. Part 512 has been replaced.
- the positive electrode 511 is different from the positive electrode 134 only in shape, and is covered with a light-transmitting resin 120, and is far from the semiconductor light-emitting element in the part where the semiconductor light-emitting element 110 is not disposed.
- the portion is inclined so as to be higher with respect to the light emitting direction than the near portion, and other features such as the material are the same as those of the positive electrode 134.
- the portion of the positive electrode 511 that is not covered with the translucent resin 120 is not inclined, but this is because the shape of the bonding pad 136 is not changed. You may make it incline similarly to the covered part.
- the reflection part 512 differs from the reflection part 132 only in shape, and at least in the part covered with the translucent resin 120, the part far from the semiconductor light emitting element is higher than the part near the light emitting direction.
- the other features such as the material are the same as those of the reflector 132.
- the portion of the reflecting portion 512 that is not covered with the translucent resin 120 is not inclined, but this is because it is aligned with the shape of the positive electrode 511 and is covered with the translucent resin 120. Tilt like the part.
- a positive photoresist is applied on the substrate, exposed through a gradation mask, developed and rinsed, and the photoresist is inclined.
- anisotropic dry etching or sandblasting is performed on the photoresist and the substrate using this as a mask, and the surface shape pattern of the photoresist is dug onto the substrate surface and transferred.
- the shape of the positive electrode and the reflecting portion is covered with at least the translucent resin and far from the semiconductor light emitting element. Since the part is inclined closer to the light emitting direction than the part, the light that attenuates and becomes weaker as the distance from the semiconductor light-emitting element can be efficiently recovered, resulting in uneven brightness. Color unevenness can be suppressed.
- Modification 2 of the present invention is an improvement of the semiconductor light-emitting device of the embodiment, and is provided with irregularities on the surface of the reflecting portion to improve the reflection efficiency by increasing the surface area, and also to reflect the wavelength by reflecting the surface.
- the unevenness of the part far from the semiconductor light emitting element is made larger than the unevenness of the near part, and the light that attenuates and becomes weaker as it gets farther from the semiconductor light emitting element is diffusely reflected in the far part.
- This is a semiconductor light emitting device that suppresses uneven luminance and uneven color.
- a semiconductor light emitting device 600 according to Modification 2 of the present invention is a device that outputs white light in the same manner as the semiconductor light emitting device 100 of the embodiment, and includes a semiconductor light emitting element 110, a translucent resin 120, And a submount 610 as a mounting member, and the submount 130 is replaced with the submount 610.
- FIG. 11 (a) is a plan view of the submount 610 before assembly when viewed from the upper surface side where the semiconductor light emitting element 110 is disposed.
- FIG. 11 (b) shows the semiconductor light emitting device 600 and
- FIG. 3 is a vertical cross-sectional view of the submount 610 shown in FIG. Note that the directions indicated by the X-axis, Y-axis, and Z-axis in Fig. 11 conform to the definition of each axis in Fig. 1 (a).
- the submount 610 in the second modification of the present invention is similar to the submount of the embodiment: L30, for example, protection of a Zener diode or the like based on silicon.
- Electrode 134, negative electrode 135, reflector 611, and microbumps 140-144 are provided, and back electrode 133 is provided on the back main surface, that is, the bottom surface, and reflector 132 is reflected. Part 611 has been replaced.
- the reflective portion 611 is different from the reflective portion 132 only in the shape of the surface, and has irregularities on the surface, and the semiconductor light emitting element force Other features such as a material that is larger than the unevenness of the distant portion of the distant portion are reflective Same as part 132.
- the positive electrode is not provided with unevenness, but may be provided with unevenness in the same manner as the reflecting portion 611.
- a positive type photoresist is applied on the substrate, exposed through a gradation mask, and the photoresist is developed and rinsed. After the surface shape pattern is formed on the substrate, anisotropic dry etching or sandblasting is performed on the photoresist and the substrate using this as a mask, and the surface shape pattern of the photoresist is dug onto the substrate surface and transferred. Good.
- the second modification of the present invention since the unevenness is provided on the surface of the reflecting portion, the surface area is increased, the reflection efficiency is improved, and the wavelength conversion efficiency is improved by irregular reflection.
- the unevenness of the semiconductor light-emitting element force is made larger than the unevenness of the near part, so that the light that attenuates and weakens as the semiconductor light-emitting element force becomes farther is diffused more diffusely in the far part, resulting in uneven brightness. Color unevenness can be suppressed.
- Modification 3 of the present invention is an improvement of the semiconductor light-emitting device of the embodiment, in which a spherical surface is provided on the surface of the reflecting portion, the reflection efficiency is improved by increasing the surface area, and the wavelength is increased by causing random reflection.
- This is a semiconductor light emitting device that suppresses uneven brightness and color unevenness by making the curvature of the spherical surface of the minute smaller than that of the near part, and light that attenuates and weakens as it gets farther from the semiconductor light emitting element, and diffuses more light in the far part. .
- a semiconductor light emitting device 700 according to Modification 3 of the present invention is a device that outputs white light in the same manner as the semiconductor light emitting device 100 of the embodiment, and includes a semiconductor light emitting element 110, a translucent resin 120, And a submount 710 as a mount member, and the submount 130 is replaced with the submount 710.
- Fig. 12 (a) is a plan view of the submount 710 before assembly
- Fig. 12 (b) shows the semiconductor light emitting device 700 along the A-A 'line of the submount 710 shown in Fig. 12 (a).
- the submount 710 according to the second modification of the present invention is similar to the submount of the embodiment: L30, for example, protecting a Zener diode or the like based on silicon.
- a silicon substrate 712 which is a diode for use in the semiconductor substrate, disposed under the semiconductor light emitting device 110 and the translucent resin 120, and on the main surface on the front side, that is, the upper surface of the silicon substrate 712 on which these are disposed
- the electrode 134, the negative electrode 135, the reflection part 711, and the micro bumps 140 to 144 are provided, and the back main electrode, that is, the back electrode 133 is provided on the lower surface, and the reflection part 132 is replaced with the reflection part 711. It is.
- the reflective portion 711 differs from the reflective portion 132 only in the shape of the surface, has a spherical surface, is far from the semiconductor light emitting element, has a close curvature of the spherical surface, and is made of other materials such as a material smaller than the portion.
- the feature is the same as that of the reflector 132.
- the positive electrode is not provided with a spherical surface, but may be provided with a spherical surface in the same manner as the reflecting portion 711.
- a conventional bump forming method may be used.
- a hemispherical shape is provided on the upper surface of the submount 710, for example, a positive photoresist is applied on the substrate, exposed through a gradation mask, and then exposed to the photoresist. After developing and rinsing the substrate, a hemispherical surface shape pattern made of photoresist is formed on the substrate, and using this as a mask, anisotropic dry etching, sandblasting, etc. are performed on the photoresist and the substrate. Just dig and transfer the photoresist surface shape pattern onto the substrate surface.
- the spherical surface is provided on the surface of the reflecting portion, the surface area is increased, the reflection efficiency is improved, and the wavelength conversion efficiency is improved by irregular reflection.
- the curvature of the spherical surface of the portion far from the semiconductor light emitting element force is made smaller than that of the near portion, the unevenness of brightness is reduced by causing the semiconductor light emitting element force to be attenuated and weakened more as the semiconductor light emitting element force is further distant. Color unevenness can be suppressed.
- FIG. 13 is a diagram showing an illumination device 200 using the semiconductor light emitting device 100 as a light source.
- one semiconductor light emitting device 100 is die-bonded on each of the lead frames 201 and 202 using an Ag paste 205, and the lead frames 203 and 204 and each semiconductor light emitting device 100 are bonded.
- the upper bonding pad 136 is wire-bonded with Au wires 206 and 207, molded with a transparent epoxy resin 208, and a microlens 209 with a total reflection parabola is attached.
- the illumination device using the semiconductor light emitting device 100 as a light source is not limited to the illumination device 200 shown in FIG. 13, and for example, indoor lighting such as a ceiling light and a downlight using a large number of semiconductor light emitting devices 100 is used.
- any lighting device such as a desk lamp such as a stand, a portable lamp such as a flashlight, and a photographing lamp such as a camera strobe may be used.
- the same effect as that of the semiconductor light emitting device can be obtained.
- high brightness and energy-saving effects can be expected for indoor lighting and tabletop lighting. Therefore, it can be expected that the brightness is increased and the continuous lighting time is extended.
- FIG. 14 shows a portable communication device 300 equipped with the lighting device 200 as a strobe for taking a picture.
- the mobile communication device equipped with the semiconductor light emitting device 100 is not limited to the mobile communication device 300 shown in FIG. 14.
- the semiconductor light emitting device 100 can be used as a backlight of a liquid crystal screen of a mobile communication device or a built-in digital camera. It may be a portable communication device used for any purpose such as a strobe for still images or lighting for moving images.
- FIG. 15 shows a camera 400 equipped with the lighting device 200 as a strobe for taking a photograph.
- the camera equipped with the semiconductor light emitting device 100 is not limited to the camera 400 shown in FIG. 15, and the semiconductor light emitting device 100 is used for, for example, a strobe for still images or illumination for moving images. Any camera such as a digital still camera, a silver-lead camera, and a video camera may be used.
- the same effect as that of the semiconductor light emitting device can be obtained.
- various cameras will be able to shoot at lower EV values, extend the duration of knottery, and reduce lightness.
- the present invention can be widely applied to lighting for portable devices such as portable communication devices and cameras.
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Abstract
Description
Claims
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
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US11/667,374 US7834370B2 (en) | 2004-11-25 | 2005-11-11 | Semiconductor light emitting device, illuminating device, mobile communication device, camera, and manufacturing method therefor |
EP05806275A EP1816686A4 (en) | 2004-11-25 | 2005-11-11 | LIGHT-EMITTING SEMICONDUCTOR ELEMENT, LIGHTING DEVICE, MOBILE COMMUNICATION DEVICE, CAMERA AND MANUFACTURING METHOD THEREFOR |
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JP2004341237A JP4176703B2 (ja) | 2004-11-25 | 2004-11-25 | 半導体発光装置、照明装置、携帯通信機器、カメラ、及び製造方法 |
JP2004-341237 | 2004-11-25 |
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US (1) | US7834370B2 (ja) |
EP (1) | EP1816686A4 (ja) |
JP (1) | JP4176703B2 (ja) |
KR (1) | KR20070084464A (ja) |
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
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US20080187762A1 (en) * | 2007-02-06 | 2008-08-07 | Masaki Hayashi | Light-emitting device, method for manufacturing same, and molded part |
EP2176895A4 (en) * | 2007-07-25 | 2015-07-15 | Lg Innotek Co Ltd | LIGHT EMITTING DEVICE AND METHOD OF MANUFACTURING THE SAME |
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US20080187762A1 (en) * | 2007-02-06 | 2008-08-07 | Masaki Hayashi | Light-emitting device, method for manufacturing same, and molded part |
US8900710B2 (en) * | 2007-02-06 | 2014-12-02 | Nichia Corporation | Light-emitting device, method for manufacturing same, and molded part |
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Also Published As
Publication number | Publication date |
---|---|
CN101527343B (zh) | 2011-04-13 |
EP1816686A4 (en) | 2013-03-13 |
CN101527344A (zh) | 2009-09-09 |
EP1816686A1 (en) | 2007-08-08 |
US20070295980A1 (en) | 2007-12-27 |
CN100541840C (zh) | 2009-09-16 |
JP4176703B2 (ja) | 2008-11-05 |
CN101527343A (zh) | 2009-09-09 |
KR20070084464A (ko) | 2007-08-24 |
JP2006156506A (ja) | 2006-06-15 |
CN101527344B (zh) | 2011-02-09 |
CN101065851A (zh) | 2007-10-31 |
US7834370B2 (en) | 2010-11-16 |
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