WO2007018222A1 - 発光ダイオード用基板及び発光ダイオード - Google Patents
発光ダイオード用基板及び発光ダイオード Download PDFInfo
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- WO2007018222A1 WO2007018222A1 PCT/JP2006/315695 JP2006315695W WO2007018222A1 WO 2007018222 A1 WO2007018222 A1 WO 2007018222A1 JP 2006315695 W JP2006315695 W JP 2006315695W WO 2007018222 A1 WO2007018222 A1 WO 2007018222A1
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- Prior art keywords
- light
- emitting diode
- substrate
- light emitting
- layer
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- 239000000758 substrate Substances 0.000 title claims abstract description 85
- 239000013078 crystal Substances 0.000 claims abstract description 75
- 239000002131 composite material Substances 0.000 claims abstract description 55
- 239000000919 ceramic Substances 0.000 claims abstract description 49
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 18
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 17
- 229910052751 metal Inorganic materials 0.000 claims abstract description 6
- 239000002184 metal Substances 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims description 31
- 239000000463 material Substances 0.000 claims description 18
- JMASRVWKEDWRBT-UHFFFAOYSA-N Gallium nitride Chemical compound [Ga]#N JMASRVWKEDWRBT-UHFFFAOYSA-N 0.000 claims description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 9
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 9
- -1 nitride compounds Chemical class 0.000 claims description 7
- 229910052684 Cerium Inorganic materials 0.000 claims description 6
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 claims description 5
- 229920005989 resin Polymers 0.000 claims description 4
- 239000011347 resin Substances 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 2
- 229910052772 Samarium Inorganic materials 0.000 claims description 2
- 229910052771 Terbium Inorganic materials 0.000 claims description 2
- 229910052727 yttrium Inorganic materials 0.000 claims description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 18
- 239000000843 powder Substances 0.000 abstract description 17
- 230000006866 deterioration Effects 0.000 abstract description 6
- 230000003287 optical effect Effects 0.000 abstract description 2
- 230000005540 biological transmission Effects 0.000 abstract 1
- 230000026683 transduction Effects 0.000 abstract 1
- 238000010361 transduction Methods 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 93
- 238000000034 method Methods 0.000 description 31
- 239000004065 semiconductor Substances 0.000 description 18
- 150000004767 nitrides Chemical class 0.000 description 10
- 229910002601 GaN Inorganic materials 0.000 description 9
- 238000002156 mixing Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 229910019655 synthetic inorganic crystalline material Inorganic materials 0.000 description 6
- 239000011247 coating layer Substances 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 238000000295 emission spectrum Methods 0.000 description 5
- 238000005304 joining Methods 0.000 description 5
- SBIBMFFZSBJNJF-UHFFFAOYSA-N selenium;zinc Chemical compound [Se]=[Zn] SBIBMFFZSBJNJF-UHFFFAOYSA-N 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000011777 magnesium Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000007711 solidification Methods 0.000 description 4
- 230000008023 solidification Effects 0.000 description 4
- 239000011787 zinc oxide Substances 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 239000003822 epoxy resin Substances 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 3
- 229920000647 polyepoxide Polymers 0.000 description 3
- 229910052693 Europium Inorganic materials 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000002019 doping agent Substances 0.000 description 2
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- 238000010030 laminating Methods 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 2
- 230000003746 surface roughness Effects 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 2
- XCZXGTMEAKBVPV-UHFFFAOYSA-N trimethylgallium Chemical compound C[Ga](C)C XCZXGTMEAKBVPV-UHFFFAOYSA-N 0.000 description 2
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- LTPBRCUWZOMYOC-UHFFFAOYSA-N Beryllium oxide Chemical compound O=[Be] LTPBRCUWZOMYOC-UHFFFAOYSA-N 0.000 description 1
- 101100257124 Caenorhabditis elegans sma-10 gene Proteins 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 229910052691 Erbium Inorganic materials 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical group [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229910018540 Si C Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- JNDMLEXHDPKVFC-UHFFFAOYSA-N aluminum;oxygen(2-);yttrium(3+) Chemical compound [O-2].[O-2].[O-2].[Al+3].[Y+3] JNDMLEXHDPKVFC-UHFFFAOYSA-N 0.000 description 1
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
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- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000011268 mixed slurry Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000005297 pyrex Substances 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 229910052594 sapphire Inorganic materials 0.000 description 1
- 239000010980 sapphire Substances 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 229910019901 yttrium aluminum garnet Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
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- C04B35/10—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on aluminium oxide
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- C04B35/58—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7766—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals
- C09K11/7774—Aluminates
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- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
- H01L33/50—Wavelength conversion elements
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- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B33/00—Electroluminescent light sources
- H05B33/12—Light sources with substantially two-dimensional radiating surfaces
- H05B33/14—Light sources with substantially two-dimensional radiating surfaces characterised by the chemical or physical composition or the arrangement of the electroluminescent material, or by the simultaneous addition of the electroluminescent material in or onto the light source
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- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3224—Rare earth oxide or oxide forming salts thereof, e.g. scandium oxide
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- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
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- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
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- C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
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- 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
- H01L2224/10—Bump connectors; Manufacturing methods related thereto
Definitions
- the present invention relates to a substrate for a light-emitting diode that can be used for a display, illumination, backlight light source, and the like, and a light-emitting diode using the light-emitting diode substrate.
- White light-emitting diodes are lightweight, do not use mercury, and have a long life, so that demand is expected to expand rapidly in the future.
- the most commonly used method for converting blue light of a blue light emitting element into white light is, for example, as described in Japanese Patent Application Laid-Open No. 2000-208815.
- a coating layer containing a phosphor that absorbs part of the light and emits yellow light, and a mold layer for mixing the blue light of the light source and the yellow light from the coating layer are provided, and are in a complementary color relationship.
- a pseudo white color is obtained by mixing blue and yellow.
- a light emitting device is attached to the substrate itself on which the blue light emitting element is formed.
- Proposals have been made for a method that does not use powder.
- a YAG: Ce phosphor single crystal is formed on a substrate whose main surface is the (1 1 1) plane.
- a nitride semiconductor layer consisting of y N (0 ⁇ x ⁇ 1, 0 ⁇ y ⁇ 1, 0 ⁇ x + y ⁇ 1) is formed, and blue light emitted from the light emitting layer is directly incident on the substrate and the substrate itself
- a method to obtain a homogeneous white color with no color unevenness using only a light emitting chip without using a coating layer containing the phosphor powder by emitting homogeneous yellow fluorescence from the YAG phosphor powder As another method not used, Japanese Patent Application Laid-Open No. 2000-082845 discloses a method for obtaining a white light emitting diode using a ZnSe single crystal. In this method, a ZnSe substrate is provided with the function of sel f-activated (SA) emission, and a ZnSe-based blue light-emitting diode is formed on this substrate. In this method, white light is obtained.
- SA sel f-activated
- YAG (1 1 1) High-quality nitride semiconductor layer due to the large difference between the lattice spacing of the substrate and the lattice spacing of I n x Gai _ x N forming the nitride semiconductor buffer layer formed on the substrate It is thought that this is because it is difficult to form.
- the white light emitting diodes based on ZnSe single crystals described in JP-A-2000-082845 have a problem of deterioration of the elements, and improvement of the quality of the Zn Se substrate is required for improvement.
- life extension requires a reduction in dislocation density, and improvements such as optimization of the device fabrication process and material changes are currently being made. This is described, for example, in the application and future prospects of white LED lighting system technology, supervised by Tsunemasa Taguchi, CMC Publishing, 2003, page 170.
- A1 2 0 3 single crystal As a substrate for InGaN blue light-emitting diodes. It is what is a (0001) plane of the A1 2 0 3 single crystal (Safuaiya), has a long track record. In addition, in a device fabricated using this A 1 2 0 3 single crystal, there has been no report of a problem of deterioration of the light emitting device due to A 1 2 0 3 degradation. Therefore, when Seisuru create a white light emitting diode using emission of the substrate itself, A1 2 0 3 is achieved by a method of constituting the blue light emitting element to the substrate is most desirable Rukoto. For this purpose, it becomes necessary light emission of the substrate itself, as described above, a method so as to obtain a yellow light emission incident blue light to A 1 2 0 3 single crystal has not been reported.
- An object of the present invention is to form a good light-emitting diode element without using phosphor powder, to reduce the deterioration, and to transmit light from the light-emitting diode element and to emit light using a part of the transmitted light. Furthermore, it is an object to provide a light emitting diode substrate capable of mixing and emitting transmitted light and new light emission, and a light emitting diode using the light emitting diode substrate.
- the present invention provides a single crystal layer capable of forming a light emitting diode element, and at least two oxide phases selected from a single metal oxide and a composite metal oxide, continuously and three-dimensionally.
- the present invention relates to a light emitting diode substrate characterized by containing a metal element oxide that emits, and a light emitting diode using the light emitting diode substrate.
- the single crystal layer A 1 2 0 3, S i C, ZnO, and it is preferable that consists of a material selected from the group consisting of GaN.
- An embodiment of the substrate for a light emitting diode according to the present invention is characterized in that a bonding layer made of a substance capable of bonding both materials is provided between the single crystal layer and the ceramic composite layer for light conversion. To do. In addition, it is preferable that a fluorescent material is present in the bonding layer.
- the solidified body is an A1 2 0 3, characterized in that it consists Yg A ls O, 2 Prefecture, which is activated by cerium.
- the substrate can be used as a light emitting surface without using phosphor powder, the formation of a light emitting diode element (semiconductor layer) is hindered, the deterioration is small, and the light mixing property is improved. It is possible to provide a light emitting diode with little color unevenness.
- the InGaN-based blue light-emitting element can produce a blue light emitting device I The InGaN-based using a single crystal substrate such as A l 2 0 3 with Oite most proven to produce the blue light-emitting device using the I The InGaN-based substrates of the present invention
- the light emitted from the InGaN-based blue light-emitting element is directly guided to the substrate in the same manner as the ZnSe substrate, and while transmitting blue light, simultaneously absorbs part of the blue light and generates yellow light, and at the same time
- the white light-emitting diode with uniform light can be obtained by effectively mixing excitation light and fluorescence by three-dimensional entanglement of multiple crystal phases.
- a white light emitting diode can be obtained simply by manufacturing a blue light emitting element on this substrate, and the manufacturing process of the light emitting diode can be greatly simplified.
- another phosphor is present on the bonding surface, thereby providing a substrate capable of controlling the color tone, and controlling the color tone of the light emitting diode is extremely high. It also has the feature that it can be easily done. For this tone control As a result, the degree of freedom in the emission wavelength of the ceramic composite increases, and as a result, the degree of freedom in the compositional design of the ceramic composite material increases.
- the light-emitting diode of the present invention is characterized in that a light-emitting diode element is formed on the single crystal layer of the light-emitting diode substrate, and light is extracted from the light-emitting diode substrate side.
- FIG. 1A is a schematic sectional view showing an embodiment of a light emitting diode substrate of the present invention.
- FIG. 1B is a schematic cross-sectional view showing another embodiment of a light emitting diode substrate of the present invention.
- FIG. 2 is a schematic view showing an embodiment of a light emitting diode using a substrate according to the present invention.
- FIG. 3 is a cross-sectional view of the structure of the ceramic composite for light conversion according to the present invention obtained in Example 1.
- FIG. 4 is a cross-sectional view showing how the substrates according to the present invention obtained in Example 1 are joined.
- FIG. 5 is a light emission spectrum diagram of the light emitting diode obtained in Example 1.
- FIG. 6 is a cross-sectional view showing a bonding layer of a substrate according to the present invention obtained in Example 2.
- FIG. 7 is a light emission spectrum diagram of the light emitting diode obtained in Example 3. BEST MODE FOR CARRYING OUT THE INVENTION
- the substrate of the present invention comprises a single crystal layer and a light as shown in FIG. 1A, for example. It is a laminated structure by bonding the ceramic composite layer for conversion.
- a light emitting diode substrate 1 is composed of a single crystal layer 2, a ceramic composite 3, and optionally a junction layer 4.
- the single crystal layer according to the present invention is a layer made of a conventional single crystal on which a semiconductor such as a light emitting diode element can be formed. For example, aluminum oxide (A 1 2 0 3 ), silicon carbide (SiC) Zinc oxide ( ⁇ ) and gallium nitride (GaN).
- the ceramic composite layer for light conversion according to the present invention is formed of a ceramic composite material including a phosphor, and a solidified body in which metal oxides are continuously and three-dimensionally entangled with each other. Consists of. Examples of the metal oxide include a single metal oxide or a complex oxide, and the single metal oxide or the complex metal oxide contains an element that exhibits a function, for example, fluorescence. Such a solidified body is a composite material made by melting and solidifying the raw metal oxide. A single metal oxide is an oxide of one kind of metal, and a composite metal oxide is an oxide of two or more kinds of metals. Each oxide has a three-dimensionally intertwined structure. In addition, other oxide phases may exist between these intertwined oxide phases.
- Such single metal oxides include aluminum oxide (A1 2 0 3 ), zirconium oxide (Zr0 2 ), magnesium oxide (MgO), silicon oxide (Si0 2 ), titanium oxide (Ti0 2 ) and barium oxide (BaO). ), Beryllium oxide (BeO), calcium oxide (CaO), chromium oxide (Cr 2 0 3 ), and other rare earth element oxides (La 2 0 3 , Y 2 0 3 , Ce0 2 , Pr 6 0, ,, Nd 2 0 3 , Sm 2 0 3 , Gd 2 0 3 , Eu 2 0 3 , Tb 4 0 Dy 2 0 3 , Ho 2 0 3 , Er 2 0 3 , Tm 2 0 3 , Yb 2 0 3 , Lu 2 0 3) and the like.
- the composite metal oxides include LaA 10 3 , CeAlO PrA10 3 , NdA10 3 , SmA10 3 , EuA10 3 , GdAlO DyA10 3 , ErA10 3 , Yb 4 Al 2 0 9 , Y 3 A1 5 0 12 , Er 3 Al 5 0 12 , Tb 3 Al 5 0 12 , 11A1 2 0 3 • La 2 0 3 , 11A 1 2 0 3 Nd 2 0 3 , 3 Dy 2 0 3 ⁇ 5 A 1 2 0 3 , 2 Dy 2 0 3 ⁇ A 1 2 0 3 , 1 1A 1 2 0 3 -Pr 2 0 3 , EuAl,, 0, 8 , 2 Gd 2 0 3 ⁇ Al 2 0 3 , 11AI 2 0 3 ⁇ Sm 2 0 3 , Yb 3 A1 5 0 12 , CeAl,, Oj 8 , Er 4 Al 2 0 9 etc. are
- a method of directly joining at a high temperature can be used. This method is the simplest method and the most ideal method in that it does not have a different phase at the interface.
- the bonding temperature and time are required to be 1700-1800 ° C and 1-50 hours. At higher temperatures, deformation of the single crystal plate and the ceramic composite plate occurs. Also, the bonding hardly proceeds at low temperatures.
- the A 1 2 0 3 single crystal layer and the ceramic composite layer need to be exposed to high temperatures for a long time, which is disadvantageous in terms of cost.
- the single crystal layer and the ceramic composite layer there is a method in which a very small amount of a low melting point material (for example, silica) is interposed as a bonding layer on the bonding surface.
- a low melting point material for example, silica
- the composition must be determined in consideration of the process temperature and atmosphere of the InGaN light emitting diode.
- typical Pyrex (registered trademark) glass 900 ° C to 1300 ° C and 1 hour to 10 hours are required.
- the joining pressure is not necessarily required, but it is more preferable to apply a pressure of 0.01 to 100 MPa using a hot press device or the like because it is more adhesive.
- a bonding layer made of a substance capable of adhering both layers is provided between the single crystal layer and the ceramic composite layer for light conversion.
- bonding adhesive
- any phosphor material can be present in the bonding layer. This phosphor makes it possible to control the color tone of the light emitting diode.
- Various fluorescent materials can be cited as the phosphor material to be present at the junction.
- Ca 2 Si 5 N 8 activated by europium emitting red fluorescence and attached by europium
- a material such as activated CaAl SiN 3 is preferred.
- Epoxy resin, silicon resin, etc. can be used as the adhesive material.
- a 1 2 0 3 single crystal as the single crystal layer, to form a blue light emitting element of the I The InGaN based on this, the light emitted from the blue light emitting element, enters the A 1 2 0 3 single crystal layer, Furthermore, it is incident on the ceramic composite layer for light conversion. Part of the blue light is transmitted as it is, and part of the blue light is absorbed by the ceramic composite layer for light conversion, for example, yellow light is newly emitted. In the ceramic composite layer for light conversion, a plurality of crystal phases are intertwined three-dimensionally, and blue light and yellow light are effectively mixed and emitted in this intertwining.
- a bonding layer as shown in Fig. 1B.
- the bonding layer lowers the bonding temperature between the single crystal layer and the ceramic composite layer for light conversion, simplifies the process, and provides new functions. For example, a new phosphor can be added to control the color tone. In addition to the color mixture of blue and yellow light as described above, it is possible to add new light (for example, red) and control the color tone.
- a method using Si C, ZnO, or GaN in addition to A 1 2 0 3 is also known.
- the same function can be realized by bonding the plate of SiC, ZnO, GaN and the plate of the present ceramic composite for light conversion.
- the substrate material for the light-emitting diode element will be described below, but this substrate is limited to this example because various applications can be considered depending on the combination of the elements of the material constituting the single crystal layer and the ceramic composite layer. It is not a thing.
- a 1 2 0 3 plate made with single-crystal layer is CZ method, is produced from the melt in such EFG process, they can be commercially available products because they are widely available commercially.
- the ceramic composite layer for light conversion also contains A 1 2 0 3 crystals. If a ceramic composite for light conversion containing A 1 2 0 3 is used, the difference in refractive index at the joint surface with the A 1 2 0 3 single crystal layer becomes very small, and light can be transmitted effectively. become able to.
- a 1 2 0 3 a (0001) to the substrate surface A 1 2 0 3 of the light conversion material is more preferable to bond with (0001) plane, In this way, A 1 2 0 3 layer This is because the difference in refractive index due to the crystal orientation disappears at the junction, and light can be transmitted most efficiently.
- the crystal phase that coexists with the A 1 2 0 3 crystal of the ceramic composite layer for light conversion must be an A 3 X 5 0 1 2 type crystal that is a composite metal oxide activated with at least cerium.
- A includes one or more elements selected from the group of Y, Tb, Sm, Gd, La, and Er.
- the structural formula includes one or more elements selected from Al and Ga. The case is particularly preferred. This is because the ceramic composite for light conversion comprising this particularly preferable combination absorbs a part of the light from purple to blue light and emits yellow fluorescence.
- the combination of Y 3 A1 5 0, 2 activated by cerium and Al 2 0 3 crystal is suitable because it emits strong fluorescence.
- a very important feature of the ceramic composite for light conversion is that the crystal phases are not independent, but the phases are integrated as an inseparable relationship.
- Y 3 A is not simply two crystals but also A 1 2 0 3
- a 1 5 0 1 2 Ce crystal from a single melt with a composition that is not even 1 5 0 1 2 , there are two crystals This is different from the case where two crystals exist independently. In this sense, the two crystals are inseparable.
- Such clots are merely A 1 2 0 3 crystal and YAG: the state of Ce crystals are mixed is different to the qualitative, Thus, the ceramic composite body exhibits specific fluorescence behavior.
- the solidified body constituting the ceramic composite layer for light conversion is produced by melting and solidifying the raw metal oxide.
- a solidified body by a simple method of cooling and condensing the melt charged in a crucible held at a predetermined temperature while controlling the cooling temperature, but the most preferable is a unidirectional solidification method. It is a thing. This is because the crystal phase contained by unidirectional solidification grows continuously in a single crystal state or a similar state, and each phase has a single crystal orientation.
- the ceramic composite for use in the present application has previously been disclosed in JP-A-7-149597, JP-A-7-187893, except that at least one phase contains a metal element oxide that emits fluorescence.
- the nitride semiconductor layer as an example of the semiconductor layer formed on the substrate of the present invention includes a plurality of nitride compound semiconductor layers.
- Each of the nitride compound semiconductor layers has a general formula: - y N (0 ⁇ X ⁇ 1 , 0 ⁇ y ⁇ l, 0 ⁇ x + y ⁇ 1) is preferably configured by a nitride-based compound represented by the.
- the nitride semiconductor layer has at least a light emitting layer that emits visible light.
- a plurality of nitride-based compound semiconductor layers and a method for forming these layers are known techniques as disclosed in, for example, Jpn. J. Appl. Pys. Vol. 34 (1995), L798, etc. is there. Specifically, a GaN buffer layer and an n-electrode are formed on a substrate.
- N-type—GaN Si contact layer
- n-type—Al. 5 Ga. g N Si layer
- n-type—In. .. 5 Ga. 95 N Si layer
- InGaN layer forming a single quantum well-structured light emitting layer
- J Ga Q 9 N Mg barrier layer
- p-type p electrode is formed - GaN: Mg-layer by a method such as M0CVD, can be obtained by laminating in this order.
- the structure of the light emitting layer may be a multiple quantum well structure, a homo structure, a hetero structure, or a double hetero structure.
- a light-emitting diode device fabricated in this manner can be used as a white light-emitting diode by simply placing it in a package as shown in Fig. 2 and connecting it to an electrode.
- reference numeral 1 is a light emitting diode substrate
- 2 is a single crystal layer
- 3 is a ceramic composite
- 5 is a light emitting element (diode element)
- 6 and 7 are electrodes
- 8 is a package.
- Example 1 HI A1 2 0 3 powder (purity 99.99%) and Y 2 0 3 powder (purity 99 ⁇ 999%) were prepared in a molar ratio of 82:18, and Ce0 2 powder (purity 99.99%) was charged. and so that weighed a 0.03 mol YsAlsO, 2 1 mole produced by the reaction of. These powders were wet-mixed in ethanol by a pole mill for 16 hours, and then ethanol was removed using an evaporator to obtain a raw material powder. The raw material powder was pre-melted in a vacuum furnace and used as a raw material for unidirectional solidification.
- the raw material was thaw under a pressure of 1.33xl (T 3 Pa (10- 5 Torr). Then the same atmosphere The crucible is lowered at a rate of 5 ⁇ / hour in 3 ⁇ 1 5 0 12 : solidified of Ce and type aluminum oxide type crystals A 1 2 0 3 The obtained solidified body was yellow.
- Figure 3 shows the cross-sectional structure parallel to the solidification direction of the solidified body.
- the white part is Y 3 ⁇ 1 5 0 12 : Ce crystal
- the black part is AI 2 0 3 crystal. It can be seen that the two crystals have a structure intertwined with each other.
- a substrate of lOmmX 10 mm and 1 mm thickness was cut out from the ceramic composite material with diamond monk cutlet, and further finished to a thickness of 0.6 mm with a grinding machine, and one surface was polished to a mirror surface.
- the average surface roughness was measured and found to be 0.014 microns.
- FIG. 4 shows the state of joining after joining.
- the upper side is an A 1 2 0 3 single crystal substrate, and the lower side is a ceramic composite substrate. It turns out that both are closely_contact
- TMG trimethylgallium
- TMA trimethylaluminum
- nitrogen gas and dopant gas are flowed along with carrier gas on the A1 2 0 3 single crystal layer (0001) surface of the substrate prepared by bonding, and then nitrided by M0CVD method
- a physical compound semiconductor was deposited to obtain a blue light-emitting layer.
- SiH 4 and Cp 2 Mg as dopant gases, n-type nitride compound semiconductors and p-type nitride compound semiconductors were formed, and pn junctions were formed.
- n-type one GaN n electrode is formed: via the A 1 2 0 3 GaN buffer layer on the single crystal layer.
- Si contactor coat layer n-type one Alo 5 Ga. 9 N: Si layer, n-type ⁇ ⁇ . .. . 5 Ga Q 95 N: Si layer, InGaN layer which forms a single quantum well structure-type light-emitting layer, p-type - A1 Q t Ga Q 9 N :.. P -type one which Mg barrier layer, a p-electrode is formed
- a GaN: Mg layer was formed. Each pn electrode was formed by the sputtering method, a scribe line was drawn on the substrate, and it was divided by applying external force to obtain a light emitting diode.
- Figure 5 shows the emission spectrum of the resulting light-emitting diode. Blue light from the nitride semiconductor layer and yellow fluorescence from the ceramic composite layer excited by it were observed. The light emitted from this substrate was evenly mixed in the substrate, and good white light was obtained.
- a solution containing 30% of spherical amorphous silica having a diameter of 10 to 20 dragons was applied onto the 10 ⁇ 10 M plate of the ceramic composite for light conversion prepared in Example 1 using a spin-coil. After coating, the substrate was heated to 60 ° C to remove the solvent component. Thereafter, put a plate of similar A1 2 0 3 single crystal in Example 1 to the optical converting ceramic composite plates of amorphous silica coated surface, was placed in hot Topuresu apparatus, pressurized with 0.03MPa While heating to 1300 ° C, the mixture was held for 2 hours and gradually cooled.
- Figure 6 shows the resulting substrate.
- the upper side is a plate of A 1 2 0 3 single crystal
- the lower side is a plate of a ceramic composite for light conversion.
- the light-emitting diode manufactured in the same manner as in Example 1 using the thus-produced light-emitting diode substrate is similar to the substrate obtained in Example 1, and the blue light from the nitride semiconductor layer is thereby generated. Yellow fluorescence from the excited ceramic composite layer was observed. The light emitted from this substrate was evenly mixed in the substrate, and good white light was obtained.
- Figure 7 shows the emission spectrum of the resulting device.
- a blue emission, a yellow emission from the substrate, and a red emission from the red phosphor were added, resulting in an emission spectrum that emphasized the emission of 650 dragons. This light was warm white. This confirms that color tone control is possible.
- Industrial applicability According to the present invention, a good light emitting diode element can be formed without using phosphor powder, the deterioration is small, light from the light emitting diode element is transmitted, and a part of the transmitted light is emitted.
- a light-emitting diode substrate capable of mixing and emitting transmitted light and new light emission and a light-emitting diode using the substrate are provided, it is industrially useful.
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Abstract
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US11/990,235 US7863636B2 (en) | 2005-08-10 | 2006-08-02 | Substrate for light-emitting diode, and light-emitting diode |
EP06768434.0A EP1914810B1 (en) | 2005-08-10 | 2006-08-02 | Substrate for light emitting diode and light emitting diode |
CN200680028839XA CN101238595B (zh) | 2005-08-10 | 2006-08-02 | 发光二极管用基板以及发光二极管 |
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Also Published As
Publication number | Publication date |
---|---|
KR101036530B1 (ko) | 2011-05-24 |
JP5029362B2 (ja) | 2012-09-19 |
EP1914810A1 (en) | 2008-04-23 |
JPWO2007018222A1 (ja) | 2009-02-19 |
EP1914810B1 (en) | 2017-10-04 |
CN101238595A (zh) | 2008-08-06 |
EP1914810A4 (en) | 2013-11-27 |
CN101238595B (zh) | 2012-07-04 |
US7863636B2 (en) | 2011-01-04 |
KR20080030089A (ko) | 2008-04-03 |
US20090166667A1 (en) | 2009-07-02 |
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