WO2011118489A1 - 発光素子の製造方法およびそれを用いてなる発光素子 - Google Patents
発光素子の製造方法およびそれを用いてなる発光素子 Download PDFInfo
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- WO2011118489A1 WO2011118489A1 PCT/JP2011/056355 JP2011056355W WO2011118489A1 WO 2011118489 A1 WO2011118489 A1 WO 2011118489A1 JP 2011056355 W JP2011056355 W JP 2011056355W WO 2011118489 A1 WO2011118489 A1 WO 2011118489A1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/02—Semiconductor devices with at least one potential-jump barrier or surface barrier 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 bodies
- H01L33/12—Semiconductor devices with at least one potential-jump barrier or surface barrier 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 bodies with a stress relaxation structure, e.g. buffer layer
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/005—Processes
- H01L33/0093—Wafer bonding; Removal of the growth substrate
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/02—Semiconductor devices with at least one potential-jump barrier or surface barrier 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 bodies
- H01L33/26—Materials of the light emitting region
- H01L33/30—Materials of the light emitting region containing only elements of group III and group V of the periodic system
- H01L33/32—Materials of the light emitting region containing only elements of group III and group V of the periodic system containing nitrogen
Definitions
- the present invention relates to a method for manufacturing a light emitting device and a light emitting device using the same.
- a light-emitting element including a semiconductor layer and a compound semiconductor layer having a light-emitting layer has been put into practical use and has begun to be used in applications such as lighting devices.
- Examples of such light emitting elements include group III nitride semiconductors such as blue light emitting elements and ultraviolet light emitting elements.
- Group III nitride semiconductors are superior to conventional III-V compound semiconductors in light emission efficiency in a wide range from the visible light to the ultraviolet region, and are also excellent in other semiconductor characteristics. It is a semiconductor that is expected to grow in the LED field.
- This group III nitride semiconductor is fabricated on a substrate by metal organic chemical vapor deposition (MOCVD), but only sapphire glass is practically used as the substrate because of the problem of lattice matching.
- MOCVD metal organic chemical vapor deposition
- the conventional face-up type or flip chip type light emitting device using this sapphire glass as a substrate requires a high level of technology to separate the sapphire glass because the sapphire glass is very hard. Since the thermal conductivity is poor, there is a case in which the problem of poor heat dissipation generated in the group III nitride semiconductor layer may occur.
- Patent Document 1 a method has been proposed in which a group III nitride semiconductor layer formed on a sapphire glass is fixed to a support substrate via a fixed layer, and the sapphire glass is peeled off by a laser lift-off method.
- Patent Document 1 a method has been proposed in which a group III nitride semiconductor layer formed on a sapphire glass is fixed to a support substrate via a fixed layer, and the sapphire glass is peeled off by a laser lift-off method.
- the group III nitride semiconductor layer is peeled off from the support base material, the residue of the fixed layer remains on the group III nitride semiconductor layer and the support base material, so that cleaning is performed to remove the residue. A process was required.
- An object of the present invention is to provide a method for manufacturing a light emitting device in which a residue of a fixed resin layer hardly remains on a group III nitride semiconductor layer and a supporting base material when the light emitting device is manufactured by a laser lift-off method. Another object is to provide a highly reliable light-emitting element manufactured by the manufacturing method of the present invention.
- a third step of bonding the thermally decomposable fixed resin layer of the support base material with the thermally decomposable fixed resin layer on which the fixed resin layer is formed and the compound semiconductor layer; and forming the compound semiconductor layer of the growth substrate By irradiating a laser beam from a surface opposite to the surface on which the surface is formed, and by separating the growth substrate and the compound semiconductor layer, and thermally decomposing the thermally decomposable fixing resin layer,
- a method for producing a light-emitting element comprising: a fifth step of peeling the compound semiconductor layer from the support substrate; and a sixth step of separating the compound semiconductor layer.
- the thermally decomposable fixing resin layer is a thermally decomposable resin selected from the group consisting of polycarbonate resins, polyester resins, polyamide resins, polyimide resins, polyether resins, polyurethane resins, and norbornene resins.
- the method for producing a light-emitting device comprising at least one component (6)
- Device manufacturing method (9) A light-emitting element manufactured by the manufacturing method according to any one of (1) to (8).
- the present invention it is possible to provide a method for manufacturing a light-emitting element in which the residue of the fixed resin layer hardly remains on the group III nitride semiconductor layer and the supporting base material when the light-emitting element is manufactured by a laser lift-off method.
- a highly reliable light-emitting element can be provided.
- FIGS. 1 and 2 are longitudinal sectional views showing an example of a light emitting device manufactured by the method for manufacturing a light emitting device of the present invention.
- the upper side in FIGS. 1 and 2 is referred to as “upper” and the lower side is referred to as “lower”.
- a light-emitting element 100 shown in FIG. 1 includes a compound semiconductor layer 1 in which a p-type semiconductor layer 20, a light-emitting layer 30, and an n-type semiconductor layer 10 are stacked in this order, and below the n-type semiconductor layer 10 and the p-type semiconductor layer.
- An n-type electrode 50 and a p-type electrode 40 are respectively formed under 20.
- n-type semiconductor layer 10 includes a p-type semiconductor layer 20, a light-emitting layer 30, and a compound semiconductor layer 1 in which an n-type semiconductor layer 10 is stacked in this order, above the n-type semiconductor layer 10, and below the p-type semiconductor layer 20.
- the n-type electrode 50 and the p-type electrode 40 are formed respectively.
- the n-type semiconductor layer 10 and the p-type semiconductor layer 20 are not particularly limited, and a known semiconductor material such as a GaN-based single crystal, a GaP-based single crystal, or a GaAs-based single crystal can be used. It is preferable to use a GaN-based single crystal that can be easily epitaxially grown on the surface (such as a sapphire glass substrate).
- a material used for the light emitting layer 30 is not particularly limited, and examples thereof include a GaN-based semiconductor such as In S Ga 1-s N (0 ⁇ S ⁇ 0.3).
- the light emitting layer 30 has a quantum well layer composed of a barrier layer having a wide forbidden band and a well layer having a narrow forbidden band, and the quantum well layer is a single quantum well layer (SQW) or a multiple quantum well layer. Any of (MQW) may be sufficient.
- the thickness of the barrier layer is not particularly limited, but is preferably about 5 to 15 nm, and the thickness of the well layer is preferably about 2 to 100 nm. Further, the total thickness of the light emitting layer 30 is not particularly limited, but is preferably about 25 to 150 nm.
- the material used for the p-type electrode 40 is not particularly limited, and examples include simple copper and copper-tungsten alloy, but simple copper having excellent thermal conductivity is preferable.
- the p-type electrode 40 may have a seed layer and a barrier layer, and examples of the material used for the seed layer include metals such as titanium. Examples of the material used for the barrier layer include May include metals such as tantalum.
- the n-type electrode 50 is not particularly limited, but a laminate of thin films of chromium, aluminum, titanium, gold, or the like can be used.
- the n-type electrode 50 is produced by a known sputtering method or vapor deposition method. can do.
- the light emitting device 100 as shown in FIG. 1 can be manufactured as follows, for example.
- a buffer layer having an intermediate lattice constant between the substrate 60 and the n-type semiconductor layer 10 is formed on the substrate 60 in advance. Is preferred. Thereby, the crystallinity of the n-type semiconductor layer can be improved.
- the material used for the buffer layer is not particularly limited, and AlN or AlGaN can be used when a sapphire glass substrate is used as the substrate.
- a method for forming the n-type semiconductor layer 10, the light emitting layer 30, and the p-type semiconductor layer 20 is not particularly limited, and sputtering, MOCVD (metal organic chemical vapor deposition), MBE (molecular beam epitaxy), Although HVPE (hydride vapor phase epitaxy) etc. are mentioned, MOCVD which can control a film thickness easily is preferable.
- MOCVD metal organic chemical vapor deposition
- MBE molecular beam epitaxy
- HVPE hydrogen vapor phase epitaxy
- the growth substrate 60 is not particularly limited and may be a sapphire glass substrate, a GaAs substrate, a silicon substrate, or the like, but a sapphire glass substrate that facilitates epitaxial growth of a semiconductor layer is preferable.
- grooves 70 are formed in the compound semiconductor layer 1 so as to partition each light emitting element.
- the method of forming the groove 70 is not particularly limited, but can be performed by applying a normal photography technique such as etching.
- the p-type electrode 40 is not particularly limited, but preferably includes an ohmic contact layer and a reflective layer. Since the p-type electrode 40 includes the reflective layer, the light emitted from the light emitting layer 30 can be reflected to the light extraction surface.
- the material used for the ohmic contact layer is not particularly limited, but is preferably a platinum group such as platinum, ruthenium, osmium, rhodium, iridium, palladium, or silver, more preferably platinum, iridium, rhodium, or ruthenium. Particularly preferred.
- the thickness of the ohmic contact layer is preferably 0.1 nm or more, and particularly preferably 1 nm or more in order to stably obtain a low contact resistance. By setting the thickness of the ohmic contact layer within the above range, stable contact resistance with the p-type semiconductor layer 20 can be obtained.
- the material used for the reflective layer is not particularly limited, but a gold alloy or a silver alloy that can ensure good reflectivity is preferable.
- the thickness of the reflective layer is preferably from 0.1 to 300 nm, particularly preferably from 1 to 200 nm. By setting the thickness of the reflective layer in the above range, both good reflectance and migration resistance can be achieved.
- the n-type electrode 50 is not particularly limited, but can be formed by laminating a gold layer on a base metal layer such as chromium, titanium, or aluminum. Thereby, ohmic contact can be obtained between the n-type electrode 50 and the n-type semiconductor layer 10 without annealing.
- examples of the structure of the n-type electrode 50 include a chromium / titanium / gold three-layer structure and a titanium / aluminum / titanium / gold four-layer structure.
- the support substrate 80 is not particularly limited as long as it has a function of supporting the compound semiconductor layer 1.
- Examples of the support substrate 80 include glass, quartz, silicon, ceramic, metal, and an organic substrate.
- the support substrate 80 has excellent light transmittance and is thermally decomposable by exposing the thermally decomposable fixing resin layer 90. Glass and quartz that can effectively lower the thermal decomposition temperature of the fixed resin layer 90 are preferable.
- the thermally decomposable fixing resin layer 90 is not particularly limited, and may be either a resin composition that is liquid at 25 ° C. or a film-like resin composition. In the case of a resin composition that is liquid at 25 ° C., The thermally decomposable fixing resin layer 90 can be formed on the support substrate 80 by dispensing or spin coating. In the case of a film-like resin composition at 25 ° C., the thermally decomposable fixed resin layer 90 can be formed on the support substrate 80 by laminating the support substrate 80.
- the thermally decomposable resin composition contains a thermally decomposable resin component as an essential component, and may contain other resin components such as an activator, a sensitizer, an antioxidant, and a solvent as necessary.
- the thermally decomposable resin component constituting the thermally decomposable resin composition preferably has a 50% weight loss temperature of 50 to 500 ° C, particularly preferably 100 to 400 ° C.
- the 5% weight loss temperature, 50% weight loss temperature, and 95% weight loss temperature are 5% when the TG / DTA (thermogravimetric / differential thermal analysis) measurement is performed on the thermally decomposable resin component, It means the temperature at which 50%, 95% weight is lost.
- the TG / DTA measurement can accurately measure about 10 mg of the resin component and can measure (atmosphere: nitrogen, temperature rising rate: 5 ° C./min) with a TG / DTA apparatus (manufactured by Seiko Instruments Inc.).
- the thermally decomposable resin component is not particularly limited.
- polycarbonate resin, polyester resin, polyamide resin, polyimide resin, polyether resin, polyurethane resin, norbornene resin examples include meth) acrylate resins and polylactic acid resins.
- thermally decomposable resin components it is possible to effectively prevent thermal decomposition of the thermally decomposable fixing resin layer 90 during the light emitting element manufacturing process, and further, thermal decomposability in the fifth step (described later).
- Polycarbonate resins, norbornene resins, and polylactic acid resins that can effectively shorten the thermal decomposition time of the fixed resin layer 90 are preferable.
- the decomposition time at a 5% weight loss temperature is preferably 1 minute or more and 60 minutes or less.
- the decomposition temperature is set to the above lower limit value or more, rapid thermal decomposition of the thermally decomposable fixing resin layer can be suppressed, and the thermally decomposed gas can be exhausted by an exhaust device. Contamination of equipment for manufacturing the light-emitting element can be prevented.
- productivity of a light emitting element can be improved.
- the pyrolysis time can be measured by the following method.
- the 5% weight reduction temperature is calculated by the above-mentioned method, then, about 10 mg of the thermally decomposable resin component is accurately weighed using a TG / DTA apparatus, and then from 25 ° C. to 5% weight reduction temperature. The temperature is raised in 30 minutes, and the measurement temperature is maintained at a 5% weight loss temperature, and measurement is performed. From the measured value obtained, the point at which the 5% weight reduction temperature is reached is defined as the starting point (0 minutes), and the time to reach the 95% weight reduction temperature is defined as the decomposition time.
- the polycarbonate resin is not particularly limited.
- examples of the polycarbonate resin include polypropylene carbonate / polycyclohexene carbonate copolymer, poly [(oxycarbonyloxy-1,1,4,4-tetramethylbutane) -alt- (oxycarbonyl).
- the polycarbonate resin has a weight average molecular weight (Mw) of preferably 1,000 to 1,000,000, and more preferably 5,000 to 800,000.
- Mw weight average molecular weight
- the polycarbonate resin has a weight average molecular weight (Mw) of preferably 1,000 to 1,000,000, and more preferably 5,000 to 800,000.
- the polymerization method of the polycarbonate-based resin is not particularly limited.
- a known polymerization method such as a phosgene method (solvent method) or a transesterification method (melting method) can be used.
- the thermally decomposable resin component is preferably blended at a ratio of 10% to 100% of the total amount of the thermally decomposable resin composition. More preferably, it is blended at a ratio of 20% to 100%. By making content of a thermally decomposable resin component more than the said lower limit, it can prevent that a thermally decomposable fixed resin layer remains on a support base material or a light emitting element after the 5th process mentioned later.
- thermoly decomposable resin component a polypropylene carbonate polymer, a 1,4-polybutylene carbonate polymer, and a polycyclohexene carbonate / polynorbornene carbonate copolymer are particularly preferable.
- the said thermally decomposable resin composition may contain the activator which generate
- the photoacid generator is not particularly limited, but tetrakis (pentafluorophenyl) borate-4-methylphenyl [4- (1-methylethyl) phenyl] iodonium (DPI-TPFPB), tris (4-t-butyl) Phenyl) sulfonium tetrakis- (pentafluorophenyl) borate (TTBPS-TPFPB), tris (4-t-butylphenyl) sulfonium hexafluorophosphate (TTBPS-HFP), triphenylsulfonium triflate (TPS-Tf), bis (4 -Tert-butylphenyl) iodonium triflate (DTBPI-Tf), triazine (TAZ-101), triphenylsulfonium he
- tetrakis (pentafluorophenyl) borate-4-methylphenyl [4- (1-methylethyl) phenyl] is particularly preferred because the thermal decomposition temperature of the thermally decomposable resin component can be efficiently lowered.
- Iodonium (DPI-TPFPB) and tris ⁇ 4-[(4-acetylphenyl) thio] phenyl ⁇ sulfonium tris (perfluoromethanesulfonyl) methide are preferred.
- the photobase generator is not particularly limited, and examples thereof include 5-benzyl-1,5-diazabicyclo (4.3.0) nonane and 1- (2-nitrobenzoylcarbamoyl) imidazole.
- 5-benzyl-1,5-diazabicyclo (4.3.0) nonane and derivatives thereof are preferable because the thermal decomposition temperature of the thermally decomposable resin component can be efficiently lowered.
- the activator is preferably blended at a ratio of 0.01% to 50% of the total amount of the thermally decomposable resin composition. More preferably, it is blended at a ratio of 0.1% to 30%.
- the thermally decomposable fixing resin layer is a support base material or a light emitting element. It can be effectively prevented from remaining as a residue.
- the polycarbonate resin is particularly preferably a polypropylene carbonate polymer, a 1,4-polybutylene carbonate polymer, a neopentyl carbonate polymer, a cyclohexene carbonate / norbornene carbonate copolymer.
- the thermally decomposable resin component is 20% to 100% of the total amount of the thermally decomposable resin composition, and the activator is 0.1% to 30% of the total amount of the thermally decomposable resin composition.
- the weight average molecular weight (Mw) of the thermally decomposable resin composition is preferably 5,000 to 800,000. This is the wettability to the support substrate or the compound semiconductor layer, the film formability of the thermally decomposable resin composition, the compatibility with each resin component constituting the thermally decomposable resin composition and the solubility in various solvents, Furthermore, it is because the thermal decomposability of the thermally decomposable fixing resin layer in the fifth step is ensured.
- the polycarbonate resin forms a structure that facilitates thermal cleavage of the main chain of the polycarbonate resin in the presence of the activator, or forms a thermal ring closure structure in which the polycarbonate resin itself is easily pyrolyzed. Therefore, it is considered that the thermal decomposition temperature can be lowered.
- reaction formula (1) shows the mechanism of thermal cleavage of the main chain of the polypropylene carbonate resin and formation of a thermal ring closure structure.
- H + derived from the activator protonates the carbonyl oxygen of the polypropylene carbonate resin, and further shifts the polar transition state to produce unstable tautomeric intermediates [A] and [B].
- an intermediate [A] is fragmented as acetone and CO 2.
- intermediate [B] produces propylene carbonate, which is fragmented as CO 2 and propylene oxide.
- the thermally decomposable resin composition may contain a solvent.
- Solvents are not particularly limited, but hydrocarbons such as mesitylene, decalin and mineral spirits, alcohols / ethers such as anisole, propylene glycol monomethyl ether, dipropylene glycol methyl ether, diethylene glycol monoethyl ether and diglyme.
- Esters such as ethylene carbonate, ethyl acetate, N-butyl acetate, ethyl lactate, ethyl 3-ethoxypropionate, propylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene carbonate, ⁇ -butyrolactone, cyclopenta Non-, cyclohexanone, methyl isobutyl ketone, ketones such as 2-heptanone, amide / lactams such as N-methyl-2-pyrrolidinone, etc. .
- the thermally decomposable resin composition contains a solvent, it becomes easy to adjust the viscosity of the thermally decomposable resin composition, and it is easy to form a thin film of the thermally decomposable fixed resin layer on the support substrate. It becomes.
- the content of the solvent is not particularly limited, but is preferably 5 to 98% by weight, and particularly preferably 10 to 95% by weight.
- the thermally decomposable resin composition may contain a sensitizer that is a component having a function of expressing or increasing the reactivity of the activator with respect to light of a specific type or wavelength together with the activator.
- the sensitizer is not particularly limited.
- the content of such a sensitizer is preferably 100 parts by weight or less and more preferably 20 parts by weight or less with respect to 100 parts by weight of the activator described above.
- the thermally decomposable resin composition may contain an antioxidant.
- the antioxidant has a function of preventing generation of undesirable acids and natural oxidation of the resin composition.
- the antioxidant is not particularly limited, but for example, Ciba IRGANOX (registered trademark) 1076 or Ciba IRGAFOS (registered trademark) 168 available from Ciba Fine Chemicals of Tarrytown, New York is preferably used. It is done.
- Ciba Irganox registered trademark
- Ciba Irganox 1330 Ciba Irganox 1010
- Ciba Cyanox registered trademark 1790
- Ciba Irganox 3114 Ciba Irganox 3114, 31 Ciga etc.
- the content of the antioxidant is preferably 0.1 to 10 parts by weight, and more preferably 0.5 to 5 parts by weight with respect to 100 parts by weight of the thermally decomposable resin component.
- the thermally decomposable resin composition may further contain additives such as acrylic, silicone, fluorine and vinyl leveling agents, silane coupling agents, diluents and the like as required.
- the silane coupling agent is not particularly limited.
- the diluent is not particularly limited, and examples thereof include cycloether compounds such as cyclohexene oxide and ⁇ -pinene oxide, and aromatic cycloethers such as [methylenebis (4,1-phenyleneoxymethylene)] bisoxirane. And cycloaliphatic vinyl ether compounds such as 1,4-cyclohexanedimethanol divinyl ether.
- cycloether compounds such as cyclohexene oxide and ⁇ -pinene oxide
- aromatic cycloethers such as [methylenebis (4,1-phenyleneoxymethylene)] bisoxirane.
- cycloaliphatic vinyl ether compounds such as 1,4-cyclohexanedimethanol divinyl ether.
- the method of bonding the compound semiconductor layer 1 to the thermally decomposable fixing resin layer 90 is not particularly limited, but can be performed by using a vacuum press apparatus or a semiconductor wafer bonder apparatus. It is preferable to use a semiconductor wafer bonder apparatus that can easily control the above.
- the conditions for bonding the compound semiconductor layer 1 to the thermally decomposable fixing resin layer 90 using the semiconductor wafer bonder device are not particularly limited, but the pressing temperature is preferably 50 to 400 ° C., particularly preferably 100 to 300 ° C.
- the pressure load is not particularly limited, but is preferably 0.01 to 30 MPa, particularly preferably 0.1 to 10 MPa.
- the laser light passes through the growth substrate 60 and is applied to the interface between the growth substrate 60 and the compound semiconductor layer 1.
- the growth substrate 60 and the compound semiconductor layer 1 have different thermal expansion coefficients. Thermal stress is generated and can be peeled off.
- the thermally decomposable sacrificial material 90 according to the present invention has high adhesion to the compound semiconductor layer 1, Furthermore, since it is excellent in stress relaxation property, the compound semiconductor layer 1 can be fixed reliably.
- the laser light is not particularly limited, but an excimer laser is preferable, and specific examples of the oscillation wavelength include ArF (193 nm), KrF (248 nm), XeCl (308 nm), XeF (353 nm), and the like. 248 nm) is particularly preferred.
- the method for manufacturing a light emitting element of the present invention may include a step of roughening the surface of the n-type semiconductor layer 10 after the growth substrate 60 is peeled from the compound semiconductor layer 1. If the surface of the n-type semiconductor layer 10 is smooth, the light emitted from the light emitting layer 30 is reflected by the surface of the n-type semiconductor layer 10, and the light extraction efficiency from the surface of the n-type semiconductor layer 10 decreases. By roughening the surface of the n-type semiconductor layer 10, reflection of light emitted from the light emitting layer 30 can be effectively suppressed.
- the method for roughening the surface of the n-type semiconductor layer 10 is not particularly limited and can be performed chemically or mechanically. Specifically, the surface of the n-type semiconductor layer is immersed in a potassium hydroxide solution. Can be done.
- the unevenness of the rough surface is not particularly limited, but is preferably an unevenness having a size of 1/4 to 1/2 of the wavelength of light emitted from the light emitting layer 30. By setting the unevenness of the rough surface within the above range, reflection of light emitted from the light emitting layer 30 can be more effectively suppressed.
- the thermally decomposable resin composition constituting the thermally decomposable fixed resin layer 90 according to the present invention is gasified and volatilized by heating, when the compound semiconductor layer 1 is peeled off from the support base material 80, the compound The effect that the residue of the thermally decomposable resin composition hardly occurs in the semiconductor layer 1 and the support base 80 can be achieved. Further, even when a residue of the thermally decomposable resin composition is generated, it is possible to obtain an effect that the residue can be easily removed by washing with a solvent or the like. Thereby, since the thermally decomposable fixed resin layer 90 adhering to the compound semiconductor layer 1 can be removed reliably, a highly reliable light emitting element can be manufactured. Further, since the thermally decomposable fixing resin layer 90 adhering to the support base material 80 can be reliably removed, the support base material 80 can be reused.
- the temperature at which the thermally decomposable fixing resin layer 90 is heated is not particularly limited, but is preferably 50 to 500 ° C, particularly preferably 100 to 350 ° C. By setting the heating temperature within the above range, the compound semiconductor layer 1 can be reliably fixed during the manufacturing process of the light emitting element, and thermal deterioration and warpage of the compound semiconductor layer 1 can be suppressed.
- a method for peeling the light emitting element assembly 110 from the support base material 80 is not particularly limited, but a method for peeling the light emitting element assembly 110 in a direction perpendicular to the surface of the support base material 80, On the other hand, there are a method in which the light emitting device assembly 110 is peeled off by sliding in a horizontal direction, and a method in which the light emitting device assembly 110 is lifted off from one side of the light emitting device assembly 110.
- the thermally decomposable fixing resin layer 90 according to the present invention hardly generates a residue in the compound semiconductor layer 1 and the support base 60 as described above, it can be peeled off without applying stress to the light emitting element assembly 110. it can. Thereby, since the damage of the light emitting element assembly 110 can be effectively suppressed, the yield of the light emitting elements can be improved.
- a method of dividing the light emitting element assembly 110 into each light emitting element unit is not particularly limited, but a method similar to a known method of obtaining a semiconductor chip by dicing a semiconductor wafer into pieces is used. Can do. Specifically, a light-emitting element 100 as shown in FIG. 5D can be obtained by attaching a dicing tape to the light-emitting element assembly 110 and dividing (dividing into pieces) with a dicing saw.
- the method for manufacturing a light-emitting element according to the present invention includes a first step of forming a compound semiconductor layer having a semiconductor layer and a light-emitting layer on a growth substrate, a second step of forming an electrode on the compound semiconductor layer, and a support.
- a third step of bonding the thermally decomposable fixing resin layer of the supporting substrate with the thermally decomposable fixing resin layer on which the thermally decomposable fixing resin layer is formed and the compound semiconductor layer; and the growth substrate A fourth step of irradiating a laser beam from a surface opposite to the surface on which the compound semiconductor layer is formed to separate the growth substrate from the compound semiconductor layer; and the compound from the support base.
- the thermally decomposable fixing resin layer The compound semiconductor layer is supported by thermal decomposition of It is characterized by peeling from the substrate.
- the pyrolyzable fixing resin layer is pyrolyzed since the temperature at which the pyrolyzable fixing resin layer is pyrolyzed is 50 to 500 ° C., the pyrolyzable fixing resin layer is reliably pyrolyzed in the fifth step. And the prevention of thermal deterioration and warpage of the compound semiconductor layer.
- the method for producing the light emitting device of the present invention is selected from the group consisting of polycarbonate resin, polyester resin, polyamide resin, polyimide resin, polyether resin, polyurethane resin, norbornene resin as the fixing resin layer. It contains at least one or more kinds of thermally decomposable resin components. Thereby, since the residue of a fixed resin layer does not remain easily, the reliability of the obtained light emitting element can be improved more.
- the method for producing the light emitting device of the present invention is selected from the group consisting of polycarbonate resin, polyester resin, polyamide resin, polyimide resin, polyether resin, polyurethane resin, norbornene resin as the fixing resin layer.
- the thermal decomposition temperature of the fixed resin layer can be lowered. It is possible to more effectively achieve both thermal decomposition of the layer and prevention of thermal deterioration and warpage of the compound semiconductor layer.
- the present invention it is possible to provide a method for manufacturing a light-emitting element in which the residue of the fixed resin layer hardly remains on the group III nitride semiconductor layer and the supporting base material when the light-emitting element is manufactured by a laser lift-off method.
- a highly reliable light-emitting element can be provided. From the above, the present invention is extremely useful industrially.
Abstract
Description
本願は、2010年3月24日に、日本に出願された特願2010-067959号に基づき優先権を主張し、その内容をここに援用する。
III族窒化物半導体は、従来のIII-V族化合物半導体に比べて、可視光から紫外光領域までの広範囲における発光効率に優れ、さらに、その他の半導体の特性においても優れるものであり、今後のLED分野で伸長が期待される半導体である。
(1)成長用基板上に半導体層、発光層を有する化合物半導体層を形成する第1の工程と、前記化合物半導体層に電極を形成する第2の工程と、支持基材上に熱分解性固定樹脂層が形成された熱分解性固定樹脂層付き支持基材の熱分解性固定樹脂層と前記化合物半導体層とを貼り合せる第3の工程と、前記成長用基板の前記化合物半導体層が形成されている面とは反対側の面からレーザー光を照射し、前記成長用基板と前記化合物半導体層とを剥離する第4の工程と、前記熱分解性固定樹脂層を熱分解させることにより、前記支持基材から前記化合物半導体層を剥離する第5の工程と、前記化合物半導体層を個片化する第6の工程と、を有することを特徴とする発光素子の製造方法、
(2)前記半導体層が、n型半導体層およびp型半導体層である、(1)に記載の発光素子の製造方法、
(3)前記成長用基板が、サファイアガラスである、(1)または(2)に記載の発光素子の製造方法、
(4)前記第5の工程で熱分解性固定樹脂層を熱分解させる温度が、50~500℃である(1)ないし(3)のいずれかに記載の発光素子の製造方法、
(5)前記熱分解性固定樹脂層が、ポリカーボネート系樹脂、ポリエステル系樹脂、ポリアミド系樹脂、ポリイミド系樹脂、ポリエーテル系樹脂、ポリウレタン系樹脂、ノルボルネン系樹脂からなる群より選ばれる熱分解性樹脂成分を少なくとも1種以上含む、(1)ないし(4)のいずれかに記載の発光素子の製造方法、
(6)前記熱分解性樹脂成分が、ポリカーボネート系樹脂である、(1)ないし(5)のいずれかに記載の発光素子の製造方法、
(7)前記熱分解性固定樹脂層が、光酸発生剤を含む、(1)ないし(6)のいずれかに記載の発光素子の製造方法、
(8)前記ポリカーボネート系樹脂が、プロピレンカーボネート、シクロヘキシレンカーボネート、ブチレンカーボネート、ノルボルナンカーボネートからなる群より選ばれる少なくとも1種以上の構造単位を含む(5)ないし(7)のいずれかに記載の発光素子の製造方法、
(9)(1)ないし(8)のいずれかに記載の製造方法で作製されたことを特徴とする発光素子。
前記障壁層の厚みは、特に制限されないが、5~15nm程度が好ましく、井戸層の厚みは2~100nm程度が好ましい。さらに、発光層30の総厚は、特に制限はないが、25~150nm程度が好ましい。
以下、発光素子100を得る発光素子の製造方法を第一の実施形態として図3~図5を用いて説明する。また、図3~図5中の上側を「上」、下側を「下」と言う。
<第一の実施形態>
(A-1)まず、図(3-a)に示すように、成長用基板60上に、n型半導体層10、発光層30、p型半導体層20をこの順に積層し、化合物半導体層1を形成する。
(C-1)次に、図(3-c)に示すように、p型半導体層20上にp型電極40を形成する。
(E-1)次に、図(4-a)に示すように、支持基材80を準備し、支持基材80上に熱分解性固定樹脂層90を形成する。
ここで、熱分解性固定樹脂層90を構成する熱分解性の樹脂組成物について説明する。
前記熱分解性の樹脂組成物は、熱分解性樹脂成分を必須成分とし、必要に応じて、活性剤、増感剤、酸化防止剤、溶剤等の他の樹脂成分を含んでいてよい。
ここで、TG/DTA測定は、樹脂成分を約10mg精秤し、TG/DTA装置(セイコーインスツルメンツ社製)により測定(雰囲気:窒素、昇温速度:5℃/分)することができる。
分解温度を上記下限値以上とすることで、熱分解性固定樹脂層の急激な熱分解を抑制することができ、熱分解したガスを排気装置で排気することが可能となるため、発光素子や発光素子を作製する設備の汚染を防止することができる。また、上記上限値以下とすることで、第5の工程に要する時間を短縮することができるため、発光素子の生産性を向上することができる。
まず、前述の方法により5%重量減少温度を算出し、次いで、TG/DTA装置を用い、前記熱分解性樹脂成分を約10mg精秤し、次に、25℃から5%重量減少温度までを30分で昇温し、さらに、測定温度を5%重量減少温度で保持し、測定を実施する。得られた測定値より、5%重量減少温度に到達したところを始点(0分)とし、95%重量減少温度に至るまでの時間を前記分解時間とする。
これらの中でも特に、前記熱分解性樹脂成分の熱分解温度を効率的に下げることができるという理由から、テトラキス(ペンタフルオロフェニル)ボレート-4-メチルフェニル[4-(1-メチルエチル)フェニル]ヨードニウム(DPI-TPFPB)、トリス{4-[(4-アセチルフェニル)チオ]フェニル}スルフォニウムトリス(パーフルオロメタンスルホニル)メチドが好ましい。
この場合、熱分解性樹脂成分は、熱分解性の樹脂組成物の全量の20%~100%、活性剤は、熱分解性の樹脂組成物の全量の0.1%~30%であり、熱分解性の樹脂組成物の重量平均分子量(Mw)は5,000~800,000であることが好ましい。これは、支持基材または化合物半導体層に対する濡れ性、熱分解性の樹脂組成物の成膜性、熱分解性の樹脂組成物を構成する各樹脂成分との相溶性や各種溶剤に対する溶解性、さらには、第5の工程における熱分解性固定樹脂層の熱分解性を確保するという理由からである。
先ず、前記活性剤由来のH+が、ポリプロピレンカーボネート樹脂のカルボニル酸素をプロトン化し、さらに極性遷移状態を転移させ不安定な互変異性中間体[A]及び[B]を生じる。
次に、主鎖の熱切断の場合には、中間体[A]は、アセトン及びCO2として断片化する。
熱閉環構造の形成(a又はb)の場合には、中間体[B]は炭酸プロピレンを生成し、炭酸プロピレンはCO2及びプロピレンオキシドとして断片化される。
前記熱分解性の樹脂組成物がシランカップリング剤を含むことにより、支持基材または化合物半導体層との密着性を向上することが可能となる。
前記熱分解性の樹脂組成物が希釈剤を含むことにより、熱分解性の樹脂組成物の流動性を向上することができ、第3の工程において、熱分解性の樹脂組成物の支持基材または化合物半導体層に対する濡れ性を向上することが可能となる。
(G-1)次に、図(4-c)に示すように、成長用基板60の化合物半導体層1が形成されている面とは反対側の面からレーザー光を照射する。
また、粗面の凹凸は、特に制限されないが、発光層30から発した光の波長の1/4~1/2の大きさの凹凸であることが好ましい。粗面の凹凸を、上記範囲とすることにより、発光層30から発した光の反射をより効果的に抑制することができる。
(J-1)次に、図(5-a)に示すように、熱分解性固定樹脂層90を加熱することにより、熱分解性固定樹脂層90を熱分解させる。
(L-1)次に、発光素子集合体110を各発光素子単位毎に分割する。
本発明の発光素子の製造方法は、成長用基板上に半導体層、発光層を有する化合物半導体層を形成する第1の工程と、前記化合物半導体層に電極を形成する第2の工程と、支持基材上に熱分解性固定樹脂層が形成された熱分解性固定樹脂層付き支持基材の熱分解性固定樹脂層と前記化合物半導体層とを貼り合せる第3の工程と、前記成長用基板の前記化合物半導体層が形成されている面とは反対側の面からレーザー光を照射し、前記成長用基板と前記化合物半導体層とを剥離する第4の工程と、前記支持基材から前記化合物半導体層を剥離する第5の工程と、前記化合物半導体層を個片化する第6の工程と、を有する発光素子の製造方法の中でも、該第5の工程において、該熱分解性固定樹脂層を熱分解させることにより化合物半導体層を支持基材から剥離することを特徴としている。これにより、化合物半導体層に、固定樹脂層の残渣が残り難いため、得られる発光素子の信頼性を高めることができる。
10 n型半導体層
20 p型半導体層
30 発光層
40 p型電極
50 n型電極
60 成長用基板
70 溝
80 支持基材
90 熱分解性固定樹脂層
100、200 発光素子
110 発光素子集合体
Claims (9)
- 成長用基板上に半導体層、発光層を有する化合物半導体層を形成する第1の工程と、
前記化合物半導体層に電極を形成する第2の工程と、
支持基材上に熱分解性固定樹脂層が形成された熱分解性固定樹脂層付き支持基材の熱分解性固定樹脂層と前記化合物半導体層とを貼り合せる第3の工程と、
前記成長用基板の前記化合物半導体層が形成されている面とは反対側の面からレーザー光を照射し、前記成長用基板と前記化合物半導体層とを剥離する第4の工程と、
前記熱分解性固定樹脂層を熱分解させることにより、前記支持基材から前記化合物半導体層を剥離する第5の工程と、
前記化合物半導体層を個片化する第6の工程と、
を有することを特徴とする発光素子の製造方法。 - 前記半導体層が、n型半導体層およびp型半導体層である、請求項1に記載の発光素子の製造方法。
- 前記成長用基板が、サファイアガラスである、請求項1または2に記載の発光素子の製造方法。
- 前記第5の工程で熱分解性固定樹脂層を熱分解させる温度が、50~500℃である請求項1ないし3のいずれかに記載の発光素子の製造方法。
- 前記熱分解性固定樹脂層が、ポリカーボネート系樹脂、ポリエステル系樹脂、ポリアミド系樹脂、ポリイミド系樹脂、ポリエーテル系樹脂、ポリウレタン系樹脂、ノルボルネン系樹脂からなる群より選ばれる熱分解性樹脂成分を少なくとも1種以上含む、請求項1ないし4のいずれかに記載の発光素子の製造方法。
- 前記熱分解性樹脂成分が、ポリカーボネート系樹脂である、請求項1ないし5のいずれかに記載の発光素子の製造方法。
- 前記熱分解性固定樹脂層が、光酸発生剤を含む、請求項1ないし6のいずれかに記載の発光素子の製造方法。
- 前記ポリカーボネート系樹脂が、プロピレンカーボネート、シクロヘキシレンカーボネート、ブチレンカーボネート、ノルボルナンカーボネートからなる群より選ばれる少なくとも1種以上の構造単位を含む請求項5ないし7のいずれかに記載の発光素
子の製造方法。 - 請求項1ないし8のいずれかに記載の製造方法で作製されたことを特徴とする発光素子。
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