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WO2011013709A1 - Élément luminescent, procédé de fabrication d'élément luminescent ainsi que composition pour la formation d'une couche de protection d'élément luminescent - Google Patents

Élément luminescent, procédé de fabrication d'élément luminescent ainsi que composition pour la formation d'une couche de protection d'élément luminescent Download PDF

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Publication number
WO2011013709A1
WO2011013709A1 PCT/JP2010/062716 JP2010062716W WO2011013709A1 WO 2011013709 A1 WO2011013709 A1 WO 2011013709A1 JP 2010062716 W JP2010062716 W JP 2010062716W WO 2011013709 A1 WO2011013709 A1 WO 2011013709A1
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Prior art keywords
layer
semiconductor layer
protective layer
light
light emitting
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English (en)
Japanese (ja)
Inventor
幸勇 前田
宏和 伊東
裕亮 村田
宣康 篠原
洋平 野辺
薫平 小林
加藤　仁史
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JSR Corp
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JSR Corp
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10H—INORGANIC LIGHT-EMITTING SEMICONDUCTOR DEVICES HAVING POTENTIAL BARRIERS
    • H10H20/00—Individual inorganic light-emitting semiconductor devices having potential barriers, e.g. light-emitting diodes [LED]
    • H10H20/80—Constructional details
    • H10H20/84—Coatings, e.g. passivation layers or antireflective coatings
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L24/00—Arrangements for connecting or disconnecting semiconductor or solid-state bodies; Methods or apparatus related thereto
    • H01L24/01—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
    • H01L24/18—High density interconnect [HDI] connectors; Manufacturing methods related thereto
    • H01L24/23—Structure, shape, material or disposition of the high density interconnect connectors after the connecting process
    • H01L24/24—Structure, shape, material or disposition of the high density interconnect connectors after the connecting process of an individual high density interconnect connector
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L25/00—Assemblies consisting of a plurality of semiconductor or other solid state devices
    • H01L25/03—Assemblies consisting of a plurality of semiconductor or other solid state devices all the devices being of a type provided for in a single subclass of subclasses H10B, H10D, H10F, H10H, H10K or H10N, e.g. assemblies of rectifier diodes
    • H01L25/04—Assemblies consisting of a plurality of semiconductor or other solid state devices all the devices being of a type provided for in a single subclass of subclasses H10B, H10D, H10F, H10H, H10K or H10N, e.g. assemblies of rectifier diodes the devices not having separate containers
    • H01L25/075—Assemblies consisting of a plurality of semiconductor or other solid state devices all the devices being of a type provided for in a single subclass of subclasses H10B, H10D, H10F, H10H, H10K or H10N, e.g. assemblies of rectifier diodes the devices not having separate containers the devices being of a type provided for in group H10H20/00
    • H01L25/0753—Assemblies consisting of a plurality of semiconductor or other solid state devices all the devices being of a type provided for in a single subclass of subclasses H10B, H10D, H10F, H10H, H10K or H10N, e.g. assemblies of rectifier diodes the devices not having separate containers the devices being of a type provided for in group H10H20/00 the devices being arranged next to each other
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/013—Alloys
    • H01L2924/0132—Binary Alloys
    • H01L2924/01322—Eutectic Alloys, i.e. obtained by a liquid transforming into two solid phases
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/10—Details of semiconductor or other solid state devices to be connected
    • H01L2924/11—Device type
    • H01L2924/12—Passive devices, e.g. 2 terminal devices
    • H01L2924/1204—Optical Diode
    • H01L2924/12041—LED

Definitions

  • the present invention relates to a light-emitting element and a composition for forming a protective layer which is a constituent part of the light-emitting element.
  • Patent Document 1 a light emitting element in which a light emitting element body is covered with a protective layer.
  • Patent Document 1 a semiconductor element that is a light-emitting element in which a resin layer made of a specific polyimide resin is formed as a support for a protective film for protecting the side surface of a semiconductor layer.
  • the oxide semiconductor light emitting device including at least the n-type cladding layer 3, the active layer 4, the p-type cladding layer 5, the p-type contact layer 6, and the electrodes 7 and 8 on the substrate 2, the oxide
  • the oxide semiconductor light emitting device characterized in that the main surface 1a including at least the side surface 1b of the semiconductor light emitting device is covered with multilayer protective films 10 and 11 made of two or more different insulating organic compounds ( Patent Document 2).
  • Patent Document 2 A plurality of light emitting cells arranged two-dimensionally on a single substrate, a wiring electrically connecting the light emitting cells, and a plurality of light emitting cells connected in series by the wiring form a serial array.
  • the single substrate is a non-polar substrate
  • the light emitting cell is composed of a non-polar gallium nitride semiconductor layer grown on the non-polar substrate.
  • an insulating layer is interposed between the light emitting cell and the wiring in order to prevent the first conductive semiconductor layer and the second conductive semiconductor layer in the light emitting cell from being short-circuited by the wiring. (Patent Document 3).
  • Patent Document 1 Since the semiconductor element described in Patent Document 1 includes a resin layer made of polyimide resin, transparency and light resistance are insufficient, and there is a problem of reducing luminance with respect to radiated light from the side surface of the semiconductor layer. is there.
  • Patent Document 2 in the process of manufacturing the semiconductor light emitting device 1, after forming the resist mask 41 on the protective film 11, the protective films 10 and 11 are etched to form the opening 42. A pad electrode 8 is formed on the p-type ohmic electrode 7. For this reason, there is a problem that the number of manufacturing steps of the light emitting element 1 is large.
  • the insulating layer 35 is formed on a silicon oxide film (SiO 2) on a substrate on which the light emitting cell 30, the transparent electrode layer 33, the first electrode pad 31, and the like are formed. ) Or a silicon nitride film (Si 3 N 4 ) or the like is deposited on the entire surface. At that time, by forming a resist mask and etching the insulating layer, patterning is performed so that the transparent electrode layer 33 and the first electrode pad 31 are exposed. For this reason, there exists a problem that there are many processes of manufacture of a light emitting diode.
  • an object of the present invention is to provide a light-emitting element that is excellent in transparency, light resistance, heat resistance, adhesion, and patterning properties and can be manufactured with a small number of steps.
  • the present inventor has found that the above object can be achieved by using a specific composition as a material for the protective layer for protecting the semiconductor layer, and has completed the present invention. That is, the present invention provides the following [1] to [16]. [1] A support substrate, a semiconductor layer formed above the support substrate, an electrode formed on an upper surface of the semiconductor layer, a protective layer formed so as to coat at least a side surface of the semiconductor layer, And the protective layer is a cured product of a composition for forming a protective layer containing the following component (A).
  • R 1 is a non-hydrolyzable organic group having 1 to 12 carbon atoms
  • X is a hydrolyzable group
  • p is an integer of 0 to 3.
  • R 1 and X may each be the same or different when a plurality of groups are present.
  • [2] The light emitting device according to [1], wherein the protective layer is formed so that at least a part of the electrode is exposed.
  • each of the semiconductor layers includes a first conductive semiconductor layer formed on an upper surface of the support substrate, and a second conductive semiconductor layer located on a region of the first conductive semiconductor layer. And an active layer interposed between the first conductive type semiconductor layer and the second conductive type semiconductor layer, The wiring is for electrically connecting the first conductive type semiconductor layer of one light emitting semiconductor layer and the second conductive type semiconductor layer of the light emitting semiconductor layer adjacent to the first conductive type semiconductor layer.
  • the light emitting device according to any one of [1] to [4], wherein the protective layer forming composition further contains silica particles.
  • the protective layer is formed through an insulating layer formed on a side surface of the semiconductor layer.
  • the insulating layer is a layer made of silicon dioxide.
  • the cured products forming the protective layer have a light transmittance of 95% or more when irradiated with light having a wavelength of 400 nm when the thickness is 2 ⁇ m.
  • the light emitting element in any one of.
  • the cured product forming the protective layer has a light transmittance when irradiated with light having a wavelength of 400 nm at each time point before and after heating at 250 ° C. for 30 minutes.
  • the cured product forming the protective layer is irradiated when irradiated with ultraviolet rays having a irradiance of 28 W / m 2 (wavelength 270 to 700 nm, peak wavelength 313 nm) at 60 ° C. for 168 hours when the thickness is 2 ⁇ m.
  • the light emitting device according to [8] or [9] above, wherein a decrease in light transmittance when irradiated with light having a wavelength of 400 nm at each time point before and after is less than 10%.
  • the protective layer forming composition further contains (B) a photoacid generator.
  • R 1 is a non-hydrolyzable organic group having 1 to 12 carbon atoms
  • X is a hydrolyzable group
  • p is an integer of 0 to 3.
  • R 1 and X may each be the same or different when a plurality of groups are present.
  • a plurality of semiconductors in which a step of forming a semiconductor layer above a support substrate, a step of forming an electrode on the upper surface of the semiconductor layer, and a semiconductor layer having an electrode formed on the upper surface are arranged apart from each other
  • a method for manufacturing a light-emitting element. [15] The method for manufacturing a light-emitting element according to [14], further including: forming a wiring for electrically connecting the electrodes on the surface of the protective layer.
  • Each of the semiconductor layers includes a first conductive semiconductor layer formed on an upper surface of the support substrate, and a second conductive semiconductor layer located on a region of the first conductive semiconductor layer. And an active layer interposed between the first conductive type semiconductor layer and the second conductive type semiconductor layer, and the wiring is a first conductive type semiconductor layer of one light emitting semiconductor layer.
  • a protective layer made of a cured product of a specific composition is formed on the side surface of the semiconductor layer, and the protective layer is excellent in transparency. It has high performance as a light-emitting element because it can be used efficiently. Moreover, since the said protective layer is excellent in light resistance, heat resistance, and adhesiveness, even if it is a severe use condition, it can be used without degrading performance over a long period of time. Moreover, since the said protective layer is excellent in patternability, it has a high dimensional accuracy regarding the boundary of a protective layer and an electrode, for example, and can exhibit the stable performance.
  • the light-emitting element of the present invention includes the protective layer, current leakage from the semiconductor layer, occurrence of a short circuit, and the like can be prevented. Furthermore, since the protective layer for protecting the semiconductor layer is formed using a specific composition, the resist is formed on the insulating layer as in the technique of the above-mentioned Patent Document 2 or 3. Compared with the case where the groove for forming an electrode is formed by etching after forming the mask, the light emitting element can be manufactured with fewer steps.
  • Embodiment Example 1 of the light emitting element of this invention It is a figure which shows the manufacturing method of Embodiment 1 of the light emitting element of this invention. It is sectional drawing which shows Embodiment Example 2 of the light emitting element of this invention. It is a figure which shows the manufacturing method of Embodiment 2 of the light emitting element of this invention. It is sectional drawing which shows Embodiment Example 3 of the light emitting element of this invention. It is a figure which shows the manufacturing method (first half process) of Embodiment 3 of the light emitting element of this invention. It is a figure which shows the manufacturing method (latter half process) of Embodiment 3 of the light emitting element of this invention.
  • the protective layer which comprises the light emitting element of this invention is the hardened
  • the protective layer forming composition will be described.
  • A At least one compound selected from the group consisting of a hydrolyzable silane compound represented by the following general formula (1), a hydrolyzate thereof, and a condensate thereof (R 1 ) P Si (X) 4 ⁇ P (1)
  • R 1 is a non-hydrolyzable organic group having 1 to 12 carbon atoms
  • X is a hydrolyzable group
  • p is an integer of 0 to 3.
  • R 1 and X may each be the same or different when a plurality of groups are present.
  • B Photoacid generator
  • the hydrolyzable group represented by X in the general formula (1) is usually hydrolyzed by heating in the temperature range of room temperature (25 ° C.) to 100 ° C. in the presence of a catalyst and excess water.
  • a group capable of forming a silanol group or a group capable of forming a siloxane condensate is usually hydrolyzed by heating in the temperature range of room temperature (25 ° C.) to 100 ° C. in the presence of a catalyst and excess water.
  • the subscript p in the general formula (1) is an integer of 0 to 3, more preferably an integer of 0 to 2, and particularly preferably 1.
  • a partially unhydrolyzed hydrolyzable group may remain. In that case, the hydrolyzable silane compound and the hydrolyzate And become a mixture.
  • the hydrolyzate of a hydrolyzable silane compound means not only a compound in which an alkoxy group is changed to a silanol group by a hydrolysis reaction but also a partial condensate in which some silanol groups are condensed with each other. . Furthermore, the hydrolyzable silane compound does not necessarily have to be hydrolyzed at the time when the protective layer forming composition is blended, and at least a part of the hydrolyzable group is hydrolyzed at the stage of light irradiation. It ’s fine.
  • hydrolyzable silane compound when used without being previously hydrolyzed, water is added in advance to hydrolyze the hydrolyzable group to produce a silanol group, thereby forming a protective layer forming composition.
  • the object can be radiation cured to form a protective layer.
  • the organic group R 1 in the general formula (1) can be selected from monovalent organic groups that are non-hydrolyzable.
  • a non-hydrolyzable organic group a non-polymerizable organic group and / or a polymerizable organic group can be selected.
  • the non-hydrolyzable property in the organic group R 1 means a property that exists stably as it is under the condition that the hydrolyzable group X is hydrolyzed.
  • examples of the non-polymerizable organic group R 1 include an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, and an aryl group having 7 to 12 carbon atoms. Aralkyl group and the like can be mentioned. These may be linear, branched, cyclic, or combinations thereof.
  • the non-polymerizable organic group R 1 is preferably a structural unit containing a hetero atom. Examples of such a structural unit include an ether bond, an ester bond, a sulfide bond, and the like. However, when it contains a hetero atom, it is preferably non-basic because it does not inhibit radiation curability.
  • the polymerizable organic group R 1 is preferably an organic group having a radical polymerizable functional group and a cationic polymerizable functional group or one of the functional groups in the molecule.
  • the radical polymerizable functional group include an alkenyl group having 2 to 10 carbon atoms and an alkynyl group having 2 to 10 carbon atoms.
  • the cationic polymerizable functional group include epoxy groups such as an oxiranyl group and an oxetanyl group.
  • Examples of the hydrolyzable group X in the general formula (1) include a hydrogen atom, an alkoxy group having 1 to 12 carbon atoms, a halogen atom, an amino-containing group, and a carboxyl group.
  • Preferable examples of the alkoxy group having 1 to 12 carbon atoms include methoxy group and ethoxy group.
  • Preferred examples of the halogen atom include fluorine, chlorine, bromine, iodine and the like.
  • Preferable examples of the amino-containing group include an amino group and a dimethylamino group.
  • Preferable examples of the carboxyl group include an acetoxy group and a ptiloyloxy group.
  • hydrolyzable silane compound represented by the general formula (1) (sometimes simply referred to as a silane compound) will be described.
  • examples of the silane compound having a non-polymerizable organic group R 1 include the following.
  • Examples of the silane compound substituted with four hydrolyzable groups include tetrachlorosilane, tetraaminosilane, tetraacetoxysilane, tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, tetraphenoxysilane, tetrabenzyloxysilane, and trimethoxysilane. And triethoxysilane.
  • silane compounds substituted with three hydrolyzable groups include methyltrichlorosilane, methyltrimethoxysilane, methyltriethoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriisopropoxysilane, and ethyltributoxysilane. , butyl trimethoxysilane, pentafluorophenyl trimethoxysilane, phenyltrimethoxysilane, d 3 - methyltrimethoxysilane, nonafluorobutyl ethyl trimethoxysilane, trifluoromethyl trimethoxy silane, and the like.
  • silane compound substituted with two hydrolyzable groups examples include dimethyldichlorosilane, dimethyldiaminosilane, dimethyldiacetoxysilane, dimethyldimethoxysilane, diphenyldimethoxysilane, and dibutyldimethoxysilane.
  • silane compound substituted with one hydrolyzable group examples include trimethylchlorosilane, hexamethyldisilazane, trimethylsilane, tributylsilane, trimethylmethoxysilane, and tributylethoxysilane.
  • silane compound having a polymerizable organic group examples include a silane compound having a polymerizable organic group in R 1 which is a non-hydrolyzable organic group, and a polymerizable organic group in X being a hydrolyzable group. Any of the silane compounds containing groups can be used.
  • the silane compound containing a polymerizable organic group in R 1 which is a non-hydrolyzable organic group includes (meth) acryloxypropyltrimethoxysilane, vinyltrimethoxysilane, glycidyloxytrimethoxy.
  • Examples include silane, 3- (3-methyl-3-oxetanemethoxy) propyltrimethoxysilane, oxacyclohexyltrimethoxysilane, and the like.
  • silane compound containing a polymerizable organic group in the hydrolyzable group X examples include tetra (meth) acryloxysilane, tetrakis [2- (meth) acryloxyethoxy] silane, tetraglycidyl.
  • Roxysilane tetrakis (2-vinyloxyethoxy) silane, tetrakis (2-vinyloxybutoxy) silane, tetrakis (3-methyl-3-oxetanemethoxy) silane, methyltri (meth) acryloxysilane, methyl [2- (meta ) Acryloxyethoxy] silane, methyl-triglycidyloxysilane, methyltris (3-methyl-3-oxetanemethoxy) silane. These can be used alone or in combination of two or more.
  • the molecular weight of the hydrolyzate of the hydrolyzable silane compound will be described. Such molecular weight can be measured as a weight average molecular weight in terms of polystyrene using gel permeation chromatography (hereinafter abbreviated as GPC) using tetrahydrofuran as a mobile phase.
  • GPC gel permeation chromatography
  • the weight average molecular weight of the hydrolyzate is usually a value within the range of 500 to 10,000.
  • the value of the weight average molecular weight is less than 500, the moldability at the time of forming the protective layer tends to be lowered.
  • the hydrolyzate has a weight average molecular weight in the range of 1,000 to 5,000.
  • the content of the component (A) is preferably 5 to 100% by mass, more preferably 15 to 85% by mass, when the total solid content in the protective layer forming composition is 100% by mass. More preferably, it is 30 to 70% by mass. When the content ratio is within the above numerical range, sufficient transparency, light resistance, heat resistance and adhesion can be obtained.
  • the photoacid generator as component (B) releases an acidic active substance capable of radiation curing (crosslinking) the hydrolyzable silane compound as component (A) by irradiating energy rays (radiation) such as light. Is defined as a compound that can.
  • the protective layer has excellent patterning properties. For example, it has high dimensional accuracy with respect to the boundary between the protective layer and the electrode, and exhibits stable performance. can do.
  • ultraviolet rays infrared rays, X-rays, ⁇ -rays, ⁇ -rays, ⁇ -rays and the like can be used as light energy rays to be irradiated to decompose the photoacid generator and generate cations.
  • radical (A) component has a radical polymerizable functional group, it may promote the polymerization of the functional group. it can. Therefore, the composition for forming a protective layer can be cured more efficiently.
  • photoacid generator examples include onium salts having a structure represented by the general formula (2) (first group of compounds) and sulfonic acid derivatives having a structure represented by the general formula (3) (second group of compounds). Compound).
  • M is a metal or metalloid constituting the central atom of the halide complex [MX m + n ], for example, B, P, As, Sb, Fe, Sn, Bi, Al, Ca, In, Ti, Zn, Sc, V, Cr, Mn, or Co.
  • Z is, for example, a halogen atom or an aryl group such as F, Cl, Br, etc.
  • m is the net charge of the halide complex ion
  • n is the valence of M.
  • Q is a monovalent or divalent organic group
  • R 6 is a monovalent organic group having 1 to 12 carbon atoms
  • the subscript s is 0 or 1
  • the subscript t is 1 or 2. is there. ]
  • an onium salt that is a compound of the first group is a compound that can release an acidic active substance by receiving light.
  • a more effective onium salt is an aromatic onium salt, and particularly preferably a diaryliodonium salt represented by the following general formula (4).
  • R 7 and R 8 are each a monovalent organic group, which may be the same or different, and at least one of R 7 and R 8 represents an alkyl group having 4 or more carbon atoms.
  • Each of Ar 1 and Ar 2 is an aromatic group, which may be the same or different, and Y ⁇ is a monovalent anion and is a group 3 or 5 fluoride anion of the periodic table. Or, it is an anion selected from ClO 4 ⁇ and CF 3 —SO 3 — . ]
  • Examples of the sulfonic acid derivative represented by the general formula (3) as the second group of compounds include disulfones, disulfonyldiazomethanes, disulfonylmethanes, sulfonylbenzoylmethanes, imidosulfonates, benzoin. Examples include sulfonates, sulfonates of 1-oxy-2-hydroxy-3-propyl alcohol, pyrogallol trisulfonates, and benzyl sulfonates. Of the sulfonic acid derivatives represented by the general formula (3), imide sulfonates are more preferable, and among imide sulfonates, a trifluoromethyl sulfonate derivative is more preferable.
  • the amount (content ratio) of the photoacid generator will be described.
  • the addition amount of the photoacid generator is not particularly limited, but it is preferably a value within the range of 0.1 to 15 parts by mass with respect to 100 parts by mass of component (A). If the addition amount is less than 0.1 parts by mass, the radiation curability tends to decrease and a sufficient curing rate tends not to be obtained. On the other hand, when the added amount exceeds 15 parts by mass, the light resistance and heat resistance of the resulting cured product tend to decrease. Therefore, from the viewpoint of a better balance between radiation curability and light resistance of the resulting cured product, the amount of photoacid generator added is 0.5 to 10 parts by mass with respect to 100 parts by mass of component (A). It is more preferable to set the value within the range.
  • the protective layer-forming composition of the present invention can improve the storage stability of the composition by adding (C) an organic solvent, and can impart an appropriate viscosity, and has a uniform thickness. Can be formed.
  • organic solvent (C) examples include ether organic solvents, ester organic solvents, ketone organic solvents, hydrocarbon organic solvents, alcohol organic solvents, and the like. Usually, it is preferable to use an organic solvent having a boiling point in the range of 50 to 200 ° C. under atmospheric pressure and capable of uniformly dissolving each component. Examples of such organic solvents include aliphatic hydrocarbon solvents, aromatic hydrocarbon solvents, monoalcohol solvents, polyhydric alcohol solvents, ketone solvents, ether solvents, ester solvents, nitrogen-containing solvents. A sulfur-containing solvent or the like can be used. These organic solvents are used singly or in combination of two or more.
  • organic solvents include at least one compound selected from the group consisting of propylene glycol monomethyl ether, ethyl lactate, methyl isobutyl ketone, methyl amyl ketone, toluene, xylene, and methanol.
  • the type of the organic solvent is preferably selected in consideration of the coating method of the composition. For example, since a cured product having a uniform thickness can be easily obtained, it is preferable to use a spin coating method.
  • examples of the organic solvent used include ethylene glycol monoethyl ether and propylene glycol monomethyl ether.
  • Glycol ethers Ethylene glycol alkyl ether acetates such as ethyl cellosolve acetate, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate; Esters such as ethyl lactate and ethyl 2-hydroxypropionate; Diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, diethylene glycol Diethylene glycols such as ethyl methyl ether; methyl isobutyl ketone, 2-heptanone, cyclohexano , It is preferred to use a ketone such as methyl amyl ketone, particularly ethyl cellosolve acetate, propylene glycol methyl ether acetate, ethyl lactate, it is preferable to use methyl isobutyl ketone and methyl amyl ketone.
  • the amount of component (C) added is 1 to 300 parts by weight, preferably 2 to 200 parts by weight, per 100 parts by weight of component (A).
  • the amount is within the range of 1 to 300 parts by mass, the storage stability of the composition can be improved, an appropriate viscosity can be imparted, and a protective layer having a uniform thickness can be formed.
  • an acid diffusion controller (hereinafter also referred to as component (D)), a reactive diluent, a radical generator (photopolymerization initiator), a photosensitizer, Metal alkoxide, inorganic fine particles, dehydrating agent, leveling agent, polymerization inhibitor, polymerization initiation aid, wettability improver, surfactant, plasticizer, ultraviolet absorber, antioxidant, antistatic agent, silane coupling agent, It is also preferable to add a polymer additive or the like.
  • the (D) component acid diffusion controlling agent is defined as a compound having an action of controlling the diffusion of the acidic active substance generated from the photoacid generator by photoirradiation in the coating and suppressing the curing reaction in the non-irradiated region.
  • the acid diffusion control agent of component (D) is a compound that does not have an acid generation function.
  • the nitrogen-containing organic compound whose basicity does not change with the exposure in a formation process or heat processing is preferable.
  • nitrogen-containing organic compounds include compounds represented by the following general formula (5).
  • NR 9 R 10 R 11 (5) [In General Formula (5), R 9 , R 10 and R 11 each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted aralkyl group. To express. ]
  • nitrogen-containing organic compounds include diamino compounds having two nitrogen atoms in the same molecule, diamino polymers having three or more nitrogen atoms, amide group-containing compounds, urea compounds, nitrogen-containing heterocycles. A compound etc. can be mentioned.
  • nitrogen-containing organic compound examples include monoalkylamines such as n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decylamine; di-n-butylamine, di-n -Dialkylamines such as pentylamine, di-n-hexylamine, di-n-heptylamine, di-n-octylamine, di-n-nonylamine, di-n-decylamine; triethylamine, tri-n-propylamine , Tri-n-butylamine, tri-n-pentylamine, tri-n-hexylamine, tri-n-heptylamine, tri-n-octylamine, tri-n-nonylamine, tri-n-decylamine, etc.
  • monoalkylamines such as n-hexylamine, n-hepty
  • an acid diffusion control agent can also be used individually by 1 type, or can also be used in mixture of 2 or more types.
  • the amount of the (D) acid diffusion controller added is preferably a value within the range of 0.001 to 15 parts by mass with respect to 100 parts by mass of the component (A).
  • the reason for this is that when the amount of the acid diffusion control agent added is less than 0.001 part by mass, the pattern shape and dimensional reproducibility of the protective layer may be lowered depending on the process conditions. It is because the photocurability of (A) component may fall when the addition amount of a control agent exceeds 15 mass parts. Therefore, the amount of the acid diffusion control agent added is more preferably in the range of 0.001 to 10 parts by mass with respect to 100 parts by mass of component (A), preferably in the range of 0.005 to 5 parts by mass. More preferably, the value is within the range.
  • the composition for protective layer formation contains silica particles, such as colloidal silica, aerosil, glass, as (E) component.
  • the surface of the silica particles is used to increase the affinity and compatibility with at least one compound selected from the group consisting of (A) the hydrolyzable silane compound, its hydrolyzate, and its condensate. , It may be hydrophobized.
  • the shape of the silica particles is not particularly limited, and may be spherical, elliptical, flat, rod-like, fiber-like, or the like.
  • the average particle size of the silica particles is 1 to 500 nm, preferably 5 to 200 nm, more preferably 10 to 100 nm.
  • the average particle diameter of the metal oxide particles is in the above range, the transparency to radiation and alkali solubility are excellent.
  • the said silica particle may be used individually by 1 type, and may be used in combination of 2 or more type.
  • the average particle diameter is a value measured by diluting a dispersion of silica particles according to a conventional method using a light scattering flow distribution measuring device (manufactured by Otsuka Electronics Co., Ltd., model number “LPA-3000”).
  • the average particle diameter can be controlled by the dispersion conditions of the silica particles.
  • the sodium content in the said silica particle is 1 ppm or less, More preferably, it is 0.5 ppm or less, More preferably, it is 0.1 ppm or less.
  • the sodium content in the obtained resin composition can be 1 ppm or less.
  • the sodium content in the hydrophobized silica can be measured with an atomic absorption spectrometer (manufactured by Perkinelmer, model number “Z5100”) or the like.
  • the content of the silica particles is preferably 10 to 500 parts by mass, more preferably 20 to 300 parts by mass, and still more preferably 40 to 200 parts by mass, when the component (A) is 100 parts by mass. It is.
  • this content ratio When this content ratio is in the above range, it has suitable thixotropic properties and can sufficiently cover the side surface of the semiconductor layer.
  • the content of the silica particles is preferably 5 to 90% by mass, more preferably 15 to 80% by mass, and still more preferably 100% by mass when the total solid content in the protective layer forming composition is 100% by mass. Is 30 to 70% by mass.
  • this content ratio is the above ratio, sufficient thixotropy can be obtained, and the side surface of the semiconductor layer can be sufficiently covered.
  • the protective layer-forming composition is composed of carbonates such as calcium carbonate and magnesium carbonate; sulfates such as barium sulfate and calcium sulfate; phosphates such as calcium phosphate and magnesium phosphate; carbides; It may contain inorganic particles.
  • the composition for protective layer formation can also contain a hydrolyzable silyl group containing vinyl polymer other than (A) component as (F) component.
  • a hydrolyzable silyl group-containing vinyl polymer other than the component (A) shrinkage during curing can be reduced, and cracking can be effectively prevented.
  • the composition for protective layer formation contains a reactive diluent as (G) component.
  • the protective layer-forming composition can also contain a dehydrating agent as the component (H).
  • a dehydrating agent used in the protective layer-forming composition is a compound that converts water into a substance other than water by a chemical reaction, or water physically adsorbs or includes water, thereby affecting the radiation curable property and storage stability. It is defined as a compound for avoiding giving. That is, by containing such a dehydrating agent, it is possible to improve contradictory characteristics such as storage stability and radiation curability without impairing the light resistance and heat resistance of the protective layer forming composition.
  • the dehydrating agent effectively absorbs water entering from the outside, so that the storage stability of the protective layer-forming composition is improved.
  • the condensation reaction which is a radiation curing reaction. It is considered that the radiation curability of the protective layer forming composition is improved by the dehydrating agent effectively absorbing the water sequentially.
  • a light-emitting element has a concept including both a semiconductor layer including one semiconductor layer and a semiconductor layer including two or more semiconductor layers.
  • the light emitting element includes each part such as a support substrate and a protective layer formed around the semiconductor layer in addition to the semiconductor layer.
  • a plurality of semiconductor layers 2 are formed above a support substrate 9 so as to be separated from each other.
  • a contact layer 10, a metal diffusion prevention layer 11, and a metal layer 12 are stacked on the support substrate 9.
  • a metal layer 7, a metal diffusion prevention layer 6, a metal diffusion prevention layer 4, and a p-electrode 3 are interposed between the metal layer 12 and each semiconductor layer 2.
  • An n electrode 13 is formed on the upper surface of each semiconductor layer 2. Details of these units will be described later.
  • a protective layer 8 is formed between the semiconductor layers 2.
  • An insulating layer 5 made of a material such as silicon dioxide is formed between the side surface of the semiconductor layer 2 and the protective layer 8. Note that in this specification, an insulating layer means a layered body for preventing current leakage or short-circuit from a side surface of a semiconductor layer. Regardless of the presence or absence of the insulating layer 5, the protective layer 8 is usually formed so as not to generate a gap between the semiconductor layers 2.
  • the reason for forming the insulating layer 5 and the protective layer 8 is as follows.
  • metal powder or the like adheres to the side surfaces of the semiconductor layer 2, and current leakage or short circuit occurs due to the metal powder or the like.
  • the insulating layer 5 is formed on the side surface of the semiconductor layer 2.
  • a protective layer 8 is further formed on the side of the insulating layer 5. Note that the light-emitting element of the present invention can be provided with only the protective layer 8 by omitting the insulating layer 5.
  • the protective layer 8 has a function of preventing current leakage and occurrence of a short circuit.
  • the semiconductor layer 2 is formed on the sapphire substrate 1 ((a) in FIG. 2).
  • the semiconductor layer 2 is made of, for example, a group III nitride semiconductor.
  • the semiconductor layer 2 has an n layer on the sapphire substrate 1 side, an MQW layer on the top, and a p layer on the top.
  • the semiconductor layer 2 is dry-etched until the surface 1a of the sapphire substrate 1 is exposed to form a groove 14, thereby forming a plurality of semiconductor layers 2 spaced apart from each other ((b) in FIG. 2). .
  • the p electrode 3 is formed in a predetermined region on the upper surface of the semiconductor layer 2 by a lift-off method, and further, a metal diffusion prevention layer 4 is formed so as to cover the p electrode 3 ((c) in FIG. 2).
  • a metal diffusion prevention layer 4 is formed so as to cover the p electrode 3 ((c) in FIG. 2).
  • the p-electrode 3 for example, Ag—Pd—Cu can be used.
  • the metal diffusion preventing layer 4 for example, a multilayer film made of Ti / Ni / Au / Al can be used. The layer thickness is, for example, 100 nm for Ti, 500 nm for Ni, 100 nm for Au, and 3 nm for Al.
  • the p-electrode 3 and the metal diffusion prevention layer 4 are first formed at predetermined positions on the upper surface of the semiconductor layer 2, and then the semiconductor layer 2 is formed into sapphire.
  • a plurality of semiconductor layers 2 separated from each other may be formed by dry etching until the substrate 1 is exposed.
  • the insulating layer 5 made of silicon dioxide is applied by CVD to the surface 1a of the sapphire substrate 1, the end surface 2a of the semiconductor layer 2, the upper surface 2b of the semiconductor layer 2 where the p-electrode 3 is not formed, and the metal diffusion preventing layer 4 (A part (d) in FIG. 2).
  • the layer thickness of the insulating layer 5 is, for example, 100 nm to 500 nm.
  • silicon dioxide for example, Si 3 N 4 (silicon nitride), ZrO 2 (zirconium oxide), NbO (niobium oxide), Al 2 O 3 (aluminum oxide), or the like is used as the material of the insulating layer 5. it can.
  • the insulating layer 5 only needs to be formed on at least the side surface 2 a of the semiconductor layer 2.
  • a metal diffusion prevention layer 6 is formed on the metal diffusion prevention layer 4 and the insulating layer 5, and further, a metal layer 7 is formed on the metal diffusion prevention layer 6 ((e) in FIG. 2).
  • the metal diffusion preventing layer 6 is, for example, a Ti / Ni / Au multilayer film.
  • the layer thickness is 100 nm for Ti, 500 nm for Ni, and 50 nm for Au.
  • the metal layer 7 is made of, for example, Sn—20% Au—Sn.
  • the layer thickness is 3 ⁇ m, for example.
  • a metal eutectic layer such as an Au—Si layer, an Ag—Sn—Cu layer, or a Sn—Bi layer, an Au layer, a Sn layer, a Cu layer, or the like can be used.
  • the metal diffusion preventing layer 6 and the metal layer 7 are formed in a predetermined pattern by photolithography.
  • the protective layer 8 made of a specific protective layer forming composition defined in the present invention is formed on the insulating layer 5 ((f) in FIG. 2).
  • the thickness of the protective layer 8 is the total thickness of the semiconductor layer 2, the p-electrode 3, the metal diffusion preventing layers 4 and 6, and the metal layer 7 from the layer thickness of the semiconductor layer 2 (hereinafter referred to as the minimum layer thickness H1). It is desirable to set the range up to a value 5 ⁇ m larger than the maximum (hereinafter referred to as the maximum layer thickness H2). If the thickness of the protective layer 8 is less than the minimum layer thickness H1, the function of the insulating layer 5 as a support is weak and undesirable.
  • the bonding with the support substrate 9 may be defective in the next step, which is not desirable.
  • the protective layer 8 is desirably formed at least in the range of the width L1 of the space between the semiconductor layers 2. If the width is smaller than L1, the function of the insulating layer 5 as a support is weakened, which is not desirable. Further, it is desirable that the protective layer 8 has a width smaller than the width L2 separating the metal diffusion prevention layers 4 on the semiconductor layers 2 at the maximum. If the width is larger than L2, the protective layer 8 may be crushed by bonding with the support substrate 9 in the next step, and there is no allowance when it is spread laterally, which is not desirable.
  • the contact layer 10, the metal diffusion preventing layer 11, and the metal layer 12 are formed on the upper surface of the support substrate 9, and the surface on which the metal layer 7 is formed and the surface on which the metal layer 12 is formed are, for example, 300 ° C. Bonding is performed by hot pressing under the condition of 30 kgf / cm 2 ((g) in FIG. 2).
  • a material of the support substrate 9 for example, Si, GaAs, Cu, Cu—W, or the like can be used.
  • the contact layer 10 is made of Al having a layer thickness of 300 nm, for example.
  • the metal diffusion preventing layer 11 can be formed of the same material as the metal diffusion preventing layer 6.
  • the metal layer 12 can be formed of the same material as the metal layer 7.
  • the metal diffusion prevention layers 4, 6, and 11 are layers for preventing the metal of the metal layers 7 and 12 from diffusing beyond the metal diffusion prevention layers 4, 6, and 11.
  • the sapphire substrate 1 is separated and removed by laser lift-off ((h) in FIG. 2).
  • Laser irradiation is performed, for example, by irradiating the wafer with a KrF laser having a wavelength of 248 nm from the sapphire substrate 1 side under the condition of 0.7 J / cm 2 or more.
  • the sapphire substrate 1 can be separated and removed by melting the semiconductor layer 2 at the joint surface between the sapphire substrate 1 and the semiconductor layer 2.
  • the surface 2c is washed with hydrochloric acid, and further wet-etched with a 50 ° C. aqueous KOH solution to flatten the surface.
  • the protective layer 8 functions as a support for the insulating layer 5. That is, it is possible to prevent the side surface 2a of the semiconductor layer 2 from being exposed due to cracking or chipping of the insulating layer 5 and causing current leakage or short circuit.
  • a lattice-shaped n-electrode 13 made of V / Al / Ti / Ni / Au is formed on the surface 2c on the side bonded to the sapphire substrate 1 ((i) in FIG. 2).
  • the film thickness is 15 nm for V, 150 nm for Al, 30 nm for Ti, 500 nm for Ni, and 500 nm for Au.
  • the present invention can be applied not only to a semiconductor element composed of a group III nitride semiconductor but also to a semiconductor element composed of a group III-V semiconductor such as GaAs or GaP.
  • the pattern of the n electrode is not limited to a lattice shape, and may be a pattern that does not hinder light extraction from the upper surface, such as a stripe shape.
  • the light emitting element 21 includes a support substrate 22, a semiconductor layer formed on the upper surface of the support substrate 22, which is a stacked body including the n-type cladding layer 23, and the like, and a p-type formed on the upper surface of the semiconductor layer.
  • the semiconductor layer is a laminated body interposed between the support substrate 22 and the p-type ohmic electrode 27 and includes an n-type cladding layer 23, an active layer (light emitting layer) 24, a p-type cladding layer 25, and a p-type contact layer 26.
  • a semiconductor layer refers to a stacked body between a supporting substrate and an electrode including a light-emitting layer (active layer). A part (specifically, part of the pad electrode 28) of the electrode (the assembly of the p-type ohmic electrode 27 and the pad electrode 28) above the support substrate 22 is exposed without being covered with the protective layer 33. Yes.
  • the side surface of the p-type ohmic electrode 27 is usually formed on the surface extending upward from the side surface of the semiconductor layer.
  • the vertical projection area of the pad electrode 28 is smaller than the vertical projection area of the p-type ohmic electrode 27.
  • the protective layer 33 is for protecting the semiconductor layer, and includes a surface of the upper surface of the support substrate 22 other than the portion where the semiconductor layer is formed, and a side surface of the stacked portion of the semiconductor layer and the p-type ohmic electrode 27 ( Vertical surface) and the surface of the upper surface of the p-type ohmic electrode 27 other than the portion where the pad electrode 28 is formed.
  • the support substrate 22 is, for example, an n-type ZnO single crystal substrate.
  • the n-type cladding layer 23 is, for example, an n-type Mg 0.1 Zn 0.9 O cladding layer having a thickness of 1 ⁇ m doped with Ga at a concentration of 3 ⁇ 10 18 cm ⁇ 3 .
  • the active layer (light emitting layer) 24 is composed of, for example, eight layers of 5 nm thick ZnO barrier layers and seven layers of 4 nm thick Cd 0.1 Zn 0.9 O well layers, which are alternately stacked. This is a non-doped quantum well light emitting layer.
  • the p-type cladding layer 25 is, for example, a p-type Mg 0.1 Zn 0.9 O cladding layer having a thickness of 1 ⁇ m doped with N at a concentration of 5 ⁇ 10 19 cm ⁇ 3 .
  • the p-type contact layer 26 is, for example, a p-type ZnO contact layer having a thickness of 0.5 ⁇ m doped with N at a concentration of 1 ⁇ 10 20 cm ⁇ 3 .
  • the p-type ohmic electrode 27 is, for example, a p-type ohmic electrode having translucency in which Ni with a thickness of 15 nm is stacked.
  • the pad electrode 28 is, for example, a bonding pad electrode having a thickness of 100 nm.
  • the n-type ohmic electrode 29 is made of, for example, Al having a thickness of 100 nm.
  • an n-type cladding layer 23, an active layer 24, a p-type cladding layer 25, a p-type contact layer 26, and a p-type ohmic electrode 27 are formed on a support substrate 22 (FIG. 4A).
  • These parts can be formed by, for example, the method described in Patent Document 2 described above.
  • a dicing apparatus a plurality of semiconductor layers separated from each other are formed by forming a groove 34 having a depth from the upper surface of the p-type ohmic electrode 27 to the upper surface of the support substrate 22 (see FIG. 4). (B)).
  • a coating layer 30 made of a specific protective layer forming composition defined in the present invention is formed on the upper surface of the support substrate 22, the side surfaces of the semiconductor layer, and the upper surface of the p-type ohmic electrode 27 (FIG. 4 ( c)).
  • the coating layer 30 is formed, for example, by applying the protective layer forming composition onto the surface to be coated using a coating means such as a spin coater and then a predetermined temperature (for example, 30 ° C. to 500 ° C., preferably 50 ° C.). At 400 ° C. to 400 ° C., more preferably 80 ° C., for a predetermined time (eg, 2 to 120 minutes, preferably 2 to 60 minutes, more preferably 2 to 5 minutes). .
  • the specific protective layer-forming composition defined in the present invention contains (B) a photoacid generator, p corresponding to the region where the pad electrode 28 on the p-type ohmic electrode 27 should be disposed, p A photomask 31 is positioned in a region above the type ohmic electrode 27.
  • the irradiation of the ultraviolet rays 32 is, for example, an illuminance of 1 to 1,000 mW / cm 2 and an irradiation amount of 0.01 to 5,000 mJ / cm 2 , preferably 0.1 to 1,000 mJ / cm 2. It is done as follows.
  • an irradiation apparatus of the ultraviolet rays 32 for example, either a lamp light source that simultaneously irradiates a wide area such as a high-pressure mercury lamp, a low-pressure mercury lamp, a metal halide lamp, or an excimer lamp, and a laser light source such as pulse or continuous light emission, or From both light sources, one that generates convergent light using a mirror, a lens, and an optical fiber can be used.
  • a lamp light source that simultaneously irradiates a wide area
  • a low-pressure mercury lamp such as a metal halide lamp, or an excimer lamp
  • a laser light source such as pulse or continuous light emission
  • examples of the developing method include a liquid piling method, a dipping method, and a shower developing method.
  • the developer include an alkaline solution and an organic solvent.
  • alkaline solutions are sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, di-n-propylamine, triethylamine, methyldiethylamine, ethanol Amine, N-methylethanolamine, N, N-dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide, tetrabutylammonium hydroxide, choline, pyrrole, piperidine, 1,8- And a solution containing a basic substance such as diazabicyclo [5.4.0] -7-undecene and 1,5-diazabicyclo [4.3.0] -5-nonane.
  • TMAH tetramethylammonium hydroxide
  • TMAH tetraethylammonium hydroxide
  • Solvents for preparing the alkaline solution include methanol, ethanol, propyl alcohol, butanol, octanol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, N-methylpyrrolidone, formamide, N, N-dimethylformamide, N, N -Organic solvents such as dimethylacetamide and water.
  • concentration of the basic substance in the alkaline solution is usually 0.05 to 25% by mass, preferably 0.1 to 3% by mass.
  • organic solvents include methanol, ethanol, propyl alcohol, butanol, octanol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, N-methylpyrrolidone, formamide, N, N-dimethylformamide, N, N-dimethyl. Examples include acetamide.
  • the development time is usually about 0.5 to 10 minutes.
  • an organic solvent is used as the developer, it is air-dried as it is.
  • an alkaline solution is used, it is washed with running water for 30 to 90 seconds and then air-dried with compressed air or compressed nitrogen.
  • a protective layer (protective film) 33 having holes for electrode formation can be formed.
  • it may be post-baked using a heating device such as a hot plate or oven at a temperature of 30 to 500 ° C., preferably 30 to 400 ° C. for 5 minutes to 72 hours.
  • the specific protective layer-forming composition defined in the present invention does not contain (B) a photoacid generator, a step of applying a photoresist on the coating layer 30 before the step of irradiating the ultraviolet rays 32 It is desirable to include.
  • a photoresist a well-known thing can be used, For example, JSR company make ELPAC THB151N etc. can be mentioned.
  • the specific protective layer forming composition defined in the present invention is (B) light. It can be performed in the same manner as in the case of containing an acid generator.
  • the pad electrode 28 is formed in the hole for electrode formation ((f) of FIG. 4).
  • the pad electrode 28 can be formed by, for example, a lift-off method. Specifically, after applying the photoresist, development and exposure are performed to form a pattern in a portion other than the hole for forming the electrode, and a metal for forming the pad electrode is deposited by a vacuum deposition method. This can be done by removing unnecessary portions.
  • an n-type ohmic electrode 29 is formed on the lower surface of the support substrate 22 ((g) in FIG. 4). The n-type ohmic electrode 29 can be formed, for example, by depositing Al by a vacuum deposition method.
  • the method for forming the pad electrode 28 in the hole for forming the electrode after forming the protective layer has been described.
  • the method is not limited to the above-described method, and the method is not limited to the upper surface of the p-type ohmic electrode.
  • a coating layer made of the specific protective layer-forming composition defined in the present invention is formed, and then the coating layer is exposed and developed to obtain a protective layer exposing the pad electrode.
  • a method can also be mentioned.
  • the pad electrode 28 can be formed, for example, by the lift-off method described above. Also, the same method as described above can be adopted for the exposure and development of the coating layer.
  • the light emitting element 41 includes a support substrate 42, a first conductive semiconductor layer 44 formed on the upper surface of the support substrate 42, and a region (for example, the upper surface) of the first conductive semiconductor layer 44.
  • a stacked body comprising a second conductive semiconductor layer 46 located above (a part of) and an active layer 45 interposed between the first conductive semiconductor layer 44 and the second conductive semiconductor layer 46.
  • a protective layer 48 formed to prevent the first conductive semiconductor layer 44 and the second conductive semiconductor layer 46 from being short-circuited by the wiring 49.
  • a part of the transparent electrode layer 47 and the first conductive type semiconductor layer 44 above the support substrate 42 are exposed without being coated with a protective layer 48 for protecting the semiconductor layer.
  • the light emitting elements are electrically connected to each other by a wiring 49.
  • the electrode pad 50 may be formed on the first conductive type semiconductor layer 44.
  • the protective layer 48 for protecting the semiconductor layer is a semiconductor layer of the support substrate 42 in order to prevent the first conductive semiconductor layer 44 and the second conductive semiconductor layer 46 from being short-circuited by the wiring 49.
  • a protective layer 51 for protecting the wiring may be formed on the substrate on which the wiring is formed.
  • a buffer layer 43 may be interposed between the first conductive semiconductor layer 44 and the support substrate 42. The buffer layer 43 is employed to alleviate the lattice mismatch between the support substrate 42 and the first conductive semiconductor layer 44.
  • the support substrate 42 is, for example, an r-plane sapphire substrate or an a-GaN substrate.
  • the first and second conductive semiconductor layers and the active layer are, for example, (Al, In, Ga) N-based nitride semiconductors.
  • the transparent electrode layer 47 is formed of a material such as an indium tin oxide (ITO) film or Ni / Au, for example.
  • the electrode pad is, for example, at least one layer or alloy layer selected from Ni, Cr, Pd, W, and Al.
  • a buffer layer 43, a first conductive type semiconductor layer 44, an active layer 45, a second conductive type semiconductor layer 46, and a transparent electrode layer 47 are formed on a support substrate 42 (FIG. 6 ( a)). These parts can be formed by, for example, the method described in Patent Document 3 described above.
  • a groove 54 having a depth from the upper surface of the transparent electrode layer 47 to the upper surface of the first conductive type semiconductor layer 44 is formed using a dicing apparatus. Further, by forming a groove 55 having a depth from the upper surface of the first conductive type semiconductor layer 44 to the upper surface of the support substrate 42, a plurality of semiconductor layers spaced apart from each other are formed (FIG.
  • the electrode pad 50 is formed on the upper surface of the first conductive type semiconductor layer ((d) of FIG. 6).
  • the electrode pad 50 can be formed by, for example, a lift-off method. Specifically, after applying the photoresist, development and exposure are performed to form a pattern in a portion other than the hole for forming the electrode, and a metal for forming the pad electrode is deposited by a vacuum deposition method. This can be done by removing unnecessary portions.
  • the coating layer 48 made of the specific protective layer forming composition defined in the present invention is applied to the upper surface of the support substrate 42, the side surfaces of the semiconductor layer, the upper and side surfaces of the transparent electrode layer 47, and the upper surface of the electrode pad 50.
  • the protective layer (coating layer) 48 is formed, for example, by applying the protective layer forming composition onto the surface to be coated using a coating means such as a spin coater and then at a predetermined temperature (for example, 30 ° C. to 500 ° C.). And preferably dried at 50 ° C. to 400 ° C., more preferably 80 ° C. for a predetermined time (eg, 2 to 120 minutes, preferably 2 to 60 minutes, more preferably 2 to 5 minutes). It can be carried out.
  • a coating means such as a spin coater
  • the specific protective layer forming composition defined in the present invention contains (B) a photoacid generator, the transparent electrode layer 47 corresponding to the region to which the wiring 49 on the transparent electrode layer 47 is to be connected.
  • the photomask 52 is positioned in a region above the electrode pad 50 and a region above the electrode pad 50 corresponding to a region to which the wiring 49 on the electrode pad 50 is to be connected.
  • the portion 48 is photocured ((g) in FIG. 6). It is preferable to heat at 30 to 200 ° C.
  • the illuminance and irradiation device of the ultraviolet ray 53 are the same as the illuminance and irradiation device of the ultraviolet ray 32 described above.
  • the portion of the protective layer (coating layer) 48 that has not been irradiated with ultraviolet rays is removed by dissolving with a phenomenon solution to form a hole for connecting the wiring 49 ((g) in FIG. 6).
  • the developing method at this time is the same as the developing method described above.
  • the specific protective layer-forming composition defined in the present invention does not contain (B) a photoacid generator
  • a photoresist is formed on the protective layer (coating layer) 48 before the step of irradiating ultraviolet rays 53. It is desirable to include the process of apply
  • a photoresist a well-known thing can be used, For example, JSR company make ELPAC THB151N etc. can be mentioned.
  • the specific protective layer-forming composition defined in the present invention is (B) light. It can be performed in the same manner as in the case of containing an acid generator.
  • the wiring 49 is formed by, for example, applying a photoresist, developing and exposing to form a pattern of an unnecessary portion of the wiring 49, vapor-depositing a metal for wiring formation by a vacuum vapor deposition method, and then using a stripping solution. This can be done by removing the part.
  • the stripper include alkaline solutions and organic solvents exemplified in the above-described developer.
  • the protective layer 51 for protecting the wiring 49 is formed by, for example, applying the protective layer forming composition of the present invention on the surface to be coated using a coating means such as a spin coater, and then applying the semiconductor layer described above. It is formed by photocuring in the same manner as the protective layer 48 for protection ((i) in FIG. 6).
  • distilled water 17.77 g was added dropwise, and after completion of the addition, the solution was stirred at 100 ° C. for 3 hours. Then, concentration was performed under reduced pressure, and finally a 1-methoxy-2-propanol solution of component (A) having a solid content adjusted to 70% by weight was obtained. This is referred to as “A-2”.
  • distilled water 50.55 g was added dropwise, and after completion of the addition, concentration was performed under reduced pressure, and finally a 1-methoxy-2-propanol solution of component (A) having a solid content adjusted to 60% by weight was prepared. Obtained. This is designated as “A-5”.
  • compositions “J-1” to “J-9” A-1 (solid content and organic solvent) 56.8 g, 1- (4,7-di-t-butoxy) -naphthyltetrahydrothiophenium trifluoromethanesulfonate 0.2 g, tri-n as a photoacid generator -0.02 g of octylamine, 0.04 g of dimethylpolysiloxane-polyoxyalkylene copolymer and 43.0 g of 1-methoxy-2-propanol were added and mixed uniformly to obtain a solid content concentration of 40% by mass.
  • the adjusted composition “J-1” was obtained.
  • “J-2” to “J-9” were prepared.
  • each of the protective layer forming compositions “J-1” to “J-9” was evaluated as follows. ⁇ Evaluation during curing> (1) Patterning shape On the sapphire substrate on which the semiconductor layer was formed, the protective layer forming composition was applied using a spin coater so that the thickness after drying was 2 ⁇ m, and then prebaked at 80 ° C. for 5 minutes. Next, using a contact mask aligner, ultraviolet rays were irradiated on the semiconductor layer through a photomask having a hole size (900 ⁇ m) so that the exposure amount was 100 mJ / cm 2 in the atmosphere. Next, after post-exposure baking at 80 ° C.
  • a protective layer-forming composition is dispensed on a 4 inch diameter fused quartz substrate, spin-coated to a thickness of about 2 ⁇ m, and cured by heating at 80 ° C. for 5 minutes and 250 ° C. for 60 minutes.
  • a membrane was prepared.
  • Adhesiveness was evaluated by a cross-cut test. The evaluation method conformed to JIS-K5400. The case where peeling was not confirmed after the test was indicated as “ ⁇ ”, and the case where peeling was observed even at one place was indicated as “x”.
  • each of the protective layer forming compositions “J-1”, “J-3” to “J-7” was evaluated as follows. As shown in FIG. 2D, the sapphire substrate 1, a plurality of semiconductor layers 2 formed on the upper surface of the sapphire substrate 1, a p-electrode 3 formed on the upper surface of the semiconductor layer 2, and p Metal diffusion prevention layer 4 formed so as to cover electrode 3, insulating layer 5 (upper surface 1a of sapphire substrate 1, end surface 2a of semiconductor layer 2, upper surface 2b of semiconductor layer 2 where p-electrode 3 is not formed, and And an element provided on a part of the metal diffusion preventing layer 4).
  • the height from the upper surface of the sapphire substrate 1 to the upper surface of the metal diffusion preventing layer 4 was 8 ⁇ m.
  • the protective layer-forming composition was applied using a spin coater so that the thickness of the insulating layer 5 after drying was 1 ⁇ m, and then prebaked at 80 ° C. for 5 minutes to form a coating layer.
  • the contact mask aligner was used to irradiate the coating layer with ultraviolet rays through a photomask having a hole size (900 ⁇ m) so that the exposure amount was 100 mJ / cm 2 in the atmosphere.
  • a 2.38 mass% TMAH aqueous solution was used as a developer and developed at room temperature for 1 minute to form a protective layer (Examples 10 to 10). 15).
  • each of the protective layer forming compositions “J-8” to “J-9” was evaluated as follows. On the same device as that prepared in Example 10, the composition for forming the protective layer was applied using a spin coater so that the thickness after drying on the surface of the insulating layer 5 was 3 ⁇ m, and then 200 ° C., 20 minutes. Pre-baked to form a coating layer. Next, baking was performed at 500 ° C. for 30 minutes in a diffusion furnace substituted with nitrogen. After applying a photoresist (ELPAC THB151N manufactured by JSR), using a contact mask aligner, an exposure amount is 100 mJ / cm 2 in the atmosphere through a photomask having a hole size (900 ⁇ m) on the coating layer.
  • ELPAC THB151N manufactured by JSR
  • compositions “K-1” to “K-7” were prepared.
  • Each of the protective layer forming compositions “K-1” to “K-7” was evaluated as follows. ⁇ Production of cured film> A protective layer forming composition “K-1” to “K-7” is dispensed onto a 4-inch diameter fused quartz substrate, spin-coated to a thickness of about 2 ⁇ m, and 80 ° C. for 5 minutes. And it heated at 250 degreeC x 60 minutes, and produced the cured film.
  • Each of the protective layer forming compositions “K-1” to “K-7” was evaluated as follows. [Examples 25 to 29] A support substrate 22 made of sapphire, an n-type cladding layer 23 formed on a region of the support substrate 22, and a p-type cladding formed on the upper surface of the n-type cladding layer 23 shown in FIG.
  • a plurality of semiconductor layers each of which includes a layer 25 and a quantum well light emitting layer (active layer) 24 interposed between the n-type cladding layer 23 and the p-type cladding layer 25;
  • An element including a p-type contact layer 26 formed on the upper surface and a p-type ohmic electrode 27 formed on the upper surface of the p-type contact layer 26 was prepared.
  • the height from the upper surface of the support substrate 22 to the upper surface of the p-type ohmic electrode 27 was 8 ⁇ m.
  • the composition for forming a protective layer is applied using a spin coater so that the thickness after drying on the surface of the p-type ohmic electrode 27 becomes 1 ⁇ m, and then at 80 ° C., 5 ° C.
  • the coating layer 30 was formed by pre-baking for minutes.
  • the semiconductor layer was irradiated with ultraviolet rays through the photomask 31 having a hole size (900 ⁇ m) so that the exposure amount was 100 mJ / cm 2 in the atmosphere.
  • a 2.38% TMAH aqueous solution was used as a developer, and development was performed at room temperature for 1 minute to form a protective layer (Examples 25 to 29). .
  • Examples 30 to 31 On the same device as that prepared in Example 25, the protective layer forming composition was applied using a spin coater so that the dried thickness on the surface of the p-type ohmic electrode 27 was 1 ⁇ m, and then 500 C. for 30 minutes to form a coating layer. Next, using a contact mask aligner, after applying a photoresist (ELPAC THB151N manufactured by JSR), baking was performed at 80 ° C. for 1 minute, and then a hole size (900 ⁇ m) photomask was applied on the coating layer. Ultraviolet rays were irradiated so that the exposure amount was 100 mJ / cm 2 in the atmosphere. Subsequently, after baking at 80 ° C. for 1 minute, a 2.38% TMAH aqueous solution was used as a developer and developed at room temperature for 1 minute to form a protective layer (Examples 30 to 31). .
  • ELPAC THB151N manufactured by JSR
  • Examples 32 to 36 6D, a support substrate 42 made of sapphire, a first conductive semiconductor layer 44 formed on the upper surface of the support substrate 42, and a region of the first conductive semiconductor layer 44.
  • a plurality of semiconductor layers which are a laminate composed of a second conductive semiconductor layer 46 positioned, and an active layer 45 interposed between the first conductive semiconductor layer 44 and the second conductive semiconductor layer 46
  • the height from the upper surface of the support substrate 42 to the upper surface of the transparent electrode layer 47 was 8 ⁇ m.
  • the protective layer-forming composition was applied using a spin coater so that the thickness of the transparent electrode layer 47 after drying was 1 ⁇ m, and then prebaked at 80 ° C. for 5 minutes to form a coating layer.
  • the contact mask aligner was used to irradiate the coating layer with ultraviolet rays through a photomask having a hole size (900 ⁇ m) so that the exposure amount was 100 mJ / cm 2 in the atmosphere.
  • a 2.38% TMAH aqueous solution was used as a developer, and development was performed at room temperature for 1 minute to form a protective layer (Examples 32-36). .
  • Examples 37 to 38 On the same device as that prepared in Example 32, the composition for forming a protective layer was applied using a spin coater so that the dried thickness on the surface of the transparent electrode layer 47 would be 1 ⁇ m, and then, 500 ° C., 30 For 5 minutes to form a coating layer. Next, using a contact mask aligner, after applying a photoresist (ELPAC THB151N manufactured by JSR), baking was performed at 80 ° C. for 1 minute, and then a hole size (900 ⁇ m) photomask was applied on the coating layer. Ultraviolet rays were irradiated so that the exposure amount was 100 mJ / cm 2 in the atmosphere. Subsequently, after baking at 80 ° C. for 1 minute, a 2.38% TMAH aqueous solution was used as a developer, and development was performed at room temperature for 1 minute to form a protective layer (Examples 37 to 38). .
  • ELPAC THB151N manufactured by JSR
  • the composition for forming a light-emitting element protective layer of the present invention is excellent in patterning property, covering property, crack resistance, and alkali resistance.
  • the light-emitting element having a protective layer formed using the composition defined in the present invention is excellent in transparency, light resistance, and heat resistance, so that, for example, effective use of emitted light from the side surface of the LED is possible. It can be seen that high performance as a light emitting element can be expected.
  • the light-emitting element of the present invention has a protective layer, it can be expected to prevent current leakage and short-circuit from the semiconductor layer over a long period of time.

Landscapes

  • Engineering & Computer Science (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Silicon Polymers (AREA)
  • Electroluminescent Light Sources (AREA)

Abstract

L'invention concerne un élément luminescent possédant d'excellentes caractéristiques de transparence, de résistance à la lumière, de résistance à la chaleur, et d'adhérence, lequel peut être produit en un nombre réduit d'étapes. Cet élément luminescent possède une plaque de support (9), une couche à semi-conducteurs (2) formée au-dessus de la plaque de support (9), une électrode (13) formée sur la face supérieure de la couche à semi-conducteurs (2) et une couche de protection (8) formée de manière à revêtir au moins la face latérale de la couche à semi-conducteurs (2). Cet élément luminescent se caractérise en ce que la couche de protection (8) est constituée d'un matériau durci d'une composition pour formation d'une couche de protection d'élément luminescent, laquelle comprend (A) au moins un élément choisi dans le groupe comprenant un composé silane hydrolysable représenté par la formule générale (1), （Ｒ1）PＳｉ（Ｘ）4-P, dans laquelle, R1 représente un groupe organique non hydrolysable possédant de 1 à 12 atomes de carbone, X représente un groupe hydrolysable et p représente un nombre entier de 0 à 3, un hydrolysat de celui-ci et un produit de condensation de celui-ci.
PCT/JP2010/062716 2009-07-31 2010-07-28 Élément luminescent, procédé de fabrication d'élément luminescent ainsi que composition pour la formation d'une couche de protection d'élément luminescent Ceased WO2011013709A1 (fr)

Applications Claiming Priority (8)

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JP2009-178713 2009-07-31
JP2009178713 2009-07-31
JP2009-235113 2009-10-09
JP2009235113 2009-10-09
JP2009235460 2009-10-09
JP2009-235460 2009-10-09
JP2009-288476 2009-12-18
JP2009288476 2009-12-18

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011125646A1 (fr) * 2010-03-31 2011-10-13 Jsr株式会社 Composition de résine durcissable et dispositif électroluminescent
CN108110116A (zh) * 2017-10-20 2018-06-01 华灿光电（浙江）有限公司 一种发光二极管芯片及其制作方法

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004247654A (ja) * 2003-02-17 2004-09-02 Sharp Corp 酸化物半導体発光素子およびその製造方法ならびに酸化物半導体発光素子を用いた半導体発光装置
JP2007243076A (ja) * 2006-03-11 2007-09-20 Nichia Chem Ind Ltd 発光装置及び発光装置の製造方法
JP2008186959A (ja) * 2007-01-29 2008-08-14 Toyoda Gosei Co Ltd Ｉｉｉ−ｖ族半導体素子、およびその製造方法
JP2009024041A (ja) * 2007-07-17 2009-02-05 Sekisui Chem Co Ltd 光半導体用封止剤及び光半導体素子
JP2009088482A (ja) * 2007-09-27 2009-04-23 Seoul Opto Devices Co Ltd 交流駆動型の発光ダイオード
JP2009102574A (ja) * 2007-10-25 2009-05-14 Sekisui Chem Co Ltd 光半導体素子用硬化性組成物
WO2009090867A1 (fr) * 2008-01-15 2009-07-23 Sekisui Chemical Co., Ltd. Matériau de réserve et stratifié

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004247654A (ja) * 2003-02-17 2004-09-02 Sharp Corp 酸化物半導体発光素子およびその製造方法ならびに酸化物半導体発光素子を用いた半導体発光装置
JP2007243076A (ja) * 2006-03-11 2007-09-20 Nichia Chem Ind Ltd 発光装置及び発光装置の製造方法
JP2008186959A (ja) * 2007-01-29 2008-08-14 Toyoda Gosei Co Ltd Ｉｉｉ−ｖ族半導体素子、およびその製造方法
JP2009024041A (ja) * 2007-07-17 2009-02-05 Sekisui Chem Co Ltd 光半導体用封止剤及び光半導体素子
JP2009088482A (ja) * 2007-09-27 2009-04-23 Seoul Opto Devices Co Ltd 交流駆動型の発光ダイオード
JP2009102574A (ja) * 2007-10-25 2009-05-14 Sekisui Chem Co Ltd 光半導体素子用硬化性組成物
WO2009090867A1 (fr) * 2008-01-15 2009-07-23 Sekisui Chemical Co., Ltd. Matériau de réserve et stratifié

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011125646A1 (fr) * 2010-03-31 2011-10-13 Jsr株式会社 Composition de résine durcissable et dispositif électroluminescent
CN108110116A (zh) * 2017-10-20 2018-06-01 华灿光电（浙江）有限公司 一种发光二极管芯片及其制作方法

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