JP2015145481A - Sealant for optical semiconductor device and optical semiconductor device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a sealant for an optical semiconductor device that can improve the intensity of light emitted from an optical semiconductor device, and can suppress the occurrence of cracks in the sealant and the peeling of the sealant even if the optical semiconductor device is exposed to a severe condition.SOLUTION: A sealant for an optical semiconductor device according to the present invention comprises a silicone compound that is liquid at 23°C, and a filler excluding a phosphor, wherein the filler has a circularity of 0.8 or more, and the filler has an average particle diameter of 0.2 μm or more and 10 μm or less.

Description

  The present invention relates to an encapsulant for an optical semiconductor device used for encapsulating an optical semiconductor element in an optical semiconductor device. The present invention also relates to an optical semiconductor device using the optical semiconductor device sealing agent.

  An optical semiconductor device such as a light emitting diode (LED) device has low power consumption and long life. Moreover, the optical semiconductor device can be used even in a harsh environment. Accordingly, optical semiconductor devices are used in a wide range of applications such as mobile phone backlights, liquid crystal television backlights, automobile lamps, lighting fixtures, and signboards.

  When an optical semiconductor element (for example, an LED), which is a light emitting element used in an optical semiconductor device, is in direct contact with the atmosphere, the light emission characteristics of the optical semiconductor element rapidly deteriorate due to moisture in the atmosphere or floating dust. For this reason, the said optical semiconductor element is normally sealed with the sealing compound for optical semiconductor devices.

In the following Patent Document 1, an epoxy resin (A) having two or more epoxy groups in one molecule, an acid anhydride curing agent (B), a curing accelerator (C), SiO ₂ , CaO and Spherical glass particles (D) containing Al ₂ O ₃ and having an average particle diameter of 5 μm or more and 100 μm or less, a benzophenone ultraviolet absorber (E), and spherical fused silica having a maximum particle diameter of 70 μm or less ( An encapsulant for optical semiconductor devices containing F) is disclosed. In the sealant, the spherical fused silica (F) is contained in an amount of 1% by weight to 5% by weight. In the cured product of the sealant, the water absorption is 2% or less, the light transmittance at a wavelength of 400 nm is 40% or more, 80% or less, and the light transmittance at a wavelength of 500 nm is 50% or more.

  Moreover, not only the sealing agent for optical semiconductor devices containing an epoxy resin but the sealing agent for optical semiconductor devices containing a silicone compound is also used widely. The sealing agent for optical semiconductor devices containing a silicone compound is disclosed by the following patent document 2, for example. The sealant described in Patent Document 2 below has a silicone resin having one or more reactive groups in one molecule and a refractive index of 1.42 to 1.51, and an average particle size of 200 nm or less. Containing certain spherical hydrophobic silica.

  Further, in Patent Document 3 below, a spherical silica having an average particle diameter in the range of 1 to 15 μm, a circularity of 0.9 or more, and containing titania in a ratio of 4 to 40 mol% with respect to silica. -Titania composite oxide particles are disclosed. In the spherical silica-titania composite oxide particles, diffraction peaks due to titania crystals are not confirmed in the X-ray diffraction measurement. Patent Document 3 describes the use of the spherical silica-titania composite oxide particles as an encapsulant for optical semiconductor devices.

JP 2005-89607 A JP 2011-162741 A JP 2012-162438 A

  In the conventional sealing agent for optical semiconductor devices as described in Patent Documents 1 and 2, the luminous intensity emitted from the optical semiconductor device using the sealing agent may not be sufficiently high. Moreover, even when the spherical silica-titania composite oxide particles described in Patent Document 3 are used as a sealant, the luminous intensity emitted from the optical semiconductor device may not be sufficiently high.

  Furthermore, in a conventional optical semiconductor device encapsulant containing an epoxy resin, if the optical semiconductor device using the encapsulant is used in a harsh environment that is repeatedly subjected to heating and cooling, the encapsulant is cracked. May occur or the sealant may peel off from the housing material or the like.

  An object of the present invention is to increase the luminous intensity emitted from an optical semiconductor device, and to suppress generation of cracks and peeling of the sealing agent even when the optical semiconductor device is exposed to harsh conditions. The sealing agent for optical semiconductor devices which can be provided is provided. Another object of the present invention is to provide an optical semiconductor device that uses the above-mentioned encapsulant for optical semiconductor devices, has a high luminous intensity, and does not easily decrease in luminous intensity even when exposed to high temperatures. .

  According to a wide aspect of the present invention, the composition contains a silicone compound that is liquid at 23 ° C. and a filler excluding a phosphor, the filler has a circularity of 0.8 or more, and the filler has an average particle size of 0. There is provided an encapsulant for optical semiconductor devices having a thickness of 2 μm or more and 10 μm or less.

  On the specific situation with the sealing compound for optical semiconductor devices which concerns on this invention, the said filler is a silica.

  It is preferable that the circularity of the filler is 0.9 or more. More preferably, the filler has a circularity of 0.96 or more.

  On the specific situation with the sealing compound for optical semiconductor devices which concerns on this invention, content of the said filler is 2 weight% or more and 30 weight% or less.

  In a specific aspect of the encapsulant for optical semiconductor devices according to the present invention, the encapsulant for optical semiconductor devices contains a hydrosilylation reaction catalyst, and the silicone compound is an organopolysiloxane capable of hydrosilylation reaction. is there.

  On the specific situation with the sealing compound for optical semiconductor devices which concerns on this invention, the said sealing compound for optical semiconductor devices contains fluorescent substance.

  An optical semiconductor device according to the present invention includes an optical semiconductor element and a sealing agent for an optical semiconductor device provided so as to seal the optical semiconductor element.

  An encapsulant for optical semiconductor devices according to the present invention contains a silicone compound that is liquid at 23 ° C. and a filler excluding a phosphor, and the circularity of the filler is 0.8 or more. Since the average particle diameter is 0.2 μm or more and 10 μm or less, the luminous intensity emitted from the optical semiconductor device using the optical semiconductor device sealing agent according to the present invention can be increased. Furthermore, even if the optical semiconductor device using the encapsulant for optical semiconductor devices according to the present invention is exposed to severe conditions, generation of cracks in the encapsulant and peeling of the encapsulant can be suppressed.

1A and 1B are a cross-sectional view and a perspective view schematically showing an optical semiconductor device using an optical semiconductor device sealing agent according to an embodiment of the present invention. FIG. 2 is a cross-sectional view schematically showing a modification of the optical semiconductor device shown in FIG. FIG. 3 is a cross-sectional view schematically showing a modification of the optical semiconductor device shown in FIG.

  Details of the present invention will be described below.

  The sealing agent for optical semiconductor devices which concerns on this invention contains the silicone compound which is liquid at 23 degreeC, and the filler except fluorescent substance. In the encapsulant for optical semiconductor devices according to the present invention, the circularity of the filler is 0.8 or more, and the average particle size of the filler is 0.2 μm or more and 10 μm or less.

  The filler has a circularity of 0.8 or more, and has a spherical shape or a nearly spherical shape. The average particle size of the filler is not more than 10 μm and is quite small.

  By adopting the above-described configuration in the encapsulant for optical semiconductor devices according to the present invention, the present inventors increase the luminous intensity emitted from the optical semiconductor device using the encapsulant for optical semiconductor devices according to the present invention. Found that you can. An optical semiconductor device in which an optical semiconductor element is disposed in a frame having a bottom surface portion (lower surface portion) and a side surface portion, and the optical semiconductor element is sealed with the optical semiconductor device sealing agent according to the present invention. It is possible to effectively increase the luminous intensity emitted from the top toward the top.

  In general, when a filler is added, it is expected that the light intensity is lowered by the filler blocking light. By controlling the circularity and the average particle diameter of the filler as described above, the present inventors rather increase the luminous intensity emitted from the optical semiconductor device using the optical semiconductor device sealing agent according to the present invention. Found that you can. In addition, the present inventors have found that in order to increase the luminous intensity emitted from the optical semiconductor device, it is necessary to control both the circularity and the average particle diameter of the filler.

  In order to increase the luminous intensity emitted from the optical semiconductor device, it is significant to control both the circularity and the average particle diameter of the filler.

  Moreover, since the sealing compound for optical semiconductor devices according to the present invention uses a silicone compound that is liquid at 23 ° C. instead of an epoxy resin, the optical semiconductor device using the sealing agent for optical semiconductor devices has a high temperature. Even if exposed to the bottom, cracking of the sealant or peeling of the sealant from the housing material or the like can be suppressed.

  Hereinafter, the detail of each component contained in the sealing compound for optical semiconductor devices which concerns on this invention is demonstrated.

(Silicone compound)
The said silicone compound contained in the said sealing agent is not specifically limited. Examples of the silicone compound include a thermosetting silicone compound, a photocurable silicone compound, and a hydrosilylation reactive silicone compound. The thermosetting silicone compound is used in combination with, for example, a thermosetting agent. The photocurable silicone compound is used in combination with, for example, a photocuring initiator. The silicone compound capable of hydrosilylation reaction is used in combination with a hydrosilylation reaction catalyst. As for the said silicone compound, only 1 type may be used and 2 or more types may be used together.

  From the viewpoint of further suppressing the generation of cracks in the sealant and the peeling of the sealant, the silicone compound is preferably an organopolysiloxane capable of a hydrosilylation reaction. In this case, it is preferable that the sealing agent contains a hydrosilylation reaction catalyst described later.

  Each of the sealing agent and the organopolysiloxane capable of hydrosilylation reaction includes a first organopolysiloxane having two or more alkenyl groups and a second organopolysiloxane having two or more hydrogen atoms bonded to silicon atoms. It is preferable to contain posilyloxane. The first organopolysiloxane preferably does not have a hydrogen atom bonded to a silicon atom. The carbon atom in the carbon-carbon double bond of the alkenyl group may be bonded to the silicon atom, and the carbon atom different from the carbon atom in the carbon-carbon double bond of the alkenyl group is in the silicon atom. It may be bonded. In the first organopolysiloxane, the alkenyl group is preferably directly bonded to a silicon atom. Each of the first and second organopolysiloxanes may be used alone or in combination of two or more.

  From the viewpoint of further suppressing the generation of cracks in the sealant and the peeling of the sealant, the first organopolysiloxane preferably has an aryl group. In the first organopolysiloxane, the aryl group is preferably directly bonded to a silicon atom. From the viewpoint of further suppressing the generation of cracks in the sealant and the peeling of the sealant, the second organopolysiloxane preferably has an aryl group. In the second organopolysiloxane, the aryl group is preferably directly bonded to the silicon atom. As said aryl group, an unsubstituted phenyl group and a substituted phenyl group are mentioned.

  Each of the number average molecular weights (Mn) of the organopolysiloxane capable of hydrosilylation reaction and the first and second organopolysiloxanes is preferably 500 or more, more preferably 800 or more, still more preferably 1000 or more, preferably 50000 or less, more preferably 15000 or less. When the number average molecular weight is not less than the above lower limit, volatile components are reduced during thermosetting, and the thickness of the sealant is difficult to decrease under a high temperature environment. When the number average molecular weight is not more than the above upper limit, viscosity adjustment is easy.

  The number average molecular weight (Mn) is a value obtained by using polystyrene as a standard substance using gel permeation chromatography (GPC). The number average molecular weight (Mn) was measured using two measuring devices manufactured by Waters (column: Shodex GPC LF-804 (length: 300 mm) manufactured by Showa Denko KK), measuring temperature: 40 ° C., flow rate: 1 mL / min, solvent: Tetrahydrofuran, standard substance: polystyrene) means a value measured.

  The method for synthesizing the organopolysiloxane capable of hydrosilylation and the first and second organopolysiloxanes is not particularly limited, and is a method in which an alkoxysilane compound is hydrolyzed to undergo a condensation reaction, and a chlorosilane compound is hydrolyzed. The method of condensing is mentioned. A method of hydrolyzing the alkoxysilane compound is preferable because the reaction can be easily controlled.

  Examples of the method for hydrolyzing and condensing the alkoxysilane compound include a method of reacting the alkoxysilane compound in the presence of water and an acidic catalyst or a basic catalyst. Further, the disiloxane compound may be hydrolyzed and used.

  Examples of the organosilicon compound for introducing an aryl group into the organopolysiloxane capable of hydrosilylation reaction and the organosilicon compound for introducing an aryl group into the first and second organopolysiloxanes include triphenylmethoxysilane. , Triphenylethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, methyl (phenyl) dimethoxysilane, and phenyltrimethoxysilane.

  Examples of the organosilicon compound for introducing an alkenyl group into the organopolysiloxane capable of hydrosilylation reaction and the organosilicon compound for introducing an alkenyl group into the first organopolysiloxane include vinyltrimethoxysilane, vinyltrimethoxysilane. Examples include ethoxysilane, vinylmethyldimethoxysilane, methoxydimethylvinylsilane, vinyldimethylethoxysilane, and 1,3-divinyl-1,1,3,3-tetramethyldisiloxane.

  Organosilicon compound for introducing hydrogen atoms bonded to silicon atoms into the organopolysiloxane capable of hydrosilylation reaction, and organosilicon compound for introducing hydrogen atoms bonded to silicon atoms into the second organopolysiloxane Examples thereof include trimethoxysilane, triethoxysilane, methyldimethoxysilane, methyldiethoxysilane, and 1,1,3,3-tetramethyldisiloxane.

  Examples of other organosilicon compounds that can be used to obtain the above hydrosilylation-responsive organopolysiloxane and the first and second organopolysiloxanes include trimethylmethoxysilane, trimethylethoxysilane, and dimethyldimethoxysilane. , Dimethyldiethoxysilane, isopropyl (methyl) dimethoxysilane, cyclohexyl (methyl) dimethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, hexyltrimethoxysilane, octyltrimethoxysilane, etc. Is mentioned.

  Examples of the acidic catalyst include inorganic acids, organic acids, acid anhydrides of inorganic acids and derivatives thereof, and acid anhydrides of organic acids and derivatives thereof. Examples of the basic catalyst include alkali metal hydroxides, alkali metal alkoxides, and alkali metal silanol compounds.

  The content of the silicone compound and the organopolysiloxane capable of hydrosilylation reaction is preferably 70% by weight or more, more preferably 80% by weight or more, and still more preferably 85% by weight or more, in 100% by weight of the sealant. Is 98% by weight or less, more preferably 97% by weight or less, and still more preferably 96% by weight or less. When the contents of the silicone compound and the organopolysiloxane capable of hydrosilylation are not less than the above lower limit and not more than the above upper limit, the light intensity emitted from the optical semiconductor device is further increased.

  The content of the second organopolysiloxane is preferably 10 parts by weight or more, more preferably 30 parts by weight or more, still more preferably 50 parts by weight or more, preferably 100 parts by weight of the first organopolysiloxane. 400 parts by weight or less, more preferably 300 parts by weight or less, still more preferably 200 parts by weight or less. When the content of the second organopolysiloxane with respect to 100 parts by weight of the first organopolysiloxane is not less than the above lower limit and not more than the above upper limit, the curability and storage stability of the sealant are further enhanced, and The heat resistance of the sealant is further increased.

(Catalyst for hydrosilylation reaction)
The sealing agent may contain a hydrosilylation reaction catalyst. The catalyst for hydrosilylation reaction is a catalyst for hydrosilylation reaction of the organopolysiloxane capable of hydrosilylation reaction. The hydrosilylation reaction catalyst is a catalyst that causes a hydrosilylation reaction between an alkenyl group in the first organopolysiloxane and a hydrogen atom bonded to a silicon atom in the second organopolysiloxane.

  As the hydrosilylation reaction catalyst, various catalysts that cause the hydrosilylation reaction to proceed can be used. Examples of the hydrosilylation reaction catalyst include platinum-based catalysts, rhodium-based catalysts, and palladium-based catalysts. Since the transparency of the sealant can be increased, a platinum-based catalyst is preferable. As for the said catalyst for hydrosilylation reaction, only 1 type may be used and 2 or more types may be used together.

  Examples of the platinum-based catalyst include platinum powder, chloroplatinic acid, a platinum-alkenylsiloxane complex, a platinum-olefin complex, and a platinum-carbonyl complex. In particular, a platinum-alkenylsiloxane complex or a platinum-olefin complex is preferable.

  Examples of the alkenylsiloxane in the platinum-alkenylsiloxane complex include 1,3-divinyl-1,1,3,3-tetramethyldisiloxane and 1,3,5,7-tetramethyl-1,3,5. , 7-tetravinylcyclotetrasiloxane and the like. Examples of the olefin in the platinum-olefin complex include allyl ether and 1,6-heptadiene.

  Since the stability of the platinum-alkenylsiloxane complex and platinum-olefin complex can be improved, alkenylsiloxane, organosiloxane oligomer, allyl ether or olefin is added to the platinum-alkenylsiloxane complex or platinum-olefin complex. Is preferred. The alkenylsiloxane is preferably 1,3-divinyl-1,1,3,3-tetramethyldisiloxane. The organosiloxane oligomer is preferably a dimethylsiloxane oligomer. The olefin is preferably 1,6-heptadiene.

  From the viewpoint of further suppressing the decrease in luminous intensity when used in a state of being energized in a harsh environment under high temperature or high humidity, and further suppressing discoloration of the sealant, the hydrosilylation reaction The catalyst is preferably an alkenyl complex of platinum. From the viewpoint of further suppressing the decrease in luminous intensity when used in a state of being energized in a harsh environment at high temperature or high humidity, and further suppressing discoloration of the sealant, the above platinum alkenyl complex Is preferably a platinum alkenyl complex obtained by reacting chloroplatinic acid hexahydrate with 6 equivalents or more of a bifunctional or higher alkenyl compound. In this case, the platinum alkenyl complex is a reaction product of chloroplatinic acid hexahydrate and 6 equivalents or more of a bifunctional or higher alkenyl compound. Moreover, the transparency of the sealant can be increased by using the platinum alkenyl complex. As for the said platinum alkenyl complex, only 1 type may be used and 2 or more types may be used together.

It is preferable to use the chloroplatinic acid hexahydrate (H ₂ PtCl ₆ .6H ₂ O) as a platinum raw material for obtaining the platinum alkenyl complex.

  Examples of the bifunctional or higher alkenyl compound of 6 equivalents or more for obtaining the platinum alkenyl include 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, 1,3-dimethyl- Examples include 1,3-diphenyl-1,3-divinyldisiloxane and 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane.

  Regarding the “equivalent” in the bifunctional or higher alkenyl compound of 6 equivalents or more, the equivalent weight of 1 mol of the bifunctional or higher alkenyl compound is 1 equivalent to 1 mol of the chloroplatinic acid hexahydrate. . It is preferable that the bifunctional or higher alkenyl compound having 6 equivalents or more is 50 equivalents or less.

  Examples of the solvent used to obtain the platinum alkenyl complex include alcohol solvents such as methanol, ethanol, 2-propanol, and 1-butanol. Aromatic solvents such as toluene and xylene may be used. As for the said solvent, only 1 type may be used and 2 or more types may be used together.

  In order to obtain the platinum alkenyl complex, a monofunctional vinyl compound may be used in addition to the above components. Examples of the monofunctional vinyl compound include trimethoxyvinylsilane, triethoxyvinylsilane, and vinylmethyldimethoxysilane.

  Regarding the reaction product of chloroplatinic acid hexahydrate and 6 equivalents or more of bifunctional or higher alkenyl compound, platinum element and 6 equivalents or more of bifunctional or higher alkenyl compound are covalently bonded or distributed. Or are covalently bonded and coordinated.

  In the sealant, the content of the hydrosilylation reaction catalyst is preferably 0.01 ppm or more, more preferably 1 ppm or more, preferably by weight unit of metal atom (in the case of platinum alkenyl complex, platinum atom). 1000 ppm or less, more preferably 500 ppm or less. When the content of the hydrosilylation catalyst is equal to or higher than the lower limit, it is easy to sufficiently cure the sealant. If the content of the hydrosilylation reaction catalyst is not more than the above upper limit, the problem of coloring of the sealant hardly occurs.

(Fillers other than phosphor)
The filler excluding the phosphor is not particularly limited as long as the circularity is 0.8 or more and the average particle size is 0.2 μm or more and 10 μm or less. As for the said filler, only 1 type may be used and 2 or more types may be used together.

  As the filler, silica, mica, beryllia, potassium titanate, barium titanate, strontium titanate, calcium titanate, antimony oxide, aluminum borate, aluminum hydroxide, magnesium oxide, calcium carbonate, magnesium carbonate, aluminum carbonate, Examples include calcium silicate, aluminum silicate, magnesium silicate, calcium phosphate, calcium sulfate, barium sulfate, silicon nitride, boron nitride, clay such as baked clay, talc, silicon carbide, crosslinked acrylic resin particles and silicone particles.

  From the viewpoint of effectively increasing the luminous intensity emitted from the optical semiconductor device and further increasing the heat resistance and light resistance of the encapsulant, the filler is preferably an inorganic filler, more preferably silica.

  The filler preferably does not contain titania (titanium dioxide), and is preferably not a silica-titania composite oxide. Since titania has the property of absorbing ultraviolet light (380 nm or less), there is a tendency to reduce the luminosity property of an optical semiconductor device using a sealant. The filler is preferably not glass particles.

  The circularity of the filler is 0.8 or more. Therefore, the filler has a shape close to a sphere. From the viewpoint of further increasing the luminous intensity emitted from the optical semiconductor device, the shape of the filler is preferably closer to a true sphere. Therefore, from the viewpoint of further increasing the luminous intensity emitted from the optical semiconductor device, the circularity of the filler is preferably 0.9 or more, more preferably 0.96 or more, still more preferably 0.97 or more, and particularly preferably 0. .98 or more, most preferably 0.99 or more. The circularity is determined from the projected image of the filler.

  The average particle size of the filler is 0.2 μm or more and 10 μm or less. The filler is not blended mainly for the purpose of reducing the viscosity of the sealant, but is blended to further increase the luminous intensity emitted from the optical semiconductor device. Therefore, the average particle size of the filler is limited to the above lower limit and the upper limit.

  From the viewpoint of further increasing the luminous intensity emitted from the optical semiconductor device, the average particle size of the filler is preferably 7 μm or less, more preferably less than 5 μm, and even more preferably 4.9 μm or less.

  The average particle size of the filler is a particle size value when the integrated value is 50% in the volume-based particle size distribution curve. The average particle size can be measured using, for example, a laser beam type particle size distribution meter. As a commercial product of the laser beam type particle size distribution analyzer, “LS 13 320” manufactured by Beckman Coulter, Inc. can be cited.

  In 100% by weight of the sealing agent, the content of the filler excluding the phosphor is preferably 2% by weight or more, more preferably 3% by weight or more, still more preferably 4% by weight or more, preferably 30% by weight or less. Preferably it is 20 weight% or less, More preferably, it is 15 weight% or less, More preferably, it is 12 weight% or less. When the content of the filler in 100% by weight of the sealing agent is not less than the above lower limit and not more than the above upper limit, the luminous intensity emitted from the optical semiconductor device is further increased.

  The filler content excluding the phosphor is preferably 2% by weight or more, more preferably 3% by weight or more, and still more preferably 4% by weight with respect to 100 parts by weight of the silicone compound and the organopolysiloxane capable of hydrosilylation reaction. % Or more, preferably 30% by weight or less, more preferably 20% by weight or less, still more preferably 15% by weight or less, and still more preferably 12% by weight or less. When the content of the filler with respect to 100 parts by weight of the silicone compound and the organopolysiloxane capable of hydrosilylation reaction is not less than the lower limit and not more than the upper limit, the luminous intensity emitted from the optical semiconductor device is further increased.

(Phosphor)
The sealing agent may further contain a phosphor. The above phosphor acts to absorb light emitted from a light emitting element that is sealed using a sealant for an optical semiconductor device and generate fluorescence to finally obtain light of a desired color. To do. The phosphor is excited by light emitted from the light emitting element to emit fluorescence, and light of a desired color can be obtained by a combination of light emitted from the light emitting element and fluorescence emitted from the phosphor.

  For example, when it is intended to finally obtain white light using an ultraviolet LED chip as a light emitting element, it is preferable to use a combination of a blue phosphor, a red phosphor and a green phosphor. When it is intended to finally obtain white light using a blue LED chip as a light emitting element, it is preferable to use a combination of a green phosphor and a red phosphor, or a yellow phosphor. As for the said fluorescent substance, only 1 type may be used and 2 or more types may be used together.

The blue phosphor is not particularly limited. For example, (Sr, Ca, Ba, Mg) ₁₀ (PO ₄ ) ₆ Cl ₂ : Eu, (Ba, Sr) MgAl ₁₀ O ₁₇ : Eu, (Sr, Ba) ₃ MgSi ₂ O ₈ : Eu and the like.

It is not particularly restricted but includes the red phosphor, for _{example, (Sr, Ca) S:} Eu, (Ca, Sr) 2 Si 5 N 8: Eu, CaSiN 2: Eu, CaAlSiN 3: Eu, Y 2 O 2 S : Eu, La ₂ O ₂ S: Eu, LiW ₂ O ₈ : (Eu, Sm), (Sr, Ca, Bs, Mg) ₁₀ (PO ₄ ) ₈ Cl ₂ : (Eu, Mn), Ba ₃ MgSi ₂ And O ₈ : (Eu, Mn).

The green phosphor is not particularly limited, and for example, Y ₃ (Al, Ga) ₅ O ₁₂ : Ce, SrGa ₂ S ₄ : Eu, Ca ₃ Sc ₂ Si ₃ O ₁₂ : Ce, SrSiON: Eu, ZnS: (Cu, Al), BaMgAl ₁₀ O ₁₇ (Eu, Mn), SrAl ₂ O ₄ : Eu, and the like.

Is not particularly restricted but includes the yellow phosphor, for _{example, Y 3 Al 5 O 12:} Ce, (Y, Gd) 3 Al 5 O 12: Ce, Tb 3 Al 5 O 12: Ce, CaGa 2 S 4: Eu , Sr ₂ SiO ₄ : Eu, and the like.

  Furthermore, examples of the phosphor include perylene compounds that are organic phosphors.

  The phosphor content can be adjusted as appropriate so as to obtain light of a desired color, and is not particularly limited. In 100% by weight of the sealant, the content of the phosphor is preferably 0.1% by weight or more, and preferably 40% by weight or less. The content of the phosphor is preferably 0.1 parts by weight or more and preferably 40 parts by weight or less with respect to 100 parts by weight of all components excluding the phosphor of the sealant.

(Coupling agent)
The sealing agent may further contain a coupling agent in order to impart adhesiveness.

  It does not specifically limit as said coupling agent, For example, a silane coupling agent etc. are mentioned. Examples of the silane coupling agent include vinyltriethoxysilane, vinyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and γ-methacryloxypropyltrimethoxy. Examples include silane, γ-aminopropyltrimethoxysilane, and N-phenyl-3-aminopropyltrimethoxysilane. As for a coupling agent, only 1 type may be used and 2 or more types may be used together.

(Other ingredients)
The sealing agent may further contain additives such as a dispersant, an antioxidant, an antifoaming agent, a colorant, a modifier, a leveling agent, a light diffusing agent, or a flame retardant, as necessary.

(Details and applications of sealants for optical semiconductor devices)
When the sealing agent has thermosetting properties, the curing temperature of the sealing agent is not particularly limited. The curing temperature of the sealing agent is preferably 80 ° C. or higher, more preferably 100 ° C. or higher, preferably 180 ° C. or lower, more preferably 150 ° C. or lower. When the curing temperature is equal to or higher than the above lower limit, the sealant is sufficiently cured. When the curing temperature is not more than the above upper limit, the package is unlikely to be thermally deteriorated.

  The curing method is not particularly limited, but it is preferable to use a step cure method. The step cure method is a method in which the resin is temporarily cured at a low temperature and then cured at a high temperature. By using the step cure method, curing shrinkage of the sealant can be suppressed.

  The method for producing the sealant is not particularly limited, for example, using a mixer such as a homodisper, a homomixer, a universal mixer, a planetarium mixer, a kneader, a three roll or a bead mill, at room temperature or under heating, Examples include a method of mixing the silicone compound, a filler excluding the phosphor, and other components blended as necessary.

  The light-emitting element is not particularly limited as long as it is a light-emitting element using a semiconductor. For example, when the light-emitting element is a light-emitting diode, for example, a structure in which a semiconductor material for forming an LED is stacked on a substrate can be given. In this case, examples of the semiconductor material include GaAs, GaP, GaAlAs, GaAsP, AlGaInP, GaN, InN, AlN, InGaAlN, and SiC.

  Examples of the material for the substrate include sapphire, spinel, SiC, Si, ZnO, and GaN single crystal. Further, a buffer layer may be formed between the substrate and the semiconductor material as necessary. Examples of the material of the buffer layer include GaN and AlN.

  Specific examples of the optical semiconductor device according to the present invention include a light emitting diode device, a semiconductor laser device, and a photocoupler. Such optical semiconductor devices include, for example, backlights such as liquid crystal displays, illumination, various sensors, light sources such as printers and copiers, vehicle measuring instrument light sources, signal lights, indicator lights, display devices, and light sources for planar light emitters. , Displays, decorations, various lights, switching elements and the like.

  In the optical semiconductor device according to the present invention, the light emitting element formed of the optical semiconductor is sealed with the optical semiconductor device sealing agent according to the present invention. In the optical semiconductor device according to the present invention, an optical semiconductor device sealing agent is disposed so as to seal a light emitting element formed of an optical semiconductor such as an LED. For this reason, the luminous intensity emitted from the optical semiconductor device can be increased. Cracks are less likely to occur in the encapsulant for optical semiconductor devices that seals the light emitting elements, and peeling from the package can be prevented. Moreover, the luminous intensity emitted from the optical semiconductor device can be increased, and heat resistance, weather resistance, and gas barrier properties can also be improved.

(Embodiment of optical semiconductor device)
1A and 1B schematically show an optical semiconductor device using an optical semiconductor device sealing agent according to an embodiment of the present invention in a cross-sectional view and a perspective view.

  The optical semiconductor device 1 according to this embodiment includes a lead frame 2, an optical semiconductor element 3, a first molded body 4, and a second molded body 5. The optical semiconductor element 3 is preferably a light emitting diode (LED). The first molded body 4 and the second molded body 5 are not formed integrally, but are two other members. The first molded body 4 and the second molded body 5 may be integrally formed. The first molded body 4 is a frame portion. The 2nd molded object 5 is a bottom part. In the optical semiconductor device 1, the molded body has a frame portion (first molded body 4) and a bottom portion (second molded body 5). The frame part which is the 1st molded object 4 is an outer wall part. The frame part which is the 1st molded object 4 is cyclic | annular.

  An optical semiconductor element 3 is mounted and arranged on the lead frame 2. A first molded body 4 (frame portion) is disposed on the lead frame 2. A second molded body 5 (bottom part) is disposed between the plurality of lead frames 2 and below the lead frames 2. Note that the molded body or the bottom member may not be disposed below the lead frame, and the lead frame may be exposed. The optical semiconductor element 3 is disposed inside the first molded body 4. A first molded body 4 is disposed on the side of the optical semiconductor element 3, and the first molded body 4 is disposed so as to surround the optical semiconductor element 3. The 1st molded object 4 has light reflectivity, and has a light reflection part in the inner surface 4a. That is, the inner surface 4a of the first molded body 4 is a light reflecting portion. Therefore, the periphery of the optical semiconductor element 3 is surrounded by the inner surface 4 a having the light reflectivity of the first molded body 4.

  The first molded body 4 (frame part) has an opening through which light emitted from the optical semiconductor element 3 is extracted. The first and second molded bodies 4 and 5 are white. The inner surface 4a of the first molded body 4 is formed such that the diameter of the inner surface 4a increases as it goes toward the opening end. Therefore, of the light emitted from the optical semiconductor element 3, the light indicated by the arrow B reaching the inner surface 4 a is reflected by the inner surface 4 a and travels forward of the optical semiconductor element 3.

  The optical semiconductor element 3 is connected to the lead frame 2 using a die bond material 6. The die bond material 6 has conductivity. A bonding pad (not shown) provided on the optical semiconductor element 3 and the lead frame 2 are electrically connected by a bonding wire 7. A sealing agent 8 is filled in the region surrounded by the inner surface 4 a of the first molded body 4 so as to seal the optical semiconductor element 3 and the bonding wire 7. As the sealant 8, the sealant for optical semiconductor devices according to an embodiment of the present invention is used. In the case where the encapsulant for optical semiconductor devices has curability, the encapsulant 8 is a cured product of the encapsulant for optical semiconductor devices.

  In the optical semiconductor device 1, when the optical semiconductor element 3 is driven, light is emitted as indicated by a broken line A. In the optical semiconductor device 1, the light reaching the inner surface 4 a of the first molded body 4 as indicated by the arrow B as well as the light irradiated from the optical semiconductor element 3 to the side opposite to the upper surface of the lead frame 2, that is, the upper side. There is also light that is reflected by the light. Therefore, the brightness of the light extracted from the optical semiconductor device 1 is bright.

  FIG. 2 shows a modification of the optical semiconductor device 1 shown in FIG. The optical semiconductor device 1 shown in FIG. 1 differs from the optical semiconductor device 21 shown in FIG. 2 only in the electrical connection structure using the die bonding materials 6 and 22 and the bonding wires 7 and 23. The die bond material 6 in the optical semiconductor device 1 has conductivity. On the other hand, the optical semiconductor device 21 has a die bond material 22, and the die bond material 22 does not have conductivity. In the optical semiconductor device 1, a bonding pad (not shown) provided on the optical semiconductor element 3 and a lead frame 2 (lead frame located on the right side in FIG. 1A) are electrically connected by a bonding wire 7. Has been. The optical semiconductor device 21 has a bonding wire 23 in addition to the bonding wire 7. In the optical semiconductor device 21, a bonding pad (not shown) provided on the optical semiconductor element 3 and a lead frame 2 (a lead frame located on the right side in FIG. 2) are electrically connected by a bonding wire 7. Further, a bonding pad (not shown) provided on the optical semiconductor element 3 and the lead frame 2 (lead frame located on the left side in FIG. 2) are electrically connected by a bonding wire 23.

  FIG. 3 shows a modification of the optical semiconductor device 21 shown in FIG. The optical semiconductor device 31 shown in FIG. 3 is also a modification of the optical semiconductor device 1 shown in FIG. The optical semiconductor device 21 shown in FIG. 2 and the optical semiconductor device 31 shown in FIG. 3 differ only in the structures of the first and second molded bodies 4 and 5 and the molded body 32. In the optical semiconductor device 21, the first and second molded bodies 4 and 5 are used. The first molded body 4 is disposed on the lead frame 2, and the second molded body 5 includes a plurality of second molded bodies 5. Between the lead frames 2 and below the lead frame 2. On the other hand, in the optical semiconductor device 31, one molded body 32 is used. The molded body 32 has a frame portion 32 a disposed on the lead frame 2 and a filling portion 32 b disposed between the plurality of lead frames 2. The frame part 32a and the filling part 32b are integrally formed. As described above, the optical semiconductor device only needs to have a frame portion disposed on the side of the optical semiconductor element in the optical semiconductor device. The molded body may not be disposed below the lead frame. The molded body may not have a bottom portion disposed below the lead frame. The back surface of the lead frame may be exposed.

  The structures shown in FIGS. 1 to 3 are merely examples of the optical semiconductor device according to the present invention, and can be appropriately modified to a structure of a molded body, a mounting structure of an optical semiconductor element, and the like.

  Hereinafter, the present invention will be clarified by giving specific examples and comparative examples of the present invention. The present invention is not limited to the following examples.

(Silicone compound)
First organopolysiloxane A ((Me ₃ SiO _1/2 ) _0.19 (Me ₂ SiO _2/2 ) _0.25 (Ph ₂ SiO _2/2 ) _0.25 (ViSiO _3/2 ) _0.31 Liquid at 23 ° C)
First organopolysiloxane B ((Me ₂ SiO _2/2 ) _0.33 (Ph ₂ SiO _2/2 ) _0.42 (ViSiO _3/2 ) _0.25 , liquid at 23 ° C.)
First organopolysiloxane C ((Me ₂ SiO _2/2 ) _0.45 (Ph ₂ SiO _2/2 ) _0.30 (ViSiO _3/2 ) _0.25 , liquid at 23 ° C.)
Second organopolysiloxane A ((Me ₃ SiO _1/2 ) _0.05 (Me ₂ SiO _2/2 ) _0.19
(Ph ₂ SiO _2/2 ) _0.26 (PhSiO _3/2 ) _0.27 (HMe ₂ SiO _1/2 ) _0.23 , liquid at 23 ° C.)
Second organopolysiloxane B ((Me ₃ SiO _1/2 ) _0.09 (Me ₂ SiO _2/2 ) _0.27 (PhSiO _3/2 ) _0.41 (HMe ₂ SiO _1/2 ) _0.23 Liquid at 23 ° C)
Second organopolysiloxane C ((Me ₃ SiO _1/2 ) _0.19 (Ph ₂ SiO _2/2 ) _0.16 (PhSiO _3/2 ) _0.46 (HMe ₂ SiO _1/2 ) _0.19 Liquid at 23 ° C)
In the above composition formula, Me represents a methyl group, Ph represents a phenyl group, and Vi represents a vinyl group.

(Epoxy resin)
Epoxy resin A ("Celoxide 2021P" manufactured by Daicel)

(Fillers excluding phosphors)
Silica A (roundness 0.98, average particle size 1.0 μm)
Silica B (circularity 0.97, average particle size 6.0 μm)
Silica C (roundness 0.97, average particle size 0.25 μm)
Silica D (roundness 0.98, average particle size 2.0 μm)
Silica E (circularity 0.72, average particle size 1.0 μm)
Silica F (roundness 0.96, average particle size 15.0 μm)

(Catalyst for hydrosilylation reaction)
Hydrosilylation catalyst A (platinum 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex)

(Thermosetting agent)
Thermosetting agent A (“Rikacid MH-700G” manufactured by Shin Nippon Chemical Co., Ltd.)

(Phosphor)
Phosphor A (NYAG-4)
Phosphor B (EY-4453)

Example 1
5 g of the first organopolysiloxane A, 5 g of the second organopolysiloxane A, and the catalyst A for hydrosilylation reaction with respect to the whole sealant in an amount of 50 ppm by weight of platinum metal, 0.5 g of silica A, Phosphor A 0.5 g was mixed and defoamed to obtain a sealant.

(Examples 2-12 and Comparative Examples 1-3)
A sealant was obtained in the same manner as in Example 1 except that the types and blending amounts of the blending components were changed as shown in Table 1 below.

(Evaluation)
In a structure in which a light emitting element having a main emission peak of 460 nm is mounted on a silver-plated polyphthalamide housing material with a lead electrode by a die bond material, and the light emitting element and the lead electrode are connected by a gold wire. The obtained sealing agent was injected, and cured by heating at 150 ° C. for 2 hours, thereby producing an optical semiconductor device. Using this optical semiconductor device, the following items were evaluated.

(Luminosity)
With respect to the obtained optical semiconductor device, the light intensity (initial light intensity) when a current of 60 mA was passed through the light emitting element was measured at a temperature of 23 ° C. using a light intensity measuring device (“OL770” manufactured by Optronic Laboratories). The initial luminous intensity was determined according to the following criteria based on the luminous intensity when no silica was added.

[Initial Luminance Criteria]
○: Initial luminous intensity improved by 3% or more △: Initial luminous intensity improved by 1% or more and less than 3% ×: Initial luminous intensity improved by less than 1%

(Thermal shock test)
The obtained optical semiconductor device was held at −45 ° C. for 5 minutes using a liquid bath thermal shock tester (“TSB-51” manufactured by ESPEC), then heated to 125 ° C., and 5 at 125 ° C. A cold cycle test was performed in which the temperature was lowered to -45 ° C after being held for 1 minute, and the cycle was one cycle. 20 samples were taken out after 500 cycles, 1000 cycles, 1500 cycles, 2000 cycles and 3000 cycles, respectively.

  The sample was observed with a stereomicroscope ("SMZ-10" manufactured by Nikon Corporation). It was observed whether or not cracks were generated in the sealants (cured products) for 20 samples of the optical semiconductor device, or whether the cured products were peeled off from the package or the electrode, and cracks or peeling occurred. The number of samples (NG number) was counted.

(High temperature and high humidity energization test)
In a state where a current of 100 mA was passed through the light emitting element, the optical semiconductor device was placed in a chamber under an atmosphere of 85 ° C. and a relative humidity of 85 RH% and left for 1000 hours. After 1000 hours, the light intensity when a current of 60 mA was passed through the light emitting element was measured at a temperature of 23 ° C. using a light intensity measuring device (“OL770” manufactured by Optronic Laboratories). The rate of decrease in luminous intensity relative to the initial luminous intensity was calculated. The high temperature and high humidity energization test was judged according to the following criteria.

[Criteria for high-temperature and high-humidity current test]
○: Decrease rate of luminosity is less than 5% △: Decrease rate of luminosity is 5% or more and less than 10% ×: Decrease rate of luminosity is 10% or more

  The composition and results are shown in Table 1 below.

DESCRIPTION OF SYMBOLS 1 ... Optical semiconductor device 2 ... Lead frame 3 ... Optical semiconductor element 4 ... 1st molded object 4a ... Inner surface 5 ... 2nd molded object 6 ... Die bond material 7 ... Bonding wire 8 ... Sealant 21 ... Optical semiconductor device 22 ... Die bond material 23 ... Bonding wire 31 ... Optical semiconductor device 32 ... Molded body 32a ... Frame part 32b ... Filling part

Claims (8)

Containing a silicone compound which is liquid at 23 ° C. and a filler excluding a phosphor,
The sealing agent for optical semiconductor devices whose circularity of the said filler is 0.8 or more, and whose average particle diameter of the said filler is 0.2 micrometer or more and 10 micrometers or less.   The encapsulant for optical semiconductor devices according to claim 1, wherein the filler is silica.   The encapsulant for optical semiconductor devices according to claim 1, wherein the filler has a circularity of 0.9 or more.   The encapsulant for optical semiconductor devices according to claim 3, wherein the filler has a circularity of 0.96 or more.   The encapsulant for optical semiconductor devices according to any one of claims 1 to 4, wherein the filler content is 2 wt% or more and 30 wt% or less. Containing a hydrosilylation catalyst,
The encapsulant for optical semiconductor devices according to claim 1, wherein the silicone compound is an organopolysiloxane capable of hydrosilylation reaction.   The sealing agent for optical semiconductor devices of any one of Claims 1-6 containing fluorescent substance.   An optical semiconductor device comprising: an optical semiconductor element; and the optical semiconductor device sealing agent according to claim 1, which is provided so as to seal the optical semiconductor element.