CN209496895U - The encapsulating structure and light source of composite fluorescence glue film, semiconductor light-emitting apparatus - Google Patents

The encapsulating structure and light source of composite fluorescence glue film, semiconductor light-emitting apparatus Download PDF

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CN209496895U
CN209496895U CN201822184253.5U CN201822184253U CN209496895U CN 209496895 U CN209496895 U CN 209496895U CN 201822184253 U CN201822184253 U CN 201822184253U CN 209496895 U CN209496895 U CN 209496895U
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light
film
glue film
composite fluorescence
fluorescence glue
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张汝志
陆加林
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Flori Photoelectric Material (suzhou) Co Ltd
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Flori Photoelectric Material (suzhou) Co Ltd
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Abstract

The utility model discloses a kind of composite fluorescence glue films comprising fluorescent film and infrared radiation diaphragm in connection.Wherein, the fluorescent film includes organic silicon substrate and fluorescent grain object.The infrared radiation diaphragm includes substrate and inorganic heat dissipation filler.The composite fluorescence glue film can be such that the light for setting wavelength penetrates.The invention also discloses a kind of encapsulating structure of semiconductor light-emitting apparatus and light sources, include the composite fluorescence glue film.Composite fluorescence glue film provided by the utility model has the characteristics such as ultra-thin, structure is simple, it is when being applied to encapsulation light emitting semiconductor device etc., it can be while effective packaging technology for simplifying light emitting semiconductor device, efficient light conversion efficiency is provided, and the heat dissipation performance of light emitting semiconductor device is greatly improved, it ensures its job stability, prolongs its service life, and can also significantly improve the light-emitting uniformity etc. of light emitting semiconductor device, and generate body-care and other effects.

Description

The encapsulating structure and light source of composite fluorescence glue film, semiconductor light-emitting apparatus
Technical field
The utility model relates to a kind of fluorescent coating of semiconductor field (Phosphor Film or Phosphor Sheet), especially a kind of composite fluorescence glue film, can be in encapsulation semiconductor light-emitting elements, such as wafer scale WLP LED, chip It is answered in the fields such as size CSP LED, quantum dot LED (QD LED), laser LED, LED filament lamp, Micro LED, mini LED With.
Background technique
LED (semiconductor light-emitting-diode) is widely used in because having many advantages, such as low energy consumption, long-life, small size The fields such as illumination, backlight.And packaging process is a very important process in LED processing procedure, for the workability of LED Energy, cost etc. have the influence of highly significant.
Existing LED packaging technology mainly has device level encapsulation technology, wafer scale LED encapsulation (WLP) technology, chip size Grade encapsulation CSP (Chip Scale Package) technology etc., these technologies are each advantageous, but also there are some defects simultaneously. In view of this, researcher is also unanimously dedicated to improving LED encapsulation technology.
For example, US7294861B, US2014091346A1 etc., which are proposed, carries out LED using fluorescent adhesive tape or fluorescence adhesive sheet The technology of encapsulation.It is dispersed with fluorescent powder, fluorescence nano etc. in these fluorescent adhesive tapes, fluorescence adhesive sheet, to realize that LED goes out Penetrate the wavelength convert of light.Although such packing forms operate convenience, in terms of compared with traditional technology have improvement, There are still defects, the heat transfer generated when for example, being unfavorable for LED operation, and this problem also has larger shadow to LED performance It rings.On the other hand, LED heat dissipation technology mostly still uses traditional heat spreader structures at present, and through heat conducting and radiating, but it is dissipated It still needs further improvement for hot property.
Summary of the invention
The main purpose of the utility model is to provide a kind of composite fluorescence glue film of improvement (Phosphor Film, PF), To overcome deficiency in the prior art.
The another object of the utility model, which is to provide, utilizes composite fluorescence glue film encapsulation semiconductor light-emitting elements Method.
For the realization goal of the invention, the technical solution adopted in the utility model includes:
The utility model embodiment provides a kind of composite fluorescence glue film comprising fluorescent film and with the fluorescent film knot The infrared radiation diaphragm of conjunction, the fluorescent film include organic silicon substrate, evenly dispersed in the organic silicon substrate to have fluorescent grain object, The infrared radiation diaphragm includes substrate and evenly dispersed inorganic heat dissipation filler in the substrate, and the composite fluorescence glue film can Penetrate the light for setting wavelength.
Wherein, the composite fluorescence glue film is after in conjunction with light emitting semiconductor device, and the light emitting semiconductor device is in work As when the heat that generates conduct to composite fluorescence glue film when, infrared radiation diaphragm therein can be efficient by modes such as heat loss through radiation Ground transfers heat in external environment.
The utility model embodiment additionally provides a kind of semiconductor light-emitting apparatus comprising light emitting semiconductor device and institute The composite fluorescence glue film stated, fluorescent film or infrared radiation diaphragm and the light emitting semiconductor device in the composite fluorescence glue film Light-emitting surface combines.The utility model embodiment additionally provides a kind of packaging method of semiconductor light-emitting apparatus comprising:
The composite fluorescence glue film is provided, and
By the light-emitting surface of fluorescent film or infrared radiation diaphragm and the light emitting semiconductor device in the composite fluorescence glue film Secure bond.
Further, the light emitting semiconductor device includes LED.
It, can be in the same of effective packaging technology for simplifying light emitting semiconductor device using the scheme of the utility model When, improve the heat dissipation of light emitting semiconductor device, to ensure the job stability of light emitting semiconductor device, extends it and use the longevity Life.
The technical solution of the utility model is more specifically illustrated with reference to embodiments, but not as to this The restriction of utility model.
Detailed description of the invention
Fig. 1 is a kind of manufacture craft schematic diagram of composite fluorescence glue film in one embodiment of the utility model;
Fig. 2 is a kind of structural schematic diagram using fluorescent film encapsulation LED in one reference examples of the utility model;
Fig. 3 is a kind of structural schematic diagram using composite fluorescence glue film encapsulation LED in one exemplary embodiments of the utility model;
Fig. 4 is a kind of structural representation using composite fluorescence glue film encapsulation LED in another exemplary embodiments of the utility model Figure.
Fig. 5 is the schematic diagram for measuring the space chromacity consistency of light in the utility model embodiment using 9 methods.
Fig. 6 A- Fig. 6 E is the package structure diagram of LED in some embodiments of the utility model.
Specific embodiment
The one aspect of the utility model embodiment provides a kind of composite fluorescence glue film comprising fluorescent film and with institute The infrared radiation diaphragm of fluorescent film combination is stated, the fluorescent film includes organic silicon substrate, evenly dispersed in the organic silicon substrate to have Fluorescent grain object, the infrared radiation diaphragm include substrate and evenly dispersed inorganic heat dissipation filler in the substrate, described multiple Closing fluorescent coating can be such that the light for setting wavelength penetrates.
Further, the inorganic heat dissipation filler include titanium dioxide, zirconium dioxide, silica, boron nitride, zinc oxide, Aluminium oxide, magnesia, mica, the combination of any one or more in rare-earth oxide, but not limited to this.
For example, the inorganic heat dissipation filler includes titanium dioxide granule, zirconium dioxide particle, silicon oxide particle, boron nitride Particle, Zinc oxide particles, alumina particle, magnesium oxide particle, mica particles, any one in rare-earth oxide particle Or a variety of combination.
Further, the inorganic heat dissipation filler can be graininess, microplate shape, threadiness, tubulose etc., and size can be with It is nanoscale, submicron order or micron-sized.
By these inorganic heat dissipation fillers evenly dispersed in the substrate, the infrared radiation diaphragm to be formed can be made to have There is heat loss through radiation function.
It, can be with by selecting type, the size etc. of the inorganic heat dissipation filler in some more preferred embodiments The radiation wavelength for generating the infrared radiation diaphragm is distributed mainly on infrared band, far infrared band, is conducive to comprising described compound Lighting device, display device of fluorescent coating etc. are applied in a home environment, and generate body-care and other effects.
In some more preferred embodiments, the partial size of the inorganic heat dissipation filler is 0.001 μm~500 μm, excellent It is selected as 0.05 μm~50 μm, more preferably 0.5 μm~10 μm.
In some more preferred embodiments, the content of inorganic heat dissipation filler is in the infrared radiation diaphragm 0.001wt%~10wt%, preferably 0.1wt%~10wt%, more preferably 1wt%~10wt%.
In some more preferred embodiments, the inorganic heat dissipation filler uses the combination of zinc oxide and magnesia And/or mica.Preferably, the content of the infrared radiation diaphragm internal oxidition zinc is 0.001wt%~10wt%, further preferably 0.1wt%~10wt%, especially preferably 1wt%~10wt%.
Preferably, the content of the infrared radiation diaphragm internal oxidition magnesium is 0.001wt%~10wt%, further preferably 0.1wt%~10wt%, especially preferably 1wt%~10wt%.
Preferably, the content of mica is 0.001wt%~10wt% in the infrared radiation diaphragm, further preferably 0.1wt%~10wt%, especially preferably 1wt%~10wt%.The addition of mica will be such that the infrared radiation diaphragm has more preferable Heat loss through radiation performance.
Further, the substrate can be formed by silicon composition.
Preferably, the silicon composition for being used to form the substrate can be with the organosilicon to form the fluorescent film The silicon composition of matrix is identical, to form matched multilayered structure, good adherency, and during device use Show excellent reliability.
In some embodiments, the infrared radiation diaphragm can be by the composition of silicon composition and fluorescent powder grain Precuring (B-stage Silicone Curables) is formed, and surface has the function of pressure sensitive adhesive (pressure sensitive adhesive PSA).In some embodiments of the utility model, following removings of the infrared radiation diaphragm The percentage of intensity is 30% or more;
The percentage of the peel strength=[peel strength under the atmosphere of peel strength/25 DEG C under 75 DEG C of atmosphere] × 100
Peel strength under 75 DEG C of atmosphere: it at 75 DEG C of temperature, is incited somebody to action with peel angle 180 degree, speed 300mm/ minutes The peel strength when infrared radiation diaphragm is removed from the light-emitting surface of light emitting semiconductor device;
Peel strength under 25 DEG C of atmosphere: it at 25 DEG C of temperature, is incited somebody to action with peel angle 180 degree, speed 300mm/ minutes The peel strength when infrared radiation diaphragm is removed from the light-emitting surface of light emitting semiconductor device.
Further, the infrared radiation diaphragm with a thickness of 0.005 μm~10000 μm, preferably 0.05 μm~5000 μm, Especially preferably 1 μm~1000 μm.
By using the preferred embodiment, infrared radiation diaphragm light transmission rate with higher also may make, And generate and be analogous to the function of light guide, light diffusion body, that is, can enable to inject the light of the infrared radiation diaphragm uniformly from The light-emitting surface of the infrared radiation diaphragm projects, and is lifted out light quality.
Further, the organic silicon substrate can be formed by silicon composition precuring or be fully cured.
Further, the fluorescent film can be formed by fluorescence encapsulating composition precuring or be fully cured, the fluorescence Encapsulating composition can be mainly by the silicon composition and the fluorescent grain object (as follows also referred to as " fluorescent material ") group At.
In some embodiments, the fluorescent film can be by fluorescence encapsulating composition precuring (B-stage Silicone Curables) it is formed, and surface has the function of pressure sensitive adhesive (pressure sensitive adhesive PSA)。
Further, the fluorescence encapsulating composition matches the fluorescent grain object and the organosilicon by following ratio Composition is simultaneously stirred to prepare.
In some embodiments, fluorescent material accounts for the content of non-solvent component and is in the fluorescence encapsulating composition 0.01wt%~90wt%, preferably 1wt%~80wt%, more preferably 3wt%~70wt%.
In some embodiments, the colour temperature of the fluorescent material is 1800K-20000K, and colour rendering index is 60~100.
In some embodiments, the fluorescent grain object is fluorescent powder, and partial size is 1~50 μm.
In some embodiments, the fluorescent powder includes rare earth phosphor, rare-earth garnet fluorescent powder, alkaline-earth metal sulphur Change gallate, alkaline earth sulfide, vulcanization zinc-type, alkali earth metal aluminate, phosphate, borate, silicate, fluorine arsenic acid Salt, fluogermanate, rare-earth sulfide, rare earth oxide, vanadate, any one two or more group in nitride phosphor It closes.Preferably, the fluorescent powder can select chemistry and the preferable aluminate of high-temperature stability, silicate, nitride and nitrogen Oxide-based fluorescent powder, especially nitride and nitrogen oxidation species fluorescent powder.Especially preferred, the fluorescent powder is rare earth member The YAG yttrium aluminium garnet fluorescent powder of element doping or the YAG yttrium aluminium garnet fluorescent powder of Ce doping.These fluorescent powders can be from market Approach freely obtains.For example, the fluorescent powder can be the composition of a variety of fluorescent powders, such as GE company can be added with The rouge and powder that (General Electric Co. Limited) produces, i.e. fluorination matter fluorescent powder, belong to potassium fluosilicate (PFS) phosphorescence series.
In some embodiments, further, the fluorescent grain object be fluorescence quantum, partial size be 1~ 100nm, preferably 1~20nm.
In some embodiments, the composition material of the fluorescence quantum includes II-VI group or iii-v element, especially To be preferred, the material of the fluorescence quantum includes any one two or more group in ZnSe, CdS, CdSe and CdSe It closes, it is further preferred that the material of the fluorescence quantum is selected from gallium arsenic, indium phosphide or gallium nitride, still more preferably, The fluorescence quantum has core-shell structure, and still more preferably, the fluorescence quantum is CdSe/ZnS core-shell structure amount Sub- point.In some embodiments, perovskite quantum dot also can be selected in the fluorescence quantum.
In some embodiments, fluorescent powder accounts for the content of non-solvent component and is preferably in the fluorescence encapsulating composition 1.0wt%~90wt%, more preferably 1.0wt%~70wt%.
In some embodiments, in the fluorescence encapsulating composition fluorescence quantum account for non-solvent component content it is preferred For 0.01~50wt%, more preferably 0.01~5.0wt%.
The silicon composition has the main chain mainly formed by siloxanes key (- Si-O-Si-) in the molecule, and Be bonded to the silicon atom (Si) of main chain, by alkyl (such as methyl etc.), aryl (such as phenyl etc.) or alkoxy (such as methoxy Base) etc. organic groups formed side chain.Specifically, as organosilicon resin composition, such as dehydrating condensation can be enumerated and consolidated Change type organic siliconresin, addition reaction curing type silicone resin, peroxide curing type silicone resin, moisture-curable have Curing type silicones resin such as machine silicone resin etc..Resin may be used singly or two or more in combination.
In some embodiments, the main component of the silicon composition is that number-average molecular weight is higher than 3 × 104g/ The silicone based rubber of mol, the silicone resin containing vinyl-functional, the silicone resin of the functional group containing Si-H, silane Alkanizing catalyst, and, to the cooperation of each component of the silicon composition and formed homogeneous phase solution organic solvent or Diluent.
In some embodiments, the silicone based rubber (also known as silicone rubber) contains vinyl-functional, preferably , 2 or more vinyl are contained in each molecule of the silicone based rubber, it is furthermore preferred that the silicone based rubber contains Phenyl functional group, it is further preferred that containing 1 or more phenyl in each molecule of the silicone based rubber.
In some embodiments, the silicone rubber is that one kind is made on main polymer chain with diorganosiloxane units For the rubber of repeating segment, wherein by following general formula-﹛ Si (R1)(R2)-O-- ﹜ indicates diorganosiloxane units, wherein R1With R2Individually monovalent organic group, or especially alkyl, such as methyl, ethyl;Aryl, such as phenyl;Alkenyl, such as ethylene Base etc.;Cyanoalkyl, such as γ-cyanogen propyl;Or fluoroalkyl, such as trifluoro propyl.
In some embodiments, the silicone rubber can be obtained by suitable pathways known in the art, including from System is obtained from market approach.For example, seeing EP 0470745A2, " Glossary of Chemical Terms " (Van Nostr and Reinhold Company, 1976), JP2005288916, DE102004050128.9, U3) 279890A, The documents such as JP 330084/1998, JP19981124, JP332821/1998, CN1212265A.
More specifically, the silicone rubber can selected from polydimethylsiloxane rubber, methyl phenyl siloxane rubber, Methyl vinyl silicone rubber, fluorinated alkyl methyl siloxane rubber, cyanoalkyl siloxanes rubber etc., but be also not necessarily limited to This.
Further, the R in the diorganosiloxane units1And/or R2Preferred vinyl, phenyl.
Further, in the silicon composition, the content that silicone rubber accounts for non-solvent component can be 1wt% ~90wt%, preferably 10wt%~70wt%, especially preferably 20wt%~50wt%.
It is ideal, the content of the silicone rubber medium vinyl be the 0.01% of the total weight of silicone rubber with On, 70% or less.
More preferably, in the silicone rubber phenyl content be silicone rubber total weight 0.01% with On, 95% or less.Preferably, the number-average molecular weight of the silicone based rubber is 3 × 104G/mol~1 × 108G/mol, it is more excellent Choosing is 1 × 105G/mol~1 × 107G/mol, especially preferably 3 × 105G/mol~1 × 106g/mol。
Further, 2 or more vinyl are contained in each molecule of the silicone resin containing vinyl-functional, Preferably, the silicone resin containing vinyl-functional includes straight chain, branch or reticular structure, it is preferred that described to contain second The number-average molecular weight (Mn) of the silicone resin of alkenyl-functional groups is 105G/mol is hereinafter, preferably 1 × 102G/mol~1 × 105G/mol, more preferably 1 × 102G/mol~1 × 104g/mol。
It is furthermore preferred that containing 1 or more phenyl in each molecule of the silicone resin containing vinyl-functional.
In some embodiments, the silicone resin containing vinyl-functional includes RSiO3/2Unit, RR' SiO2/2Unit, RR'R " SiO1/2Unit and SiO4/2The combination of any one or more in unit, wherein R, R', R " are to take Generation or unsubstituted univalence hydrocarbyl.
In some embodiments, the silicone resin of the functional group containing Si-H includes RSiO3/2Unit, RR'SiO2/2 Unit, RR'R " SiO1/2Unit and SiO4/2The combination of any one or more in unit, wherein R, R', R " be replace or Unsubstituted univalence hydrocarbyl.
More specifically, in some embodiments, the structure of the silicone resin containing vinyl-functional is as follows:
In some embodiments, the silicone resin containing vinyl-functional can be (R1[OR2]SiO)m- (R3CH2=CH-SiO) n, wherein R1、R2、R3It can be vinyl, m, n can be 0 or a positive integer.
In some embodiments, the silicone resin containing vinyl-functional, which can be selected from, contains vinyl POSS。
Further, in the silicon composition, the silicone resin containing vinyl-functional accounts for non-solvent component Content can be 1wt%~90wt%, preferably 10wt%~70wt%, especially preferably 20wt%~50wt%.
In the present invention, 2 or more Si- are contained in each molecule of the silicone resin of the functional group containing Si-H H base, it is preferred that the silicone resin of the functional group containing Si-H includes straight chain, branch or reticular structure;Preferably, described to contain The number-average molecular weight of the silicone resin of Si-H functional group is lower than 105G/mol, preferably 102G/mol~105G/mol, it is more excellent Choosing is 1 × 102G/mol~1 × 104g/mol。
It is furthermore preferred that containing 1 or more phenyl in each molecule of the silicone resin of the functional group containing Si-H.
In the silicone resin of the functional group containing Si-H described in the utility model, in addition to the hydrogen atom with silicon bonding with The group of silicon bonding can be the optionally substituted monovalent hydrocarbon in addition to alkenyl, such as methyl, ethyl, propyl or similar Alkyl;Phenyl, tolyl, xylyl, naphthalene or similar aryl;Benzyl, phenethyl or similar aralkyl;3- chlorine third Base, 3,3,3- trifluoro propyls or similar halogenated alkyl, but it is preferable that there is at least one virtue in a molecule of the component Base, especially phenyl, especially more than two phenyl.The molecular structure of the component does not have special limitation, it can have directly Chain, branching or part branching straight chain, ring-type or dendritic molecular structure.It is described to contain Si- in some case study on implementation The silicone resin of H functional group can be represented by following substance: by formula (CH3)2HSiO1/2And C6H5SiO3/2Unit composition Organopolysiloxane resins;By formula (CH3)2HSiO1/2、(CH3)3SiO1/2With formula C6H5SiO3/2Unit composition organic poly- silicon Oxygen alkane resin;By formula (CH3)2HSiO1/2And SiO4/2Unit composition organopolysiloxane resins;By formula (CH3)2HSiO1/2、 (CH3)2SiO2/2And SiO4/2Unit composition organopolysiloxane resins, etc..
More specifically, in some embodiments, the structure of the silicone resin of the functional group containing Si-H is as follows:
Wherein, p is the integer more than or equal to 1.
In some embodiments, the silicone resin of the functional group containing Si-H also can be selected from containing Si-H functional group POSS.In the silicon composition, the content of the silicone resin of the functional group containing Si-H is 1wt%~90wt%, preferably For 2wt%~50wt%, especially preferably 5wt%~30wt%.
Further, in the present invention, the content of Si-H base exists in the silicone resin of the functional group containing Si-H 0.1mol%~100mol%, preferably in 0.2mol%~95mol%, particularly preferably in 0.5mol%~90mol%.
Further, in the present invention, Si-H base contains with described in the silicone resin of the functional group containing Si-H The molar ratio of vinyl is 0.02~50:1 in the silicone resin of vinyl-functional, preferably in 0.1~10:1, particularly preferably In 0.5~5:1.
Further, the selection about the silicone resin of this functional group containing Si-H and preparation process can refer to CN101151328A, CN102464887A etc..
Further, the silicone resin (silicone resin containing vinyl-functional, the functional group containing Si-H silicon oxygen Alkane resin) it is a kind of such as liquid hydrocarbon of benzene,toluene,xylene, heptane and analog, ketone, rouge, photoresist of dissolving in molten Agent dissolves in the cyclic annular polydiorganosiloxanepolyurea of such as low viscosity and the liquid organosilicon chemical combination of straight chain polydiorganosiloxanepolyurea Object may include by R3 3SiO1/2Simple function (M) unit, the R of representative3 2SiO2/2Difunctionality (D) unit, the R of representative3SiO3/2Generation Trifunctional (T) unit of table and by SiO4/2Tetrafunctional (Q) unit of representative.R3The organic group of unit price is represented, to replace Or unsubstituted univalence hydrocarbyl.Wherein, the unsubstituted alkyl of unit price may be selected from but not limited to following group: alkyl, all Such as methyl, ethyl, propyl, amyl, octyl, undecyl and octadecyl;Alkenyl, such as vinyl, allyl, butylene Base, pentenyl and hexenyl;Alicyclic group, such as cyclohexyl and cyclohexenylethyl;Alkynyl, such as acetenyl, propinyl And butynyl;Naphthenic base such as cyclopenta and cyclohexyl;And aromatic group, such as Ethylbenzyl, naphthalene, phenyl, toluene Base, xylyl, benzyl, styryl, 1- phenethyl and 2- phenethyl, are optionally phenyl.It may be present in R3On it is non-live Property substituent group includes but is not limited to halogen and cyano.Monovalent organic groups as substituted alkyl may be selected from but not limited to following Group: halogenated alkyl, such as chloromethyl, 3- chloropropyl and 3,3,3- trifluoro propyls, methyl fluoride, 2- fluoropropyl, 3,3,3- trifluoropropyls Base, 4,4,4- triRuorobutyls, 4,4,4,3,3- five fluorine butyl, 5,5,5,4,4,3,3- seven fluorine amyl groups, 6,6,6,5,5,4,4, 3,3- nine fluorine hexyls and 8,8,8,7,7- five fluorine octyls etc..Preferably, unit price is unsubstituted in the silicone resin of the utility model Alkyl be vinyl, 2 or more phenyl are contained in each molecule of the especially described silicone resin.About the utility model The selection of middle silicone resin and preparation process can refer to US6,124,407, US2,676,182, U2), 774,310, US6, 124,407 etc..
The dosage of the hydrosilylation catalysts should be enough to promote the solidification of the utility model silicon composition.These Hydrosilylation catalysts are as known in the art and are commercially available, such as may be selected from but not limited to following object Matter: platinum group metal: platinum, rhodium, ruthenium, palladium, osmium or iridium metals or its organo-metallic compound and combinations thereof.More specifically, may be used To be selected from platinum black, the compound such as reaction product of chloroplatinic acid, chloroplatinic acid hexahydrate and monohydric alcohol, bis- (ethyl second Acid) platinum, bis- (acetopyruvic acid) platinum, platinous chloride and the compound and alkene or low molecular weight organopolysiloxane or The compound of the platinum compounds of microencapsulation in matrix or core-shell type structure.Platinum and the organopolysiloxane of low molecular weight it is compound Object, including 1,3- divinyl -1,1 with platinum, 3,3- tetramethyl disiloxane compounds.These compounds can be in resin Microencapsulation in matrix.Optionally, catalyst may include 1, the 3- divinyl -1,1 with platinum, and 3,3- tetramethyl disiloxanes are multiple Close object.These hydrosilylation catalysts can refer to CN1863875A (0020-0021 sections of specification), US 3,159,601, ), U1 220,972, U1), 296,291, U1), No. 419,593, U1) and, 516,946, U1), 814,730, U1), 989,668, ), U2 784,879, U3), 036,117, U3), No. 175,325, EP 0 347 895B, U2) and, 766,176, U3), 017,654 etc. Document.And/or at least one UV active Pt catalyst, it can refer to US8,314,200.
In some case study on implementation, based on the weight of the silicon composition, the amounts of hydrosilylation catalysts can be with It is optionally 1ppm to 1000ppm, and is optionally 10ppm for following range of platinum group metal: 0.1ppm to 1,0000ppm In the present invention to 100ppm., the solvent can be applicable any type, such as water, organic solvent or both Mixture, preferably be selected from organic solvent, such as may be selected from but not limited to n-hexane, toluene, chloroform, methylene chloride, ethyl alcohol, third Ketone, 2- butanone, 4-methyl-2 pentanone, rouge, photoresist solvent (such as PGME, PGMEA) etc., to in the composition Remaining combination of materials is the liquid with good fluidity, especially homogeneous phase solution.
In the silicon composition, the content of the solvent can be about 10wt%~90wt%, preferably 20wt%~80wt%, especially preferably 30wt%~70wt%, the boiling point of the especially described solvent under normal pressure be 60 DEG C~ 250℃。
In the silicon composition, the content of the diluent can be about 10wt%~90wt%, preferably 20wt%~80wt%, especially preferably 30wt%~70wt%.
In some embodiments, the diluent includes at least one response type diluent, it is preferred that the response type Diluent using can participate in the monovinyl compound of hydrosilylation, the compound containing Si-H functional group or Monovinyl compound containing a Si-H functional group.Especially preferred, the response type diluent can be selected from mono-vinyl Silane compound and/or monoallyl silane compound.Preferably, the viscosity of the diluent at room temperature is less than 100cPs, Particularly preferably less than 50cPs, particularly preferably less than 10cPs.By using the response type diluent, can avoid organic molten The use of agent, reduces environmental pollution, and can also promote the compatibility of each component in the silicon composition.
More specifically, the monovinyl compound for being suitable for the diluent can be with reference to US6, the texts such as 333,375B It offers.Such as can be selected from one or more aromatic vinyl compounds, it is typical such as styrene, α-methylstyrene, 2- methylbenzene Ethylene, methyl styrene, methyl styrene, 4- diisopropyl styrene, dimethyl styrene, 4- t-butyl styrene, 5-t- - 2 methyl styrene of butyl, chlorobenzene, styrene and styrene list fluorine chlorine etc..Especially preferably using styrene etc..
The polymerized monomer intramolecular of postscript, the monovinyl compound can also be comprising at least one with hetero atom Polar group, such as can be the vinyl monomer comprising amido, the vinyl monomer comprising hydroxyl, the oxygen containing vinyl of packet Monomer, especially preferably the above two.There is the vinyl monomer containing heteroatomic polar group can make alone or in combination for these With.
Further, the vinyl monomer comprising amido is polymerizable monomer, at least one amine in molecule Base is primary amine (such as acrylamide, Methacrylamide, p-aminophenyl, aminomethyl (methyl) acrylic-amino ethyl (methyl) Acrylic-amino propyl (methyl) acrylic-amino (methyl) butyl acrylate), secondary amine (such as see JP130355/86A, Such as mono-substituted (methyl) acrylamide of aniiinophenyl butadiene such as N- methyl (methyl) acrylamide, N- ethyl (methyl) Acrylamide, N hydroxymethyl acrylamide, N- (4- aniiinophenyl) Methacrylamide) or tertiary amine (the substitution ammonia of such as N, N- bis- Base alkyl acrylate, N, N- dialkylaminoalkyl acrylamide, N, the disubstituted amino aromatic ethenyl compound of N- With the pyridine compounds containing vinyl), especially preferably tertiary amine.It more specifically, include acrylic or methacrylic acid group N, N- disubstituted amido alkyl acrylate can be selected from N, N- dimethylaminomethyl (methyl) acrylic acid, N, N- dimethyl Amino-ethyl (methyl) acrylic acid, N, N- dimethylaminopropyl (methyl) acrylic acid, N, N- dimethrlaminobutyl (methyl) Acrylic acid, N, N- diethylamino ethyl (methyl) acrylic acid, N, N- diethyl amino propyl (methyl) acrylic acid, N, N- bis- Ethylamino butyl (methyl) acrylic acid, N- methyl-N-ethylamino ethyl (methyl) acrylic acid, N, N- dipropylamino second Base (methyl) acrylic acid, N, N- Dibutylaminoethyl (methyl) acrylic acid, N, N- dibutylamino propyl (methyl) acrylic acid, N, N- dibutylamino butyl (methyl) acrylic acid, N, N- dihexyl amino-ethyl (methyl) acrylic acid, N, N- dioctylamino Ethyl (methyl) acrylic acid and acryloyl morpholine (acryloylmorpholine).Wherein, N, N- bis- (methyl) acrylic acid, N, N- Two (methyl) acrylic acid, N, N- dipropylamino ethyl (methyl) acrylic acid, N, N- dioctylamino ethyl (methyl) acrylic acid Particularly preferably with N- methyl-N-ethylamino ethyl ester (methyl) acrylate.In another example the N, N- disubstituted amido aromatics second Alkenyl compound may include styrene derivative, such as N, N- dimethylamino ethyl styrene, N, N- diethylamino second Base styrene, N, N- dipropylamino ethyl styrene and N, N- dioctylamino ethyl styrene.In another example containing vinyl Pyridine compounds may include vinylpyridine, 4-vinylpridine, 5- methyl -2- vinylpyridine, 5- ethyl -2- ethylene Yl pyridines, especially preferably the above two.
Further, the vinyl monomer of the hydroxyl can be to include at least one primary hydroxyl, secondary hydroxyl or tert-hydroxyl Polymerizable monomer.The vinyl monomer of these hydroxyls includes such as unsaturated carboxylic acid monomer containing hydroxyl, hydroxyl Vinyl ether monomers and hydroxyl vinyl ketone monomer, the preferably unsaturated carboxylic acid monomer of hydroxyl.Hydroxyl is not The example of unsaturated carboxylic monomer includes derivative (such as ester, acyl of acrylic acid, methacrylic acid, itaconic acid, fumaric acid and maleic acid Amine, acid anhydrides).Wherein, acrylic acid and methyl acrylic ester compound be particularly preferably.More specifically, the vinyl of hydroxyl Monomer may include methylol (methyl) acrylic acid, hydroxy propyl methacrylate (methyl), (methyl) acrylic acid hydroxypropyl (first Base) acrylic acid, (methyl) acrylic acid -2- hydroxypropyl, 3- phenoxy group -2- hydroxypropyl (methyl) glycerol acrylate (methyl) third Olefin(e) acid butyl ester (methyl) acrylic acid, chloro- 3- hydroxypropyl (methyl) acrylic acid of 2-, hydroxyl hexyl (methyl) acrylate, hydroxyl octyl (first Base) acrylic acid, methylol (methyl) acrylamide, 2- hydroxypropyl (methyl) acrylamide, (methyl) acrylamide, hydroxypropyl two (ethylene glycol) itaconic acid, itaconic acid two (propylene glycol), bis- (2- hydroxypropyls) bis- (2- ethoxy) itaconic acids, itaconic acid, bis- (2- hydroxyls Base ethyl) ester, double maleic acids (2- ethoxy), methyl vinyl ether, methylol ketenes and allyl alcohol.Wherein, methylol (first Base) hydroxy-ethyl acrylate, (methyl) hydroxypropyl acrylate, (methyl) acrylic acid, acrylic acid hydroxypropyl (methyl), 3- phenoxy group- 2- hydroxypropyl (methyl) glycerol acrylate (methyl) butyl acrylate (methyl) acrylic acid (methyl) acrylic acid hydroxyl hexyl, hydroxyl Propyl (methyl) acrylic acid, methylol (methyl) acrylamide, 2- hydroxypropyl (methyl) acrylamide and hydroxypropyl (methyl) third Acrylamide is preferred.
Further, the oxygen-containing vinyl monomer may include the vinyl monomer containing alkoxy (refering to JP188356/ 95A), such as trimethoxyvinyl silane, Triethoxyvinylsilane, 6- methoxy silane base -1,2- hexene, to trimethoxy First silicon ring-alkylated styrenes, 3- trimethoxy silicon propyl ester and 3- triethoxysilyl propyl acrylate, etc..
Among some embodiments, the silicon composition also may include additive, such as inhibitor, small molecule Silane (can be with or without ethylene or Si-H functional group), adhesion promoters, heat or the cured epoxy/acrylic acid of UV/poly- ammonia The resins such as ester/bismaleimide, inorganic filler, rheology modifier, tackifier, wetting agent, defoaming agent, levelling agent, dyestuff With any one of fluorescent powder antisettling agent (such as SHIN-ETSU HANTOTAI DM-30, Sanwell SH series LED fluorescent powder anti-settling agent etc.) or two Kind or more combination.
Wherein, the inhibitor, i.e. hydrosilylation inhibitor, which refer to, can result in the undesirable object of hydrosilylation Matter can be selected from alkynol compound, alkene-alkine compounds, siloxanes or benzo with reference to CN1863875A (the 0025th section) etc. Triazole and other hydrosilanes reaction suppressors.For example, alkynol compound inhibitor can be selected from 2- phenyl -3- butyne-2-alcohol, 2- methyl -3- butyne-2-alcohol, 3,5- dimethyl -1- hexin -3- alcohol etc.;Alkene-alkine compounds can be selected from such as 3- methyl -3- penta Alkene -1- alkynes etc., siloxanes can be selected from 1,3,5,7- tetramethyls -1,3,5,7- tetra- hexenyl cyclotetrasiloxanes, 1,3,5,7- tetramethyls Base -1,3,5,7- tetravinyl cyclotetrasiloxane etc..Wherein preferred alkynol compound, particularly preferred 2- phenyl -3- crotonylene - Alcohol.
Wherein, the tackifier or adhesive accelerant can be selected from ethyl orthosilicate, vinyltrimethoxysilane, boric acid N-butyl, boric acid isopropyl ester, isooctyl acid titanium, zirconium iso-octoate, tetrabutyl titanate, isopropyl titanate, KH-171, KH-560 and KH- 570 equal (referring to the 0026th section of CN1863875A specification etc.), the adhesive accelerant that commercially available approach can obtain can be road health Ning company produce JCR6101, JCR6101UP, EG6301, OE6336, JCR6175, JCR6109, Hipec4939, Hipec1-9224, OE6250, SR7010, SE9207, SE1740, SE9187L etc., but not limited to this.
Wherein, the inorganic filler can be as known in the art and be commercially available, such as may include Inorganic filler such as silica, for example, colloidal silicon dioxide, pyrogenic silica, silica flour, titanium oxide, glass, oxidation Aluminium, zinc oxide, or combinations thereof, filler can have 50 nanometers or smaller average grain diameter and will not by scatter or absorb reduce it is saturating Light percentage.And about such as rheology modifier, wetting agent, defoaming agent, levelling agent, dyestuff etc., definition is that industry notes, And it can freely be chosen out of industry common respective material.
The silicon composition can be prepared by any conventional method, such as in suitable temperature, such as at room temperature Mix all the components.
The viscosity of the silicon composition be 1,000mPa.s~500,000mPa.s, preferably 5,000mPa.s~ 100,000mPa.s, especially preferably 7,000mPa.s~50,000mPa.s.
In some embodiments, the fluorescent film can be by described fluorescence encapsulating composition semi-solid preparation (precuring) shape At, and preferably fexible film.
Further, the condition of the semi-solid preparation includes: heating ventilation condition, and temperature condition is 20 DEG C~200 DEG C, preferably It is 80 DEG C~120 DEG C, the time is 10~100000s, preferably 10~8000s.
Further, the condition that the fluorescent film is fully cured includes: to make the fluorescence by heating or electromagnetic irradiation Film is fully cured.Further, the thickness of the fluorescent film can it is very thin (such as can achieve 10 μm~10000 μm or so, it is excellent It is selected in 20~500 μm or so).
Further, the fluorescent film can save steadily in the long term.It, can be in its table to avoid it from being polluted by external environment Face covers separated type material (such as release paper), and when in use removes separated type material.
It can specifically include in the preparation method of some embodiments, the fluorescent film:
S1: the fluorescence encapsulating composition is passed through solution film forming, curtain coating coating, silk screen/steel mesh printing, rotation by film The modes such as coating, (vacuum) film extrusion form a film;
S2: primary solidification forms the pre-cured film that surface is not viscous and can uncover, i.e., the described fluorescent film, with pressure-sensitive The similar characteristic of glue.
Among an optional embodiment, the step S2) it may include: down in radiation and/or heating ventilation condition Except the organic solvent in the film, to form the pre-cured film.The heating temperature wherein used can be 20~200 DEG C, Preferably 80~120 DEG C, heating time is 10~100000 seconds, preferably 10~8000 seconds.
In some embodiments of the utility model, the preparation method of the composite fluorescence glue film may include: by institute It states infrared radiation diaphragm to be bonded with the fluorescent film, forms the composite fluorescence glue film.
The infrared radiation diaphragm, the fluorescent film may each be self-supported membrane.
In some embodiments of the utility model, fluorescent film and heat dissipation radiation film are one in the composite fluorescence glue film Body setting.In some embodiments of the utility model, the preparation method of the composite fluorescence glue film may include: that will make The standby infrared radiation diaphragm completed is bonded with the fluorescent film that preparation is completed, and forms the composite fluorescence glue film.
Wherein, the preparation method of the infrared radiation diaphragm can be known to industry, such as may include: will be described in composition The polymer etc. of substrate, which is dissolved in coordinative solvent, forms solution, and is dispensed into inorganic heat dissipation filler, then by the dispersion liquid of formation or Slurry prepares to form film by various ways such as spin coating, spraying, printing, casting films.In the process, according to actual demand, also It may include the processes such as dry.
In some embodiments of the utility model, the composite fluorescence can also be made using following preparation process Glue film, such as: prepare the fluorescent film;
The polymer etc. for forming the substrate is dissolved in coordinative solvent and forms solution, and is dispensed into inorganic heat dissipation filler, The dispersion liquid of formation or slurry are coated directly onto preparation on the fluorescent film again and form the infrared radiation diaphragm.
In some embodiments, the composite fluorescence glue film with a thickness of 0.010 μm~10000 μm, preferably 0.05 μ M~5000 μm, especially preferably 1 μm~1000 μm.
Composite fluorescence glue film provided by the utility model has the characteristics such as ultra-thin, structure is simple, is being applied to encapsulation half Whens conductor luminescent device etc., efficient light can be provided and turned while effective packaging technology for simplifying light emitting semiconductor device Efficiency is changed, and greatly improves the heat dissipation performance of light emitting semiconductor device, its job stability is ensured, prolongs its service life, with And it can also improve the luminescent quality of light emitting semiconductor device, including and be not limited to its light-emitting uniformity etc..
The other side of the utility model additionally provides a kind of packaging method of semiconductor light-emitting apparatus comprising:
The composite fluorescence glue film is provided, and
By the fluorescent film in the composite fluorescence glue film or radiation film is radiated in conjunction with the light emitting semiconductor device.
It in some embodiments, can be by the fluorescent film or heat dissipation radiation film and described half in the composite fluorescence glue film The light-emitting surface secure bond of conductor luminescent device.
The other side of the utility model additionally provides a kind of packaging method of semiconductor light-emitting apparatus comprising:
The composite fluorescence glue film is provided, and
By the light-emitting surface of fluorescent film or heat dissipation radiation film and the light emitting semiconductor device in the composite fluorescence glue film Secure bond.
In the present invention, the connotation of " encapsulation " (packaging) be it is known to those skilled in the art know, Such as may is that and be formed by curing protective layer (coating) by the silicon composition in some regions of article surface, or Person is immersed the part of one or more articles in the solidfied material formed by the silicon composition, alternatively, by one or more A article integrally embeds sealing (encapsulation) in the solidfied material formed by the silicon composition.
Further, in some more specifically embodiments, the packaging method be may include steps of:
1): the composite fluorescence glue film is covered on the light-emitting surface of the light emitting semiconductor devices such as LED by pad pasting, by Under high temperature and/or applying pressure keeps the fluorescent film Nian Jie with the light-emitting surface of light emitting semiconductor device;
2): solidification, by the light emitting semiconductor device for being pasted with the composite fluorescence glue film be placed in constant temperature (heating, Elevated temperature) in environment, and solidify the fluorescent film;
3): solidification post-processing, such as the product after solidification is cut into smaller unit.
Among one more preferred embodiment, the step 1)) it may include: to be applied to the composite fluorescence glue film During stressed, also at least the composite fluorescence glue film is heated, is bonded in fluorescent film therein described On the light-emitting surface of light emitting semiconductor device.The pressure size wherein applied can be 0.001Pa~10000Pa, preferably 0.1Pa ~1000Pa, applying pressure time is 0.001~100000 second, preferably 0.1~100 second.The heating temperature wherein used can Think 0~260 DEG C, preferably 50~200 DEG C, especially preferably 80~150 DEG C, the time is preferably 10~100000 seconds.
Certainly, in step 1)) in, the heat treatment to the composite fluorescence glue film can also be substituted using other way, or Person cooperates with the heating method to handle the composite fluorescence glue film, these modes may include irradiation (such as far infrared, Ultraviolet, visible light, microwave, any one or more of electron beam), medium wavelength can be 10-8~103M, the time can for 10~ 100000 seconds.
The light emitting semiconductor device can with the LED chip of chip-scale, be also possible to wafer scale LED component, LD (laser Device) etc..
The other side of the utility model embodiment additionally provides a kind of semiconductor light-emitting apparatus comprising semiconductor hair Optical device and the composite fluorescence glue film, fluorescent film or heat dissipation radiation film in the composite fluorescence glue film are partly led with described Body luminescent device combines.
In some embodiments, the fluorescent film in the composite fluorescence glue film or heat dissipation radiation film and the semiconductor are sent out The light-emitting surface secure bond of optical device.
The other side of the utility model embodiment additionally provides a kind of semiconductor light-emitting apparatus comprising semiconductor hair The body that is fully cured of optical device and the composite fluorescence glue film, the fluorescent film in the composite fluorescence glue film is partly led with described The light-emitting surface of body luminescent device combines.
In some embodiments of the utility model, the percentage of following peel strengths of the fluorescent film be 30% with On;
The percentage of the peel strength=[peel strength under the atmosphere of peel strength/25 DEG C under 75 DEG C of atmosphere] × 100
Peel strength under 75 DEG C of atmosphere: it at 75 DEG C of temperature, is incited somebody to action with peel angle 180 degree, speed 300mm/ minutes The peel strength when fluorescent film is removed from the light-emitting surface of the light emitting semiconductor device;
Peel strength under 25 DEG C of atmosphere: it at 25 DEG C of temperature, is incited somebody to action with peel angle 180 degree, speed 300mm/ minutes The peel strength when fluorescent film is removed from the light-emitting surface of the light emitting semiconductor device.
Further, the body that is fully cured is combined as a whole with the light emitting semiconductor device, or is believed that The described mode that body is fully cured in a manner of almost peelable is firmly combined in the light-emitting surface of the light emitting semiconductor device.
Further, the light out that body and the light emitting semiconductor device is fully cured of the fluorescent film or fluorescent film Face is bound directly.Further, following thermal weight loss rates that body is fully cured (≤5wt%) below 5%;
The thermal weight loss rate is defined as: by the body that is fully cured in the weight-loss ratio of 150 DEG C of temperature placement 1000h.
Preferably, the thermal weight loss rate is below 2%.
For example, the packaging technology of a kind of LED light emission device may include: in some more specific case study on implementation
Under heating condition at normal temperature or centainly, the light-emitting surface of a LED chip is attached to a composite fluorescence glue film It on the surface of fluorescent film, and the modes such as rolls by rubber rollers and applies certain pressure, both make to fit closely (bubble-free);
Sharp processing is carried out to composite fluorescence glue film by modes such as cross cuttings, makes its form fit with LED chip;
LED chip merging uv equipment (such as UV lamp case) of composite fluorescence glue film will be pasted with or Thermocuring equipment is (such as Baking box) in, after a period of time, fluorescent film therein is fully cured.Body and LED chip is fully cured in the fluorescent film Be it is joined integrally, the two can hardly be removed mutually, saying more precisely, and the described body that is fully cured can only be high-intensitive After being cracked under impact, the surface layer fragment being consequently formed can fall off, without being completely stripped from LED chip surface.
It certainly, in some embodiments, can also be by the infrared radiation diaphragm and described half in the composite fluorescence glue film The light-emitting surface of conductor luminescent device combines.
In some embodiments, the encapsulating structure of a kind of semiconductor light-emitting apparatus, semiconductor light emitting therein are provided Device has more than two light-emitting surfaces, and the composite fluorescence glue film covers all light out of the light emitting semiconductor device Face.
In some embodiments, there are five light-emitting surfaces for the light emitting semiconductor device tool.
In some embodiments, the light emitting semiconductor device has a light-emitting surface, is covered on the light-emitting surface The composite fluorescence glue film.
In some embodiments, the encapsulating structure of the semiconductor light-emitting apparatus further includes sending out around the semiconductor The reflective structure of optical device setting, the light-emitting surface are arranged within the space that the reflective structure is enclosed or from described Expose in the space that reflective structure is enclosed.
In some embodiments, the light-emitting surface is arranged in the space that the reflective structure is enclosed, and covers Expose from the space that the reflective structure is enclosed on the surface of the composite fluorescence glue film on the light-emitting surface.
In some embodiments, at least local interior wall of the reflective structure is in the side far from light emitting semiconductor device It is gradually inclined outwardly setting upwards, and between the light emitting semiconductor device and the inclined surface of the reflective structure inner wall Filled with transparent enclosure glue.Such design can further improve the light extraction efficiency of light emitting semiconductor device.
In some embodiments, the light-emitting surface exposes from the space that the reflective structure is enclosed, described multiple Close at least local surface that fluorescent coating continuously covers the light-emitting surface and the reflective structure.
In some embodiments, the light emitting semiconductor device is the light emitting semiconductor device of inverted structure.
For example, the light emitting semiconductor device is LED chip, can be installed on substrate in advance.It is also set in LED chip There is the LED side terminal being electrically connected for the substrate side terminal with substrate.Substrate can be by such as silicon substrate, ceramic substrate, gather The insulating substrates such as multilayer board made of insulating layer are laminated on imide resin substrate, metal substrate to be formed.For example, substrate is upper Surface is formed with the conductor figure having for the substrate side terminal being electrically connected and wiring connected to it of the LED side terminal with LED Case.Conductive pattern is, for example, to be formed by conductors such as gold, copper, silver, nickel.LED chip can be to be installed for example, by flip-chip Or wire bonding is connected on substrate.
Thereafter, it also can according to need and other transparent encapsulated layers be set on the complex of LED and composite fluorescence glue film, Such transparent encapsulated layer can be formed by transparent resin.Then also according to needing to adjust this for example, by the modes such as grinding, cutting The size of class transparent encapsulated layer.
In some more specifically case study on implementation of the utility model, a kind of processing procedure of CSP LED packaging can be with Include:
Set crystalline substance: by the array arrangement of a LED chip or multiple LED chips on substrate;
It encloses white wall, polish: applying the white wall glue of CSP in the LED chip, polish later, at least make going out for each LED chip Smooth surface is exposed to outer;
Pad pasting: the fluorescent film in the composite fluorescence glue film is closely attached on the light-emitting surface of each LED chip, is made later Fluorescent film is fully cured;
Cutting: the device formed to previous step carries out the processing such as cutting, then carries out other post-processing operations, acquisition at Product.
The process conditions used in the film process may include: temperature for 100~150 DEG C, and pressure is 0.003~ 0.015Mpa, time are 1~5min.And the process conditions that the fluorescent film is fully cured can be with are as follows:~180 DEG C, 2~4h.
The utility model other more specifically in case study on implementation, a kind of processing procedure of CSP LED packaging can To include: die bond: the array of a LED chip or multiple LED chips is adhered to the fluorescent film in the composite fluorescence glue film On;
It encloses white wall, polish: applying the white wall glue of CSP in the LED chip, polish later, at least make going out for each LED chip Smooth surface is exposed to outer;
Solidify: the fluorescent film is fully cured;
Cutting: the device formed to previous step carries out the processing such as cutting, then carries out other post-processing operations, acquisition at Product.
The technical solution of the utility model is made more below in conjunction with several more specifically embodiments and corresponding comparative example Detailed explanation.But still it is emphasized that these embodiments are not to be construed as constituting the protection scope of the utility model Any restrictions.Postscript, unless otherwise specified, all numbers, percentage, the ratio etc. in the utility model specification are pressed Poidometer.
Related fluorescence encapsulating composition can refer to the widely applied organosilicon of current industry in the following example The group mode of glue mixture is prepared, for example, the component of silicon composition therein is divided into component A (mainly includes Silicone resin, platinum catalyst, additive containing vinyl-functional etc.) and component B it is ((main comprising containing vinyl-functional Silicone resin, silicone resin, the additive of the functional group containing Si-H etc.), two components are mixed by a certain percentage when in use It closes, the fluorescent powder or phosphor combination of corresponding content is then added.
The inorganic filler that is used in following examples, silicon composition (being also regarded as organosilicon sizing material), fluorescent powder Deng can be obtained from market approach.For example, inorganic filler therein can be TiO2(Du Pont TS6300, D50=0.53um), SiO2(Cabot TS720), Al2O3(Betu new high-tech material limited liability company, TPA-5, D50=5um), ZnO (rise too chemical industry, D50=50nm), BN (Betu new high-tech material limited liability company ABN-5, D50=5um), (Betu new high-tech material share is limited by MgO Company, partial size are about 10-20um) in one or more combination.Organosilicon sizing material therein can for low folding PF1 slurry or Height folding PF2 slurry (being purchased from Florey photoelectric material (Suzhou) Co., Ltd).
The processing procedure of related composite fluorescence glue film can be in the following example are as follows:
The preparation of fluorescent film: fluorescence encapsulating composition is inverted on plate or PET film, uses film forming device (such as Shanghai The single side preparing device of Pu Shen chemical machinery Co., Ltd) certain thickness film is made, it is not flowed in heating platform by solidifying to obtain Dynamic, strippable glue film (B-stage, free-standing), i.e. fluorescent film.
The preparation of infrared radiation diaphragm: 1) inorganic filler centainly matched being sequentially added in organic silica gel PF1 slurry, mixing Uniformly, and in certain thickness infra-red radiation film (each infrared radiation diaphragm in embodiment 1- embodiment 6 is made in PET film Raw material composition can be refering to table 1);2) film layer of step 1 is put into precuring 10min in 150 DEG C of baking ovens;3) above film layer again It covers one layer of PET film, obtains infrared radiation diaphragm (with reference to shown in Fig. 1).Certainly, also the infrared spoke can be used to form by described The composition for penetrating film is inverted on plate, certain thickness film is made using film forming device, cured processing forms infrared radiation diaphragm. The preparation of composite fluorescence glue film: the infrared radiation diaphragm is bonded with fluorescent film, obtains the composite fluorescence glue film (with reference to Fig. 1 It is shown).
It is of course also possible to by the composition for being used to form the infrared radiation diaphragm (including be used to form substrate polymer, Solvent or diluent and evenly dispersed inorganic heat dissipation filler can be dispersion liquid or slurry) it is coated directly onto the fluorescent film On, resolidification forms the infrared radiation diaphragm, obtains the composite fluorescence glue film.
The present invention also provides a kind of light sources comprising the encapsulating structure of semiconductor light-emitting apparatus above-mentioned.The light Source can be applied to lighting device, display device etc., and without being limited thereto.
A kind of preparation method of the composite fluorescence glue film of embodiment 1 includes the following steps:
(1) a kind of organic silica gel PF1 slurry (purchased from Florey photoelectric material (Suzhou) Co., Ltd) is provided, for one kind Silicon composition is higher than 3 × 10 comprising number-average molecular weight5G/mol vinylsiloxane base rubber (component 1, SG6066, Vinyl-dimethyl base silane base blocks methyl vinyl silicone rubber, vinyldimethylsilyl terminated Methyl Vinyl Silicone Gum, Power Chemicals Ltd, number-average molecular weight 450,000-600,000g/mol, vinyl Content about 0.90-1.10wt%), silicone resin (component 2, A05-01-A, Florey photoelectric material containing vinyl-functional (Suzhou) Co., Ltd), silicone resin (component 3, A05-01-B, the Florey photoelectric material (Suzhou) of the functional group containing Si-H Co., Ltd), hydrosilylation catalysts (component 4, SIP6832.2, Gelest, 200ppm), solvent (4-methyl-2 pentanone, The basic components such as 200g), also may include other helper components certainly.
(2) commercially available yellow fluorescent powder SDY558-15 is mixed into the PF1 slurry with the mass ratio of 10:1 (to wish in Yantai Er De new material Co., Ltd), then after mixing through double planetary mixer, form fluorescence encapsulating composition.
(3) fluorescence is encapsulated using film applicator (such as 1mm film applicator) or mode of printing, especially screen printing mode and is combined Object is coated on substrate and forms a film, and later in 100 DEG C (heating platform in draught cupboard) heating 20min, obtains fluorescent film.
(4) by TiO2(Du Pont TS6300) and SiO2(Cabot white carbon black TS720) is successively starched with the organic silica gel PF1 Material mixing, forms and contains 1.0wt%TiO2And 1wt%SiO2Slurry, be formed by curing infrared heat dissipation film at about 150 DEG C later.Wherein Organic silica gel PF1 slurry also can be replaced other silicon compositions with similarity.
(5) infrared heat dissipation film is bonded with fluorescent film, forms composite fluorescence glue film.
The embodiment of embodiment 2 is substantially the same manner as Example 1, and difference place is:
Fluorescence encapsulating composition involved in step (1) also (is purchased from Florey photoelectricity material by a kind of organic silica gel PF1 slurry Material (Suzhou) Co., Ltd) it is formed with phosphor combination, component is as follows: number-average molecular weight is higher than 3 × 105The ethylene of g/mol Radical siloxane base rubber (SG6066, vinyl-dimethyl base silane base block methyl vinyl silicone rubber, Vinyldimethylsilyl terminated Methyl Vinyl Silicone Gum, Power Chemicals Ltd, Number-average molecular weight about 450,000-600,000g/mol, contents of ethylene about 0.90-1.10wt%) 4g, contain vinyl-functional Silicone resin (A05-01-A, Florey photoelectric material (Suzhou) Co., Ltd) 12.8g, ethenylmethoxy siloxanes it is equal Polymers (Vinylmethoxysiloxane Homopolymer VMM-010, Gelest) 0.35g, the functional group containing Si-H silicon oxygen Alkane resin (A05-01-B, Florey photoelectric material (Suzhou) Co., Ltd) 6.8g, hydrosilylation catalysts (SIP6832.2, Gelest) 20ppm, -2 pentanone 20g of solvent 4- methyl, the Yantai yellow fluorescent powder SDY558-15from Anthony Heald New material Co., Ltd 35.5g.
The precuring condition used in step (3) are as follows: 110 DEG C of (heating platform in draught cupboard) 10min.
The slurry formed in step (4) includes 1.5wt%TiO2(Du Pont TS6300) and and 0.5wt%SiO2(Cabot is white Carbon black TS720), surplus is the organic silica gel PF1 slurry.Organic silica gel PF1 slurry also can be replaced other with similar The silicon composition of property.
Composite fluorescence glue film made from the present embodiment is transparent inclined white film.
The embodiment of embodiment 3 is substantially the same manner as Example 1, and difference place is:
Fluorescence encapsulating composition involved in step (1) also (is purchased from Florey photoelectricity material by a kind of organic silica gel PF1 slurry Material (Suzhou) Co., Ltd) it is formed with phosphor combination, number-average molecular weight is higher than 3 × 105The vinylsiloxane of g/mol (SG6066, vinyl-dimethyl base silane base block methyl vinyl silicone rubber, vinyldimethylsilyl to base rubber Terminated Methyl Vinyl Silicone Gum, Power Chemicals Ltd, number-average molecular weight about 450,000- 600,000g/mol, contents of ethylene about 0.90-1.10wt%) 1.8g, the silicone resin (A05- containing vinyl-functional 01-A, Florey photoelectric material (Suzhou) Co., Ltd) 4.6g, ethenylmethoxy silicone homopolymer (Vinylmethoxysiloxane Homopolymer, VMM-010, Gelest) 0.35g, the functional group containing Si-H siloxanes Resin (A05-01-B, Florey photoelectric material (Suzhou) Co., Ltd) 4.6g, hydrosilylation catalysts (SIP6832.2, Gelest) 10ppm, -2 pentanone 9.0g, 0.34g yellow fluorescent powder SDY558-15,20.1g green emitting phosphor of solvent 4- methyl SDG530H, 1.2g red fluorescence powder SSDR630Q-2 (being purchased from Yantai Shield Advanced Materials Co., Ltd.).
The slurry formed in step (4) includes 0.3wt%TiO2(Du Pont TS6300), 0.5wt%SiO2(Cabot hard charcoal Black TS720), 0.3wt%SiO2(TPA-5), 0.3wt%ZnO (purchased from too chemical industry is risen), 0.3wt% boron nitride (ABN-5), 0.3wt% mica powder (JTX heat dissipation powder), surplus is the organic silica gel PF1 slurry.
Composite fluorescence film thickness made from the present embodiment is transparent inclined white film.
The embodiment of embodiment 4 is substantially the same manner as Example 1, and difference place is:
Fluorescence encapsulating composition involved in step (1) also (is purchased from Florey photoelectricity material by a kind of organic silica gel PF1 slurry Material (Suzhou) Co., Ltd) it is formed with phosphor combination, number-average molecular weight is higher than 3 × 105The methyl phenyl vinyl of g/mol Radical siloxane base rubber (Methyl Phenyl Vinyl Silicone Rubber, Florey photoelectric material (Suzhou) limited public affairs Department, number-average molecular weight about 500,000g/mol, phenyl content about 30wt%, contents of ethylene about 0.35-0.40wt%) 3.7g, Silicone resin (H20-01-A, Florey photoelectric material (Suzhou) Co., Ltd) 7.7g containing phenyl and vinyl-functional, Silicone resin (H20-01-B, Florey photoelectric material (Suzhou) Co., Ltd) 7.7g, hydrogen containing phenyl and Si-H functional group SiClx Alkanizing catalyst (SIP6832.2, Gelest) 10ppm, -2 pentanone 1.2g, 0.48g yellow fluorescent powder of solvent 4- methyl SDY558-15,14.3g green emitting phosphor SDG530H, 0.86g red fluorescence powder SSDR630Q-2 (are purchased from Yantai Anthony Heald New material Co., Ltd).The above group lease making double planetary mixer is obtained a fluorescence powder content after mixing is The mixture of 44.9wt%.The slurry formed in step (4) includes 0.3wt%TiO2(Du Pont TS6300), 0.5wt%SiO2(card Rich extra white carbon black TS720), 0.3wt%SiO2(TPA-5), 0.3wt%ZnO (purchased from too chemical industry is risen), 0.3wt% boron nitride (ABN-5), 0.3wt%MgO (about 10-20 μm of partial size), surplus are the organic silica gel PF1 slurry.
Composite fluorescence glue film made from the present embodiment is transparent inclined white film.
The embodiment of embodiment 5 is substantially the same manner as Example 1, and difference place is:
Fluorescence encapsulating composition involved in step (1) also (is purchased from Florey photoelectricity material by a kind of organic silica gel PF1 slurry Material (Suzhou) Co., Ltd) it is formed with phosphor combination, solvent composition PGMEA is 50wt% in organic silica gel PF1 slurry, Wherein non-solvent component includes: 5wt% γ-cyanogen propyl-siloxane rubber (MW=4.12 × 105G/mol), 90wt% compound of formula I (MW=1.2 × 102G/mol), 5wt% Formula V compound, 1ppm chloroplatinic acid.
The slurry formed in step (4) includes 1.0wt%ZnO (purchased from too chemical industry is risen), 1.0wt%MgO (partial size about 10- 20 μm), surplus is the organic silica gel PF1 slurry.
Composite fluorescence glue film made from the present embodiment is the higher film of transparency.
The embodiment of embodiment 6 is substantially the same manner as Example 1, and difference place is:
Fluorescence encapsulating composition involved in step (1) also (is purchased from Florey photoelectricity material by a kind of organic silica gel PF1 slurry Material (Suzhou) Co., Ltd) it is formed with phosphor combination, organic silica gel PF1 slurry solvent component 4-methyl-2 pentanone is 50wt%, wherein non-solvent component includes: 51wt% trifluoropropyl siloxane rubber (MW=1 × 108G/mol), 21wt% formula III compound (MW=1.05 × 104G/mol), bis- (oacetic acid) platinum of 28wt% Formula II compound, 100ppm.
The slurry formed in step (4) includes 1.0wt%ZnO (purchased from too chemical industry is risen), 1.0wt%MgO (partial size about 10- 20 μm), surplus is the organic silica gel PF1 slurry.
Composite fluorescence glue film made from the present embodiment is the higher film of transparency.
Control group 1~6: the reference examples 1~6 and Examples 1 to 6 are essentially identical, and difference place is: only comprising step (1)-step (3).
In the fluorescence encapsulating composition of previous embodiment solvent be also replaced with α-methylstyrene, styrene list fluorine chlorine, N, N- bis- (methyl) acrylic acid, N- methyl-N-ethylamino ethyl ester (methyl) acrylate, methylol (methyl) acrylamide etc. Diluent.
Table 1
The composite fluorescence glue film obtained to previous embodiment (being referred to as composite membrane as follows) and reference examples are obtained as follows glimmering The application performance of light film (following referred to as PF film) is tested.The testing tool etc. wherein used may each be industry and commonly use , such as may include: OMEGA HH806AU temperature measuring device, heat sink, COB, DC power supply, distant place hand-held illumination instrument, etc. Deng.Corresponding test method is specific as follows:
1) heat dissipation performance is tested:
1. the fluorescent film that the composite fluorescence glue film of foregoing embodiments, reference examples are obtained is fitted to organic silica gel envelope respectively (when necessary, also the integrated surface COB (with reference to shown in Fig. 2, Fig. 3) for installing (the naked glue encapsulation of A05-01L), guarantees bubble-free residual Need to make fluorescent film therein in 150 DEG C~180 DEG C constant temperature dryings to being fully cured).In some embodiments, it can also will answer The infrared radiation diaphragm closed in fluorescent coating is bonded with LED chip, refering to Fig. 4.
2. COB is placed on heat sink, the thermally conductive glue connection of silicone is used between the two;
3. omega temperature measuring device two probes are contacted with the integrated center COB and substrate connections respectively;
4. the integrated COB for welding conducting wire is connect with constant-current supply, it is ensured that contact is good;
5. powering on;
6. OMEGA thermocouple autorun, interval 30s records a data, records duration 1 hour or so;
7. the data obtained is exported at the end PC, stable data record average value is taken, is aggregated.
The sample of test is as shown in Fig. 2, the temperature test result of OMEGA thermocouple is as shown in table 2.
Note: in the heat dissipation performance test process, each embodiment can take multiple samples, such as three samples to be surveyed Examination.Each reference examples also take multiple samples to be tested (results are averaged is shown in table 2).
Table 2
2) chrominance space uniformity test:
The space chromacity consistency of light is measured in the test with 9 methods, and test device is as shown in Figure 5.
1. with reference to aforementioned step, composite membrane, PF1 film are attached in COB light source respectively, then the light source is parallel with screen It places, LED light source distance test screen distance L1=15cm, 9 arranged at equal intervals (interval L2=15cm), intermediate on screen Point is on a horizontal surface (as shown in Figure 4) with LED light central point.
9 methods test the standard deviation of 9 chromaticity coordinates and colour temperature with hand-held illumination photometer to measure the space chromacity of light source Uniformity, test result are as shown in table 3.
3 nine methods of table measure the space chromacity consistency result of composite film light
Note: " reference examples ★ " test number in upper table 3 is after taking multiple samples corresponding with reference examples 1-6 to test respectively The average value of obtained test result.
Obvious, composite fluorescence glue film provided by the embodiment of the utility model is being applied to encapsulation semiconductor luminous chip When, its heat dissipation performance can be significantly improved, while also greatly improving its light-emitting uniformity.
In addition, using the composite fluorescence glue film of the utility model, and cooperate the encapsulation work known to those skilled in the art known Skill can also realize the encapsulation of other forms to semiconductor luminous chip etc., wherein typical some packing forms can be refering to figure Shown in 6A- Fig. 6 E.It should be noted that, in this document, the terms "include", "comprise" or its any other variant are intended to Non-exclusive inclusion, so that the process, method, article or equipment including a series of elements is not only wanted including those Element, but also including other elements that are not explicitly listed, or further include for this process, method, article or equipment Intrinsic element.It should be appreciated that above-described embodiment is only to illustrate the technical ideas and features of the present invention, its object is to It enables those skilled in the art to understand the contents of the present invention and implement them accordingly, it is practical new that this can not be limited with this The protection scope of type.All equivalent change or modifications according to made by the spirit of the present invention essence should all cover practical new at this Within the protection scope of type.

Claims (18)

1. a kind of composite fluorescence glue film, it is characterised in that the infrared radiation diaphragm including fluorescent film and in conjunction with the fluorescent film, The infrared radiation diaphragm with a thickness of 0.005 μm~10000 μm, the fluorescent film with a thickness of 0.005 μm~10000 μm, and The composite fluorescence glue film with a thickness of 0.010 μm~10000 μm;And the fluorescent film includes organic silicon substrate, it is described to have It is evenly dispersed in machine silicon substrate to have fluorescent grain object, wherein the fluorescent grain object is the fluorescent powder that partial size is 0.001~50 μm, Alternatively, the fluorescent grain object is the fluorescence quantum that partial size is 1.0~100 nm;The infrared radiation diaphragm include substrate and in The partial size of evenly dispersed inorganic heat dissipation filler in the substrate, the inorganic heat dissipation filler is 0.001 μm~500 μm.
2. composite fluorescence glue film as described in claim 1, it is characterised in that: the composite fluorescence glue film can make to set wavelength Light penetrates;And/or the surface of the fluorescent film or infrared radiation diaphragm has the function of pressure sensitive adhesive;And/or the fluorescent film with Infrared radiation diaphragm is wholely set.
3. composite fluorescence glue film as claimed in claim 2, it is characterised in that: the infrared radiation diaphragm with a thickness of 0.05 μm ~ 5000μm;And/or the fluorescent film with a thickness of 20~500 μm;And/or the composite fluorescence glue film with a thickness of 0.05 μm ~5000μm。
4. composite fluorescence glue film as claimed in claim 3, it is characterised in that: the infrared radiation diaphragm with a thickness of 1 μm ~ 1000 μm;And/or the composite fluorescence glue film with a thickness of 1 μm ~ 1000 μm.
5. composite fluorescence glue film as described in claim 1, it is characterised in that: the inorganic heat dissipation filler includes titanium dioxide Grain, zirconium dioxide particle, silicon oxide particle, boron nitride particle, Zinc oxide particles, alumina particle, magnesium oxide particle, mica The combination of any one or more in grain, rare-earth oxide particle.
6. composite fluorescence glue film as described in claim 1, it is characterised in that: the partial size of the inorganic heat dissipation filler is 0.05 μm ~50μm。
7. composite fluorescence glue film as claimed in claim 6, it is characterised in that: it is described it is inorganic heat dissipation filler partial size be 0.5 μm ~ 10μm。
8. a kind of encapsulating structure of semiconductor light-emitting apparatus, it is characterised in that including light emitting semiconductor device and claim 1- Composite fluorescence glue film described in any one of 7, fluorescent film or infrared radiation diaphragm in the composite fluorescence glue film are partly led with described Body luminescent device combines.
9. the encapsulating structure of semiconductor light-emitting apparatus according to claim 8, it is characterised in that: the fluorescent film is infrared The light-emitting surface of radiation film and the light emitting semiconductor device is bound directly;And/or the light emitting semiconductor device includes LED.
10. the encapsulating structure of semiconductor light-emitting apparatus according to claim 8, it is characterised in that: the semiconductor light emitting Device has more than two light-emitting surfaces, and the composite fluorescence glue film covers all light out of the light emitting semiconductor device Face.
11. the encapsulating structure of semiconductor light-emitting apparatus according to claim 10, it is characterised in that: the semiconductor light emitting There are five light-emitting surfaces for device tool.
12. the encapsulating structure of semiconductor light-emitting apparatus according to claim 8, it is characterised in that: the semiconductor light emitting Device has a light-emitting surface, is covered with the composite fluorescence glue film on the light-emitting surface.
13. the encapsulating structure of semiconductor light-emitting apparatus according to claim 12, it is characterised in that further include around described Light emitting semiconductor device setting reflective structure, the light-emitting surface be arranged within the space that the reflective structure is enclosed or Person exposes from the space that the reflective structure is enclosed.
14. the encapsulating structure of semiconductor light-emitting apparatus according to claim 13, it is characterised in that: the light-emitting surface setting In the space that the reflective structure is enclosed, and the surface for the composite fluorescence glue film being covered on the light-emitting surface is from described Expose in the space that reflective structure is enclosed.
15. the encapsulating structure of semiconductor light-emitting apparatus according to claim 14, it is characterised in that: the reflective structure At least local interior wall is gradually to be inclined outwardly setting on the direction far from light emitting semiconductor device, and in the semiconductor Transparent enclosure glue is filled between luminescent device and the inclined surface of the reflective structure inner wall.
16. the encapsulating structure of semiconductor light-emitting apparatus according to claim 13, it is characterised in that: the light-emitting surface is from institute It states and exposes in the space that reflective structure is enclosed, the composite fluorescence glue film continuously covers the light-emitting surface and the reflective knot At least local surface of structure.
17. the encapsulating structure of semiconductor light-emitting apparatus described in any one of 0-16 according to claim 1, it is characterised in that: institute State the light emitting semiconductor device that light emitting semiconductor device is inverted structure.
18. a kind of light source, it is characterised in that the encapsulation including semiconductor light-emitting apparatus described in any one of claim 8-17 Structure.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111370563A (en) * 2018-12-25 2020-07-03 弗洛里光电材料(苏州)有限公司 Composite fluorescent glue film and application thereof

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111370563A (en) * 2018-12-25 2020-07-03 弗洛里光电材料(苏州)有限公司 Composite fluorescent glue film and application thereof

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