WO2020133160A1 - Composite phosphor film and application thereof - Google Patents

Abstract

A composite phosphor film, comprising a fluorescent film and an infrared radiation film combined with the fluorescent film. The fluorescent film comprises an organic silicon matrix. Fluorescent particles are evenly distributed in the organic silicon matrix. The infrared radiation film comprises a base material and an inorganic dissipating filler which is uniformly dispersed in the base material. The composite phosphor film allows light with a set wavelength to pass through. Also provided is use of the composite phosphor film, for example, an application in packaging of a semiconductor light emitting apparatus.

Description

Composite fluorescent adhesive film and its application Technical field

This application relates to a phosphor film (Phosphor Film or Phosphor Sheet) in the field of semiconductors, especially a composite fluorescent film, which can be used to encapsulate semiconductor light-emitting components, such as wafer-level WLP LEDs, chip size CSP LEDs, quantum dots LED (QD LED), laser LED, LED filament lamp, Micro LED, mini LED and other fields.

Background technique

LEDs (semiconductor light-emitting diodes) are widely used in lighting, backlighting, etc. due to their advantages of low energy consumption, long life, and small size. The packaging process is a very important process in the LED manufacturing process, which has a very significant impact on the working performance and cost of the LED.

The existing LED packaging processes mainly include device-level packaging technology, wafer-level LED packaging (WLP) technology, and chip-scale packaging CSP (Chip Scale Package) technology. These technologies have their own advantages, but they also have some defects. In view of this, the researchers are also unanimously committed to improving the LED packaging technology.

For example, US7294861B, US2014091346A1, etc. have proposed the use of fluorescent tape or fluorescent adhesive sheet for LED packaging technology. Phosphor powder, fluorescent nanocrystals, etc. are dispersed in these fluorescent tapes and fluorescent adhesive sheets to realize the wavelength conversion of the light emitted from the LED. Although this type of packaging has improved operation convenience and cost compared with traditional technologies, it still has defects, for example, it is not conducive to the heat transfer generated when the LED is working, and this problem also has a large impact on the performance of the LED. On the other hand, most of the current LED heat dissipation technology still uses the traditional heat sink structure to dissipate heat through heat conduction, but its heat dissipation performance needs to be further improved.

Summary of the invention

The main purpose of the present application is to provide an improved composite phosphor film (Phosphor Film, PF) to overcome the deficiencies in the prior art.

Another object of the present application is to provide a method for packaging semiconductor light-emitting elements using the composite fluorescent glue film.

To achieve the purpose of the invention, the technical solutions adopted in this application include:

An embodiment of the present application provides a composite fluorescent adhesive film, which includes a fluorescent film and an infrared radiation film combined with the fluorescent film, the fluorescent film includes an organic silicon matrix, and fluorescent particles are uniformly dispersed in the organic silicon matrix, The infrared radiation film includes a base material and an inorganic heat dissipation filler uniformly dispersed in the base material, and the composite fluorescent adhesive film can transmit light of a set wavelength.

After the composite fluorescent glue film is combined with the semiconductor light emitting device, when the heat generated by the semiconductor light emitting device during operation is conducted to the composite fluorescent glue film, the infrared radiation film therein can efficiently dissipate the heat through radiation and heat dissipation Move to the external environment.

An embodiment of the present application further provides a semiconductor light-emitting device, which includes a semiconductor light-emitting device and the composite fluorescent glue film, the fluorescent film or the infrared radiation film in the composite fluorescent glue film and the light emitting surface of the semiconductor light-emitting device Combine.

An embodiment of the present application also provides a packaging method of a semiconductor light emitting device, which includes:

Provide the composite fluorescent adhesive film, and

The fluorescent film or infrared radiation film in the composite fluorescent glue film is fixedly combined with the light emitting surface of the semiconductor light emitting device.

Further, the semiconductor light emitting device includes an LED.

By adopting the solution of the present application, while effectively simplifying the packaging process of the semiconductor light emitting device, the heat dissipation of the semiconductor light emitting device can be improved, thereby ensuring the working stability of the semiconductor light emitting device and extending its service life.

The technical solutions of the present application will be explained more specifically in conjunction with the embodiments below, but it is not intended to limit the present application.

BRIEF DESCRIPTION

1 is a schematic diagram of a manufacturing process of a composite fluorescent adhesive film in an embodiment of the present application;

2 is a schematic structural view of a fluorescent film encapsulating LED in a comparative example of this application;

FIG. 3 is a schematic structural view of a composite fluorescent adhesive film encapsulating LED in a typical embodiment of the present application;

FIG. 4 is a schematic structural diagram of a compound fluorescent adhesive film encapsulating LED in another exemplary embodiment of the present application.

FIG. 5 is a schematic diagram of measuring the spatial chromaticity consistency of light using the nine-point method in the embodiment of the present application.

6A-6E are schematic diagrams of LED package structures in some embodiments of the present application.

detailed description

An aspect of an embodiment of the present application provides a composite fluorescent adhesive film, which includes a fluorescent film and an infrared radiation film combined with the fluorescent film, the fluorescent film includes an organic silicon matrix, and the organic silicon matrix is uniformly dispersed For fluorescent particles, the infrared radiation film includes a base material and an inorganic heat dissipating filler uniformly dispersed in the base material, and the composite fluorescent adhesive film can transmit light of a set wavelength.

Further, the inorganic heat dissipation filler includes any one or a combination of titanium dioxide, zirconium dioxide, silicon oxide, boron nitride, zinc oxide, aluminum oxide, magnesium oxide, mica, and rare earth metal oxide, but not Limited to this.

Further, the inorganic heat-dissipating filler may be in the form of particles, microplates, wires, tubes, etc., and the size thereof may be on the order of nanometers, submicrometers, or micrometers.

By uniformly dispersing these inorganic heat dissipation fillers in the base material, the infrared radiation film formed can have a radiation heat dissipation function.

In some more preferred embodiments, by selecting the type and size of the inorganic heat dissipating filler, the radiation wavelength generated by the infrared radiation film can be mainly distributed in the infrared band and the far-infrared band, which is beneficial to contain the composite fluorescent glue The lighting device and display device of the film are used in the home environment, and produce human body health care and other functions.

In some more preferred embodiments, the particle size of the inorganic heat-dissipating filler is 0.001 μm to 500 μm, preferably 0.05 μm to 50 μm, more preferably 0.5 μm to 10 μm

In some more preferred embodiments, the content of the inorganic radiation filler in the infrared radiation film is 0.001wt% ~ 10wt%, preferably 0.1wt% ~ 10wt%, more preferably 1wt% ~ 10wt%.

In some more preferred embodiments, the inorganic heat dissipation filler uses a combination of zinc oxide and magnesium oxide and/or mica.

Preferably, the content of zinc oxide in the infrared radiation film is 0.001 wt% to 10 wt%, further preferably 0.1 wt% to 10 wt%, and particularly preferably 1 wt% to 10 wt%.

Preferably, the content of magnesium oxide in the infrared radiation film is 0.001 wt% to 10 wt%, further preferably 0.1 wt% to 10 wt%, and particularly preferably 1 wt% to 10 wt%.

Preferably, the content of mica in the infrared radiation film is 0.001 wt% to 10 wt%, further preferably 0.1 wt% to 10 wt%, and particularly preferably 1 wt% to 10 wt%. The addition of mica will make the infrared radiation film have better radiation heat dissipation performance.

Further, the substrate may be formed of a silicone composition.

Preferably, the silicone composition used to form the substrate may be the same as the silicone composition used to form the phosphor matrix of the phosphor film, so as to form a matched multilayer structure, good adhesion, and Demonstrates excellent reliability during device use.

In some embodiments, the infrared radiation film may be formed by pre-curing (B-stage, Silicone, Curables) a composition of a silicone composition and phosphor particles, and the surface has a pressure sensitive adhesive (PSA) function. In some embodiments of the present application, the percentage of the following peel strength of the infrared radiation film is more than 30%;

Percentage of the peel strength=[Peel strength in 75°C atmosphere/Peel strength in 25°C atmosphere]×100

Peeling strength in the 75°C atmosphere: peeling strength when peeling the infrared radiation film from the light emitting surface of the semiconductor light emitting device at a peeling angle of 180° and a speed of 300 mm/min at a temperature of 75°C;

Peeling strength in the 25°C atmosphere: Peeling strength when peeling the infrared radiation film from the light exit surface of the semiconductor light emitting device at a temperature of 25°C at a peeling angle of 180 degrees and a speed of 300 mm/min.

Further, the thickness of the infrared radiation film is 0.005 μm to 10000 μm, preferably 0.05 μm to 5000 μm, and particularly preferably 1 μm to 1000 μm.

By adopting the preferred embodiment, the infrared radiation film can also have a higher light transmittance and produce functions similar to the light guide and light diffuser, that is, the infrared radiation film can be injected into the infrared The light of the radiation film can be evenly emitted from the light exit surface of the infrared radiation film to improve the light quality.

Further, the silicone matrix may be formed by pre-curing or completely curing the silicone composition.

Further, the fluorescent film may be formed by pre-curing or completely curing the fluorescent encapsulating composition, and the fluorescent encapsulating composition may be mainly composed of the silicone composition and the fluorescent particles (hereinafter also referred to as "fluorescent material") .

In some embodiments, the fluorescent film may be formed by pre-curing the fluorescent encapsulating composition (B-stage, Silicones, Curables), and the surface has a pressure-sensitive adhesive (PSA) function.

Furthermore, the fluorescent encapsulating composition is prepared by mixing the fluorescent particles and the silicone composition in the following ratio and stirring and mixing.

In some embodiments, the fluorescent material in the fluorescent encapsulating composition accounts for 0.01 wt% to 90 wt% of the non-solvent component, preferably 1 wt% to 80 wt%, and more preferably 3 wt% to 70 wt%.

In some embodiments, the color temperature of the fluorescent material is 1800K-20000K, and the color rendering index is 60-100.

In some embodiments, the fluorescent particles are fluorescent powders with a particle size of 1-50 μm.

In some embodiments, the phosphor includes rare earth phosphor, rare earth garnet phosphor, alkaline earth metal sulfide gallate, alkaline earth metal sulfide, zinc sulfide type, alkaline earth metal aluminate, phosphate, borate, Any combination of two or more of silicate, fluoroarsenate, fluorogermanate, rare earth sulfide, rare earth oxide, vanadate, and nitride phosphor. Preferably, the phosphor can be selected from aluminate, silicate, nitride and oxynitride phosphors with better chemical and high temperature stability, especially nitride and oxynitride phosphors. Particularly preferably, the phosphor is YAG yttrium aluminum garnet phosphor doped with rare earth elements or Ce doped YAG yttrium aluminum garnet phosphor. These phosphors can be freely obtained from the market. For example, the phosphor may be a combination of various phosphors, for example, a red phosphor produced by GE Corporation (General Electric Company), that is, a phosphor phosphor, which belongs to the potassium fluorosilicate (PFS) phosphor series, may be added.

In some embodiments, further, the fluorescent particles are fluorescent quantum dots with a particle size of 1-100 nm, preferably 1-20 nm.

In some embodiments, the composition material of the fluorescent quantum dots includes group II-VI or group III-V elements, and it is particularly preferred that the material of the fluorescent quantum dots includes any one of ZnSe, CdS, CdSe, and CdSe A combination of two or more, further preferably, the material of the fluorescent quantum dot is selected from arsenic gallium, indium phosphide, or gallium nitride, still more preferably, the fluorescent quantum dot has a core-shell structure, still more preferably The fluorescent quantum dots are CdSe/ZnS core-shell structure quantum dots.

In some embodiments, the fluorescent quantum dots may also be perovskite quantum dots.

In some embodiments, the content of the phosphor in the non-solvent component in the fluorescent encapsulating composition is preferably 1.0 wt% to 90 wt%, and more preferably 1.0 wt% to 70 wt%.

In some embodiments, the content of fluorescent quantum dots in the non-solvent component in the fluorescent encapsulating composition is preferably 0.01-50 wt%, and more preferably 0.01-5.0 wt%.

The silicone composition has a main chain formed mainly of siloxane bonds (-Si-O-Si-) in the molecule, and a silicon atom (Si) bonded to the main chain and composed of an alkyl group Side chains formed by organic groups such as aryl groups (eg phenyl) and alkoxy groups (eg methoxy). Specifically, examples of the silicone resin composition include dehydration condensation curing type silicone resin, addition reaction curing type silicone resin, peroxide curing type silicone resin, moisture curing type silicone resin, etc. Type silicone resin, etc. The resin can be used alone or in combination of two or more.

In some embodiments, the main component of the silicone composition is a siloxane-based rubber with a number average molecular weight higher than 3×10 ⁴ g/mol, a silicone resin containing vinyl functional groups, a Si-H functional group-containing A silicone resin, a hydrosilylation catalyst, and an organic solvent or diluent used to form a homogeneous solution with the components of the silicone composition.

In some embodiments, the silicone-based rubber (also known as silicone rubber) contains vinyl functional groups, preferably, the silicone-based rubber contains more than 2 vinyl groups per molecule, more preferably Preferably, the silicone-based rubber contains phenyl functional groups. It is further preferred that the silicone-based rubber contains more than one phenyl group per molecule.

In some embodiments, the silicone rubber is a rubber having organosiloxane units as repeating links on the polymer backbone, wherein the following general formula-{Si(R ¹ )(R ² )-O--﹜ represents an organosiloxane unit, wherein R ¹ and R ² are each a monovalent organic group, or especially an alkyl group, such as methyl, ethyl, etc.; an aryl group, such as phenyl, etc.; Alkenyl, such as vinyl, etc.; cyanoalkyl, such as γ-cyanopropyl, etc.; or fluoroalkyl, such as trifluoropropyl, etc.

In some embodiments, the silicone rubber may be obtained through suitable sources known in the industry, including homemade or from market sources. For example, refer to EP 0470745A2, "Glossary of Chemical Terms" (Van Nostrand and Reinhold Company, 1976), JP2005288916, DE102004050128.9, U3) 279890A, JP 330084/1998, JP19981124, JP332821/1998, CN1212265A, etc.

More specifically, the silicone rubber may be selected from dimethyl silicone rubber, methyl phenyl silicone rubber, methyl vinyl silicone rubber, fluorinated alkyl methyl silicone Rubber, cyanoalkyl silicone rubber, etc., but not limited to this.

Further, R ¹ and/or R ² in the organosiloxane unit are preferably vinyl or phenyl.

Further, in the silicone composition, the content of the silicone rubber in the non-solvent component may be 1 wt% to 90 wt%, preferably 10 wt% to 70 wt%, and particularly preferably 20 wt% to 50 wt%.

Preferably, the content of vinyl groups in the silicone rubber is 0.01% or more and 70% or less of the total weight of the silicone rubber.

More preferably, the content of phenyl in the silicone rubber is 0.01% or more and 95% or less of the total weight of the silicone rubber. Preferably, the number average molecular weight of the silicone-based rubber is 3×10 ⁴ g/mol to 1×10 ⁸ g/mol, and more preferably 1×10 ⁵ g/mol to 1×10 ⁷ g/mol In particular, it is preferably 3×10 ⁵ g/mol to 1×10 ⁶ g/mol.

Further, the vinyl functional group-containing siloxane resin contains more than two vinyl groups per molecule. Preferably, the vinyl functional group-containing siloxane resin includes a linear, branched, or network structure Preferably, the vinyl functional group-containing siloxane resin has a number average molecular weight (Mn) of 10 ⁵ g/mol or less, preferably 1×10 ² g/mol to 1×10 ⁵ g/mol, more preferably The range is from 1×10 ² g/mol to 1×10 ⁴ g/mol.

More preferably, the vinyl functional group-containing siloxane resin contains more than one phenyl group per molecule.

In some embodiments, the vinyl functional group-containing siloxane resin comprises any of RSiO _3/2 units, RR′SiO _2/2 units, RR′R″SiO _1/2 units, and SiO _4/2 units One or more combinations in which R, R', R" are substituted or unsubstituted monovalent hydrocarbon groups.

In some embodiments, the Si-H functional group-containing siloxane resin comprises RSiO _3/2 units, RR′SiO _2/2 units, RR′R″SiO _1/2 units, and SiO _4/2 units. Any one or more combinations, wherein R, R', R" are substituted or unsubstituted monovalent hydrocarbon groups.

More specifically, in some embodiments, the structure of the vinyl functional group-containing siloxane resin is as follows:

In some embodiments, the vinyl functional group-containing siloxane resin may be (R ¹ [OR ² ]SiO)m-(R ³ CH ₂ =CH-SiO)n, where R ¹ , R ² , R ³ can be vinyl, m and n can be 0 or a positive integer.

In some embodiments, the vinyl functional group-containing silicone resin may be selected from vinyl-containing POSS.

Further, in the silicone composition, the content of the non-solvent component of the silicone resin containing vinyl functional groups may be 1 wt% to 90 wt%, preferably 10 wt% to 70 wt%, and particularly preferably 20 wt% to 50wt%.

In the present application, the Si-H functional group-containing siloxane resin contains two or more Si-H groups per molecule. Preferably, the Si-H functional group-containing siloxane resin contains a linear, a branched or network structure; preferably, the silicone resin containing Si-H functional groups of the number average molecular weight below 10 ⁵ g / mol, preferably from ^{10 2 g / mol ~ 10 5} g / mol, more preferably The range is from 1×10 ² g/mol to 1×10 ⁴ g/mol.

More preferably, the Si-H functional group-containing siloxane resin contains more than one phenyl group per molecule.

In the silicone resin containing Si-H functional groups described in this application, the silicon-bonded groups other than silicon-bonded hydrogen atoms may be optionally substituted monovalent hydrocarbon groups other than alkenyl groups, For example, methyl, ethyl, propyl or similar alkyl; phenyl, tolyl, xylyl, naphthyl or similar aryl; benzyl, phenethyl or similar aralkyl; 3-chloro Propyl, 3,3,3-trifluoropropyl or similar haloalkyl, but preferably, there is at least one aryl group in one molecule of this component, especially phenyl, especially more than two phenyl groups. The molecular structure of this component is not particularly limited, and it may have a linear, branched, or partially branched linear, cyclic, or dendritic molecular structure. In some embodiments, the Si-H functional group-containing siloxane resin may be represented by the following substance: an organic polymer composed of units of formula (CH ₃ ) ₂ HSiO _1/2 and C ₆ H ₅ SiO _3/2 Silicone resin; organopolysiloxane resin composed of units of formula (CH ₃ ) ₂ HSiO _1/2 , (CH ₃ ) ₃ SiO _1/2 and formula C ₆ H ₅ SiO _3/2 ; by formula ( CH ₃ ) ₂ HSiO _1/2 and SiO _4/2 organopolysiloxane resin; composed of the formula (CH ₃ ) ₂ HSiO _1/2 , (CH ₃ ) ₂ SiO _2/2 and SiO _4/2 The unit is composed of organopolysiloxane resin, etc.

More specifically, in some embodiments, the structure of the Si-H functional group-containing siloxane resin is as follows:

Where p is an integer greater than or equal to 1.

In some embodiments, the Si-H functional group-containing silicone resin may also be selected from POS containing Si-H functional groups.

In the silicone composition, the content of the Si-H functional group-containing siloxane resin is 1 wt% to 90 wt%, preferably 2 wt% to 50 wt%, and particularly preferably 5 wt% to 30 wt%.

Further, in the present application, the content of Si-H groups in the Si-H functional group-containing silicone resin is 0.1 mol% to 100 mol%, preferably 0.2 mol% to 95 mol%, particularly preferably 0.5 mol% ~90mol%.

Further, in this application, the molar ratio of Si-H groups in the Si-H functional group-containing siloxane resin to vinyl groups in the vinyl functional group-containing siloxane resin is 0.02-50:1, It is preferably 0.1 to 10:1, and particularly preferably 0.5 to 5:1.

Further, regarding the selection and preparation process of this Si-H functional group-containing siloxane resin, reference may be made to CN101151328A, CN102464887A, and so on.

Further, the silicone resin (silicone resin containing vinyl functional groups, silicone resin containing Si-H functional groups) is a class of soluble materials such as benzene, toluene, xylene, heptane and the like Liquid hydrocarbons, ketones, greases, solvents for photoresists or liquid organosilicon compounds soluble in low viscosity cyclic polydiorganosiloxanes and linear polydiorganosiloxanes, which may include R ³ ₃ monofunctional (M) units represented by SiO _1/2 , bifunctional (D) units represented by R ³ ₂ SiO _2/2 , trifunctional (T) units represented by R ³ SiO _3/2 and SiO _4/2 Representative tetrafunctional (Q) unit. R ³ represents a monovalent organic group, which is a substituted or unsubstituted monovalent hydrocarbon group. Wherein, the monovalent unsubstituted hydrocarbon group may be selected from but not limited to the following groups: alkyl groups such as methyl, ethyl, propyl, pentyl, octyl, undecyl and octadecyl; alkenes Groups such as vinyl, allyl, butenyl, pentenyl and hexenyl; alicyclic groups such as cyclohexyl and cyclohexenylethyl; alkynyl groups such as ethynyl, propynyl and butylene Alkynyl; cycloalkyl such as cyclopentyl and cyclohexyl; and, aromatic groups such as ethylbenzyl, naphthyl, phenyl, tolyl, xylyl, benzyl, styryl, 1-benzene Ethyl and 2-phenethyl, optionally phenyl. Non-reactive substituents that may be present on R ³ include but are not limited to halogen and cyano. The monovalent organic group as a substituted hydrocarbon group may be selected from but not limited to the following groups: halogenated alkyl groups such as chloromethyl, 3-chloropropyl and 3,3,3-trifluoropropyl, fluoromethyl, 2 -Fluoropropyl, 3,3,3-trifluoropropyl, 4,4,4-trifluorobutyl, 4,4,4,3,3-pentafluorobutyl, 5,5,5,4, 4,3,3-heptafluoropentyl, 6,6,6,5,5,4,4,3,3-nonafluorohexyl, 8,8,8,7,7-pentafluorooctyl, etc. Preferably, the monovalent unsubstituted hydrocarbon group in the silicone resin of the present application is a vinyl group, in particular, the silicone resin contains more than two phenyl groups per molecule. For the selection and preparation process of the silicone resin in this application, reference may be made to US 6,124,407, US 2,676,182, U2), 774,310, US 6,124,407, etc.

The amount of the hydrosilylation catalyst should be sufficient to promote the curing of the silicone composition of the present application. These hydrosilylation catalysts are known in the art and are commercially available, for example, can be selected from, but not limited to, the following: platinum group metals: platinum, rhodium, ruthenium, palladium, osmium or iridium metals or their organic metals Compounds and their combinations. More specifically, it may be selected from platinum black, compounds such as chloroplatinic acid, the reaction product of chloroplatinic acid hexahydrate, and monohydric alcohol, bis(ethylacetoacetate) platinum, bis(acetylpyruvate) platinum, di A complex of platinum chloride and the compound with an olefin or a low molecular weight organopolysiloxane or a platinum compound microencapsulated in a matrix or core-shell type structure. The complex of platinum and low molecular weight organopolysiloxane includes 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex with platinum. These complexes can be microencapsulated in a resin matrix. Alternatively, the catalyst may include a 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex with platinum. These hydrosilylation catalysts can refer to CN1863875A (paragraph 0020-0021 of the specification), US 3,159,601, U1), 220,972, U1), 296,291, U1), 419,593, U1), 516,946, U1), 814,730, U1), 989,668 , U2), 784,879, U3), 036,117, U3), 175,325, EP 0 347 895 B, U2), 766,176, U3), 017,654 and other documents. And/or, for at least one UV active Pt catalyst, reference may be made to US 8,314,200.

In some embodiments, based on the weight of the silicone composition, the amount of the hydrosilylation catalyst may be a platinum group metal in the following range: 0.1 ppm to 1.000 ppm, optionally 1 ppm to 1000 ppm, and optionally 10ppm to 100ppm. In this application, the solvent may be of any suitable type, such as water, organic solvents or a mixture of the two, preferably from organic solvents, such as but not limited to n-hexane, toluene, chloroform , Dichloromethane, ethanol, acetone, 2-butanone, 4-methyl-2-pentanone, grease, photoresist solvents (eg PGME, PGMEA), etc., to be combined with the rest of the materials in the composition It is a liquid with good fluidity, especially a homogeneous solution.

In the silicone composition, the content of the solvent may be about 10wt% to 90wt%, preferably 20wt% to 80wt%, particularly preferably 30wt% to 70wt%, especially the solvent under normal pressure The boiling point is 60℃～250℃.

In the silicone composition, the content of the diluent may be about 10 wt% to 90 wt%, preferably 20 wt% to 80 wt%, and particularly preferably 30 wt% to 70 wt%.

In some embodiments, the diluent includes at least one reactive diluent. Preferably, the reactive diluent uses a monovinyl compound capable of participating in the hydrosilylation reaction and a compound containing one Si-H functional group Or a monovinyl compound containing a Si-H functional group. Particularly preferably, the reactive diluent may be selected from monovinylsilane compounds and/or monoallylsilane compounds. Preferably, the viscosity of the diluent at room temperature is less than 100 cPs, particularly preferably less than 50 cPs, particularly preferably less than 10 cPs. . By using the reactive diluent, the use of organic solvents can be avoided, environmental pollution can be reduced, and the compatibility of each component in the silicone composition can also be improved.

More specifically, the monovinyl compound suitable as the diluent can refer to US 6,333,375B and other documents. For example, it can be selected from one or more aromatic vinyl compounds, typically such as styrene, α-methylstyrene, 2-methylstyrene, methylstyrene, methylstyrene, 4-diisopropyl Styrene, dimethylstyrene, 4-tert-butylstyrene, 5-t-butyl-2methylstyrene, chlorobenzene, styrene and styrene monofluorochloride. In particular, styrene or the like can be preferably used.

Furthermore, the polymerized monomer of the monovinyl compound may also contain at least one polar group having a hetero atom, for example, it may be a vinyl monomer containing an amine group, a vinyl monomer containing a hydroxyl group, Among the oxygen-containing vinyl monomers, the first two are particularly preferred. These vinyl monomers having a polar group containing a hetero atom may be used alone or in combination.

Further, the vinyl monomer containing an amine group is a polymerizable monomer, and at least one amine group in the molecule is a primary amine (such as acrylamide, methacrylamide, p-aminobenzene, aminomethyl (methyl Group) Acrylic acid aminoethyl (meth)acrylic acid aminopropyl (meth)acrylic acid amino (meth)acrylic acid butyl ester), secondary amine (for example, see JP130355/86A, for example, anilinophenyl butadiene monosubstituted (Meth) acrylamide such as N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-hydroxymethyl acrylamide, N-(4-anilinophenyl) methacryl Amides) or tertiary amines (such as N,N-disubstituted aminoalkyl acrylates, N,N-dialkylaminoalkyl acrylamides, N,N-disubstituted amino aromatic vinyl compounds and vinyl-containing Pyridine compounds), especially tertiary amines. More specifically, the N,N-disubstituted aminoalkyl acrylate containing an acrylic group or a methacrylic group may be selected from N,N-dimethylaminomethyl (meth)acrylic acid, N,N-dimethyl Aminoethyl (meth)acrylic acid, N,N-dimethylaminopropyl (meth)acrylic acid, N,N-dimethylaminobutyl (meth)acrylic acid, N,N-diethylamino Ethyl (meth)acrylic acid, N,N-diethylaminopropyl (meth)acrylic acid, N,N-diethylaminobutyl (meth)acrylic acid, N-methyl-N-ethylamino Ethyl (meth)acrylic acid, N,N-dipropylaminoethyl (meth)acrylic acid, N,N-dibutylaminoethyl (meth)acrylic acid, N,N-dibutylaminopropyl (Meth)acrylic acid, N,N-dibutylaminobutyl (meth)acrylic acid, N,N-dihexylaminoethyl (meth)acrylic acid, N,N-dioctylaminoethyl (meth) ) Acrylic acid and acryloylmorpholine. Among them, N,N-di(meth)acrylic acid, N,N-di(meth)acrylic acid, N,N-dipropylaminoethyl (meth)acrylic acid, N,N-dioctylaminoethyl (Meth)acrylic acid and N-methyl-N-ethylaminoethyl (meth)acrylate are particularly preferred. For another example, the N,N-disubstituted amino aromatic vinyl compound may include styrene derivatives, such as N,N-dimethylaminoethylstyrene, N,N-diethylaminoethylstyrene , N,N-dipropylaminoethylstyrene and N,N-dioctylaminoethylstyrene. As another example, the vinyl-containing pyridine compound may include vinyl pyridine, 4-vinyl pyridine, 5-methyl-2-vinyl pyridine, 5-ethyl-2-vinyl pyridine, and the former two are particularly preferred.

Further, the hydroxyl group-containing vinyl monomer may be a polymerizable monomer containing at least one primary hydroxyl group, secondary hydroxyl group or tertiary hydroxyl group. These hydroxyl group-containing vinyl monomers include, for example, hydroxyl group-containing unsaturated carboxylic acid monomers, hydroxyl group-containing vinyl ether monomers and hydroxyl group-containing vinyl ketone monomers, preferably hydroxyl group-containing unsaturated carboxylic acid monomers. Examples of hydroxyl-containing unsaturated carboxylic acid monomers include acrylic acid, methacrylic acid, itaconic acid, fumaric acid, and maleic acid derivatives (such as esters, amides, anhydrides). Among them, acrylic and methacrylate compounds are particularly preferred. More specifically, the hydroxyl-containing vinyl monomer may include hydroxymethyl (meth)acrylic acid, hydroxypropyl methacrylate (meth), hydroxypropyl (meth)acrylate (meth)acrylic acid, (meth) ) Acrylic acid 2-hydroxypropyl, 3-phenoxy-2-hydroxypropyl (meth)acrylic acid glyceride (meth)acrylic acid butyl (meth)acrylic acid, 2-chloro-3-hydroxypropyl (Meth)acrylic acid, hydroxyhexyl (meth)acrylate, hydroxyoctyl (meth)acrylic acid, hydroxymethyl (meth)acrylamide, 2-hydroxypropyl (meth)acrylamide, (meth) Acrylamide, hydroxypropyl di (ethylene glycol) itaconic acid, itaconic acid di (propylene glycol), bis (2-hydroxypropyl) bis (2-hydroxyethyl) itaconic acid, itaconic acid, bis ( 2-hydroxyethyl) ester, bismaleic acid (2-hydroxyethyl), methyl vinyl ether, hydroxymethyl ketene and allyl alcohol. Among them, hydroxymethyl (meth) acrylate, hydroxypropyl (meth) acrylate, (meth) acrylic acid, hydroxypropyl (meth) acrylate, 3-phenoxy-2-hydroxypropyl ( Glycerin methacrylate (butyl) methacrylate (meth)acrylic acid (meth)acrylic acid hydroxyhexyl, hydroxypropyl (meth)acrylic acid, hydroxymethyl (meth)acrylamide, 2-hydroxypropyl (Meth) acrylamide and hydroxypropyl (meth) acrylamide are preferred.

Further, the oxygen-containing vinyl monomer may include an alkoxy-containing vinyl monomer (see JP188356/95A), such as trimethoxyvinylsilane, triethoxyvinylsilane, 6-methoxy Silyl-1,2-hexene, p-trimethoxysilyl styrene, 3-trimethoxysilyl propyl and 3-triethoxysilyl acrylate, etc.

In some embodiments, the silicone composition may further include additives such as inhibitors, small molecular silanes (which may or may not contain ethylene or Si-H functional groups), adhesion promoters, heat or UV Cured epoxy/acrylic/polyurethane/bismaleimide and other resins, inorganic fillers, rheology modifiers, tackifiers, wetting agents, defoamers, leveling agents, dyes and phosphors to prevent precipitation Any one or a combination of two or more agents (such as Shin-Etsu DM-30, Sanwell SH series LED phosphor anti-settling agent, etc.).

Wherein, the inhibitor, that is, a hydrosilylation reaction inhibitor refers to a substance that can cause a poor hydrosilylation reaction, refer to CN1863875A (paragraph 0025), etc., which can be selected from the group consisting of acetylene alcohol compounds and ene-yne compounds , Siloxane or benzotriazole and other hydrosilane reaction inhibitors. For example, the acetylene alcohol compound inhibitor may be selected from 2-phenyl-3-butyn-2-ol, 2-methyl-3-butyn-2-ol, 3,5-dimethyl-1-hexyl Alkyn-3-ol and the like; the ene-yne compound can be selected from 3-methyl-3-pentene-1-yne and the like, and the siloxane can be selected from 1,3,5,7-tetramethyl-1, 3,5,7-tetrahexenylcyclotetrasiloxane, 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane, etc. Among them, acetylene alcohol compounds are preferred, and 2-phenyl-3-butyn-2-ol is particularly preferred.

Wherein, the tackifier or adhesion promoter can be selected from ethyl orthosilicate, vinyl trimethoxysilane, n-butyl borate, isopropyl borate, titanium isooctanoate, zirconium isooctanoate, n-butyl titanate Ester, isopropyl titanate, KH-171, KH-560, KH-570, etc. (refer to paragraph 0026 of CN1863875A specification, etc.), the adhesion promoters available on the market can be JCR6101, JCR6101UP produced by Dow Corning, EG6301, OE6336, JCR6175, JCR6109, Hipec4939, Hipec1-9224, OE6250, SR7010, SE9207, SE1740, SE9187L, etc., but not limited thereto.

Wherein, the inorganic filler may be known in the art and is commercially available, for example, may include inorganic fillers such as silica, for example, colloidal silica, fumed silica, quartz powder, Titanium oxide, glass, aluminum oxide, zinc oxide, or a combination thereof, the filler may have an average particle size of 50 nanometers or less and not reduce the percentage of light transmission through scattering or absorption. As for the definitions such as rheology modifiers, wetting agents, defoamers, leveling agents, dyes, etc., their definitions are well known in the industry and can be freely selected from the corresponding materials commonly used in the industry.

The silicone composition can be prepared by any conventional method, such as mixing all ingredients at a suitable temperature, for example room temperature.

The viscosity of the silicone composition is 1,000 mPa.s to 500,000 mPa.s, preferably 5,000 mPa.s to 100,000 mPa.s, and particularly preferably 7,000 mPa.s to 50,000 mPa.s.

In some embodiments, the fluorescent film may be formed by semi-curing (pre-curing) the fluorescent encapsulating composition, and is preferably a flexible film.

Further, the conditions of the semi-curing include heating and ventilating conditions, the temperature condition is 20° C. to 200° C., preferably 80° C. to 120° C., and the time is 10 to 100000 s, preferably 10 to 8000 s.

Further, the conditions for completely curing the fluorescent film include: completely curing the fluorescent film by heating or electromagnetic irradiation.

Further, the thickness of the fluorescent film may be extremely thin (for example, it may be about 10 μm to 10000 μm, preferably about 20 to 500 μm).

Further, the fluorescent film can be stored stably for a long time. In order to prevent it from being polluted by the external environment, the surface can be covered with release material (such as release paper, etc.), and the release material is torn off during use.

In some embodiments, the method for preparing the fluorescent film may specifically include:

S1: film formation, film formation of the fluorescent encapsulation composition through solution formation, casting coating, screen/steel screen printing, spin coating, (vacuum) extrusion film formation, etc.;

S2: Initial curing, forming a pre-cured film that is not sticky on the surface and can be peeled off, that is, the fluorescent film, which has similar characteristics as pressure-sensitive adhesive.

In an alternative embodiment, the step S2) may include: removing the organic solvent in the film under radiation and/or heating and ventilation conditions, thereby forming the pre-cured film. The heating temperature used therein may be 20 to 200°C, preferably 80 to 120°C, and the heating time is 10 to 100,000 seconds, preferably 10 to 8000 seconds.

In some embodiments of the present application, the method for preparing the composite fluorescent adhesive film may include: bonding the infrared radiation film and the fluorescent film to form the composite fluorescent adhesive film.

Both the infrared radiation film and the fluorescent film may be self-supporting films.

In some embodiments of the present application, in the composite fluorescent adhesive film, the fluorescent film and the heat radiation film are integrally provided.

In some embodiments of the present application, the method for preparing the composite fluorescent adhesive film may include: pasting the prepared infrared radiation film and the prepared fluorescent film to form the composite fluorescent adhesive film.

Wherein, the preparation method of the infrared radiation film may be known in the industry, for example, it may include: dissolving the polymer constituting the base material in a corresponding solvent to form a solution, and dispersing it into the inorganic heat dissipating filler, and then forming the The dispersion or slurry is prepared by spin coating, spray coating, printing, film casting and other methods to form a thin film. In this process, depending on the actual needs, it can also include drying and other processes.

In some embodiments of the present application, the following preparation process may also be used to make the composite fluorescent adhesive film, for example:

Preparing the fluorescent film;

Dissolve the polymer constituting the base material in a corresponding solvent to form a solution, and disperse it into an inorganic heat-dissipating filler, and then directly coat the formed dispersion or slurry on the fluorescent film to form the infrared radiation film .

In some embodiments, the thickness of the composite fluorescent adhesive film is 0.010 μm to 10000 μm, preferably 0.05 μm to 5000 μm, and particularly preferably 1 μm to 1000 μm.

The composite fluorescent adhesive film provided by the present application has the characteristics of ultra-thin, simple structure, etc. When it is applied to the packaging of semiconductor light-emitting devices, etc., it can effectively simplify the packaging process of semiconductor light-emitting devices, while providing efficient light conversion efficiency, and greatly Improve the heat dissipation performance of the semiconductor light-emitting device, ensure its working stability, extend its service life, and also improve the light-emitting quality of the semiconductor light-emitting device, including but not limited to its light uniformity.

Another aspect of the present application also provides a packaging method of a semiconductor light emitting device, which includes:

Provide the composite fluorescent adhesive film, and

The fluorescent film or the heat radiation film in the composite fluorescent glue film is combined with the semiconductor light emitting device.

In some embodiments, the fluorescent film or the heat radiation film in the composite fluorescent glue film may be fixedly combined with the light emitting surface of the semiconductor light emitting device.

In some embodiments, a package structure of a semiconductor light emitting device is provided, in which the semiconductor light emitting device has more than two light emitting surfaces, and the composite fluorescent glue film covers all light emitting surfaces of the semiconductor light emitting device.

In some embodiments, the semiconductor light emitting device has five light exit surfaces.

In some embodiments, the semiconductor light emitting device has a light exit surface, and the light exit surface is covered with the composite fluorescent glue film.

In some embodiments, the packaging structure of the semiconductor light emitting device further includes a reflective structure disposed around the semiconductor light emitting device, and the light exit surface is disposed within a space formed by or surrounded by the reflective structure The space enclosed by the structure is exposed.

In some embodiments, the light exit surface is disposed in a space enclosed by the reflective structure, and the surface of the composite fluorescent adhesive film covering the light exit surface is exposed from the space enclosed by the reflective structure .

In some embodiments, at least a part of the inner wall of the light reflecting structure is gradually inclined outward in a direction away from the semiconductor light emitting device, and the inclined surface between the semiconductor light emitting device and the inner wall of the light reflecting structure is filled Transparent encapsulant. Such a design can further improve the light extraction efficiency of the semiconductor light emitting device.

In some embodiments, the light exit surface is exposed from a space formed by the reflective structure, and the composite fluorescent glue film continuously covers at least a part of the surface of the light exit surface and the reflective structure.

In some embodiments, the semiconductor light emitting device is a semiconductor light emitting device with a flip-chip structure.

Another aspect of the present application also provides a packaging method of a semiconductor light emitting device, which includes:

Provide the composite fluorescent adhesive film, and

The fluorescent film or the heat radiation film in the composite fluorescent glue film is fixedly combined with the light emitting surface of the semiconductor light emitting device.

In the present application, the meaning of "packaging" is known to those skilled in the art, for example, it may be that the silicone composition is cured in certain areas on the surface of the article to form a coating Or, partly immerse one or more articles in the cured product formed from the silicone composition, or encapsulate the one or more articles integrally formed on the silicone composition In the cured product.

Further, in some more specific embodiments, the packaging method may include the following steps:

1): Sticking a film, covering the composite fluorescent glue film on the light emitting surface of a semiconductor light emitting device such as an LED, and bonding the fluorescent film to the light emitting surface of the semiconductor light emitting device under high temperature and/or applying pressure;

2): curing, placing the semiconductor light emitting device with the composite fluorescent glue film on in a constant temperature (elevated temperature) environment, and curing the fluorescent film;

3): Post-curing treatment, for example, cutting the cured product into smaller units.

In a more preferred embodiment, the step 1)) may include: during the process of applying pressure to the composite fluorescent adhesive film, at least the composite fluorescent adhesive film is further subjected to a heat treatment to make the fluorescence therein The film is adhered to the light emitting surface of the semiconductor light emitting device. The applied pressure may be 0.001 Pa to 10000 Pa, preferably 0.1 Pa to 1000 Pa, and the pressure applied time is 0.001 to 100,000 seconds, preferably 0.1 to 100 seconds. The heating temperature employed therein may be 0 to 260°C, preferably 50 to 200°C, particularly preferably 80 to 150°C, and the time is preferably 10 to 100,000 seconds.

Of course, in step 1)), other methods may be used to replace the heat treatment of the composite fluorescent adhesive film, or to process the composite fluorescent adhesive film in cooperation with the heating method, and these methods may include irradiation (such as remote Infrared, ultraviolet, visible light, microwave, any one or more of electron beam), where the wavelength can be 10 ^-8 to 10 ³ m, and the time can be 10 to 100,000 seconds.

The semiconductor light emitting device may be a chip-level LED chip, a wafer-level LED device, an LD (laser), or the like.

Another aspect of the embodiments of the present application further provides a semiconductor light-emitting device, which includes a semiconductor light-emitting device and the composite fluorescent glue film, and the fluorescent film or the heat-radiating radiation film in the composite fluorescent glue film emits light with the semiconductor Device bonding. In some embodiments, the fluorescent film or the heat radiation film in the composite fluorescent adhesive film is fixedly combined with the light exit surface of the semiconductor light emitting device.

Another aspect of the embodiments of the present application further provides a semiconductor light-emitting device, which includes a semiconductor light-emitting device and the composite fluorescent glue film, and the fully cured body of the fluorescent film in the composite fluorescent glue film emits light with the semiconductor The light emitting surface of the device is combined.

In some embodiments of the present application, the percentage of the following peel strength of the fluorescent film is more than 30%;

Percentage of the peel strength=[Peel strength in 75°C atmosphere/Peel strength in 25°C atmosphere]×100

Peeling strength in the 75°C atmosphere: peeling strength when the fluorescent film is peeled from the light exit surface of the semiconductor light emitting device at a peeling angle of 180° and a speed of 300 mm/min at a temperature of 75°C;

Peeling strength in the 25°C atmosphere: Peeling strength when the fluorescent film is peeled from the light exit surface of the semiconductor light emitting device at a peeling angle of 180° and a speed of 300 mm/min at a temperature of 25°C.

Further, the completely cured body is integrated with the semiconductor light emitting device, or it can be considered that the completely cured body is firmly bonded to the light exit surface of the semiconductor light emitting device in a manner that is not peelable.

Furthermore, the fluorescent film or the completely cured body of the fluorescent film is directly combined with the light exit surface of the semiconductor light emitting device. Further, the following thermal weight loss rate of the fully cured body is below 5% (≤5wt%);

The thermal weight loss rate is defined as the weight loss rate of placing the fully cured body at a temperature of 150°C for 1000 h.

Preferably, the thermal weight loss rate is below 2%.

For example, in some more specific implementation cases, the packaging process of a type of LED light-emitting device may include:

At normal temperature or under certain heating conditions, the light emitting surface of an LED chip is attached to the surface of a fluorescent film of a composite fluorescent adhesive film, and a certain pressure is applied by rubber roller rolling to make the two closely adhere Close (no bubbles);

The shape of the composite fluorescent adhesive film is processed by die-cutting and other methods to match the shape of the LED chip;

The LED chip with the compound fluorescent glue film attached is placed in a light curing device (such as a UV light box) or a thermal curing device (such as a baking box), and after a period of time, the fluorescent film therein is completely cured. The fully cured body of the fluorescent film is integrated with the LED chip, and the two can hardly be peeled away from each other. More precisely, the fully cured body can only be formed after cracking under high-strength impact. The surface debris will come off without being completely peeled off from the surface of the LED chip.

Of course, in some embodiments, the infrared radiation film in the composite fluorescent glue film may also be combined with the light emitting surface of the semiconductor light emitting device.

Among them, the LED chip may be pre-mounted on the substrate. The LED chip is also provided with LED-side terminals for electrically connecting with the substrate-side terminals of the substrate. The substrate may be formed of an insulating substrate such as a silicon substrate, a ceramic substrate, a polyimide resin substrate, or a laminated substrate formed by laminating insulating layers on a metal substrate. For example, on the upper surface of the substrate, a conductor pattern including a substrate-side terminal for electrically connecting to the LED-side terminal of the LED and a wiring connected thereto is formed. The conductor pattern is formed of conductors such as gold, copper, silver, and nickel. The LED chip may be connected to the substrate by, for example, flip chip mounting or wire bonding.

Thereafter, other transparent encapsulation layers may also be provided on the composite of the LED and the composite fluorescent glue film as needed, and such transparent encapsulation layers may be formed of transparent resin. Then, the size of such a transparent encapsulation layer is adjusted according to the need, such as grinding and cutting.

In some more specific implementation cases of this application, the manufacturing process of a CSP LED package device may include:

Crystal placement: arrange an LED chip or an array of multiple LED chips on the substrate;

Enclosing white walls and smoothing: apply CSP white wall glue on the LED chips, and then smooth them to expose at least the light emitting surface of each LED chip;

Film: the fluorescent film in the composite fluorescent adhesive film is closely attached to the light emitting surface of each LED chip, and then the fluorescent film is completely cured;

Cutting: The device formed in the previous step is cut and processed, and then other post-processing operations are performed to obtain a finished product.

The process conditions used in the film sticking process may include: a temperature of 100 to 150° C., a pressure of 0.003 to 0.015 MPa, and a time of 1 to 5 min. The process conditions for completely curing the fluorescent film may be: ~180°C, 2~4h.

In other more specific implementation cases of this application, the manufacturing process of a CSP LED package device may include:

Solid crystal: attach an LED chip or an array of multiple LED chips to the fluorescent film in the composite fluorescent glue film;

Enclosing white walls and smoothing: apply CSP white wall glue on the LED chips, and then smooth them to expose at least the light emitting surface of each LED chip;

Curing: completely curing the fluorescent film;

Cutting: The device formed in the previous step is cut and processed, and then other post-processing operations are performed to obtain a finished product.

The technical solution of the present application will be explained in more detail in combination with several more specific embodiments and corresponding comparative examples. However, it still needs to be emphasized that these embodiments should not be regarded as any limitation on the scope of protection of the present application. Also, unless otherwise specified, all parts, percentages, ratios, etc. in the specification of this application are by weight.

The fluorescent encapsulation composition involved in the following examples can be formulated with reference to the currently widely used organosilicon mixtures in the industry. For example, the components of the silicone composition can be divided into component A (mainly containing Silicone resins with vinyl functional groups, platinum catalysts, additives, etc.) and component B ((mainly containing silicone resins with vinyl functional groups, silicone resins with Si-H functional groups, additives, etc.), in use When mixing the two components in a certain ratio, then add the corresponding content of phosphor or phosphor combination.

The inorganic fillers, silicone compositions (which can also be regarded as organic silica gel materials), phosphors, etc. used in the following examples can be obtained from the market. For example, the inorganic filler may be TiO ₂ (DuPont TS6300, D ₅₀ =0.53um), SiO ₂ (Cabot TS720), Al ₂ O ₃ (Baito High-Tech Materials Co., Ltd., TPA-5, D ₅₀ = 5um), ZnO (Teng too _{Chemical, D 50 = 50nm), BN} ( one hundred Performance materials Co., _{ABN-5, D 50 = 5um} ), MgO ( one hundred Performance materials Co., Ltd., particle size of about 10- 20um) one or more combinations. The organic silicone material may be a low-fold PF1 slurry or a high-fold PF2 slurry (purchased from Flory Optoelectronics (Suzhou) Co., Ltd.).

The manufacturing process of the composite fluorescent adhesive film involved in the following embodiments may be:

Preparation of fluorescent film: put the fluorescent packaging composition upside down on a flat plate or PET film, use a film former (such as the single-sided preparation device of Shanghai Pushen Chemical Machinery Co., Ltd.) to make a film of a certain thickness, and obtain it by curing on a heating platform A non-flowing, peelable adhesive film (B-stage, free-standing), that is, a fluorescent film.

Preparation of infrared radiation film: 1) Add a certain proportion of inorganic filler in order to the organic silica gel PF1 slurry, mix evenly, and make a certain thickness of infrared radiation film on the PET film (Example 1 to Example 6) The raw material composition of each infrared radiation film can refer to Table 1); 2) Put the film layer of step 1 into a 150°C oven for pre-curing for 10 minutes; 3) Cover the film layer with a PET film to obtain an infrared radiation film (reference (Figure 1). Of course, the composition for forming the infrared radiation film can also be placed upside down on a flat plate, a film of a certain thickness can be made using a film former, and cured to form an infrared radiation film. Preparation of composite fluorescent adhesive film: the infrared radiation film and the fluorescent film are pasted together to obtain the composite fluorescent adhesive film (refer to FIG. 1).

Of course, the composition for forming the infrared radiation film (including the polymer, solvent or diluent for forming the substrate and the uniformly dispersed inorganic heat dissipating filler, which may be a dispersion or slurry) may also be directly coated On the fluorescent film, the infrared radiation film is cured again to obtain the composite fluorescent adhesive film.

Embodiment 1 A method for preparing a composite fluorescent adhesive film includes the following steps:

(1) Provide an organic silicone PF1 slurry (purchased from Flory Optoelectronics (Suzhou) Co., Ltd.), which is an organic silicon composition containing ethylene having a number average molecular weight higher than 3×10 ⁵ g/mol Silicone-based rubber (component 1, SG6066, vinyldimethylsilyl terminated Methyl Vinyl Silicone Gum, Power Chemicals Ltd, number average molecular weight 450,000-600,000g/mol, Vinyl content of about 0.90-1.10wt%), silicone resin containing vinyl functional groups (component 2, A05-01-A, Flory Optoelectronics (Suzhou) Co., Ltd.), silicon containing Si-H functional groups Oxane resin (component 3, A05-01-B, Flory Optoelectronics (Suzhou) Co., Ltd.), hydrosilylation catalyst (component 4, SIP6832.2, Gelest, 200ppm), solvent (4-methyl -2-pentanone, 200g) and other basic components, of course, can also contain other auxiliary components.

(2) Mix the commercially available yellow phosphor SDY558-15 (Yantai Hild New Material Co., Ltd.) in the PF1 slurry at a mass ratio of 10:1, and then mix evenly by a double planetary mixer to form a fluorescent package combination.

(3) Apply the fluorescent encapsulation composition to the substrate by a film maker (such as a 1mm film maker) or a printing method, especially a screen printing method, and then heat at 100°C (heating platform in a fume hood) After 20 minutes, a fluorescent film was obtained.

(4) TiO ₂ (DuPont TS6300) and SiO ₂ (Cabot White Carbon Black TS720) are sequentially mixed with the organic silica gel PF1 slurry to form a slurry containing 1.0wt% TiO ₂ and 1wt% SiO ₂ and then Curing at about 150°C forms an infrared heat dissipation film. The silicone PF1 slurry can also be replaced with other silicone compositions with similar properties.

(5) Laminate the infrared heat dissipation film and the fluorescent film to form a composite fluorescent adhesive film.

Embodiment 2 This embodiment is basically the same as Embodiment 1, except that:

The fluorescent encapsulation composition involved in step (1) is also formed by combining an organic silicone PF1 slurry (purchased from Flory Optoelectronics (Suzhou) Co., Ltd.) with phosphor powder, and its components are as follows: the number average molecular weight is higher than 3×10 ⁵ g/mol of vinyl siloxane-based rubber (SG6066, vinyl dimethyl silyl terminated methyl vinyl silicone rubber, vinyldimethylsilyl terminated Methyl Vinyl Silicone Gum, Power Chemicals Ltd, number average molecular weight about 450,000 -600,000g/mol, vinyl content about 0.90-1.10wt%) 4g, siloxane resin containing vinyl functional groups (A05-01-A, Flori Optoelectronics (Suzhou) Co., Ltd.) 12.8g, vinyl Vinylmethoxysiloxane Homopolymer VMM-010, Gelest 0.35g, siloxane resin containing Si-H functional groups (A05-01-B, Flory Optoelectronics (Suzhou) Co., Ltd.) 6.8 g. Hydrosilylation catalyst (SIP6832.2, Gelest) 20ppm, solvent 4-methyl-2pentanone 20g, yellow phosphor SDY558-15from Yantai Hild New Material Co., Ltd. 35.5g.

The pre-curing conditions used in step (3) are: 110°C (heating platform in fume hood) for 10 minutes.

The slurry formed in step (4) includes 1.5 wt% TiO ₂ (DuPont TS6300) and 0.5 wt% SiO ₂ (Cabot white carbon black TS720), and the balance is the organic silica gel PF1 slurry. The silicone PF1 slurry can also be replaced with other silicone compositions with similar properties.

The composite fluorescent adhesive film prepared in this embodiment is a transparent off-white film.

Embodiment 3 This embodiment is basically the same as Embodiment 1, except that:

The fluorescent encapsulation composition involved in step (1) is also formed from a combination of an organic silicone PF1 slurry (purchased from Flory Optoelectronics (Suzhou) Co., Ltd.) and phosphor powder, the number average molecular weight of which is higher than 3×10 ⁵ g/mol of vinyl siloxane-based rubber (SG6066, vinyl dimethyl silyl terminated methyl vinyl silicone rubber, vinyl dimethylsilyl terminated Methyl Vinyl Silicone Gum, Power Chemicals Ltd, number average molecular weight about 450,000-600,000 g/ mol, vinyl content about 0.90-1.10wt%) 1.8g, siloxane resin containing vinyl functional groups (A05-01-A, Flory Optoelectronics (Suzhou) Co., Ltd.) 4.6g, vinyl methoxy Silicone homopolymer (Vinylmethoxysiloxane Homopolymer, VMM-010, Gelest) 0.35g, siloxane resin containing Si-H functional group (A05-01-B, Flori Optoelectronics (Suzhou) Co., Ltd.) 4.6g, Hydrosilylation catalyst (SIP6832.2, Gelest) 10ppm, solvent 4-methyl-2pentanone 9.0g, 0.34g yellow phosphor SDY558-15, 20.1g green phosphor SDG530H, 1.2g red phosphor SSDR630Q-2 ( All were purchased from Yantai Hild New Material Co., Ltd.).

The slurry formed in step (4) contains 0.3wt% TiO ₂ (DuPont TS6300), 0.5wt% SiO ₂ (Cabot White Carbon Black TS720), 0.3wt% SiO ₂ (TPA-5), 0.3wt% ZnO (Purchased from Tengtai Chemical), 0.3wt% boron nitride (ABN-5), 0.3wt% mica powder (JTX heat dissipation powder), and the balance is the organic silicone PF1 slurry.

The thickness of the composite fluorescent adhesive film prepared in this embodiment is a transparent white film.

Embodiment 4 This embodiment is basically the same as Embodiment 1, except that:

The fluorescent encapsulation composition involved in step (1) is also formed from a combination of an organic silicone PF1 slurry (purchased from Flory Optoelectronics (Suzhou) Co., Ltd.) and phosphor powder, the number average molecular weight of which is higher than 3×10 ⁵ g/mol Methyl Phenyl Vinyl Silicone Rubber (Flory Optoelectronic Materials (Suzhou) Co., Ltd., number average molecular weight about 500,000g/mol, phenyl content about 30wt%, ethylene Base content about 0.35-0.40wt%) 3.7g, silicone resin containing phenyl and vinyl functional groups (H20-01-A, Flory Optoelectronics (Suzhou) Co., Ltd.) 7.7g, containing phenyl and Si -H functional silicone resin (H20-01-B, Flory Optoelectronics (Suzhou) Co., Ltd.) 7.7g, hydrosilylation catalyst (SIP6832.2, Gelest) 10ppm, solvent 4-methyl-2pentane Ketone 1.2g, 0.48g yellow phosphor SDY558-15, 14.3g green phosphor SDG530H, 0.86g red phosphor SSDR630Q-2 (all purchased from Yantai Hild New Material Co., Ltd.). After the above components are mixed evenly by a double planetary mixer, a mixture with a phosphor content of 44.9% by weight is obtained. The slurry formed in step (4) contains 0.3wt% TiO ₂ (DuPont TS6300), 0.5wt% SiO ₂ (Cabot White Carbon Black TS720), 0.3wt% SiO ₂ (TPA-5), 0.3wt% ZnO (Purchased from Tengtai Chemical), 0.3 wt% boron nitride (ABN-5), 0.3 wt% MgO (particle size about 10-20 μm), the balance is the organic silicone PF1 slurry.

The composite fluorescent adhesive film prepared in this embodiment is a transparent off-white film.

Embodiment 5 This embodiment is basically the same as Embodiment 1, except that:

The fluorescent encapsulation composition involved in step (1) is also formed by combining an organic silicone PF1 slurry (purchased from Flory Optoelectronics (Suzhou) Co., Ltd.) with phosphor powder, and the solvent component in the organic silicone PF1 slurry PGMEA was 50wt%, wherein the non-solvent component comprising: 5wt% γ- cyanopropyl silicone rubber ^{(MW = 4.12 × 10 5 g} / mol), 90wt% a compound of formula ^{I (MW = 1.2 × 10 2} g / mol ), 5wt% compound of formula V, 1ppm chloroplatinic acid.

The slurry formed in step (4) contains 1.0 wt% ZnO (purchased from Tengtai Chemical), 1.0 wt% MgO (particle size about 10-20 μm), and the remainder is the organo-silica gel PF1 slurry.

The composite fluorescent adhesive film prepared in this embodiment is a film with high transparency.

Embodiment 6 This embodiment is basically the same as Embodiment 1, except that:

The fluorescent encapsulating composition involved in step (1) is also formed by combining an organic silica gel PF1 slurry (purchased from Flory Optoelectronics (Suzhou) Co., Ltd.) with phosphor powder, the organic silica gel PF1 slurry solvent component 4 -Methyl-2-pentanone is 50% by weight, wherein the non-solvent component includes: 51% by weight of trifluoropropyl siloxane rubber (MW = 1 × 10 ⁸ g/mol), 21% by weight of compound of formula III (MW = 1.05 ×10 ⁴ g/mol), 28 wt% compound of formula II, 100 ppm bis(ethylacetoacetate) platinum.

The slurry formed in step (4) contains 1.0 wt% ZnO (purchased from Tengtai Chemical), 1.0 wt% MgO (particle size about 10-20 μm), and the remainder is the organo-silica gel PF1 slurry.

The composite fluorescent adhesive film prepared in this embodiment is a film with high transparency.

Control groups 1 to 6: The control examples 1 to 6 are basically the same as the examples 1 to 6, except that they only include step (1) to step (3).

The solvent in the fluorescent encapsulating composition of the foregoing embodiment is also replaced with α-methylstyrene, styrene monofluorochloride, N,N-di(meth)acrylic acid, N-methyl-N-ethylaminoethyl (Meth) acrylate, methylol (meth) acrylamide and other diluents.

Table 1

The application performance of the composite fluorescent adhesive film obtained in the foregoing examples (hereinafter referred to as a composite film) and the fluorescent film obtained in a comparative example (hereinafter referred to as PF film) will be tested as follows. The test tools used in it can all be used in the industry, for example: OMEGA HH806AU temperature tester, heat sink, COB, DC power supply, remote handheld illuminance meter, etc. The corresponding test methods are as follows:

1) Thermal performance test:

① The composite fluorescent adhesive film of each of the foregoing examples and the fluorescent film obtained in the comparative example are attached to the integrated COB surface (refer to FIG. 2 and FIG. 3) of organic silicone encapsulation (A05-01L bare adhesive encapsulation), Ensure that no bubbles remain (if necessary, the fluorescent film must be dried at 150 ℃ ~ 180 ℃ constant temperature until fully cured). In some embodiments, the infrared radiation film in the composite fluorescent glue film can also be attached to the LED chip, see FIG. 4.

②Place the COB on the heat sink, and connect the two with silicone thermal conductive adhesive;

③ Put the two probes of the Omega temperature tester into contact with the integrated COB center and the solder joint of the substrate;

④Connect the integrated COB of the welded wire to the constant current power supply to ensure good contact;

⑤ Connect the power supply;

⑥ OMEGA thermocouple automatic test function, record data once every 30s, the recording time is about 1 hour;

⑦Export the obtained data on the PC, take the average of the stable data records, and organize and summarize them.

The tested samples are shown in Figure 2, and the temperature test results of OMEGA thermocouples are shown in Table 2.

Note: During this heat dissipation performance test, each embodiment can take multiple samples, for example three samples for testing. Each control example also took multiple samples for testing (the results are shown in Table 2).

Table 2

2) Color space uniformity test:

The test uses the nine-point method to measure the spatial chromaticity consistency of light. The test device is shown in Figure 5.

Refer to the previous step ①, attach the composite film and PF1 film to the COB light source respectively, and then place the light source parallel to the screen, the distance between the LED light source and the test screen is L1=15cm, and the 9 points on the screen are arranged at equal intervals (interval L2=15cm ), the middle point and the center point of the LED lamp are on a horizontal plane (as shown in Figure 4).

The 9-point method uses a hand-held illuminance meter to test the 9-point color coordinates and the standard deviation of the color temperature to measure the spatial chromaticity uniformity of the light source. The test results are shown in Table 3.

Table 3 The nine-point method to measure the spatial chromaticity consistency of the composite film light

Note: The test value of "Control Example ^★ " in Table 3 above is the average value of the test results obtained after testing multiple samples corresponding to Control Examples 1-6 respectively.

Obviously, the composite fluorescent adhesive film provided in the embodiments of the present application can significantly improve the heat dissipation performance when it is used to encapsulate a semiconductor light-emitting chip, and at the same time greatly improve the uniformity of its light output.

In addition, the application of the composite fluorescent adhesive film of this application, together with the packaging process known to those skilled in the art, can also implement other forms of packaging for semiconductor light-emitting chips, etc., some typical packaging forms can refer to FIGS. 6A-6E Show.

It should be noted that in this article, the terms "include", "include" or any other variants thereof are intended to cover non-exclusive inclusion, so that a process, method, article or device that includes a series of elements includes not only those elements, It also includes other elements that are not explicitly listed, or include elements inherent to this process, method, article, or equipment.

It should be understood that the above embodiments are only to illustrate the technical concept and characteristics of the present application, and the purpose thereof is to enable those familiar with the technology to understand the content of the present application and implement it accordingly, but not to limit the scope of protection of the present application. All equivalent changes or modifications based on the spirit of this application should be covered within the scope of protection of this application.

Claims (16)

1. A composite fluorescent adhesive film, characterized by comprising a fluorescent film and an infrared radiation film combined with the fluorescent film, the fluorescent film comprises an organic silicon matrix, fluorescent particles are uniformly dispersed in the organic silicon matrix, the infrared radiation The film includes a base material and an inorganic heat dissipation filler uniformly dispersed in the base material, and the composite fluorescent adhesive film can transmit light of a set wavelength.
2. The composite fluorescent adhesive film of claim 1, wherein the inorganic heat dissipation filler includes titanium dioxide, zirconium dioxide, silicon oxide, boron nitride, zinc oxide, aluminum oxide, magnesium oxide, mica, rare earth metal oxide Any one or more of the combination.
3. The composite fluorescent adhesive film according to claim 1, wherein the particle diameter of the inorganic heat dissipation filler is 0.001 μm to 500 μm, preferably 0.05 μm to 50 μm, and more preferably 0.5 μm to 10 μm.
4. The composite fluorescent adhesive film according to claim 1, wherein the content of the inorganic heat dissipating filler in the infrared radiation film is 0.001 wt% to 10 wt%, preferably 0.1 wt% to 10 wt%, and more preferably 1 wt% to 10wt%.
5. The composite fluorescent adhesive film according to claim 2, 3 or 4, characterized in that: the inorganic heat dissipation filler uses a combination of zinc oxide and magnesium oxide and/or mica; preferably, the zinc oxide in the infrared radiation film The content is 0.001wt% to 10wt%, further preferably 0.1wt% to 10wt%, particularly preferably 1wt% to 10wt%; preferably, the content of magnesium oxide in the infrared radiation film is 0.001wt% to 10wt%, further Preferably it is 0.1wt%-10wt%, especially preferably 1wt%-10wt%; preferably, the content of mica in the infrared radiation film is 0.001wt%-10wt%, further preferably 0.1wt%-10wt%, especially preferred It is 1 wt% to 10 wt%.
6. The composite fluorescent adhesive film according to claim 1, wherein the substrate is formed of a silicone composition.
7. The composite fluorescent adhesive film according to claim 1, wherein the silicone composition in the fluorescent film or infrared radiation film is pre-cured, and the surface of the fluorescent film or infrared radiation film has a pressure-sensitive adhesive function .
8. The composite fluorescent adhesive film according to claim 1, wherein the percentage of the following peel strength of the fluorescent film or infrared radiation film is 30% or more;

   Percentage of the peel strength=[Peel strength in 75°C atmosphere/Peel strength in 25°C atmosphere]×100

   Peeling strength in the 75°C atmosphere: peeling strength when the fluorescent film or infrared radiation film is peeled from the light emitting surface of the semiconductor light emitting device at a peeling angle of 180° and a speed of 300 mm/min at a temperature of 75°C;

   Peeling strength in the 25°C atmosphere: Peeling strength when peeling the fluorescent film or infrared radiation film from the light emitting surface of the semiconductor light emitting device at a peeling angle of 180° and a speed of 300 mm/min at a temperature of 25°C.
9. The composite fluorescent adhesive film according to claim 1, wherein the thickness of the infrared radiation film is 0.005 μm to 10000 μm, preferably 0.05 μm to 5000 μm, and particularly preferably 1 μm to 1000 μm.
10. The composite fluorescent adhesive film according to claim 1, wherein the fluorescent particles are fluorescent powder with a particle size of 0.001-50 μm, or the fluorescent particles are fluorescent quantum dots with a particle size of 1.0-100 nm .
11. The composite fluorescent adhesive film according to claim 1, wherein the thickness of the fluorescent film is 0.005 μm to 10000 μm, preferably 20 to 500 μm.
12. The composite fluorescent adhesive film according to claim 1, wherein the thickness of the composite fluorescent adhesive film is 0.010 μm to 10000 μm, preferably 0.05 μm to 5000 μm, and particularly preferably 1 μm to 1000 μm.
13. A semiconductor light-emitting device, characterized by comprising a semiconductor light-emitting device and the composite fluorescent glue film according to any one of claims 1-12, wherein the fluorescent film or infrared radiation film in the composite fluorescent glue film and the semiconductor emit light Device combination; preferably, the fluorescent film or infrared radiation film is directly combined with the light exit surface of the semiconductor light emitting device.
14. The semiconductor light emitting device according to claim 13, wherein the semiconductor light emitting device includes an LED.
15. A method for packaging a semiconductor light emitting device, characterized in that it includes:

    Providing the composite fluorescent adhesive film according to any one of claims 1-12, and

    The fluorescent film or infrared radiation film in the composite fluorescent glue film is fixedly combined with the light emitting surface of the semiconductor light emitting device.
16. The packaging method according to claim 15, wherein the semiconductor light emitting device includes an LED.

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