WO2016145652A1 - Procédé de fabrication d'un dispositif semi-conducteur optique, une composition de résine thermodurcissable associée, et un semi-conducteur optique obtenu à partir de celle-ci - Google Patents

Procédé de fabrication d'un dispositif semi-conducteur optique, une composition de résine thermodurcissable associée, et un semi-conducteur optique obtenu à partir de celle-ci Download PDF

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Publication number
WO2016145652A1
WO2016145652A1 PCT/CN2015/074578 CN2015074578W WO2016145652A1 WO 2016145652 A1 WO2016145652 A1 WO 2016145652A1 CN 2015074578 W CN2015074578 W CN 2015074578W WO 2016145652 A1 WO2016145652 A1 WO 2016145652A1
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WO
WIPO (PCT)
Prior art keywords
thermosetting resin
resin composition
reflector
carbon atoms
optical semiconductor
Prior art date
Application number
PCT/CN2015/074578
Other languages
English (en)
Inventor
Qingxu YANG
Qili WU
Hikita AYA
Yuting Wang
George HE
Jin Song
Yao WEI
Justin QIN
Lufang JIA
Guanghui BIN
Ning Du
Guangchao Xie
Original Assignee
Ablestik (Shanghai) Ltd.
Henkel Electronics Materials Llc
Henkel Huawei Electronics Co.Ltd.
Henkel Japan Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
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Publication date
Application filed by Ablestik (Shanghai) Ltd., Henkel Electronics Materials Llc, Henkel Huawei Electronics Co.Ltd., Henkel Japan Ltd. filed Critical Ablestik (Shanghai) Ltd.
Priority to PCT/CN2015/074578 priority Critical patent/WO2016145652A1/fr
Priority to CN201580080038.7A priority patent/CN108292692B/zh
Priority to TW105105879A priority patent/TW201638254A/zh
Publication of WO2016145652A1 publication Critical patent/WO2016145652A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
    • H01L33/58—Optical field-shaping elements
    • H01L33/60—Reflective elements
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/22—Di-epoxy compounds
    • C08G59/24—Di-epoxy compounds carbocyclic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
    • C08G59/4215—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof cycloaliphatic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/68—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used
    • C08G59/686—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used containing nitrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • C08K5/5403—Silicon-containing compounds containing no other elements than carbon or hydrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2237—Oxides; Hydroxides of metals of titanium
    • C08K2003/2241—Titanium dioxide
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2933/00—Details relating to devices covered by the group H01L33/00 but not provided for in its subgroups
    • H01L2933/0008—Processes
    • H01L2933/0033—Processes relating to semiconductor body packages
    • H01L2933/0058—Processes relating to semiconductor body packages relating to optical field-shaping elements

Definitions

  • the present invention relates to a method for manufacturing an optical semiconductor device, particularly an LED device, and to a thermosetting resin composition suitable for using in the method, and to an optical semiconductor device, particularly an LED device, manufactured by the method or from the thermosetting resin composition.
  • An optical semiconductor device such as a light emitting diode (LED) device has now been widely used as various indicators or light sources for such as exterior illumination, automobile lamp and home lighting due to their low power consumption, high efficiency, quick reaction time, long life and the absence of toxic elements such as mercury in the manufacturing process.
  • LED light emitting diode
  • such an optical semiconductor device is in a form of package, and comprises a substrate having electric circuit, an optical semiconductor chip mounted on the substrate, reflectors surrounding at least part of the optical semiconductor chip, and an encapsulant enclosing the optical semiconductor chip.
  • Molding is the most commonly used technology to form a reflector for the optical semiconductor devices.
  • various molding methods including injection molding, transfer molding and compression molding have been widely used in the art for forming the reflector made from resinous materials.
  • US 20130274398 A discloses a thermosetting silicone resin composition for the reflector of LED, and further teaches that the reflectors for an LED therein may be formed by transfer molding or compression molding.
  • US 8466483 A discloses an epoxy resin composition for forming the reflector of an optical semiconductor device. In the manufacturing process, the reflector is produced by transfer molding.
  • WO2009005084 A1 discloses a polyester resin composition for forming the reflector of an optical semiconductor device, the manufacturing process is injection molding.
  • thermosetting materials have a better adhesion with lead frame material than thermoplastic materials since some chemical reactions occur during the curing process, and thermoplastic materials only have van der waals force with the lead frame.
  • Printing methods have been proposed in the art for replacing molding methods for forming a reflector of an optical semiconductor device, since printing methods only require a traditional printer and will bring about lower initial investment cost, faster production speed and less waste of the reflector material compared to the molding methods.
  • JP 2014057090 A discloses that in the manufacturing process of an optical semiconductor device, the reflector can be formed by screen printing to improve the adhesion between the substrate and reflector material.
  • the reflector and package are individually and separately formed therein, so that such manufacturing process still has a drawback of low production speed and the waste of the reflector material.
  • thermosetting resin composition suitable for using in the manufacturing method, especially for screen printing. It is yet another object of the present invention to develop an optical semiconductor device obtained by the manufacturing method or from the thermosetting resin composition.
  • One aspect discloses a method for manufacturing an optical semiconductor device, comprising the steps of:
  • thermosetting resin composition for reflector on each substrate unit by a printing process
  • thermosetting resin composition for reflector 3)curing the thermosetting resin composition for reflector, and obtaining a reflector which defines a cavity on each substrate unit;
  • composition suitable for using in the method according to the present invention is a composition suitable for using in the method according to the present invention.
  • thermosetting resin a)5%-95%by weight of a thermosetting resin
  • weight percentages are based on the total weights of all components of the thermosetting resin composition for reflector.
  • Yet another aspect discloses an optical semiconductor device manufactured by the method according to the present invention or from the thermosetting resin composition according to the present invention.
  • Figs. 1 to 3 are cross-sectional views of a method for manufacturing LED chip devices according to an exemplary embodiment of the present invention
  • Fig. 4 is a cross-sectional view of one example of a LED device manufactured by the method according to the present invention.
  • Fig. 5 is a cross-sectional view of another example of a LED device manufactured by the method according to the present invention.
  • Fig. 6 is a top view of the substrate used in the manufacturing method according to the present invention.
  • Fig. 7 is a cross-sectional view of the partially molded LED devices manufactured by the method according to a conventional method.
  • the present disclosure is generally directed to a method for manufacturing an optical semiconductor device, comprising the steps of:
  • thermosetting resin composition for reflector on each substrate unit by a printing process
  • thermosetting resin composition for reflector 3)curing the thermosetting resin composition for reflector, and obtaining a reflector which defines a cavity on each substrate unit;
  • the method according to the present invention integrally prepares the reflector as a whole, especially prints the thermosetting resin composition for all reflectors in one step, thus brings about lower initial investment cost, faster production speed, higher efficiency and less waste.
  • the inventive thermosetting resin composition possesses an excellent viscosity and an improved thiotropic property, thus facilitates the printing process for forming the reflector of the optical semiconductor devices.
  • the inventive thermosetting resin composition exhibits a superior heat stability.
  • the reflector thus obtained exhibits an improved heat stability and a better adhesion with the electrode or lead frame below it.
  • a substrate consisting of more than one substrate unit 101 each having an electrical circuit.
  • the substrate may be formed from the materials including, but not limited to glass, epoxy resin, ceramic, metal, TAB and silicon.
  • the substrate is made of ceramic or silicon.
  • the substrate may be divided into several substrate units by the dicing process in step 6) as described below.
  • a circuit is included on the top and back of the substrate unit, constituting a circuit pattern.
  • Each circuit has a first electrode and a second electrode, as shown in Figs. 4 and 5, which can be connected to the optical semiconductor chip in the step 4) described later.
  • the electrodes may be made of a metal or some other conductive materials, including but not limited to silver, copper, gold, nickel, aluminum, or any alloy of them.
  • thermosetting resin composition for reflector is provided on each substrate unit by a printing process.
  • a thermosetting resin composition for reflector as described below in details is used.
  • the printing process is selected from screen printing, stencil printing and offset printing.
  • the printing process is screen printing process.
  • the screen printing process is conducted by placing a mask having through holes on more than one substrate unit, and squeezing the thermosetting resin composition for reflector into each through hole, for example, with the use of a spatula. It is understood that the number of the through holes for each substrate unit will depend on the practical need and the design of the optical semiconductor device. Typically, as exemplified in Figs. 1 to 3, in each unit of optical semiconductor device of the present invention, two through holes are arranged on each substrate unit.
  • the more than one substrate unit may form an array of substrate units corresponding to the optical semiconductor devices to be manufactured in a mass production, and thus further forms an array of optical semiconductor devices by using a screen printing mask having an array of through holes.
  • an array of refers to that the units of substrate, chip, through hole, reflector, etc. constitute a two dimensional array or matrix having “m” lines and “n” columns, represented by a m X n array, in which “m” and “n” each represents a integer of from 1 to 100, preferably from 2 to 50.
  • a screen printing mask having a 3 X 4 array of through hole units containing 2 through holes in each unit is used, and thus totally 24 reflectors surrounding 12 chips each electrically connecting to a circle are produced on 12 substrate units.
  • step 3 of the manufacturing method according to the present invention the thermosetting resin composition for reflector are cured, and thus a reflector which defines a cavity on each substrate unit are obtained.
  • the thermosetting resin composition for reflector is cured at a temperature of from 120 to 200 °C, preferably from 140 to 180 °C for 20 seconds to 2 hours, preferably 1 minute to 1.5 hours.
  • Suitable sources of heat to cure the thermosetting resin composition the present invention include induction heating coils, ovens, hot plates, heat guns, IR sources including lasers, microwave sources, etc.
  • the reflector after curing has a light reflectance of more than 70%, preferably more than 80%at the wavelength from 350 nm to 800 nm, so that the light emitted by the optical semiconductor chip, for example, an LED chip can be collected, and thus increasing the efficiency of LED device.
  • the height of the reflector is in the range of from 0.1 mm to 3.0 mm, preferably from 0.3 mm to 2.0 mm. If the reflector height is lower than 0.1 mm, it will be difficult to obtain sufficient brightness and luminous efficiency of the optical semiconductor device. If the reflector height is larger than 3.0 mm, the reflector will not reach the height of the chip (die) conventional used in the art, and the chip will not been fully covered by the reflector, partially exposing to the environment after the encapsulation.
  • the mask may be removed, preferably after curing the thermosetting resin composition in step 3) .
  • Any method commonly used in removing a mask may be used herein.
  • the mask may be partially or completely kept so long as it do not adversely affect the manufacturing method or the final product.
  • step 4) of the manufacturing method according to the present invention an optical semiconductor chip is attached on each substrate unit in each cavity, and each optical semiconductor chip is electrically connected to each electrical circuit on the substrate unit.
  • the circuit comprises a top surface and a bottom surface opposite to each other, wherein the first electrode 102 comprises a top face and a bottom face, and the second electrode 103 comprises a top face and a bottom face.
  • the first electrode 102 and the second electrode 103 are separated.
  • an optical semiconductor chip is preferably used in which a semiconductor such as GaAlN, ZnS, SnSe, SiC, GaP, GaAlAs, AlN, InN, AlInGaP, InGaN, GaN or AlInGaN is formed on a substrate as a light emitting layer, the semiconductor is not limited to these.
  • the light emitting element which provides a light emission peak wavelength between 360 nm and 520 nm is preferable, and a light emitting element which provides a light emission peak wavelength between 350 nm and 800 nm can be used. More preferably, the optical semiconductor chip has the light emission peak wavelength in the short wavelength region of visible light between 420 nm and 480 nm.
  • the surface of the optical semiconductor chip attached on each substrate unit is facing upward, and thus the optical semiconductor chip is located on the top face of the first electrode 102 and is electrically connected to the first and the second electrodes 102, 103 via wire leads 107 as shown in Fig. 5.
  • a non-conductive adhesive may be applied as a bonding material to the gap between the optical semiconductor chip and each of the first and the second electrodes 102, 103.
  • the surface of the optical semiconductor chip attached on each substrate unit is facing downward, and thus the electrical connection can also be achieved by flip chip or eutectic as shown in Fig. 4, wherein a conductive adhesive (represented by the ellipses) is applied to the gap between the optical semiconductor chip and each of the first and the second electrodes 102, 103. Any conductive adhesive commonly used may be used herein, which bonds and electrically connects the optical semiconductor chip with each of the first and the second electrodes 102, 103.
  • the size of the optical semiconductor chip is not particularly limited, and light emitting elements having sizes of 350 ⁇ m (350- ⁇ m-square) , 500 ⁇ m (500- ⁇ m-square) and 1 mm (1-mm-square) can be used. Further, a plurality of light emitting elements can be used, and all of the light emitting elements may be the same type or may be different types which emit emission colors of red, green and blue of three primary colors of light.
  • step 5) of the manufacturing method according to the present invention as shown in Fig. 2, an encapsulant is provided in each cavity, cured, and thus each optical semiconductor device is obtained.
  • the encapsulant is preferably formed from a thermosetting resin.
  • the encapsulant is preferably made of at least one selected from the group consisting of an epoxy resin, modified epoxy resin, silicone resin, modified silicone resin, acrylate resin and urethane resin of a thermosetting resin, and is more preferably made of an epoxy resin, modified epoxy resin, silicone resin or modified silicone resin.
  • the encapsulant is preferably made of a hard material to protect the light emitting element. Further, it is preferable to use a resin having good thermal resistance, weather resistance and light resistance.
  • the encapsulant may be mixed with at least one selected from the group consisting of filler, diffusing agent, pigment, fluorescent material and reflecting material.
  • the encapsulant may contain a diffusing agent.
  • a diffusing agent for example, barium titanate, titanium oxide, aluminum oxide or silicon oxide is adequately used.
  • the encapsulant can contain an organic or inorganic colored dye or colored pigment in order to cut an undesirable wavelength.
  • the encapsulant can also contain a fluorescent material which absorbs light from the light emitting element and converts the wavelength.
  • the encapsulant comprises silicone resin, filler and phosphor.
  • the filler may include, for example, fine powder silica, fine powder alumina, fused silica, crystalline silica, cristobalite, alumina, aluminum silicate, titanium silicate, silicon nitride, aluminum nitride, boron nitride and antimony trioxide. Moreover, it is also possible to use a fibrous filler such as glass fiber and wollastonite.
  • the fluorescent material may be a material which absorbs light from the light emitting element, and converts the wavelengths into light of a different wavelength.
  • the fluorescent material is preferably selected from, for example, at least any one of a nitride phosphor, oxynitride phosphor or sialon phosphor mainly activated by a lanthanoid element such as Eu or Ce, alkaline-earth halogen apatite phosphor, alkaline-earth metal boric acid halogen phosphor, alkaline-earth metal aluminate phosphor, alkaline-earth silicate, alkaline-earth sulfide, alkaline-earth thiogallate, alkaline-earth silicon nitride or germanate mainly activated by a lanthanoid element such as Eu or a transition metal such as Mn, rare-earth aluminate or rare-earth silicon nitride mainly activated by a lanthanoi
  • the nitride phosphor mainly activated by a lanthanoid element such as Eu or Ce includes, for example, M 2 Si 5 N 8 : Eu or MAlSiN 3 : Eu (where M is at least one or more selected from Sr, Ca, Ba, Mg and Zn) . Further, the nitride phosphor also includes MSi 7 N 10 : Eu, M 1.8 Si 5 O 0.2 N 8 : Eu or M 0.9 Si 7 O 0.1 N 10 : Eu in addition to M 2 Si 5 N 8 : Eu (where M is at least one or more selected from Sr, Ca, Ba, Mg and Zn) .
  • the oxynitride phosphor mainly activated by a lanthanoid element such as Eu or Ce includes, for example, MSi 2 O 2 N 2 : Eu (where M is at least one or more selected from Sr, Ca, Ba, Mg and Zn) .
  • the sialon phosphor mainly activated by a lanthanoid element such as Eu or Ce includes, for example, M p/2 Si 12-p-q Al p+q O q N 16-p : Ce or M-Al-Si-O-N (M is at least one selected from Sr, Ca, Ba, Mg and Zn, q is 0 to 2.5, and p is 1.5 to 3) .
  • the alkaline-earth halogen apatite phosphor mainly activated by a lanthanoid element such as Eu or a transition metal such as Mn includes, for example, M 5 (PO 4 ) 3 X: R (M is at least one or more selected from Sr, Ca, Ba, Mg and Zn, X is at least one or more selected from F, Cl, Br and I, and R is at least one or more selected from Eu, Mn, Eu and Mn) .
  • the alkaline-earth metal boric acid halogen phosphor includes, for example, M 2 B 5 O 9 X: R (M is at least one or more selected from Sr, Ca, Ba, Mg and Zn, X is at least one or more selected from F, Cl, Br and I, and R is at least one or more selected from Eu, Mn, Eu and Mn) .
  • the alkaline-earth metal aluminate phosphor includes, for example, SrAl 2 O 4 : R, Sr 4 Al 14 O 25 : R, CaAl 2 O 4 : R, BaMg 2 Al 16 O 27 : R, BaMg 2 Al 16 O 12 : R, or BaMgAl 10 O 17 : R (R is at least one or more selected from Eu, Mn, Eu and Mn) .
  • the alkaline-earth sulfide phosphor includes, for example, La 2 O 2 S: Eu, Y 2 O 2 S: Eu or Gd 2 O 2 S: Eu.
  • the rare-earth aluminate phosphor mainly activated by a lanthanoid element such as Ce includes, for example, YAG phosphors represented by composition formulae of Y 3 Al 5 O 12 : Ce, (Y 0.8 Gd 0.2 ) 3 Al 5 O 12 : Ce, Y 3 (Al 0.8 Ga 0.2 ) 5 O 12 : Ce and (Y,Gd) 3 (Al, Ga) 5 O 12 : Ce. Further, the rare-earth aluminate phosphor also includes Tb 3 Al 5 O 12 : Ce or Lu 3 Al 5 O 12 : Ce where part or all of Y is substituted with, for example, Tb or Lu.
  • the other phosphors include, for example, ZnS: Eu, Zn 2 GeO 4 : Mn or MGa 2 S 4 : Eu (where M is at least one or more selected from Sr, Ca, Ba, Mg and Zn) .
  • these phosphors can realize blue, green, yellow and red and, in addition, tinges such as turquoise, greenish yellow and orange which are intermediate colors of blue, green, yellow and red.
  • the curing process for the encapsulant in step 5) is achieved at a temperature of from 120 to 180 °C, preferably from 140 to 160 °C for 1 to 10 hours, preferably 2 minutes to 8 hours.
  • Suitable sources of heat to cure the thermosetting resin composition include induction heating coils, ovens, hot plates, heat guns, IR sources including lasers, microwave sources, etc.
  • step 6) of the manufacturing method according to the present invention as shown in Fig. 3, the optical semiconductor devices are diced by a cutting device to obtain individual optical semiconductor devices.
  • the cutting device is a rotary blade.
  • optical semiconductor devices are optionally cleaned and dried.
  • the optical semiconductor devices thus obtained have high product-dimensional accuracy and cause less waste of the reflector material.
  • the present invention provides a method for manufacturing an optical semiconductor device, comprising the steps of, in this sequence: steps 1) through 6).
  • the present invention provides a method for manufacturing an optical semiconductor device, comprising the steps of, in this sequence: steps 1) , 4), 2) , 3) , 5) and 6) , wherein the specific operations in each step may be correspondingly adjusted, for example, in step 4) , the optical semiconductor chip is directly attaching on the surface of each substrate (not in each cavity) , since cavities haven’ t formed on these surfaces.
  • Another aspect of the present invention is the optical semiconductor device manufactured by the method according to the present invention.
  • the optical semiconductor device 10 comprises a substrate 101, a circuit having a first electrode 102 and a second electrode 103 on the substrate 101, reflectors 105, an optical semiconductor chip 104 in a flip chip form, and an encapsulant 106.
  • the optical semiconductor device 10 comprises a substrate 101, a circuit having a first electrode 102 and a second electrode 103 on the substrate 101, reflectors 105, an optical semiconductor chip 104, wire leads 107 electrically connecting the chip to the electrodes, and an encapsulant 106.
  • thermosetting resin composition for reflector suitable for using in the manufacturing method.
  • thermosetting resin composition for reflector may comprise at least one thermosetting resin selected from epoxy resins, (meth) acrylates, vinyl ethers, polyesters, benzocyclobutene, siliconized olefins, silicone resins, styrene resins, cyanate ester resins, polyolefins, derivatives thereof, and mixtures of these resins and/or their derivatives, wherein the polyolefins are preferably polybutadienes.
  • thermosetting resin selected from epoxy resins, (meth) acrylates, vinyl ethers, polyesters, benzocyclobutene, siliconized olefins, silicone resins, styrene resins, cyanate ester resins, polyolefins, derivatives thereof, and mixtures of these resins and/or their derivatives, wherein the polyolefins are preferably polybutadienes.
  • thermosetting resin composition for reflector may further comprise a white pigment.
  • thermosetting resin composition for reflector may further comprise a filler, an additive, or any mixture thereof.
  • the additive is different from the filler.
  • thermosetting resin compositions according to the present invention possess an excellent viscosity and thixotropic property so that they are suitable for printing process for forming the reflector of optical semiconductor devices. Moreover, the thermosetting resin composition of the present invention exhibits a superior heat stability. Furthermore, the thermosetting resin composition of the present invention advantageously provides a better adhesion with the electrode or lead frame located below it.
  • thermosetting resin commonly used may be used herein.
  • the thermosetting resin exhibits a superior heat stability, and advantageously provides a better adhesion with the electrode or lead frame located below it.
  • the thermosetting resin composition for reflector comprises at least one thermosetting resin selected from epoxy resins, (meth) acrylates, vinyl ethers, polyesters, benzocyclobutene, siliconized olefins, silicone resins, styrene resins, cyanate ester resins, polyolefins, derivatives thereof, and mixtures of these resins and/or their derivatives.
  • the polyolefins are preferably polybutadienes.
  • the component a) is present in an amount of from 5%to 95%by weight, preferably from 30%to 70%by weight.
  • the silicone resins include reactive silicone resins having the following generic structure:
  • X 4 and X 5 are hydrogen, a linear or branched alkyl group having 1 to 20 carbon atoms (such as methyl, ethyl or any alkyl group with more than two carbons) , an alkenyl group having 2 to 20 carbon atoms (such as vinyl) , cycloalkyl groups having 5 to 25 carbon atoms, cycloalkenyls having 5 to 25 carbon atoms, amine, epoxy, carboxyl, hydroxy, acrylate, methacrylate, mercapto, an alkylhydroxy having 1 to 20 carbon atoms, or a phenol group having 6 to 30 carbon atoms;
  • R 32 and R 33 can be hydrogen, a linear or branched alkyl group having 1 to 20 carbon atoms (such as methyl, ethyl or any alkyl group with more than two carbons) , an alkenyl group having 2 to 20 carbon atoms (such as vinyl) , cycloalky
  • silicone resins suitable for inclusion in the thermosetting resin composition for reflector may include elastomeric polymers comprising a backbone and pendant from the backbone at least one siloxane moiety that imparts permeability, and at least one reactive moiety capable of reacting to form a new covalent bond.
  • siloxanes examples include elastomeric polymers prepared from: 3- (tris (trimethylsilyloxy) silyl) -propyl methacrylate, n-butyl acrylate, glycidyl methacrylate, acrylonitrile, and cyanoethyl acrylate; 3-(tris (trimethylsilyloxy) silyl) -propyl methacrylate, n-butyl acrylate, glycidyl methacrylate, and acrylonitrile; and 3- (tris (trimethylsilyloxy) silyl) -propyl methacrylate, n-butyl acrylate, glycidyl methacrylate, and cyanoethyl acrylate.
  • the silicone resin comprises a mixture of a silicone resin containing at least two alkenyl groups reactive with a Si-H group per molecule, and a silicone resin containing at least two Si-H groups per molecule.
  • the silicone resin comprises:
  • weight percentages are based on the total weights of the silicone resin.
  • thermosetting resin composition for reflector may comprise a silicone resin containing at least two alkenyl groups reactive with a Si-H group per molecule as component a1) .
  • the component a1) may be represented by the average compositional formula (1) :
  • R 1 to R 6 are identical or different groups independently selected from the group consisting of organic groups and an alkenyl group, with the proviso that at least one of R 1 to R 6 is an alkenyl group,
  • a a number ranging from larger than 0 to less than 1
  • b, c and d each represent a number ranging from 0 to less than 1
  • a+b+c+d 1.0
  • the number of alkenyl groups per molecule of the silicone resin is at least 2.
  • the organic groups for R 1 to R 6 are preferably selected from the group consisting of linear or branched alkyl groups having 1 to 20 carbon atoms, alkenyl groups having 2 to 20 carbon atoms, cycloalkyl groups having 5 to 25 carbon atoms, cycloalkenyl groups having 5 to 25 carbon atoms, aryl groups having 6 to 30 carbon atoms, arylalkyl groups having 7 to 30 carbon atoms, and halides of said alkyl, alkenyl, cycloalcyl, cycloalkenyl, aryl and arylalkyl groups.
  • halides used in the present invention refers to one or more halogen-substituted hydrocarbyl groups represented by R 1 to R 6 .
  • halogen-substituted refers to fluoro-, chloro-, bromo-or iodo-radicals.
  • said organic groups are selected from the group consisting of linear or branched alkyl groups having 1 to 10 carbon atoms, alkenyl groups having 2 to 10 carbon atoms, cycloalkyl groups having 5 to 15 carbon atoms, cycloalkenyl groups having 5 to 15 carbon atoms, aryl groups having 6 to 15 carbon atoms, arylalkyl groups having 7 to 15 carbon atoms, and fluorides or chlorides thereof. Still particularly preferably, said organic groups are selected from the group consisting of alkyl groups having 1 to 3 carbon atoms and phenyl. Alkyl groups having 1 to 3 carbon atoms can be methyl, ethyl, n-propyl and i-propyl.
  • R 1 R 2 R 3 SiO 1/2 ) a (R 4 R 5 SiO 2/2 ) b (R 6 SiO 3/2 ) c (SiO 4/2 ) d can be identified with reference to certain units contained in a silicone resin structure. These units have been designated as M, D, T and Q units, which represent, respectively, units with the empirical formulae R 1 R 2 R 3 SiO 1/2 , R 4 R 5 SiO 2/2 , R 6 SiO 3/2 and SiO 4/2 , wherein each of R 1 to R 6 represents a monovalent substituent as defined above.
  • the letter designations M, D, T and Q refer respectively, to the fact that the unit is monofunctional, difunctional, trifunctional or tetrafunctional.
  • the component a1) comprises an alkenyl functional MD silicone resin represented by formula (2) and an alkenyl functional QM resin represented by formula (3) :
  • R 7 to R 11 are identical or different groups independently selected from the group consisting of organic groups and an alkenyl group, with the proviso that at least one of R 7 to R 11 is an alkenyl group,
  • the number of alkenyl group per molecule of the alkenyl functional MD silicone resin is at least 2;
  • R 12 to R 14 are identical or different groups independently selected from the group consisting of organic groups and an alkenyl group, with the proviso that at least one of R 12 to R 14 is an alkenyl group,
  • the number of alkenyl group per molecule of the alkenyl functional MQ silicone resin is at least 2.
  • Suitable example of the alkenyl functional MD silicone resin may be silicone resin represented by formula (4) :
  • q is a number of 1 to 100, preferably 1 to 50
  • r is a number of 1 to 100, preferably 1 to 50.
  • the alkenyl content of component a1) is ranging from 0.3mmole/g to 0.5 mmole/g.
  • the weight ratio of the alkenyl functional MD silicone resin to the alkenyl functional MQ silicone resin is ranging from 0.5: 9.5 to 9: 1, preferably from 1: 9 to 6: 4.
  • Such silicone resins for component a1) can be purchased for example from AB Specialty Silicones under the trade name of Andisil VQM 0.6, VQM 0.8, VQM 1.0 and VQM 1.2. While the silicone resins are commercially available, methods for synthesizing such silicone resins are well known in the art.
  • the component a1) is present in an amount of from1%to 96%, preferably from 87%to 95.9%by weight of the total weight of the silicone resins.
  • thermosetting resin composition for reflector may comprise a silicone resin containing at least two Si-H groups per molecule as component a2) .
  • the component a2) is represented by the average compositional formula (5) :
  • R 21 to R 26 are identical or different groups independently selected from the group consisting of organic groups and hydrogen atom bonded directly to a silicon atom, with the proviso that at least one of R 21 to R 26 is a hydrogen atom bonded directly to a silicon atom,
  • j and n each represent a number ranging from larger than 0 to less than 1
  • k and m each represent a number ranging from 0 to less than 1
  • j+k+m+n 1.0
  • the number of hydrogen atom bonded directly to a silicon atom per molecule of the silicone resin is at least 2.
  • the organic groups for R 21 to R 26 are preferably selected from the group consisting of linear or branched alkyl groups having 1 to 20 carbon atoms, alkenyl groups having 2 to 20 carbon atoms, cycloalkyl groups having 5 to 25 carbon atoms, cycloalkenyl groups having 5 to 25 carbon atoms, aryl groups having 6 to 30 carbon atoms, arylalkyl groups having 7 to 30 carbon atoms, and halides of said alkyl, alkenyl, cycloalcyl, cycloalkenyl, aryl and arylalkyl groups.
  • said organic groups are selected from the group consisting of linear or branched alkyl groups having 1 to 10 carbon atoms, alkenyl groups having 2 to 10 carbon atoms, cycloalkyl groups having 5 to 15 carbon atoms, cycloalkenyl groups having 5 to 15 carbon atoms, aryl groups having 6 to 15 carbon atoms, arylalkyl groups having 7 to 15 carbon atoms, and fluorides or chlorides thereof. Still particularly preferably, said organic groups are selected from the group consisting of alkyl groups having 1 to 3 carbon atoms and phenyl. Alkyl groups having 1 to 3 carbon atoms can be methyl, ethyl, n-propyl and i-propyl.
  • component a2) is preferably selected from the silicone resins represented by formula (6) :
  • s is a number of 1 to 100, preferably 1 to 50
  • t is a number of 1 to 100, preferably 1 to 50.
  • Such silicone resins containing Si-H groups are commercially available under the trade name of Syl-Off 7672, 7048, and 7678 from Dow Corning Company. While the silicone resins are commercially available, methods for synthesizing such silicone resins are well known in the art.
  • the component a2) is present in an amount of from 2%to 50%, preferably from 4.1%to 13.0%by weight of the total weight of the silicone resins.
  • Suitable epoxy resins include, but not limited to, bisphenol, naphthalene, and aliphatic type epoxies, such as bisphenol-Atype epoxy resins, bisphenol-F type epoxy resins.
  • Other suitable epoxy resins include, but not limited to, cycloaliphatic epoxy resins, epoxy novolac resins, biphenyl type epoxy resins, dicyclopentadiene-phenol type epoxy resins, reactive epoxy diluents, and mixtures thereof.
  • Commercially available materials include bisphenol type epoxy resins (Epiclon 830LVP, 830CRP, 835LV, 850CRP) available from Dainippon Ink &Chemicals, Inc.
  • naphthalene type epoxy (Epiclon HP4032) available from Dainippon Ink &Chemicals, Inc. ; aliphatic epoxy resins (Araldite CY179, 184, 192, 175, 179) available from Ciba Specialty Chemicals, (Epoxy 1234, 249, 206) available from Union Carbide Corporation, and (EHPE-3150) available from Daicel Chemical Industries, Ltd.
  • a hardener also referred to as curing agent
  • the epoxy resins if present
  • a hardener is used in combination with the epoxy resins (if present) so as to promote the crosslinking reaction for curing.
  • Any hardener which is reactive with epoxy resins can be used.
  • a hardener is required for the composition, its selection is dependent on the polymer chemistry used and the processing conditions employed.
  • the compositions may use anhydrides, aromatic amines, alicyclic amines, aliphatic amines, tertiary phosphines, triazines, metal salts, aromatic hydroxyl compounds, or a combination of these substances.
  • hardeners include imidazoles, such as 2-methylimidazole, 2-undecylimidazole, 2-heptadecyl imidazole, 2-phenylimidazole, 2-ethyl 4-methylimidazole,
  • N,N-dimethylaniline N, N-dimethyltoluidine, N, N-dimethyl-p-anisidine,
  • (meth) acrylate includes acrylate, methacrylate and any combination
  • Suitable (meth) acrylates include those having the generic structure
  • X 6 is an aromatic or aliphatic group.
  • exemplary X 6 entities include poly (butadienes) , poly (carbonates) , poly (urethanes) , poly (ethers) , poly (esters) , simple hydrocarbons, and modified hydrocarbons containing functionalities such as carbonyl, carboxyl, amide,carbamate, urea, or ether.
  • acrylated aliphatic urethane oligomers (Ebecryl 230, 264, 265, 270, 284, 4830, 4833, 4834, 4835, 4866, 4881, 4883, 8402, 8800-20R, 8803, 8804) available from Radcure Specialities, Inc; polyester acrylate oligomers (Ebecryl 657, 770, 810, 830, 1657, 1810, 1830) available from Radcure Specialities, Inc. ; and epoxy acrylate resins (CN104, 111, 112, 115, 116, 117, 118, 119, 120, 124, 136) available from Sartomer Company, Inc.
  • the (meth) acrylate resins are preferably selected from the group consisting of isobornyl acrylate, isobornyl methacrylate, lauryl acrylate, lauryl methacrylate, poly (butadiene) with acrylate functionality and poly (butadiene) with methacrylate functionality.
  • Suitable vinyl ether resins include those having the generic structure in which v is 1 to 6.
  • X 3 includes an aromatic group having 6 to 30 carbon atoms, and an aliphatic group having 1 to 25 carbon atoms, wherein the aliphatic group may be linear, branched or cyclic; saturated or unsaturated.
  • Exemplary X 3 entities also include polyolefins such as poly (butadienes) , poly (carbonates) , poly (urethanes) , poly (ethers) , poly (esters) , simple hydrocarbons, and modified hydrocarbons containing functionalities such as carbonyl, carboxyl, amide, carbamate, urea, or ether.
  • resins include cyclohenanedimethanol divinylether, dodecylvinylether, cyclohexyl vinylether, 2-ethylhexyl vinylether, dipropyleneglycol divinylether, hexanediol divinylether, octadecylvinylether, and butandiol divinylether available from International Speciality Products (ISP) ; Vectomer 4010, 4020, 4030, 4040, 4051, 4210, 4220, 4230, 4060, 5015 available from Sigma-Aldrich, Inc.
  • ISP International Speciality Products
  • Suitable poly (butadiene) resins include poly (butadienes) , epoxidized poly (butadienes) , maleic poly (butadienes) , acrylated poly (butadienes) , butadiene-styrene copolymers, and butadiene–acrylonitrile copolymers.
  • acrylated poly (butadienes) (CN302, NTX6513, CN301, NTX6039, PRO6270, Ricacryl 3100, Ricacryl 3500) available from Sartomer Inc. ; epoxydized poly (butadienes) (Polybd 600, 605) available from Sartomer Company. Inc. and Epolead PB3600 available from Daicel Chemical Industries, Ltd; and acrylonitrile and butadiene copolymers (Hycar CTBN series, ATBN series, VTBN series and ETBN series) available from Hanse Chemical.
  • poly (butadiene) s used herein.
  • Suitable poly (butadiene) sinclude homopolymers of butadiene; copolymers of butadiene and other monomers; and functionalized of these polymers.
  • Examplary poly (butadiene) sinclude epoxidized poly (butadiene) s, maleic poly (butadiene) s, acrylated poly (butadiene) s, butadiene-styrene copolymers, and butadiene–acrylonitrile copolymers.
  • poly (butadiene) s include homopolymer butadiene (Ricon130, 131, 134, 142, 150, 152, 153, 154, 156, 157, P30D) available from Sartomer Company, Inc; random copolymer of butadiene and styrene (Ricon 100, 181, 184) available from Sartomer Company Inc.
  • maleinized poly (butadiene) (Ricon 130MA8, 130MA13, 130MA20, 131 MA5, 131 MA10, 131 MA17, 131 MA20, 156MA17) available from Sartomer Company, Inc.; acrylated poly (butadienes) (CN302, NTX6513, CN301, NTX6039, PRO6270, Ricacryl 3100, Ricacryl 3500) available from Sartomer Inc.; epoxydized poly (butadienes) (Polybd 600, 605) available from Sartomer Company. Inc. and Epolead PB3600 available from Daicel Chemical Industries, Ltd; and acrylonitrile and butadiene copolymers (Hycar CTBN series, ATBN series, VTBN series and ETBN series) available from Hanse Chemical.
  • siliconized olefins used herein. Suitable siliconized olefins have the following generic structure, which are obtainable by a selective hydrosilation reaction of silicone and divinyl materials:
  • n 1 is 2 or more, n 2 is 1 or more and n 1 >n 2 .
  • These materials are commercially available and can be obtained, for example, from National Starch and Chemical Company.
  • styrene resins used herein. Suitable styrene resins include those resins having the generic structure in which w is 1 or greater, R 16 is –H or –CH 3 .
  • X 16 may be an aliphatic group having 1 to 25 carbon atoms, wherein the aliphatic group may be linear, branched or cyclic; saturated or unsaturated.
  • Exemplary X 16 entities also include poly (butadiene) s, poly (carbonate) s, poly (urethane) s, poly (ether) s, poly (ester) s, simple hydrocarbons, and modified hydrocarbons containing functionalities such as carbonyl, carboxyl, amide, carbamate, urea, or ether.
  • poly (butadiene) s poly (carbonate) s, poly (urethane) s, poly (ether) s, poly (ester) s, simple hydrocarbons, and modified hydrocarbons containing functionalities such as carbonyl, carboxyl, amide, carbamate, urea, or ether.
  • poly (butadiene) s poly (carbonate) s, poly (urethane) s, poly (ether) s, poly (ester) s, simple hydrocarbons, and modified hydrocarbons containing functionalities such as carbonyl, carboxyl, amide, carbamate, urea, or ether.
  • Suitable cyanate ester resins include those having the generic structure in which y is 1 or larger.
  • X 7 may be a hydrocarbon group, including an aromatic group having 6 to 30 carbon atoms, and an aliphatic group having 1 to 25 carbon atoms, wherein the aliphatic group may be linear, branched or cyclic; saturated or unsaturated.
  • Exemplary X 7 entities also include bisphenol, phenol or cresol novolac, dicyclopentadiene, polybutadiene, polycarbonate, polyurethane, polyether, or polyester.
  • AroCy L-10 AroCy XU366, AroCy XU371, AroCy XU378, XU71787.02L, and XU 71787.07L
  • AroCy L-10 AroCy L-10, AroCy XU366, AroCy XU371, AroCy XU378, XU71787.02L, and XU 71787.07L
  • Huntsman LLC Chemicalset PT30, Primaset PT30 S75, Primaset PT60, Primaset PT60S, Primaset BADCY, Primaset DA230S, Primaset MethylCy, and Primaset LECY, available from Lonza Group Limited
  • 2-allyphenol cyanate ester 4-methoxyphenol cyanate ester
  • thermosetting resin composition for reflector comprises a white pigment, preferably selected from the group consisting of titanium oxide, zinc oxide, magnesium oxide, barium carbonate, magnesium silicate, zinc sulfate, barium sulfate, and any combination thereof.
  • the white pigment is to be blended as a white colorant to heighten brightness, and to improve reflection efficiency of the silicone reflector.
  • the average particle diameter and the shape thereof are also not limited, for example, it may range from nano size to several mm. The choice of such size for any particular package configuration is within the expertise of one skilled in the art.
  • An average particle diameter which is a weight average diameter D 50 (or median size) in a particle size distribution measurement by laser diffraction analysis is preferably 0.05 to 5.0 ⁇ m. These may be used alone or in combination of several kinds.
  • titanium dioxide is preferred, and a unit lattice of the titanium dioxide may be either a rutile-type, an anatase-type or a brookite-type one.
  • the above-mentioned titanium dioxide can be previously subjected to surface treatment by a hydrous oxide of Al or Si to increase compatibility or dispersibility with a rein or an inorganic filler.
  • the titanium dioxide useful in the present invention may be commercially available from Dupont under the trade name of R101, R102, R103, R104, R105, R106, R107, R108, R109, R110, R350, R706 and R900.
  • the component b) may be present in an amount of from 5%to 95%, preferably from 10%to 50%by weight of the total weight of all components of the thermosetting resin composition for reflector.
  • thermosetting resin composition for reflector may further comprise a filler, preferably an inorganic filler.
  • the component c) is preferably selected from the group consisting of fine powder silica, fine powder alumina, fused silica, crystalline silica, cristobalite, alumina, aluminum silicate, titianium silicate, silicon nitride, aluminum nitride, boron nitride, anitmony trioxide, and any combination thereof.
  • a fibrous inorganic filer such as glass fiber and wollastonite.
  • fused silicas are preferred and are commercially available for example from Denka under the tradename of FB-570, FB-950, FB-980.
  • the component c) may be present in an amount of from 0%to 95%, preferably from 30%to 60%by weight of the total weight of all components of the thermosetting resin composition for reflector.
  • thermosetting resin composition for reflector may further comprise additives.
  • the additives, if any, are different from the fillers in component c) .
  • the additives may include a reaction inhibitor, a coupling agent, an antioxidant, a stabilizer (such as a light stabilizer) , an adhesion promoter, a leveling agent, a wetting agent, an impact modifier, a catalyst (such as a hydrosilylation catalyst, a curing accelerator, and a cationic initiator) , and any combination thereof for further improving the various properties of the thermosetting resin composition for printing process and/or after curing.
  • a reaction inhibitor such as a coupling agent, an antioxidant, a stabilizer (such as a light stabilizer) , an adhesion promoter, a leveling agent, a wetting agent, an impact modifier, a catalyst (such as a hydrosilylation catalyst, a curing accelerator, and a cationic initiator) , and any combination thereof for further improving the various properties of the thermosetting resin composition for printing process and/or after curing.
  • the component d) may be present in an amount of from 0%to 5%, preferably from 0.5%to 2%by weight of the total weight of all components of the thermosetting resin composition for reflector.
  • the reaction inhibitor may be selected from the group consisting of the following compounds: 1-ethynyl-1-cyclopentanol; 1-ethynyl-1-cyclohexanol; 1-ethynyl-1-cycloheptanol; 1-ethynyl-1-cyclooctanol; 3-methyl-1-butyn-3-ol; 3-methyl-1-pentyn-3-ol; 3-methyl-1-hexyn-3-ol; 3-methyl-1-heptyn-3-ol; 3-methyl-1-octyn-3-ol; 3-methyl-1-nonyl-3-ol; 3-methyl-1-decyn-3-ol; 3-methyl-1-dodecyn-3-ol; 3-ethyl-1-pentyn-3-ol; 3-ethyl-1-hexyn-3-ol; 3-ethyl-1-heptyn-3-ol; 3-butyn-2-ol; 1-pentyn-3-
  • reaction inhibitor is comprised in an amount of from 0.2%to 0.35%, by weight of the total weight of all components of the thermosetting resin composition for reflector.
  • Examples of the coupling agent which can be used in the present invention include ⁇ -mercaptopropyl trimethoxysilane; N- ⁇ (aminoethyl) ⁇ -aminopropylmethyl dimethoxysilane, N- ⁇ (aminoethyl) ⁇ -aminopropyl trimethoxysilane, N- ⁇ (aminoethyl) ⁇ -aminopropyl triethoxysilane, ⁇ -aminopropyl trimethoxysilane, ⁇ -aminopropyl triethoxysilane, and N-phenyl- ⁇ -aminopropyl trimethoxysilane; and ⁇ -glycidoxypropyl trimethoxysilane, ⁇ -glycidoxypropylmethyl diethoxysilane, ⁇ -glycidoxypropyl triethoxysilane, and ⁇ - (3, 4-epoxycyclohexyl) ethyl
  • the thermosetting resin composition for reflector preferably further comprises a hydrosilylation catalyst.
  • all catalysts which are useful for the addition of Si-bonded hydrogen in the compound of component a2) onto the compound of component a1) having alkenyl groups can be used as the hydrosilylation catalyst.
  • hydrosilylation catalysts are compounds or complexes of precious metals comprising platinum, ruthenium, iridium, rhodium and palladium, such as, for example, platinum halides, platinum-olefin complexes, platinum-alcohol complexes, platinum-alcoholate complexes, platinum-ether complexes, platinum-aldehyde complexes, platinum-ketone complexes, including reaction products of H 2 PtCl 6 .6H 2 O and cyclohexanone, platinum-vinylsiloxane complexes, in particular platinum-divinyltetramethyldisiloxane complexes with or without a content of detectable inorganically bonded halogen, bis ( ⁇ -picolin) -platinum dichloride, trimethylenedipyridine-platinum dichloride, dicyclopentadiene-platinum dichloride, dimethylsulfoxide ethylene-platinum (II) dichloride and also reaction
  • complexes of iridium with cyclooctadienes such as, for example, ⁇ -dichlorobis (cyclooctadiene) -diiridium (I) , can also be used in the present invention.
  • the hydrosilylation catalyst is a compound or complex of platinum, preferably selected from the group consisting of chloroplatinic acid, allylsiloxane-platinum complex catalyst, supported platinum catalysts, methylvinylsiloxane-platinum complex catalysts, reaction products of dicarbonyldichloroplatinum and 2, 4, 6-triethyl-2, 4, 6-trimethylcyclotrisiloxane, platinum divinyltetramethyldisiloxane complex, and the combination thereof, and most preferably platinum-divinyltetramethyldisiloxane complexes.
  • platinum preferably selected from the group consisting of chloroplatinic acid, allylsiloxane-platinum complex catalyst, supported platinum catalysts, methylvinylsiloxane-platinum complex catalysts, reaction products of dicarbonyldichloroplatinum and 2, 4, 6-triethyl-2, 4, 6-trimethylcyclotrisiloxane, platinum divinyltetra
  • the hydrosilylation catalyst is a methylvinylsiloxane-platinum complex catalyst, and are commercial available for example from the Gelest under the tradename of 6829, 6830, 6831 and 6832 series.
  • the hydrosilylation catalyst may be used in the present invention in an amount of 1 to 500 ppm, and more preferably 2 to 100 ppm, calculated as the elemental precious metal, by weight of the total weight of all components of the thermosetting resin composition for reflector, or in an amount of from 0.2%to 0.33%, preferably from 0.2%to 0.31%by weight of the total weight of all components of the thermosetting resin composition for reflector.
  • a curing accelerator may be selected from the group consisting of triphenylphosphine, alkyl-substituted imidazoles, imidazolium salts, onium salts (such as onium borates) , quartenary phosphonium compounds, onium borates, metal chelates, 1, 8-diazacyclo [5.4.0] undex-7-ene or a mixture thereof.
  • the curing accelerator can be either a free radical initiator or cationic initiator, depending on whether a radical or ionic curing resin is chosen. If a free radical initiator is used, it will be present in an effective amount. An effective amount typically is 0.1 to 10 percent by weight of the organic compounds (excluding any filler) in the thermosetting resin composition.
  • Free-radical initiators include peroxides, such as butyl peroctoates and dicumyl peroxide, and azo compounds, such as 2, 2’ -azobis (2-methyl-propanenitrile) and 2, 2’ -azobis (2-methyl-butanenitrile) .
  • Commercially available curing accelerator includes 2-methyl imidazole (2-MZ) available from Shikoku.
  • a cationic initiator it will be present in an effective amount.
  • An effective amount typically is 0.1 to 10 percent by weight of the organic compounds (excluding any filler) in the thermosetting resin composition.
  • Suitable cationic curing agents include dicyandiamide, phenol novolak, adipic dihydrazide, diallyl melamine, diamino malconitrile, BF3-amine complexes, amine salts and modified imidazole compounds.
  • Metal compounds also can be employed as cure accelerators for cyanate ester systems and include, but are not limited to, metal napthenates, metal acetylacetonates (chelates) , metal octoates, metal acetates, metal halides, metal imidazole complexes, and metal amine complexes.
  • both cationic and free radical initiators may be desirable, in which case both free radical cure and ionic cure resins can be used in the composition.
  • These compositions would contain effective amounts of initiators for each type of resin. Such a composition would permit, for example, the curing process to be started by cationic initiation using UV irradiation, and in a later processing step, to be completed by free radical initiation upon the application of heat.
  • Suitable polymers for the adhesive composition further include polyamides, phenoxies, polybenzoxazine, polyether sulfone, benzoxazine, polybenzoxyzole, polyformaldehyde, polyacetaldehyde, poly (b-propiolacetone) , poly (10-decanoate) , poly (ethylene terephthalate) , polycaprolactam, poly (11-undecanoamide) , poly (m-phenylene-terephthalamide) , poly (tetramethlyene-m-benzenesulfonamide) , polyester polyarylate, poly (phenylene oxide) , poly (phenylene sulfide) , polysulfone, polyetheretherketone, poly-iosindolo-quinazolinedione, polythioetherimide poly-phenyl-quinoxaline, polyquuinixalone, imide-aryl ether phenylquinoxaline copo
  • suitable materials for inclusion in adhesive compositions include rubber polymers such as block copolymers of monovinyl aromatic hydrocarbons and conjugated diene, e. g. , styrene-butadiene, styrene-butadiene-styrene (SBS) , styrene-isoprene-styrene (SIS) , styrene-ethylene-butylene-styrene (SEBS) , and styrene-ethylene-propylene-styrene (SEPS) .
  • rubber polymers such as block copolymers of monovinyl aromatic hydrocarbons and conjugated diene, e. g. , styrene-butadiene, styrene-butadiene-styrene (SBS) , styrene-isoprene-styrene (SIS) , styrene-ethylene-but
  • Suitable materials for inclusion in adhesive compositions include ethylene-vinyl acetate polymers, other ethylene esters and copolymers, e.g., ethylene methacrylate, ethylene n-butyl acrylate and ethylene acrylic acid; polyvinyl acetate and random copolymers thereof; polyacrylates; polyamides; and polyvinyl alcohols and copolymers thereof.
  • Thermoplastic rubbers suitable for inclusion in the composition include carboxy terminated butadiene-nitrile (CTBN) /epoxy adduct, acrylate rubber, vinyl-terminated butadiene rubber, and nitrile butadiene rubber (NBR) .
  • CTBN epoxy adduct consists of about 20-80 wt%CTBN and about 20-80 wt% diglycidyl ether bisphenol A: bisphenol A epoxy (DGEBA) .
  • CTBN materials are available from Noveon Inc.
  • a variety of bisphenol A epoxy materials are available from Dainippon Ink and Chemicals, Inc., and Shell Chemicals.
  • NBR rubbers are commercially available from Zeon Corporation.
  • the present invention provides a thermosetting resin
  • composition for reflector comprising:
  • thermosetting resin a thermosetting resin
  • weight percentages are based on the total weights of all components of the thermosetting resin composition for reflector.
  • thermosetting resin composition for reflector can be prepared by mixing all components by a vacuum mixer and/or a three roll mill.
  • the thermosetting resin composition for reflector preferably exhibits a thixotropic index represented by the ratio of the viscosity measured at a shearing rate of 2 s-1 to the viscosity measured at a shearing rate of 20 s-1 in the range of from 1 to 6, preferably from 2 to 4.
  • the viscosity is measured on an AR 2000 ex instrument from TA company with equilibrating for 2 min before testing.
  • thermosetting resin composition for reflector possesses an excellent thixotropic property for the printing process in step b) of the manufacturing method according to the present invention.
  • the thermosetting resin composition may have reduced printing capability and/or performance. For example, it may be difficult to press the thermosetting resin composition through the screen printing mask.
  • the thixotropic index is larger than 6, the thermosetting resin composition may induce procedural faults. For example, the resin may bleed out or flow to unintended areas of the substrate unit after the printing process.
  • thermosetting resin composition for reflector preferably exhibits an excellent reflectance of larger than 85%, more preferably larger than 93%, measured on Lambda 35, from Perkin Elmer at a wavelength range of 300 to 800 nm.
  • compositions of the inventive Examples 1 to 3 as shown below were prepared by the following procedure: weighing all of the components into a 100 mL polystyrene bottle; adding the mixture into a high speed centrifugal machine under vacuum, and mixing at a rotation speed of 2000 r/min for 5 min; removing the mixture and passing through a three roller mill for 3 runs; adding the mixture into a high speed centrifugal machine under vacuum again, and mixing at a rotation speed of 2000 r/min for 5 min.
  • thermosetting resin compositions were tested for the thixotropic index (TI) , which indicates the thixotropic property of the compositions.
  • TI thixotropic index
  • the viscosity was measured on an AR 2000 ex instrument from TA Company with equilibrating for 2 min before testing.
  • thermosetting resin compositions in liquid
  • the thermosetting resin compositions were put into a flat bottom container, then heated to about 200°C for 15min so as to cure. Subsequently, the cured compositions in the form of plate were removed from the container. The cured plates were round or quadrate, and their thicknesses were about 2mm.
  • Example1 The composition of Example1 was used as the thermosetting resin composition for reflector in the manufacturing method according to the present invention which is shown as follows.
  • a screen printing mask (a) having two through holes (e) was covered on ceramic substrate (b) having a circuit (not shown) formed thereon.
  • Each substrate unit (b) was aligned with the array of through holes (e) .
  • the substrate has a dimension of 54 mm wide and 66 mm long, including an outer frame.
  • the substrate array is composed of 14 lines and 17 columns of units, i.e. a 14 X 17 array.
  • Each substrate unit has a dimension of 3 mm in width, 3 mm in length and 0.4 mm in height.
  • the silicone resin (c) of EXAMPLE 1 was dispensed on the screen printing mask (a) , and squeezed by a spatula (d) .
  • each through hole was filled with silicone resin (c) , and the silicone resin (c) was screen printed onto each substrate unit (b) . Then, the printing screen mask (a) was removed, and thus an array of cavities generated between the printed resins on each substrate unit (b) . Then, the printed resin was cured at 150°C for 1 hr in an oven, and reflectors each having a height of 0.4 mm was produced. The mask was subsequently peeled off.
  • a LED flip chip (f) having a size of 1 mm in width and 1 mm in length was attached to the circle (not shown) on the substrate unit in each cavity.
  • a silicone encapsulant (g) substantially containing a dimethyl silicone commercially available from ShinEtsu under the trade name of KER-2500, and also containing a filler and phosphor was dispensed into the cavity to the extent that the top surface of the encapsulant layer was not above the top surface of the reflector, and meanwhile the LED chip (f) was completely encapsulated. Then, the silicone encapsulant (g) was cured at 150°C for 5hr in an oven.
  • the array of LED devices was diced by applying a rotating blade to cut through in the middle of each reflector.
  • the obtained individual LED devices were further cleaned and dried.
  • the manufacturing method is the same as that used in the inventive example, except that a conventional manufacturing method by partially molding is applied, and there is a clearance having 1 mm wide between every two neighbouring through reflectors as shown in Fig. 7.
  • the substrate having the same total size as that in the inventive example is composed of a 11 X 13 array.
  • the resin for each reflector is individually and separately applied to the substrate.
  • the reflector is formed one by one.
  • the thermosetting resin composition for all reflectors is integrally printed as a whole.
  • the array of LED devices was diced by applying a rotating blade to cut through the substrate in the middle of each clearance.
  • the manufacturing method according to the present invention brings about lower initial investment cost, faster production speed, higher efficiency and less waste.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Manufacturing & Machinery (AREA)
  • Computer Hardware Design (AREA)
  • Power Engineering (AREA)
  • Led Device Packages (AREA)

Abstract

La présente invention décrit un procédé de fabrication d'un dispositif semi-conducteur optique, en particulier un dispositif à Diodes Électroluminescentes (DEL), une composition de résine thermodurcissable appropriée pour être utilisée dans le procédé, et un dispositif optique à semi-conducteur, en particulier un dispositif à DEL, fabriqué par le procédé ou à partir de la composition de résine thermodurcissable.
PCT/CN2015/074578 2015-03-19 2015-03-19 Procédé de fabrication d'un dispositif semi-conducteur optique, une composition de résine thermodurcissable associée, et un semi-conducteur optique obtenu à partir de celle-ci WO2016145652A1 (fr)

Priority Applications (3)

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PCT/CN2015/074578 WO2016145652A1 (fr) 2015-03-19 2015-03-19 Procédé de fabrication d'un dispositif semi-conducteur optique, une composition de résine thermodurcissable associée, et un semi-conducteur optique obtenu à partir de celle-ci
CN201580080038.7A CN108292692B (zh) 2015-03-19 2015-03-19 一种光学半导体装置的制造方法、用于其的热固性树脂组合物以及由其获得的光学半导体
TW105105879A TW201638254A (zh) 2015-03-19 2016-02-26 製造光學半導體裝置之方法、其所用之熱固性樹脂組成物及由其獲得之光學半導體

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PCT/CN2015/074578 WO2016145652A1 (fr) 2015-03-19 2015-03-19 Procédé de fabrication d'un dispositif semi-conducteur optique, une composition de résine thermodurcissable associée, et un semi-conducteur optique obtenu à partir de celle-ci

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CN108017879A (zh) * 2016-11-04 2018-05-11 无锡创达新材料股份有限公司 一种大功率led封装用白色环氧模塑料的制备
JPWO2017090759A1 (ja) * 2015-11-26 2018-09-20 株式会社スリーボンド 熱硬化性組成物およびそれを用いた導電性接着剤

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US20090141504A1 (en) * 2007-11-30 2009-06-04 Taiyo Ink Mfg. Co., Ltd. White hardening resin composition, hardened material, printed-wiring board and reflection board for light emitting device
US20090304961A1 (en) * 2008-06-09 2009-12-10 Taguchi Yusuke White heat-curable silicone resin composition and optoelectronic part case
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US20120025243A1 (en) * 2010-08-02 2012-02-02 Advanced Optoelectronic Technology, Inc. Led package and method for manufacturing the same
US20120319154A1 (en) * 2011-06-16 2012-12-20 Nitto Denko Corporation Silicone resin composition, encapsulating layer, reflector, and optical semiconductor device
US20130271999A1 (en) * 2012-04-16 2013-10-17 Shin-Etsu Chemical Co., Ltd. Thermosetting silicone resin composition for reflector of led, reflector for led using the same and optical semiconductor apparatus

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US20090141504A1 (en) * 2007-11-30 2009-06-04 Taiyo Ink Mfg. Co., Ltd. White hardening resin composition, hardened material, printed-wiring board and reflection board for light emitting device
US20090304961A1 (en) * 2008-06-09 2009-12-10 Taguchi Yusuke White heat-curable silicone resin composition and optoelectronic part case
JP2010229221A (ja) * 2009-03-26 2010-10-14 Taiyo Ink Mfg Ltd 熱硬化性樹脂組成物
US20120025243A1 (en) * 2010-08-02 2012-02-02 Advanced Optoelectronic Technology, Inc. Led package and method for manufacturing the same
US20120319154A1 (en) * 2011-06-16 2012-12-20 Nitto Denko Corporation Silicone resin composition, encapsulating layer, reflector, and optical semiconductor device
US20130271999A1 (en) * 2012-04-16 2013-10-17 Shin-Etsu Chemical Co., Ltd. Thermosetting silicone resin composition for reflector of led, reflector for led using the same and optical semiconductor apparatus

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPWO2017090759A1 (ja) * 2015-11-26 2018-09-20 株式会社スリーボンド 熱硬化性組成物およびそれを用いた導電性接着剤
CN108017879A (zh) * 2016-11-04 2018-05-11 无锡创达新材料股份有限公司 一种大功率led封装用白色环氧模塑料的制备

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TW201638254A (zh) 2016-11-01
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