CN108369928A - Sealing material for semiconductor - Google Patents
Sealing material for semiconductor Download PDFInfo
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- CN108369928A CN108369928A CN201680073780.XA CN201680073780A CN108369928A CN 108369928 A CN108369928 A CN 108369928A CN 201680073780 A CN201680073780 A CN 201680073780A CN 108369928 A CN108369928 A CN 108369928A
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- semiconductor
- sealing material
- resin
- mass parts
- semiconductor chip
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
- H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/12—Mountings, e.g. non-detachable insulating substrates
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
- H01L23/31—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the arrangement or shape
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- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Structures Or Materials For Encapsulating Or Coating Semiconductor Devices Or Solid State Devices (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Epoxy Resins (AREA)
Abstract
A kind of sealing material for semiconductor is provided, can inhibit to form gap between semiconductor chip and sealing material for semiconductor.The sealing material for semiconductor of the present invention is characterized in that, is formed it includes that can make the oxidant of semiconductor oxide.
Description
Technical field
The present invention relates to the sealing material for semiconductor protected to semiconductor chip, more particularly, to external connection
It is more than the semiconductor sealing for being fanned out to (Fan-out) type wafer-class encapsulation of the planar dimension of semiconductor with the configuring area of electrode
Material.
Background technology
In recent years, it is gradually increased in the requirement of the fields such as semiconductor circuit miniaturization, in order to cope with the requirement, semiconductor
Circuit is installed to be the encapsulation (Chip Size Package, chip size packages) close to its chip size sometimes.As realization
One of means of chip size packages, it is proposed that engaged with wafer scale and carry out fragmentation is referred to as wafer-class encapsulation (Wafer
Level Package, hereinafter sometimes referred to simply as WLP) packaging method.WLP can help to it is cost effective, miniaturization, therefore by
To concern.WLP is mounted in a manner of upside-down mounting and is formed in the circuit board of electrode.
In addition, along with the minimizing of semiconductor chip, highly integrated, the electrode of the external connection of semiconductor chip
The quantity of (terminal, convex block) has the trend increased, and therefore, the spacing of the electrode of the external connection of semiconductor chip, which has, to be subtracted
Small trend.But the semiconductor chip for being formed with convex block with fine pitch is mounted directly in circuit board and may not be easy.
For the above subject, it is proposed that following scheme：Sealing material for semiconductor is formed in the periphery of semiconductor chip
Region is also provided with the wiring layer again being connect with electrode in the region of sealing material for semiconductor, increases the spacing of convex block.It is this
The size of configuring areas of the WLP due to making convex block relative to the size of semiconductor chip increases, and is referred to as fan-out-type chip
Grade encapsulation (hereinafter, sometimes referred to simply as FO-WLP).
In FO-WLP, semiconductor chip is embedded to by sealing material for semiconductor.The circuit face of semiconductor chip exposes outside
Side forms the boundary of semiconductor chip and sealing material for semiconductor.In the sealing material for semiconductor of embedded with semi-conductor chip
Region be also provided with the wiring layer again being connect with the electrode of semiconductor chip, convex block by wiring layer again and semiconductor chip electricity
Pole is electrically connected.The spacing of the convex block can be set to larger relative to the spacing of the electrode of semiconductor chip.
In addition, also contemplate be not only semiconductor chip, also by multiple electronic units be accommodated in one encapsulation in, or will
A semiconductor device is formed in multiple semiconductor chip embedment sealing material for semiconductor.In such packaging, Duo Ge electricity
Subassembly is embedded to by sealing material for semiconductor.In the sealing material for semiconductor setting and the ministry of electronics industry for being embedded to multiple electronic units
The wiring layer again of the electrode connection of part, convex block are electrically connected by wiring layer again with the electrode of electronic unit.In this case, convex block
The size of configuring area increases also relative to the size of semiconductor chip, therefore can be known as FO-WLP.
In such packaging, certain interval configuring semiconductor chip or electronic unit are usually set on supporter, and
It is embedded to using sealing material for semiconductor, after so that sealing material is heating and curing, is removed from supporter, make simulated wafer.Then,
From the semiconductor circuit chip face of simulated wafer to the sealing material for semiconductor region of expansion, wiring layer again is formed.In this way, energy
The spacing of convex block is enough set to be set to relative to the spacing of the electrode of semiconductor chip larger.
In the formation of wiring layer again, in general, the irritability resin of eurymeric to be applied to the semiconductor chip of simulated wafer
Circuit face simultaneously carries out preliminary drying, across photomask etc. to the area illumination UV light isoreactivity light to be open, followed by TMAH
Developer solutions such as (tetramethylammonium hydroxide) develop, and are heating and curing, oxygen plasma treatment etc., carry out metal electrode
Sputtering, and then form photoresist layer and by wiring pattern, form wiring layer (for example, patent document 1 etc.) again.
Existing technical literature
Patent document
Patent document 1：Japanese Unexamined Patent Publication 2013-38270 bulletins
Invention content
Problems to be solved by the invention
But if FO-WLP is manufactured through above-mentioned operation, in the boundary meeting of semiconductor chip and sealing material for semiconductor
Gap is generated, there are problems that the reliability of the wiring layer again formed after being allowed to reduces.In addition, due to the gap and exist made
At FO-WLP product reliability reduce the problem of.
Therefore, the purpose of the present invention is to provide one kind can inhibit semiconductor chip and sealing material for semiconductor it
Between form gap sealing material for semiconductor, especially FO-WLP sealing materials.
Means for solving the problems
The phenomenon that boundary of the present inventor to generating semiconductor chip and sealing material for semiconductor, is studied in detail,
As a result, it has been found that the gap is generated in the developing procedure used when forming wiring layer again.Also, the result further studied
It was found that in developing procedure, developer solution can also immerse the side for the semiconductor chip side being embedded to by sealing material for semiconductor
Boundary can according to circumstances penetrate into sealing material for semiconductor, and the developer solution of the immersion or infiltration can etch semiconductor chip side,
Thus gap is generated in semiconductor chip side and the boundary of sealing material for semiconductor.
In addition, the present inventor is had made intensive studies based on above-mentioned opinion, as a result, it has been found that, by by semiconductor wafer not by
The ingredient of developer solution etching is added in sealing material for semiconductor in advance, even if when wiring layer again is formed using developer solution,
Also can inhibit to form gap in semiconductor chip side and the boundary of sealing material for semiconductor, as a result, making again wiring layer
It is formed and is easy, the reliability of the FO-WLP after the completion of capable of improving.
The sealing material for semiconductor of the present invention is characterized in that, it includes the oxidant that can make semiconductor oxide
At.
In the mode of the present invention, sealing material for semiconductor can include curability composition, curing agent component, solidification promotion
Agent ingredient and inorganic filler.
In the mode of the present invention, sealing material for semiconductor can be with the shape of sheet.
In the mode of the present invention, it can be used for the wafer-class encapsulation of fan-out-type.
The effect of invention
Sealing material for semiconductor through the invention, particularly with can inhibit for FO-WLP semiconductor chip with
Gap is formed between sealing material for semiconductor.The formation of wiring layer again when as a result, it is possible to make FO-WLP manufacture is easy, energy
The reliability of FO-WLP after the completion of enough raisings.
Specific implementation mode
Sealing material for semiconductor is to the semiconductor element (such as semiconductor chip etc.) that is process semiconductor wafer
Protected, protect it from the injury of heat, dust, semiconductor packages is made, in such a way that coating semiconductor element is whole into
Row sealing, insulation.The sealing material for semiconductor includes aftermentioned each ingredient as sealing material, and semiconductor of the invention is used
Sealing material has the feature for including the oxidant that can make semiconductor oxide.As described above, for example when manufacturing FO-WLP,
The semiconductor circuit chip face of simulated wafer buried semiconductor chip etc. using sealing material for semiconductor and formed is formed again
Wiring layer uses the developer solutions such as TMAH when being formed this is connected up pattern layers again.In development treatment, developer solution can soak
Enter inbuilt semiconductor chip and sealing material for semiconductor interface.For example, for silicon semiconductor chip, silicon
It is etched by TMAH developer solutions, meeting generates gap between the inbuilt semiconductor wafer of institute and sealing material for semiconductor.This hair
In bright, due to, comprising the oxidant that semiconductor wafer can be made to aoxidize, being used with semiconductor in sealing material for semiconductor
When sealing material sealing semiconductor chips, the surface of semiconductor chip is aoxidized.For example, silicon (Si) semiconductor chip the case where
Under, form SiO on the surface of semiconductor chip2Very thin overlay film.Even if result, it is believed that developing in development treatment later
Liquid immerses the interface of semiconductor chip and sealing material for semiconductor, can also utilize oxidation overlay film (SiO2) inhibit silicon semiconductor quilt
Developer solution etches.This is only the supposition of the present inventor, and the present invention is not limited to the logics.
As the semiconductor chip sealed using sealing material for semiconductor, silicon (Si), germanium (Ge), SiGe can be enumerated
Deng usually silicon semiconductor.
As workable oxidant in the present invention, without spy as long as the oxidant that can make above-mentioned semiconductor oxide
Do not limit, can be any one of the oxidant of the oxidant and inorganic system of organic system, from aftermentioned composition semiconductor with close
It sets out in terms of the compatibility of the other compositions of closure material, can preferably use the oxidant of organic system.
As the oxidant of organic system, it is preferable to use organic oxidizing agent or organic peroxides.As organic oxidation
Agent can enumerate hydroperoxide kind, quinones, pyridines, organic nitro-compound etc..It, can be in addition, as organic peroxide
Enumerate metachloroperbenzoic acid, benzylhydroperoxide, peracetic acid, performic acid, benzoyl peroxide, diethyl peroxide, peroxidating two
Acetyl etc..
As hydroperoxide kind, tertiary butyl hydroxide, cumene hydroxide, bis- (trimethyl silyls) can be enumerated
Peroxide, ethyl hydrogen peroxide, tert-butyl hydroperoxide, succinic acid peroxide, 1,1,3,3- tetramethyl butyl peroxidating
Hydrogen etc..
As quinones, can enumerate to chloranil (chloranil), adjacent chloranil, four bromo- Isosorbide-5-Nitrae-benzoquinones, 2,3- bis- chloro- 5,
6- dicyano -1,4- benzoquinones, chloranil, dichloro quinone, benzoquinones, naphthoquinones, anthraquinone, substituted anthraquinone, 2,3,5,6- chloranils
Deng.
As pyridines, pyridine-N-oxide, pyridine N-oxides, dimethylamino naphthyridine oxide, 2 can be enumerated, 2,6,
6,-tetramethyl -1- piperidines base oxide, trimethylamine N-oxide etc..
As organic nitro-compound, m-nitrobenzene sulfonate, paranitrobenzoic acid salt, nitroguanidine (ニ ト ロ can be enumerated
ガ ニ ジ Application), aromatic nitrosulfonate etc..
Alternatively, it is also possible to using commercially available peroxide, can be used for example NOF Corp with
The ketal peroxide of the trade name sale of Pertetra A, Perhexa HC, Perhexa C, Perhexa V, Perhexa 22
Class；The peroxide sold with the trade name of Perbutyl H, Percumyl H, Percumyl P, Permenta H, Perocta H
Change hydrogen species；The dialkyl peroxide class sold with the trade name of Perbutyl C, Perbutyl D, Perhexyl D；With
PEROYL IB, 355 PEROYL, PEROYL L, PEROYL SA, NYPER BW, NYPER BMT-K40, NYPER BMT-M
The peroxidating two acyl class of trade name sale；With PEROYL IPP, PEROYL NPP, PEROYL TCP, PEROYL OPP, PEROYL
The peroxy dicarbonates of the trade name sale of SBP；With Percumyl ND, Perocta ND, Perhexa ND,
Perbutyl ND、Perhexa PV、Perbutyl PV、Perhexa 25O、Perocta O、Perhexa O、Perbutyl
O、Perbutyl L、Perbutyl 355、Perhexa I、Perbutyl I、Perbutyl E、Perhexa 25Z、
The trade name pin of Perbutyl A, Perhexa Z, Perbutyl ZT, Perbutyl Z and ペ ロ マ ー AC, BTTB-25
The peroxyesters sold.
Above-mentioned oxidant can be used alone, and can also be use mixing two or more.
In addition, in the present invention, in above-mentioned oxidant, oxide skin(coating) is formed on the surface of semiconductor chip from taking into account
It sets out, it is preferable to use organic in terms of the reactivity (oxidisability) of semiconductor and the stability as sealing material for semiconductor
Peroxide, quinones.
As inorganic system's oxidant, silver oxide, copper oxide, germanium oxide, indium oxide, manganese oxide, lead oxide, oxygen can be enumerated
Change rhenium, tellurium oxide.Among these, from as oxidant reactivity with the balance as the stability of sealing material in terms of go out
Hair, preferably manganese oxide, lead oxide.In above-mentioned oxidant, compared with inorganic system's oxidant, organic system oxidant can utilize half
The resin component of conductor sealing material mixes in heterogeneity, as a result, by the resin closely sealed with the surface of semiconductor chip at
Divide and has an effect more in heterogeneity, it is thus also excellent in terms of moisture-proof, inhibit the reliable of gap formation as a result, further increasing
Property, therefore it is preferred that.
When the gross mass with solid constituent conversion of ingredient other than oxidant is set as 100 mass parts, oxidant contains
Amount is preferably the range of the mass parts of 0.01 mass parts~10, the range of the mass parts of more preferably 0.05 mass parts~8, particularly preferably
For the range of the mass parts of 0.1 mass parts~5.By making the content of oxidant be above range, can not make semiconductor with close
The gap of semiconductor chip side is inhibited to be formed in the case of closure material oxygenolysis.
As described above, according to the type of oxidant, the resin component for constituting sealing material for semiconductor is aoxidized sometimes.
Therefore, in the present invention, antioxidant can be contained in sealing material for semiconductor.As antioxidant, conduct can be enumerated
Phenolic antioxidant or amine antioxidant that free radical chain preventing agent functions are functioned as peroxide decomposer
Phosphorous antioxidant, sulfur antioxidant, the hydrazine system antioxidant functioned as matal deactivator, amide system it is anti-oxidant
Agent etc..Among these, phenolic antioxidant or amine antioxidant can be preferably used.It is commercially available anti-alternatively, it is also possible to use
Oxidant, for example, ADKSTAB AO-20, AO-30, AO-40, AO-50, AO-50F, AO-60, AO-60G, AO-80,
AO-330、ADKSTAB PEP-36/36A、HP-10、2112、2112RG、PEP-8、PEP-8W、1178、1500、C、135A、
3010, TPPADEKASTAB AO-412S, AO-503 etc..
Comprising in the case of antioxidant in the semiconductor-encapsulating material of the present invention, about its content, by oxidant
When the molal quantity of functional group is set as 100%, the molal quantity of the functional group of antioxidant is preferably 5%~99% range, more excellent
It is selected as 8%~90% range, particularly preferably 10%~80% range.By making the content of antioxidant be above-mentioned model
It encloses, the reactivity of oxidant can be adjusted while maintaining reactivity (oxidisability) of oxidant and semiconductor, inhibit resin
The oxygenolysis of ingredient.
Can include aftermentioned curability composition, curing agent component, solidification in the sealing material for semiconductor of the present invention
Accelerating agent ingredient, inorganic filler etc..Hereinafter, to the ingredient other than the oxidant and antioxidant of composition sealing material for semiconductor
It illustrates.
<Curability composition>
It as the curability composition of sealing material for semiconductor, is not particularly limited, conventionally known resin can be used,
It is preferable to use epoxy resin.Epoxy resin epoxy resin with solid-state, semisolid, liquid from the point of view of the shape before reaction.It
Can be used alone, or be used in combination of two or more.If using halogen-containing epoxy resin is wrapped, by being given birth to by hydrolysis
At halide ion and oxidant redox reaction, have reduce added oxidant reactive effect, i.e.,
It is possible that the inhibition formed to gap has an impact, thus epoxy resin is preferably halogen-free, particularly preferably substantive in halogen
It is upper to be free of chlorine, bromine, iodine.
Specifically, it is preferable that the chlorinity in epoxy resin is 2500ppm or less, bromine content is 1000ppm or less, chlorine and
The total content of bromine is 3000ppm or less.Chlorinity is more preferably 2000ppm or less, further preferably 1500ppm or less, spy
It You Xuanwei not 1000ppm or less.In addition, it is preferably also halogen-free as sealing material, specifically, it is preferable that chlorinity is
900ppm or less, bromine content be 900ppm or less, the total content of chlorine and bromine is 1500ppm or less.It should be noted that as halogen
The assay method of cellulose content can utilize the flask based on JPCA standards to burn the processing chromatography of ions to measure.
As solid epoxy resin, HP-4700 (naphthalene type epoxy resin), the DIC corporations of the manufacture of DIC companies can be enumerated
NC-7000 (the multifunctional solid-states containing naphthalene skeleton that the EXA4700 (4 function naphthalene type epoxy resin) that makes, Japanese chemical drug corporation are made
Epoxy resin) etc. naphthalene type epoxy resins；The phenols such as the EPPN-502H (trisphenol epoxy resin) that Japanese chemical drug corporation is made and tool
There is the epoxides (triphen phenol-type epoxy resin) of the condensation product of the aromatic aldehyde of phenolic hydroxyl group；The EPICLON of DIC companies manufacture
The dicyclopentadienes aralkyl-type epoxy resins such as HP-7200H (the multifunctional solid epoxy resin of the skeleton containing dicyclopentadiene)；Day
The biphenyl aralkyl type epoxy trees such as the NC-3000H (the multifunctional solid epoxy resin containing biphenyl backbone) of this chemical drug company manufacture
Fat；Biphenyl/the phenol novolak type epoxy resins such as the NC-3000L that Japanese chemical drug corporation is made；The manufacture of DIC companies
The phenolic resin varnish type epoxy resins such as the EOCN-104S that EPICLON N660, EPICLON N690, Japanese chemical drug corporation are made；Three
The biphenyl type epoxy resins such as the YX-4000 of water chestnut chemical company manufacture；It is phosphorous that TX0712 of aurification company manufacture etc. lives in Nippon Steel
Epoxy resin；Three (2,3- glycidyl) isocyanuric acid esters such as the TEPIC of Nissan Chemical Industries company manufacture etc..
As semisolid epoxy resin, can enumerate the EPICLON 860 of DIC companies manufacture, EPICLON 900-IM,
EPICLON EXA-4816, EPICLON EXA-4822, EPOTOHTO YD-134 of Dongdu chemical conversion company manufacture, Mitsubishi Chemical
The bisphenol A type epoxy resins such as jER834, jER872 of company's manufacture, the ELA-134 of Sumitomo Chemical Co. Ltd.'s manufacture；DIC is public
Take charge of the naphthalene type epoxy resins such as the EPICLON HP-4032 of manufacture；The phenol novolacs such as the EPICLON N-740 of DIC companies manufacture are clear
Paint shaped epoxy resin etc..
As liquid-state epoxy resin, bisphenol A type epoxy resin, bisphenol f type epoxy resin, bisphenol-A D-ring oxygen can be enumerated
Resin, phenol novolak type epoxy resin, tert-butyl catechol type epoxy resin, glycidyl group amine type epoxy resin,
Aminobenzene phenol-type epoxy resin, alicyclic epoxy resin etc..
Above-mentioned curability composition can be used alone or be used in combination of two or more.It is used relative to semiconductor is constituted
100 mass parts of total solid content of sealing material, the blend amount of curability composition is preferably the mass parts of 5 mass parts~50, more excellent
It is selected as the mass parts of 10 mass parts~40.In addition, relative to 100 mass parts of curability composition, the blend amount of liquid-state epoxy resin is excellent
It is selected as 0~45 mass parts, more preferably 0~30 mass parts, particularly preferably 0~5 mass parts.If the mixture of liquid-state epoxy resin
Amount is the range of 0~45 mass parts, then the glass transition temperature (Tg) of solidfied material increases, resistance to anti-thread breakage to improve sometimes.
<Curing agent component>
Can include curing agent component as the ingredient for the sealing material for semiconductor for constituting the present invention.Curing agent component
With the functional group reacted with above-mentioned curability composition.Ingredient as such curing agent can enumerate phenolic resin, polynary carboxylic
Acid and its acid anhydrides, cyanate ester resin, active ester resin etc., preferably phenolic resin.It can be used alone or incite somebody to action among these
It is used in combination.
It, can be by phenol resol resins, alkyl phenol novolac resin, bisphenol A novolac as phenolic resin
Resin, dicyclopentadiene type phenolic resin, Xylok types phenolic resin, terpene modified phenolic resin, cresols/naphthol resin, poly- second
Alkenyl phenol, phenol/naphthol resin, the phenolic resin of the skeleton containing alpha-Naphthol, the cresol phenols novolac resin containing triazine
It is used alone a kind of etc. conventionally known phenolic resin or is used in combination of two or more.
Polybasic carboxylic acid and its acid anhydrides are the compound and its acid anhydrides for having in a molecule more than two carboxyls, such as can be with
Enumerate condensation product of the copolymer of (methyl) acrylic acid, the copolymer of maleic anhydride, binary acid etc. and carboxylic acid terminal's acid imide
Resin etc. has the resin of carboxylic acid terminal.
Cyanate ester resin is the compound for having in a molecule more than two cyanic acid ester groups (- OCN).Cyanate ester resin can be with
Use conventionally known any cyanate ester resin.As cyanate ester resin, for example, phenol novolak type cyanic acid
It is ester resin, alkyl phenol phenolic varnish type cyanate ester resin, dicyclopentadiene type ethylene rhodanate resin, bisphenol A cyanate ester resin, double
Phenol F types cyanate ester resin, bisphenol S type cyanate ester resin.Alternatively, it is also possible to for the prepolymer of triazine partly has occurred.
Active ester resin is the resin for having in a molecule more than two active ester groups.Active ester resin can usually pass through
The condensation reaction of carboxylic acid compound and hydroxy compounds obtains.Wherein, as hydroxy compounds, it is preferable to use oxybenzene compound
Or the active ester compound that naphthol compound obtains.As oxybenzene compound or naphthol compound, quinhydrones, isophthalic two can be enumerated
Phenol, bisphenol-A, Bisphenol F, bisphenol S, phenolphthalein, the bisphenol-A that methylates, the Bisphenol F that methylates, the bisphenol S that methylates, phenol, o-cresol,
Cresols, paracresol, catechol, alpha-Naphthol, betanaphthol, 1,5- dihydroxy naphthlenes, 1,6- dihydroxy naphthlenes, 2,6- dihydroxy naphthlenes, two
Dihydroxy benaophenonel, trihydroxybenzophenone, tetrahydroxybenzophenone, 1,3,5-trihydroxybenzene, benzenetriol, bicyclopentadiene xenol,
Phenol novolacs etc..
As curing agent component, ester ring type olefin polymer can also be used in addition to the foregoing.As can preferably make
Ester ring type olefin polymer can be enumerated：(1) will have in carboxyl and acid anhydride's (hereinafter referred to as " carboxyl etc. ") extremely
The substance that few any ester ring type alkene is polymerized together with other monomers as needed；(2) by the virtue with carboxyl etc.
Object made of the aromatic moiety hydrogenation of (co) polymer obtained from fragrant race's alkene polymerize together with other monomers as needed
Matter；(3) by the ester ring type alkene without carboxyl etc. and substance made of the monomer copolymerization with carboxyl etc.；(4) will not have
Made of the aromatic moiety of the aromatic olefin of carboxyl etc. and copolymer obtained from the monomer copolymerization with carboxyl etc. hydrogenates
Substance；(5) it will be imported in the ester ring type olefin polymer for not having carboxyl etc. with the compound of carboxyl etc. by modified-reaction
Made of substance；Or the carboxylic of the ester ring type olefin polymer with carboxylate that (6) will be obtained as above-mentioned (1)~(5)
Perester radical is such as the substance by being converted into carboxyl hydrolysis；Etc..
In above-mentioned curing agent component, preferably phenolic resin, cyanate ester resin, active ester resin, ester ring type olefinic polymerization
Object.Especially since polarity is high, is easy to inhibit relative dielectric constant, to more preferably use phenolic resin.
Curing agent component preferably (can be cured the function of reaction according to functional groups such as the epoxy groups of curability composition
Group) with can with the ratio of the functional group of the curing agent component of the functional group reactions (Gu the number of the functional group of curing agent component/
The number of the functional group of the property changed ingredient：Equivalent proportion) contain for 0.2~5 ratio.By making equivalent proportion be above range, energy
Access the more excellent sealing material for semiconductor of protection feature.
<Curing accelerator ingredient>
Can include curing accelerator ingredient as the ingredient for the sealing material for semiconductor for constituting the present invention.Solidification promotees
It is the substance for the curing reaction for promoting curability composition into agent ingredient, sealing material can be further increased to semiconductor wafer
Adaptation and heat resistance.As curing accelerator ingredient, imidazole and its derivants can be enumerated；Acetylguanamine, benzoguanamine etc.
Guanamines；Diaminodiphenyl-methane, m-phenylene diamine (MPD), m-xylene diamine, diamino diphenyl sulfone, dicyandiamide, urea, urea derive
The polynary amines such as object, melamine, polynary hydrazides；At least any one in their acylate and epoxy adduct；Trifluoro
Change the amine complex of boron；Ethyl diamino-s-triazine, 2,4- diamino-s-triazine, 2,4- diamino -6- xylyls-equal three
The triazine derivatives species such as piperazine；Trimethylamine, triethanolamine, N, N- dimethyl octylame, N- benzyl dimethylamines, pyridine, N-methylmorpholine,
The amines such as six (N- methyl) melamines, 2,4,6- tri- (dimethyl p-aminophenol), tetramethylguanidine, m-aminophenol；Polyvinyl
The Polyphenols such as phenol, polyvinylphenol bromide, phenol novolacs, alkyl phenol novolaks；Tributylphosphine, triphenyl
Organic phosphines such as phosphine, three -2- cyano ethyl phosphines；Three normal-butyls (2,5- dihydroxy phenyl) phosphonium bromides, cetyltributylphosphonium chlorine
Hua Phosphonium Deng phosphonium salts classes；The quaternary ammonium salts such as benzyltrimethylammonium chloride, phenyl tributyl ammonium chloride；Above-mentioned multi-anhydride；Diphenyl
The light cationic polymerizations such as iodine tetrafluoroborate, triphenylsulfonium hexafluoro antimonate, 2,4,6- triphenyl thiapyran hexafluorophosphates
Catalyst；Phenylethylene-maleic anhydride resin；The reaction with same mole object of phenyl isocyanate and dimethylamine, toluene di-isocyanate(TDI),
The reaction with same mole object of the organic multiple isocyanates such as isophorone diisocyanate and dimethylamine, metallic catalyst etc. are existing known
Curing accelerator, these can be used alone or are use mixing two or more.
Curing accelerator ingredient is not essential, in the case where particularling hope to promote curing reaction, relative to above-mentioned solid
The property changed 100 mass parts of ingredient can preferably be used in the range of the mass parts of 0.01 mass parts~20.Using metallic catalyst as
In the case of curing accelerator ingredient, content is relative to 100 mass parts of curability composition preferably 10ppm in terms of metal conversion
~550ppm, preferably 25ppm~200ppm.
<Inorganic filler components>
Can include inorganic filler components in the sealing material for semiconductor of the present invention.By containing inorganic filler components,
The reliability of sealing material for semiconductor improves.In addition, laser labelling is implemented by the back side etc. to sealing material for semiconductor,
Inorganic filler components expose in the part pruned by laser, reflect light diffusion, thus in the color close to white.As a result, half
In the case that conductor sealing material contains aftermentioned coloring agent component, contrast is obtained in laser labelling part and other parts
There is difference label (lettering) to become clearly effect.
As inorganic filler components, conventionally known inorganic filler components can be used without limitation, such as can lift
Go out silica, aluminium oxide, talcum, aluminium hydroxide, calcium carbonate, titanium dioxide, iron oxide, silicon carbide, boron nitride etc. powder,
By pearl, mono-crystlling fibre and glass fibre etc. made of their spheroidizations, it can be used alone or make two or more mixing
With.Among these, preferably silica, aluminium oxide, titanium dioxide.
Inorganic filler components it is preferable to use average grain diameter are preferably 0.01 μm~15 μm, more preferably 0.02 μm~12 μm,
Particularly preferably 0.03 μm~10 μm of inorganic filler components.It should be noted that in this specification, for average grain diameter, profit
It is calculated a as its arithmetic mean of instantaneous value with the long diameter of axle of randomly selected 20 inorganic filler components of determination of electron microscopy
Number average particle diameter is the average grain diameter.
Relative to 100 mass parts of all solids ingredient for constituting sealing material for semiconductor, the content of inorganic filler components
The mass parts of the mass parts of preferably 10 mass parts~2000, more preferably 30 mass parts~1800, particularly preferably 60 mass parts~
1500 mass parts.
<Coloring agent component>
Can include coloring agent component in the sealing material for semiconductor of the present invention.By comprising coloring agent component,
When will be provided with the semiconductor chip of protective film and being assembled into equipment, it can prevent caused by infrared ray generated by peripheral devices etc.
The operating of semiconductor device is slipped up.In addition, in the case of engraving the marking to protective film by means such as laser labellings, word, note
Number equal labels easily identify.That is, in the semiconductor chip for being formed with protective film, laser mark is usually utilized on the surface of protective film
Notation (method protected film surface and carry out lettering is pruned using laser) is printed on piece number etc., by making protective film contain coloring
Agent, the part of protective film pruned by laser can fully obtain poor contrast with the non-part, it is seen that property improves.
It, can be a kind of by the pigment of organic or inorganic and dyestuff exclusive use or by two or more groups as coloring agent component
It closes and uses, among these, from the aspect of electromagnetic wave or infrared shield, preferred black pigment.As black pigment, make
With carbon black, black, iron oxide, nigrosine, activated carbon etc., but it is not limited to these.It slips up from the operating of semiconductor device is prevented
Aspect set out, particularly preferred carbon black.In addition, instead of carbon black, the pigment such as red, blue, green, yellow can also be mixed, formed black or
Connect the color of pullous black system.
Relative to 100 mass parts of total solid content for constituting sealing material for semiconductor, to be preferably 0.1 mass parts~35
The ratio of the mass parts of mass parts, the further preferably mass parts of 0.5 mass parts~25, particularly preferably 1 mass parts~15 contains
Coloring agent component.
<Coupling agent ingredient>
In order to improve sealing material for semiconductor for the cementability of adherend (semiconductor wafer), adaptation and protection
At least either in the compendency of film can include to react with the functional group reacted with inorganic matter and with organo-functional group
The coupling agent ingredient of functional group.In addition, by comprising coupling agent ingredient, it will not damage and sealing material for semiconductor is cured and obtained
The heat resistance of the protective film arrived can improve its water resistance.As such coupling agent, can enumerate titanate esters system coupling agent,
Aluminate-series coupling agent, silane coupling agent etc..Among these, preferred silane coupling agent.
As the organic group contained in silane coupling agent, for example, vinyl, epoxy group, styryl, first
Base acryloxy, acryloxy, amino, urea groups, chloropropyl, sulfydryl, polysulfide base, isocyanate group etc..As silicon
Alkane coupling agent, can use commercially available substance, for example, KA-1003, KBM-1003, KBE-1003, KBM-303,
KBM-403、KBE-402、KBE-403、KBM-1403、KBM-502、KBM-503、KBE-502、KBE-503、KBM-5103、
KBM-602、KBM-603、KBE-603、KBM-903、KBE-903、KBE-9103、KBM-9103、KBM-573、KBM-575、
KBM-6123, KBE-585, KBM-703, KBM-802, KBM-803, KBE-846, KBE-9007 (are trade name；Shin-
Etsu Silicone companies manufacture) etc..These can be used alone, and can also share two or more.
<Film property assigns component of polymer>
The sealing material for semiconductor of the present invention can be the forms such as liquid, graininess, sheet.Wherein forming sheet
When sealing material for semiconductor, the component of polymer (film property imparting polymer) for assigning film formative can be added.This specification
In, it is distinguished to assign component of polymer with aftermentioned reactive film property, it refers to not having reaction that film property, which assigns component of polymer,
The component of polymer of property functional group.Component of polymer is assigned as such film property, thermoplasticity multi-hydroxy polyether tree can be enumerated
Fat or as epoxychloropropane and the condensation product of various 2 function phenolic compounds phenoxy resin or will exist in its skeleton
Hydroxy ether portion hydroxyl phenoxy resin, polyvinyl acetal resin, polyamide made of various acid anhydrides or esterification of acyl chloride
Resin, polyamide-imide resin, block copolymer etc..These polymer can be used alone or by two or more combinations
It uses.In order to maintain film (or piece) shape, the weight average molecular weight (Mw) of these polymer is usually 2 × 104Above, it is preferably 2
×104~3 × 106。
It should be noted that in this specification, the value of weight average molecular weight (Mw) can pass through gel permeation chromatography (GPC)
Method (polystyrene standard) is measured using following measurement devices, determination condition.
Measurement device：Waters manufactures " Waters 2695 "
Detector：Waters manufactures " Waters2414 ", RI (differential refraction rate meter)
Column：" HSP gel columns, HR MB-L, 3 μm, 6mm × 150mm " × 2+Waters manufactures " HSP gels for Waters manufactures
Column, HR1,3 μm, 6mm × 150mm " × 2
Determination condition：
Column temperature：40℃
RI detector set temperatures：35℃
Eluant, eluent：Tetrahydrofuran
Flow velocity：0.5ml/ minutes
Sample size：10μl
Sample concentration：0.7wt%
Polyvinyl acetal resin is for example obtained by polyvinyl alcohol resin is carried out acetalation with aldehyde.As above-mentioned
Aldehyde is not particularly limited, for example, formaldehyde, acetaldehyde, propionic aldehyde, butyraldehyde etc..
As the concrete example of phenoxy resin, FX280, FX293, the Mitsubishi Chemical of the manufacture of Dongdu chemical conversion company can be enumerated
YX8100, YL6954, YL6974 etc. of company's manufacture.
As the concrete example of polyvinyl acetal resin, the S-LEC KS systems of ponding chemical industrial company manufacture can be enumerated
Row can enumerate the KS5000 series of chemical conversion company of Hitachi manufacture, the BP systems that Japanese chemical drug corporation is made as polyamide
Row.
As polyamide-imide resin, the KS9000 series etc. of chemical conversion company of Hitachi manufacture can be enumerated.
In the case that thermoplasticity polyhydroxy polyether resin has fluorene skeleton, have high glass-transition temperature, heat resistance excellent
It is different, it is thus possible to maintain its glass transition temperature while maintaining the low thermal expansion rate based on semisolid or solid epoxy resin
Degree, obtained curing overlay film balancedly have both low thermal expansion rate and high glass-transition temperature.In addition, due to thermoplasticity polyhydroxy
Base polyether resin has hydroxyl, thus shows good adaptation to semiconductor wafer.
It can be substance made of constituting the monomer block copolymerization of mentioned component that film property, which assigns component of polymer,.Block copolymerization
Object refers to the copolymer for the molecular structure that the different two or more polymer of property form long-chain to be covalently keyed.As
Block copolymer, preferably X-Y-X types or X-Y-X ' type block copolymers.It is excellent in X-Y-X types and X-Y-X ' type block copolymers
Choosing be soft segment by the Y in center and glass transition temperature (Tg) is low, it is on the outside of two X or X ' are hard block and glass transition
Temperature (Tg) is constituted higher than the polymer unit of the Y blocks in center.Glass transition temperature (Tg) is surveyed using Differential Scanning Calorimetry
(DSC) is determined to measure.X and X ' can be mutually different polymer unit, or identical polymer unit.
In addition, in X-Y-X types and X-Y-X ' type block copolymers, more preferable X or X ' include that Tg is 50 DEG C or more poly-
The block copolymer for the Tg polymer units below that compound units, the glass transition temperature (Tg) comprising Y are X or X '.Separately
Outside, in X-Y-X types and X-Y-X ' type block copolymers, X or X ' are preferably high with the compatibility of aftermentioned curability composition, and Y is preferred
It is low with the compatibility of curability composition.In this way, compatible, central embedding by forming block and the matrix (curability composition) at both ends
The section block copolymer incompatible with matrix (curability composition), it is believed that be easy to show the structure of specificity in the base.
In above-mentioned various polymer, preferably phenoxy resin, polyvinyl acetal resin, the thermoplasticity with fluorene skeleton
Polyhydroxy polyether resin, block copolymer.
Film property assigns component of polymer ratio shared in the whole components for constituting sealing material for semiconductor without spy
It does not limit, when whole components total is set as 100 mass parts, the mass parts of preferably 10 mass parts~50, more preferably 15 matter
Measure the mass parts of part~45.
<Reactive film property assigns component of polymer>
Can include the aftermentioned film property that can be reacted with curability composition as the ingredient for constituting sealing material for semiconductor
Assign component of polymer.Polymer is assigned, it is preferable to use carboxylic resin or phenolic resin as such reactive film property.
If in particular, using carboxylic resin, it is easy comprising epoxy resin as curability composition and epoxy resin
Reaction improves while assigning film formative as the characteristic of semiconductor protection film, therefore it is preferred that.
As carboxylic resin, the resin of (1) below~(7) can be preferably used.
It is preferred that can use：
(1) by aliphatic diisocyanate, Branched fatty (cyclo) aliphatic diisocyanates, ester ring type diisocyanate, aromatic series two
The diisocyanate such as isocyanates and dihydromethyl propionic acid, dimethylolpropionic acid etc. are carboxylic, diol compound, makrolon
Be polyalcohol, polyether system polyalcohol, polyester-based polyols, polyolefin polyalcohol, bisphenol-A system alkylene oxide adducts glycol,
The carboxylic carbamate resins that the sudden reaction of the diol compounds such as the compound with phenolic hydroxyl group and alcoholic extract hydroxyl group obtains；
(2) the carboxylic carbamate obtained by the sudden reaction of diisocyanate and carboxylic diol compound
Resin；
(3) by the unsaturated carboxylic acids such as (methyl) acrylic acid and styrene, α-methylstyrene, (methyl) acrylic acid lower alkane
Carboxylic resin obtained from the copolymerization of the compound containing unsaturated group such as base ester, isobutene；
(4) make the dicarboxylic acids such as adipic acid, phthalic acid, hexahydrophthalic acid and 2 functional epoxy resins or 2 function oxygen
Azetidine resin reaction, to hydroxyl addition phthalic anhydride, tetrabydrophthalic anhydride, the hexahydrophthalic acid of generation
Carboxylic polyester resin made of 2 yuan of acid anhydrides such as acid anhydride；
(5) make epoxy resin or oxetane resin open loop, obtained from so that the hydroxyl of generation is reacted with multi-anhydride
Carboxylic resin；
(6) make compound, i.e. polyphenol compound and ethylene oxide, ring with 2 or more phenolic hydroxyl groups in a molecule
The epoxyalkane such as Ethylene Oxide react, and carboxylic is contained obtained from so that the reaction products such as obtained polyol resin is reacted with multi-anhydride
The resin of base；And
(7) make compound, i.e. polyphenol compound and ethylene oxide, ring with 2 or more phenolic hydroxyl groups in a molecule
The epoxyalkane such as Ethylene Oxide react, and the reaction products such as obtained polyol resin and (methyl) acrylic acid etc. is made to contain unsaturated group
Monocarboxylic acid reaction, carboxylic resin obtained from making obtained reaction product further be reacted with multi-anhydride；Deng
Resin.It should be noted that in this specification, (methyl) acrylate refer to acrylate, methacrylate and they
Mixture.
In above-mentioned resin, above-mentioned (1), (2), (6) and (7) serves not only as the carboxylic resin of photonasty, may be used also
For use as the carboxylic resin of non-photosensitive.Wherein, the resin of (6) and (7) because the balance of complete characteristic it is good and preferred.
The weight average molecular weight that reactive film property assigns polymer is different due to resin matrix, it is often preferred that 2 × 103~
1.5×105Range, more preferably 3 × 103~1 × 105Range, but be not limited to these ranges.
Reactive film property assigns component of polymer ratio shared in the whole components for constituting sealing material for semiconductor
Be not particularly limited, for example, preferably by above-mentioned film property assign 100 mass parts of polymer in 20 mass parts~60 mass parts replace
Polymer is assigned for reactive film property.
<Other compositions>
It, can the various additions of mixture as needed in the sealing material for semiconductor of the present invention other than mentioned component
Agent.As various additives, levelling agent, plasticizer, ion capturing agent, getter, chain-transferring agent, remover etc. can be enumerated.
Wherein it is possible to the fire retardants such as mixture antimony trioxide in the range of lossless characteristic, from environmental pressure aspect, preferably substantially
It is upper to be free of the fire retardants such as antimony trioxide.
As long as thickness when film shape is made in sealing material for semiconductor is than the semiconductor chip or electronics that are sealed
The thickness of component is thicker, is not particularly limited, preferably 3 μm~800 μm, more preferably 5 μm~700 μm, particularly preferably
It is 7 μm~600 μm.
The sealing material for semiconductor of the present invention can be single layer structure, in addition may be multilayered structure.
At least any one of the sealing material for semiconductor of the present invention in indicating luminous ray, infrared ray and ultraviolet light
Maximum transmission rate under radioparent standard, that is, wavelength 300nm~1200nm is preferably 20% or less, more preferably 0~15%,
Further preferably more than 0% and for 10% or less, be particularly preferably 0.001%~8%.By making wavelength 300nm~1200nm
Under sealing material for semiconductor maximum transmission rate be above range, in visible wavelength region and infrared wavelength region
The transmittance of at least any one reduces, and can obtain operating error caused by preventing the infrared ray of semiconductor device, improve print
Visibility of word and other effects.The maximum transmission rate of sealing material for semiconductor under wavelength 300nm~1200nm can be by upper
The type and content of coloring agent component are stated to adjust.It should be noted that in this specification, the maximum of sealing material for semiconductor
Transmissivity refers to：Using UV-vis spectrum check device (manufacture of (strain) Shimadzu Seisakusho Ltd.), the semiconductor after solidification is measured with close
Full light transmittance of the closure material (25 μm of thickness) at 300nm~1200nm, the highest value (maximum transmission rate) of transmissivity is i.e.
For the maximum transmission rate.
The form of the sealing material for semiconductor of the present invention can be liquid, particle, tabular, any one of sheet,
Due to can easily operate, thus the preferably shape with sheet.
<The manufacturing method of sealing material for semiconductor>
The sealing material for semiconductor of the present invention uses the composition for being mixed to get above-mentioned each ingredient with defined ratio
(mixture) and obtain.The composition can be diluted with solvent in advance, or can also be added in solvent in mixing.Separately
Outside, when making sealing material for semiconductor using composition, dilution solvent composition can be used.As solvent, can enumerate
Ethyl acetate, methyl acetate, diethyl ether, dimethyl ether, acetone, methyl ethyl ketone, acetonitrile, hexane, hexamethylene, toluene, heptane etc..
The sealing material for semiconductor of liquid object can be obtained using this method.
It is film-made by the way that the composition prepared as described above (mixture) to be applied on supporter, sheet can be made
Sealing material for semiconductor.As film-forming method, conventionally known method can be applied, tablet pressing, roller blade cloth are utilized
Composition (mixture) is applied on supporter and goes forward side by side by means well known to machine, gravure coater, die coating machine, reversed coating machine etc.
Row drying, it is hereby achieved that sealing material for semiconductor.It, can be in addition, by adjusting the coating weight of composition (mixture)
Obtain the sealing material for semiconductor of above-mentioned thickness.
As supporter, separate paper (セ パ レ ー ト Paper), antiadhesion barrier, separate paper (セ パ Paper), stripping can be preferably used
The conventionally known supporter such as film, peeling paper.Alternatively, it is also possible to use by polyethylene terephthalate (PET) or poly-
The plastic foils such as polyolefin films, the polyimide films such as the polyester films such as (ethylene naphthalate) (PEN), stretched polypropylene films (OPP)
The separate paper (From type Paper of composition) supporter of peeling layer is formed with the single or double of base material.As peeling layer, as long as
Material with antistick characteristic is just not particularly limited, for example, silicone resin, organic resin modification silicone resin, fluorine tree
Fat etc..
The sealing material for semiconductor of the present invention can also be used to the sealing material of printed circuit board, solar cell material
Sealing material, the sealing material substrate of electric wire/cable and the cement of semiconductor chip of material.In particular, the present invention's partly leads
Body can be preferably used for following fan-out-type wafer-class encapsulations with sealing material, which has semiconductor core
Piece, the semiconductor sealing for burying semiconductor chip in such a way that surface is exposed by the circuit forming face of above-mentioned semiconductor chip
Material and the circuit for being set to above-mentioned semiconductor chip form the wiring layer again of surface side, and above-mentioned wiring layer again, which is also disposed on, partly leads
Sealing material for semiconductor region other than body chip area.
Embodiment
In the following, illustrate the present invention by embodiment, but the present invention and it is not limited to these examples.It needs to illustrate
It is that as long as no special declaration, then " part " refers to mass parts.
<Reactive film property assigns the synthesis of polymer (carboxylic resin) 1>
Bis-phenol is put into having in thermometer, nitrogen gatherer and the autoclave of epoxyalkane gatherer and agitating device
A- formaldehyde types phenolic resin (bright and the manufacture of chemical conversion Co., Ltd., trade name " BPA-D ", OH equivalents：120) 120.0g, hydroxide
Potassium 1.20g and toluene 120.0g, under stiring to carrying out nitrogen displacement, heat temperature raising in system.Then, epoxy is added dropwise at leisure
Propane 63.8g, with 125 DEG C~132 DEG C, 0~4.8kg/cm2Reaction 16 hours.
Later, reaction solution is cooled to room temperature, the addition 89% phosphatase 11 .56g of mixing into the reaction solution and by hydrogen-oxygen
Change potassium to neutralize, obtains the epoxy for the bisphenol A-formaldehyde type phenolic resin that nonvolatile component is 62.1%, hydroxyl value is 182.2g/eq.
Propane reaction solution.It is to be averaged substance made of 1.08 mol of alkylene oxide hydrocarbon of addition relative to 1 equivalent of phenolic hydroxyl.
By the epoxyalkane reaction solution 293.0g of obtained phenolic varnish type cresol resin, acrylic acid 43.2g, methylsulphur
Sour 11.53g, methylnaphthohydroquinone 0.18g and toluene 252.9g inputs have the reactor that blender, thermometer and air are blown into pipe
In, air was blown into 10ml/ minutes speed, is reacted 12 hours in 110 DEG C under stiring.
Water by reacting generation is used as distillates 12.6g with the azeotropic mixture of toluene.Later, reaction solution is cooled to
Room temperature neutralizes 15% sodium hydrate aqueous solution 35.35g of obtained reaction solution, followed by washing.Later, exist
It is simultaneously distilled off simultaneously with propylene glycol methyl ether acetate 118.1g displacements toluene in evaporator, obtains phenolic varnish type acrylic acid
Ester resin solution.
Then, by obtained phenolic varnish type acrylic ester resin solution 332.5g and triphenylphosphine 1.22g input tools
Standby blender, thermometer and air are blown into the reactor of pipe, are blown into air with 10ml/ minutes speed, under stiring slowly
Tetrabydrophthalic anhydride 60.8g is added in ground, is reacted 6 hours at 95 DEG C~101 DEG C, the acid value for obtaining solid matter is
88mgKOH/g, the reactive film property that nonvolatile component is 71% assign polymer (carboxylic resin) 1.As resin
Solution A.The weight average molecular weight that the reactive film property for including in resin solution A assigns polymer (carboxylic resin) 1 ingredient is 4
×103。
It should be noted that the value of weight average molecular weight (Mw) is by gel permeation chromatography (GPC) method (polystyrene mark
It is accurate) it is measured using following measurement devices, determination condition.
Measurement device：Waters manufactures " Waters 2695 "
Detector：Waters manufactures " Waters2414 ", RI (differential refraction rate meter)
Column：" HSP gel columns, HR MB-L, 3 μm, 6mm × 150mm " × 2+Waters manufactures " HSP gels for Waters manufactures
Column, HR1,3 μm, 6mm × 150mm " × 2
Determination condition：
Column temperature：40℃
RI detector set temperatures：35℃
Eluant, eluent：Tetrahydrofuran
Flow velocity：0.5ml/ minutes
Sample size：10μl
Sample concentration：0.7wt%
<The making of sealing material for semiconductor 1>
It by following component dissolving, is scattered in methyl ethyl ketone, prepares the sealing that solid constituent mass concentration is 20%
Material composition solution 1.
Sealing material use composition solution 1 is applied to the polyethylene terephthalate film that surface implements lift-off processing
It is 10 minutes dry at 100 DEG C on (PET film), produce the sealing material for semiconductor 1 of 50 μm of thickness.The film layer is 6 folded,
Produce the sealing material for semiconductor 1 of 300 μm of thickness.
<The making of sealing material for semiconductor 2>
Mixture following compositions are heated 4 minutes at 70 DEG C using roll-type kneading machine, are then heated 6 minutes at 120 DEG C, with conjunction
10 minutes are counted in decompression (0.01kg/cm2) under melting mixing, produce mixture 2.
Obtained mixture 2 is configured in a manner of in the cover film (Supreme Being people Purex films) for sandwiching 50 μm of two panels, using flat
Mixture is formed as sheet by plate pressing, obtains the sealing material for semiconductor 2 of the sheet of 300 μm of thickness.
<The making of sealing material for semiconductor 3>
Mixture following compositions are heated 4 minutes at 70 DEG C using roll-type kneading machine, are then heated 6 minutes at 120 DEG C, with conjunction
10 minutes are counted in decompression (0.01kg/cm2) under melting mixing, produce mixture 3.
Obtained mixture 3 is configured in a manner of in the PET film (Supreme Being people Purex films) for sandwiching 50 μm of two panels, using flat
Mixture is formed as sheet by plate pressing, obtains the sealing material for semiconductor 3 of the sheet of 300 μm of thickness.
<The making of sealing material for semiconductor 4>
Mixture following compositions are heated 4 minutes at 70 DEG C using roll-type kneading machine, are then heated 6 minutes at 120 DEG C, with conjunction
10 minutes are counted in decompression (0.01kg/cm2) under melting mixing, produce mixture 4.
Obtained mixture 4 is configured in a manner of in the cover film (Supreme Being people Purex films) for sandwiching 50 μm of two panels, using flat
Mixture is formed as sheet by plate pressing, obtains the sealing material for semiconductor 4 of the sheet of 300 μm of thickness.
<The making of sealing material for semiconductor 5>
Mixture following compositions are heated 4 minutes at 70 DEG C using roll-type kneading machine, are then heated 6 minutes at 120 DEG C, with conjunction
10 minutes are counted in decompression (0.01kg/cm2) under melting mixing, produce mixture 5.
It should be noted that in sealing material for semiconductor 5, if by mole as the functional group of the anthraquinone of oxidant
Number is set as 100%, then the molal quantity of the functional group of antioxidant is about 12%.
Obtained mixture 5 is configured in a manner of in the cover film (Supreme Being people Purex films) for sandwiching 50 μm of two panels, using flat
Mixture is formed as sheet by plate pressing, obtains the sealing material for semiconductor 5 of the sheet of 300 μm of thickness.
<The making of sealing material for semiconductor 6>
It other than not using anthraquinone, is operated in the same manner as sealing material for semiconductor 1, produces the half of 300 μm of thickness
Conductor sealing material 6.
<The making of sealing material for semiconductor 7>
It other than not using anthraquinone, is operated in the same manner as sealing material for semiconductor 2, produces the half of 300 μm of thickness
Conductor sealing material 7.
<The making of sealing material for semiconductor 8>
It other than not using manganese dioxide, is operated in the same manner as sealing material for semiconductor 3, produces 300 μm of thickness
Sealing material for semiconductor 8.
<The making of sealing material for semiconductor 9>
Other than not using benzoyl peroxide, is operated in the same manner as sealing material for semiconductor 4, produce thickness
300 μm of sealing material for semiconductor 9.
<The making of sealing material for semiconductor 10>
It other than not using anthraquinone and ADKSTAB AO-60, operates, makes in the same manner as sealing material for semiconductor 5
Go out the sealing material for semiconductor 10 of 300 μm of thickness.
<The preparation of semiconductor wafer>
As semiconductor wafer, the single side for having prepared the manufacture of Canosis Co., Ltd.s is formed with the SiO of 100nm2Film,
4 inches, be ground into the P-type silicon chip of 200 μm of thickness.
<The making of semiconductor packages>
Above-mentioned semiconductor wafer is cut using cutter device, obtains the semiconductor chip of 10mm × 10mm square.
Film will be fixed temporarily to be configured on SUS planar substrates, according to SiO2Face is further configured with the mode that film contacts is fixed temporarily
Above-mentioned semiconductor chip.The sealing material for semiconductor of 20mm × 20mm square sheets is laminated on it, keeps center big
Cause it is consistent, using heated type compacting press-connection machine in 150 DEG C of compression formings 1 hour.Film will be fixed temporarily from obtained laminated body
Stripping, obtains semiconductor packages.
As the confirmation method that the gap inhibited between semiconductor chip and sealing material for semiconductor is formed, to adaptation
It is evaluated.Evaluation is following to be carried out.
<Evaluation>
2.38% aqueous solutions of TMAH (trade name AD-10, Tama Chemicals Co., Ltd.'s manufacture) for preparing 25 DEG C,
Made semiconductor packages is wherein impregnated, the SiO of semiconductor chip is made2Up, it carries out handling for 5 minutes.It will partly lead later
Body encapsulation is taken out, and is rinsed 2 times with pure water.Later by blowing away moisture, 5 points are placed in the heating plate for being set as 100 DEG C
Clock simultaneously recycles.For obtained treated semiconductor packages, using light microscope and electron microscope from semiconductor core
The boundary part of the observation of piece side semiconductor chip and sealing material, will not generate gap and closely sealed situation is determined as 〇, will see
The case where observing gap be determined as ×.Evaluation result is as described in Table 1.
[table 1]
| Used sealing material for semiconductor | Adaptation | |
| Embodiment 1 | Sealing material for semiconductor 1 | ○ |
| Embodiment 2 | Sealing material for semiconductor 2 | ○ |
| Embodiment 3 | Sealing material for semiconductor 3 | ○ |
| Embodiment 4 | Sealing material for semiconductor 4 | ○ |
| Embodiment 5 | Sealing material for semiconductor 5 | ○ |
| Comparative example 1 | Sealing material for semiconductor 6 | × |
| Comparative example 2 | Sealing material for semiconductor 7 | × |
| Comparative example 3 | Sealing material for semiconductor 8 | × |
| Comparative example 4 | Sealing material for semiconductor 9 | × |
| Comparative example 5 | Sealing material for semiconductor 10 | × |
Evaluation result as shown in Table 1 it is found that used the embodiment 1 of the sealing material for semiconductor comprising oxidant~
It is good even if the boundary of 5 progress alkali process, semiconductor chip and sealing material is also closely sealed.On the other hand, it is using not
In the Comparative Examples 1 to 5 of semiconductor-encapsulating material containing oxidant, the side of semiconductor chip and sealing material is made by alkali process
Boundary produces gap.Though to speculate, think：In the semiconductor wafer of Examples 1 to 5, due to sealing material for semiconductor
In include oxidant and so that the surface of the Si as semiconductor chip is aoxidized, formed include SiO2Film, as a result, suppression
The etching of the side of semiconductor chip caused by alkali process is made.
Claims (4)
1. a kind of sealing material for semiconductor is formed it includes that can make the oxidant of semiconductor oxide.
2. sealing material for semiconductor as described in claim 1, it includes curability composition, curing agent component, solidifications to promote
Agent ingredient and inorganic filler form.
3. sealing material for semiconductor as described in claim 1, the shape with sheet.
4. sealing material for semiconductor as described in claim 1 is used for the wafer-class encapsulation of fan-out-type.
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|---|---|---|---|
| JP2015-254480 | 2015-12-25 | ||
| JP2015254480A JP5978380B1 (en) | 2015-12-25 | 2015-12-25 | Sealant for semiconductor |
| PCT/JP2016/088444 WO2017111057A1 (en) | 2015-12-25 | 2016-12-22 | Sealant for semiconductor |
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| JP (1) | JP5978380B1 (en) |
| KR (1) | KR102384582B1 (en) |
| CN (1) | CN108369928B (en) |
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| EP3725860A4 (en) | 2017-12-18 | 2021-01-20 | Lg Chem, Ltd. | Composition for encapsulation |
| JP2019196475A (en) * | 2018-05-11 | 2019-11-14 | サムスン エレクトロニクス カンパニー リミテッド | Low-loss insulating resin composition and insulating film using the same |
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| US5272377A (en) * | 1990-10-31 | 1993-12-21 | Kabushiki Kaisha Toshiba | Maleimide resin composition and resin encapsulated semiconductor device manufactured using the composition |
| JP2000109543A (en) * | 1998-10-07 | 2000-04-18 | Hitachi Chem Co Ltd | Epoxy resin composition for semiconductor sealing use and semiconductor device using the same |
| WO2015037458A1 (en) * | 2013-09-12 | 2015-03-19 | 日東電工株式会社 | Method for manufacturing semiconductor device |
| WO2015098842A1 (en) * | 2013-12-26 | 2015-07-02 | 日東電工株式会社 | Method for manufacturing semiconductor device |
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| JP2558293B2 (en) * | 1987-09-14 | 1996-11-27 | 日東電工株式会社 | Semiconductor device |
| JP2000036552A (en) * | 1998-07-17 | 2000-02-02 | Fujitsu Ltd | Semiconductor device and separately taking out method of metal component in sealing material used therein |
| KR101005948B1 (en) * | 2002-09-05 | 2011-01-05 | 다이셀 가가꾸 고교 가부시끼가이샤 | Process for preparation of alicyclic diepoxy compounds, curable epoxy resin compositions, epoxy resin compositions for the encapsulation of electronic components, stabilizers for electrical insulating oils, and casting epoxy resin compositions for electrical insulation |
| JP3998564B2 (en) * | 2002-11-13 | 2007-10-31 | 株式会社巴川製紙所 | Curable adhesive composition for semiconductor encapsulation and adhesive sheet |
| JP6019550B2 (en) | 2011-08-09 | 2016-11-02 | 富士通株式会社 | Manufacturing method of electronic device |
| KR101393700B1 (en) * | 2012-11-29 | 2014-05-13 | 서울과학기술대학교 산학협력단 | Manufacturing of fan-out wafer level packaging fortified preventing warpage of wafer |
| JP2015041663A (en) * | 2013-08-21 | 2015-03-02 | 日東電工株式会社 | Sealing sheet, and method of manufacturing semiconductor device |
| JP2015056458A (en) * | 2013-09-10 | 2015-03-23 | 株式会社東芝 | Semiconductor device |
| JP6546378B2 (en) * | 2013-11-19 | 2019-07-17 | 日東電工株式会社 | Resin sheet |
| JP2015126124A (en) * | 2013-12-26 | 2015-07-06 | 日東電工株式会社 | Semiconductor package manufacturing method |
-
2015
- 2015-12-25 JP JP2015254480A patent/JP5978380B1/en active Active
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2016
- 2016-12-22 CN CN201680073780.XA patent/CN108369928B/en active Active
- 2016-12-22 KR KR1020187017963A patent/KR102384582B1/en active IP Right Grant
- 2016-12-22 WO PCT/JP2016/088444 patent/WO2017111057A1/en active Application Filing
- 2016-12-22 MY MYPI2018000991A patent/MY196462A/en unknown
- 2016-12-23 TW TW105143052A patent/TWI750145B/en active
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| US5272377A (en) * | 1990-10-31 | 1993-12-21 | Kabushiki Kaisha Toshiba | Maleimide resin composition and resin encapsulated semiconductor device manufactured using the composition |
| JP2000109543A (en) * | 1998-10-07 | 2000-04-18 | Hitachi Chem Co Ltd | Epoxy resin composition for semiconductor sealing use and semiconductor device using the same |
| WO2015037458A1 (en) * | 2013-09-12 | 2015-03-19 | 日東電工株式会社 | Method for manufacturing semiconductor device |
| WO2015098842A1 (en) * | 2013-12-26 | 2015-07-02 | 日東電工株式会社 | Method for manufacturing semiconductor device |
Also Published As
| Publication number | Publication date |
|---|---|
| KR102384582B1 (en) | 2022-04-08 |
| TW201737429A (en) | 2017-10-16 |
| WO2017111057A1 (en) | 2017-06-29 |
| JP5978380B1 (en) | 2016-08-24 |
| JP2017118045A (en) | 2017-06-29 |
| TWI750145B (en) | 2021-12-21 |
| CN108369928B (en) | 2022-01-18 |
| PH12018501308A1 (en) | 2019-02-11 |
| MY196462A (en) | 2023-04-12 |
| KR20180098558A (en) | 2018-09-04 |
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