Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
  • B32B7/04—Interconnection of layers
  • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J177/00—Adhesives based on polyamides obtained by reactions forming a carboxylic amide link in the main chain; Adhesives based on derivatives of such polymers
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J7/00—Adhesives in the form of films or foils
  • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
  • C09J7/35—Heat-activated
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
  • H10P95/00—Generic processes or apparatus for manufacture or treatments not covered by the other groups of this subclass

Definitions

• the present invention relates to a laminate having a layer containing an adhesive composition containing a polyamide, and more specifically, to a temporary fixing material used to temporarily fix a semiconductor wafer to a support substrate (carrier) in order to perform wafer processing such as grinding, film formation, and etching of the back surface of the semiconductor wafer. Furthermore, the present invention relates to a method for manufacturing a wafer and a method for manufacturing electronic components.
• Adhesive tapes are widely used in the manufacturing process of electronic parts and semiconductor parts for the purpose of temporary fixing of members and parts, fixing during transportation, reinforcement, protection, masking, etc.
• the adhesive composition used in such adhesive tapes is required to have high adhesion enough to firmly fix the adherend such as wafers and semiconductor chips during the processing process, and to be able to peel off the adherend without damaging it after the process is completed.
• semiconductors in recent years, there has been a demand for semiconductors to be integrated at a higher density, and it is required to grind semiconductor wafers to an extremely thin thickness in the back grinding process.
• next-generation materials called compound semiconductors such as SiC are emerging, but these are harder and more brittle than silicon wafers and are considered to be extremely difficult to process.
• Patent Document 1 discloses a temporary fixing material for temporarily fixing a wafer and a support base using a photocurable acrylic acid ester polymer.
• Patent Document 2 discloses a temporary fixing material for temporarily fixing a wafer and a support base using a pressure-sensitive adhesive composition containing a photocurable polyimide and a maleimide group.
• Patent Document 3 discloses a temporary fixing material for temporarily fixing a wafer and a support base using a pressure-sensitive adhesive composition containing a polyimide containing a siloxane skeleton.
• the temporary fixing material of Patent Document 1 uses an acrylic acid ester polymer as a base polymer in the adhesive composition, and therefore has a problem with heat resistance.
• the temporary fixing material of Patent Document 2 uses a polymer containing an imide skeleton in the adhesive composition, and essentially uses polyimide as a base polymer. Since polyimide is prone to leaving carboxylic acid functional groups in its polymerization process, there is a concern that the adhesive strength to the adherend will be high, which may damage the wafer during peeling or make peeling impossible.
• the temporary fixing material of Patent Document 3 is not in the form of a tape, but is a liquid adhesive, and therefore requires processes such as coating and drying, which may complicate the processing process.
• the temporary fixing material is required to have the following properties: it can easily bond the wafer and the support (ability to conform to the irregularities on the wafer surface), it can withstand the external forces and high heat involved in the semiconductor manufacturing process (heat resistance), and it can also be easily peeled off after the process is completed without damaging or contaminating the adherend.
• the adhesive composition contained in the temporary fixing material is crosslinked by heat curing or photocuring, but there is a limit to its heat resistance (up to about 250°C), and temporary fixing materials with even higher heat resistance are required (up to 300°C).
• an object of the present invention is to provide a laminate (temporary fixing material) for use in a wafer support system, the laminate (temporary fixing material) having heat resistance and ability to conform to irregularities on a wafer surface, and a method for manufacturing a wafer using the laminate.
• the present invention provides: [1] A laminate comprising at least a layer containing an adhesive composition,
• the adhesive composition comprises a polyamide and a curable resin having a radical reactive group,
• the layer containing the adhesive composition after curing has a modulus of elasticity at 300° C. of 1 MPa or more.
• the present invention relates to the laminate.
• [2] to [7] are each a preferred aspect or embodiment of the present invention.
• the multilayer film includes a substrate and a device-side adhesive layer; The device-side adhesive layer comprises the adhesive composition.
• [5] The laminate according to any one of [1] to [4], wherein the curable resin having a radical reactive group is a maleimide compound.
• [6] (a) forming a laminate including a wafer, an adhesive layer, and a substrate; (b) curing the adhesive layer by heating; (c) after step (b), subjecting the wafer to a heat treatment, a mechanical processing treatment, a chemical treatment, a physical treatment, a laser processing treatment, and/or a film forming treatment; (d) removing the substrate from the laminate after step (c); and (e) removing the adhesive layer from the laminate comprising the wafer and the adhesive layer after step (d).
• a method for manufacturing a wafer comprising: the adhesive layer comprises an adhesive composition comprising a polyamide and a curable resin having a radical reactive group, A method for manufacturing a wafer, wherein the adhesive layer after curing in step (b) has a modulus of elasticity at 300° C. of 1 MPa or more.
• a method for producing an electronic component comprising the method for producing a wafer according to [6].
• the laminate of the present invention combines sufficient heat resistance with the ability to conform to uneven surfaces, and can be cross-linked by thermal curing to further improve heat resistance, making it suitable for use in wafer support systems.
• the present invention relates to A laminate comprising at least a layer containing an adhesive composition,
• the adhesive composition comprises a polyamide and a curable resin having a radical reactive group,
• the layer containing the adhesive composition after curing has a modulus of elasticity at 300° C. of 1 MPa or more.
• the laminate of the present invention is a laminate having at least a layer containing an adhesive composition, and is used to temporarily fix a wafer and a support (substrate).
• it is a laminate that comes into contact with a wafer. It is easily peeled off from the wafer after wafer processing, and the layer containing the adhesive composition after curing has a 300°C elastic modulus of 1 MPa or more.
• the elastic modulus is preferably 1.1 MPa or more, more preferably 1.2 MPa or more. When the elastic modulus is in such a range, the laminate of the present invention has both sufficient heat resistance and unevenness-following ability, and can prevent adhesive residue. When the elastic modulus is less than 1 MPa, adhesion is likely to increase.
• the layer containing the adhesive composition after curing has a 300°C weight loss of preferably 2.0% or less, more preferably 0.8% or less, and even more preferably 0.4% or less.
• the 350°C weight loss is preferably 3% or less, more preferably 2% or less, and even more preferably 1.5% or less.
• the laminate of the present invention can be a multilayer film and can be used as a temporary fixing material in a wafer support system.
• the multilayer film can include a substrate and a device-side adhesive layer (a layer on the side in contact with a wafer), and the device-side adhesive layer can include the adhesive composition.
• the multilayer film may also include a device-side adhesive layer and a carrier-side adhesive layer (the layer in contact with the substrate), and the carrier-side adhesive layer may include the adhesive composition.
• Adhesive composition contains a polyamide and a curable resin having a radical reactive group.
• the adhesive composition is contained in the layer containing the adhesive composition in an amount of preferably 50 to 100% by mass, more preferably 80 to 100% by mass.
• the laminate of the present invention and the adhesive composition used in the present invention preferably do not contain an acrylic polymer.
• polyamides used in the present invention include, for example, polyesteramides, aliphatic polyamides, and polyetheresteramides.
• Polyesteramide Polyesteramide is a block copolymer in which a polyester block and a polyamide block are bonded by an amide bond or an ester bond, and the polyester block contains an aliphatic dicarboxylic acid and a diol compound as monomers, and the aliphatic dicarboxylic acid preferably has 4 to 60 carbon atoms, and more preferably has 4 to 36 carbon atoms. Specific examples include adipic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, hexadecanedioic acid, eicosanedioic acid, dimer acid, and the like, but are not limited thereto. In addition, aromatic dicarboxylic acid units may be contained.
• aromatic dicarboxylic acids include isophthalic acid, terephthalic acid, 2,6-naphthalenedicarboxylic acid, and biphenyl-4,4'-dicarboxylic acid.
• diol compound include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,12-dodecanediol, 3-methyl-1,5-pentanediol, 2-methyl-2,4-pentanediol, 2,2,4-trimethyl-1,3-pentanediol, 2,
• the polyamide block contains either or both of an aliphatic dicarboxylic acid and an aliphatic diamine as a monomer, and the aliphatic dicarboxylic acid preferably has 4 to 60 carbon atoms, more preferably 4 to 36 carbon atoms. Specific examples include adipic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, hexadecanedioic acid, eicosanedioic acid, dimer acid, etc., but are not limited thereto. In addition, aromatic dicarboxylic acid units may be contained.
• aromatic dicarboxylic acids include isophthalic acid, terephthalic acid, 2,6-naphthalenedicarboxylic acid, and biphenyl-4,4'-dicarboxylic acid.
• the aliphatic diamine preferably has 4 to 60 carbon atoms, more preferably 4 to 36 carbon atoms. Specific examples include, but are not limited to, hexamethylenediamine, tetramethylenediamine, nonamethylenediamine, undecamethylenediamine, dodecamethylenediamine, methylpentamethylenediamine, 2,2,4- or 2,4,4-trimethylhexamethylenediamine, and dimer diamine derived from dimer acid.
• the diamine may also contain an aromatic diamine unit.
• aromatic diamines examples include 4,4'-bis(4-aminophenoxy)biphenyl, 4,4'-diaminodiphenyl ether, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 4,4'-diaminodiphenyl sulfone, 1,3-bis(4-aminophenoxy)benzene, and 1,4-bis(4-aminophenoxy)benzene.
• polyesteramides include block copolymers in which a polyester block and a polyamide block are bonded via an amide bond or an ester bond.
• polyesteramides include TPAE-617 (manufactured by T&K Toka Corporation, softening point 153° C.) and TPAE-617C (manufactured by T&K Toka Corporation, softening point 161° C.).
• Aliphatic polyamides are polyamides containing either or both of an aliphatic dicarboxylic acid and an aliphatic diamine as monomers, and the aliphatic dicarboxylic acid preferably has 4 to 60 carbon atoms, more preferably 4 to 36 carbon atoms. Specific examples include adipic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, hexadecanedioic acid, eicosanedioic acid, dimer acid, etc., but are not limited thereto. Dimer acids are dimers of unsaturated fatty acids such as oleic acid, linoleic acid, erucic acid, etc.
• aromatic dicarboxylic acid units may be included.
• aromatic dicarboxylic acids include isophthalic acid, terephthalic acid, 2,6-naphthalenedicarboxylic acid, and biphenyl-4,4'-dicarboxylic acid.
• the aliphatic diamine preferably has 4 to 60 carbon atoms, more preferably 4 to 36 carbon atoms.
• diamine may also contain an aromatic diamine unit.
• aromatic diamines examples include 4,4'-bis(4-aminophenoxy)biphenyl, 4,4'-diaminodiphenyl ether, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 4,4'-diaminodiphenyl sulfone, 1,3-bis(4-aminophenoxy)benzene, and 1,4-bis(4-aminophenoxy)benzene.
• aliphatic polyamides examples include polyamides containing 50% by weight or more of a dimer acid skeleton, and specific examples thereof include PA-100 (manufactured by T&K Toka Corporation, melting point 84° C.) and TOMAID 1310 (manufactured by T&K Toka Corporation, softening point 120 ⁇ 5° C.).
• Polyetheresteramide polyetheresteramide is a block copolymer in which a polyetherester block and a polyamide block are bonded by an amide bond or an ester bond, and the polyetherester block contains an aliphatic dicarboxylic acid and a diol compound as monomers, and further has a plurality of ether bonds formed by condensation of diols.
• the aliphatic dicarboxylic acid preferably has 4 to 60 carbon atoms, and more preferably has 4 to 36 carbon atoms.
• aromatic dicarboxylic acid units may be contained.
• aromatic dicarboxylic acids include isophthalic acid, terephthalic acid, 2,6-naphthalenedicarboxylic acid, and biphenyl-4,4'-dicarboxylic acid.
• diol compound examples include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,12-dodecanediol, 3-methyl-1,5-pentanediol, 2-methyl-2,4-pentanediol, 2,2,4-trimethyl-1,3-pentanediol, 2,4-heptanediol, 2,2-diethyl-1,3-propanediol, 2-ethyl-1,3-hexanediol, 2-butyl-2-e
• the polyamide block contains either or both of an aliphatic dicarboxylic acid and an aliphatic diamine as a monomer, and the aliphatic dicarboxylic acid preferably has 4 to 60 carbon atoms, more preferably 4 to 36 carbon atoms. Specific examples include adipic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, hexadecanedioic acid, eicosanedioic acid, dimer acid, etc., but are not limited thereto. In addition, aromatic dicarboxylic acid units may be contained.
• aromatic dicarboxylic acids include isophthalic acid, terephthalic acid, 2,6-naphthalenedicarboxylic acid, and biphenyl-4,4'-dicarboxylic acid.
• the aliphatic diamine preferably has 4 to 60 carbon atoms, more preferably 4 to 36 carbon atoms. Specific examples include, but are not limited to, hexamethylenediamine, tetramethylenediamine, nonamethylenediamine, undecamethylenediamine, dodecamethylenediamine, methylpentamethylenediamine, 2,2,4- or 2,4,4-trimethylhexamethylenediamine, and dimer diamine derived from dimer acid.
• the diamine may also contain an aromatic diamine unit.
• aromatic diamines examples include 4,4'-bis(4-aminophenoxy)biphenyl, 4,4'-diaminodiphenyl ether, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 4,4'-diaminodiphenyl sulfone, 1,3-bis(4-aminophenoxy)benzene, and 1,4-bis(4-aminophenoxy)benzene.
• polyether ester amides include block copolymers of polyether ester blocks and polyamide resins, and specific examples thereof include PA-201 (manufactured by T&K Toka Corporation, melting point 122° C.) and TPAE-32C (manufactured by T&K Toka Corporation, melting point 124° C.).
• Curable resin having radical reactive group The curable resin having radical reactive group (radical curable resin) used in the present invention is a curable adhesive component, etc., which is cured before wafer processing, so that voids are unlikely to occur during heat treatment in the wafer manufacturing process, and adhesion promotion due to high temperature during heat treatment is suppressed, and peeling can be easily performed without leaving adhesive residue.
• the curable adhesive component include a photocurable adhesive component that crosslinks and hardens when irradiated with light, and a thermosetting adhesive component that crosslinks and hardens when heated.
• examples of the curable resin having a radical reactive group used in the present invention include an olefin-based curing agent, and a thermosetting adhesive component containing a monomer, oligomer, or polymer such as acrylic, epoxy, urethane acrylate, epoxy acrylate, silicone acrylate, or polyester acrylate as a curing component and containing a thermal polymerization initiator.
• a bismaleimide crosslinking agent e.g., BMI-5100 having the following chemical formula
• an alicyclic crosslinking agent e.g., IRR-214K having the following chemical formula
• an epoxy acrylate crosslinking agent e.g., EBECRYL3700 having the following chemical formula
• the curable resin having a radical reactive group is a maleimide compound.
• the curable resin having a radical reactive group is contained in the adhesive composition in an amount of preferably 10 to 100 parts by mass, more preferably 20 to 75 parts by mass, based on 100 parts by mass of polyamide.
• the adhesive composition used in the present invention may contain an organic peroxide as a thermal polymerization initiator.
• organic peroxides include those that decompose when heated to generate active radicals that initiate polymerization curing. Specific examples include 2-ethyl t-butylperoxy hexanoate, bis(4-methylbenzoyl)peroxide, benzoyl peroxide, 1,1-bis(t-hexylperoxy)cyclohexane, 1,1-bis(t-butylperoxy)cyclohexane, 2,2-bis(4,4-bis-(t-butylperoxy)cyclohexyl)propane, t-hexylperoxyisopropyl monocarboxylate, t-butylperoxyacetate, 2,2-bis-( t-butylperoxy)butane, n-butyl 4,4-bis-(t-butylperoxy)pentanoate, bis-t
• thermal polymerization initiators commercially available ones are not particularly limited, but suitable examples include Perbutyl O, Niper BMT, Niper BW, Perhexa HC, Perhexa C, Pertetra A, Perhexyl I, Perbutyl A, Perhexa 22, Perhexa V, Perhexyl D, Percumyl D, Perhexa 25B, Perbutyl P, Perbutyl C, Perhexine 25B, Percumyl P (all manufactured by NOF Corp.), Perkadox 12XL25 (manufactured by Noury Chemical Co., Ltd.), etc.
• thermal polymerization initiators may be used alone or in combination of two or more kinds.
• the amount of the organic peroxide is preferably 0.1 to 3.0 parts by mass per 100 parts by mass of the polyamide.
• the amount is more preferably 0.1 to 1.0 part by mass. When the amount of the organic peroxide is within this range, it can function sufficiently as a thermal polymerization initiator.
• the adhesive composition of the present invention may contain various thermal crosslinking agents such as melamine compounds and epoxy compounds, as well as known additives such as release agents, plasticizers, resins, surfactants, waxes, and particulate fillers, if desired.
• thermal crosslinking agents such as melamine compounds and epoxy compounds
• additives such as release agents, plasticizers, resins, surfactants, waxes, and particulate fillers, if desired.
• the release agent is not particularly limited as long as it generally exhibits a release effect.
• hydrocarbon compounds, silicone compounds, fluorine compounds, polyethylene wax, carnauba wax, montanic acid, stearic acid, etc. which are known as release agents for plastic materials, can be mentioned.
• silicone and fluorine compounds are preferred, and silicone and fluorine compounds having a functional group capable of crosslinking with the curable adhesive are more preferred.
• silicone compounds have excellent heat resistance, so they prevent the adhesive from burning even after treatment involving heating at 200°C or higher, and they bleed out to the interface with the adherend during peeling, making peeling easy.
• the silicone compound Since the silicone compound has a functional group that can crosslink with the curing adhesive, it chemically reacts with the curing adhesive when irradiated with light or heated, and is incorporated into the curing adhesive, so the silicone compound does not adhere to the adherend and contaminate it. In addition, the incorporation of a silicone compound also has the effect of preventing glue from remaining on the semiconductor chip.
• the release agent include plasticizers.
• the plasticizer is not particularly limited as long as it generally reduces the adhesive strength of the adhesive material to the adherend. Examples of the plasticizer include trimellitic acid esters, pyromellitic acid esters, phthalic acid esters, and adipic acid esters.
• the amount of release agent added is not particularly limited, but is appropriately determined so as to obtain a release effect.
• the amount added is controlled so as not to be excessive so as not to significantly impair the adhesive function of the adhesive composition used in the present invention.
• it is desirable to adjust the amount according to the peel strength aiming at an amount of usually 0.1 to 5 parts by mass, preferably 0.1 to 3 parts by mass, and more preferably 0.1 to 1 part by mass, per 100 parts by mass of the total adhesive composition.
• the amount of the plasticizer according to the peel strength usually about 5 to 50 parts by weight, preferably about 10 to 50 parts by weight, and more preferably about 20 to 40 parts by weight.
• these release agents can be used alone or in combination.
• the thickness of the layer containing the adhesive composition used in the present invention is not particularly limited, but the preferred lower limit is 5 ⁇ m and the preferred upper limit is 250 ⁇ m, and the more preferred lower limit of the thickness is 10 ⁇ m and the more preferred upper limit is 200 ⁇ m. If the thickness is within this range, the unevenness of the wafer can be absorbed and the temporary fixation to the support can be performed with sufficient strength, and the peeling force can be easily adjusted to a suitable range when peeling off the adhesive material.
• a tape including the laminate of the present invention is provided.
• a tape having a substrate film and a layer including the adhesive composition used in the present invention as a device-side adhesive layer (wafer-side adhesive layer).
• the tape may also be a so-called double-sided adhesive tape having a carrier-side adhesive layer (support-side adhesive layer) on the surface of the substrate film opposite to the wafer-side adhesive layer.
• the adhesive strength on the support side can be appropriately adjusted, so that the support (substrate) can be easily removed after the wafer is processed.
• the substrate film can be designed from the viewpoint of the mechanical strength and handling properties of the entire laminate, which is particularly advantageous from the viewpoint of optimizing the performance of the tape.
• the material of the substrate film is not particularly limited, but it is preferable to use a plastic film, and examples of such materials include films, sheets, sheets having a mesh-like structure, sheets with holes, etc., such as acrylic, olefin, polycarbonate, vinyl chloride, ABS, polyethylene terephthalate (PET), polyethylene naphthalate (PEN), nylon, urethane, polyether ether ketone (PEEK), liquid crystal polymer (LCP), polyimide, etc. From the viewpoint of handling, etc., PET, PEN, or polyimide films are preferable.
• Wafer there is no particular limitation on the wafer to be temporarily fixed to a support using the laminate of the present invention and processed, and any wafer generally used in semiconductor manufacturing processes can be used. Among them, wafers that require careful handling during processing due to reasons such as thinness and fragility, and therefore require temporary fixing, are preferably used.
• the thinness and fragility of the wafer are assumed to be, for example, a case in which the thickness temporarily becomes thin during processing, causing problems in handling, and the laminate of the present invention is used for temporarily fixing such a wafer to a support.
• cases in which a wafer becomes temporarily thin include a case in which a thin wafer is processed starting from a thin wafer, a case in which a relatively thick wafer is thinned during a process, and a case in which the thin wafer is further processed.
• the thickness of the temporarily thinned wafer is usually 1 to 200 ⁇ m.
• the semiconductor wafer during the process corresponds to a wafer.
• the wafers temporarily fixed using the laminate of the present invention include those whose state changes during the process.
• the wafer to be temporarily fixed using the laminate of the present invention there are no particular limitations on the wafer to be temporarily fixed using the laminate of the present invention. More specific examples thereof include semiconductor wafers such as silicon wafers, compound semiconductor wafers such as SiC, AlSb, AlAs, AlN, AlP, BN, BP, BAs, GaSb, GaAs, GaN, GaP, InSb, InAs, InN, or InP, quartz wafers, sapphire, glass, and mold wafers.
• the silicon wafer or compound semiconductor wafer may be doped.
• An electric/electronic functional layer may be formed on or in the wafer. Suitable examples of the functional layer include electronic circuits, capacitors, transistors, resistors, electrodes, optical elements, MEMS, etc., but may also be other microdevices.
• the surfaces of these functional layers may have structures, typically electrodes, formed from one or more of the following materials: silicon, polysilicon, silicon dioxide, silicon (oxy)nitride, metals (e.g., copper, aluminum, gold, tungsten, tantalum), low-k dielectrics, polymer dielectrics, and various metal nitrides and metal silicides.
• the side of the wafer on which the functional layers are formed may also have raised structures such as solder bumps, metal posts, and pillars.
• the wafer surface may be covered with an oxide film or a nitride film for forming a functional layer or for protecting the functional layer, or may be covered with a passivation film for protecting the wafer.
• the present invention relates to a method for manufacturing a wafer comprising : (a) forming a laminate including a wafer, an adhesive layer, and a substrate; (b) curing the adhesive layer by heating; (c) after step (b), subjecting the wafer to a heat treatment, a mechanical processing treatment, a chemical treatment, a physical treatment, a laser processing treatment, and/or a film forming treatment; (d) removing the substrate from the laminate after step (c); and (e) removing the adhesive layer from the laminate comprising the wafer and the adhesive layer after step (d).
• a method for manufacturing a wafer comprising: the adhesive layer comprises an adhesive composition comprising a polyamide and a curable resin having a radical reactive group, A method for manufacturing a wafer, wherein the adhesive layer after curing in step (b) has a modulus of elasticity at 300° C. of 1 MPa or more.
• Step (a) is a step of forming a laminate including a wafer, an adhesive layer, and a substrate, that is, a step of laminating the wafer and the substrate in order to temporarily fix the wafer and the substrate via the adhesive layer.
• the adhesive layer may be the same as the layer containing the adhesive composition described above.
• an adhesive layer containing a photocurable adhesive component that is crosslinked and cured by irradiation with light may be used.
• the photocurable adhesive component may, for example, contain a monomer, oligomer, or polymer such as epoxy, urethane acrylate, epoxy acrylate, silicone acrylate, or polyester acrylate as a curing component, and may include a photocurable adhesive component containing a photopolymerization initiator.
• the photopolymerization initiator may be activated by irradiation with light having a wavelength of 250 to 800 nm.
• photopolymerization initiators include acetophenone derivative compounds such as methoxyacetophenone, benzoin ether compounds such as benzoin propyl ether and benzoin isobutyl ether, ketal derivative compounds such as benzyl dimethyl ketal and acetophenone diethyl ketal, phosphine oxide derivative compounds, bis( ⁇ 5-cyclopentadienyl)titanocene derivative compounds, benzophenone, Michler's ketone, chlorothioxanthone, todecylthioxanthone, dimethylthioxanthone, diethylthioxanthone, ⁇ -hydroxycyclohexylphenyl ketone, and 2-hydroxymethylphenylpropane.
• photopolymerization initiators may be used alone or in combination of two or more.
• Wafer The above-mentioned wafers can be used as the wafer .
• the substrate substrate (support) can be the same as the substrate described above, and preferably has sufficient strength and rigidity, and is excellent in heat resistance and chemical resistance.
• the wafer can be stably handled, and the wafer can be subjected to a large number and/or a wide variety of processes without bending or the like.
• a wafer on which an electronic circuit is formed can be subjected to various processes required for manufacturing an electronic device having a structure in which semiconductor chips are stacked, such as TSV connection.
• Materials that are preferably used for the substrate include silicon, sapphire, quartz, metals (e.g., aluminum, copper, steel), and various glasses and ceramics.
• the substrate may be composed of a single material, but may also be composed of multiple materials and may include other materials deposited on the substrate.
• a silicon wafer may have a vapor deposition layer of silicon nitride or the like.
• the substrate may also be surface-treated, such as by providing a silicone layer.
• the substrate may be made of plastic.
• a sheet made of a plastic such as polyimide, acrylic, polyolefin, polycarbonate, vinyl chloride, ABS, polyethylene terephthalate (PET), nylon, or urethane can be preferably used as the support.
• Polyimide can be used because it has a certain degree of heat resistance.
• the thickness of the substrate is desirable for the thickness of the substrate to be uniform in order to obtain uniformity in the thickness after grinding the wafer, etc.
• the variation in the thickness of the substrate should be suppressed to ⁇ 2 ⁇ m or less.
• the thickness of the substrate is not particularly limited, but from the viewpoint of effectively preventing the wafer from curving, it is preferably 300 ⁇ m or more, and particularly preferably 500 ⁇ m or more. From the viewpoint of suppressing the total weight during handling or reducing the stress required for mechanical peeling, it is preferably 1500 ⁇ m or less, and particularly preferably 1000 ⁇ m or less.
• a laminate including a wafer, an adhesive layer, and a substrate can be obtained.
• the adhesive layer in the laminate in the step (b) described below the laminate has sufficient strength and rigidity, and the wafer can be subjected to various semiconductor manufacturing processes while preventing bending and breakage.
• the substrate, adhesive layer, and wafer can be laminated in that order.
• the order of lamination is not particularly limited, and these layers can be laminated at once or sequentially.
• the adhesive layer is supplied as a liquid curable adhesive
• the liquid curable adhesive is applied to either the wafer or the support, or both, by spin coating or the like to form a wafer/adhesive layer or adhesive layer/substrate laminate, and then the two adhesive layers are bonded together under reduced pressure to produce a laminate including the wafer, adhesive layer, and substrate.
• the adhesive layer is supplied as a solid film
• the solid film can be attached to either the wafer or the substrate, and then the other can be attached under reduced pressure to create a laminate including the wafer, adhesive layer, and substrate.
• Step (b) is a step of curing the adhesive layer by heating, that is, a step of curing the adhesive layer in the laminate obtained in step (a).
• the adhesive layer (e.g., curable adhesive component) that has been crosslinked and hardened by heating has dramatically improved chemical resistance, and even if the back surface of the wafer is treated with a chemical solution during the wafer processing process, the adhesive layer can be prevented from dissolving in the chemical solution.
• the crosslinked and hardened curable adhesive component has an increased elastic modulus, so adhesion is less likely to increase even at high temperatures, and peeling is relatively easy.
• thermosetting adhesive component when an adhesive layer containing a polymer having an unsaturated double bond such as a vinyl group in the side chain and a thermal polymerization initiator that is activated by heating at about 50 to 200°C is used as the thermosetting adhesive component that crosslinks and hardens when heated, the thermosetting adhesive component can be crosslinked and hardened by heating at a temperature of about 50 to 200°C for 5 to 40 minutes.
• step (b) may harden the adhesive layer by heating at 140 to 200°C for 5 to 60 minutes. Heating at 140°C or higher for 15 minutes or more can sufficiently harden the adhesive layer. In addition, it is sufficient to harden the adhesive layer to an extent that the laminate can withstand the wafer processing step, and from the viewpoint of cost, it is preferable to set the heating conditions to 180°C or 40 minutes or less.
• the adhesive layer contains an adhesive composition that includes a polyamide and a curable resin having a radical reactive group
• the heating temperature can be higher than the conventional heating temperature of more than 160°C and up to about 300°C, making it possible to provide even higher heat resistance.
• Step (c) is a step of subjecting the wafer to a heat treatment, a mechanical processing treatment, a chemical treatment, a physical treatment, a laser processing treatment, and/or a film formation treatment after step (b).
• the laminate formed through steps (a) and (b) can be subjected to at least one wafer treatment selected from heat treatment (including treatment involving heat generation; the same applies below), mechanical processing, chemical processing, physical processing, laser processing, and film formation processing.
• the laminate formed through steps (a) and (b) can also be subjected to TSV processing and processing required for forming a structure in which TSV-processed semiconductor chips are stacked.
• the above heat treatments include, but are not limited to, for example, thermal curing of the resin composition, heat drying of the resin composition, baking of the resin composition, reflow, resin sealing, etc.
• the machining process is typically a polishing, grinding, drilling, cutting process of the wafer, but is not limited to this, and also includes singulation and the like.
• the surface on which the electrodes are not formed (back surface) is ground or polished.
• the thickness of the wafer after grinding and polishing the back surface varies depending on the electronic device in which the obtained electronic device is used, but is usually set to 1 ⁇ m or more and 200 ⁇ m or less, preferably 5 ⁇ m or more and 100 ⁇ m or less, and more preferably 5 ⁇ m or more and 50 ⁇ m or less. This allows the obtained electronic device to be made thinner, and the electronic device using the electronic device to be made smaller.
• the wafer when grinding and polishing the wafer, the wafer is laminated to a rigid support via an adhesive layer, which allows the wafer to be ground with greater precision, and after grinding, the wafer can be subjected to further processing steps without damaging the wafer, and the wafer and adhesive layer can be easily separated.
• the above-mentioned chemical treatments include, for example, polishing treatments such as CMP, treatments using acids, alkalis or organic solvents, such as plating treatments such as electrolytic plating and electroless plating, wet etching treatments using hydrofluoric acid, tetramethylammonium hydroxide aqueous solution (TMAH) or the like, resist stripping processes using N-methyl-2-pyrrolidone, monoethanolamine, DMSO or the like, cleaning processes using concentrated sulfuric acid, ammonia water, hydrogen peroxide water or the like, but are not limited to these.
• polishing treatments such as CMP
• treatments using acids such as electrolytic plating and electroless plating
• TMAH tetramethylammonium hydroxide aqueous solution
• resist stripping processes using N-methyl-2-pyrrolidone, monoethanolamine, DMSO or the
• the above physical treatments include, but are not limited to, plasma treatment, ion implantation, laser annealing, etc.
• the above-mentioned laser processing treatments include, but are not limited to, annealing, via processing, circuit formation processing by direct drawing, and pre-processing for separation from the support.
• the above-mentioned film formation processes include, but are not limited to, coating processes such as spin coating, inkjet, and screen printing, sputtering, deposition, etching, chemical vapor deposition (CVD), physical vapor deposition (PVD), resist coating and patterning, heat lamination of resin composition films, back metal, etc.
• coating processes such as spin coating, inkjet, and screen printing, sputtering, deposition, etching, chemical vapor deposition (CVD), physical vapor deposition (PVD), resist coating and patterning, heat lamination of resin composition films, back metal, etc.
• the wafer even though the wafer undergoes heat treatment, mechanical processing, chemical processing, physical processing, laser processing, and film formation processing in the wafer processing process, sufficient adhesive strength is maintained during the wafer processing, and after the wafer processing process is completed, the wafer can be peeled off from the adhesive layer without being damaged or leaving any glue residue in the process of peeling the wafer off from the laminate.
• step (c) chip bonding, wire bonding, flip chip bonding, surface activation direct bonding, etc. can be performed.
• a dicing tape may be attached to the treatment surface (preferably the grinding surface) of the wafer. By attaching the dicing tape in advance, dicing can be performed quickly after peeling off the base material and adhesive layer.
• Step (d) is a step of removing the substrate from the laminate after step (c).
• the method of removing the substrate from the laminate is not particularly limited, but it is preferable to perform the method by laser peeling or mechanical peeling, since the apparatus can be simplified and therefore it is cost-effective.
• a pre-peeling treatment may be performed in advance, and a method such as swelling or dissolution of the adhesive layer by a solvent may be appropriately adopted as a pre-peeling treatment.
• the adhesive layer after curing in step (b) has a 300°C elastic modulus of 1 MPa or more.
• the elastic modulus is preferably 1.1 MPa or more, more preferably 1.2 MPa or more.
• the laminate of the present invention has both sufficient heat resistance and unevenness-following ability, and can prevent adhesive residue.
• adhesion is likely to increase.
• the adhesive layer after curing has a weight loss at 300°C of preferably 1.1% or less, more preferably 1.0% or less. When the weight loss at 300°C is within this range, the shape of the laminate can be maintained. When the weight loss at 300°C is outside this range (when the weight loss at 300°C is large), the shape of the laminate cannot be maintained.
• Step (e) is a step of removing the adhesive layer from the laminate including the wafer and the adhesive layer after step (d). Since the substrate is removed from the laminate through step (d), the adhesive layer can be separated from the wafer without applying excessive stress to the wafer, so that the risk of damaging the functional layer formed on the wafer can be limited.
• a peeling tape can be attached to the adhesive layer, and the adhesive layer can be peeled off from the wafer together with the peeling tape, and since no special equipment or the like is required, it is also excellent in terms of cost.
• the electronic component manufacturing method of the present invention includes the above-mentioned wafer manufacturing method.
• the wafer can be stably processed and further subjected to subsequent processes to manufacture final products such as electronic components.
• a functional layer is formed on the wafer, dicing, bonding, packaging, sealing, and other processes that are commonly used in the manufacture of electronic devices such as semiconductor devices can be performed to manufacture final products such as electronic components.
• Example production procedure 100 parts by weight of polyamides, 25 parts by weight of radical curing resin, and 0.8 parts by weight of peroxide (Perbutyl P, manufactured by NOF Corp.) as a curing initiator were added to a suitable solvent to prepare a 25 wt % adhesive coating.
• the prepared adhesive coating material was applied to the release-treated surface of a release PET film (T-15, manufactured by Mitsui Chemicals Tocello Co., Ltd.) using a simple roll coater so that the coating thickness after drying would be 25 ⁇ m, and the coating was dried by heating at 120° C. for 2 minutes in a ventilated oven to obtain a single-layer adhesive film.
• the obtained single-layer adhesive film was laminated to a thickness of about 100 ⁇ m while being heated to 100° C. using a roll laminator to prepare a laminated adhesive film.
• (Cured adhesive) The laminated adhesive film was heated at 180° C. for 30 minutes in a nitrogen atmosphere to obtain a cured adhesive product.
• (Making single-sided adhesive tape) The prepared adhesive coating material was applied to the inside of a polyimide film (Kapton 100EN, manufactured by Toray DuPont Co., Ltd.) using a simple roll coater so that the coating thickness after drying would be 25 ⁇ m, and the film was heated and dried at 120° C. for 2 minutes in a ventilated oven to obtain a single-sided adhesive tape.
• Preparation of double-sided adhesive tape A single-layer adhesive film was laminated on the polyimide surface of the obtained single-sided adhesive tape while heating at 100° C. using a roll laminator to prepare a double-sided adhesive tape.
• the double-sided adhesive tape was cut into a 50 mm square and attached to a 1 mm thick glass plate using a hand roller while heating to 100° C. on a hot plate.
• a silicon wafer with a 10 ⁇ m high pattern made of polyimide was prepared and cut into a 30 mm square to obtain a patterned wafer chip.
• the patterned wafer chip was placed on the adhesive surface of a double-sided tape with a glass plate attached, and pressurized at 130° C. and 0.8 MPa for 2 minutes under reduced pressure using a vacuum laminator. The appearance of the sample after pressure application was visually checked to check for peeling, air bubbles, and defective filling. OK: No peeling from the glass plate or pattern wafer chip, no air bubbles, and no defective embedding of the pattern were observed. NG: Peeling or air bubbles from the glass plate or pattern wafer chip, or defective embedding of the pattern occurred.
• Example 1 An aliphatic polyamide (manufactured by T&K Toka, PA-100) was used as the polyimide, and a bismaleimide (manufactured by Daiwa Kasei Kogyo, BMI-5100) was used as the radical curable resin.
• Example 2 Aliphatic polyamide (PA-100, manufactured by T&K Toka) was used as the polyimide, and tricyclodecane dimethanol diacrylate (IRR 214-K, manufactured by Daicel Allnex) was used as the radical curable resin.
• Example 3 An aliphatic polyamide (PA-100, manufactured by T&K Toka Corporation) was used as the polyimide, and an epoxy acrylate (EBECRYL 3700, manufactured by Daicel Allnex Corporation) was used as the radical curable resin.
• EBECRYL 3700 epoxy acrylate
• Example 4 Polyether ester amide (manufactured by T&K Toka, PA-201) was used as the polyimide, and bismaleimide (manufactured by Daiwa Kasei Kogyo, BMI-5100) was used as the radical curable resin.
• Example 5 Polyether ester amide (PA-201, manufactured by T&K Toka Corporation) was used as the polyimide, and tricyclodecane dimethanol diacrylate (IRR 214-K, manufactured by Daicel Allnex Corporation) was used as the radical curable resin.
• Example 6 Aliphatic polyamide polyether ester amide (PA-201, manufactured by T&K Toka) was used as the polyimide, and epoxy acrylate (EBECRYL 3700, manufactured by Daicel Allnex) was used as the radical curable resin.
• Example 7 Polyesteramide (TPAE-617C, manufactured by T&K Toka Corporation) was used as the polyimide, and bismaleimide (BMI-5100, manufactured by Daiwa Kasei Kogyo Co., Ltd.) was used as the radical curable resin.
• Comparative Example 1 acrylic rubber (NV-11) was used, and bismaleimide (manufactured by Daiwa Kasei Kogyo Co., Ltd., BMI-5100) was used as the radical curing resin.
• ⁇ Physical property measurement equipment Differential thermal and thermogravimetric simultaneous measurement device (Hitachi High-Tech, TG/DTA7300) Dynamic viscoelasticity measuring device (TA Instruments, RSA-G2)
• the laminate of the present invention by using a laminate having a layer containing an adhesive composition containing polyamide as a temporary fixing material, it can be easily peeled off from the wafer even after exposure to a high-temperature environment, and at the same time, the laminate of the present invention combines sufficient heat resistance with unevenness-following ability, and can be crosslinked by thermal curing to further improve heat resistance, making it usable for wafer support systems.
• the present invention greatly contributes to improving the productivity of electronic devices, and has high applicability in various fields of industries such as the electronic parts industry, including the semiconductor process industry, the electrical and electronics industry that uses electronic parts, the transport machinery industry, the information and communications industry, and the precision equipment industry.

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