WO2021220929A1 - ウエハ加工用仮接着剤、ウエハ積層体及び薄型ウエハの製造方法 - Google Patents

ウエハ加工用仮接着剤、ウエハ積層体及び薄型ウエハの製造方法 Download PDF

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Publication number
WO2021220929A1
WO2021220929A1 PCT/JP2021/016272 JP2021016272W WO2021220929A1 WO 2021220929 A1 WO2021220929 A1 WO 2021220929A1 JP 2021016272 W JP2021016272 W JP 2021016272W WO 2021220929 A1 WO2021220929 A1 WO 2021220929A1
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Prior art keywords
wafer
temporary adhesive
mass
silicone resin
support
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Ceased
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PCT/JP2021/016272
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English (en)
French (fr)
Japanese (ja)
Inventor
光夫 武藤
道博 菅生
昭平 田上
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Shin Etsu Chemical Co Ltd
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Shin Etsu Chemical Co Ltd
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Priority to US17/921,440 priority Critical patent/US11970639B2/en
Priority to KR1020227039904A priority patent/KR20230005219A/ko
Priority to EP21797814.7A priority patent/EP4144808A4/en
Priority to JP2022517686A priority patent/JP7658367B2/ja
Priority to CN202180031672.7A priority patent/CN115485814B/zh
Publication of WO2021220929A1 publication Critical patent/WO2021220929A1/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • 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
    • C09J183/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Adhesives based on derivatives of such polymers
    • C09J183/04—Polysiloxanes
    • C09J183/06—Polysiloxanes containing silicon bound to oxygen-containing groups
    • 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
    • C09J183/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Adhesives based on derivatives of such polymers
    • C09J183/04—Polysiloxanes
    • 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
    • C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
    • 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
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • 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
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/08—Macromolecular additives
    • 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
    • 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
    • C09J7/38—Pressure-sensitive adhesives [PSA]
    • 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
    • H10P52/00—Grinding, lapping or polishing of wafers, substrates or parts of devices
    • H10P52/40—Chemomechanical polishing [CMP]
    • H10P52/402—Chemomechanical polishing [CMP] of semiconductor materials
    • 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
    • H10P72/00—Handling or holding of wafers, substrates or devices during manufacture or treatment thereof
    • H10P72/70—Handling or holding of wafers, substrates or devices during manufacture or treatment thereof for supporting or gripping
    • H10P72/74—Handling or holding of wafers, substrates or devices during manufacture or treatment thereof for supporting or gripping using temporarily an auxiliary support
    • 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
    • H10P72/00—Handling or holding of wafers, substrates or devices during manufacture or treatment thereof
    • H10P72/70—Handling or holding of wafers, substrates or devices during manufacture or treatment thereof for supporting or gripping
    • H10P72/74—Handling or holding of wafers, substrates or devices during manufacture or treatment thereof for supporting or gripping using temporarily an auxiliary support
    • H10P72/7402—Wafer tapes, e.g. grinding or dicing support tapes
    • 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
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • 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
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B38/0012—Mechanical treatment, e.g. roughening, deforming, stretching
    • B32B2038/0016—Abrading
    • 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
    • B32B2255/00—Coating on the layer surface
    • B32B2255/26—Polymeric coating
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/748—Releasability
    • 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
    • B32B2457/00—Electrical equipment
    • B32B2457/14—Semiconductor wafers
    • 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
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • B32B9/005—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising one layer of ceramic material, e.g. porcelain, ceramic tile
    • 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
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • B32B9/04—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising such particular substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/12—Polysiloxanes containing silicon bound to hydrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
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    • 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
    • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/326—Applications of adhesives in processes or use of adhesives in the form of films or foils for bonding electronic components such as wafers, chips or semiconductors
    • 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
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/312—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
    • C09J2301/416—Additional features of adhesives in the form of films or foils characterized by the presence of essential components use of irradiation
    • 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
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/50—Additional features of adhesives in the form of films or foils characterized by process specific features
    • C09J2301/502—Additional features of adhesives in the form of films or foils characterized by process specific features process for debonding adherents
    • 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
    • C09J2483/00—Presence of polysiloxane
    • 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
    • H10P52/00—Grinding, lapping or polishing of wafers, substrates or parts of devices
    • 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
    • H10P72/00—Handling or holding of wafers, substrates or devices during manufacture or treatment thereof
    • H10P72/70—Handling or holding of wafers, substrates or devices during manufacture or treatment thereof for supporting or gripping
    • H10P72/74—Handling or holding of wafers, substrates or devices during manufacture or treatment thereof for supporting or gripping using temporarily an auxiliary support
    • H10P72/7416—Handling or holding of wafers, substrates or devices during manufacture or treatment thereof for supporting or gripping using temporarily an auxiliary support used during dicing or grinding
    • 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
    • H10P72/00—Handling or holding of wafers, substrates or devices during manufacture or treatment thereof
    • H10P72/70—Handling or holding of wafers, substrates or devices during manufacture or treatment thereof for supporting or gripping
    • H10P72/74—Handling or holding of wafers, substrates or devices during manufacture or treatment thereof for supporting or gripping using temporarily an auxiliary support
    • H10P72/7422—Handling or holding of wafers, substrates or devices during manufacture or treatment thereof for supporting or gripping using temporarily an auxiliary support used to protect an active side of a device or wafer
    • 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
    • H10P72/00—Handling or holding of wafers, substrates or devices during manufacture or treatment thereof
    • H10P72/70—Handling or holding of wafers, substrates or devices during manufacture or treatment thereof for supporting or gripping
    • H10P72/74—Handling or holding of wafers, substrates or devices during manufacture or treatment thereof for supporting or gripping using temporarily an auxiliary support
    • H10P72/744—Details of chemical or physical process used for separating the auxiliary support from a device or a wafer
    • 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
    • H10P72/00—Handling or holding of wafers, substrates or devices during manufacture or treatment thereof
    • H10P72/70—Handling or holding of wafers, substrates or devices during manufacture or treatment thereof for supporting or gripping
    • H10P72/74—Handling or holding of wafers, substrates or devices during manufacture or treatment thereof for supporting or gripping using temporarily an auxiliary support
    • H10P72/744—Details of chemical or physical process used for separating the auxiliary support from a device or a wafer
    • H10P72/7442—Separation by peeling

Definitions

  • the present invention relates to a temporary adhesive for wafer processing, a wafer laminate, and a method for manufacturing a thin wafer.
  • the three-dimensional mounting technology is a semiconductor manufacturing technology in which one semiconductor chip is made thinner and then laminated in multiple layers while being connected by a through silicon via (TSV).
  • TSV through silicon via
  • a back surface protective tape is attached to the opposite side of the ground surface to prevent wafer damage during grinding.
  • this tape uses an organic resin film as a supporting base material and is flexible, it has insufficient strength and heat resistance, and is not suitable for performing a TSV forming step or a wiring layer forming step on the back surface. ..
  • Patent Document 1 As a method of peeling the temporary adhesive layer known so far, the adhesive layer containing a light-absorbing substance is irradiated with high-intensity light, and the adhesive layer is decomposed to peel the adhesive layer from the support.
  • Patent Document 2 A technique (Patent Document 1) and a technique (Patent Document 2) of joining and peeling in a heat-melted state using a heat-meltable hydrocarbon compound as an adhesive have been proposed.
  • the former technique requires an expensive device such as a laser, and has problems such as a long processing time per substrate. Further, the latter technique is simple because it is controlled only by heating, but its application range is narrow because the thermal stability at a high temperature exceeding 200 ° C. is insufficient. Further, these temporary adhesive layers are not suitable for forming a uniform film thickness of a high-step substrate and for complete adhesion to a support.
  • a technique has been proposed in which a silicone pressure-sensitive adhesive is used for the temporary adhesive layer.
  • a substrate is bonded to a support using a heat-curable silicone pressure-sensitive adhesive, and the silicone resin is melted or decomposed at the time of peeling.
  • the substrate is separated from the support by immersing it in such a chemical agent (Patent Document 3). Therefore, it takes a very long time to peel off, and it is difficult to apply it to an actual manufacturing process. Further, after peeling, it takes a long time to clean the silicone adhesive remaining as a residue on the substrate, which also has a problem in terms of cleaning and removing property.
  • the bonding step in the case of heat-curable silicone, heating of about 150 ° C.
  • the present invention has been made in view of the above problems, and it is possible to join a substrate and a support at a relatively low temperature in a short time, thereby improving workability and wafer warpage at the time of joining, and also having a high step. Even when a substrate is used, it has sufficient substrate retention after bonding, is highly adaptable to the wafer back surface grinding process, TSV forming process, and wafer back surface wiring process, and has excellent wafer thermal process resistance, while in the peeling process.
  • a temporary adhesive for wafer processing, a wafer laminate, and a method for manufacturing a thin wafer using the temporary adhesive for wafer processing which is easy to peel off and has excellent residue cleanability of the substrate after peeling, which leads to improvement in productivity of thin wafers. The purpose is to do.
  • the present invention provides the following temporary adhesive for wafer processing, a wafer laminate, and a method for producing a thin wafer.
  • a temporary adhesive for wafer processing for temporarily adhering a wafer to a support which comprises a photocurable silicone resin composition containing a non-functional organopolysiloxane.
  • the photocurable silicone resin composition containing the non-functional organopolysiloxane (A) Organopolysiloxane having two or more alkenyl groups in one molecule: 100 parts by mass, (B) Organohydrogenpolysiloxane containing a hydrogen atom (SiH group) bonded to two or more silicon atoms in one molecule: SiH group in the component (B) with respect to the total number of alkenyl groups in the component (A).
  • the photocurable silicone resin composition containing the non-functional organopolysiloxane further contains a hydrosilylation reaction control agent as the component (E) at 0 with respect to the total mass of the components (A), (B) and (C).
  • a temporary adhesive for wafer processing according to any one of 1 to 3 containing .001 to 10 parts by mass. 5. After curing the photocurable silicone resin composition containing the non-functional organopolysiloxane, any of 1 to 4 in which the 180 ° peel peeling force of the 25 mm wide test piece against the silicon substrate at 25 ° C. is 2 gf or more and 50 gf or less. Temporary adhesive for wafer processing. 6.
  • steps (a) and (b) After curing of the photocurable silicone resin composition containing the non-functional organopolysiloxane, temporary bonding for wafer processing according to any one of 1 to 5 having a storage elastic modulus at 25 ° C. of 1,000 Pa or more and 1,000 MPa or less. Agent. 7.
  • steps (a) and (b) the non-functional organopolysiloxane containing any of the following aspects is used.
  • the steps (c) to (e) are common.
  • Step of applying the adhesive composition and joining (b1) Step of photocuring the temporary adhesive of the bonded wafer (Aspect 2) (A2) Step of irradiating the temporary adhesive composition for wafer processing according to any one of 1 to 6 with light (b2)
  • the circuit forming surface of a wafer having a circuit forming surface on the front surface and a circuit non-forming surface on the back surface, and /
  • a step of applying the temporary adhesive composition for wafer processing subjected to light irradiation in (a2) to the bonding surface of the support with the wafer, joining and curing the wafer (c) Wafer circuit of the wafer laminate.
  • Step of grinding or polishing the non-formed surface (d) Step of processing the circuit non-formed surface of the wafer (e) Step of peeling the processed wafer from the support.
  • the support is provided with a temporary adhesive layer obtained from the temporary adhesive for wafer processing according to any one of 1 to 6 laminated on the support, and a wafer having a circuit forming surface on the front surface and a circuit non-forming surface on the back surface.
  • the temporary adhesive for wafer processing of the present invention uses a photocurable silicone resin composition containing a non-functional organopolysiloxane, which enables the bonding of substrates at a relatively low temperature and in a short time by light irradiation. As a result, the warp of the wafer at the time of bonding is suppressed, and the bonding time can be shortened. Further, even after joining, not only the resin does not undergo thermal decomposition, but also the resin does not flow even at a high temperature of 200 ° C. or higher, and the heat resistance is high.
  • the wafer can be easily peeled from the support from the support after the thin wafer is manufactured, for example, at room temperature, and the fragile thin wafer can be easily peeled. It becomes possible to manufacture.
  • the temporary adhesive of the present invention can be selectively adhered to the support, after peeling, no residue derived from the temporary adhesive remains on the thin wafer, and the subsequent cleaning and removing property is also excellent. According to the method for manufacturing a thin wafer of the present invention, a thin wafer having a through electrode structure or a bump connection structure can be easily manufactured.
  • the temporary adhesive for wafer processing of the present invention comprises a photocurable silicone resin composition containing a non-functional organopolysiloxane. From the viewpoint of applicability to silicon wafers and the like having steps, a silicone resin composition having good spin coating properties is preferably used as a temporary adhesive for wafer processing.
  • Such a photocurable silicone resin composition preferably contains, for example, the following components (A) to (D).
  • (A) Organopolysiloxane having two or more alkenyl groups in one molecule: 100 parts by mass
  • (B) Organohydrogenpolysiloxane containing a hydrogen atom (SiH group) bonded to two or more silicon atoms in one molecule: SiH group in the component (B) with respect to the total number of alkenyl groups in the component (A).
  • the component (A) is an organopolysiloxane having two or more alkenyl groups in one molecule.
  • the component (A) is a linear or branched diorganopolysiloxane containing two or more alkenyl groups in one molecule, and contains two or more alkenyl groups in one molecule in units of SiO 4/2.
  • Examples thereof include an organopolysiloxane having a three-dimensional network structure having a represented siloxane unit (Q unit). Of these, diorganopolysiloxane or organopolysiloxane having a three-dimensional network structure having an alkenyl group content of 0.6 to 9 mol% is preferable.
  • the alkenyl group content is the ratio (mol%) of the number of alkenyl groups to the number of Si atoms in the molecule.
  • organopolysiloxane examples include those represented by the following formulas (A-1), (A-2) or (A-3). These may be used individually by 1 type, and may be used in combination of 2 or more type.
  • R 1 to R 16 are independently monovalent hydrocarbon groups other than aliphatic unsaturated hydrocarbon groups.
  • X 1 to X 5 are independently alkenyl group-containing monovalent organic groups.
  • a and b are independently integers of 0 to 3.
  • c 1 , c 2 , d 1 and d 2 are 0 ⁇ c 1 ⁇ 10, 2 ⁇ c 2 ⁇ 10, 0 ⁇ d 1 ⁇ 100 and 0 ⁇ d. It is an integer that satisfies 2 ⁇ 100.
  • a, b, c 1 , c 2 , d 1 and d 2 are a combination of numbers such that the alkenyl group content is 0.6 to 9 mol%.
  • e is an integer of 1 to 3.
  • f 1 , f 2 and f 3 (f 2 + f 3 ) / f 1 is 0.3 to 3.0, and f 3 / (f 1 + f 2 + f 3 ) is 0.01 to 0.6. Is a number like.
  • the monovalent hydrocarbon group other than the aliphatic unsaturated hydrocarbon group preferably has 1 to 10 carbon atoms, and is, for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, or a tert.
  • -Alkyl groups such as butyl group, n-pentyl group and n-hexyl group
  • cycloalkyl groups such as cyclopentyl group and cyclohexyl group
  • aryl groups such as phenyl group and tolyl group can be mentioned.
  • an alkyl group such as a methyl group or a phenyl group is preferable.
  • the alkenyl group-containing monovalent organic group preferably has 2 to 10 carbon atoms, and is, for example, an alkenyl group such as a vinyl group, an allyl group, a hexenyl group, or an octenyl group; an acryloylpropyl group, an acryloylethyl group, or an acryloylmethyl group.
  • (Meta) acryloylalkyl groups such as methacryloylpropyl groups; (meth) acryloylalkyl groups such as acryloxypropyl groups, acryloxyethyl groups, acryloxymethyl groups, methacryoxypropyl groups, methacryloxyethyl groups, and methacryloxymethyl groups.
  • a and b are independently integers of 0 to 3, but if a and b are 1 to 3, the molecular chain ends are blocked with an alkenyl group, so that the reaction occurs. It is preferable because the reaction can be completed in a short time by the alkenyl group at the end of the molecular chain having good properties. Further, from the viewpoint of cost, it is industrially preferable that a and b are 1.
  • the properties of the alkenyl group-containing diorganopolysiloxane represented by the formula (A-1) or (A-2) are preferably oily or raw rubber.
  • the organopolysiloxane represented by the formula (A-3) contains 4/2 units of SiO and has a three-dimensional network structure.
  • e is an integer of 1 to 3 independently, but it is industrially preferable that it is 1 from the viewpoint of cost.
  • the product of the average value of e and f 3 / (f 1 + f 2 + f 3 ) is preferably 0.02 to 1.5, and more preferably 0.03 to 1.0.
  • the organopolysiloxane represented by the formula (A-3) may be used as a solution dissolved in an organic solvent.
  • the number average molecular weight (Mn) of the organopolysiloxane of the component (A) is preferably 100 to 1,000,000, more preferably 1,000 to 100,000.
  • Mn is a polystyrene-equivalent measured value obtained by gel permeation chromatography using toluene as a solvent.
  • the component (A) may be used alone or in combination of two or more.
  • an organopolysiloxane represented by the formula (A-1) in combination with an organopolysiloxane represented by the formula (A-3).
  • the amount of the organopolysiloxane represented by the formula (A-3) is preferably 1 to 1,000 parts by mass with respect to 100 parts by mass of the organopolysiloxane represented by the formula (A-1). More preferably, 10 to 500 parts by mass.
  • the component (B) is a cross-linking agent, and is an organohydrogenpolysiloxane having at least two, preferably three or more hydrogen atoms (SiH groups) bonded to silicon atoms in one molecule.
  • the organohydrogenpolysiloxane may be linear, branched or cyclic. Further, the organohydrogenpolysiloxane may be used alone or in combination of two or more.
  • the viscosity of the organohydrogenpolysiloxane of the component (B) at 25 ° C. is preferably 1 to 5,000 mPa ⁇ s, more preferably 5 to 500 mPa ⁇ s.
  • the viscosity is a value measured at 25 ° C. by a rotational viscometer.
  • the Mn of the organohydrogenpolysiloxane as the component (B) is preferably 100 to 100,000, more preferably 500 to 10,000. When Mn is in the above range, it is preferable in terms of workability associated with the viscosity of the composition and processability associated with the storage elastic modulus after curing.
  • the total amount of SiH groups in the component (B) to the total number of alkenyl groups in the component (A) is in the range of 0.3 to 10 in terms of molar ratio (SiH group / alkenyl group). It is preferably blended, and more preferably blended in the range of 1.0 to 8.0.
  • the molar ratio is 0.3 or more, the crosslink density does not decrease, and the problem that the temporary adhesive layer does not cure does not occur. Further, when the molar ratio is 10 or less, the crosslink density does not become too high, sufficient adhesive strength and tack can be obtained, and the usable time of the treatment liquid can be lengthened.
  • the component (C) is a non-functional organopolysiloxane.
  • “non-functional” has a reactive group such as an alkenyl group, a hydrogen atom, a hydroxy group, an alkoxy group, a halogen atom, an epoxy group, etc., which are bonded to a silicon atom directly or via an arbitrary group in the molecule. It means not to.
  • Such a non-functional organopolysiloxane includes, for example, an unsubstituted or substituted organosole having a monovalent hydrocarbon group other than an aliphatic unsaturated hydrocarbon group having 1 to 12 carbon atoms, preferably 1 to 10 carbon atoms.
  • a monovalent hydrocarbon group include an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group and a heptyl group; a cycloalkyl group such as a cyclohexyl group; a phenyl group and a trill.
  • Aryl groups such as groups, xsilyl groups and naphthyl groups; aralkyl groups such as benzyl groups and phenethyl groups can be mentioned. Further, a part or all of the hydrogen atoms of these groups may be substituted with halogen atoms such as chlorine atom, fluorine atom and bromine atom, and such groups include chloromethyl group and 3-chloropropyl group. Examples thereof include alkyl halide groups such as groups 3,3,3-trifluoropropyl groups.
  • the monovalent hydrocarbon group is preferably an alkyl group or an aryl group, and more preferably a methyl group or a phenyl group.
  • the molecular structure of the non-functional organopolysiloxane of the component (C) is not particularly limited and may be linear, branched, cyclic or the like, but a linear or branched organopolysiloxane is preferable. It is preferably a linear diorganopolysiloxane in which the chain basically consists of repeating diorganosiloxane units and both ends of the molecular chain are sealed with a triorganosyloxy group.
  • the component (C), the non-functional organopolysiloxane has a viscosity (25 ° C.) in a 30 mass% toluene solution of the workability of the composition, the coatability on the substrate, the mechanical properties of the cured product, and the support. From the viewpoint of peelability and the like, the one having 100 to 500,000 mPa ⁇ s is preferable, and the one having 200 to 100,000 mPa ⁇ s is more preferable. Within the above range, since the silicone resin composition has an appropriate molecular weight, it volatilizes when the silicone resin composition is heat-cured, making it difficult to obtain an effect, or causing wafer cracking in a wafer thermal process such as CVD. It is preferable because it does not spill and has good workability and coatability.
  • non-functional organopolysiloxane examples include a trimethylsiloxy group-blocked dimethylsiloxane polymer at both ends of the molecular chain, a trimethylsiloxy group-blocked phenylmethylpolysiloxane at both ends of the molecular chain, and a trimethylsiloxy group-blocked 3,3,3- at both ends of the molecular chain.
  • Trifluoropropylmethylsiloxane polymer trimethylsiloxy group-blocked dimethylsiloxane at both ends of the molecular chain, methylphenylsiloxane copolymer, trimethylsiloxy group-blocked dimethylsiloxane at both ends of the molecular chain, 3,3,3-trifluoropropylmethyl copolymer , Molecular chain double-ended trimethylsiloxy group-blocked methylphenylsiloxane ⁇ 3,3,3-trifluoropropylmethyl copolymer, Molecular chain double-ended trimethylsiloxy group-blocked dimethylsiloxane ⁇ 3,3,3-trifluoropropylmethylsiloxane ⁇ Methylphenylsiloxane copolymer, dimethylphenylsiloxy group-blocked dimethylpolysiloxane at both ends of the molecular chain, dimethylphenylsiloxy group-blocked methylphenylpoly
  • the non-functional organopolysiloxane of the component (C) may be used alone or in combination of two or more. Moreover, the property is preferably oil-like or raw rubber-like.
  • the component (D) is a photoactive hydrosilylation reaction catalyst, and the photoactive hydrosilylation reaction catalyst is activated by irradiation with light, particularly ultraviolet rays having a wavelength of 300 to 400 nm, and an alkenyl group in the component (A). And a catalyst that promotes the addition reaction with the Si—H group in the component (B).
  • This accelerating effect is temperature-dependent, and a high accelerating effect can be obtained at a higher temperature. Therefore, it is preferable to use the product under an environmental temperature of 0 to 200 ° C., more preferably 10 to 100 ° C. after preferable light irradiation, in that the reaction is completed within an appropriate reaction time.
  • the photoactive hydrosilylation reaction catalyst mainly corresponds to a platinum group metal catalyst or an iron group metal catalyst, and the platinum group metal catalyst includes a platinum group, a palladium group, a rhodium group metal complex, and an iron group type.
  • the metal catalyst include nickel-based, iron-based, and cobalt-based iron group complexes. Among them, platinum-based metal complexes are preferable because they are relatively easy to obtain and exhibit good catalytic activity, and are often used.
  • a ligand that exhibits catalytic activity with UV light having a medium to long wavelength of UV-B to UV-A is preferable in terms of suppressing damage to the wafer.
  • examples of such a ligand include a cyclic diene ligand, a ⁇ -diketonato ligand and the like.
  • the cyclic diene ligand type for example, a ( ⁇ 5 -cyclopentadienyl) tri ( ⁇ -alkyl) platinum (IV) complex, particularly specific (Methylcyclopentadienyl) trimethylplatinum (IV), (cyclopentadienyl) trimethylplatinum (IV), (1,2,3,4,5-pentamethylcyclopentadienyl) trimethylplatinum (IV) , (Cyclopentadienyl) dimethylethyl platinum (IV), (cyclopentadienyl) dimethylacetyl platinum (IV), (trimethylsilylcyclopentadienyl) trimethylplatinum (IV), (methoxycarbonylcyclopentadienyl) trimethylplatinum Examples thereof include (IV), (dimethylphenylsilylcyclopentadienyl) trimethylplatinum (
  • the component (A) when they are solid catalysts, they can be used in a solid state, but in order to obtain a more uniform cured product, those dissolved in an appropriate solvent are used as the component (A). It is preferably used by being compatible with an organopolysiloxane having an alkenyl group.
  • the solvent include isononane, toluene, 2- (2-butoxyethoxy) ethyl acetate and the like.
  • the amount of the component (D) added may be an effective amount, but is usually 0.1 to 5,000 ppm as the platinum content (in terms of metal atomic weight) with respect to the total mass of (A), (B), and (C). Yes, 0.5 to 2,000 ppm, more preferably 1 to 500 ppm. If it is 0.1 ppm or more, the curability of the composition does not decrease, the crosslink density does not decrease, and the holding power does not decrease. If it is 0.5% or less, the usable time of the treatment bath can be lengthened.
  • the photocurable silicone resin composition may further contain a reaction control agent as the component (E).
  • the reaction control agent is optionally added when the composition is prepared or applied to the base material in order to prevent the composition from thickening or gelling.
  • reaction control agent examples include 3-methyl-1-butyne-3-ol, 3-methyl-1-pentyne-3-ol, 3,5-dimethyl-1-hexin-3-ol, and 1-ethynylcyclohexanol.
  • the control ability differs depending on the chemical structure. Therefore, the content thereof should be adjusted to the optimum amount, but the curability, storage stability, and the like.
  • the total mass of the components (A), (B) and (C) is preferably 0.001 to 10 parts by mass, more preferably 0.01 to 10 parts by mass. Is.
  • the content of the component (E) is within the above range, the composition can be used for a long time, long-term storage stability can be obtained, and curability and workability are good.
  • the photocurable silicone resin composition further contains 0.5 units of RA 3 SiO (in the formula, RA is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, respectively). and comprises SiO 2 units, may be added to the organopolysiloxane molar ratio of R a 3 SiO 0.5 units to SiO 2 units (R a 3 SiO 0.5 / SiO 2) is from 0.3 to 1.8.
  • the amount added is preferably 0 to 500 parts by mass with respect to 100 parts by mass of the component (A). More preferably, it is larger than 0 to 300 parts by mass.
  • a filler such as silica may be added to the photocurable silicone resin composition within a range that does not impair its performance.
  • the photocurable silicone resin composition is used as a solution by adding a solvent for the reasons of improving workability and miscibility by lowering the viscosity of the composition, adjusting the film thickness of the temporary adhesive layer, and the like. May be good.
  • the solvent used is not particularly limited as long as it can dissolve the above components, but hydrocarbon solvents such as pentane, hexane, cyclohexane, isooctane, nonane, decane, p-mentane, pinene, isododecane, and limonene are preferable.
  • a method of solutionization a method of preparing the photocurable silicone resin composition and finally adding a solvent to adjust the viscosity to a desired value, or a method of adjusting the viscosity to a desired value, or high viscosity (A), (B) and / or ( C) Examples thereof include a method in which the components are diluted with a solvent in advance to improve workability and miscibility, and then the remaining components are mixed. Further, as a mixing method at the time of solution formation, a mixing method may be appropriately selected from the viscosity and workability of the composition, such as a shaking mixer, a magnetic stirrer, and various mixers.
  • the blending amount of the solvent may be appropriately set from the viewpoint of adjusting the viscosity and workability of the composition, the film thickness of the temporary adhesive layer, and the like.
  • the temporary adhesive layer can be formed by applying the photocurable silicone resin composition onto the substrate by a method such as spin coating or roll coating. Of these, when the temporary adhesive layer is formed on the substrate by a method such as spin coating, it is preferable to solution the photocurable silicone resin composition and coat it.
  • the solution-coated photocurable silicone resin composition preferably has a viscosity at 25 ° C. of 1 to 100,000 mPa ⁇ s, more preferably 10 to 10,000 mPa ⁇ s, from the viewpoint of coatability.
  • the 180 ° peel peeling force of a test piece having a width of 25 mm (for example, a silicon substrate test piece) at 25 ° C. after curing is usually 2 to 50 gf, preferably 3 to 30 gf. It is more preferably 5 to 20 gf. If it is 2 gf or more, there is no possibility that the wafer is displaced during wafer grinding, and if it is 50 gf or less, the wafer can be easily peeled off.
  • the photocurable silicone resin composition has a storage elastic modulus at 25 ° C. after curing of 1,000 Pa or more and 1,000 MPa or less, preferably 10,000 Pa or more and 500 MPa or less. If the storage elastic modulus is 1,000 Pa or more, the film to be formed is tough, there is no risk of wafer misalignment and accompanying wafer cracking during wafer grinding, and if it is 1,000 MPa or less, a wafer such as CVD. The deformation stress during the thermal process can be relaxed, and it is stable during the thermal process on the wafer.
  • the method for producing a thin wafer of the present invention is characterized in that a temporary adhesive layer made of a photocurable silicone resin composition is used as an adhesive layer between a wafer having a semiconductor circuit or the like and a support. Two aspects and their illustrations are shown in FIG. In any aspect, the thickness of the thin wafer obtained by the production method of the present invention is typically 5 to 300 ⁇ m, more typically 10 to 100 ⁇ m.
  • the method for producing a thin wafer of the present invention has the following steps (a1) to (e) as a first aspect. Further, if necessary, the steps (f) to (i) are included.
  • Step (a1) is a temporary bonding step, in which the circuit forming surface of a wafer having a circuit forming surface on the front surface and a circuit non-forming surface on the back surface is detachably bonded to the support using the temporary adhesive for wafer processing. This is a step of forming a wafer laminate.
  • a method and a support method in which a temporary adhesive layer is formed on the surface of the wafer using the temporary adhesive for processing the wafer, and the support and the surface of the wafer are bonded to each other via the temporary adhesive layer.
  • Wafers applicable to the present invention are usually semiconductor wafers.
  • the semiconductor wafer include not only silicon wafers but also germanium wafers, gallium-arsenide wafers, gallium-phosphorus wafers, gallium-arsenide-aluminum wafers and the like.
  • the thickness of the wafer is not particularly limited, but is typically 600 to 800 ⁇ m, and more typically 625 to 775 ⁇ m.
  • the support since the photocurable silicone resin composition is irradiated with light through a support, the support includes light transmission of a glass plate, a quartz plate, an acrylic plate, a polycarbonate plate, a polyethylene terephthalate plate, or the like.
  • a plastic substrate can be used.
  • the glass plate is preferable because it is transparent to ultraviolet rays and has excellent heat resistance.
  • the temporary adhesive layer may be formed by laminating a film-shaped photocurable silicone resin composition on a wafer or a support, and the photocurable silicone resin composition is spin-coated and rolled. It may be formed by applying it by a method such as coating.
  • the photocurable silicone resin composition is a solution containing a solvent
  • prebaking is performed in advance at a temperature of preferably 20 to 200 ° C., more preferably 30 to 150 ° C., depending on the volatilization conditions of the solvent. Later, it will be used.
  • the temporary adhesive layer is preferably formed and used with a film thickness of 0.1 to 500 ⁇ m, preferably 1.0 to 200 ⁇ m.
  • a film thickness of 0.1 to 500 ⁇ m, preferably 1.0 to 200 ⁇ m.
  • the film thickness is 0.1 ⁇ m or more, when it is applied on the base material, it can be applied to the entire surface without causing a portion that cannot be applied.
  • the film thickness is 500 ⁇ m or less, it can withstand the grinding process when forming a thin wafer.
  • a method of uniformly pressure bonding under reduced pressure in a temperature range of preferably 0 to 200 ° C., more preferably 20 to 100 ° C. is used. Can be mentioned.
  • the pressure at which the wafer and the support on which the temporary adhesive layer is formed is pressure-bonded is preferably 0.01 to 10 MPa, more preferably 0.05 to 1.0 MPa, although it depends on the viscosity of the temporary adhesive layer. be.
  • the pressure is 0.01 MPa or more, the circuit forming surface and the space between the wafer and the support can be filled with the temporary adhesive layer, and when the pressure is 10 MPa or less, the wafer is cracked and the wafer and the temporary adhesive layer are flat. There is no risk of deterioration of the wafer, and the subsequent wafer processing is good.
  • Wafer bonding can be performed using a commercially available wafer bonder, for example, EVG520IS, 850TB from EVG, XBS300 from SUS MicroTech, or the like.
  • the step (b1) is a step of photocuring the temporary adhesive layer. After the wafer processed body (laminated body substrate) is formed, light irradiation is performed from the light-transmitting support side to photocure the temporary adhesive layer.
  • the active ray type at that time is not particularly limited, but ultraviolet rays are preferable, and ultraviolet rays having a wavelength of 300 to 400 nm are preferable.
  • UV irradiation amount (illuminance) is, 100mJ / cm 2 ⁇ 100,000mJ / cm 2 as the accumulated light quantity is preferably 500mJ / cm 2 ⁇ 10,000mJ / cm 2, more preferably 1,000 ⁇ 5,000mJ / cm 2 Is desirable in order to obtain good curability.
  • the ultraviolet irradiation amount (illuminance) is equal to or higher than the above range, sufficient energy can be obtained to activate the photoactive hydrosilylation reaction catalyst in the temporary adhesive layer, and a sufficient cured product can be obtained.
  • the ultraviolet irradiation amount (illuminance) is less than the above range, the composition is irradiated with sufficient energy, and the components in the polymer layer are not decomposed or a part of the catalyst is not deactivated. , A sufficient cured product can be obtained.
  • Ultraviolet irradiation may be light having a plurality of emission spectra or light having a single emission spectrum. Further, the single emission spectrum may have a broad spectrum in the region of 300 nm to 400 nm. Light having a single emission spectrum is light having a peak (ie, maximum peak wavelength) in the range of 300 nm to 400 nm, preferably 350 nm to 380 nm. Examples of the light source for irradiating such light include an ultraviolet light emitting diode (ultraviolet LED) and an ultraviolet light emitting semiconductor element light source such as an ultraviolet light emitting semiconductor laser.
  • an ultraviolet light emitting diode ultraviolet light emitting diode
  • an ultraviolet light emitting semiconductor element light source such as an ultraviolet light emitting semiconductor laser.
  • Light sources that irradiate light with multiple emission spectra include metal halide lamps, xenon lamps, carbon arc lamps, chemical lamps, sodium lamps, low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, and other lamps. Examples thereof include a gas laser, a liquid laser of an organic dye solution, and a solid laser in which an inorganic single crystal contains rare earth ions.
  • the light has a peak in a wavelength region shorter than 300 nm in the emission spectrum, or when there is a wavelength in the wavelength region shorter than 300 nm having a emission illuminance larger than 5% of the emission illuminance of the maximum peak wavelength in the emission spectrum (for example, when the emission spectrum is broad over a wide wavelength region) and when a substrate such as a quartz wafer having light transmission to a wavelength shorter than 300 nm is used as the support, a wavelength shorter than 300 nm is used by an optical filter. It is preferable to remove light having a wavelength in the region in order to obtain a sufficiently cured product.
  • the irradiance of each wavelength in the wavelength region shorter than 300 nm is set to 5% or less, preferably 1% or less, more preferably 0.1% or less, still more preferably 0% of the irradiance of the maximum peak wavelength.
  • the peak wavelength showing the maximum absorbance among them is set as the maximum peak wavelength.
  • the optical filter is not particularly limited as long as it cuts a wavelength shorter than 300 nm, and a known optical filter may be used. For example, a 365 nm bandpass filter or the like can be used.
  • the illuminance and spectral distribution of ultraviolet rays can be measured with a spectral irradiance meter, for example, USR-45D (Ushio, Inc.).
  • the light irradiation device is not particularly limited, but for example, an irradiation device such as a spot type irradiation device, a surface type irradiation device, a line type irradiation device, or a conveyor type irradiation device can be used.
  • an irradiation device such as a spot type irradiation device, a surface type irradiation device, a line type irradiation device, or a conveyor type irradiation device can be used.
  • the light irradiation time depends on the illuminance and cannot be unconditionally specified. However, for example, it is 1 to 300 seconds, preferably 10 to 200 seconds, and more preferably 30 to 150 seconds. If the illuminance is adjusted so as to be seconds, the irradiation time is also appropriately short, and there is no particular problem in the work process. Further, the photocurable silicone resin composition subjected to light irradiation gels after 1 to 120 minutes of irradiation, particularly 5 to 60 minutes. In the present invention, gelation means a state in which the curing reaction of the photocurable silicone resin composition partially proceeds and the composition loses its fluidity.
  • the step (c) is a step of grinding or polishing the circuit non-formed surface of the wafer temporarily bonded to the support, that is, the back surface side of the wafer laminate obtained in the step is ground to reduce the thickness of the wafer. This is the process of thinning.
  • the method of grinding the back surface of the wafer is not particularly limited, and a known grinding method is adopted. Grinding is preferably performed while cooling the wafer and the grindstone (diamond or the like) with water. Examples of the apparatus for grinding the back surface of the wafer include DAG-810 (trade name) manufactured by Disco Corporation. Further, the back surface side of the wafer may be chemically mechanically polished (CMP).
  • the step (d) is a step of processing the circuit non-formed surface of the wafer laminate obtained by grinding the circuit non-formed surface in the step (c). That is, it is a step of processing the circuit non-formed surface of the wafer of the wafer laminate thinned by backside grinding.
  • This process involves various processes used at the wafer level. Examples include electrode formation, metal wiring formation, protective film formation, and the like. More specifically, metal sputtering for forming electrodes and the like, wet etching for etching a metal sputtering layer, application of resist for forming a mask for metal wiring, pattern formation by exposure and development, and peeling of resist. , Dry etching, metal plating formation, silicon etching for TSV formation, oxide film formation on the silicon surface, and the like.
  • the step (e) is a step of peeling the wafer processed in the step (d) from the support, that is, after performing various processing on the thinned wafer, the wafer is peeled from the support before dicing. It is a process.
  • This peeling step is generally carried out under relatively mild conditions of about room temperature to about 60 ° C.
  • a peeling method one of the wafer or the support of the wafer laminate is fixed horizontally and the other is lifted at a certain angle from the horizontal direction. The wafer laminate is immersed in a solvent in advance and temporarily bonded.
  • Examples thereof include a method in which the material layer is swollen and then peeled off in the same manner as described above, a method in which a protective film is attached to the ground surface of the ground wafer, and the wafer and the protective film are peeled off from the wafer laminate by a peeling method.
  • a peeling step is performed by these peeling methods, it is usually carried out at room temperature.
  • step (e) is (E1) A step of attaching a dicing tape to the wafer surface of the processed wafer, (E2) includes a step of vacuum-adsorbing the dicing tape surface to the suction surface, and (e3) a step of peeling off the support from the processed wafer when the temperature of the suction surface is in the range of 10 to 100 ° C. Is preferable. By doing so, the support can be easily peeled off from the processed wafer, and the subsequent dicing step can be easily performed.
  • step (F) It is preferable to perform a step of removing the temporary adhesive layer remaining on the circuit forming surface of the peeled wafer.
  • a part of the temporary adhesive layer may remain on the circuit forming surface of the wafer peeled off from the support in the step (e), and the removal of the temporary adhesive layer is, for example, cleaning the wafer.
  • any cleaning solution that dissolves the silicone resin of the temporary adhesive layer can be used.
  • pentane, hexane, cyclohexane, decane, isononan, p-mentane, and pinene can be used.
  • Isododecane, limonene and the like These solvents may be used alone or in combination of two or more.
  • bases and acids may be added to the cleaning solution.
  • bases amines such as ethanolamine, diethanolamine, triethanolamine, triethylamine and ammonia; and ammonium salts such as tetramethylammonium hydroxide can be used.
  • acids organic acids such as acetic acid, oxalic acid, benzenesulfonic acid, and dodecylbenzenesulfonic acid can be used.
  • the amount of the bases and acids added is such that the concentration in the cleaning liquid is preferably 0.01 to 10% by mass, more preferably 0.1 to 5% by mass.
  • an existing surfactant may be added in order to improve the removability of the residue.
  • the SPIS-TA-CLEANER series manufactured by Shin-Etsu Chemical Co., Ltd.
  • Examples of the wafer cleaning method include a method of cleaning with a paddle using the cleaning liquid, a method of spraying and cleaning, and a method of immersing in a cleaning liquid tank.
  • the temperature for cleaning is preferably 10 to 80 ° C, more preferably 15 to 65 ° C, and if necessary, the temporary adhesive layer is dissolved with these cleaning liquids, and finally rinsed with water or alcohol. And the drying treatment may be carried out.
  • steps (a2) and (b2) below are shown.
  • steps (c) to (e), preferably steps (c) to (f) are the same as those in the first aspect described above.
  • Step (a2) is a step of forming the photocurable silicone resin composition layer subjected to light irradiation on the wafer and / or on the support.
  • light irradiation of the photocurable silicone resin composition before bonding eliminates the need for a light irradiation step through the support, and as a result.
  • the support does not require light transmission. Therefore, according to this aspect, in addition to the application example of the support, a substrate that does not transmit light such as silicon, aluminum, SUS, copper, germanium, gallium-arsenide, gallium-phosphosphide, and gallium-arsenide-aluminum is also a support. Applicable as. Further, according to this method, the influence of curing inhibition from the wafer can be reduced, so that the applicable range of the wafer can be expanded.
  • the photocurable silicone resin composition subjected to light irradiation it can be applied to either [1] wafer [2] support [3] wafer and both sides of the support.
  • the method of irradiating the photocurable silicone resin composition with light before joining the method of applying light on the wafer and / or the support while irradiating the composition with light, and after irradiating the entire composition with light.
  • a method of coating on a wafer and / or a support, a method of applying light on a wafer and / or a support and then irradiating light, etc. but there is no particular limitation and in consideration of workability. It may be selected as appropriate.
  • the ultraviolet irradiation amount (illuminance), the light source, the emission spectrum, the light irradiation device, and the light irradiation time in the light irradiation the method described in [Step (b1)] of the first aspect can be used. ..
  • the method for forming the first and second temporary adhesive layers can be carried out in the same manner as in the first aspect, and the film or the corresponding composition or a solution thereof can be applied onto the wafer and / or by a method such as spin coating or a roll coater, respectively. It can be formed on a support.
  • a method such as spin coating or a roll coater, respectively. It can be formed on a support.
  • spin coating it is prebaked in advance at a temperature of 20 to 200 ° C., preferably 30 to 150 ° C., depending on the volatilization conditions of the solvent, and then used.
  • the step (b2) is a step of joining the wafer with a circuit and / or the support on which the photocurable silicone resin composition layer produced in the step (a2) is formed under vacuum. At this time, the wafer is bonded to the support by uniformly crimping the substrate under reduced pressure (vacuum) at this temperature in a temperature range of preferably 0 to 200 ° C., more preferably 20 to 100 ° C. A work piece (laminated body substrate) is formed.
  • the wafer bonding device the same device as in the first aspect can be used.
  • the viscosity is a value measured at 25 ° C. by a TVB-10M type rotational viscometer (manufactured by Toki Sangyo Co., Ltd.).
  • a solution consisting of 50 parts by mass of dimethylpolysiloxane and 120 parts by mass of toluene and 0.6 parts by mass of 1-ethynylcyclohexanol were added and mixed. Further, a photoactive hydrosilylation reaction catalyst; 0.4 parts by mass of a toluene solution (platinum concentration 1.0% by mass) of (methylcyclopentadienyl) trimethylplatinum (IV) was added thereto, and a 0.2 ⁇ m membrane was added.
  • a photocurable silicone resin solution A1 was prepared by filtering with a filter. The viscosity of the resin solution A1 at 25 ° C. was 230 mPa ⁇ s.
  • a photoactive hydrosilylation reaction catalyst 0.4 parts by mass of a toluene solution of (methylcyclopentadienyl) trimethylplatinum (IV) (platinum concentration 1.0% by mass) was added thereto, and a 0.2 ⁇ m membrane was added.
  • a photocurable silicone resin solution A2 was prepared by filtering with a filter. The viscosity of the resin solution A2 at 25 ° C. was 100 mPa ⁇ s.
  • Preparation Example 3 4/2 units of SiO (Q units) in a solution consisting of 100 parts by mass of dimethylpolysiloxane and 200 parts by mass of toluene having 2.5 mol% vinyl groups at both ends and side chains of the molecule and Mn of 30,000.
  • a solution consisting of 50 parts by mass of methylpolysiloxane and 100 parts by mass of toluene, 230 parts by mass of organohydrogenpolysiloxane having a Mn of 2,800 represented by the formula (M-1), and a viscosity (25 ° C.) of a 30% by mass toluene solution.
  • a photocurable silicone resin solution A3 was prepared by filtering with a filter. The viscosity of the resin solution A3 at 25 ° C. was 330 mPa ⁇ s.
  • Preparation Example 4 4/2 units of SiO (Q units) in a solution consisting of 100 parts by mass of dimethylpolysiloxane and 200 parts by mass of toluene having 2.5 mol% vinyl groups at both ends and side chains of the molecule and Mn of 30,000.
  • a solution consisting of 200 parts by mass of methylpolysiloxane and 400 parts by mass of toluene, 430 parts by mass of organohydrogenpolysiloxane having a Mn of 2,800 represented by the formula (M-1), and a viscosity (25 ° C.) of a 30% by mass toluene solution.
  • a photocurable silicone resin solution A4 was prepared by filtering with a filter. The viscosity of the resin solution A4 at 25 ° C. was 120 mPa ⁇ s.
  • organohydrogenpolysiloxane 150 parts by mass of dimethylpolysiloxane with both ends of the molecular chain having a viscosity (25 ° C.) of 1,000 mPa ⁇ s in a 30 mass% toluene solution, and 1 -1.2 parts by mass of ethynylcyclohexanol was added and mixed. Further, a photoactive hydrosilylation reaction catalyst; 0.8 parts by mass of a toluene solution of (methylcyclopentadienyl) trimethylplatinum (IV) (platinum concentration 1.0% by mass) was added thereto, and a 0.2 ⁇ m membrane was added.
  • a photocurable silicone resin solution A5 was prepared by filtering with a filter. The viscosity of the resin solution A5 at 25 ° C. was 80 mPa ⁇ s.
  • Preparation Example 6 4/2 units of SiO (Q units) in a solution consisting of 100 parts by mass of dimethylpolysiloxane and 200 parts by mass of toluene having 2.5 mol% vinyl groups at both ends and side chains of the molecule and Mn of 30,000.
  • a solution consisting of 50 parts by mass of methylpolysiloxane and 100 parts by mass of toluene, 230 parts by mass of organohydrogenpolysiloxane having a Mn of 2,800 represented by the formula (M-1), and a viscosity (25 ° C.) of a 30% by mass toluene solution.
  • organohydrogenpolysiloxane 150 parts by mass of dimethylpolysiloxane with both ends of the molecular chain having a viscosity (25 ° C.) of 1,000 mPa ⁇ s in a 30 mass% toluene solution, and 1 -1.2 parts by mass of ethynylcyclohexanol was added and mixed.
  • a photoactive hydrosilylation reaction catalyst a solution of bis (2,4-heptandionat) platinum (II) in 2- (2-butoxyethoxy) ethyl acetate (platinum concentration 0.5% by mass) was added thereto in 1.6.
  • a part of a photocurable silicone resin solution A7 was added and filtered through a 0.2 ⁇ m membrane filter to prepare a photocurable silicone resin solution A7.
  • the viscosity of the resin solution A7 at 25 ° C. was 80 mPa ⁇ s.
  • thermoactive hydrosilylation reaction catalyst 0.4 parts by mass of a toluene solution of (methylcyclopentadienyl) trimethylplatinum (IV) (platinum concentration 1.0% by mass) is a thermoactive hydrosilylation reaction catalyst;
  • CAT-PL- A thermosetting silicone resin solution CA1 was prepared in the same manner as in Preparation Example 1 except that it was changed to 0.4 parts by mass of 5 (manufactured by Shin-Etsu Chemical Industry Co., Ltd., platinum concentration 1.0% by mass).
  • the viscosity of the resin solution CA1 at 25 ° C. was 230 mPa ⁇ s.
  • a photocurable silicone resin solution CA2 was prepared in the same manner as in Preparation Example 1 except that a solution consisting of 50 parts by mass of dimethylpolysiloxane and 120 parts by mass of toluene was not added.
  • the viscosity of the resin solution CA2 at 25 ° C. was 150 mPa ⁇ s.
  • a photocurable silicone resin solution CA3 was prepared in the same manner as in Preparation Example 2 except that 30 parts by mass of dimethylpolysiloxane, which was a trimethylsiloxy group-sealed trimethylsiloxy group at both ends of the molecular chain, was not added.
  • the viscosity of the resin solution CA3 at 25 ° C. was 180 mPa ⁇ s.
  • a silicon wafer having a temporary adhesive layer and a glass plate are respectively joined by EVG's wafer bonding device EVG520IS so that the temporary adhesive layer and the glass plate are combined.
  • vacuum bonding was performed at 25 ° C., 10 -3 mbar or less, and a load of 5 kN.
  • a surface irradiation type UV-LED (wavelength 365 nm) irradiator was used to irradiate the curable silicone resin composition layer with light under the conditions shown in Table 1 to prepare a wafer laminate.
  • heating was performed on a hot plate under the conditions shown in Table 1 to prepare a wafer laminate.
  • CVD resistance test (3) After the back surface grinding resistance test is completed, the wafer laminate is introduced into the CVD device, a film formation experiment of a 2 ⁇ m SiO 2 film is performed, and the presence or absence of an appearance abnormality at that time is visually observed. Investigated by. The case where no appearance abnormality occurred was evaluated as good and indicated by " ⁇ ", and the case where appearance abnormality such as voids, wafer swelling, and wafer breakage occurred was evaluated as defective and indicated by "x”.
  • Peelability test For the peelability of the substrate, first, (4) use a dicing frame on the wafer side of the wafer laminate that has undergone the CVD resistance test, and apply a dicing tape (ELP UB-3083D manufactured by Nitto Denko Corporation). The dicing tape surface was attached and set on the adsorption plate by vacuum adsorption. Then, at room temperature, one point of the glass was lifted with tweezers to peel off the glass substrate. The case where the wafer having a thickness of 50 ⁇ m could be peeled off without breaking was indicated by “ ⁇ ”, and the case where an abnormality such as cracking occurred was evaluated as defective and indicated by “x”.
  • a silicone resin solution A1 to A7 and CA1 to CA5 are spin-coated on a silicon wafer (thickness: 725 ⁇ m) having a diameter of 200 mm, and heated on a hot plate at 100 ° C. for 2 minutes.
  • a silicone resin layer was formed with the film thickness shown in Table 1.
  • the curable silicone resin composition layer was irradiated with light under the conditions shown in Table 1 to cure the temporary adhesive layer.
  • heating was performed on a hot plate under the conditions shown in Table 1 to cure the temporary adhesive layer.
  • the silicon substrate containing the obtained temporary adhesive layer was sandwiched between 25 mm aluminum plates so that a load of 50 gf was applied to the temporary adhesive layer using Ares G2 manufactured by TA Instruments, Inc. at 25 ° C. and 1 Hz.
  • the elastic modulus was measured, and the obtained elastic modulus was taken as the storage elastic modulus of the silicone resin layer.
  • the wafer laminates of Examples 1 to 7 containing the temporary adhesive layer of the present invention can be cured at a relatively low temperature in a short time, and the wafer warp during curing accordingly. Has also been reduced. It was also confirmed that the product has sufficient processing durability, is excellent in peelability, and has good cleaning and removing property after peeling. On the other hand, as shown in Table 2, in Comparative Examples 1 and 2 using the thermoactive catalyst, insufficient curing due to insufficient heating and wafer warpage during curing were confirmed.
  • Example 8 The photocurable silicone resin solution A1 was irradiated with light under the conditions shown in Table 2 using a surface irradiation type UV-LED (wavelength 365 nm) irradiator, and then a copper post having a height of 10 ⁇ m and a diameter of 40 ⁇ m was formed on the surface.
  • a silicon wafer Si wafer with circuit, thickness: 725 ⁇ m
  • the agent layer was formed on the wafer bump forming surface.
  • a Si wafer with a diameter of 200 mm Si wafer, thickness: 770 ⁇ m
  • a Si wafer with a circuit having a temporary adhesive layer and a Si wafer of the support are combined so that the temporary adhesive layer and the Si wafer are combined.
  • a wafer laminate was produced by vacuum bonding at 25 ° C., 10 -3 mbar or less, and a load of 5 kN using a wafer bonding device EVG520IS manufactured by EVG.
  • Example 9 In Example 8, a wafer laminate was produced in the same manner except that the object to which the light-irradiated photocurable silicone resin solution A1 was applied was changed from the silicon wafer with a circuit to the Si wafer of the support. ..
  • Example 10 The same applies to Example 8 except that the object to which the light-irradiated photocurable silicone resin solution A1 is applied is changed from the silicon wafer with a circuit to the Si wafer with a circuit and the Si wafer of the support. To prepare a wafer laminate.
  • Example 11 A wafer laminate was produced in the same manner except that the photocurable silicone resin solution used in Example 8 was changed from A1 to A6.
  • Example 12 A wafer laminate was produced in the same manner except that the photocurable silicone resin solution used in Example 9 was changed from A1 to A6.
  • Example 13 A wafer laminate was produced in the same manner except that the photocurable silicone resin solution used in Example 10 was changed from A1 to A6.
  • Examples 8 to 13 the obtained wafer laminates were subjected to the same tests as in the above (1) wafer warp test to (6) wash removability test. The results are shown in Table 3.
  • a photocurable silicone resin solution previously irradiated with light was spun on a silicon wafer (Si wafer, thickness: 770 ⁇ m) having a diameter of 200 mm.
  • the silicone resin layer was cured by coating and heating on a hot plate at 100 ° C. for 5 minutes to prepare a test sample. After that, the peel peeling force test and the elastic modulus measurement test were carried out in the same manner as described above, and the results are shown in Table 3.
  • the wafer is equivalent to the case where light irradiation is performed after coating and bonding. It was confirmed that workability was obtained. In this case, since it is not necessary to irradiate light through the support, the applicable range of the support can be expanded, and light damage to the device wafer can be avoided.

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PCT/JP2021/016272 2020-04-30 2021-04-22 ウエハ加工用仮接着剤、ウエハ積層体及び薄型ウエハの製造方法 Ceased WO2021220929A1 (ja)

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KR1020227039904A KR20230005219A (ko) 2020-04-30 2021-04-22 웨이퍼 가공용 가접착제, 웨이퍼 적층체 및 박형 웨이퍼의 제조 방법
EP21797814.7A EP4144808A4 (en) 2020-04-30 2021-04-22 TEMPORARY ADHESIVE FOR WAFER PROCESSING, WAFER LAMINATE AND METHOD FOR PRODUCING A THIN WAFER
JP2022517686A JP7658367B2 (ja) 2020-04-30 2021-04-22 ウエハ加工用仮接着剤、ウエハ積層体及び薄型ウエハの製造方法
CN202180031672.7A CN115485814B (zh) 2020-04-30 2021-04-22 晶片加工用临时粘接剂、晶片层叠体以及薄型晶片的制造方法

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