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US-12617988-B2 - Temporary adhesive containing epoxy-modified polysiloxane

US12617988B2US 12617988 B2US12617988 B2US 12617988B2US-12617988-B2

Abstract

A temporary adhesive having excellent spin coating properties of a circuit side of a wafer and a support, and excellent heat resistance when the circuit side of the wafer or the support is attached to an adhesion layer or a rear surface of the wafer is processed, and is capable of easily separating the circuit side of the wafer from the support after polishing the rear surface of the wafer, and simply removing a adhesive attached to the wafer or the support after the separation. The adhesive contains a component (A) to be cured by a hydrosilylation reaction, and a component (B) containing an epoxy-modified polyorganosiloxane at a ratio in % by mass of the component (A) to the component (B) of 99.995:0.005 to 30:70. The component (B) is an epoxy-modified polyorganosiloxane having an epoxy value of 0.1 to 5.

Inventors

  • Kazuhiro Sawada
  • Tetsuya Shinjo
  • Hiroshi Ogino
  • Satoshi KAMIBAYASHI
  • Shunsuke MORIYA

Assignees

  • NISSAN CHEMICAL CORPORATION

Dates

Publication Date
20260505
Application Date
20240723
Priority Date
20170524

Claims (20)

  1. 1 . A method for forming a layered body comprising: a first step of applying an adhesive to a surface of a first body to form an adhesion layer, a second step of attaching a surface of a second body to the adhesion layer, and a third step of heating the adhesion layer from a side of the first body to cure the adhesion layer, wherein the adhesive comprises a mixture of a component (A) to be cured by a hydrosilylation reaction, and a component (B) containing an epoxy-modified polyorganosiloxane at a ratio in % by mass of the component (A) to the component (B) of 99.995:0.005 to 30:70, wherein the component (A) contains a polysiloxane (A1) and a platinum group metal-based catalyst (A2), wherein the polysiloxane (A1) contains: a polyorganosiloxane (a1) selected from the group consisting of a siloxane unit (Q′ unit) of SiO 2 , a siloxane unit (M′ unit) of R 1 ′R 2 ′R 3 ′SiO 1/2 , a siloxane unit (D′ unit) of R 4 ′R 5 ′SiO 2/2 , a siloxane unit (T′ unit) of R 6 ′SiO 3/2 , and a combination thereof, and R 1 ′ to R 6 ′ are each independently a monovalent chemical group that is a C 1-10 alkyl group or a C 2-10 alkenyl group; and a polyorganosiloxane (a2) selected from the group consisting of a siloxane unit (Q″ unit) of SiO 2 , a siloxane unit (M″ unit) of R 1 ″R 2 ″R 3 ″SiO 1/2 , a siloxane unit (D″ unit) of R 4 ″R 5 ″SiO 2/2 , a siloxane unit (T″ unit) of R 6 ″SiO 3/2 , and a combination thereof, and R 1 ″ to R 6 ″ are each independently a C 1-10 alkyl group or a hydrogen atom, and wherein the epoxy-modified polyorganosiloxane of component (B) contains a siloxane unit (D′″ unit) of R 1′″ R 2′″ SiO 2/2 , wherein R 1′″ is a C 1-10 alkyl group, and R 2′″ is a C 1-10 alkyl group or an epoxy group, provided that R 1′″ and R 2′″ are each bonded to a silicon atom through a Si—C bond, and the epoxy-modified polyorganosiloxane of component (B) may optionally further contain one or more units selected from the group consisting of a siloxane unit (Q unit) of SiO 2 , a siloxane unit (M unit) of R 1 R 2 R 3 SiO 1/2 , and a siloxane unit (T unit) of R 6 SiO 3/2 , wherein R 1 , R 2 , R 3 , and R 6 are each independently a monovalent chemical group that is a C 1-10 alkyl group, a C 2-10 alkenyl group, or a hydrogen atom.
  2. 2 . The method according to claim 1 , wherein component (B) is selected from the group consisting of (B-1), (B-3), and (B-5): m, n, and o represent respective numbers of repeating units, and R is a C 1-10 alkylene group.
  3. 3 . The method according to claim 2 , wherein the epoxy-modified polyorganosiloxane of component (B) is
  4. 4 . The method according to claim 2 , wherein the epoxy-modified polyorganosiloxane of component (B) is
  5. 5 . The method according to claim 2 , wherein the epoxy-modified polyorganosiloxane of component (B) is
  6. 6 . The method according to claim 1 , wherein R 2′″ is an epoxy group.
  7. 7 . The method according to claim 6 , wherein R 2′″ is a 3-glycidoxypropyl group.
  8. 8 . The method according to claim 1 , wherein the first body is a support, the second body is a wafer, and in the second step, a circuit side of the wafer is a face facing the surface of the first body.
  9. 9 . The method according to claim 1 , wherein the first body is a wafer, the second body is a support, and in the second step, a circuit side of the wafer is a face facing the surface of the second body.
  10. 10 . The method according to claim 1 , wherein the component (B) is an epoxy-modified polyorganosiloxane having an epoxy value of 0.1 to 5.
  11. 11 . A separation method comprising: a first step of applying an adhesive to a surface of a first body to form an adhesion layer, a second step of attaching a surface of a second body to the adhesion layer, a third step of heating the adhesion layer from a side of the first body to cure the adhesion layer, forming a layered body, a fourth step of processing the layered body, and a fifth step of separating the adhesion layer from the first or second body, wherein the adhesive comprises a mixture of a component (A) to be cured by a hydrosilylation reaction, and a component (B) containing an epoxy-modified polyorganosiloxane at a ratio in % by mass of the component (A) to the component (B) of 99.995:0.005 to 30:70, wherein the component (A) contains a polysiloxane (A1) and a platinum group metal-based catalyst (A2), wherein the polysiloxane (A1) contains: a polyorganosiloxane (a1) selected from the group consisting of a siloxane unit (Q′ unit) of SiO 2 , a siloxane unit (M′ unit) of R 1 ′R 2 ′R 3 ′SiO 1/2 , a siloxane unit (D′ unit) of R 4 ′R 5 ′SiO 2/2 , a siloxane unit (T′ unit) of R 6 ′SiO 3/2 , and a combination thereof, and R 1 ′ to R 6 ′ are each independently a monovalent chemical group that is a C 1-10 alkyl group or a C 2-10 alkenyl group; and a polyorganosiloxane (a2) selected from the group consisting of a siloxane unit (Q″ unit) of SiO 2 , a siloxane unit (M″ unit) of R 1 ″R 2 ″R 3 ″SiO 1/2 , a siloxane unit (D″ unit) of R 4 ″R 5 ″SiO 2/2 , a siloxane unit (T″ unit) of R 6 ″SiO 3/2 , and a combination thereof, and R 1 ″ to R 6 ″ are each independently a C 1-10 alkyl group or a hydrogen atom, and wherein the epoxy-modified polyorganosiloxane of component (B) contains a siloxane unit (D′″ unit) of R 1′″ R 2′″ SiO 2/2 , wherein R 1′″ is a C 1-10 alkyl group, and R 2′″ is a C 1-10 alkyl group or an epoxy group, provided that R 1′″ and R 2′″ are each bonded to a silicon atom through a Si—C bond, and the epoxy-modified polyorganosiloxane of component (B) may optionally further contain one or more units selected from the group consisting of a siloxane unit (Q unit) of SiO 2 , a siloxane unit (M unit) of R 1 R 2 R 3 SiO 1/2 , and a siloxane unit (T unit) of R 6 SiO 3/2 , wherein R 1 , R 2 , R 3 , and R 6 are each independently a monovalent chemical group that is a C 1-10 alkyl group, a C 2-10 alkenyl group, or a hydrogen atom.
  12. 12 . The separation method according to claim 11 , wherein component (B) is selected from the group consisting of (B-1), (B-3), and (B-5): m, n, and o represent respective numbers of repeating units, and R is a C 1-10 alkylene group.
  13. 13 . The separation method according to claim 12 , wherein the epoxy-modified polyorganosiloxane of component (B) is
  14. 14 . The separation method according to claim 12 , wherein the epoxy-modified polyorganosiloxane of component (B) is
  15. 15 . The separation method according to claim 12 , wherein the epoxy-modified polyorganosiloxane of component (B) is
  16. 16 . The separation method according to claim 11 , wherein R 2′″ is an epoxy group.
  17. 17 . The separation method according to claim 16 , wherein R 2′″ is a 3-glycidoxypropyl group.
  18. 18 . The separation method according to claim 11 , wherein the first body is a support, the second body is a wafer, and in the second step, a circuit side of the wafer is a face facing the surface of the first body.
  19. 19 . The separation method according to claim 11 , wherein the first body is a wafer, the second body is a support, and in the second step, a circuit side of the wafer is a face facing the surface of the second body.
  20. 20 . The separation method according to claim 11 , wherein the processing is polishing the rear surface of the wafer.

Description

This application is a continuation application of U.S. application Ser. No. 16/615,981 filed Nov. 22, 2019, which is the U.S. national phase of PCT Application No. PCT/JP2018/019849 filed May 23, 2018, the entire disclosures of which are incorporated herein by reference. TECHNICAL FIELD The present invention relates to a temporary adhesive for fixing a wafer on a support when a rear surface of the wafer is polished, and a layered body using the same. BACKGROUND ART For conventional semiconductor wafers that are two-dimensionally integrated in a plane direction, a semiconductor integration technology of further integrating (layering) planes of wafers in a three-dimensional direction for further integration has been required. The layering in the three-dimensional direction is a technology in which wafers are integrated into a multilayer so as to be connected with a through silicon via (TSV). When semiconductor wafers are integrated into a multilayer, each of the semiconductor wafers to be integrated is thinned by polishing a surface (i.e., a rear surface) opposite to a surface on which a circuit is formed, and the thinned semiconductor wafers are layered. In order to polish a surface with a polisher, a semiconductor wafer (herein, simply referred to as wafer) before thinning is attached to a support. In this case, attachment means temporary adhesion since easy separation is needed after polishing. When a large force is applied for detachment, a thinned semiconductor wafer may be broken or deformed. For a countermeasure against this, the thinned semiconductor wafer is easily detached from the support in temporary adhesion. However, it is not preferable that the semiconductor wafer be detached or shifted from the support by polishing stress when a rear surface of the semiconductor wafer is polished. Therefore, a performance required for the temporary adhesion is resistance to stress in polishing and easy detachment after polishing. For example, performances such as high stress in a plane direction during polishing (high adhesion force) and low stress in a longitudinal direction during detachment (low adhesion force) are required. As a process of such adhesion, a method in which an adhesion layer and a separation layer are provided and the separation layer is formed by plasma polymerization of dimethylsiloxane and mechanically separated after polishing (see Patent Documents 1 and 2), a method in which a semiconductor wafer is attached to a supporting substrate through an adhesive composition, a rear surface of the semiconductor wafer is polished, and the adhesive is then removed by an etching solution (see Patent Document 3), and a wafer processed body including, as an adhesion layer for attachment of a semiconductor wafer to a support, a combination of a polymerized layer obtained by polymerizing an alkenyl group-containing organopolysiloxane and a hydrosilyl group-containing organopolysiloxane using a platinum catalyst and a polymerized layer including a thermosetting polysiloxane (see Patent Documents 4 to 7) are disclosed. PRIOR ART DOCUMENTS Patent Documents Patent Document 1: Japanese Patent Application Publication (Translation of PCT Application) No. 2012-510715 (JP 2012-510715 A) Patent Document 2: Japanese Patent Application Publication (Translation of PCT Application) No. 2012-513684 (JP 2012-513684 A) Patent Document 3: Japanese Patent Application Publication (Translation of PCT Application) No. 2008-532313 (JP 2008-532313 A) Patent Document 4: Japanese Patent Application Publication No. 2013-179135 (JP 2013-179135 A) Patent Document 5: Japanese Patent Application Publication No. 2013-232459 (JP 2013-232459 A) Patent Document 6: Japanese Patent Application Publication No. 2006-508540 (JP 2006-508540 A) Patent Document 7: Japanese Patent Application Publication No. 2009-528688 (JP 2009-528688 A) SUMMARY OF THE INVENTION Problem to be Solved by the Invention Provided are a temporary adhesive that has excellent spin coating properties of a circuit side of a wafer and a support (supporting substrate), and excellent heat resistance when the circuit side of the wafer or the support is attached to an adhesion layer (an adhesion layer is cured) or a rear surface of the wafer is processed, and is capable of easily separating the circuit side of the wafer from the support after polishing the rear surface of the wafer, and simply removing the adhesion layer attached to the wafer or the support after the separation, a layered body using the temporary adhesive, and a processing method using the layered body. Means for Solving the Problems A first aspect of the present invention is an adhesive used to separatably attach a support to a circuit side of a wafer and process a rear surface of the wafer, the adhesive containing a component (A) to be cured by a hydrosilylation reaction, and a component (B) containing an epoxy-modified polyorganosiloxane at a ratio in % by mass of the component (A) to the component (B) of