Method for manufacturing wafer and method for removing cured film of temporary fixing composition

Abstract

To provide a method for manufacturing a wafer that suppresses re-adhesion between the wafer and a support member by a simple method, after bonding the wafer and the support member, irradiating the temporary fixing composition with the UV laser to generate carbon particles and thereby peeling the wafer from the support member.SOLUTION: A method for manufacturing a wafer includes a peeling process for a structure (A) comprising, in this order, a support member, a cured film of a temporary fixing composition, and a wafer (a): irradiating the structure with the UV laser having a wavelength of 300 nm or more and 385 nm or less from the support member side to decompose at least a portion of the cured film of the temporary fixing composition, thereby generating carbon particles, and peeling the wafer from the support member.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a method for producing a wafer and a method for removing a cured film of a temporary fixing composition. [Background technology]

[0002] In the manufacture of wafers used for electronic devices, etc., measures are required to prevent breakage due to thinning during processing. To achieve this, a method has been adopted in which a temporary fixing composition that can be peeled off after processing is applied to the surface (back surface) of the wafer opposite to the surface to be ground, and the wafer is temporarily fixed to a support member.

[0003] Patent Document 1 describes a temporary fixing composition containing the following (A) to (C): (A) a (meth)acrylate containing the following (A-1) and (A-2): (A-1) A monofunctional (meth)acrylate having an alkyl group with 18 or more carbon atoms in the side chain and a Tg of the homopolymer of -100°C to 60°C (A-2) Polyfunctional (meth)acrylate (B) a polyisobutene homopolymer and / or a polyisobutene copolymer; and (C) a photoradical polymerization initiator. Furthermore, Patent Document 1 describes the problems to be solved, including insufficient curing speed, compatibility with spin coating processes, heat resistance, low outgassing under high temperature and vacuum conditions, and peeling speed, and in particular suitability for UV laser peeling processes. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] International Publication No. 2021 / 235406 Summary of the Invention [Problem to be solved by the invention]

[0005] The present invention provides a wafer manufacturing method capable of suppressing re-adhesion between a wafer and a support member by a simple method in which, after bonding the wafer and a support member, a temporary fixing composition is irradiated with a UV laser to generate carbon particles, which are then peeled off. [Means for solving the problem]

[0006] According to the present invention, there are provided a method for producing a wafer and a method for removing a cured film of a temporary fixing composition, which are described below.

[0007] 1. A method for manufacturing a wafer, comprising: A method for manufacturing a wafer, comprising: a peeling step of irradiating a structure (A) including a support member, a cured film of a temporary fixing composition, and a wafer (a) in this order with a UV laser having a wavelength of 300 nm or more and 385 nm or less from the support member side to decompose at least a part of the cured film of the temporary fixing composition to generate carbon particles, thereby peeling the wafer from the support member. 2. Before the peeling step, 1. The method for producing a wafer according to 1., further comprising a thinning step of obtaining the structure (A) by thinning the wafer (b) in the structure (B) which includes the support member, the cured film of the temporary fixing composition, and the wafer (b) in this order. 3. Before the thinning step, 1. The method for producing a wafer according to 2., further comprising a curing step of irradiating light to a structure (C) including the support member, a temporary fixing film made of the temporary fixing composition, and the wafer (b) in this order, to cure the temporary fixing film, thereby obtaining the structure (B). 4. The method for producing a wafer according to any one of 1. to 3., wherein the ratio of the area where the carbon particles are generated in the temporary fixing composition by the following method 1 is 0.20% or more. (Method 1) A disk-shaped temporary fixing film (150 mm diameter × 50 μm thickness) made of the temporary fixing composition is applied between a disk-shaped silicon wafer (150 mm diameter × 625 μm thickness) and a disk-shaped glass support member (150 mm diameter × 700 μm thickness), thereby bonding the silicon wafer and the glass support member. Next, under a nitrogen atmosphere, a UV-LED with a wavelength of 405 nm (illuminance 100 mW / cm 2 , irradiation time 50 seconds, cumulative light intensity 5000mJ / cm 2 ) is irradiated onto the temporary fixing film from the glass support member side to harden the temporary fixing film, thereby obtaining a hardened film. Next, the resulting cured film is irradiated from the glass support member side with a UV laser (YAG laser, output 6.5 W, spot diameter 150 μm, irradiation pitch 200 μm, scan speed 8 m / sec, frequency 40 kHz) having a wavelength of 355 nm, scanning the entire cured film. Next, the glass support member is peeled off from the silicon wafer, and the surface of the central part of the glass support member on the side of the cured film is observed and photographed using an optical microscope at a magnification of 20 times. When the area of ​​one field of view (200 μm × 200 μm) is taken as 100%, the area (%) of the black part per field of view is calculated using image processing software, and this is defined as the area (%) where carbon particles are generated. 5. The method for producing a wafer according to any one of 1. to 4., wherein the spot diameter of the UV laser in the peeling step is 60 μm or more and 500 μm or less. 6. The method for producing a wafer according to any one of 1. to 5., wherein the output of the UV laser in the peeling step is 4.1 W or more and 50.0 W or less. 7. The method for producing a wafer according to any one of 1. to 6., wherein the scanning speed of the UV laser in the peeling step is 0.1 m / s or more and 100 m / s or less. 8. The method for producing a wafer according to any one of 1. to 7., wherein the thickness of the cured film is 0.1 μm or more and 500 μm or less. 9. The method for producing a wafer according to any one of 1. to 8., wherein the cured film is a single layer. 10. The method for producing a wafer according to any one of 1. to 9., wherein the temporary fixing composition has a transmittance of 10.0% or less to a laser beam having a wavelength of 355 nm when the following method 2 is carried out. (Method 2) Two rectangular Tempax glass sheets (33 mm×50 mm, thickness 700 μm) were prepared, 0.1 g of the temporary fixing composition was dropped onto one of them, and the two sheets were sandwiched together. Next, the obtained laminate was irradiated with a UV-LED (illuminance 100 mW / cm ) with a wavelength of 405 nm under a nitrogen atmosphere. 2 , irradiation time 50 seconds, cumulative light intensity 5000mJ / cm 2 ) to cure the temporary fixing composition, thereby obtaining a test piece for transmittance measurement. Next, the transmittance of the obtained test piece for transmittance measurement is measured using a spectrophotometer at a pitch of 1.0 nm and in a wavelength range of 300 to 800 nm. Next, the transmittance at 355 nm is read from the obtained transmittance data and is defined as the transmittance at a wavelength of 355 nm. 11. The method for producing a wafer according to any one of 1. to 10., wherein the temporary fixing composition contains a polymerizable component (A) containing a (meth)acrylate, a photoradical polymerization initiator (B), and an ultraviolet absorber (C). 12. The method for producing a wafer according to 11, wherein the ultraviolet absorber (C) has one or more skeletons selected from the group consisting of a benzophenone skeleton, a triazole skeleton, a hydroxyphenyltriazine skeleton, and a phenol skeleton. 13. The method for producing a wafer according to 11. or 12., wherein the ultraviolet absorber (C) has a polymerizable functional group. 14. The method for producing a wafer according to 13, wherein the polymerizable functional group is present at the end of the ultraviolet absorber (C). 15. The method for producing a wafer according to 13. or 14., wherein the polymerizable functional group includes a (meth)acryloyl group. 16. The method for producing a wafer according to any one of items 11 to 15, wherein the content of the ultraviolet absorber (C) is 0.1 parts by mass or more and 20 parts by mass or less per 100 parts by mass of the polymerizable component (A) containing the (meth)acrylate. 17. The method for producing a wafer according to any one of Items 11 to 16, wherein the content of the polymerizable component (A) containing the (meth)acrylate is 50% by mass or more and 99% by mass or less, relative to 100% by mass of the temporary fixing composition. 18. The method for producing a wafer according to any one of items 11 to 17, wherein the content of the photoradical polymerization initiator (B) is 0.1 parts by mass or more and 10 parts by mass or less per 100 parts by mass of the polymerizable component (A) containing the (meth)acrylate. 19. Using an E-type viscometer, the temperature was 23°C and the shear rate was 75 s -1 19. The method for producing a wafer according to any one of 1. to 18., wherein the viscosity of the temporary fixing composition measured by the above method is 100 mPa·s or more and 5000 mPa·s or less. 20. The method for producing a wafer according to any one of 1. to 19., wherein the temporary fixing composition produced by the following method 3 has a peel strength P1 of 0.01 N or more and 30.0 N or less immediately after laser irradiation. (Method 3) A disk-shaped temporary fixing film (150 mm diameter × 50 μm thickness) made of the temporary fixing composition is applied between a disk-shaped silicon wafer (150 mm diameter × 625 μm thickness) and a disk-shaped glass support member (150 mm diameter × 700 μm thickness), thereby bonding the silicon wafer and the glass support member. Next, under a nitrogen atmosphere, a UV-LED with a wavelength of 405 nm (illuminance 100 mW / cm 2 , irradiation time 50 seconds, cumulative light intensity 5000mJ / cm 2 ) is irradiated onto the temporary fixing film from the glass support member side to harden the temporary fixing film, thereby obtaining a hardened film. Next, the resulting cured film is irradiated from the glass support member side with a UV laser (YAG laser, output 6.5 W, spot diameter 150 μm, irradiation pitch 200 μm, scan speed 8 m / sec, frequency 40 kHz) having a wavelength of 355 nm, scanning the entire cured film to obtain a laminate. Next, within 1 minute after the end of UV laser irradiation, the obtained laminate was placed and fixed on an adsorption table with the silicon wafer side facing down, and an adsorption arm equipped with three suction cups with a diameter of 10 mm was attached to the glass support member. The adsorption arm was then vertically pulled upward at a speed of 0.5 mm / sec to peel off the glass support member. The load applied to the adsorption arm when the glass support member was lifted was measured and recorded as the peel strength P1 (N). 21. The method for producing a wafer according to any one of 1. to 20., wherein the temporary fixing composition according to Method 4 below has a peel strength P2 of 0.01 N or more and 50.0 N or less 10 minutes after completion of laser irradiation. (Method 4) A disk-shaped temporary fixing film (150 mm diameter × 50 μm thickness) made of the temporary fixing composition is applied between a disk-shaped silicon wafer (150 mm diameter × 625 μm thickness) and a disk-shaped glass support member (150 mm diameter × 700 μm thickness), thereby bonding the silicon wafer and the glass support member. Next, under a nitrogen atmosphere, a UV-LED with a wavelength of 405 nm (illuminance 100 mW / cm 2 , irradiation time 50 seconds, cumulative light intensity 5000mJ / cm 2 ) is irradiated onto the temporary fixing film from the glass support member side to harden the temporary fixing film, thereby obtaining a hardened film. Next, the resulting cured film is irradiated from the glass support member side with a UV laser (YAG laser, output 6.5 W, spot diameter 150 μm, irradiation pitch 200 μm, scan speed 8 m / sec, frequency 40 kHz) having a wavelength of 355 nm, scanning the entire cured film to obtain a laminate. Next, 10 minutes after the completion of the UV laser irradiation, the obtained laminate was placed and fixed on an adsorption table with the silicon wafer side facing down, and an adsorption arm equipped with three suction cups with a diameter of 10 mm was attached to the glass support member. The adsorption arm was then pulled vertically upward at a speed of 0.5 mm / sec to peel off the glass support member, and the load applied to the adsorption arm when the glass support member was lifted was measured and recorded as the peel strength P2 (N). 22. The method for producing a wafer according to any one of 1. to 21., wherein the ratio (P2 / P1) of the peel strength P2 10 minutes after laser irradiation to the peel strength P1 immediately after laser irradiation of the temporary fixing composition by Method 5 below is 2.0 or less. (Method 5) A disk-shaped temporary fixing film (150 mm diameter × 50 μm thickness) made of the temporary fixing composition is applied between a disk-shaped silicon wafer (150 mm diameter × 625 μm thickness) and a disk-shaped glass support member (150 mm diameter × 700 μm thickness), thereby bonding the silicon wafer and the glass support member. Next, under a nitrogen atmosphere, a UV-LED with a wavelength of 405 nm (illuminance 100 mW / cm 2 , irradiation time 50 seconds, cumulative light intensity 5000mJ / cm 2 ) is irradiated onto the temporary fixing film from the glass support member side to harden the temporary fixing film, thereby obtaining a hardened film. Next, the resulting cured film is irradiated from the glass support member side with a UV laser (YAG laser, output 6.5 W, spot diameter 150 μm, irradiation pitch 200 μm, scan speed 8 m / sec, frequency 40 kHz) having a wavelength of 355 nm, scanning the entire cured film to obtain a laminate. Next, within 1 minute after the end of UV laser irradiation, the obtained laminate was placed and fixed on an adsorption table with the silicon wafer side facing down, and an adsorption arm equipped with three suction cups with a diameter of 10 mm was attached to the glass support member. The adsorption arm was then vertically pulled upward at a speed of 0.5 mm / sec to peel off the glass support member. The load applied to the adsorption arm when the glass support member was lifted was measured and recorded as the peel strength P1 (N). Next, a laminate was obtained under the same conditions as above, and 10 minutes after the completion of the UV laser irradiation, the obtained laminate was placed and fixed on an adsorption table with the silicon wafer side facing down, and an adsorption arm equipped with three suction cups with a diameter of 10 mm was attached to the glass support member. The adsorption arm was then vertically pulled upward at a speed of 0.5 mm / sec to peel off the glass support member, and the load applied to the adsorption arm when the glass support member was lifted was measured and recorded as the peel strength P2 (N). P2 / P1 is calculated from P1 and P2 calculated by the above method. 23. The method for manufacturing a wafer according to any one of 1. to 22., wherein the support member includes a glass support member. 24. The method for producing a wafer according to any one of 1. to 23., wherein the wafer includes a semiconductor wafer. 25. A method for removing a cured film of a temporary fixing composition, comprising: A method for removing a cured film of a temporary fixing composition, comprising: irradiating a structure (A) including a support member, a cured film of the temporary fixing composition, and a wafer (a) in this order with a UV laser having a wavelength of 300 nm or more and 385 nm or less from the support member side to decompose at least a part of the cured film of the temporary fixing composition, thereby generating carbon particles, peeling the wafer and the support member, and removing the cured film of the temporary fixing composition. 26. A method for manufacturing a wafer, comprising a peeling step of irradiating a structure (A) having a support member, a cured film of a composition, and a wafer (a) in this order from the support member side with a UV laser having a wavelength of 300 nm or more and 385 nm or less to decompose at least a portion of the cured film of the composition, thereby generating carbon particles and peeling the wafer from the support member. 27. A method for removing a cured film of a composition, comprising irradiating a structure (A) having a support member, a cured film of a composition, and a wafer (a) in this order with a UV laser having a wavelength of 300 nm or more and 385 nm or less from the support member side to decompose at least a portion of the cured film of the composition, thereby generating carbon particles, peeling the wafer and the support member, and removing the cured film of the composition. [Effects of the Invention]

[0008] According to the present invention, it is possible to provide a method for producing a wafer and a method for removing a cured film of a temporary fixing composition, which can prevent re-adhesion between the wafer and a support member by a simple method in which, after bonding the wafer and a support member, the temporary fixing composition is irradiated with a UV laser to generate carbon particles and then peeled off. [Brief explanation of the drawings]

[0009] [Figure 1] 1 is a micrograph of the surface of the cured film side in the center part of the glass support member of Example 1. [Figure 2] 1 is a micrograph of the surface of the cured film side in the center part of the glass support member of Comparative Example 1. [Figure 3] 10 is a micrograph of the surface of the cured film side in the center part of the glass support member of Comparative Example 3. [Figure 4] FIG. 2 is a diagram illustrating a method for measuring peel strength. DETAILED DESCRIPTION OF THE INVENTION

[0010] The present invention will be described below based on embodiments.

[0011] In the present embodiment, the term "(meth)acrylate" represents a concept that encompasses both acrylate and methacrylate. The same applies to similar terms such as "(meth)acrylic."

[0012] 1. Wafer manufacturing method A method for producing a wafer according to this embodiment will be described below. The composition according to this embodiment is preferably a temporary fixing composition.

[0013] The method for producing a wafer of the present embodiment includes a peeling step of irradiating a structure (A) including a support member, a cured film of the temporary fixing composition, and a wafer (a) in this order with a UV laser having a wavelength of 300 nm or more and 385 nm or less from the support member side to decompose at least a part of the cured film of the temporary fixing composition, thereby generating carbon particles and peeling the wafer from the support member.

[0014] The mechanism by which the temporary fixing composition of this embodiment can prevent re-sticking between a wafer and a support member after a certain time has elapsed since laser irradiation (hereinafter, this may be simply referred to as re-sticking) is not clear, but it is speculated that carbon particles generated when the temporary fixing composition of this embodiment is irradiated with light such as a UV laser contribute to the prevention of re-sticking.

[0015] <Peeling process> The peeling step of this embodiment will be described below.

[0016] As described above, in the peeling step of this embodiment, carbon particles are generated by decomposing at least a part of the cured film of the temporary fixing composition, and the wafer and the support member are peeled off. In other words, in the peeling step of this embodiment, carbon particles are generated in an amount that enables the wafer and the support member to be peeled off.

[0017] The ratio of the area where carbon particles are generated in the temporary fixing composition of this embodiment by the following method 1 is, from the viewpoint of being able to further suppress re-fixing, preferably 0.20% or more, more preferably 0.30% or more, even more preferably 0.40% or more, even more preferably 0.50% or more, even more preferably 0.60% or more, even more preferably 0.70% or more, even more preferably 0.80% or more, even more preferably 0.90% or more, even more preferably 1.00% or more, even more preferably 1.10% or more, and even more preferably 1.20% or more, and, from the viewpoint of being able to suppress contamination by carbon particles, is preferably 20.00% or less, more preferably 10.00% or less, even more preferably 5.00% or less, and even more preferably From the viewpoint of the balance between suppressing re-adhesion and suppressing contamination by carbon particles, the content is preferably 0.20% or more and 20.00% or less, more preferably 0.30% or more and 20.00% or less, even more preferably 0.40% or more and 20.00% or less, even more preferably 0.50% or more and 10.00% or less, even more preferably 0.60% or more and 10.00% or less, even more preferably 0.70% or more and 10.00% or less, even more preferably 0.80% or more and 5.00% or less, even more preferably 0.90% or more and 5.00% or less, even more preferably 1.00% or more and 5.00% or less, even more preferably 1.10% or more and 3.00% or less, and even more preferably 1.20% or more and 3.00% or less. (Method 1) A disk-shaped temporary fixing film (150 mm diameter × 50 μm thickness) made of a temporary fixing composition is applied between a disk-shaped silicon wafer (150 mm diameter × 625 μm thickness) and a disk-shaped glass support member (150 mm diameter × 700 μm thickness), thereby bonding the silicon wafer and the glass support member. Next, under a nitrogen atmosphere, a UV-LED with a wavelength of 405 nm (illuminance 100 mW / cm 2 , irradiation time 50 seconds, cumulative light intensity 5000mJ / cm 2 ) is irradiated onto the temporary fixing film from the glass support member side to harden the temporary fixing film, thereby obtaining a hardened film. Next, the resulting cured film is irradiated from the glass support member side with a UV laser (YAG laser, output 6.5 W, spot diameter 150 μm, irradiation pitch 200 μm, scan speed 8 m / sec, frequency 40 kHz) having a wavelength of 355 nm, scanning the entire cured film. Next, the glass support member was peeled off from the silicon wafer, and the surface of the cured film side in the center part of the glass support member was observed and photographed using an optical microscope at 20x magnification. The area (%) of the black part per field of view, where the area of ​​one field of view (200 μm × 200 μm) is taken as 100%, was calculated using image processing software to determine the area (%) where carbon particles were generated.

[0018] The image processing software used to calculate the area in the above method 1 is not particularly limited, but for example, Fiji manufactured by the National Institutes of Health can be used.

[0019] The carbon particles of the present embodiment preferably contain carbon black, from the viewpoint of further suppressing re-adhesion.

[0020] In the peeling step of this embodiment, the spot diameter of the UV laser is preferably 60 μm or more, preferably 60 μm or more and 500 μm or less, more preferably 70 μm or more and 400 μm or less, even more preferably 80 μm or more and 300 μm or less, and even more preferably 90 μm or more and 280 μm or less, from the viewpoint of further suppressing re-adhesion.

[0021] In the peeling step of this embodiment, the output of the UV laser is preferably 4.1 W or more, preferably 4.1 W or more and 50.0 W or less, more preferably 4.1 W or more and 20.0 W or less, even more preferably 4.1 W or more and 15.0 W or less, and even more preferably 4.2 W or more and 10.0 W or less, from the viewpoint of further suppressing re-adhesion.

[0022] In the peeling step of this embodiment, the scanning speed of the UV laser is preferably 0.1 m / s or more, more preferably 1.0 m / s or more, even more preferably 2.0 m / s or more, and even more preferably 5.0 m / s or more, from the viewpoint of improving production efficiency, and is preferably 100 m / s or less, more preferably 50 m / s or less, even more preferably 20 m / s or less, and even more preferably 10 m / s or less, from the viewpoint of further suppressing re-adhesion, and is preferably 0.1 m / s or more and 100 m / s or less, more preferably 1.0 m / s or more and 50 m / s or less, even more preferably 2.0 m / s or more and 20 m / s or less, and even more preferably 5.0 m / s or more and 10 m / s or less, from the viewpoint of balancing improving production efficiency and suppressing re-adhesion.

[0023] The thickness of the cured film of this embodiment is preferably 0.1 μm or more and 500 μm or less, more preferably 1.0 μm or more and 200 μm or less, even more preferably 10 μm or more and 100 μm or less, and still more preferably 20 μm or more and 80 μm or less.

[0024] The cured film of this embodiment is preferably a single layer.

[0025] When the temporary fixing composition of this embodiment is subjected to the following method 2, the transmittance of a laser beam with a wavelength of 355 nm is preferably 10.0% or less, more preferably 5.0% or less, even more preferably 1.0% or less, even more preferably 0.5% or less, and even more preferably 0.1% or less. This allows the laser to be well absorbed by the cured product of the temporary fixing composition, facilitating peeling. (Method 2) Two rectangular Tempax glass sheets (33 mm x 50 mm, 700 μm thick) were prepared, 0.1 g of the temporary fixing composition was dropped onto one of them, and the two sheets were sandwiched together. Next, the obtained laminate was irradiated with a UV-LED (illuminance 100 mW / cm ) with a wavelength of 405 nm under a nitrogen atmosphere. 2 , irradiation time 50 seconds, cumulative light intensity 5000mJ / cm 2 ) to cure the temporary fixing composition, thereby obtaining a test piece for transmittance measurement. Next, the transmittance of the obtained test piece for transmittance measurement is measured using a spectrophotometer at a pitch of 1.0 nm and in a wavelength range of 300 to 800 nm. Next, the transmittance at 355 nm is read from the obtained transmittance data and is defined as the transmittance at a wavelength of 355 nm. Before measuring the transmittance, two rectangular Tempax glass sheets (33 mm × 50 mm, 700 μm thick) were prepared, 0.1 g of water was dropped onto one of them, and the other was sandwiched between them to obtain a test piece for baseline measurement. The baseline of the spectrophotometer was measured using the test piece for baseline measurement obtained.

[0026] The cumulative light amount of the light irradiation in the curing step of this embodiment is preferably 1000 mJ / cm from the viewpoint of improving adhesiveness. 2 From the viewpoint of improving productivity, it is preferably 20,000 mJ / cm 2 From the viewpoint of a balance between improving adhesion and improving productivity, it is preferably 1000 mJ / cm 2 More than 10000mJ / cm 2 Less than or equal to 3000 mJ / cm 2 More than 8000mJ / cm 2 or less, and more preferably 4000 mJ / cm 2 More than 6000mJ / cm 2 The following is the result.

[0027] The peel strength P1 of the temporary fixing composition of this embodiment immediately after laser irradiation by the following Method 3 is, for example, 0.01 N or more, and preferably 30.0 N or less, more preferably 25.0 N or less, even more preferably 20.0 N or less, even more preferably 18.0 N or less, even more preferably 16.0 N or less, even more preferably 14.0 N or less, even more preferably 12.0 N or less, and even more preferably 10.0 N or less, and preferably 0.01 N or more and 30.0 N or less, more preferably 0.01 N or more and 25.0 N or less, even more preferably 0.01 N or more and 20.0 N or less, even more preferably 0.01 N or more and 18.0 N or less, even more preferably 0.01 N or more and 16.0 N or less, even more preferably 0.01 N or more and 14.0 N or less, even more preferably 0.01 N or more and 12.0 N or less, and even more preferably 0.01 N or more and 10.0 N or less. (Method 3) A disk-shaped temporary fixing film (150 mm diameter × 50 μm thickness) made of a temporary fixing composition is applied between a disk-shaped silicon wafer (150 mm diameter × 625 μm thickness) and a disk-shaped glass support member (150 mm diameter × 700 μm thickness), thereby bonding the silicon wafer and the glass support member. Next, under a nitrogen atmosphere, a UV-LED with a wavelength of 405 nm (illuminance 100 mW / cm 2 , irradiation time 50 seconds, cumulative light intensity 5000mJ / cm 2 ) is irradiated onto the temporary fixing film from the glass support member side to harden the temporary fixing film, thereby obtaining a hardened film. Next, the resulting cured film is irradiated from the glass support member side with a UV laser (YAG laser, output 6.5 W, spot diameter 150 μm, irradiation pitch 200 μm, scan speed 8 m / sec, frequency 40 kHz) having a wavelength of 355 nm, scanning the entire cured film to obtain a laminate. Next, within 1 minute after the end of UV laser irradiation, the obtained laminate was placed and fixed on an adsorption table with the silicon wafer side facing down, and an adsorption arm equipped with three 10 mm diameter suction cups was attached to the glass support member. The adsorption arm was then pulled vertically upward at a speed of 0.5 mm / sec to peel off the glass support member. The load applied to the adsorption arm when the glass support member was lifted was measured and recorded as the peel strength P1 (N).

[0028] The peel strength P2 of the temporary fixing composition of this embodiment according to the following Method 4 10 minutes after the completion of laser irradiation is, for example, 0.01 N or more, and preferably 50.0 N or less, more preferably 40.0 N or less, even more preferably 30.0 N or less, even more preferably 25.0 N or less, even more preferably 20.0 N or less, even more preferably 18.0 N or less, even more preferably 16.0 N or less, even more preferably 14.0 N or less, even more preferably 12.0 N or less, and even more preferably 10.0 N or less; and , preferably 0.01N or more and 50.0N or less, more preferably 0.01N or more and 40.0N or less, even more preferably 0.01N or more and 30.0N or less, even more preferably 0.01N or more and 25.0N or less, even more preferably 0.01N or more and 20.0N or less, even more preferably 0.01N or more and 18.0N or less, even more preferably 0.01N or more and 16.0N or less, even more preferably 0.01N or more and 14.0N or less, even more preferably 0.01N or more and 12.0N or less, and even more preferably 0.01N or more and 10.0N or less. (Method 4) A disk-shaped temporary fixing film (150 mm diameter × 50 μm thickness) made of a temporary fixing composition is applied between a disk-shaped silicon wafer (150 mm diameter × 625 μm thickness) and a disk-shaped glass support member (150 mm diameter × 700 μm thickness), thereby bonding the silicon wafer and the glass support member. Next, under a nitrogen atmosphere, a UV-LED with a wavelength of 405 nm (illuminance 100 mW / cm 2 , irradiation time 50 seconds, cumulative light intensity 5000mJ / cm 2 ) is irradiated onto the temporary fixing film from the glass support member side to harden the temporary fixing film, thereby obtaining a hardened film. Next, the resulting cured film is irradiated from the glass support member side with a UV laser (YAG laser, output 6.5 W, spot diameter 150 μm, irradiation pitch 200 μm, scan speed 8 m / sec, frequency 40 kHz) having a wavelength of 355 nm, scanning the entire cured film to obtain a laminate. Next, 10 minutes after the completion of UV laser irradiation, the obtained laminate was placed and fixed on an adsorption table with the silicon wafer side facing down, and an adsorption arm equipped with three 10 mm diameter suction cups was attached to the glass support member. The adsorption arm was then pulled vertically upward at a speed of 0.5 mm / sec to peel off the glass support member, and the load applied to the adsorption arm when the glass support member was lifted was measured and recorded as the peel strength P2 (N).

[0029] The ratio (P2 / P1) of the peel strength P2 10 minutes after laser irradiation to the peel strength P1 immediately after laser irradiation of the temporary fixing composition of this embodiment obtained by Method 5 below is preferably 3.0 or less, more preferably 2.5 or less, even more preferably 2.0 or less, and even more preferably 1.8 or less. (Method 5) A disk-shaped temporary fixing film (150 mm diameter × 50 μm thickness) made of a temporary fixing composition is applied between a disk-shaped silicon wafer (150 mm diameter × 625 μm thickness) and a disk-shaped glass support member (150 mm diameter × 700 μm thickness), thereby bonding the silicon wafer and the glass support member. Next, under a nitrogen atmosphere, a UV-LED with a wavelength of 405 nm (illuminance 100 mW / cm 2 , irradiation time 50 seconds, cumulative light intensity 5000mJ / cm 2 ) is irradiated onto the temporary fixing film from the glass support member side to harden the temporary fixing film, thereby obtaining a hardened film. Next, the resulting cured film is irradiated from the glass support member side with a UV laser (YAG laser, output 6.5 W, spot diameter 150 μm, irradiation pitch 200 μm, scan speed 8 m / sec, frequency 40 kHz) having a wavelength of 355 nm, scanning the entire cured film to obtain a laminate. Next, within 1 minute after the end of UV laser irradiation, the obtained laminate was placed and fixed on an adsorption table with the silicon wafer side facing down, and an adsorption arm equipped with three 10 mm diameter suction cups was attached to the glass support member. The adsorption arm was then pulled vertically upward at a speed of 0.5 mm / sec to peel off the glass support member. The load applied to the adsorption arm when the glass support member was lifted was measured and recorded as the peel strength P1 (N). Next, a laminate was obtained under the same conditions as above, and 10 minutes after the completion of UV laser irradiation, the obtained laminate was placed and fixed on an adsorption table with the silicon wafer side facing down. An adsorption arm equipped with three 10 mm diameter suction cups was attached to the glass support member, and the adsorption arm was pulled vertically upward at a speed of 0.5 mm / sec to peel off the glass support member. The load applied to the adsorption arm when the glass support member was lifted was measured and recorded as the peel strength P2 (N). P2 / P1 is calculated from P1 and P2 calculated by the above method.

[0030] The support member of this embodiment is not particularly limited, but preferably includes a light-transmitting material. This facilitates peeling of the wafer by light irradiation such as UV laser irradiation. Examples of light-transmitting materials include inorganic substrates such as crystal, glass, quartz, calcium fluoride, and magnesium fluoride, and organic substrates such as plastic.

[0031] The support member of this embodiment preferably includes one or more types selected from the group consisting of a quartz support member and a glass support member, and more preferably includes a glass support member.

[0032] The wafer of this embodiment preferably comprises a semiconductor wafer.

[0033] <Thinning process> The thinning process of this embodiment will be described below.

[0034] The method for producing a wafer of the present embodiment preferably further includes, before the peeling step of the present embodiment, a thinning step of obtaining the structure (A) by thinning the wafer (b) in the structure (B) which includes a support member, a cured film of the temporary fixing composition, and the wafer (b) in this order.

[0035] <Curing process> The curing step of this embodiment will be described below.

[0036] The method for producing a wafer of this embodiment preferably further includes, before the thinning step of this embodiment, a curing step of irradiating light onto a structure (C) including a support member, a temporary fixing film made of a temporary fixing composition, and a wafer (b) in this order, to cure the temporary fixing film, thereby obtaining a structure (B).

[0037] <Temporary fixing composition> The temporary fixing composition of this embodiment will be described below.

[0038] The temporary fixing composition of the present embodiment preferably contains a polymerizable component (A) containing a (meth)acrylate, a photoradical polymerization initiator (B), and an ultraviolet absorber (C).

[0039] From the viewpoint of suppressing contamination by carbon particles, the content of carbon particles in the temporary fixing composition of this embodiment is preferably 1.0 mass % or less, more preferably 0.1 mass % or less, even more preferably 0.01 mass % or less, even more preferably 0.001 mass % or less, and even more preferably 0.0001 mass % or less. That is, the temporary fixing composition of the present embodiment preferably does not contain carbon particles as a blending component, and even if it contains a small amount of carbon particles as a blending component, the amount is preferably not more than the above upper limit. The carbon particles contained as a compounding component in the temporary fixing composition of this embodiment include, for example, carbon black, hard carbon, soft carbon, graphite, etc., and are mainly carbon black.

[0040] (Polymerizable component (A) containing (meth)acrylate) The (meth)acrylate-containing polymerizable component (A) of this embodiment will be described below.

[0041] The (meth)acrylate-containing polymerizable component (A) of the present embodiment preferably contains one or more selected from the group consisting of monofunctional (meth)acrylates and polyfunctional (meth)acrylates, and more preferably contains one or more selected from the group consisting of monofunctional (meth)acrylates and bifunctional (meth)acrylates.

[0042] The polyfunctional (meth)acrylate of the present embodiment refers to a bifunctional or higher functional (meth)acrylate. The bifunctional (meth)acrylate will be described later. Examples of trifunctional (meth)acrylates include ethylene oxide isocyanurate modified tri(meth)acrylate, pentaerythritol tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, and tris[(meth)acryloyloxyethyl]isocyanurate. Examples of tetrafunctional or higher (meth)acrylates include ditrimethylolpropane tetra(meth)acrylate, dimethylolpropane tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, pentaerythritol ethoxy tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, and dipentaerythritol hexa(meth)acrylate.

[0043] The polyfunctional (meth)acrylate of the present embodiment may be a polyfunctional (meth)acrylate monomer or a polyfunctional (meth)acrylate polymer, or a mixture thereof, but preferably includes a polyfunctional (meth)acrylate polymer, more preferably includes a (meth)acrylic group-containing polybutyl (meth)acrylate, and even more preferably includes an acrylic group-containing polybutyl acrylate. (Meth)acrylic group-containing polybutyl(meth)acrylate can be produced by, for example, the methods described in JP-A Nos. 61-207478, 61-31330, 10-278207, 9-40741, and 8-357621. In this embodiment, the weight-average molecular weight of the polyfunctional (meth)acrylate polymer is preferably 5,000 or more and 500,000 or less, more preferably 10,000 or more and 300,000 or less, even more preferably 30,000 or more and 200,000 or less, and even more preferably 50,000 or more and 100,000 or less. When the weight-average molecular weight is within the above range, the viscosity of the temporary fixing composition and the crosslink density of the cured product can be within preferred ranges. In this embodiment, the weight-average molecular weight of the polyfunctional (meth)acrylate polymer is a value measured by gel permeation chromatography (GPC) in terms of standard polystyrene. Specifically, for example, the weight-average molecular weight can be determined by using tetrahydrofuran as a solvent, a GPC system (SC-8010 manufactured by Tosoh Corporation), and creating a calibration curve using commercially available standard polystyrene under the following conditions: Flow rate: 1.0ml / min Set temperature: 40℃ Column configuration: One Tosoh "TSK guardcolumn MP (xL)" 6.0 mm ID x 4.0 cm, and two Tosoh "TSK-GELMULTIPOREHXL-M" 7.8 mm ID x 30.0 cm (16,000 theoretical plates), for a total of three columns (total theoretical plate count: 32,000). Sample injection volume: 100 μl (sample solution concentration 1 mg / ml) Liquid delivery pressure: 39 kg / cm 2 Detector: RI detector

[0044] The (meth)acrylate-containing polymerizable component (A) of the present embodiment preferably contains one or more selected from the group consisting of monofunctional alkyl (meth)acrylates having an alkyl group, aromatic (meth)acrylates, alicyclic bifunctional (meth)acrylates, and acyclic bifunctional (meth)acrylates, and from the viewpoint of being able to provide a rigid structure, more preferably contains one or more selected from the group consisting of aromatic (meth)acrylates and alicyclic bifunctional (meth)acrylates, and even more preferably contains an aromatic (meth)acrylate.

[0045] The alkyl group of the monofunctional alkyl (meth)acrylate having an alkyl group of this embodiment (hereinafter, may be simply referred to as the alkyl group of this embodiment) preferably includes one or more types selected from the group consisting of a linear alkyl group, a branched alkyl group, and an alicyclic alkyl group.

[0046] The alkyl group of this embodiment preferably contains an alkyl group having 18 to 40 carbon atoms, and more preferably an alkyl group having 18 to 32 carbon atoms. This can enhance the aliphatic hydrocarbon properties of the polymerizable component (A) containing the (meth)acrylate of this embodiment (preferably the aliphatic hydrocarbon properties of the entire system), thereby improving low volatility, chemical resistance, and heat resistance.

[0047] The alkyl group of this embodiment preferably includes one or more selected from the group consisting of branched alkyl groups and alicyclic alkyl groups, and more preferably includes one or more selected from the group consisting of branched alkyl groups and cycloalkyl groups such as isostearyl groups, isotetracosanyl groups (e.g., 2-decyl-1-tetradecanyl groups), and isotriacontanyl groups (e.g., 2-tetradecyl-1-octadecanyl groups), etc. This can improve the compatibility of the polymerizable component (A) containing the (meth)acrylate of this embodiment with other components.

[0048] The monofunctional alkyl (meth)acrylate having an alkyl group of the present embodiment preferably includes one or more selected from the group consisting of stearyl (meth)acrylate, isostearyl (meth)acrylate, behenyl (meth)acrylate, 2-decyl-1-tetradecanyl (meth)acrylate, 2-dodecyl-1-hexadecanyl (meth)acrylate, and 2-tetradecyl-1-octadecanyl (meth)acrylate, more preferably includes one or more selected from the group consisting of stearyl (meth)acrylate and isostearyl (meth)acrylate, and even more preferably includes isostearyl (meth)acrylate.

[0049] The aromatic (meth)acrylate of the present embodiment is preferably 9,9-bis[4-(2-hydroxy C1-C 20 9,9-bis[4-(2-(meth)acryloyloxy)C1-C alkoxyphenyl]fluorene di(meth)acrylate 20 alkoxy)phenyl)]fluorene, C1-C 20 Alkoxylated bisphenol A di(meth)acrylate, benzyl di(meth)acrylate, 1,3-bis(2-(meth)acryloyloxy)C1-C 20 The compound preferably contains one or more selected from the group consisting of 9,9-bis[4-(2-(meth)acryloyloxy)C1-C alkyl]benzene, 2,2-bis(4-(meth)acryloxydiethoxyphenyl)propane, nonylphenol ethylene oxide modified (meth)acrylate, and structural isomers thereof, and more preferably contains 9,9-bis[4-(2-(meth)acryloyloxy)C1-C alkyl]benzene, 2,2-bis(4-(meth)acryloxydiethoxyphenyl)propane, nonylphenol ethylene oxide modified (meth)acrylate, and structural isomers thereof. 20 The compound preferably contains one or more selected from the group consisting of 9,9-bis[4-(2-acryloyloxyethoxy)phenyl)]fluorene and nonylphenol ethylene oxide-modified (meth)acrylate, and more preferably contains one or two selected from the group consisting of 9,9-bis[4-(2-acryloyloxyethoxy)phenyl)]fluorene and nonylphenol ethylene oxide-modified acrylate.

[0050] The alicyclic bifunctional (meth)acrylate of the present embodiment is preferably a C1 to C6 alicyclic (meth)acrylate from the viewpoint of providing a rigid structure. 20 Alkoxylated hydrogenated bisphenol A di(meth)acrylate, 1,3-di(meth)acryloyloxyadamantane, tricyclo C 10 ~C 20 Alkanedimethanol di(meth)acrylate, dicyclo C5-C 20 The compound includes one or more selected from the group consisting of di(meth)acrylates and structural isomers thereof, and more preferably C1 to C 20 It includes alkoxylated hydrogenated bisphenol A di(meth)acrylate, and more preferably includes ethoxylated hydrogenated bisphenol A di(meth)acrylate.

[0051] The acyclic bifunctional (meth)acrylate of the present embodiment preferably includes one or more selected from the group consisting of 1,3-butanediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, neopentyl glycol-modified trimethylolpropane di(meth)acrylate, stearic acid-modified pentaerythritol di(meth)acrylate, tripropylene glycol di(meth)acrylate, and caprolactone-modified hydroxypivalic acid neopentyl glycol di(meth)acrylate, and more preferably includes 1,10-decanediol di(meth)acrylate.

[0052] The content of the polymerizable component (A) containing a (meth)acrylate in the temporary fixing composition of this embodiment is preferably 50% by mass or more and 99% by mass or less, more preferably 60% by mass or more and 99% by mass or less, more preferably 70% by mass or more and 99% by mass or less, even more preferably 80% by mass or more and 99% by mass or less, and even more preferably 85% by mass or more and 99% by mass or less, relative to 100% by mass of the temporary fixing composition of this embodiment.

[0053] (Photoradical polymerization initiator (B)) The photoradical polymerization initiator (B) of this embodiment will be described below.

[0054] The photoradical polymerization initiator (B) of this embodiment is a compound whose molecules are cleaved and split into two or more radicals when irradiated with, for example, ultraviolet light or visible light (for example, a wavelength of 350 to 700 nm, preferably 365 to 500 nm, more preferably 385 to 450 nm).

[0055] The photoradical polymerization initiator (B) of this embodiment may be, from the viewpoint of a balance between suppressing re-adhesion, improving the reaction rate, and improving the heat resistance after curing, for example, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis(η5-2,4-cyclopentadiene-1-yl)-bis(2,6-difluoro-3-(1H-pyrrol-1-yl)-phenyl)titanium, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholin-4-ylphenyl)-butan-1-one, 1-[ The compound contains one or more compounds selected from the group consisting of 4-(phenylthio)phenyl]-1,2-octanedione 2-O-benzoyloxime and 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone 1-(O-acetyloxime), preferably one or more compounds selected from the group consisting of bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide and 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone 1-(O-acetyloxime), more preferably bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide.

[0056] The content of the photoradical polymerization initiator (B) in the temporary fixing composition of this embodiment is preferably 0.1 parts by mass or more and 10 parts by mass or less, more preferably 0.5 parts by mass or more and 5.0 parts by mass or less, even more preferably 1.0 parts by mass or more and 3.0 parts by mass or less, and even more preferably 1.2 parts by mass or more and 2.0 parts by mass or less, relative to 100 parts by mass of the polymerizable component (A) containing the (meth)acrylate of this embodiment, from the viewpoint of a balance between suppressing re-sticking, improving the reaction rate, and improving the heat resistance after curing.

[0057] (Ultraviolet absorber (C)) The ultraviolet absorbent (C) of this embodiment will be described below.

[0058] From the viewpoints of suppressing re-adhesion, the degree of overlap of the UV absorption wavelength region with the UV laser wavelength, and the balance of UV absorption properties at the same wavelength, the ultraviolet absorber (C) of the present embodiment preferably has one or more skeletons selected from the group consisting of a benzophenone skeleton, a triazole skeleton (preferably a benzotriazole skeleton), a hydroxyphenyltriazine skeleton, and a phenol skeleton (preferably a hindered phenol skeleton), more preferably one or more skeletons selected from the group consisting of a benzophenone skeleton and a triazole skeleton (preferably a benzotriazole skeleton), and even more preferably one or more skeletons selected from the group consisting of a benzophenone skeleton and a benzotriazole skeleton.

[0059] The ultraviolet absorber (C) of this embodiment preferably has a polymerizable functional group.

[0060] The polymerizable functional group of this embodiment is preferably present at the terminal of the ultraviolet absorber (C) of this embodiment.

[0061] The polymerizable functional group in this embodiment is preferably a (meth)acryloyl group.

[0062] The content of the ultraviolet absorber (C) in the temporary fixing composition of this embodiment, relative to 100 parts by mass of the polymerizable component (A) containing a (meth)acrylate of this embodiment, is preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, even more preferably 1.0 parts by mass or more, even more preferably 1.5 parts by mass or more, even more preferably 2.0 parts by mass or more, and even more preferably 2.5 parts by mass or more, from the viewpoint of improving heat resistance and durability, it is preferably 20 parts by mass or less, more preferably 15 parts by mass or less, and even more preferably 10 parts by mass or less, and from the viewpoint of a balance between the prevention of re-sticking, the improvement of heat resistance, and the improvement of durability, it is preferably 0.1 parts by mass or more and 20 parts by mass or less, more preferably 0.5 parts by mass or more and 20 parts by mass or less, even more preferably 1.0 parts by mass or more and 15 parts by mass or less, even more preferably 1.5 parts by mass or more and 15 parts by mass or less, even more preferably 2.0 parts by mass or more and 10 parts by mass or less, and even more preferably 2.5 parts by mass or more and 10 parts by mass or less, from the viewpoint of a balance between the prevention of re-sticking, the improvement of heat resistance, and the improvement of durability.

[0063] (Other ingredients) The temporary fixing composition of the present embodiment may contain components other than those described above, and may contain known components such as, for example, a solvent, an antifoaming agent, a surfactant, a colorant, a polymerization inhibitor, a stabilizer, an adhesion modifier, a release agent, a filler, etc. The contents of these other components can be set arbitrarily as necessary.

[0064] (viscosity) Using an E-type viscometer, the temperature was 23°C and the shear rate was 75 s -1 The viscosity of the temporary fixing composition of this embodiment, measured by the above method, is preferably 100 mPa·s or more and 5000 mPa·s or less, more preferably 500 mPa·s or more and 4000 mPa·s or less, even more preferably 1000 mPa·s or more and 3000 mPa·s or less, even more preferably 1000 mPa·s or more and 2000 mPa·s or less, and still more preferably 1100 mPa·s or more and 1500 mPa·s or less. This can improve the workability when applying the temporary fixing composition of this embodiment.

[0065] 2. Method for removing the cured film of the temporary fixing composition Hereinafter, a method for removing the cured film of the temporary fixing composition of this embodiment will be described.

[0066] The method for removing a cured film of a temporary fixing composition of the present embodiment involves irradiating a structure (A) including a support member, a cured film of the temporary fixing composition, and a wafer (a) in this order with a UV laser having a wavelength of 300 nm or more and 385 nm or less from the support member side to decompose at least a part of the cured film of the temporary fixing composition, thereby generating carbon particles, peeling the wafer and the support member, and removing the cured film of the temporary fixing composition.

[0067] Although the embodiments of the present invention have been described above, these are merely examples of the present invention, and various other configurations can be adopted. Furthermore, the present invention is not limited to the above-described embodiments, and modifications and improvements within the scope of achieving the object of the present invention are included in the present invention. [Example]

[0068] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.

[0069] Unless otherwise stated, experiments were conducted at 23°C and 50% humidity.

[0070] <Examples 1 to 12 and Comparative Example 1> (Preparation of temporary fixing composition) The components were mixed at 60° C. in the compositions (units: parts by mass) shown in Tables 1 and 2 below to obtain temporary fixing compositions of the respective examples. The contents of each component are as follows.

[0071] The following was used as the (meth)acrylate-containing polymerizable component (A). A1 (acrylic group-containing polybutyl acrylate represented by the following chemical formula, weight average molecular weight: 72,000)

[0072] [ka]

[0073] A-BPEF-2 (9,9-bis[4-(2-acryloyloxyethoxy)phenyl)]fluorene, product name: NK Ester A-BPEF-2, manufactured by Shin-Nakamura Chemical Co., Ltd.) HBPE-4 (ethoxylated hydrogenated bisphenol A diacrylate represented by the following chemical formula, product name: HBPE-4, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.)

[0074] [ka]

[0075] A-DOD-N (1,10-decanediol diacrylate, product name: A-DOD-N, manufactured by Shin-Nakamura Chemical Co., Ltd.) M-113 (nonylphenol ethylene oxide modified acrylate, product name: Aronix M-113, manufactured by Toagosei Co., Ltd.) ISTA (Isostearyl acrylate, product name: ISTA, manufactured by Osaka Organic Chemical Industry Ltd.)

[0076] The following was used as the photoradical polymerization initiator (B). Omnirad 819 (bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, product name: Omnirad 819, manufactured by IGM Resins)

[0077] The following was used as the ultraviolet absorber (C). RUVA-93 (2-[2-hydroxy-5-[2-(methacryloyloxy)ethyl]phenyl]-2H-benzotriazole, product name: RUVA-93, manufactured by Otsuka Chemical Co., Ltd.) P-66 (2,2'-dihydroxy-4,4'-diacryloyloxybenzophenone, product name: DAINSORB P-66, manufactured by Daiwa Kasei Co., Ltd.)

[0078] (Ratio of carbon particle generation area) The ratio of the area where carbon particles were generated was determined by the following method 1. The results are shown in the following Tables 1 to 3. Microscopic images of Example 1 and Comparative Examples 1 and 3 are shown in Figures 1 to 3. (Method 1) A disk-shaped temporary fixing film (diameter 150 mm × thickness 50 μm) made of the temporary fixing composition was applied between a disk-shaped silicon wafer (manufactured by Silicon Technology Co., Ltd., surface: mirror finish, conductive type: P-type, diameter 150 mm × thickness 625 μm) and a disk-shaped glass support member (product name: Tempax Glass, manufactured by OPC Corporation, diameter 150 mm × thickness 700 μm), thereby bonding the silicon wafer and the glass support member. Next, under a nitrogen atmosphere, a UV-LED with a wavelength of 405 nm (device name: LPDCJ1A-48102W, manufactured by Altec, illuminance 100 mW / cm) was used. 2 , irradiation time 50 seconds, cumulative light intensity 5000mJ / cm 2 The temporary fixing film was cured by irradiating the temporary fixing film with the light from the glass support member side, thereby obtaining a cured film. Next, the resulting cured film was irradiated from the glass support member side with a UV laser (device name: TWD-D3000, manufactured by Tatsumo Co., Ltd., YAG laser, output 6.5 W, spot diameter 150 μm, irradiation pitch 200 μm, scan speed 8 m / sec, frequency 40 kHz) having a wavelength of 355 nm, scanning the entire cured film. Next, the glass support member was peeled off from the silicon wafer, and the surface of the cured film side in the center part of the glass support member was observed and photographed at 20x magnification using an optical microscope (device name: MX-63L, manufactured by Evident). The area of ​​one field of view (200 μm × 200 μm) was taken as 100%, and the area (%) of the black part per field of view was calculated using image processing software (product name: Fiji, manufactured by the National Institutes of Health, USA) to determine the area (%) where carbon particles were generated.

[0079] (viscosity) Using an E-type viscometer (device name: DVNXHBCBG, manufactured by Brookfield, cone part number: CPA-40Z, rotation speed: 10 rpm), the temperature was 23°C, the shear rate was 75 s -1 The viscosity of the temporary fixing composition was measured by the following method. The results are shown in Tables 1 to 3 below.

[0080] (Transmittance of 355nm wavelength laser) The transmittance of the temporary fixing composition to a laser with a wavelength of 355 nm was determined by the following method 2. The results are shown in Tables 1 to 3 below. (Method 2) Two rectangular Tempax glass sheets (33 mm×50 mm, 700 μm thick) were prepared, and 0.1 g of the temporary fixing composition was dropped onto one of them, which was then sandwiched with the other. Next, the obtained laminate was irradiated with a UV-LED (device name: LPDCJ1A-48102W, manufactured by Altec Co., Ltd., illuminance: 100 mW / cm) with a wavelength of 405 nm under a nitrogen atmosphere. 2 , irradiation time 50 seconds, cumulative light intensity 5000mJ / cm 2 ) to cure the temporary fixing composition, thereby obtaining a test piece for transmittance measurement. Next, the transmittance of the obtained test piece for transmittance measurement was measured using a spectrophotometer (device name: UV-2550, manufactured by Shimadzu Corporation) at a pitch of 1.0 nm in a wavelength range of 300 to 800 nm. Next, the transmittance at 355 nm was read from the obtained transmittance data and used as the transmittance at a wavelength of 355 nm. Before measuring the transmittance, two rectangular Tempax glass sheets (33 mm × 50 mm, 700 μm thick) were prepared, 0.1 g of water was dropped onto one of them, and the other was sandwiched between them to obtain a test piece for baseline measurement. The baseline of the spectrophotometer was measured using the test piece for baseline measurement obtained.

[0081] (Peel strength P1 immediately after laser irradiation) The peel strength P1 immediately after laser irradiation was determined by the following method 3. The results are shown in the following Tables 1 to 3. The device used to measure the peel strength is shown in FIG. (Method 3) A disk-shaped temporary fixing film (diameter 150 mm × thickness 50 μm) made of the temporary fixing composition was applied between a disk-shaped silicon wafer (manufactured by Silicon Technology Co., Ltd., surface: mirror finish, conductive type: P-type, diameter 150 mm × thickness 625 μm) and a disk-shaped glass support member (product name: Tempax Glass, manufactured by OPC Corporation, diameter 150 mm × thickness 700 μm), thereby bonding the silicon wafer and the glass support member. Next, under a nitrogen atmosphere, a UV-LED with a wavelength of 405 nm (illuminance 100 mW / cm 2 , irradiation time 50 seconds, cumulative light intensity 5000mJ / cm 2 The temporary fixing film was cured by irradiating the temporary fixing film with the light from the glass support member side, thereby obtaining a cured film. Next, the resulting cured film was irradiated from the glass support member side with a UV laser (device name: TWD-D3000, manufactured by Tatsumo Co., Ltd., YAG laser, output 6.5 W, spot diameter 150 μm, irradiation pitch 200 μm, scan speed 8 m / sec, frequency 40 kHz) having a wavelength of 355 nm, scanning the entire cured film to obtain a laminate. Next, within 1 minute after the end of UV laser irradiation, the obtained laminate was placed and fixed on an adsorption table with the silicon wafer side facing down, and an adsorption arm equipped with three 10 mm diameter suction cups was attached to the glass support member. The adsorption arm was then pulled vertically upward at a speed of 0.5 mm / sec to peel off the glass support member. The load applied to the adsorption arm when the glass support member was lifted was measured and recorded as the peel strength P1 (N).

[0082] (Peel strength P2 10 minutes after laser irradiation is completed) The peel strength P2 was determined 10 minutes after completion of the laser irradiation by the following method 4. The results are shown in Tables 1 to 3 below. (Method 4) A disk-shaped temporary fixing film (diameter 150 mm × thickness 50 μm) made of the temporary fixing composition was applied between a disk-shaped silicon wafer (manufactured by Silicon Technology Co., Ltd., surface: mirror finish, conductive type: P-type, diameter 150 mm × thickness 625 μm) and a disk-shaped glass support member (product name: Tempax Glass, manufactured by OPC Corporation, diameter 150 mm × thickness 700 μm), thereby bonding the silicon wafer and the glass support member. Next, under a nitrogen atmosphere, a UV-LED with a wavelength of 405 nm (illuminance 100 mW / cm 2 , irradiation time 50 seconds, cumulative light intensity 5000mJ / cm 2 The temporary fixing film was cured by irradiating the temporary fixing film with the light from the glass support member side, thereby obtaining a cured film. Next, the resulting cured film was irradiated from the glass support member side with a UV laser (device name: TWD-D3000, manufactured by Tatsumo Co., Ltd., YAG laser, output 6.5 W, spot diameter 150 μm, irradiation pitch 200 μm, scan speed 8 m / sec, frequency 40 kHz) having a wavelength of 355 nm, scanning the entire cured film to obtain a laminate. Next, 10 minutes after the completion of the UV laser irradiation, the obtained laminate was placed and fixed on an adsorption table with the silicon wafer side facing down, and an adsorption arm equipped with three 10 mm diameter suction cups was attached to the glass support member. The adsorption arm was then pulled vertically upward at a speed of 0.5 mm / sec to peel off the glass support member. The load applied to the adsorption arm when the glass support member was lifted was measured and recorded as the peel strength P2 (N).

[0083] (P2 / P1) The ratio (P2 / P1) of the peel strength P2 measured 10 minutes after laser irradiation to the peel strength P1 measured immediately after laser irradiation was determined by the following method 5. The results are shown in Tables 1 to 3 below. (Method 5) A disk-shaped temporary fixing film (diameter 150 mm × thickness 50 μm) made of the temporary fixing composition was applied between a disk-shaped silicon wafer (manufactured by Silicon Technology Co., Ltd., surface: mirror finish, conductive type: P-type, diameter 150 mm × thickness 625 μm) and a disk-shaped glass support member (product name: Tempax Glass, manufactured by OPC Corporation, diameter 150 mm × thickness 700 μm), thereby bonding the silicon wafer and the glass support member. Next, under a nitrogen atmosphere, a UV-LED with a wavelength of 405 nm (illuminance 100 mW / cm 2 , irradiation time 50 seconds, cumulative light intensity 5000mJ / cm 2 The temporary fixing film was cured by irradiating the temporary fixing film with the light from the glass support member side, thereby obtaining a cured film. Next, the resulting cured film was irradiated from the glass support member side with a UV laser (device name: TWD-D3000, manufactured by Tatsumo Co., Ltd., YAG laser, output 6.5 W, spot diameter 150 μm, irradiation pitch 200 μm, scan speed 8 m / sec, frequency 40 kHz) having a wavelength of 355 nm, scanning the entire cured film to obtain a laminate. Next, within 1 minute after the end of UV laser irradiation, the obtained laminate was placed and fixed on an adsorption table with the silicon wafer side facing down, and an adsorption arm equipped with three 10 mm diameter suction cups was attached to the glass support member. The adsorption arm was then pulled vertically upward at a speed of 0.5 mm / sec to peel off the glass support member. The load applied to the adsorption arm when the glass support member was lifted was measured and recorded as the peel strength P1 (N). Next, a laminate was obtained under the same conditions as above, and 10 minutes after the completion of UV laser irradiation, the obtained laminate was placed and fixed on an adsorption table with the silicon wafer side facing down. An adsorption arm equipped with three suction cups with a diameter of 10 mm was attached to the glass support member, and the adsorption arm was pulled vertically upward at a speed of 0.5 mm / sec to peel off the glass support member. The load applied to the adsorption arm when the glass support member was lifted was measured and recorded as the peel strength P2 (N). P2 / P1 was calculated from P1 and P2 calculated by the above method.

[0084] <Examples 13 to 18 and Comparative Examples 2 to 4> The same procedures as in Example 1 were carried out except that the components were mixed at 60°C in the compositions (units: parts by mass) shown in Table 3 below to obtain the temporary fixing compositions of each example, and that the laser irradiation conditions shown in Table 3 below were used.

[0085] [Table 1]

[0086] [Table 2]

[0087] [Table 3]

[0088] From the results of the examples, it can be seen that according to the wafer manufacturing method of the present embodiment, after bonding the wafer and the support member, re-adhesion between the wafer and the support member can be suppressed by a simple method in which the temporary fixing composition is irradiated with a UV laser to generate carbon particles for peeling. Furthermore, in the comparative example, the wafer could not be peeled from the support member 10 minutes after the UV laser irradiation was completed, and therefore it can be determined that the configuration of the "peeling step" of the present invention is not satisfied.

Claims

1. A method for manufacturing a wafer, comprising: A method for manufacturing a wafer, comprising: a peeling step of irradiating a structure (A) including a support member, a cured film of a temporary fixing composition, and a wafer (a) in this order with a UV laser having a wavelength of 300 nm or more and 385 nm or less from the support member side to decompose at least a part of the cured film of the temporary fixing composition to generate carbon particles, thereby peeling the wafer from the support member.

2. Before the peeling step, 2. The method for producing a wafer according to claim 1, further comprising a thinning step of obtaining the structure (A) by thinning the wafer (b) in a structure (B) including the support member, the cured film of the temporary fixing composition, and a wafer (b) in this order.

3. Before the thinning step, 3. The method for producing a wafer according to claim 2, further comprising a curing step of irradiating light to a structure (C) including the support member, a temporary fixing film made of the temporary fixing composition, and the wafer (b) in this order, to cure the temporary fixing film, thereby obtaining the structure (B).

4. 3. The method for producing a wafer according to claim 1, wherein the ratio of the area where the carbon particles are generated in the temporary fixing composition obtained by the following method 1 is 0.20% or more. (Method 1) A disk-shaped temporary fixing film (diameter 150 mm × thickness 50 μm) made of the temporary fixing composition is applied between a disk-shaped silicon wafer (diameter 150 mm × thickness 625 μm) and a disk-shaped glass support member (diameter 150 mm × thickness 700 μm), thereby bonding the silicon wafer and the glass support member. Next, under a nitrogen atmosphere, a UV-LED with a wavelength of 405 nm (illuminance 100 mW / cm ２ , irradiation time 50 seconds, cumulative light amount 5000 mJ / cm ２ ) is irradiated onto the temporary fixing film from the glass support member side to harden the temporary fixing film, thereby obtaining a hardened film. Next, the obtained cured film is irradiated from the glass support member side with a UV laser having a wavelength of 355 nm (YAG laser, output 6.5 W, spot diameter 150 μm, irradiation pitch 200 μm, scan speed 8 m / sec, frequency 40 kHz) so as to scan the entire cured film. Next, the glass support member was peeled off from the silicon wafer, and the surface of the central part of the glass support member on the side of the cured film was observed and photographed using an optical microscope at a magnification of 20 times. When the area of ​​one visual field (200 μm × 200 μm) was taken as 100%, the area (%) of the black part per visual field was calculated using image processing software, and this was defined as the area (%) where carbon particles were generated.

5. 3. The method for manufacturing a wafer according to claim 1, wherein a spot diameter of the UV laser in the peeling step is 60 μm or more and 500 μm or less.

6. 3. The method for manufacturing a wafer according to claim 1, wherein an output of the UV laser in the peeling step is 4.1 W or more and 50.0 W or less.

7. 3. The method for manufacturing a wafer according to claim 1, wherein the scanning speed of the UV laser in the peeling step is 0.1 m / s or more and 100 m / s or less.

8. The method for producing a wafer according to claim 1 or 2, wherein the thickness of the cured film is 0.1 μm or more and 500 μm or less.

9. The method for producing a wafer according to claim 1 or 2, wherein the cured film is a single layer.

10. 3. The method for producing a wafer according to claim 1, wherein the temporary fixing composition has a transmittance of 10.0% or less for a laser beam having a wavelength of 355 nm when the following method 2 is carried out: (Method 2) Two rectangular Tempax glass sheets (33 mm×50 mm, 700 μm thick) were prepared, and 0.1 g of the temporary fixing composition was dropped onto one of them, and the two sheets were sandwiched together. Next, the obtained laminate was irradiated with a UV-LED having a wavelength of 405 nm (illuminance 100 mW / cm) under a nitrogen atmosphere. ２ , irradiation time 50 seconds, cumulative light amount 5000 mJ / cm ２ ) to cure the temporary fixing composition, thereby obtaining a test piece for transmittance measurement. Next, the transmittance of the obtained test piece for transmittance measurement is measured using a spectrophotometer at a pitch of 1.0 nm in the wavelength range of 300 to 800 nm. Next, the transmittance at 355 nm is read from the obtained transmittance data and is defined as the transmittance at a wavelength of 355 nm.

11. 3. The method for manufacturing a wafer according to claim 1, wherein the temporary fixing composition contains a polymerizable component (A) containing a (meth)acrylate, a photoradical polymerization initiator (B), and an ultraviolet absorber (C).

12. 12. The method for producing a wafer according to claim 11, wherein the ultraviolet absorber (C) has one or more skeletons selected from the group consisting of a benzophenone skeleton, a triazole skeleton, a hydroxyphenyltriazine skeleton, and a phenol skeleton.

13. The method for producing a wafer according to claim 11 , wherein the ultraviolet absorber (C) has a polymerizable functional group.

14. The method for producing a wafer according to claim 13 , wherein the polymerizable functional group is present at an end of the ultraviolet absorber (C).

15. The method for producing a wafer according to claim 13 , wherein the polymerizable functional group includes a (meth)acryloyl group.

16. 12. The method for producing a wafer according to claim 11, wherein the content of the ultraviolet absorber (C) is 0.1 parts by mass or more and 20 parts by mass or less relative to 100 parts by mass of the polymerizable component (A) containing the (meth)acrylate.

17. The method for producing a wafer according to claim 11, wherein the content of the polymerizable component (A) containing the (meth)acrylate is 50% by mass or more and 99% by mass or less with respect to 100% by mass of the temporary fixing composition.

18. 12. The method for producing a wafer according to claim 11, wherein the content of the photoradical polymerization initiator (B) is 0.1 parts by mass or more and 10 parts by mass or less relative to 100 parts by mass of the polymerizable component (A) containing the (meth)acrylate.

19. Using an E-type viscometer, the temperature was 23°C and the shear rate was 75 s －１ 3. The method for manufacturing a wafer according to claim 1, wherein the viscosity of the temporary fixing composition measured by a .times. ...

20. The peel strength P of the temporary fixing composition immediately after laser irradiation by the following method 3 １ 3. The method for manufacturing a wafer according to claim 1, wherein the force is 0.01 N or more and 30.0 N or less. (Method 3) A disk-shaped temporary fixing film (diameter 150 mm × thickness 50 μm) made of the temporary fixing composition is applied between a disk-shaped silicon wafer (diameter 150 mm × thickness 625 μm) and a disk-shaped glass support member (diameter 150 mm × thickness 700 μm), thereby bonding the silicon wafer and the glass support member. Next, under a nitrogen atmosphere, a UV-LED with a wavelength of 405 nm (illuminance 100 mW / cm ２ , irradiation time 50 seconds, cumulative light amount 5000 mJ / cm ２ ) is irradiated onto the temporary fixing film from the glass support member side to harden the temporary fixing film, thereby obtaining a hardened film. Next, the obtained cured film is irradiated from the glass support member side with a UV laser having a wavelength of 355 nm (YAG laser, output 6.5 W, spot diameter 150 μm, irradiation pitch 200 μm, scan speed 8 m / sec, frequency 40 kHz) so as to scan the entire cured film, thereby obtaining a laminate. Next, within one minute after the end of the UV laser irradiation, the obtained laminate was placed and fixed on a suction table with the silicon wafer side facing downwards, a suction arm equipped with three suction cups with a diameter of 10 mm was attached to the glass support member, and the suction arm was vertically pulled upward at a speed of 0.5 mm / sec to peel off the glass support member. The load applied to the suction arm when the glass support member was lifted was measured, and the peel strength P １ Let (N).

21. The peel strength P of the temporary fixing composition according to the following method 4 10 minutes after the completion of the laser irradiation ２ 3. The method for manufacturing a wafer according to claim 1, wherein the force is 0.01 N or more and 50.0 N or less. (Method 4) A disk-shaped temporary fixing film (diameter 150 mm × thickness 50 μm) made of the temporary fixing composition is applied between a disk-shaped silicon wafer (diameter 150 mm × thickness 625 μm) and a disk-shaped glass support member (diameter 150 mm × thickness 700 μm), thereby bonding the silicon wafer and the glass support member. Next, under a nitrogen atmosphere, a UV-LED with a wavelength of 405 nm (illuminance 100 mW / cm ２ , irradiation time 50 seconds, cumulative light amount 5000 mJ / cm ２ ) is irradiated onto the temporary fixing film from the glass support member side to harden the temporary fixing film, thereby obtaining a hardened film. Next, the obtained cured film is irradiated from the glass support member side with a UV laser having a wavelength of 355 nm (YAG laser, output 6.5 W, spot diameter 150 μm, irradiation pitch 200 μm, scan speed 8 m / sec, frequency 40 kHz) so as to scan the entire cured film, thereby obtaining a laminate. Next, 10 minutes after the completion of the UV laser irradiation, the obtained laminate was placed and fixed on a suction table with the silicon wafer side facing downwards, and a suction arm equipped with three suction cups with a diameter of 10 mm was attached to the glass support member. The suction arm was then vertically pulled upward at a speed of 0.5 mm / sec to peel off the glass support member. The load applied to the suction arm when the glass support member was lifted was measured, and the peel strength P ２ Let (N).

22. The peel strength P of the temporary fixing composition immediately after laser irradiation by the following method 5 １ Peel strength P after 10 minutes of laser irradiation ２ The ratio (P ２ / P １ 3. The method for producing a wafer according to claim 1, wherein the value of the surface roughness (μm) is 2.0 or less. (Method 5) A disk-shaped temporary fixing film (diameter 150 mm × thickness 50 μm) made of the temporary fixing composition is applied between a disk-shaped silicon wafer (diameter 150 mm × thickness 625 μm) and a disk-shaped glass support member (diameter 150 mm × thickness 700 μm), thereby bonding the silicon wafer and the glass support member. Next, under a nitrogen atmosphere, a UV-LED with a wavelength of 405 nm (illuminance 100 mW / cm ２ , irradiation time 50 seconds, cumulative light amount 5000 mJ / cm ２ ) is irradiated onto the temporary fixing film from the glass support member side to harden the temporary fixing film, thereby obtaining a hardened film. Next, the obtained cured film is irradiated from the glass support member side with a UV laser having a wavelength of 355 nm (YAG laser, output 6.5 W, spot diameter 150 μm, irradiation pitch 200 μm, scan speed 8 m / sec, frequency 40 kHz) so as to scan the entire cured film, thereby obtaining a laminate. Next, within one minute after the end of the UV laser irradiation, the obtained laminate was placed and fixed on a suction table with the silicon wafer side facing downwards, a suction arm equipped with three suction cups with a diameter of 10 mm was attached to the glass support member, and the suction arm was vertically pulled upward at a speed of 0.5 mm / sec to peel off the glass support member. The load applied to the suction arm when the glass support member was lifted was measured, and the peel strength P １ Let (N). Next, a laminate was obtained under the same conditions as above, and 10 minutes after the completion of the UV laser irradiation, the obtained laminate was placed and fixed on a suction table with the silicon wafer side facing downwards. A suction arm equipped with three suction cups with a diameter of 10 mm was attached to the glass support member, and the suction arm was vertically pulled upward at a speed of 0.5 mm / sec to peel off the glass support member. The load applied to the suction arm when the glass support member was lifted was measured, and the peel strength P ２ Let (N). P calculated by the above method １ and P ２ From P ２ / P １ Calculate.

23. The method for manufacturing a wafer according to claim 1 or 2, wherein the support member comprises a glass support member.

24. The method for manufacturing a wafer according to claim 1 or 2, wherein the wafer comprises a semiconductor wafer.

25. A method for removing a cured film of a temporary fixing composition, comprising: A method for removing a cured film of a temporary fixing composition, comprising: irradiating a structure (A) including a support member, a cured film of the temporary fixing composition, and a wafer (a) in this order with a UV laser having a wavelength of 300 nm or more and 385 nm or less from the support member side to decompose at least a part of the cured film of the temporary fixing composition to generate carbon particles, thereby peeling the wafer and the support member apart and removing the cured film of the temporary fixing composition.

26. A method for manufacturing a wafer, comprising: a peeling step of irradiating a structure (A) having a support member, a cured film of a composition, and a wafer (a) in this order with a UV laser having a wavelength of 300 nm or more and 385 nm or less from the support member side to decompose at least a portion of the cured film of the composition, thereby generating carbon particles and peeling the wafer from the support member.

27. A method for removing a cured film of a composition, comprising: irradiating a structure (A) having a support member, a cured film of a composition, and a wafer (a) in this order with a UV laser having a wavelength of 300 nm or more and 385 nm or less from the support member side to decompose at least a portion of the cured film of the composition, thereby generating carbon particles, peeling the wafer and the support member, and removing the cured film of the composition.

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