Temporary-fixing composition, temporary-fixing method, and method for manufacturing semiconductor wafer

Abstract

A temporary-fixing composition according to the present invention contains a polymerizable monomer (A) and a photoradical polymerization initiator (B), and satisfies the following condition 1. (Condition 1) The temporary-fixing composition is applied to a silicon wafer (150 mm in diameter and 625 μm in thickness) to a thickness of 50 μm by spin coating, and is formed into a film. Then, a glass base material (700 μm in thickness) is laminated on the coating film of the temporary-fixing composition under vacuum. Then, under a nitrogen atmosphere, the temporary-fixing composition is irradiated from the surface thereof on the glass base material side with light under conditions of a wavelength of 405 nm, an illuminance of 350 mW / cm2, and a cumulative irradiation dose of 5,600 mJ / cm2, thereby curing the temporary-fixing composition and obtaining a joined body. The joined body is placed in a vacuum chamber at 23°C, and heating is started at the temperature rise rate of 33°C / min at 20 Pa or less. When heated to and held at 350°C at 20 Pa or less, peeling does not occur in the joined body 30 minutes after reaching 350°C.

Description

Temporary fixing composition, temporary fixing method, and method for manufacturing semiconductor wafers

[0001] The present invention relates to a temporary fixing composition, a temporary fixing method, and a method for manufacturing a semiconductor wafer. More specifically, it relates to a temporary fixing composition, a composition, a cured product, a film, a structure, a temporary fixing method, and a method for manufacturing a semiconductor wafer.

[0002] In the manufacture of electronic devices, wafer-type substrates with a thickness of several hundred micrometers are commonly used, obtained by using inorganic materials such as silicon as the substrate and applying processes such as insulating film formation, circuit formation, and thinning by grinding to the surface. However, since many substrates are made of brittle and easily broken materials, measures to prevent damage are necessary, especially during thinning by grinding. Conventionally, this measure involves applying a temporary fixing protective tape, which can be peeled off after the processing is completed, to the side opposite the surface to be ground (also called the back surface). This tape uses an organic resin film as its base material, and while it is flexible, its strength and heat resistance are insufficient, making it unsuitable for use in processes involving high temperatures.

[0003] Therefore, a system has been proposed that provides sufficient durability to the conditions of processes such as backside grinding and backside electrode formation by bonding the substrate for electronic devices to a support member such as silicon or glass via an adhesive. What is important in this process is the adhesive layer used when bonding the substrate to the support member. This layer must be able to bond the substrate to the support member without any gaps, have sufficient durability to withstand subsequent processes, and finally, allow the thinned wafer to be easily peeled off the support member, i.e., allow for temporary fixing.

[0004] Specifically, the processing of such wafers mainly involves spin coating, vacuum bonding and photocuring, thinning by grinding and polishing, high-temperature processing, laser stripping, and removal of the temporary fixative. Therefore, the temporary fixative must have properties suitable for these processes.

[0005] For example, in the spin coating process, good applicability is required to uniformly form a film of temporary fixative on the wafer. In the vacuum bonding and photocuring processes, the temporary fixative needs to be able to cure quickly by light irradiation such as ultraviolet (UV) on a support member such as glass, and to have low outgassing properties. In the thinning process, in order to avoid damage caused by localized application of the grinding machine load to the substrate, the temporary fixative needs to have an appropriate hardness that can distribute the load in the in-plane direction while preventing localized sinking of the substrate and maintaining flatness. In addition, adhesive strength to the support member, an appropriate high modulus of elasticity to protect the edges, and chemical resistance are also required. In the high-temperature processing process, the temporary fixative needs to have heat resistance that can withstand long-term high-temperature processing in a vacuum (for example, 300°C to 400°C for more than one hour). In the laser peeling process, the temporary fixative needs to be able to be peeled off at high speed by a laser such as a UV laser. In the removal process, the substrate must be easily detachable from the support material, and the material must also have good adhesion properties to prevent adhesive residue from remaining on the substrate after detachment, as well as be easy to clean.

[0006] For example, Patent Document 1 discloses a technique that focuses on the peelability of temporary fixatives and involves irradiating an adhesive containing a light-absorbing substance with high-intensity light to decompose the adhesive layer and peel it off from the support. Also, for example, Patent Document 2 discloses a technique that uses a heat-meltable hydrocarbon compound as an adhesive and performs bonding and peeling in a heated and molten state.

[0007] Japanese Patent Publication No. 2004-064040 Japanese Patent Publication No. 2006-328104

[0008] However, with the increasing sophistication and miniaturization of electronic devices in recent years, there is a demand for improved functionality in various properties due to changes in the manufacturing process. Conventional temporary fixatives, such as those disclosed in Patent Documents 1 and 2, have room for improvement in terms of heat resistance, while still achieving good peelability during the manufacturing process. The object of the present invention is to obtain a temporary fixative composition that can improve heat resistance while achieving good peelability.

[0009] According to the present invention, the following temporary fixing compositions, temporary fixing methods, methods for manufacturing semiconductor wafers, and technologies related thereto are provided.

[0010] [1] A temporary fixation composition comprising a polymerizable monomer (A) and a photoradical polymerization initiator (B), wherein the temporary fixation composition satisfies the following condition 1. (Condition 1) The temporary fixation composition is applied to a silicon wafer (diameter 150 mm, thickness 625 μm) to a thickness of 50 μm by spin coating to form a film. Next, a glass substrate (thickness 700 μm) is laminated on the coated film of the temporary fixation composition under vacuum. Next, under a nitrogen atmosphere, a wavelength of 405 nm and an illuminance of 350 mW / cm are applied from the surface on the glass substrate side. ２ Total irradiation dose: 5,600 mJ / cm² ２ The temporary fixing composition is cured by light irradiation under the following conditions to obtain a bond. The bond is placed in a vacuum chamber at 23°C, heating is started at a rate of 33°C / min with a pressure of 20 Pa or less, and the temperature is raised to 350°C while maintaining a pressure of 20 Pa or less. After 30 minutes from reaching 350°C, no delamination occurs in the bond. [2] The temporary fixing composition described in [1], further wherein the cured product obtained by the following procedure 1 satisfies the following condition 2. (Procedure 1) The temporary fixing composition is formed into a film by sandwiching it between two polyethylene terephthalate films (thickness 50 μm), and irradiated with ultraviolet light (UV-LED) with a wavelength of 405 nm at a temperature of 23°C at an intensity of 100 mW / cm ２ For 50 seconds (5000 mJ / cm²) ２ ) A cured material with a thickness of 70 μm is produced by irradiation. (Condition 2) The absorbance of the temporary fixing composition and the absorbance of the cured material are measured and the reaction rate is determined by applying them to the following formula (1), and the reaction rate is 85% or more and 99% or less. Reaction rate (%) = {1 - (Bx / Ax) / (Bo / Ao)} Formula (1) (In formula (1), the symbols are as follows: Ao: Wavelength of the temporary fixing composition, 1720 cm －１ Absorbance Bo: Wavelength of the temporary fixing composition at 1635 cm －１ Absorbance Ax: Wavelength of the cured product at 1720 cm －１ Absorbance Bx: Wavelength of the cured product at 1635 cm －１Absorbance of) [3] A temporary fixing composition according to [1] or [2], wherein the 5% weight loss temperature of the cured product obtained by the procedure 1 is 300°C or more and 450°C or less. [4] A temporary fixing composition according to any one of [1] to [3], wherein the storage modulus E' at 200°C measured by a viscoelasticity measuring device of the cured product obtained by the procedure 1 is 3 MPa or more and 30 MPa or less. [5] A temporary fixing composition according to any one of [1] to [4], wherein the viscosity of the temporary fixing composition at 23°C is 2000 mPa·s or more and 30,000 mPa·s or less. [6] A temporary fixing composition according to any one of [1] to [5], wherein the polymerizable monomer (A) comprises a (meth)acrylate compound (a1). [7] A temporary fixing composition according to any one of [1] to [6], further comprising a release component (C). [8] A temporary fixing composition according to any one of [1] to [7], further comprising an inorganic filler (D). [9] A temporary fixing composition comprising a polymerizable monomer (A) and a photoradical polymerization initiator (B), wherein the polymerizable monomer (A) comprises a (meth)acrylate compound (a1), has a 10% weight loss temperature of 350°C or higher, and has a storage modulus E' at 200°C measured by a viscoelasticity measuring device of 3 MPa or more and 30 MPa or less.

[10] A temporary fixing method using a temporary fixing composition according to any one of [1] to [8], comprising the steps of: curing the temporary fixing composition by irradiating it with light and fixing it to an adherend; and peeling off the cured product obtained by curing the temporary fixing composition from the adherend by irradiating it with laser light.

[11] A cured product obtained by curing a temporary fixing composition according to any one of [1] to [8].

[12] A film made of a cured product obtained by curing a temporary fixing composition according to any one of [1] to [8], wherein a wafer is attached to one side of the film and a support member is attached to the other side of the film.

[13] A structure in which a wafer is attached to one side of the film described in

[12] and a support member is attached to the other side of the film.

[14] A method for manufacturing a semiconductor wafer using a temporary fixing composition described in any one of [1] to [8], comprising: a step of applying the temporary fixing composition to a wafer and / or a support member to laminate the wafer and the support member; a step of curing the temporary fixing composition by irradiating it with light to obtain a structure; and a step of irradiating the cured product of the temporary fixing composition of the structure with laser light to peel off the support member.

[15] A method for manufacturing a semiconductor wafer according to

[14] , wherein a semiconductor chip is mounted on the side of the wafer that is the cured product side of the temporary fixing composition.

[0011] According to the present invention, a temporary fixing composition and related technologies can be provided that can improve heat resistance while obtaining good peelability.

[0012] In this specification, the notation "a to b" in descriptions of numerical ranges means a or more and b or less, unless otherwise specified. For example, "1 to 5 mass%" means "1 mass% or more and 5 mass% or less." Furthermore, the lower and upper limits of a numerical range can be arbitrarily combined with the lower and upper limits of other numerical ranges.

[0013] Unless otherwise specified, each component and material exemplified herein may be used alone or in combination of two or more.

[0014] When the embodiments exemplified and preferred described herein constitute a set of options, any number of options can be extracted from that set, and the extracted options can be arbitrarily combined with embodiments described elsewhere. Embodiments that arbitrarily combine the matters described herein are also included in the present invention.

[0015] In this specification, the term "(meth)acrylic" refers to a concept that encompasses both acrylic and methacrylic. The same applies to similar terms such as "(meth)acrylate."

[0016] The term "temporary fixing composition" refers to a composition that can be cured to exert an adhesive function to achieve fixing, and has a function of being peelable from an adherend by physical or chemical methods after curing. Examples of the peeling method include a method of cutting bonds of polymers in the cured product by irradiating laser light to reduce fixing force, a thermal peeling method, and a method of swelling with a solvent.

[0017] Hereinafter, the composition used for temporary fixing will be described, but the composition of the present invention is not limited to use for temporary fixing.

[0018] <Temporary Fixing Composition> The temporary fixing composition of the present embodiment comprises a polymerizable monomer (A) and a photoradical polymerization initiator (B), and satisfies the following condition 1. This makes it possible to improve heat resistance while achieving good easy peelability of the temporary fixing composition.

[0019] (Condition 1) The temporary fixing composition is applied onto a silicon wafer (150 mm in diameter, 625 μm in thickness) by spin coating to a thickness of 50 μm to form a film. Next, a glass substrate (700 μm in thickness) is laminated on the coating film of the temporary fixing composition under vacuum. Then, under a nitrogen atmosphere, from the surface on the glass substrate side, a wavelength of 405 nm and an illuminance of 350 mW / cm ２ , an integrated irradiation dose of 5,600 mJ / cm ２ is irradiated under the conditions to cure the temporary fixing composition, thereby obtaining a joined body. When the joined body is placed in a vacuum chamber, heated at a temperature increase rate of 33°C / min under a pressure of 20 Pa or less, and heated to and held at 350°C while maintaining the pressure of 20 Pa or less, no peeling occurs in the joined body 30 minutes after the temperature reaches 350°C.

[0020] Furthermore, in condition 1, when the joined body is placed in a vacuum chamber, heated at a temperature increase rate of 33°C / min under vacuum (20 Pa or less), and heated to and held at 350°C under vacuum, it is preferable that no peeling occurs even 120 minutes after the temperature reaches 350°C. This allows further improvement of heat resistance.

[0021] Under Condition 1, when applying the temporary fixing composition onto a silicon wafer (150 mm diameter, 625 μm thickness) into a film with a thickness of 50 μm by spin coating, it is preferable to perform the step in an atmospheric environment. Spin coating refers to, for example, a method in which a liquid temporary fixing composition is dropped onto a silicon wafer, and the silicon wafer is rotated at a predetermined rotation speed to uniformly apply the temporary fixing composition onto the surface of the silicon wafer.

[0022] In addition, when placing the bonded body into a vacuum chamber, the bonded body is placed at room temperature, and the temperature is raised rapidly after the bonded body is placed. When placing the bonded body into the vacuum chamber, the initial pressure inside the chamber is set to 20 Pa or less, and the vacuum state is maintained by a vacuum pump. However, unavoidably, the degree of vacuum inside the vacuum chamber may decrease from the initial vacuum state as time passes.

[0023] Under Condition 1, each operation shall be performed promptly, and the interval between each operation shall also be short. For example, the spin coating takes about 20 seconds to 50 seconds; the bonding of the glass substrate onto the coating film, including the evacuation time, takes about 1 minute; and the light irradiation and curing takes about 1 minute. From spin coating to curing and obtaining the bonded body, it is preferable to perform all steps in one apparatus. This can prevent dust from entering, and suppress unevenness in the thickness of the film of the temporary fixing composition. However, after the bonded body is obtained, as long as it is stored under normal conditions (10 to 40°C), it may be stored for several days or longer.

[0024] In addition, the bonded body placed in the vacuum chamber is left to stand. The bonded body is left standing with the silicon wafer side facing down and the glass substrate side facing up.

[0025] The statement that no peeling occurs in the bonded body means that when the bonded body is observed from the glass substrate side, no change in appearance, particularly color tone, occurs at the interface between the glass substrate and the silicon wafer due to peeling. The observation may be performed visually, or may be performed while irradiating green light. Alternatively, the presence or absence of peeling may be confirmed by photographing the bonded body from above, analyzing the change in color tone through image analysis. In addition, peeling of the bonded body may refer to peeling occurring in a region within 2 mm from the outer edge of the bonded body.

[0026] The detailed reason why satisfying Condition 1 allows for improved heat resistance while maintaining good peelability is not entirely clear, but it is presumed that: Condition 1 assumes the photothermal history when an electronic device is manufactured using the temporary fixing composition of this embodiment. Therefore, by using Condition 1 as an indicator, it is thought that the heat resistance suitable for the manufacture of electronic devices can be controlled with greater precision.

[0027] Furthermore, the temporary fixing composition of this embodiment may include a polymerizable monomer (A) and a photoradical polymerization initiator (B), wherein the polymerizable monomer (A) may include a (meth)acrylate compound (a1), have a 10% weight loss temperature of 350°C or higher, and have a storage modulus E' at 200°C measured by a viscoelasticity measuring device of 3 MPa or more and 30 MPa or less. This makes it possible to improve the heat resistance while obtaining good peelability of the temporary fixing composition.

[0028] In this embodiment, it is preferable that the cured product obtained by the following procedure 1 satisfies the following condition 2. This enables the curing of the fixing composition at room temperature and further improves heat resistance.

[0029] (Procedure 1) The temporary fixing composition is formed into a film by sandwiching it between two polyethylene terephthalate films (50 μm thick), and then irradiated with ultraviolet light (UV-LED) with a wavelength of 405 nm at a temperature of 23°C at an intensity of 100 mW / cm². ２ For 50 seconds (5000 mJ / cm²) ２ ) A cured material with a thickness of 70 μm is produced by irradiation. (Condition 2) The absorbance of the temporary fixing composition and the absorbance of the cured material are measured and the reaction rate is determined by applying them to the following formula (1), and the reaction rate is 85% or more and 99% or less. Reaction rate (%) = {1 - (Bx / Ax) / (Bo / Ao)} Formula (1) (In formula (1), the symbols are as follows: Ao: Wavelength of the temporary fixing composition, 1720 cm －１ Absorbance Bo: Wavelength of the temporary fixing composition at 1635 cm －１ Absorbance Ax: Wavelength of the cured product at 1720 cm －１ Absorbance Bx: Wavelength of the cured product at 1635 cm－１ (absorbance)

[0030] In other words, the wavelength of the temporary fixing composition is 1720 cm. －１ The absorbance originates from the C=C carbonyl group, and the wavelength is 1635 cm. －１ The absorbance of this substance originates from the C=O group of the acrylic and is less susceptible to chemical changes, so it is used as an internal standard peak. Therefore, the wavelength is 1720 cm. －１ The absorbance is at a wavelength of 1635 cm. －１ By controlling the ratio of to the absorbance, the reaction rate of the temporary fixation composition can be controlled.

[0031] Under condition 2, the reaction rate is preferably 86% or higher, more preferably 88% or higher, and even more preferably 90% or higher.

[0032] The temporary fixing composition of this embodiment is further preferably such that the temperature at which the cured product obtained by the above procedure 1 has a 10% weight loss of 350°C or higher, and more preferably 370°C or higher. That is, a low weight loss rate due to heating of the cured product is intended to reduce degassing of the cured product during heating. As a result of reduced degassing during heating, peeling of the cured product becomes less likely, and thus high heat resistance of the cured product can be obtained. Heat resistance can be improved by setting the temperature at which the cured product has a 10% weight loss of 350°C or higher. On the other hand, the upper limit of the temperature at which the cured product has a 10% weight loss of 350°C or higher is not particularly limited, but it may be set to 420°C or lower in order to prevent the storage modulus of the cured product from becoming too high and reducing its stress relaxation properties.

[0033] The temporary fixing composition of this embodiment is further preferably such that the 5% weight loss temperature of the cured product obtained by the above procedure 1 is 300°C or higher, and more preferably 320°C or higher. By setting the 5% weight loss temperature of the cured product to be above the lower limit, the heat resistance can be improved. On the other hand, the upper limit of the 5% weight loss temperature of the cured product is not particularly limited, but it may be set to 400°C or lower in order to suppress the storage modulus of the cured product from becoming too high and reducing its stress relaxation properties.

[0034] The weight loss rate can be measured using a thermogravimetric analyzer.

[0035] Furthermore, the storage modulus E' at 200°C measured by a viscoelasticity measuring device for the cured product obtained by the above procedure 1 is preferably 3 MPa or more, more preferably 5 MPa or more, and even more preferably 7 MPa or more. Also, the storage modulus E' is preferably 30 MPa or less, more preferably 28 MPa or less, and even more preferably 22 MPa or less. Furthermore, the storage modulus E' at 200°C measured by a viscoelasticity measuring device for the cured product obtained by the above procedure 1 is preferably 3 MPa or more and 30 MPa or less, more preferably 5 MPa or more and 28 MPa or less, and even more preferably 7 MPa or more and 22 MPa or less. In other words, by setting the storage modulus E' of the cured product at 200°C to be above the above lower limit, it is possible to maintain heat resistance while suppressing excessive softening due to heat during the manufacturing process, which reduces adhesion to the substrate and causes peeling. It is also possible to suppress an increase in tack. On the other hand, by keeping the storage modulus E' of the cured material at 200°C below the above upper limit, heat resistance can be improved while obtaining appropriate flexibility at high temperatures, and adhesion can be enhanced by improving conformability to the wafer.

[0036] A temporary fixation composition that satisfies conditions 1 and 2 can be realized by selecting a polymerizable monomer (A) as described later, or by devising a combination of polymerizable monomer (A) and a photoradical polymerization initiator (B). Specifically, for example, polymerizable monomers (A) can be those with a highly rigid structure, those with high molecular symmetry, those with bonds of high bond energy, or those with an increased number of functional groups. Multiple types of polymerizable monomers (A) may be combined according to their properties.

[0037] (Viscosity) The viscosity of the temporary fixing composition of this embodiment at 23°C is preferably 2,000 mPa·s or more, more preferably 2,200 mPa·s or more. By setting the viscosity to be above the lower limit, good handling properties can be achieved. The viscosity of the temporary fixing composition of this embodiment at 23°C is preferably 30,000 mPa·s or less, more preferably 25,000 mPa·s or less, and even more preferably 20,000 mPa·s or less. By setting the viscosity to be below the upper limit, good applicability and workability can be obtained.

[0038] The viscosity can be measured using an E-type viscometer in accordance with JIS Z 8803:2011.

[0039] The following describes the components contained in the temporary fixation composition.

[0040] The temporary fixation composition of this embodiment comprises a polymerizable monomer (A) and a photoradical polymerization initiator (B).

[0041] [Polymerizable Monomer (A)] Polymerizable monomer (A) is a monomer having a polymerizable group. The polymerizable group is not particularly limited as long as it has an ethylenically unsaturated bond, but examples include one or more selected from the group consisting of (meth)acryloyl group, allyl group, isopropenyl group, 1-propenyl group, styryl group, styrylmethyl group, maleimide group, vinyl ether group and (meth)acrylamide group. Among these, allyl group, (meth)acryloyl group and maleimide group are preferred, and (meth)acryloyl group is more preferred.

[0042] Furthermore, the polymerizable monomer (A) may have a highly rigid structure within the molecule to improve heat resistance, and in this case, it is preferable that it has a cyclic structure. Specifically, examples include compounds having aromatic rings and alicyclic compounds. The alicyclic compound has a cyclic structure with 4 to 20 carbon atoms and may be any of monocyclic alkanes, bicyclic alkanes, or bicyclic alkenes.

[0043] The polymerizable monomer (A) may also be a polyfunctional monomer in order to improve heat resistance, and in this case, it is preferable that the polyfunctional monomer contains two or three or more polymerizable groups in one molecule.

[0044] Furthermore, the polymerizable monomer (A) may have improved molecular symmetry in order to improve heat resistance. For example, the ortho isomer has higher molecular symmetry than the meta isomer, and the para isomer has higher molecular symmetry than the ortho isomer.

[0045] Furthermore, the polymerizable monomer (A) may have at least one of a metal-oxygen bond or a metal-carbon bond, in order to improve heat resistance. Examples of metals include silicon and aluminum. Specifically, examples include C-Si bonds, O-Si bonds, and O-Al bonds. By using a monomer having a metal-oxygen bond, the thermal decomposition onset temperature in the high-temperature range of 350°C or higher can be further improved compared to the case of an organic skeleton alone. This is due to the fact that the bond energy of the Si-O bond is higher than that of the C-C bond. More specifically, polymerizable monomer (A) includes silicone (meth)acrylate compounds, maleimide-modified silicone compounds, and silicone oils. In this specification, polymerizable monomer (A) is an organic material, and an inorganic material that acquires monomer functionality by surface modification with polymerizable groups is referred to as the inorganic filler (D) described later.

[0046] ((meth)acrylate compound (a1)) The polymerizable monomer (A) preferably contains a (meth)acrylate compound (a1) having a (meth)acrylate group. The (meth)acrylate compound (a1) is a compound having only an acryloyl group, only a methacryloyl group, or both an acryloyl group and a methacryloyl group.

[0047] Examples of monofunctional (meth)acrylate monomers include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, pentyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, amyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, octyl (meth)acrylate, nonyl (meth)acrylate, dodecyl (meth)acrylate, hexadecyl (meth)acrylate, and octadecyl (meth)acrylate. methyl phosphate, cyclohexyl (meth)acrylate, methoxyethyl (meth)acrylate, butoxyethyl (meth)acrylate, phenoxyethyl (meth)acrylate, nonylphenoxyethyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, isobornyl (meth)acrylate, adamantyl mono (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate Tetrahydrofurfuryl (meth)acrylate, benzyl (meth)acrylate, phenyl (meth)acrylate, N-[2-(acryloyloxy)ethyl]phthalimide, N-[2-(acryloyloxy)ethyl]tetrahydrophthalimide, 2-(2-vinyloxyethoxy)ethyl (meth)acrylate, benzyl acrylate, benzyl methacrylate, tetrahydrofurfuryl acrylate, phenyl acrylate, phenylbenzyl acrylate, phenoxyacrylate, phenoxyethyl acrylate, Examples include phenoxyethoxyethyl acrylate, phenoxybenzyl acrylate, phenylphenoxyethyl acrylate, phenyl methacrylate, phenylbenzyl methacrylate, phenoxybenzyl methacrylate, biphenylmethyl methacrylate, phenol EO modified methacrylate, phenol PO modified methacrylate, nonylphenol EO modified methacrylate, nonylphenol PO modified methacrylate, phenylphenol EO modified methacrylate, or phenylphenol PO modified methacrylate.

[0048] Examples of difunctional (meth)acrylates include 1,3-di(meth)acryloyloxyadamantane, tricyclodecanedimethanol di(meth)acrylate, 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, dicyclopentanyl di(meth)acrylate, and neopentyl glycol-modified trimethylol proacrylate. Examples include pandi(meth)acrylate, stearic acid-modified pentaerythritol di(meth)acrylate, tripropylene glycol di(meth)acrylate, 2,2-bis(4-(meth)acryloxydiethoxyphenyl)propane, 2,2-bis(4-(meth)acryloxypropoxyphenyl)propane, 2,2-bis(4-(meth)acryloxytetraethoxyphenyl)propane, isocyanurate ethylene oxide-modified di(meth)acrylate, and 9,9-bis[4-(2-hydroxyethoxy)phenyl]ful orange (meth)acrylate.

[0049] Examples of trifunctional (meth)acrylates include ethylene oxide-modified isocyanurate tri(meth)acrylate, pentaerythritol tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, and tris[(meth)acryloyloxyethyl]isocyanurate.

[0050] Examples of (meth)acrylates with four or more functionalities include ditrimethylolpropanetetra(meth)acrylate, dimethylolpropanetetra(meth)acrylate, pentaerythritoltetra(meth)acrylate, pentaerythritolethoxytetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, and dipentaerythritol hexa(meth)acrylate.

[0051] In particular, the (meth)acrylate compound (a1) is more preferably having an alicyclic skeleton or an aromatic ring. For example, one or more polyfunctional (meth)acrylates having an alicyclic skeleton with 5 or more carbon atoms can be selected from tricyclodecanedimethanol di(meth)acrylate and 1,3-di(meth)acryloyloxyadamantane.

[0052] (Compounds having a maleimide group (a2)) The polymerizable monomer (A) may contain compounds having a maleimide group (a2). Compounds having a maleimide group (a2) include maleimide; alkylmaleimides such as methylmaleimide, ethylmaleimide, and cyclohexylmaleimide; arylmaleimides such as phenylmaleimide; 1,6-bis(maleimide)hexane, 1,10-bis(maleimide)decane, 1,3-phenylenebismaleimide, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethanebismaleimide, m-xylenebismaleimide, N,N'-bismaleimide-4 Examples of bismaleimides include 4'-diphenylmethane, 1,6-bismaleimide(2,2,4-trimethyl)hexane, 4-methyl-1,3-phenylenebismaleimide, 1,3-bis(3-maleimidephenoxy)benzene, 1,3-bis(4-maleimidephenoxy)benzene, 1,3-bis(citraconimidemethyl)benzene, bisphenol A diphenyl ether bismaleimide, and 2,2'-bis-[4-(4-maleimidephenoxy)phenyl]propane.

[0053] When polymerizable monomer (A) contains a (meth)acrylate compound (a1), the content of (meth)acrylate compound (a1) is preferably 50 parts by mass or more, more preferably 60 parts by mass or more, even more preferably 70 parts by mass or more, and especially preferably 80 parts by mass or more, when polymerizable monomer (A) is 100 parts by mass. Furthermore, when (meth)acrylate compound (a1) having an aromatic ring is included, the content of (meth)acrylate compound (a1) is preferably 50 parts by mass or more, more preferably 60 parts by mass or more, even more preferably 70 parts by mass or more, and especially preferably 80 parts by mass or more, when polymerizable monomer (A) is 100 parts by mass.

[0054] Furthermore, the polymerizable monomer (A) may be a combination of a (meth)acrylate compound (a1) and a compound that does not have a (meth)acryloyl group but has polymerizable groups other than a (meth)acryloyl group. For example, the polymerizable monomer (A) may be a combination of a (meth)acrylate compound (a1) and a compound (a2) having a maleimide group.

[0055] The molecular weight of the polymerizable monomer (A) is preferably 900 or less, and more preferably 800 or less.

[0056] [Photoradical polymerization initiator (B)] Photoradical polymerization initiator (B) refers to a compound whose molecule is cleaved and split into two or more radicals by irradiation with ultraviolet light or visible light (for example, wavelengths of 350 nm to 700 nm, preferably 385 nm to 700 nm or 365 nm to 500 nm, more preferably 385 nm to 450 nm). This can accelerate the curing of the temporary fixation composition.

[0057] The photoradical polymerization initiator (B) is preferably one that has absorption characteristics in a region different from the wavelength of the UV laser used in the UV laser stripping described later. Specifically, the photoradical polymerization initiator (B) is one or more selected from acylphosphine oxide compounds, titanocene compounds, or α-aminoalkylphenone compounds.

[0058] Examples of acylphosphine oxide compounds include bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide and 2,4,6-trimethylbenzoyldiphenylphosphine oxide. Among these, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide is preferred.

[0059] Examples of titanocene compounds include bis(η5-2,4-cyclopentadiene-1-yl)-bis(2,6-difluoro-3-(1H-pyrrole-1-yl)-phenyl)titanium.

[0060] Examples of α-aminoalkylphenone compounds include 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one and 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholin-4-ylphenyl)-butan-1-one.

[0061] Examples of oxime ester compounds include 1-[4-(phenylthio)phenyl]-1,2-octanedione 2-O-benzoyl oxime and 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]ethanone 1-(O-acetyl oxime). Among these, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]ethanone 1-(O-acetyl oxime) is preferred.

[0062] In particular, one or more selected from the group consisting of bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis(η5-2,4-cyclopentadien-1-yl)-bis(2,6-difluoro-3-(1H-pyrrole-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-[4-(phenylthio)phenyl]-1,2-octanedione 2-O-benzoyl oxime, and 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]ethanone 1-(O-acetyl oxime) are preferred.

[0063] The content of the photoradical polymerization initiator (B) is preferably 0.01 parts by mass or more, and more preferably 0.1 parts by mass or more, per 100 parts by mass of polymerizable monomer (A). On the other hand, the content of the photoradical polymerization initiator (B) is preferably 5 parts by mass or less, and more preferably 3 parts by mass or less. Furthermore, the content of the photoradical polymerization initiator (B) is preferably 0.01 to 5 parts by mass, and more preferably 0.1 to 3 parts by mass, per 100 parts by mass of polymerizable monomer (A). By setting the content of the photoradical polymerization initiator (B) to be above the lower limit, sufficient curability and heat resistance can be obtained. On the other hand, by setting the content of the photoradical polymerization initiator (B) to be below the upper limit, good low outgassing and heat resistance can be maintained.

[0064] The temporary fixation composition of this embodiment may further contain various components depending on the purpose, application, etc., in addition to the polymerizable monomer (A) and the photoradical polymerization initiator (B).

[0065] [Removal component (C)] The temporary fixation composition of this embodiment may further contain a removal component (C). The removal component (C) is not particularly limited as long as it can impart removable properties by laser removal after temporary fixation using the temporary fixation composition. In other words, it is preferable that the removal property is exhibited by generating radicals and breaking double bonds upon absorption of laser light. Examples of removal component (C) include compounds having a benzophenone skeleton, a benzotriazole skeleton, and a fluorene skeleton.

[0066] Examples of compounds having a benzophenone skeleton include 2-xanthencarboxy-4-dodecyloxybenzophenone and 2-o-nitrobenzyloxy-4-dodecyloxybenzophenone.

[0067] Examples of benzotriazole compounds include one or more selected from the group consisting of 2-(2H-benzotriazole-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol, 2,2'-methylenebis[6-(2H-benzotriazole-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol], 2-(2H-benzotriazole-2-yl)-6-(1-methyl-1-phenylethyl)-4-(1,1,3,3-tetramethylbutyl)phenol, and 2-[2-hydroxy-3-(3,4,5,6-tetrahydrophthalimidomethyl)-5-methylphenyl]benzotriazole.

[0068] Compounds containing a fluorene skeleton include those in which the hydrogen atoms at the 9,9 and 2,7 positions of fluorene are substituted with aliphatic or aromatic structures. This allows for the acquisition of absorption performance at specific wavelengths.

[0069] The content of the release component (C) is preferably 0.5 parts by mass or more, and more preferably 1.0 part by mass or more, per 100 parts by mass of polymerizable monomer (A). On the other hand, the content of the release component (C) is preferably 3 parts by mass or less, and more preferably 2.5 parts by mass or less. Furthermore, the content of the release component (C) is preferably 0.5 to 3 parts by mass, and more preferably 1.0 to 2.5 parts by mass, per 100 parts by mass of polymerizable monomer (A). A good laser release speed can be obtained by setting the content of the release component (C) to above the lower limit. On the other hand, good low outgassing and heat resistance can be maintained by setting the content of the release component (C) to below the upper limit.

[0070] [Inorganic Filler (D)] The temporary fixing composition of this embodiment may further contain an inorganic filler (D). The inorganic filler (D) is used to maintain release properties after exposure to high temperatures. The inorganic filler (D) is preferably one that has at least one of metal-oxygen bonds or metal-carbon bonds. Examples include oxides such as alumina, silica, titania, zirconia, magnesia, ceria, yttria, zinc oxide, and iron oxide; nitrides such as silicon nitride, titanium nitride, and boron nitride; carbides such as silicon carbide and calcium carbonate; sulfates such as magnesium sulfate and aluminum sulfate; hydroxides such as aluminum hydroxide and aluminum hydroxide oxide; silicates such as talc, kaolinite, decite, nacrite, halloysite, pyrophyllite, montmorillonite, sericite, mica, amethyst, bentonite, asbestos, zeolite, calcium silicate, magnesium silicate, diatomaceous earth, silica sand, and glass; and potassium titanate, with one or more selected from these. Furthermore, the inorganic filler (D) may be surface-modified with (meth)acrylate groups.

[0071] When an inorganic filler (D) is included, the content of the inorganic filler (D) is preferably 1 part by mass or more, and more preferably 2 parts by mass or more, per 100 parts by mass of polymerizable monomer (A). On the other hand, the content of the inorganic filler (D) is preferably 10 parts by mass or less, and more preferably 5 parts by mass or less. Furthermore, when an inorganic filler (D) is included, the content of the inorganic filler (D) is preferably 1 to 10 parts by mass, and more preferably 2 to 5 parts by mass, per 100 parts by mass of polymerizable monomer (A). By setting the content of the inorganic filler (D) to be above the lower limit above, good peelability can be obtained even after exposure to high temperatures. On the other hand, by setting the content of the inorganic filler (D) to be below the upper limit above, good adhesion and curability can be maintained.

[0072] [Antioxidant] The temporary fixing composition of this embodiment may further contain an antioxidant. The antioxidant is used to maintain peelability after exposure to high temperatures. Examples of antioxidants include methyl hydroquinone, hydroquinone, 2,2-methine-bis(4-methyl-6-tert-butylphenol), catechol, hydroquinone monomethyl ether, monotert-butylhydroquinone, 2,5-ditert-butylhydroquinone, p-benzoquinone, 2,5-diphenyl-p-benzoquinone, 2,5-ditert-butyl-p-benzoquinone, picric acid, citric acid, phenothiazine, tert-butylcatechol, 2-butyl-4-hydroxyanisole, 2,6-ditert-butyl-p-cresol, and 4-((4,6-bis(octylthio)-1,3,5-triazine-2-yl)amino)-2,6-di-t-butylphenol.

[0073] When an antioxidant is included, the antioxidant content is preferably 0.001 parts by mass or more per 100 parts by mass of polymerizable monomer (A). On the other hand, the antioxidant content is preferably 3 parts by mass or less. When an antioxidant is included, the antioxidant content is preferably 0.001 to 3 parts by mass per 100 parts by mass of polymerizable monomer (A). By setting the antioxidant content to above the lower limit, good peelability can be obtained even after exposure to high temperatures. On the other hand, by setting the antioxidant content to below the upper limit, good adhesion and curability can be maintained.

[0074] [Applications] The temporary fixing composition of this embodiment is suitable for joining, sealing, and coating various optical components, optical devices, and electronic components. In particular, it is suitable for use in the manufacture of semiconductor devices.

[0075] <Temporary Fixing Method Using Temporary Fixing Composition> The temporary fixing method of this embodiment is a method using the temporary fixing composition described above, and includes the steps of: curing the temporary fixing composition by irradiating it with light and fixing it to the adherend; and peeling the cured product obtained by curing the temporary fixing composition with laser light to remove the cured product from the adherend. Details will be described below.

[0076] First, the temporary fixing composition of this embodiment is applied to the substrate. Known application methods such as spin coating, screen printing, and various coaters can be used.

[0077] The adherends to be bonded by the temporary fixing composition of this embodiment are not particularly limited. Furthermore, when bonding a pair of adherends, it is preferable that at least one of them be a transparent substrate that transmits light. This allows the temporary fixing composition to be cured by light irradiation through the transparent substrate. Examples of transparent substrates include inorganic substrates such as quartz, glass, silica, calcium fluoride, and magnesium fluoride, and organic substrates such as plastics. Among these, inorganic substrates are preferred because they are versatile and provide a great effect. Among inorganic substrates, one or more selected from glass and silica are preferred.

[0078] When curing the temporary fixing composition by irradiation with light, the energy amount of visible light or ultraviolet light (wavelength or central wavelength 365-405 nm) should be 1 to 20,000 mJ / cm². ２ It is preferable to irradiate in such a manner. By setting the energy amount to above the lower limit, sufficient adhesion can be obtained, and by setting it to below the upper limit, good productivity can be obtained, and the generation of decomposition products from the photoradical polymerization initiator (B) can be suppressed.

[0079] Next, the cured material of the temporary fixing composition is irradiated with laser light. This causes the molecules within the cured material to break down, decompose, and vaporize, thereby reducing the adhesive strength. As a result, the cured material can be easily peeled off.

[0080] Peelability can be achieved by using a laser light with a wavelength different from the visible light or ultraviolet light (wavelength or central wavelength 365-405 nm) mentioned above. For example, a laser light with a wavelength of 350-360 nm can be used. The irradiation time and irradiation amount of the laser light are adjusted as appropriate according to the size and purpose of the cured product of the temporary fixing composition.

[0081] <Cured Product / Film> The cured product of this embodiment is obtained by curing the temporary fixing composition described above. The cured product of this embodiment can be used in processes over a wide temperature range from room temperature to high temperatures. For example, it can maintain its fixation even at high temperatures of 300 to 400°C. The film of this embodiment is a film made of the cured product of the temporary fixing composition described above. The film of this embodiment may have a wafer attached to one side and a support member attached to the other side of the film. The support member is preferably transparent.

[0082] <Structure> The structure of this embodiment has a wafer attached to one side of the above-mentioned film, and a support member attached to the other side. A semiconductor chip may also be mounted on the side of the wafer that faces the film. In the structure of this embodiment, the film is preferably a single layer. This improves the productivity and quality stability of the film.

[0083] <Method for Manufacturing Semiconductor Wafers> The method for manufacturing semiconductor wafers according to this embodiment is a method using the temporary fixing composition described above, and includes the steps of: applying the temporary fixing composition to a wafer and / or a support member to laminate the wafer and the support member; curing the temporary fixing composition by irradiating it with light to obtain a structure; and irradiating the cured product of the temporary fixing composition of the structure with laser light to peel off the support member. Details will be described below.

[0084] First, the temporary fixing composition is applied to the wafer and / or the support member, and the wafer and the support member are laminated together. That is, when bonding the wafer and the support member, the temporary fixing composition is applied to at least one of the surfaces that will be the bonding surface between the two.

[0085] A wafer has a circuit-forming surface on one side on which semiconductor chips are mounted. The wafers are stacked with the circuit-forming surface facing the support member.

[0086] The wafer is typically a semiconductor wafer. Examples of semiconductor wafers include not only silicon wafers, but also gallium nitride wafers, lithium tantalate wafers, lithium niobate wafers, silicon carbide wafers, germanium wafers, gallium-arsenide wafers, gallium-phosphorus wafers, gallium-arsenide-aluminum wafers, and the like. The thickness of the wafer is not particularly limited, but 600 to 800 μm is preferred, and 625 to 775 μm is more preferred. As a support, for example, a transparent substrate that transmits light is used.

[0087] Next, the temporary fixing composition is cured by irradiating it with light to obtain a structure. At this time, it is preferable that the cured product of the temporary fixing composition interposed between the wafer and the support member be a single layer. This simplifies the semiconductor wafer manufacturing method. Furthermore, it is preferable that the support member is transparent. This allows light irradiation to be performed through the support member.

[0088] Light irradiation is performed in the visible light or ultraviolet region (preferably with a wavelength or central wavelength of 350 to 405 nm, more preferably 365 to 405 nm, and even more preferably 385 to 405 nm) with an energy of 1 to 20,000 mJ / cm². ２ It is preferable to irradiate in such a manner.

[0089] The obtained structure may then be subjected to a process of grinding and / or polishing the non-circuit-formed surface of the wafer, thereby reducing the thickness of the wafer. The thickness of the thinned wafer is preferably 10 to 300 μm, and more preferably 30 to 100 μm. There are no particular restrictions on the method of grinding / polishing the back surface of the wafer, and known grinding / polishing methods can be used. Grinding is preferably performed while cooling the wafer and grinding wheel (such as a grinding wheel with a diamond blade) by applying water.

[0090] Next, the wafer-side surface of the structure is processed. The processing includes various processes used at the wafer level. Examples include electrode formation, metal wiring formation, and protective film formation. More specifically, conventionally known processes include metal sputtering for electrode formation, wet etching for etching the metal sputtering layer, application of resist to serve as a mask for metal wiring formation, exposure and development for pattern formation, resist peeling, dry etching, metal plating formation, silicon etching for TSV formation, and oxide film formation on the silicon surface. At this time, the structure is exposed to high heat during electrode formation, metal wiring formation, etc., but high heat resistance can be obtained by using the temporary fixing composition of this embodiment, so that adhesion between the wafer and the support member is maintained even at high temperatures.

[0091] After processing, the wafer is detached from the support member. That is, the support member is detached by irradiating the cured material of the temporary fixing composition of the structure with laser light. For example, the support member and wafer are detached by irradiating the entire surface with a UV laser in a linear, back-and-forth motion from the end of the structure on the support member side, and decomposing the cured material of the temporary fixing composition with the energy of the laser. When using a laser, a YAG laser or YVO ４ It is preferable to use a laser. It is preferable to perform the delamination before dicing.

[0092] Furthermore, a step may be taken to remove any cured material of the temporary fixing composition remaining on the surface of the wafer. Removal methods include a method in which, while the thinned surface is vacuum-adhered to an adsorption surface, an adhesive tape such as dicing tape is applied to the entire surface of the other remaining surface, and the cured material of the temporary fixing composition is peeled off together with the tape; and a method in which the wafer is immersed in a solvent (for example, an aliphatic or aromatic hydrocarbon solvent such as pentane, hexane, heptane, octane, nonane, decane, benzene, toluene, xylene, mesitylene, etc.) to swell and peel off the cured material. Of these methods, the tape peeling method is preferred in terms of the number of steps and the time required.

[0093] In this way, semiconductor wafers can be obtained.

[0094] The embodiments of the present invention have been described above with reference to the drawings, but these are examples of the present invention, and various other configurations can be adopted. Reference embodiments are noted below. [1] A temporary fixation composition comprising a polymerizable monomer (A) and a photoradical polymerization initiator (B), wherein the following condition 1 is satisfied. (Condition 1) The temporary fixation composition is applied to a silicon wafer (diameter 150 mm, thickness 625 μm) to a thickness of 50 μm by spin coating to form a film. Next, a glass substrate (thickness 700 μm) is laminated on the coated film of the temporary fixation composition under vacuum. Next, under a nitrogen atmosphere, a wavelength of 405 nm and an illuminance of 350 mW / cm are applied from the surface on the glass substrate side. ２ Total irradiation dose: 5,600 mJ / cm² ２ The temporary fixing composition is cured by light irradiation under the following conditions to obtain a bond. The bond is placed in a vacuum chamber, heating is started at a rate of 33°C / min with a pressure of 20 Pa or less, and the temperature is raised to 350°C while maintaining a pressure of 20 Pa or less. After 30 minutes from reaching 350°C, no delamination occurs in the bond. [2] The temporary fixing composition described in [1], wherein the cured product obtained by the following procedure 1 satisfies the following condition 2. (Procedure 1) The temporary fixing composition is formed into a film by sandwiching it between two polyethylene terephthalate films (thickness 50 μm), and irradiated with ultraviolet light (UV-LED) with a wavelength of 405 nm at a temperature of 23°C at an intensity of 100 mW / cm ２ For 50 seconds (5000 mJ / cm²) ２ ) A cured material with a thickness of 70 μm is produced by irradiation. (Condition 2) The absorbance of the temporary fixing composition and the absorbance of the cured material are measured and the reaction rate is determined by applying them to the following formula (1), and the reaction rate is 85% or more and 99% or less. Reaction rate (%) = {1 - (Bx / Ax) / (Bo / Ao)} Formula (1) (In formula (1), the symbols are as follows: Ao: Wavelength of the temporary fixing composition, 1720 cm －１ Absorbance Bo: Wavelength of the temporary fixing composition at 1635 cm －１ Absorbance Ax: Wavelength of the cured product at 1720 cm－１ Absorbance Bx: Wavelength of the cured product at 1635 cm －１Absorbance of) [3] A temporary fixing composition according to [1] or [2], wherein the 5% weight loss temperature of the cured product obtained by the procedure 1 is 300°C or more and 450°C or less. [4] A temporary fixing composition according to any one of [1] to [3], wherein the storage modulus E' at 200°C measured by a viscoelasticity measuring device of the cured product obtained by the procedure 1 is 3 MPa or more and 30 MPa or less. [5] A temporary fixing composition according to any one of [1] to [4], wherein, under condition 1, when the joint is placed in a vacuum chamber, heating is started at a heating rate of 33°C / min with the pressure at 20 Pa or less, and the temperature is raised to 350°C and held at 20 Pa or less, no peeling occurs in the joint 120 minutes after reaching 350°C. [6] A temporary fixing composition according to any one of [1] to [5], wherein the viscosity of the temporary fixing composition at 23°C is 2,000 mPa·s or more and 30,000 mPa·s or less. [7] A temporary fixing composition according to any one of [1] to [6], wherein the polymerizable monomer (A) comprises a (meth)acrylate compound (a1). [8] A temporary fixing composition according to any one of [1] to [7], wherein the polymerizable monomer (A) comprises a (meth)acrylate compound (a1), and the (meth)acrylate compound (a1) has an aromatic ring. [9] A temporary fixing composition according to any one of [1] to [8], wherein when the polymerizable monomer (A) is 100 parts by mass, the content of the (meth)acrylate compound (a1) having an aromatic ring is 50 parts by mass or more.

[10] A temporary fixing composition according to any one of [1] to [9], further comprising a release component (C).

[11] A temporary fixing composition according to any one of [1] to

[10] , wherein the polymerizable monomer (A) has at least one of a metal-oxygen bond or a metal-carbon bond.

[12] A temporary fixing composition according to any one of [1] to

[11] , further comprising an inorganic filler (D).

[13] A temporary fixing composition according to

[12] , wherein the inorganic filler (D) has at least one of a metal-oxygen bond or a metal-carbon bond.

[14] A temporary fixing composition according to any one of [1] to

[13] , which is used in the manufacture of a semiconductor device.

[15] A temporary fixing composition comprising a polymerizable monomer (A) and a photoradical polymerization initiator (B), wherein the polymerizable monomer (A) comprises a (meth)acrylate compound (a1), has a 10% weight loss temperature of 350°C or higher, and has a storage modulus E' at 200°C measured by a viscoelasticity measuring device of 30 MPa or less.

[16] A temporary fixing method using a temporary fixing composition according to any one of [1] to

[15] , comprising the steps of: curing the temporary fixing composition by irradiating it with light and fixing it to an adherend; and peeling off the cured product obtained by curing the temporary fixing composition by irradiating it with laser light.

[17] A cured product obtained by curing a temporary fixing composition according to any one of [1] to

[15] .

[18] A film made of a cured product of a temporary fixing composition according to any one of [1] to

[15] .

[19] The film according to

[18] , wherein a wafer is attached to one side of the film and a support member is attached to the other side of the film.

[20] A structure in which a wafer is attached to one side of the film according to

[18] or

[19] and a support member is attached to the other side of the film.

[21] The structure according to

[20] , wherein a semiconductor chip is mounted on the side of the wafer that faces the film.

[22] A structure according to

[20] or

[21] , wherein the film is a single layer.

[23] A structure according to any one of

[20] to

[22] , wherein the support member is transparent.

[24] A method for manufacturing a semiconductor wafer using a temporary fixing composition according to any one of [1] to

[15] , comprising: a step of applying the temporary fixing composition to a wafer and / or a support member to laminate the wafer and the support member; a step of curing the temporary fixing composition by irradiating it with light to obtain a structure; and a step of irradiating the cured product of the temporary fixing composition of the structure with laser light to peel off the support member.

[25] A method for manufacturing a semiconductor wafer according to

[24] , wherein the wafer has a semiconductor chip mounted on the side of the cured product of the temporary fixing composition.

[26] A method for manufacturing a semiconductor wafer according to

[24] or

[25] , wherein the cured product of the temporary fixing composition is a single layer.

[27] A method for manufacturing a semiconductor wafer according to any one of

[24] to

[26] , wherein the support member is transparent.

[28] A composition comprising a polymerizable monomer (A) and a photoradical polymerization initiator (B), wherein the polymerizable monomer (A) comprises a (meth)acrylate compound (a1) and satisfies the following condition 1: (Condition 1) The composition is applied to a silicon wafer (150 mm in diameter, 625 μm thick) to a thickness of 50 μm by spin coating, and a glass substrate (700 μm thick) is laminated on top of it. From the surface on the glass substrate side, the wavelength is 405 nm and the illuminance is 350 mW / cm. ２ Total irradiation dose: 5,600 mJ / cm² ２ The composition is cured by light irradiation under the following conditions to obtain a bonded body. When the bonded body is left standing for 30 minutes in an environment maintained at 350°C under vacuum, there is no peeling.

[29] A composition comprising a polymerizable monomer (A) and a photoradical polymerization initiator (B), wherein the polymerizable monomer (A) comprises a (meth)acrylate compound (a1), has a 10% weight loss temperature of 350°C or higher, and has a storage modulus E' at 200°C measured by a viscoelasticity measuring device of 3 MPa or more and 30 MPa or less.

[0095] Next, the present invention will be described in detail with reference to examples, but the content of the present invention is not limited to these examples.

[0096] (1) Preparation of Compositions Compositions with the compositions shown in Table 1 (in parts by mass) were prepared and evaluated using the following raw materials. The compositions were prepared by heating and mixing each raw material at 80°C. [Raw Materials] (Polymerizable Monomer (A)) Polymerizable Monomer 1: 9,9-bis[4-(2-hydroxyethoxy)phenyl]ful orange acrylate "A-BPEF-2" manufactured by Shin Nakamura Chemical Co., Ltd. Polymerizable Monomer 2: Difunctional acrylate-methacrylate mixture "PEAM1044" manufactured by Designer Molecules Co., Ltd. Polymerizable Monomer 3: Ethoxyca-o-phenylphenol acrylate "A-LEN-10" manufactured by Shin Nakamura Chemical Co., Ltd. Polymerizable Monomer 4: Dicyclopentanyl acrylate "FA-513AS" manufactured by Resonaq Co., Ltd. Polymerizable Monomer 5: EO-modified hydrogenated bisphenol A diacrylate "HBPE-4" manufactured by Daiichi Kogyo Seiyaku Co., Ltd. Polymerizable Monomer 6: Trimethylolpropane triacrylate "A-TMPT" manufactured by Shin Nakamura Chemical Co., Ltd. Polymerizable Monomer 7: Nonylphenol EO-modified acrylate Polymerizable monomer 8: N≒4 "M-113" manufactured by Toagosei Co., Ltd. Polymerizable monomer 9: Terminal silicone acrylate "KP-423" manufactured by Shin-Etsu Chemical Co., Ltd. Polymerizable monomer 10: Polymer with amine, C36-alkylenediamine, 5,5'-oxybis(1,3-isobenzofrangione), reaction product with maleic anhydride "BMI-1500" manufactured by Designer Molecules Co., Ltd. Polymerizable monomer 11: Silicone polyether diacrylate "TEGORAD2300" manufactured by EVONIK Co., Ltd. Polymerizable monomer 12: Isostearyl acrylate "ISTA" manufactured by Osaka Organic Chemical Co., Ltd.

[0097] (Photopolymerization Initiator (B)) Photopolymerization Initiator 1: Acylphosphine oxide-based photopolymerization initiator "Omnirad 819" manufactured by IGM Resins B.V.

[0098] (Removal component (C)) Removal component 1: Reactive benzotriazole-based UV absorber "JF-031" manufactured by Johoku Chemical Co., Ltd.

[0099] (Inorganic filler (D)) Inorganic filler 1: Halloysite (Al ２ SiO ５ (OH) ４) "AFF-HP:M" manufactured by Fimatec

[0100] (2) The following measurements were performed on the compositions obtained by the measurements. The results are shown in Table 1.

[0101] Regarding (Condition 1): <Method for fabricating the bonded body> Each composition was applied to a silicon wafer (150 mm in diameter, 625 μm thick) by spin coating to a thickness of 50 μm to form a film. Next, a glass substrate (700 μm thick) was laminated onto the coated film of the composition under vacuum. Then, under a nitrogen atmosphere, a wavelength of 405 nm and an illuminance of 350 mW / cm were applied from the surface on the glass substrate side. ２ Total irradiation dose: 5,600 mJ / cm² ２ The temporary fixing composition was cured by light irradiation under the following conditions to obtain a bonded body. <Substrates used> Silicon wafer: 150 mm in diameter x 625 μm in thickness (manufactured by Semitech) Disc-shaped glass support member: 151 mm in diameter x 700 μm in thickness (manufactured by OBC) <Heat resistance test conditions> The bonded body was placed in a vacuum chamber with the silicon wafer side facing down, and heating was started at a rate of 33°C / min under vacuum (20 Pa or less). After heating to 350°C under vacuum, it was maintained at that temperature for 3 hours. Apparatus: Vacuum hot plate chamber PH224S (manufactured by MSAFACTORY) Heating rate: 30°C / min Holding temperature: 350°C Holding time: 0 to 3 hours Atmosphere: <20 Pa (vacuum) <Observation of delamination> The bonded body in the vacuum chamber was observed from the glass support substrate side, and the temperature and time when delamination occurred were measured. However, the time was measured from the point when 350°C was reached. The results are shown in Table 1.

[0102] • (Condition 2) Reaction rate <Procedure 1: Test specimen preparation conditions> Each composition was formed into a film by sandwiching it between two polyethylene terephthalate films (thickness 50 μm), and irradiated with ultraviolet light (UV-LED) with a wavelength of 405 nm at a temperature of 23°C at an intensity of 100 mW / cm ２ For 50 seconds (5000 mJ / cm²) ２ A cured material with a thickness of 70 μm was produced by irradiation. <Measurement conditions> Measurement device: NICOLET iS5 FT-IR (manufactured by Thermo Fisher Scientific) Number of cumulative measurements: 16 Measurement range: 4000 cm－１ ~500cm －１ (Condition 2) The absorbance of the composition and the absorbance of the cured product were measured, and the reaction rate was determined by applying them to the following formula (1). The results are shown in Table 1. Reaction rate (%) = {1 - (Bx / Ax) / (Bo / Ao)} Formula (1) In formula (1), the symbols are as follows: Ao: Wavelength of the composition, 1720 cm －１ Absorbance Bo: Wavelength of the composition at 1635 cm －１ Absorbance Ax: Wavelength of the cured product at 1720 cm －１ Absorbance Bx: Wavelength of the cured product at 1635 cm －１ absorbance

[0103] ・Regarding the weight loss temperature <Thermogravimetric measurement> <Test specimen preparation conditions> Using the hardened material obtained in procedure 1 above, the hardened material was weighed into an aluminum pan. <Measurement conditions> Measurement equipment: See below Differential differential thermobalance TG-TA2000SR (manufactured by netzsch) Humidity-controlled differential balance MTC1000SA Gas flow control device GC9130 Heating rate: 10℃ / min Measurement temperature: Room temperature to 500℃ Sample amount: 0.010 mg Atmosphere: N ２

[0104] ・Viscoelasticity measurement; Storage modulus <Test specimen preparation method> The cured material obtained in procedure 1 above was used. <Measurement conditions> The cured material was placed in the following apparatus and heated, and the temperature (°C) when the weight reduction rate reached 5% and the temperature (°C) when the weight reduction rate reached 10% were measured relative to the weight of the cured material before measurement. Measurement apparatus: RSA-3 (manufactured by TA Instruments) Measurement mode: Tensile Measurement Temperature: -30 to 250°C Measurement frequency: 1 Hz Measurement strain: 0.025% Heating rate: 3°C / min Test specimen: 7 mm wide x 50 mm long x 0.07 mm thick Chuck distance: 7 mm

[0105] Regarding viscosity, the viscosity of each composition was measured according to the following measurement conditions. <Measurement conditions> Measuring device: E-type viscometer DV3T-HB (manufactured by Eiko Seiki Co., Ltd.) Measuring jig: Cone plate CPA-40Z (manufactured by Eiko Seiki Co., Ltd.) Measurement temperature: 23℃ Liquid volume: 0.5 mL Rotation speed: 10 rpm (500 mPa·s to 2500 mPa·s); 2 rpm (2501 mPa·s to 10000 mPa·s) Standard: JIS Z 8803:2011

[0106] (3) Evaluation The heat resistance of the composition obtained in (1) was evaluated as follows. First, two glass substrates (size: 25 mm x 25 mm x 2 mm thick) were prepared. The composition was applied to one of the glass substrates by spin coating, and the other glass substrate was placed on top while inserting a polyethylene terephthalate spacer (50 μm thick), and the two glass substrates were pressed together. The coating film of the composition sandwiched between the glass substrates was 8φ (diameter 8 mm) and 50 μm thick. Next, the glass substrates were subjected to irradiation at a wavelength of 405 nm and an integrated dose of 5000 mJ / cm. ２ The composition was cured by light irradiation under the specified conditions, and then the spacer was removed to obtain a test specimen in which two glass substrates were integrated. The obtained test specimen was heated at 350°C for 5 minutes, then removed and allowed to cool to room temperature. Subsequently, a tensile test (testing machine: AGX-V 50kN (manufactured by Shimazu)) was performed in accordance with JIS K 6850:1999, with a tensile direction of 180°, a tensile speed of 10 mm / min, and a temperature of 23°C, and the tensile shear strength (MPa) between the cured composition and the glass substrate was measured. The results are shown in Table 1. In the comparative example, the glass substrates of the test specimen separated due to the chuck fixture of the testing machine during the tensile test, making it impossible to measure the tensile shear strength. Furthermore, the test specimen could be easily separated by irradiating it with laser light (wavelength 355 nm) through the glass substrate.

[0107]

[0108] This application claims priority based on Japanese Patent Application No. 2025-049741, filed on 25 March 2025, and incorporates all of its disclosures herein.

Claims

1. A temporary fixation composition comprising a polymerizable monomer (A) and a photoradical polymerization initiator (B), wherein the temporary fixation composition satisfies the following condition 1. (Condition 1) The temporary fixation composition is applied to a silicon wafer (diameter 150 mm, thickness 625 μm) to a thickness of 50 μm by spin coating to form a film. Next, a glass substrate (thickness 700 μm) is laminated on the coated film of the temporary fixation composition under vacuum. Next, under a nitrogen atmosphere, a wavelength of 405 nm and an illuminance of 350 mW / cm are applied from the surface on the glass substrate side. ２ Total irradiation dose: 5,600 mJ / cm² ２ The temporary fixing composition is cured by light irradiation under the specified conditions to obtain a bonded body. The bonded body is placed in a vacuum chamber at 23°C, and heating is started at a rate of 33°C / min with a pressure of 20 Pa or less. When the temperature is raised to 350°C while maintaining a pressure of 20 Pa or less, no delamination occurs in the bonded body 30 minutes after reaching 350°C.

2. A temporary fixing composition according to claim 1, wherein the cured product obtained by the following procedure 1 satisfies the following condition 2. (Procedure 1) The temporary fixing composition is formed into a film by sandwiching it between two polyethylene terephthalate films (thickness 50 μm), and irradiated with ultraviolet light (UV-LED) with a wavelength of 405 nm at a temperature of 23°C at an intensity of 100 mW / cm ２ For 50 seconds (5000 mJ / cm²) ２ ) A cured material with a thickness of 70 μm is produced by irradiation. (Condition 2) The absorbance of the temporary fixing composition and the absorbance of the cured material are measured and the reaction rate is determined by applying them to the following formula (1), and the reaction rate is 85% or more and 99% or less. Reaction rate (%) = {1 - (Bx / Ax) / (Bo / Ao)} Formula (1) (In formula (1), the symbols are as follows: Ao: Wavelength of the temporary fixing composition, 1720 cm －１ Absorbance Bo: Wavelength of the temporary fixing composition at 1635 cm －１ Absorbance Ax: Wavelength of the cured product at 1720 cm －１ Absorbance Bx: Wavelength of the cured product at 1635 cm －１ (absorbance) 3. A temporary fixing composition according to claim 1 or 2, wherein the temperature at which the cured product obtained by the procedure 1 is reduced by 5% is 300°C or more and 450°C or less.

4. A temporary fixing composition according to claim 1 or 2, wherein the storage modulus E' at 200°C, as measured by a viscoelasticity measuring device for the cured product obtained by the procedure 1, is 3 MPa or more and 30 MPa or less.

5. A temporary fixing composition according to claim 1 or 2, wherein the viscosity of the temporary fixing composition at 23°C is 2,000 mPa·s or more and 30,000 mPa·s or less.

6. A temporary fixation composition according to claim 1 or 2, wherein the polymerizable monomer (A) comprises a (meth)acrylate compound (a1).

7. A temporary fixing composition according to claim 1 or 2, further comprising a release component (C).

8. A temporary fixing composition according to claim 1 or 2, further comprising an inorganic filler (D).

9. A temporary fixation composition comprising a polymerizable monomer (A) and a photoradical polymerization initiator (B), wherein the polymerizable monomer (A) comprises a (meth)acrylate compound (a1), has a 10% weight loss temperature of 350°C or higher, and has a storage modulus E' at 200°C measured by a viscoelasticity measuring device of 3 MPa or higher and 30 MPa or lower.

10. A temporary fixing method using the temporary fixing composition according to claim 1 or 2, comprising the steps of: curing the temporary fixing composition by irradiating it with light and fixing it to an adherend; and irradiating the cured product obtained by curing the temporary fixing composition with laser light to peel the cured product from the adherend.

11. A cured product obtained by curing the temporary fixing composition according to claim 1 or 2.

12. A film comprising a cured product obtained by curing the temporary fixing composition according to claim 1 or 2, wherein a wafer is attached to one side of the film and a support member is attached to the other side of the film.

13. A structure comprising a wafer attached to one side of the film described in claim 12, and a support member attached to the other side of the film.

14. A method for manufacturing a semiconductor wafer using the temporary fixing composition according to claim 1 or 2, comprising: a step of applying the temporary fixing composition to a wafer and / or a support member to laminate the wafer and the support member; a step of curing the temporary fixing composition by irradiating it with light to obtain a structure; and a step of irradiating the cured product of the temporary fixing composition of the structure with laser light to peel off the support member.

15. A method for manufacturing a semiconductor wafer according to claim 14, wherein the wafer has a semiconductor chip mounted on the cured side of the temporary fixing composition.

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