Method for manufacturing semiconductor device and semi-cured film

Abstract

Provided is a method for manufacturing a semiconductor device, the method comprising: a coating step for forming a resin layer (30) by applying a resin composition containing a photocurable resin composition to a first surface side of a substrate (10) to obtain a structure (x); a step for forming recesses (35) by exposing and developing the resin layer (30) in the structure (x); a semi-curing step for obtaining a structure (y) by semi-curing the resin layer (30) in the structure (x) through heating to form a semi-cured resin layer (40); a filling step for filling the recesses (35) in the structure (y) with a metal layer (20); a step for polishing the structure (y) from the first surface side to form a layer including the metal layer (20) and the semi-cured resin layer (40); a step for obtaining a bonded structure (y) by bonding first surfaces of two of the structures (y); and a full-curing step for obtaining a structure (z') by fully curing the semi-cured resin layer (40) in the bonded structure (y) by heating the semi-cured resin layer at a temperature T1 to form a cured resin layer (50), wherein, when a weight change of the semi-cured resin layer (40) is measured by heating the semi-cured resin layer (40) from 30 °C to 500 °C under a nitrogen flow at a heating rate of 10 °C / min using a simultaneous differential thermogravimetric analyzer, a weight loss rate from 30 °C to the temperature T1 is at most 3.0 mass%. In the measurement, the mass of the semi-cured resin layer (40) is 0.005 g and the flow rate of nitrogen gas is 200 mL / min.

Description

Method for manufacturing a semiconductor device and a semi-cured film

[0001] This invention relates to a method for manufacturing a semiconductor device and a semi-cured film.

[0002] In the manufacture of semiconductor devices, a resin composition containing one or more types selected from the group consisting of photocurable resin compositions and thermosetting resin compositions may be used.

[0003] For example, Patent Document 1 describes a resin composition for use in producing at least one of a first organic insulating film and a second organic insulating film in a semiconductor device manufacturing method comprising the following steps (1) to (5), with the aim of providing a resin composition that can manufacture a semiconductor device having an insulating film with excellent heat resistance and suppressed generation of voids at the bonding interface, comprising (A) at least one polyimide precursor which is at least one resin selected from the group consisting of polyamic acid, polyamic acid ester, polyamic acid salt and polyamic acid amide, and a polyimide resin, and (B) a solvent. Step (1) Prepare a first semiconductor substrate having a first substrate body and the first organic insulating film and first electrode provided on one surface of the first substrate body. Step (2) Prepare a second semiconductor substrate having a second substrate body and the second organic insulating film and a plurality of second electrodes provided on one surface of the second substrate body. Step (3) Separate the second semiconductor substrate into individual pieces to obtain a plurality of semiconductor chips, each having an organic insulating film portion corresponding to a part of the second organic insulating film and at least one of the second electrodes. Step (4) The first organic insulating film of the first semiconductor substrate and the organic insulating film portion of the semiconductor chip are bonded together. Step (5) The first electrode of the first semiconductor substrate and the second electrode of the semiconductor chip are joined together.

[0004] International Publication No. 2022 / 071329

[0005] The present invention provides a method for manufacturing a semiconductor device and a semi-cured film that can produce a semiconductor device in which the generation of voids is suppressed.

[0006] The inventors diligently conducted research to solve the above problems. As a result, they found a coating step to obtain a structure (x) by forming a resin layer by applying a resin composition containing one or more selected from the group consisting of photocurable resin compositions and thermosetting resin compositions to the first surface side of a substrate; a semi-curing step to obtain a structure (y) by semi-curing the resin layer in the structure (x) by heating to form a semi-cured resin layer; and heating the semi-cured resin layer in the structure (y) to a temperature T １ The process includes a main curing step in which the semi-cured resin layer is heated to obtain a structure (z) by heating to obtain a cured resin layer, and when the weight change of the semi-cured resin layer is measured using a differential thermogravimetric analyzer under nitrogen flow conditions and a heating rate of 10°C / min, the weight change of the semi-cured resin layer is measured from 30°C to 500°C. １ We have discovered that a method for manufacturing a semiconductor device in which the weight reduction rate is 3.0% by mass or less can suppress the generation of voids in the resulting semiconductor device, and thus completed the present invention.

[0007] According to the present invention, a method for manufacturing a semiconductor device and a semi-cured film are provided as described below.

[0008] [1] A coating step to obtain a structure (x) by applying a resin composition containing a photocurable resin composition to the first surface side of a substrate to form a resin layer; a step to form a recess by exposing and developing the resin layer in the structure (x); a semi-curing step to obtain a structure (y) by semi-curing the resin layer in the structure (x) by heating to form a semi-cured resin layer; an embedding step to embed a metal layer in the recess in the structure (y); a step to polish the structure (y) from the first surface side to form a layer including the metal layer and the semi-cured resin layer; a step to obtain a structure (y) joint by joining the first surfaces of two of the structure (y); and a step to heat the semi-cured resin layer in the structure (y) joint to a temperature T １ The process includes a main curing step in which a structure (z') is obtained by heating to fully cure the resin to form a cured resin layer, and when the weight change of the semi-cured resin layer is measured using a differential thermogravimetric analyzer under nitrogen flow conditions and a heating rate of 10°C / min, the weight change of the semi-cured resin layer is measured when the semi-cured resin layer is heated from 30°C to 500°C, from 30°C to the T１ A method for manufacturing a semiconductor device in which the weight reduction rate up to 3.0% by mass or less. In the above measurement, the mass of the semi-cured resin layer is 0.005 g and the nitrogen gas flow rate is 200 mL / min. [2] A step of forming a metal layer in a part of the first surface area of ​​a substrate; a coating step of forming a resin layer to obtain a structure (x) by applying a resin composition containing one or more selected from the group consisting of a photocurable resin composition and a thermosetting resin composition to the first surface area of ​​the substrate; a semi-curing step of obtaining a structure (y) by semi-curing the resin layer in the structure (x) by heating to make it a semi-cured resin layer; a step of polishing the structure (y) from the first surface area to form a layer containing the metal layer and the semi-cured resin layer; a step of obtaining a structure (y) joint by joining the first surfaces of two of the structure (y) together; and heating the semi-cured resin layer in the structure (y) joint to a temperature T １ The process includes a main curing step in which a structure (z') is obtained by heating to fully cure the resin to form a cured resin layer, and when the weight change of the semi-cured resin layer is measured using a differential thermogravimetric analyzer under nitrogen flow conditions and a heating rate of 10°C / min, the weight change of the semi-cured resin layer is measured when the semi-cured resin layer is heated from 30°C to 500°C, from 30°C to the T １ A method for manufacturing a semiconductor device in which the weight reduction rate up to 3.0% by mass or less. In the measurement, the mass of the semi-cured resin layer is 0.005 g and the nitrogen gas flow rate is 200 mL / min. [3] A method for manufacturing a semiconductor device according to [1] or [2], wherein the heating temperature of the semi-curing step is 150°C or more and 400°C or less. [4] A method for manufacturing a semiconductor device according to any one of [1] to [3], wherein the heating time of the semi-curing step is 0.1 min or more and 30 min or less. [5] The T １A method for manufacturing a semiconductor device according to any one of [1] to [4], wherein the curing temperature is 150°C or more and 400°C or less. [6] A method for manufacturing a semiconductor device according to any one of [1] to [5], wherein the heating time for the curing step is 10 min or more and 600 min or less. [7] A method for manufacturing a semiconductor device according to any one of [1] to [6], wherein the resin composition comprises a polymer (A) having an imide skeleton. [8] A method for manufacturing a semiconductor device according to [7], wherein the polymer (A) comprises one or more polymers selected from the group consisting of polyimide and polyimide precursors. [9] A method for manufacturing a semiconductor device according to [7] or [8], wherein the polymer (A) contains a carbon-carbon double bond in its side chain.

[10] A method for manufacturing a semiconductor device according to any one of [1] to [9], wherein when the total amount of solids in the resin composition is 100 parts by mass, the content of fluorine atoms is 10 parts by mass or less.

[11] A method for manufacturing a semiconductor device according to any one of [1] to

[10] , wherein when the total amount of solids in the resin composition is 100 parts by mass, the content of polymers containing fluorine atoms is 30 parts by mass or less.

[12] The method for manufacturing a semiconductor device according to any one of [1] to

[11] , wherein when the total amount of solids in the resin composition is 100 parts by mass, the content of alkali-soluble resin is 30 parts by mass or less.

[13] The method for manufacturing a semiconductor device according to any one of [1] to

[12] , wherein the die shear strength S of the structure (y) measured by the method 1 below is 8 MPa or more. (Method 1) A part of the structure (y), which has the substrate and the semi-cured resin layer on the first surface side of the substrate, is cut out to create a bottom die with dimensions of 10 mm x 10 mm and a top die with dimensions of 3 mm x 3 mm. Next, the bottom die is placed on a stage at 25°C with the side on which the semi-cured resin layer is formed facing upwards. Next, the top die is lifted with the top tool of a bond tester set to 250°C with the side on which the semi-cured resin layer is formed facing downwards. Next, the top die is pressed against the bottom die with a force of 25 N for 10 seconds. Next, the resulting top die-bottom die joint is subjected to a nitrogen atmosphere using an oven, and the T １Heat for 120 min to obtain a sample. Next, using a dicing device, measure the dicing strength S (MPa) of the sample under the conditions of a dicing speed of 300 μm / sec and a dicing height of 10 μm.

[14] A semi-cured film including a semi-cured resin layer of a resin composition containing a polymer (A) having an imide skeleton, wherein the resin composition includes one or more selected from the group consisting of a photocurable resin composition and a thermosettable resin composition. When measuring the weight change of the semi-cured film when heating the semi-cured film from 30°C to 500°C under a nitrogen flow using a differential thermal thermogravimetric simultaneous measurement device under the condition of a heating rate of 10°C / min, a semi-cured film having a weight reduction rate of 3.0 mass% or less from 30°C to 250°C.

[15] The method for manufacturing a semiconductor device according to any one of [1] to

[13] , wherein the weight reduction rate is 0.1 mass% or more and 2.8 mass% or less.

[16] The method for manufacturing a semiconductor device according to [3], wherein the heating temperature of the semi-curing step is 180°C or more and 320°C or less.

[17] The method for manufacturing a semiconductor device according to [4], wherein the heating time of the semi-curing step is 1 min or more and 10 min or less.

[18] The T １ is 240°C or more and 310°C or less, the method for manufacturing a semiconductor device according to [5].

[19] The method for manufacturing a semiconductor device according to [6], wherein the heating time of the full-curing step is 90 min or more and 180 min or less.

[20] The method for manufacturing a semiconductor device according to any one of [7] to [9], wherein the polymer (A) includes a structural unit represented by the following general formula (1). (In the general formula (1), Y represents a divalent organic group, and from the viewpoint of improving the environmental compatibility and the performance balance of suppressing the generation of voids in the obtained semiconductor device, it is preferably a divalent group containing an alkylene group or a divalent group containing at least one aromatic ring.)

[21] In the general formula (1), Y is selected from the group consisting of a group represented by the following general formula (1a), a group represented by the following general formula (1b), and a group represented by the following general formula (1c), the method for manufacturing a semiconductor device according to

[20] . (In the general formula (1a), R １ and R ２Each of these independently represents a hydrogen atom, a C1-C3 alkyl group, or a C1-C3 alkoxy group, and there are multiple R groups. １ Multiple Rs exist ２ They may be the same or different, R ３ R represents a hydrogen atom, a C1-C3 alkyl group, or a C1-C3 alkoxy group, and there are multiple R groups. ３ The elements may be the same or different, and * indicates a bonding. In the general formula (1b) above, R ４ and R ５ Each of these independently represents a hydrogen atom, a C1-C3 alkyl group, or a C1-C3 alkoxy group, and there are multiple R groups. ４ Multiple Rs exist ５ The members may be the same or different, and * indicates a bond. In the general formula (1c), Z represents an alkylene group having 1 to 5 carbon atoms or a divalent aromatic group, and * indicates a bond.)

[22] A method for manufacturing a semiconductor device according to any one of [7] to [9],

[20] and

[21] , wherein the polymer (A) comprises a constituent unit represented by the following general formula (2). (In the above general formula (2), m1 and m2 each independently represent an integer from 0 to 3, Q represents a hydrogen atom, a hydroxyl group, or a monovalent organic group having 1 to 10 carbon atoms when m1 or m2 is 0, and a single bond or a divalent to tetravalent organic group having 1 to 10 carbon atoms when m1 or m2 is 1 to 3, and multiple Qs may be the same or different, R represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or an alkoxy group having 1 to 3 carbon atoms, and multiple Rs may be the same or different, X represents a single bond, -SO ２ -, -C(=O)-, linear and branched alkylene groups having 1 to 5 carbon atoms, linear and branched fluoroalkylene groups having 1 to 5 carbon atoms, or substituted or unsubstituted fluorene groups.)

[23] A method for manufacturing a semiconductor device according to any one of [7] to [9] and

[20] to

[22] , wherein the polymer (A) comprises a constituent unit (a) represented by the following general formula (3). (In the above general formula (3), m1 and m2 each independently represent an integer from 0 to 3, Q represents a hydrogen atom, a hydroxyl group, or a monovalent organic group having 1 to 10 carbon atoms when m1 or m2 is 0, and a single bond or a divalent to tetravalent organic group having 1 to 10 carbon atoms when m1 or m2 is 1 to 3, and multiple Qs may be the same or different, R represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or an alkoxy group having 1 to 3 carbon atoms, and multiple Rs may be the same or different, X represents a single bond, -SO ２) -, -C(=O)-, linear and branched alkylene groups having 1 to 5 carbon atoms, linear and branched fluoroalkylene groups having 1 to 5 carbon atoms, or substituted or unsubstituted fluorene groups, where Y represents a divalent organic group.

[24] A method for manufacturing a semiconductor device according to any one of [7] to [9] and

[20] to

[23] , wherein the content of the polymer (A) in the resin composition is 20 parts by mass or more and 95 parts by mass or less when the total amount of solids in the resin composition is 100 parts by mass.

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

[24] , wherein the content of the polymer (A) in the resin composition is 35 parts by mass or more and 80 parts by mass or less when the total amount of solids in the resin composition is 100 parts by mass.

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

[25] , wherein the content of the polymer (A) in the resin composition is 50 parts by mass or more and 65 parts by mass or less when the total amount of solids in the resin composition is 100 parts by mass.

[27] The method for manufacturing a semiconductor device according to any one of [1] to

[13] and

[15] to

[26] , wherein the resin composition further comprises a crosslinking agent (B).

[28] The method for manufacturing a semiconductor device according to any one of [1] to

[13] and

[15] to

[27] , wherein the resin composition further comprises a polymerization initiator (C).

[29] The method for manufacturing a semiconductor device according to any one of [1] to

[13] and

[15] to

[28] , wherein the resin composition further comprises an antioxidant (D) having an isocyanuric acid skeleton.

[30] The method for manufacturing a semiconductor device according to any one of [1] to

[13] and

[15] to

[29] , wherein the resin composition further comprises an adhesion aid.

[31] The method for manufacturing a semiconductor device according to any one of [1] to

[13] and

[15] to

[30] , wherein the resin composition further comprises a surfactant.

[32] The method for manufacturing a semiconductor device according to any one of [1] to

[13] and

[15] to

[31] , wherein the resin composition further comprises a curing catalyst.

[33] A method for manufacturing a semiconductor device according to any one of [1] to

[13] and

[15] to

[32] , wherein the resin composition further comprises an organic solvent.

[0009] According to the present invention, it is possible to provide a method for manufacturing a semiconductor device and a semi-cured film that can produce a semiconductor device in which the generation of voids is suppressed.

[0010] It is a schematic cross-sectional view schematically showing an example of a method for manufacturing a semiconductor device. It is a schematic cross-sectional view schematically showing an example of a method for manufacturing a semiconductor device. It is a schematic cross-sectional view schematically showing an example of a method for manufacturing a semiconductor device. It is a schematic cross-sectional view schematically showing an example of a method for manufacturing a semiconductor device. It is a schematic cross-sectional view schematically showing an example of a method for manufacturing a semiconductor device. It is a SEM image of the cross-section of the structure (z') of Example 7.

[0011] Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings. The drawings are for illustrative purposes only. The shapes, dimensional ratios, etc. of each member in the drawings do not necessarily correspond to actual articles.

[0012] In this embodiment, "A to B" indicating a numerical range represents A or more and B or less unless otherwise specified.

[0013] In the notation of a group (atomic group) in this embodiment, a notation that does not indicate whether it is substituted or unsubstituted includes both those having no substituent and those having a substituent. For example, the "alkyl group" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group). The notation "(meth)acryl" in this embodiment represents a concept including both acryl and methacryl. The same applies to similar notations such as "(meth)acrylate". The term "organic group" in this embodiment means, unless otherwise specified, an atomic group obtained by removing one or more hydrogen atoms from an organic compound. For example, the "monovalent organic group" represents an atomic group obtained by removing one hydrogen atom from an arbitrary organic compound.

[0014] The method for manufacturing a semiconductor device of this embodiment includes: a coating step of forming a resin layer by applying one or more resin compositions selected from the group consisting of a photocurable resin composition and a thermosetting resin composition on the first surface side of a substrate to obtain a structure (x); a semi-curing step of obtaining a structure (y) by semi-curing the resin layer in the structure (x) by heating to obtain a semi-cured resin layer; and the semi-cured resin layer in the structure (y) at a temperature T １The process includes a main curing step in which a structure (z) is obtained by heating to fully cure the resin to form a cured resin layer, and when the weight change of the semi-cured resin layer was measured using a differential thermogravimetric analyzer under nitrogen flow conditions and a heating rate of 10°C / min when the semi-cured resin layer was heated from 30°C to 500°C, the weight change was measured from 30°C to T １ The weight loss rate up to 3.0% by mass is 3.0% or less. In the measurement, the mass of the semi-cured resin layer is 0.005 g, and the nitrogen gas flow rate is 200 mL / min.

[0015] According to the inventors' research, in a method for manufacturing a semiconductor device using a resin composition, comprising a coating step, a semi-curing step, and a full curing step, a correlation was found between the weight loss rate when the semi-cured resin layer is heated to the heating temperature of the full curing step and the occurrence of voids in the resulting semiconductor device. Based on the above findings, the inventors conducted further investigations and found that when measuring the weight change of the semi-cured resin layer when it was heated from 30°C to 500°C under nitrogen flow conditions and a heating rate of 10°C / min using a differential thermogravimetric analyzer, the correlation was found between the weight loss rate when the semi-cured resin layer was heated from 30°C to the heating temperature of the full curing step T １ We discovered that the generation of voids in the resulting semiconductor device can be suppressed by keeping the weight reduction rate to 3.0% by mass or less, thus completing the present invention.

[0016] The semiconductor device manufacturing method of this embodiment: 30°C to T １ The weight reduction rate is 3.0% by mass or less, preferably 2.9% by mass or less, and more preferably 2.8% by mass or less, from the viewpoint of further suppressing the generation of voids in the resulting semiconductor device. The lower limit of the above weight reduction rate is not particularly limited, but may be, for example, 0.1% by mass or more.

[0017] The semiconductor device manufacturing method of this embodiment: 30°C to T １ The weight reduction rate is preferably 0.1% by mass or more and 3.0% by mass or less, more preferably 0.1% by mass or more and 2.9% by mass or less, and even more preferably 0.1% by mass or more and 2.8% by mass or less, from the viewpoint of further suppressing the generation of voids in the resulting semiconductor device.

[0018] In this embodiment, the heating temperature for the semi-curing process is preferably 150°C to 400°C, more preferably 170°C to 350°C, and even more preferably 180°C to 320°C, from the viewpoint of further suppressing the generation of voids in the resulting semiconductor device.

[0019] From the viewpoint of further suppressing the generation of voids in the resulting semiconductor device, the heating time in the semi-curing process of this embodiment is preferably 0.1 min to 30 min, more preferably 0.5 min to 20 min, and even more preferably 1 min to 10 min.

[0020] T of this embodiment １ From the viewpoint of further suppressing the generation of voids in the resulting semiconductor device, the temperature is preferably 150°C to 400°C, more preferably 170°C to 350°C, even more preferably 200°C to 330°C, and even more preferably 240°C to 310°C.

[0021] In this embodiment, the heating time for the curing process is preferably 10 min to 600 min, more preferably 30 min to 450 min, even more preferably 60 min to 300 min, and even more preferably 90 min to 180 min, from the viewpoint of further suppressing the generation of voids in the resulting semiconductor device.

[0022] <Polymer having an imide skeleton (A)> The resin composition of this embodiment preferably includes polymer (A) having an imide skeleton.

[0023] The polymer (A) of this embodiment preferably comprises one or more polymers selected from the group consisting of polyimides and polyimide precursors, and more preferably comprises polyimide.

[0024] The polymer (A) of this embodiment preferably contains a carbon-carbon double bond in its side chain, and more preferably contains a polymerizable carbon-carbon double bond in its side chain.

[0025] In recent years, there has been a growing demand to avoid using fluorine-containing compounds, such as perfluoroalkyl and polyfluoroalkyl compounds, which have poor environmental compatibility, in products. On the other hand, fluorine-containing polymers are sometimes used in the field of resin compositions used in the manufacture of semiconductor devices.

[0026] The polymer (A) of this embodiment preferably includes a constituent unit represented by the following general formula (1) from the viewpoint of further improving the balance between environmental compatibility and the performance of suppressing the generation of voids in the resulting semiconductor device.

[0027]

[0028] In general formula (1), Y represents a divalent organic group, and from the viewpoint of further improving the balance between environmental compatibility and the performance of suppressing void generation in the resulting semiconductor device, it is preferably a divalent group containing an alkylene group or a divalent group containing at least one aromatic ring. The alkylene group is preferably an alkylene group having 1 to 5 carbon atoms, more preferably an alkylene group having 1 to 3 carbon atoms. The aromatic ring is preferably a divalent benzene ring, a divalent naphthalene ring, a divalent anthracene ring, or a divalent biphenyl group, more preferably a divalent benzene ring or a divalent biphenyl group.

[0029] In general formula (1), Y is preferably selected from the group consisting of the group represented by the following general formula (1a), the group represented by the following general formula (1b), and the group represented by the following general formula (1c), from the viewpoint of further improving the balance between environmental compatibility and the performance of suppressing the generation of voids in the resulting semiconductor device, and more preferably is the group represented by the following general formula (1b).

[0030]

[0031] In general formula (1a), R １ and R ２ Each of these independently represents a hydrogen atom, a C1-C3 alkyl group, or a C1-C3 alkoxy group, and there are multiple R groups. １ Multiple Rs exist ２ They may be the same or different, R ３R represents a hydrogen atom, a C1-C3 alkyl group, or a C1-C3 alkoxy group, and there are multiple R groups. ３ The elements may be the same or different, and * indicates a bond. In general formula (1b), R ４ and R ５ Each of these independently represents a hydrogen atom, a C1-C3 alkyl group, or a C1-C3 alkoxy group, and there are multiple R groups. ４ Multiple Rs exist ５ The elements may be the same or different, and * indicates a bond. In general formula (1c), Z represents an alkylene group or a divalent aromatic group having 1 to 5 carbon atoms, and * indicates a bond.

[0032] In general formula (1a), R １ and R ２ R is preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, and even more preferably a hydrogen atom or a methyl group. In general formula (1a), R １ and R ２ Each of these independently preferably consists of 0 to 3 hydrogen atoms, more preferably 0 to 2 hydrogen atoms, and even more preferably 1 hydrogen atom. In general formula (1a), R ３ Preferably, it is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, even more preferably a hydrogen atom or a methyl group, and even more preferably a hydrogen atom.

[0033] In general formula (1b), R ４ and R ５ R is preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, and even more preferably a hydrogen atom or a methyl group. In general formula (1b), R ４ and R ５ Each of these atoms independently preferably has 0 to 3 hydrogen atoms, more preferably 0 to 2 hydrogen atoms, and even more preferably 1 hydrogen atom.

[0034] The polymer (A) of this embodiment preferably includes a constituent unit represented by the following general formula (2) from the viewpoint of further improving the balance between environmental compatibility and the performance of suppressing the generation of voids in the resulting semiconductor device.

[0035]

[0036] In general formula (2), m1 and m2 each independently represent an integer from 0 to 3, Q represents a hydrogen atom, a hydroxyl group, or a monovalent organic group having 1 to 10 carbon atoms when m1 or m2 is 0, and a single bond or a divalent to tetravalent organic group having 1 to 10 carbon atoms when m1 or m2 is 1 to 3, and multiple Qs may be the same or different, R represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or an alkoxy group having 1 to 3 carbon atoms, and multiple Rs may be the same or different, X represents a single bond, -SO ２ This represents -, -C(=O)-, linear and branched alkylene groups having 1 to 5 carbon atoms, linear and branched fluoroalkylene groups having 1 to 5 carbon atoms, or substituted or unsubstituted fluorene groups.

[0037] In general formula (2), m1 and m2 are preferably 0 to 2, more preferably 0 or 1, from the viewpoint of further improving the balance between environmental compatibility and the performance of suppressing void generation in the resulting semiconductor device. In general formula (2), Q is preferably a hydroxyl group or an alkyl group having 1 to 2 carbon atoms when m1 or m2 is 0, and when m1 or m2 is 1 to 3, it is preferably a divalent organic group having 1 to 5 carbon atoms, more preferably a divalent organic group having 1 to 5 carbon atoms containing a urethane bond, and even more preferably a divalent organic group having 2 to 4 carbon atoms containing a urethane bond. In general formula (2), R is preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably a hydrogen atom or a methyl group, and even more preferably a hydrogen atom. In general formula (2), X is preferably selected from the group consisting of a linear or branched alkylene group having 1 to 5 carbon atoms and a substituted or unsubstituted fluorene group, more preferably selected from the group consisting of a linear or branched alkylene group having 1 to 3 carbon atoms and an unsubstituted fluorene group, and even more preferably a linear or branched alkylene group having 1 to 3 carbon atoms. Here, in the substituted or unsubstituted fluorene group, the 9th position of the fluorene is the bonding site.

[0038] For these reasons, the polymer (A) of this embodiment preferably includes a constituent unit (a) represented by the following general formula (3) from the viewpoint of further improving the balance between environmental compatibility and the performance of suppressing the generation of voids in the resulting semiconductor device.

[0039]

[0040] In general formula (3), m1 and m2 each independently represent an integer from 0 to 3, Q represents a hydrogen atom, a hydroxyl group, or a monovalent organic group having 1 to 10 carbon atoms when m1 or m2 is 0, and a single bond or a divalent to tetravalent organic group having 1 to 10 carbon atoms when m1 or m2 is 1 to 3, and multiple Qs may be the same or different, R represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or an alkoxy group having 1 to 3 carbon atoms, and multiple Rs may be the same or different, X represents a single bond, -SO ２-, -C(=O)-, linear and branched alkylene groups having 1 to 5 carbon atoms, linear and branched fluoroalkylene groups having 1 to 5 carbon atoms, or substituted or unsubstituted fluorene groups, where Y represents a divalent organic group.

[0041] In general formula (3), preferred embodiments of Q, R, X, and Y are the same as preferred embodiments of X, Q, and R in general formula (2) and Y in general formula (1), respectively.

[0042] When the number of moles of imide groups contained in polymer (A) of this embodiment is IM, and the number of moles of amide groups contained in polymer (A) of this embodiment is AM, the imidization rate expressed as {IM / (IM+AM)} × 100 (%) is preferably 90% or more, more preferably 95% or more, and even more preferably 98% or more, from the viewpoint of further improving the balance between environmental compatibility and the performance of suppressing the generation of voids in the resulting semiconductor device. The upper limit of the imidization rate of polymer (A) of this embodiment is not particularly limited, but for example, it may be 100% or less. Furthermore, from the viewpoint of further improving the balance between environmental compatibility and the performance of suppressing the generation of voids in the resulting semiconductor device, the imidization rate of polymer (A) of this embodiment is preferably 90% or more and 100% or less, more preferably 95% or more and 100% or less, and even more preferably 98% or more and 100% or less.

[0043] From the viewpoint of further improving the balance between environmental compatibility and the performance of suppressing the generation of voids in the resulting semiconductor device, the content of polymer (A) in the resin composition of this embodiment is preferably 20 parts by mass or more and 95 parts by mass or less, more preferably 30 parts by mass or more and 85 parts by mass or less, even more preferably 35 parts by mass or more and 80 parts by mass or less, even more preferably 40 parts by mass or more and 75 parts by mass or less, even more preferably 45 parts by mass or more and 70 parts by mass or less, and even more preferably 50 parts by mass or more and 65 parts by mass or less, when the total amount of solids in the resin composition is 100 parts by mass.

[0044] <Crosslinking agent (B)> The resin composition of this embodiment preferably further comprises a crosslinking agent (B). The crosslinking agent (B) of this embodiment preferably comprises a (meth)acrylate compound, and more preferably comprises a polyfunctional (meth)acrylate compound.

[0045] Examples of the polyfunctional (meth)acrylate compounds in this embodiment include difunctional (meth)acrylates such as diethylene glycol di(meth)acrylate, polyethylene glycol #200 di(meth)acrylate, and polyethylene glycol #400 di(meth)acrylate; trifunctional (meth)acrylates such as trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, and ethoxylated isocyanuric acid triacrylate; and pentaerythritol tetra(meth)acrylate. Examples include tetrafunctional (meth)acrylates such as rilate and ditrimethylolpropanetetra(meth)acrylate; hexafunctional (meth)acrylates such as dipentaerythritol hexa(meth)acrylate; octafunctional (meth)acrylates such as tripentaerythritol octa(meth)acrylate; and decafunctional (meth)acrylates such as tetrapentaerythritol deca(meth)acrylate. The polyfunctional (meth)acrylate compound of this embodiment may contain one or more of these.

[0046] The crosslinking agent (B) of this embodiment preferably comprises a polyfunctional (meth)acrylate compound having 3 to 20 (meth)acryloyloxy groups or (meth)acryloyl groups in the molecule, more preferably comprises a polyfunctional (meth)acrylate compound having 4 to 15 (meth)acryloyloxy groups or (meth)acryloyl groups in the molecule, and even more preferably comprises a polyfunctional (meth)acrylate compound having 5 to 10 (meth)acryloyloxy groups or (meth)acryloyl groups in the molecule.

[0047] The crosslinking agent (B) in this embodiment preferably comprises an epoxy compound.

[0048] The epoxy compounds of this embodiment preferably include epoxy compounds having a (meth)acryloyloxy group or a (meth)acryloyl group. The number of glycidyl groups contained in the molecule of the epoxy compound having a (meth)acryloyloxy group or a (meth)acryloyl group of this embodiment is preferably 1 to 6, more preferably 1 to 3, and even more preferably 1. The number of (meth)acryloyloxy group or (meth)acryloyl group contained in the molecule of the epoxy compound having a (meth)acryloyloxy group or a (meth)acryloyl group of this embodiment is preferably 0 to 6, more preferably 0 to 2, and even more preferably 1.

[0049] From the viewpoint of further improving the balance between environmental compatibility and the performance of suppressing void generation in the resulting semiconductor device, the content of the crosslinking agent (B) in the resin composition of this embodiment is preferably 5 to 50 parts by mass, more preferably 10 to 45 parts by mass, even more preferably 15 to 40 parts by mass, and even more preferably 17 to 35 parts by mass, when the total amount of solids in the resin composition is 100 parts by mass.

[0050] <Polymerization Initiator (C)> The resin composition of this embodiment preferably further comprises a polymerization initiator (C). As the polymerization initiator (C) of this embodiment, conventionally known polymerization initiators can be used within the range in which the effects of the present invention can be exhibited, and examples include photoradical generators and thermal radical generators.

[0051] If the resin composition of this embodiment includes a photocurable resin composition, it includes a photoradical generator as the polymerization initiator (C). If the resin composition of this embodiment includes a thermosetting resin composition, it includes a thermal radical generator as the polymerization initiator (C).

[0052] Examples of photoradical generators in this embodiment include alkylphenone type polymerization initiators, oxime ester type polymerization initiators, acylphosphine oxide type polymerization initiators, and more specifically, 1-hydroxycyclohexylphenyl ketone, 2,2-dimethoxy-1,2-diphenylethane-1-one, 2-methyl-1[4-(methylthio)phenyl]-2-molifolinopropan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-[4-(2-hydroxyethoxy)-phenyl Examples include Irgacure OXE01 (manufactured by BASF Japan), Irgacure OXE02 (manufactured by BASF Japan), Irgacure OXE03 (manufactured by BASF Japan), Irgacure OXE04 (manufactured by BASF Japan), etc. The polymerization initiator (C) of this embodiment may include one or more of these. The polymerization initiator (C) of this embodiment preferably includes an oxime ester type polymerization initiator, and more preferably includes Irgacure OXE01.

[0053] Examples of the thermal radical generating agent in this embodiment include 1,1-bis(t-butylperoxy)2-methylcyclohexane, 1,1-bis(t-hexylperoxy)-3,3,5-trimethylcyclohexane, 1,1-bis(t-hexylperoxy)cyclohexane, 1,1-bis(t-butylperoxy)-3,3,5-trimethylcyclohexane, 1,1-bis(t-butylperoxy)cyclohexane, and 2,2-bis(4,4-di-butylperoxycyclohexyl)propane. , 1,1-bis(t-butylperoxy)cyclododecane, t-hexylperoxyisopropyl monocarbonate, t-butylperoxymaleic acid, t-butylperoxy-3,5,5-trimethylhexanoate, t-butylperoxylaurate, 2,5-dimethyl-2,5-di(m-toluylperoxy)hexane, t-butylperoxyisopropyl monocarbonate, t-butylperoxy-2-ethylhexyl monocarbonate, t-hexylperoxybenzoate 2,5-dimethyl-2,5-di(benzoylperoxy)hexane, t-butylperoxyacetate, 2,2-bis(t-butylperoxy)butane, t-butylperoxybenzoate, n-butyl-4,4-bis(t-butylperoxy)valerate, di-t-butylperoxyisophthalate, α,α'-bis(t-butylperoxy)diisopropylbenzene, dicumylperoxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, t-butyl Organic peroxides such as methyl peroxide, di-t-butyl peroxide, p-menthane hydroperoxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexyn-3, diisopropylbenzene hydroperoxide, t-butyltrimethylsilyl peroxide, 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, t-hexyl hydroperoxide, t-butyl hydroperoxide, and benzoyl peroxide;Examples of azo compounds include azobisisobutyronitrile, 1,1'-azobis(cyclohexane-1-carbonitride), 2-(carbamoylazo)isobutyronitrile, 2-phenylazo-4-methoxy-2,4-dimethylvaleronitrile, azodi-t-octane, azodi-t-butane, and 2,2'-azobis[N-(2-propenyl)-2-methylpropionamide]; and the polymerization initiator (C) of this embodiment may include one or more of these. The polymerization initiator (C) of this embodiment preferably includes an organic peroxide, and more preferably includes a dicumyl peroxide.

[0054] From the viewpoint of further improving the balance between environmental compatibility and the performance of suppressing void generation in the resulting semiconductor device, the content of the polymerization initiator (C) in the resin composition of this embodiment is preferably 1 to 30 parts by mass, more preferably 3 to 25 parts by mass, even more preferably 5 to 20 parts by mass, and even more preferably 8 to 15 parts by mass, when the total amount of solids in the resin composition is 100 parts by mass.

[0055] The total content of polymer (A), crosslinking agent (B), and polymerization initiator (C) in the resin composition of this embodiment is preferably 80 parts by mass or more and 100 parts by mass or less, more preferably 85 parts by mass or more and 99 parts by mass or less, even more preferably 90 parts by mass or more and 98 parts by mass or less, even more preferably 92 parts by mass or more and 97 parts by mass or less, and even more preferably 93 parts by mass or more and 96 parts by mass or less, when the total amount of solids in the resin composition is 100 parts by mass.

[0056] When the polymer (A) content of this embodiment is 100 parts by mass, the crosslinking agent (B) content of this embodiment is preferably 10 parts by mass or more and 80 parts by mass or less, more preferably 15 parts by mass or more and 75 parts by mass or less, even more preferably 20 parts by mass or more and 70 parts by mass or less, and even more preferably 25 parts by mass or more and 65 parts by mass or less, from the viewpoint of further improving the balance between environmental compatibility and the performance of suppressing the generation of voids in the resulting semiconductor device.

[0057] When the polymer (A) content of this embodiment is 100 parts by mass, the content of the polymerization initiator (C) of this embodiment is preferably 1 to 40 parts by mass, more preferably 5 to 35 parts by mass, even more preferably 10 to 30 parts by mass, and even more preferably 15 to 25 parts by mass, from the viewpoint of further improving the balance between environmental compatibility and the performance of suppressing the generation of voids in the resulting semiconductor device.

[0058] <Antioxidant (D)> The resin composition of this embodiment further preferably comprises an antioxidant (D) having an isocyanuric acid skeleton.

[0059] The antioxidant (D) in this embodiment is not particularly limited as long as it is an antioxidant having an isocyanuric acid skeleton, and includes, for example, at least one selected from the group consisting of phenolic antioxidants, phosphite antioxidants, and thioether antioxidants, preferably a phenolic antioxidant, and more preferably a hindered phenolic antioxidant.

[0060] From the viewpoint of further improving the balance between environmental compatibility and the performance of suppressing the generation of voids in the resulting semiconductor device, the content of the antioxidant (D) in the resin 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 parts by mass or less, and even more preferably 1 part by mass or more and 3 parts by mass or less, when the content of polymer (A) is 100 parts by mass.

[0061] <Adhesion Aid> The resin composition of this embodiment preferably further contains an adhesion aid from the viewpoint of further improving adhesion. Examples of the adhesion aid of this embodiment include aminosilanes such as bis(2-hydroxyethyl)-3-aminopropyltriethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropylmethyldiethoxysilane, γ-aminopropylmethyldimethoxysilane, N-β(aminoethyl)γ-aminopropyltrimethoxysilane, N-β(aminoethyl)γ-aminopropyltriethoxysilane, N-β(aminoethyl)γ-aminopropylmethyldimethoxysilane, N-β(aminoethyl)γ-aminopropylmethyldiethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane; γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, or β-(3,4-epoxycyclohexyl Examples of adhesive agents include epoxysilanes such as ethyltrimethoxysilane and γ-glycidylpropyltrimethoxysilane; acrylicsilanes such as γ-(methacryloxypropyl)trimethoxysilane, γ-(methacryloxypropyl)methyldimethoxysilane, or γ-(methacryloxypropyl)methyldiethoxysilane; mercaptosilanes such as 3-mercaptopropyltrimethoxysilane; vinylsilanes such as vinyltris(β-methoxyethoxy)silane, vinyltriethoxysilane, and vinyltrimethoxysilane; ureidosilanes such as 3-ureidopropyltriethoxysilane; acid anhydride-functionalized silanes such as 3-trimethoxysilylpropyl succinic anhydride; and tetrazole derivatives such as 5-aminotetrazole monohydrate. The adhesion aid of this embodiment may contain one or more of these. Among these, the adhesion aid of this embodiment preferably comprises one or more selected from the group consisting of acrylic silane, acid anhydride-functionalized silane, and tetrazole derivatives, and more preferably comprises one or more selected from the group consisting of 3-methacryloxypropyltrimethoxysilane, 3-trimethoxysilylpropyl succinic anhydride, and 5-aminotetrazole monohydrate.

[0062] From the viewpoint of further improving adhesion, the content of the adhesion aid in the resin composition of this embodiment is preferably 1 to 10 parts by mass, more preferably 3 to 8 parts by mass, and even more preferably 5 to 7 parts by mass, when the content of polymer (A) is 100 parts by mass.

[0063] <Surfactants> The resin composition of this embodiment preferably further comprises surfactants. Examples of surfactants of this embodiment include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, and polyoxyethylene oleyl ether; polyoxyethylene aryl ethers such as polyoxyethylene octylphenyl ether and polyoxyethylene nonylphenyl ether; nonionic surfactants such as polyoxyethylene dialkyl esters such as polyoxyethylene dilaurate and polyoxyethylene distearate; F-Top EF301, F-Top EF303, F-Top EF352 (manufactured by Shin Akita Chemical Co., Ltd.), Megafac F171, Megafac F172, Megafac F173, Megafac F177, Megafac F444, Me Fluorine-based surfactants commercially available under names such as Gafac F470, Megafac F471, Megafac F475, Megafac F482, Megafac F477 (manufactured by DIC Corporation), Florard FC-430, Florard FC-431, Novec FC4430, Novec FC4432 (manufactured by 3M Japan), Surflon S-381, Surflon S-382, Surflon S-383, Surflon S-393, Surflon SC-101, Surflon SC-102, Surflon SC-103, Surflon SC-104, Surflon SC-105, Surflon SC-106 (manufactured by AGC Seimi Chemical Co., Ltd.); organosiloxane copolymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.); (meth)acrylic acid copolymer Polyflow No. Examples include silicone-based surfactants such as 57 and 95 (manufactured by Kyoeisha Chemical Co., Ltd.), and the surfactant of this embodiment may include one or more of these. Among these, the surfactant of this embodiment preferably includes a silicone-based surfactant.

[0064] The surfactant content in the resin composition of this embodiment is preferably 0.001 parts by mass or more and 0.5 parts by mass or less, and more preferably 0.01 parts by mass or more and 0.1 parts by mass or less, when the polymer (A) content is 100 parts by mass.

[0065] <Curing Catalyst> The resin composition of this embodiment preferably further comprises a curing catalyst. Examples of curing catalysts of this embodiment include phosphorus atom-containing compounds such as organophosphines, tetrasubstituted phosphonium compounds, phosphobetaine compounds, adducts of phosphine compounds and quinone compounds, and adducts of phosphonium compounds and silane compounds; amidines such as dicyandiamide, 2-phenyl-4,5-dihydroxymethylimidazole, 1,8-diazabicyclo[5.4.0]undecene-7, and benzyldimethylamine, tertiary amines and their derivatives; and nitrogen atom-containing compounds such as quaternary ammonium salts of the above amidines or tertiary amines. The curing catalyst of this embodiment may contain one or more of these. The curing catalyst of this embodiment preferably contains a phosphorus atom-containing compound, and more preferably contains a tetrasubstituted phosphonium compound.

[0066] The content of the curing catalyst in the resin composition of this embodiment is preferably 0.1 parts by mass or more and 5 parts by mass or less, and more preferably 0.5 parts by mass or more and 2 parts by mass or less, when the content of polymer (A) is 100 parts by mass.

[0067] <Other Additives> The resin composition of this embodiment may further contain other additives such as leveling agents, flame retardants, and plasticizers, as needed.

[0068] <Organic Solvents> The resin composition of this embodiment preferably further comprises an organic solvent. The organic solvent of this embodiment is preferably γ-butyrolactone (GBL), γ-valerolactone (GVL), 2,6-lutidine, N,N-dimethylacetamide pyruvate, 3-methoxy-N,N-dimethylpropionamide, dimethyl sulfoxide (DMSO), diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether acetate (PGMEA), methyl lactate, ethyl lactate (EL ), comprising one or more selected from the group consisting of butyl lactate, methyl-1,3-butylene glycol acetate, 1,3-butylene glycol-3-monomethyl ether, methyl pyruvate, ethyl pyruvate, methyl-3-methoxypropionate, N-ethyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, and 3-methyl-2-oxazolidone, more preferably comprising one or more selected from the group consisting of γ-butyrolactone (GBL) and ethyl lactate (EL), and even more preferably comprising both γ-butyrolactone (GBL) and ethyl lactate (EL).

[0069] The content of the organic solvent in the resin composition of this embodiment is preferably 50 parts by mass or more and 1000 parts by mass or less, more preferably 100 parts by mass or more and 700 parts by mass or less, even more preferably 150 parts by mass or more and 500 parts by mass or less, even more preferably 200 parts by mass or more and 400 parts by mass or less, and even more preferably 220 parts by mass or more and 300 parts by mass or less, when the total amount of solids in the resin composition is 100 parts by mass.

[0070] From the viewpoint of further improving environmental compatibility, the fluorine atom content in the resin composition of this embodiment is preferably 10 parts by mass or less, more preferably 5 parts by mass or less, even more preferably 3 parts by mass or less, even more preferably 1 part by mass or less, even more preferably 0.1 parts by mass or less, even more preferably 0.05 parts by mass or less, and even more preferably 0.01 parts by mass or less, when the total amount of solids in the resin composition is 100 parts by mass. The lower limit of the fluorine atom content in the resin composition of this embodiment is not particularly limited, but when the total amount of solids in the resin composition is 100 parts by mass or less, it may be, for example, 0 parts by mass or more.

[0071] From the viewpoint of further improving environmental compatibility, the fluorine atom content in the resin composition of this embodiment is preferably 0 parts by mass or more and 10 parts by mass or less, more preferably 0 parts by mass or more and 5 parts by mass or less, even more preferably 0 parts by mass or more and 3 parts by mass or less, even more preferably 0 parts by mass or more and 1 part by mass or less, even more preferably 0 parts by mass or more and 0.1 parts by mass or less, even more preferably 0 parts by mass or more and 0.05 parts by mass or less, and even more preferably 0 parts by mass or more and 0.01 parts by mass or less, when the total amount of solids in the resin composition is 100 parts by mass.

[0072] From the viewpoint of further improving environmental compatibility, the content of the polymer containing fluorine atoms in the resin composition of this embodiment is preferably 30 parts by mass or less, more preferably 20 parts by mass or less, even more preferably 10 parts by mass or less, even more preferably 5 parts by mass or less, even more preferably 1 part by mass or less, even more preferably 0.1 parts by mass or less, even more preferably 0.05 parts by mass or less, and even more preferably 0.01 parts by mass or less, when the total amount of solids in the resin composition is 100 parts by mass. The lower limit of the content of the polymer containing fluorine atoms in the resin composition of this embodiment is not particularly limited, but when the total amount of solids in the resin composition is 100 parts by mass or less, it may be, for example, 0 parts by mass or more.

[0073] From the viewpoint of further improving environmental compatibility, the content of the polymer containing fluorine atoms in the resin composition of this embodiment is preferably 0 to 30 parts by mass, more preferably 0 to 20 parts by mass, even more preferably 0 to 10 parts by mass, even more preferably 0 to 5 parts by mass, even more preferably 0 to 1 part by mass, even more preferably 0 to 0.1 parts by mass, even more preferably 0 to 0.05 parts by mass, and even more preferably 0 to 0.01 parts by mass, when the total amount of solids in the resin composition is 100 parts by mass.

[0074] The content of alkali-soluble resin in the resin composition of this embodiment is preferably 30 parts by mass or less, more preferably 20 parts by mass or less, even more preferably 10 parts by mass or less, even more preferably 5 parts by mass or less, even more preferably 1 part by mass or less, even more preferably 0.1 parts by mass or less, even more preferably 0.05 parts by mass or less, and even more preferably 0.01 parts by mass or less, when the total amount of solids in the resin composition is 100 parts by mass, from the viewpoint of further improving the balance between environmental compatibility and the performance of suppressing the generation of voids in the resulting semiconductor device. The lower limit of the content of alkali-soluble resin in the resin composition of this embodiment is not particularly limited, but when the total amount of solids in the resin composition is 100 parts by mass, it may be, for example, 0 parts by mass or more. In this specification, alkali-soluble resin is a resin that dissolves in an alkaline developer to a degree sufficient for patterning.

[0075] From the viewpoint of further improving the balance between environmental compatibility and the performance of suppressing the generation of voids in the resulting semiconductor device, the content of alkali-soluble resin in the resin composition of this embodiment is preferably 0 to 30 parts by mass, more preferably 0 to 20 parts by mass, even more preferably 0 to 10 parts by mass, even more preferably 0 to 5 parts by mass, even more preferably 0 to 1 part by mass, even more preferably 0 to 0.1 parts by mass, even more preferably 0 to 0.05 parts by mass, and even more preferably 0 to 0.01 parts by mass, when the total amount of solids in the resin composition is 100 parts by mass.

[0076] <Method for preparing the resin composition> The method for preparing the resin composition in this embodiment is not limited, and known methods can be used depending on the components contained in the resin composition. For example, it can be prepared by mixing and dissolving each of the above-mentioned components in a solvent.

[0077] <Die Shear Strength S> The die shear strength S of the structure (y) of this embodiment, measured by Method 1 below, is preferably 8 MPa or more, more preferably 9 MPa or more, from the viewpoint of further improving the bonding strength of the cured resin layer. The upper limit of the die shear strength S is not particularly limited, but for example it may be 50 MPa or less, or 25 MPa or less. (Method 1) A part of the structure (y), which has a substrate and a semi-cured resin layer on the first surface side of the substrate, is cut out to create a bottom die with dimensions of 10 mm x 10 mm and a top die with dimensions of 3 mm x 3 mm. Next, the bottom die is placed on a 25°C stage with the side on which the semi-cured resin layer is formed facing upwards. Next, the top die is lifted with the top tool of a bond tester set to 250°C with the side on which the semi-cured resin layer is formed facing downwards. Next, the top die is pressed against the bottom die with a force of 25 N for 10 seconds. Next, the resulting top die-bottom die joint is heated in an oven under a nitrogen atmosphere at the heating temperature T of the main curing process. １ The sample is heated for 120 mins to obtain the sample. Next, using a die shear device, the die shear strength S (MPa) of the sample is measured under the conditions of a shear rate of 300 μm / sec and a shear height of 10 μm.

[0078] The die shear strength S of the structure (y) of this embodiment, measured by method 1 above, is preferably 8 MPa to 50 MPa, more preferably 9 MPa to 25 MPa, from the viewpoint of further improving the balance between the bonding strength of the cured resin layer and the suppression of void generation in the resulting semiconductor device. The semiconductor device manufacturing method of this embodiment can further improve the balance between the bonding strength of the cured resin layer and the suppression of void generation in the resulting semiconductor device by setting the die shear strength S within the above range, thereby further suppressing the generation of voids in the resulting semiconductor device while maintaining the necessary bonding strength of the cured resin layer.

[0079] <Semi-cured film> The semi-cured film of this embodiment is a semi-cured film comprising a semi-cured resin layer of a resin composition containing a polymer (A) having an imide skeleton, wherein the resin composition comprises one or more selected from the group consisting of photocurable resin compositions and thermosetting resin compositions, and when the weight change of the semi-cured film is measured using a differential thermogravimetric analyzer under nitrogen flow and a heating rate of 10°C / min when the semi-cured film is heated from 30°C to 500°C, the weight loss rate from 30°C to 250°C is 3.0% by mass or less.

[0080] From the viewpoint of further suppressing the generation of voids in the resulting semiconductor device, the resin composition included in the semi-cured film of this embodiment preferably includes the resin composition used in the semiconductor device manufacturing method of this embodiment.

[0081] The weight loss rate of the semi-cured film in this embodiment from 30°C to 250°C is 3.0% by mass or less, preferably 2.5% by mass or less, more preferably 2.2% by mass or less, even more preferably 2.0% by mass or less, and even more preferably 1.8% by mass or less, from the viewpoint of further suppressing the generation of voids in the resulting semiconductor device. The lower limit of the above weight loss rate is not particularly limited, but for example, it may be 0.1% by mass or more.

[0082] From the viewpoint of further suppressing the generation of voids in the resulting semiconductor device, the weight loss rate of the semi-cured film in this embodiment from 30°C to 250°C is preferably 0.1% by mass or more and 3.0% by mass or less, more preferably 0.1% by mass or more and 2.5% by mass or less, even more preferably 0.1% by mass or more and 2.2% by mass or less, even more preferably 0.1% by mass or more and 2.0% by mass or less, and even more preferably 0.1% by mass or more and 1.8% by mass or less.

[0083] <Method of Manufacturing a Semiconductor Device> Figure 1 shows a schematic cross-sectional view illustrating the method of manufacturing a semiconductor device according to this embodiment. The method of manufacturing a semiconductor device according to this embodiment includes: a coating step (I) to obtain a structure (x) by forming a resin layer 30 by applying a resin composition containing one or more selected from the group consisting of photocurable resin compositions and thermosetting resin compositions to the first surface side of a substrate 10; a semi-curing step (II) to obtain a structure (y) by semi-curing the resin layer 30 in the structure (x) by heating to form a semi-cured resin layer 40; and heating the semi-cured resin layer 40 in the structure (y) to a temperature T １ The process includes a main curing step (III) to obtain a structure (z) by heating to cure the material and forming a cured resin layer 50.

[0084] In the coating step (I) of this embodiment, a resin layer 30 is formed by coating the first surface side of the substrate 10 with a resin composition containing one or more selected from the group consisting of photocurable resin compositions and thermosetting resin compositions to obtain a structure (x). The resin layer 30 can be formed by rotary coating using a spinner, spray coating using a spray coater, dipping, printing, roll coating, inkjet method, etc. When forming the resin layer 30, a heat treatment may be performed to dry the solvent contained in the resin composition. The conditions for this heat treatment are usually 80 to 140°C, preferably 90 to 130°C, and usually 0.5 to 10 min, preferably 1 to 5 min. The thickness of the resin layer 30 is typically 3 to 30 μm, preferably 5 to 20 μm.

[0085] In the semi-curing step (II) of this embodiment, the resin layer 30 in the structure (x) is semi-cured by heating to form a semi-cured resin layer 40, thereby obtaining the structure (y). The degree of curing of the semi-cured resin layer 40 may be adjusted by supplementary exposure treatment. As a light source, for example, X-rays, electron beams, ultraviolet light, visible light, etc., can be used. In terms of wavelength, active light with a wavelength of 200 to 500 nm is preferred. For ease of handling, the light source is preferably the g-line, h-line, or i-line of a mercury lamp. Alternatively, two or more light rays may be mixed and used. The integrated light intensity is, for example, 100 to 1500 mJ / cm². ２ Preferably 200 to 1000 mJ / cm²２ The irradiation intensity is, for example, 1 to 25 mW / cm². ２ The irradiation time is, for example, 5 to 300 seconds.

[0086] Here, "partially cured" refers to a state in which some of the (meth)acryloyl groups of the polyfunctional (meth)acrylate compound contained in the partially cured resin layer 40 have reacted, but not all of them have reacted, and when additional light irradiation is applied, the unreacted (meth)acryloyl groups will react further, allowing the curing to proceed.

[0087] In the semiconductor device manufacturing method of this embodiment, the material of the substrate 10 is not particularly limited and can be appropriately selected depending on the semiconductor device to be manufactured. The substrate 10 of this embodiment includes, for example, a semiconductor wafer containing one or more selected from the group consisting of silicon wafers, gallium nitride wafers, lithium tantalate wafers, lithium niobate wafers, silicon carbide wafers, germanium wafers, gallium-arsenide wafers, gallium-phosphorus wafers, and gallium-arsenide-aluminum wafers.

[0088] The semiconductor device manufacturing method of this embodiment may further include a step (II') before the main curing step (III) in which the first surfaces of two structures (y) are joined together to obtain a structure (y) joint. Specifically, the structures (y) are brought into contact such that the first surface of the first structure (y) and the first surface of the second structure (y) are in contact. Then, the first structure (y) and the second structure (y) can be joined by applying an appropriate treatment, preferably such as heat treatment. When heat treatment is applied to the joining, the heating conditions are, for example, 140 to 400°C, preferably 150 to 300°C, and for, for example, 10 to 240 min, preferably 30 to 180 min. Alternatively, the first structure (y) and the second structure (y) may be joined at room temperature without applying heat treatment.

[0089] If the semiconductor device manufacturing method of this embodiment further includes step (II'), the structure (y) to be cured in the main curing step (III) may be a structure (y) bond.

[0090] In a second embodiment, the method for manufacturing a semiconductor device of this embodiment may further include a step in which the structure (y) has a metal layer 20 in a portion of the first surface side of the substrate 10, and after the semi-curing step (II), the structure (y) is polished from the first surface side to form a layer including the metal layer 20 and the semi-cured resin layer 40. The method for polishing the structure (y) is not particularly limited, but chemical mechanical polishing is preferred.

[0091] Preferably, a portion of the semi-cured resin layer 40 is removed for a later process and flattened to the same height as the metal layer 20. In this case, in order to achieve high-precision flattening, a portion of the upper part of the metal layer 20 may be removed in addition to a portion of the semi-cured resin layer 40. However, the first surface of the structure (y) does not have to be perfectly coplanar with the metal layer 20 and the semi-cured resin layer 40. Specifically, the first surface of the structure (y) may have a convex shape with the metal layer 20 and a convex shape with the semi-cured resin layer 40.

[0092] The method for manufacturing a semiconductor device according to the second embodiment may further include a step of forming a metal layer 20 on a portion of the first surface side of the substrate 10 before the coating step (I). The method for forming the metal layer 20 on a portion of the first surface side of the substrate 10 is not particularly limited, and known methods can be used.

[0093] Based on these considerations, the method for manufacturing a semiconductor device according to the second embodiment preferably comprises: a step of forming a metal layer 20 in a portion of the first surface area of ​​the substrate 10; a coating step (I) of forming a resin layer 30 to obtain a structure (x) by applying a resin composition containing one or more selected from the group consisting of photocurable resin compositions and thermosetting resin compositions to the first surface area of ​​the substrate 10; a semi-curing step (II) of obtaining a structure (y) by semi-curing the resin layer 30 in the structure (x) by heating to form a semi-cured resin layer 40; a step of polishing the structure (y) from the first surface to form a layer containing the metal layer 20 and the semi-cured resin layer 40; and heating the semi-cured resin layer 40 in the structure (y) to a temperature T １ The method includes a main curing step (III) to obtain a structure (z) by heating to cure the material and forming a cured resin layer 50. A schematic cross-sectional view illustrating the method for manufacturing a semiconductor device according to the second embodiment is shown in Figure 2.

[0094] A second embodiment of the method for manufacturing a semiconductor device more preferably comprises: a step of forming a metal layer 20 in a portion of the first surface area of ​​a substrate 10; a coating step (I) of forming a resin layer 30 to obtain a structure (x) by applying a resin composition containing one or more selected from the group consisting of photocurable resin compositions and thermosetting resin compositions to the first surface area of ​​the substrate 10; a semi-curing step (II) of obtaining a structure (y) by semi-curing the resin layer 30 in the structure (x) by heating to form a semi-cured resin layer 40; a step of polishing the structure (y) from the first surface to form a layer containing the metal layer 20 and the semi-cured resin layer 40; a step (II') of obtaining a structure (y) joint by joining the first surfaces of two structures (y); and heating the semi-cured resin layer 40 in the structure (y) joint to a temperature T １ The process includes a main curing step (III) to obtain a structure (z') by heating to cure the material and forming a cured resin layer 50. A schematic cross-sectional view illustrating the manufacturing method of a semiconductor device according to the second embodiment, which includes step (II'), is shown in Figure 3.

[0095] In a third embodiment, the method for manufacturing a semiconductor device of this embodiment may further include a step of forming a recess 35 by exposing and developing the resin layer 30 in the structure (x) after a coating step (I), and an embedding step of embedding the metal layer 20 in the recess 35 in the structure (y) after a semi-curing step (II), wherein the resin composition includes a photocurable resin composition. The method for exposing and developing the resin layer 30 in the structure (x) and the method for embedding the metal layer 20 in the recess 35 in the structure (y) are not particularly limited, and known methods can be used.

[0096] The third embodiment of the semiconductor device manufacturing method may further include, after the embedding step, a step of polishing the structure (y) from the first surface side to form a layer including the metal layer 20 and the semi-cured resin layer 40. As a method for polishing the structure (y), for example, the same method as in the second embodiment can be used.

[0097] Based on these considerations, the manufacturing method of the semiconductor device according to the third embodiment preferably comprises: a coating step (I) to obtain a structure (x) by forming a resin layer 30 by applying a resin composition containing one or more selected from the group consisting of photocurable resin compositions and thermosetting resin compositions to the first surface side of a substrate 10; a step of forming a recess 35 by exposing and developing the resin layer 30 in the structure (x); a semi-curing step (II) to obtain a structure (y) by semi-curing the resin layer 30 in the structure (x) by heating to form a semi-cured resin layer 40; an embedding step of embedding a metal layer 20 in the recess 35 in the structure (y); a step of polishing the structure (y) from the first surface side to form a layer including the metal layer 20 and the semi-cured resin layer 40; and heating the semi-cured resin layer 40 in the structure (y) to a temperature T １ The method includes a main curing step (III) to obtain a structure (z) by heating to cure the material and forming a cured resin layer 50. A schematic cross-sectional view illustrating the manufacturing method of the semiconductor device according to the third embodiment is shown in Figure 4.

[0098] A third embodiment of a semiconductor device manufacturing method more preferably comprises: a coating step (I) to obtain a structure (x) by forming a resin layer 30 by applying a resin composition containing one or more selected from the group consisting of photocurable resin compositions and thermosetting resin compositions to the first surface side of a substrate 10; a step of forming a recess 35 by exposing and developing the resin layer 30 in the structure (x); a semi-curing step (II) to obtain a structure (y) by semi-curing the resin layer 30 in the structure (x) by heating to form a semi-cured resin layer 40; an embedding step of embedding a metal layer 20 in the recess 35 in the structure (y); a step of polishing the structure (y) from the first surface side to form a layer containing the metal layer 20 and the semi-cured resin layer 40; a step (II') to obtain a structure (y) joint by joining the first surfaces of two structures (y); and heating the semi-cured resin layer 40 in the structure (y) joint to a temperature T １ The process includes a main curing step (III) to obtain a structure (z') by heating to cure the material and forming a cured resin layer 50. A schematic cross-sectional view illustrating the manufacturing method of a semiconductor device according to the third embodiment, which includes step (II'), is shown in Figure 5.

[0099] In the manufacturing method of the semiconductor device according to the second and third embodiments, the metal layer 20 preferably contains one or more copper-containing metals selected from the group consisting of copper, copper-aluminum alloys, and copper-silver alloys.

[0100] In the semiconductor device manufacturing methods of the second and third embodiments, polishing is preferably performed by chemical mechanical polishing. The polishing slurry used for chemical mechanical polishing preferably contains one or more polishing particles selected from the group consisting of silica particles, alumina particles, and polymer beads.

[0101] The semiconductor device manufacturing method of this embodiment is preferably applicable to various bonding processes in the manufacturing of semiconductor devices. More specifically, the semiconductor device manufacturing method of this embodiment is preferably applicable to circuit board lamination processes (bonding processes) such as COW (Chip On Wafer), COC (Chip On Chip), and WOW (Wafer On Wafer).

[0102] In this embodiment, the metal layer, resin layer, semi-cured resin layer, and cured resin layer can also be interpreted as the metal phase, resin phase, semi-cured resin phase, and cured resin phase, respectively.

[0103] Although embodiments of the present invention have been described above, these are merely examples, and various other configurations can be adopted as long as they do not impair the effects of the present invention.

[0104] Embodiments of the present invention will be described in detail based on examples and comparative examples. However, the present invention is not limited to these examples.

[0105] <Compounds used in the synthesis of polyimides> The following compounds were used in the synthesis of polyimides.

[0106] 2,2-bis(3-amino-4-hydroxyphenyl)propane (hereinafter also referred to as BAPA), represented by the following formula.

[0107]

[0108] The compound is represented by the following formula: 4-[4-(1,3-dioxoisobenzofuran-5-ylcarbonyloxy)-2,3,5-trimethylphenyl]-2,3,6-trimethylphenyl-1,3-dioxoisobenzofuran-5-carboxylate (hereinafter also referred to as TMPBP-TME).

[0109]

[0110] 4,4-diamino-3,3-diethyl-5,5-dimethyldiphenylmethane (hereinafter also referred to as MED-J), represented by the following formula.

[0111]

[0112] <Synthesis of Polyimide 1> First, 27.5 g (106.6 mmol) of BAPA, 146.5 g (236.8 mmol) of TMPBP-TME, and 30.1 g (106.6 mmol) of MED-J were placed in a reaction vessel of appropriate size equipped with a stirrer and a condenser. Then, 767.6 g of γ-butyrolactone (GBL) was added to the reaction vessel. After aeration with nitrogen for 10 mins, the temperature was raised to 60°C while stirring and the reaction was carried out for 1.5 hours. After that, the reaction was carried out at 180°C for 3 hours to polymerize BAPA, TMPBP-TME, and MED-J, and a polymerization solution was prepared. Next, to the entire volume of the obtained polyimide solution (213.2 mmol in terms of hydroxyl groups), 60.2 g (426.3 mmol) of 2-isocyanatoethyl acrylate (manufactured by Tokyo Chemical Industry Co., Ltd.), 1.6 g (10.0 mmol) of 2-hydroxy-1,4-naphthoquinone (manufactured by Tokyo Chemical Industry Co., Ltd.), and 3.3 g of GBL 8 were added. The mixture was then stirred and the temperature was raised to 120°C for 6 hours. The resulting reaction solution was diluted with tetrahydrofuran to prepare a dilution, and then the dilution was added dropwise to methanol to precipitate a white solid. The obtained white solid was collected and vacuum-dried at 40°C to obtain 218.1 g of polyimide 1. １¹H-NMR measurements revealed peaks in the aromatic region (6.8 ppm to 8.9 ppm) with area ratios corresponding to the number of protons. Furthermore, the area ratio between the aromatic region (6.8 ppm to 8.9 ppm) and the alkene region (5.8 ppm to 6.5 ppm) indicated a crosslinking group introduction rate of 93%. The obtained polyimide 1 contained repeating units represented by the following formula in part.

[0113] (In the above equation, x:y = 50:50)

[0114] <Synthesis of Polyimide 2> Polyimide 2 was obtained in the same manner as the synthesis of Polyimide 1, except that the amounts of BAPA and TMPBP-TME added were changed so that the ratio of x to y in the repeating units contained in the polyimide was x:y = 100:0, and MED-J was not added.

[0115] <Components used in the preparation of the resin composition> The following components were used in the preparation of the resin composition.

[0116] • Acrylate compound 1: A polyfunctional acrylate compound represented by the following formula (manufactured by Shin-Nakamura Chemical Industry Co., Ltd., A-DPH)

[0117] • Acrylate compound 2: A polyfunctional acrylate compound represented by the following formula (manufactured by Shin-Nakamura Chemical Industry Co., Ltd., A-9300S-NT)

[0118] Epoxy compound 1: 4-hydroxybutyl acrylate glycidyl ether represented by the following formula (manufactured by Shinryo Co., Ltd., 4HBAGE)

[0119] • Epoxy compound 2: A trifunctional epoxy compound represented by the following formula (Printec Co., Ltd., VG3101L)

[0120] • Polymerization initiator 1: Compound represented by the following formula (BASF, Irgacure OXE01)

[0121] • Polymerization initiator 2: Dicumyl peroxide represented by the following formula (Nurion Co., Ltd., Percadox BC-FF)

[0122] Antioxidant 1: Compound represented by the following formula (KEMINOX 179, manufactured by Chemipro Chemical Co., Ltd.)

[0123] • Adhesion aid 1: 3-trimethoxysilylpropyl succinic anhydride represented by the following formula (manufactured by Shin-Etsu Chemical Co., Ltd., X-12-967C)

[0124] • Adhesion aid 2: 3-methacryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-503), represented by the following formula.

[0125] • Adhesion aid 3: 5-aminotetrazole monohydrate represented by the following formula (manufactured by Masuda Chemical Industries, Ltd., 5AT)

[0126] • Curing catalyst 1: Tetrasubstituted phosphonium compound represented by the following formula (manufactured by Sumitomo Bakelite Co., Ltd., tetraphenylphosphonium 4,4'-sulfonyl diphenolate)

[0127] • Surfactant 1: Silicone-based surfactant (BYK Corporation, BYK-349)

[0128] • Solvent 1: γ-butyrolactone (GBL) • Solvent 2: Ethyl lactate (EL)

[0129] <Preparation of Resin Composition 1> Resin composition 1 was prepared by mixing polyimide 1 (100 parts by mass), acrylate compound 1 (40 parts by mass), acrylate compound 2 (15 parts by mass), epoxy compound 1 (5 parts by mass), epoxy compound 2 (2 parts by mass), polymerization initiator 1 (10 parts by mass), polymerization initiator 2 (10 parts by mass), antioxidant 1 (2 parts by mass), adhesion aid 1 (2 parts by mass), adhesion aid 2 (2 parts by mass), adhesion aid 3 (2 parts by mass), curing catalyst 1 (1 part by mass), surfactant 1 (0.02 parts by mass), solvent 1 (350 parts by mass), and solvent 2 (90 parts by mass).

[0130] <Preparation of Resin Composition 2> Resin composition 2 was prepared by mixing polyimide 2 (100 parts by mass), acrylate compound 1 (20 parts by mass), acrylate compound 2 (5 parts by mass), epoxy compound 1 (2 parts by mass), epoxy compound 2 (2 parts by mass), polymerization initiator 1 (10 parts by mass), polymerization initiator 2 (10 parts by mass), antioxidant 1 (2 parts by mass), adhesion aid 1 (2 parts by mass), adhesion aid 2 (2 parts by mass), adhesion aid 3 (2 parts by mass), curing catalyst 1 (1 part by mass), surfactant 1 (0.02 parts by mass), solvent 1 (350 parts by mass), and solvent 2 (90 parts by mass).

[0131] <Fabrication of the structure> (Example 1) A resin layer was formed on a silicon wafer by spin coating with resin composition 1 and soft baking at 110°C for 3 minutes. Next, a high-pressure mercury lamp was used to apply 300 mJ / cm² to the resin layer. ２ , irradiation intensity 4mW / cm ２ Next, exposure was performed for an irradiation time of 75 seconds. Then, the resin layer was heated together with the silicon wafer at 300°C for 2 min to obtain structure (y) of Example 1 having a semi-cured resin layer with a thickness of 3 μm. Then, structure (y) was heated in an oven under a nitrogen atmosphere at a heating temperature T １ The mixture was heated to 250°C for 120 min to obtain structure (z) of Example 1 having a cured resin layer.

[0132] (Example 2) Except for changing the heating time of the resin layer to 5 min, the structures (y) and (z) of Example 2 were obtained in the same manner as in Example 1.

[0133] (Example 3) The heating time of the resin layer was changed to 5 min, and the heating temperature T of the structure (y) was changed. １ Except for changing the temperature to 300°C, the structures (y) and (z) of Example 3 were obtained in the same manner as in Example 1.

[0134] (Example 4) Except for changing the resin composition used to resin composition 2 and changing the heating temperature of the resin layer to 200°C, structures (y) and (z) of Example 4 were obtained in the same manner as in Example 1.

[0135] (Example 5) The resin composition used was changed to resin composition 2, the heating temperature of the resin layer was changed to 200°C, and the heating temperature of the structure (y) was changed to T １ Except for changing the temperature to 300°C, the structures (y) and (z) of Example 5 were obtained in the same manner as in Example 1.

[0136] (Example 6) The heating temperature of the resin layer was changed to 250°C, and the heating temperature of the structure (y) was changed to T １ Except for changing the temperature to 300°C, the structures (y) and (z) of Example 6 were obtained in the same manner as in Example 1.

[0137] (Comparative Example 1) Structures (y) and (z) of Comparative Example 1 were obtained in the same manner as in Example 1, except that the resin composition used was changed to resin composition 2 and the heating temperature of the resin layer was changed to 120°C.

[0138] (Comparative Example 2) The resin composition used was changed to resin composition 2, the heating temperature of the resin layer was changed to 120°C, and the heating temperature of the structure (y) was changed to T １ Structure (y) and structure (z) of Comparative Example 2 were obtained in the same manner as in Example 1, except that the temperature was changed to 300°C.

[0139] <Weight Loss Rate> For each example and comparative example, the semi-cured resin layer was removed from the structure (y). Then, using a differential thermogravimetric analyzer (STA7200, Hitachi High-Tech Science Corporation), the weight change of the semi-cured resin layer was measured when it was heated from 30°C to 500°C under nitrogen flow conditions and a heating rate of 10°C / min, and the heating temperature T of the structure (y) in each example and comparative example was measured from 30°C. １ The weight loss rate (mass %) was calculated. In the measurement, the mass of the semi-cured resin layer was 0.005 g, and the nitrogen gas flow rate was 200 mL / min. The results are shown in Tables 1 and 2.

[0140] <Die Shear Strength S> For each example and comparative example, a portion of a structure (y) having a substrate and a semi-cured resin layer on the first surface side of the substrate was cut out to create a bottom die with dimensions of 10 mm x 10 mm and a top die with dimensions of 3 mm x 3 mm. Next, the bottom die was placed on a stage at 25°C with the side where the semi-cured resin layer was formed facing upwards. Next, the top die was lifted with the top tool of a bond tester set to 250°C with the side where the semi-cured resin layer was formed facing downwards. Next, the top die was pressed against the bottom die with a force of 25 N for 10 seconds. Next, the resulting top die-bottom die joint (structure (y) joint) was heated in an oven under a nitrogen atmosphere at the heating temperature T of the structure (y) in each example and comparative example. １ The sample (structure (z')) was heated for 120 min. Next, the die shear strength S (MPa) of the sample was measured using a die shear device (Nordson, DAGE4000) under conditions of a shear rate of 300 μm / sec and a shear height of 10 μm. The results are shown in Tables 1 and 2.

[0141] <Void Evaluation by SAT> For each example and comparative example, a sample prepared in the same manner as for measuring the die shear strength S was cut perpendicular to the first surface, the cross-section was polished, and the cross-section was observed using an ultrasonic imaging device (SAT, Hitachi High-Tech Corporation, FS300II). Next, the voids in the cured resin layer of the sample prepared in the same manner as for measuring the die shear strength S for each example and comparative example were evaluated according to the following criteria. The results are shown in Tables 1 and 2. A: No voids were present in the cured resin layer B: Voids were present in the cured resin layer

[0142] <Void Evaluation by SEM> For each example and comparative example, a sample prepared in the same manner as for measuring the die shear strength S was cut perpendicular to the first surface, the cross-section was polished, and the cross-section was observed using a scanning electron microscope (SEM, Hitachi High-Tech Corporation, TM3030Plus). Next, the voids in the cured resin layer of the sample prepared in the same manner as for measuring the die shear strength S for each example and comparative example were evaluated according to the following criteria. The results are shown in Tables 1 and 2. A: No voids were present in the cured resin layer B: Voids were present in the cured resin layer

[0143] While no difference was found between Examples 1-6 and Comparative Examples 1-2 in the void evaluation using SAT, a higher-resolution measuring device, void evaluation using SEM revealed that no voids were present in the cured resin layers of Examples 1-6, while voids were present in the cured resin layers of Comparative Examples 1-2.

[0144] (Example 7) Resin composition 1 was applied to a silicon wafer by spin coating and a resin layer was formed by soft baking at 110°C for 3 minutes. Then, a high-pressure mercury lamp was used to heat the resin layer at 300 mJ / cm² through a mask on which a via pattern with a width of 5 μm was drawn. ２ , irradiation intensity 4mW / cm ２ The material was exposed for 75 seconds. Next, the resin layer was sprayed with cyclopentanone for 10 seconds while spinning it at 2500 rpm, then sprayed with propylene glycol methyl ether acetate for 10 seconds, then spun for 20 seconds to dry and develop. This formed depressions in the resin layer. Next, the resin layer, together with the silicon wafer, was heated at 250°C for 2 mins to obtain a structure (y) having a semi-cured resin layer with a thickness of 3 μm. Next, a barrier metal was sputtered onto the first surface of the structure (y), and then copper plating with a thickness of 10 μm was performed to fill the depressions in the structure (y) with a copper layer. Next, the structure (y) was chemically and mechanically polished from the first surface until the semi-cured resin layer was exposed, forming a layer containing the copper layer and the semi-cured resin layer, and obtaining the structure (y) of Example 7.

[0145] <Defect Evaluation of Polished Surface> The surface of the semi-cured resin layer in structure (y) of Example 7 was observed using an optical microscope (Keyence Corporation, VHX-5000). Next, the defects of the polished surface of the semi-cured resin layer were evaluated according to the following criteria. The results are shown in Table 2. A: No scratches on the surface of the semi-cured resin layer B: Scratches were present on the surface of the semi-cured resin layer

[0146] <Evaluation of Polished Surface Smoothness> The arithmetic mean roughness Ra of the surface of the semi-cured resin layer in structure (y) of Example 7 was measured using an atomic force microscope (AFM, Shimadzu Corporation, SPM-9700HT). Next, the smoothness of the polished surface of the semi-cured resin layer was evaluated according to the following criteria. The results are shown in Table 2. A: The arithmetic mean roughness Ra of the surface of the semi-cured resin layer was less than 2.0 nm. B: The arithmetic mean roughness Ra of the surface of the semi-cured resin layer was 2.0 nm or more.

[0147] <Bonding Evaluation> For Example 7, a portion of a structure (y) having a substrate and a semi-cured resin layer on the first surface side of the substrate was cut out to create a bottom die with dimensions of 9 mm x 9 mm and a top die with dimensions of 6 mm x 6 mm. Next, the bottom die was placed on a stage at 25°C with the side where the semi-cured resin layer was formed facing upwards. Next, the top die was lifted with the top tool of a bond tester set to 250°C with the side where the semi-cured resin layer was formed facing downwards. Next, the top die was pressed against the bottom die with a pressure of 2.5 MPa for 10 seconds so that the respective semi-cured resin layers were in contact. Next, the resulting top die-bottom die joint (structure (y) joint) was heated in an oven under a nitrogen atmosphere at 300°C for 120 mins to fully cure the semi-cured resin layer into a cured resin layer, thereby obtaining the structure (z') of Example 7. Next, the structure (z') was cut perpendicular to the first surface, the cross-section was polished, and then the cross-section was observed using a scanning electron microscope (SEM, Hitachi High-Tech Corporation, TM3030Plus). Figure 6 shows the SEM image of the cross-section of structure (z') of Example 7. Next, the bonding properties of the cured resin layer in structure (z') were evaluated according to the following criteria. The results are shown in Table 2. A: No boundary line was found at the bonding interface of the cured resin layer. B: A boundary line was found at the bonding interface of the cured resin layer.

[0148]

[0149]

[0150] Some or all of the above embodiments and examples may also be described as follows, but are not limited to the following: [1] A coating step to obtain a structure (x) by forming a resin layer by applying a resin composition containing one or more selected from the group consisting of photocurable resin compositions and thermosetting resin compositions to the first surface side of a substrate; a semi-curing step to obtain a structure (y) by semi-curing the resin layer in the structure (x) by heating to a semi-cured resin layer; and heating the semi-cured resin layer in the structure (y) to a temperature T １ The process includes a main curing step in which a structure (z) is obtained by heating to fully cure the resin to form a cured resin layer, and when the weight change of the semi-cured resin layer is measured using a differential thermogravimetric analyzer under nitrogen flow conditions and a heating rate of 10°C / min, the weight change of the semi-cured resin layer is measured when the semi-cured resin layer is heated from 30°C to 500°C, from 30°C to the T １ A method for manufacturing a semiconductor device in which the weight reduction rate up to is 3.0% by mass or less. [2] The method for manufacturing a semiconductor device according to [1], wherein the heating temperature of the semi-curing step is 150°C or more and 400°C or less. [3] The method for manufacturing a semiconductor device according to [1] or [2], wherein the heating time of the semi-curing step is 0.1 min or more and 30 min or less. [4] The T １A method for manufacturing a semiconductor device according to any one of [1] to [3], wherein the curing temperature is 150°C or more and 400°C or less. [5] A method for manufacturing a semiconductor device according to any one of [1] to [4], wherein the heating time for the curing step is 10 min or more and 600 min or less. [6] A method for manufacturing a semiconductor device according to any one of [1] to [5], wherein the resin composition comprises a polymer (A) having an imide skeleton. [7] A method for manufacturing a semiconductor device according to [6], wherein the polymer (A) comprises one or more polymers selected from the group consisting of polyimide and polyimide precursors. [8] A method for manufacturing a semiconductor device according to [6] or [7], wherein the polymer (A) contains a carbon-carbon double bond in its side chain. [9] A method for manufacturing a semiconductor device according to any one of [1] to [8], wherein when the total amount of solids in the resin composition is 100 parts by mass, the content of fluorine atoms is 10 parts by mass or less.

[10] A method for manufacturing a semiconductor device according to any one of [1] to [9], wherein when the total amount of solids in the resin composition is 100 parts by mass, the content of polymers containing fluorine atoms is 30 parts by mass or less.

[11] The method for manufacturing a semiconductor device according to any one of [1] to

[10] , wherein when the total amount of solids in the resin composition is 100 parts by mass, the content of alkali-soluble resin is 30 parts by mass or less.

[12] The method for manufacturing a semiconductor device according to any one of [1] to

[11] , wherein the die shear strength S of the structure (y) measured by the method 1 below is 8 MPa or more. (Method 1) A part of the structure (y), which has the substrate and the semi-cured resin layer on the first surface side of the substrate, is cut out to create a bottom die with dimensions of 10 mm x 10 mm and a top die with dimensions of 3 mm x 3 mm. Next, the bottom die is placed on a stage at 25°C with the side on which the semi-cured resin layer is formed facing upwards. Next, the top die is lifted with the top tool of a bond tester set to 250°C with the side on which the semi-cured resin layer is formed facing downwards. Next, the top die is pressed against the bottom die with a force of 25 N for 10 seconds. Next, the resulting top die-bottom die joint is subjected to a nitrogen atmosphere using an oven, and the T １The sample is heated for 120 min to obtain a sample. Then, using a die shear device, the die shear strength S (MPa) of the sample is measured under the conditions of a shear rate of 300 μm / sec and a shear height of 10 μm.

[13] A method for manufacturing a semiconductor device according to any one of [1] to

[12] , further comprising a step of obtaining a structure (y) joint by joining the first faces of two of the structures (y) before the main curing step.

[14] A method for manufacturing a semiconductor device according to

[13] , wherein the structure (y) to be cured in the main curing step is the structure (y) joint.

[15] A method for manufacturing a semiconductor device according to any one of [1] to

[14] , wherein the structure (y) further has a metal layer in a part of the area on the first face side of the substrate, and further comprising a step of polishing the structure (y) from the first face side after the semi-curing step to form a layer including the metal layer and the semi-cured resin layer.

[16] The method for manufacturing a semiconductor device according to

[15] , further comprising the step of forming the metal layer in a portion of the first surface side of the substrate before the coating step.

[17] The method for manufacturing a semiconductor device according to any one of [1] to

[14] , wherein the resin composition comprises a photocurable resin composition, and further comprising the steps of forming a recess by exposing and developing the resin layer in the structure (x) after the coating step, and embedding the metal layer in the recess in the structure (y) after the semi-curing step.

[18] The method for manufacturing a semiconductor device according to

[17] , further comprising the step of polishing the structure (y) from the first surface side after the embedding step to form a layer including the metal layer and the semi-cured resin layer.

[19] A semi-cured film comprising a semi-cured resin layer of a resin composition comprising a polymer (A) having an imide skeleton, wherein the resin composition comprises one or more selected from the group consisting of photocurable resin compositions and thermosetting resin compositions, and the weight change of the semi-cured film is measured when the semi-cured film is heated from 30°C to 500°C under nitrogen flow conditions and a heating rate of 10°C / min using a differential thermogravimetric analyzer, and the weight loss rate from 30°C to 250°C is 3.0% by mass or less.

[0151] This application claims priority based on Japanese Patent Application No. 2025-008628, filed on 21 January 2025, and Japanese Patent Application No. 2025-024404, filed on 18 February 2025, and incorporates all of their disclosures herein.

[0152] 10 Substrate 20 Metal layer 30 Resin layer 35 Recess 40 Semi-cured resin layer 50 Cured resin layer (I) Coating process (II) Semi-curing process (III) Full curing process

Claims

1. A coating step to obtain a structure (x) by forming a resin layer by applying a resin composition containing a photocurable resin composition to the first surface side of a substrate; a step to form a recess by exposing and developing the resin layer in the structure (x); a semi-curing step to obtain a structure (y) by semi-curing the resin layer in the structure (x) by heating to form a semi-cured resin layer; an embedding step to embed a metal layer in the recess in the structure (y); a step to polish the structure (y) from the first surface side to form a layer including the metal layer and the semi-cured resin layer; a step to obtain a structure (y) joint by joining the first surfaces of two of the structure (y); and a step to heat the semi-cured resin layer in the structure (y) joint to a temperature T １ The process includes a main curing step in which a structure (z') is obtained by heating to fully cure the resin to form a cured resin layer, and when the weight change of the semi-cured resin layer is measured using a differential thermogravimetric analyzer under nitrogen flow conditions and a heating rate of 10°C / min, the weight change of the semi-cured resin layer is measured when the semi-cured resin layer is heated from 30°C to 500°C, from 30°C to the T １ A method for manufacturing a semiconductor device in which the weight reduction rate up to 3.0% by mass or less. In the above measurement, the mass of the semi-cured resin layer is 0.005 g, and the nitrogen gas flow rate is 200 mL / min.

2. A step of forming a metal layer on a portion of the first surface of a substrate; a coating step of forming a resin layer to obtain a structure (x) by applying a resin composition containing one or more selected from the group consisting of a photocurable resin composition and a thermosetting resin composition to the first surface of the substrate; a semi-curing step of obtaining a structure (y) by semi-curing the resin layer in the structure (x) by heating to form a semi-cured resin layer; a step of polishing the structure (y) from the first surface to form a layer containing the metal layer and the semi-cured resin layer; a step of obtaining a structure (y) joint by joining the first surfaces of two of the structure (y); and a step of heating the semi-cured resin layer in the structure (y) joint to a temperature T １ The process includes a main curing step in which a structure (z') is obtained by heating to fully cure the resin to form a cured resin layer, and when the weight change of the semi-cured resin layer is measured using a differential thermogravimetric analyzer under nitrogen flow conditions and a heating rate of 10°C / min, the weight change of the semi-cured resin layer is measured when the semi-cured resin layer is heated from 30°C to 500°C, from 30°C to the T １ A method for manufacturing a semiconductor device in which the weight reduction rate up to 3.0% by mass or less. In the above measurement, the mass of the semi-cured resin layer is 0.005 g, and the nitrogen gas flow rate is 200 mL / min.

3. The method for manufacturing a semiconductor device according to claim 1 or 2, wherein the heating temperature of the semi-curing step is 150°C or higher and 400°C or lower.

4. The method for manufacturing a semiconductor device according to any one of claims 1 to 3, wherein the heating time for the semi-curing step is 0.1 min or more and 30 min or less.

5. Said T １ A method for manufacturing a semiconductor device according to any one of claims 1 to 4, wherein the temperature is 150°C or higher and 400°C or lower.

6. The method for manufacturing a semiconductor device according to any one of claims 1 to 5, wherein the heating time for the curing step is 10 min or more and 600 min or less.

7. A method for manufacturing a semiconductor device according to any one of claims 1 to 6, wherein the resin composition comprises a polymer (A) having an imide skeleton.

8. The method for manufacturing a semiconductor device according to claim 7, wherein the polymer (A) comprises one or more polymers selected from the group consisting of polyimides and polyimide precursors.

9. The method for manufacturing a semiconductor device according to claim 7 or 8, wherein the polymer (A) contains a carbon-carbon double bond in its side chain.

10. A method for manufacturing a semiconductor device according to any one of claims 1 to 9, wherein the content of fluorine atoms is 10 parts by mass or less when the total amount of solids in the resin composition is 100 parts by mass.

11. A method for manufacturing a semiconductor device according to any one of claims 1 to 10, wherein, when the total amount of solids in the resin composition is 100 parts by mass, the content of a polymer containing fluorine atoms is 30 parts by mass or less.

12. The method for manufacturing a semiconductor device according to any one of claims 1 to 11, wherein the content of alkali-soluble resin is 30 parts by mass or less when the total amount of solids in the resin composition is 100 parts by mass.

13. A method for manufacturing a semiconductor device according to any one of claims 1 to 12, wherein the die shear strength S of the structure (y) measured by the method 1 below is 8 MPa or more. (Method 1) A part of the structure (y), which has the substrate and the semi-cured resin layer on the first surface side of the substrate, is cut out to create a bottom die with dimensions of 10 mm x 10 mm and a top die with dimensions of 3 mm x 3 mm. Next, the bottom die is placed on a stage at 25°C with the side on which the semi-cured resin layer is formed facing upwards. Next, the top die is lifted with the top tool of a bond tester set to 250°C with the side on which the semi-cured resin layer is formed facing downwards. Next, the top die is pressed against the bottom die with a force of 25 N for 10 seconds. Next, the resulting top die-bottom die bond is subjected to the T １ The sample is heated for 120 mins to obtain a sample. Next, using a die shear device, the die shear strength S (MPa) of the sample is measured under the conditions of a shear rate of 300 μm / sec and a shear height of 10 μm.

14. A semi-cured film comprising a semi-cured resin layer of a resin composition containing a polymer (A) having an imide skeleton, wherein the resin composition comprises one or more selected from the group consisting of photocurable resin compositions and thermosetting resin compositions, and the weight change of the semi-cured film is measured when the semi-cured film is heated from 30°C to 500°C under nitrogen flow conditions and a heating rate of 10°C / min using a differential thermogravimetric analyzer, and the weight loss rate from 30°C to 250°C is 3.0% by mass or less.

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