Laminate, resin composition, laminate with semiconductor element, and semiconductor device manufacturing method using same

Abstract

The present invention addresses the problem of providing: a laminate having excellent catching properties when used as a catching material for semiconductor elements transferred by a laser transfer method; and a semiconductor device manufacturing method capable of mounting a large number of semiconductor elements at a high rate by using the laminate. In order to solve the problem, proposed is a laminate formed of a support substrate and a resin film containing at least one resin selected from the group consisting of polyimides, polyimide precursors, polybenzoxazoles, polybenzoxazole precursors, silicone resins, acrylic resins, and polyurethanes. The resin film has a storage modulus of 0.1-80 MPa at -30°C at a frequency of 1 Hz.

Description

Laminate, resin composition, laminate with semiconductor element, and method for manufacturing semiconductor device using them

[0001] The present invention relates to a laminate, a resin composition, and a method for manufacturing a semiconductor device. More specifically, the present invention relates to a laminate that is suitably used as a catch material when mounting a semiconductor element by laser transfer, and a method for manufacturing a semiconductor device using the laminate.

[0002] Generally, semiconductor elements incorporated into semiconductor devices are transferred and mounted on circuit boards, etc., by a pick-and-place method using a flip-chip bonder, etc. As semiconductor devices become more sophisticated and smaller, the semiconductor elements incorporated in the semiconductor devices are also becoming smaller and thinner, and the number of elements mounted is increasing.

[0003] As a method capable of mounting a large number of semiconductor elements at high speed, a method of mounting chips from a wafer to a circuit board using an adhesive stamp made of silicone resin or the like has been disclosed (Patent Documents 1 and 2). In this technique, the adhesive stamp can hold multiple semiconductor elements, so that semiconductor elements can be mounted on a large number of circuit boards in a single pick-and-place process.

[0004] A different method, laser transfer, has also been disclosed. In this method, a laminate is first prepared by mounting semiconductor elements on the side of the transfer material opposite the support substrate, which is made of a laser-transparent support substrate and a laser-absorbent transfer material. Next, a laser is irradiated from the support substrate side of the laminate, selectively transferring the semiconductor elements in a desired arrangement to a catch material located below the laminate at a certain distance (transfer process). A mounting carrier, with the semiconductor elements held in the desired arrangement on the catch material, is then bonded to a circuit board, and the semiconductor elements are electrically bonded to the circuit board by peeling them from the mounting carrier (mounting process) (Patent Documents 3 and 4). The transfer process may be performed multiple times before the mounting process. That is, before mounting the semiconductor elements on the circuit board, the semiconductor elements are transferred onto a catch material, and then re-transferred to another catch material, in order to subject them to a processing step or to flip the semiconductor elements over.

[0005] As a catch material used in a mounting carrier, for example, a polyimide-based adhesive material that has excellent heat resistance during the mounting process has been disclosed (Patent Document 5).

[0006] Japanese Patent Publication No. 2017-531915 Japanese Patent Publication No. 2020-129638 Japanese Patent Publication No. 2020-188037 Japanese Patent Publication No. 2020-251359 International Publication No. 2023 / 032888

[0007] In the inventions described in Patent Documents 1 and 2, the size of the stamp depends on the wafer size, so there is a limit to the number of semiconductor elements that can be transferred simultaneously. Also, in the inventions described in Patent Documents 1 and 2, it is necessary to prepare a stamp according to the design of the circuit board each time.

[0008] With the laser transfer method, there are no area restrictions or the need to create stamps with different designs, and it is expected that costs will be reduced. However, it has become clear that there is room for improvement in the catchability when receiving the semiconductor element during laser transfer in the invention described in Patent Document 5. Here, the ability to receive the semiconductor element without damage or misalignment is referred to as excellent catchability.

[0009] Therefore, the present invention aims to provide a laminate that has excellent catching properties when used as a catching material for semiconductor elements transferred by laser transfer method, and to provide a method for manufacturing a semiconductor device that can use the laminate to mount a large number of semiconductor elements at high speed.

[0010] In order to solve the above problems, the present invention has the following configurations: [1] A laminate comprising a support substrate and a resin film, wherein the resin film contains at least one resin selected from the group consisting of polyimide, polyimide precursor (hereinafter, polyimide, polyimide precursor, and copolymers thereof may be collectively referred to as "polyimides"), polybenzoxazole, polybenzoxazole precursor (hereinafter, polybenzoxazole, polybenzoxazole precursor, and copolymers thereof may be collectively referred to as "polybenzoxazoles"), silicone resin, acrylic resin, and polyurethane, and the resin film has a storage modulus of 0.1 MPa or more and 80 MPa or less at a frequency of 1 Hz and at -30°C. [2] The laminate according to [1] above, wherein the peel strength at 25°C of the surface of the resin film opposite to the support substrate side of the laminate is 0.02 N / cm or more and 0.3 N / cm or less. [3] The laminate according to [1] or [2], wherein the resin film has a storage modulus of 0.1 MPa or more and 5 MPa or less at a frequency of 1 Hz and 150°C. [4] The resin film is a resin film containing polyimides, at least one of which has a structural unit represented by formula (1) or a structural unit represented by formula (2), or both, and wherein the structural unit is an acid dianhydride residue (X １ ) and an acid dianhydride residue (X ２ ) and diamine residues (Y １ ) and diamine residue (Y ２ ), the total content of the acid dianhydride residue (A1) represented by formula (3) and the diamine residue (A2) represented by formula (4) is 40 mol % or more and 99 mol % or less, and the content of the diamine residue (A3) represented by formula (5) is 1 mol % or more and 25 mol % or less.

[0011]

[0012] (X １ and X ２ each independently represents a tetravalent acid dianhydride residue having 4 or more carbon atoms, Y １ and Y ２R each independently represents a divalent diamine residue having two or more carbon atoms. １ and R ２ each independently represents a hydrogen atom, a hydrocarbon group having from 1 to 10 carbon atoms, an alkylsilyl group having from 1 to 10 carbon atoms, an alkali metal atom, an ammonium group, an imidazolium group, or a pyridinium group.

[0013]

[0014] (R ３ ~R ６ , R ９ ~R １２ R each independently represents an alkyl group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, a phenyl group, or a phenoxy group. ７ ~R ８ , R １３ ~R １４ each independently represents an alkylene group or a phenylene group having 1 to 30 carbon atoms. Each n independently represents an integer of 15 to 60. *3a and *3b represent a bonding site connected to an imide group in the structural unit represented by formula (1), or *3a represents a bonding site connected to a carbon atom of an amide bond in the structural unit represented by formula (2), and *3b represents a bonding site connected to a carbon atom of a carboxylic acid or carboxylic acid ester in the structural unit represented by formula (2). *4 represents an imide group in the structural unit represented by formula (1) or a bonding site connected to a nitrogen atom of an amide bond in the structural unit represented by formula (2).

[0015]

[0016] (R １５ ~R １６ each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a hydroxyl group, or a halogen. k and l each independently represent an integer of 0 to 3. R １７represents a single bond or a divalent organic group having one or more carbon atoms. *5 represents a bonding site connected to the nitrogen atom of the imide group in the structural unit represented by formula (1) or the amide bond in the structural unit represented by formula (2).) [5] The laminate according to [4] above, wherein the diamine residue (A3) has a structure represented by any one of formulas (6) to (10).

[0017]

[0018] (* indicates a bonding site connected to the nitrogen atom of the imide group in the structural unit represented by formula (1) or the amide bond in the structural unit represented by formula (2).) [6] The laminate according to any one of [1] to [5] above, wherein the resin film further contains a light absorbing agent. [7] The laminate according to any one of [1] to [6] above, wherein the resin film further contains a siloxane diamine. [8] The laminate according to any one of [1] to [7] above, wherein the resin film further contains a crosslinking agent having at least one functional group selected from the group consisting of an epoxy group, an alkoxymethyl group, and a methylol group. [9] The laminate according to any one of [1] to [8] above, wherein the resin film contains a structure in which crosslinking agents having at least one functional group selected from the group consisting of an epoxy group, an alkoxymethyl group, and a methylol group are combined with each other or with other components.

[10] A laminate with a semiconductor element, in which a semiconductor element is further laminated on the surface of the resin film of the laminate according to any one of [1] to [9] above, opposite to the support substrate side.

[11] A resin composition containing a polyimide having either or both of a structural unit represented by formula (1) and a structural unit represented by formula (2), and a solvent, wherein the polyimide has an acid dianhydride residue (X １ ) and an acid dianhydride residue (X ２ ) and diamine residues (Y １ ) and diamine residue (Y ２ a resin composition in which the total content of the acid dianhydride residue (A1) represented by formula (3) and the diamine residue (A2) represented by formula (4) is 40 mol % or more and 99 mol % or less, relative to 100 mol % of the total of the above-mentioned components (a) and (b), and the content of the diamine residue (A3) represented by formula (5) is 1 mol % or more and 25 mol % or less.

[0019]

[0020] (X １ and X ２ each independently represents a tetravalent acid dianhydride residue having 4 or more carbon atoms, Y １ and Y ２ R each independently represents a divalent diamine residue having two or more carbon atoms. １ and R ２ each independently represents a hydrogen atom, a hydrocarbon group having from 1 to 10 carbon atoms, an alkylsilyl group having from 1 to 10 carbon atoms, an alkali metal atom, an ammonium group, an imidazolium group, or a pyridinium group.

[0021]

[0022] (R ３ ~R ６ , R ９ ~R １２ R each independently represents an alkyl group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, a phenyl group, or a phenoxy group. ７ ~R ８ , R １３ ~R １４ each independently represents an alkylene group or a phenylene group having 1 to 30 carbon atoms. Each n independently represents an integer of 15 to 60. *3a and *3b represent a bonding site connected to an imide group in the structural unit represented by formula (1), or *3a represents a bonding site connected to a carbon atom of an amide bond in the structural unit represented by formula (2), and *3b represents a bonding site connected to a carbon atom of a carboxylic acid or carboxylic acid ester in the structural unit represented by formula (2). *4 represents an imide group in the structural unit represented by formula (1) or a bonding site connected to a nitrogen atom of an amide bond in the structural unit represented by formula (2).

[0023]

[0024] (R １５ ~R １６each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a hydroxyl group, or a halogen. k and l each independently represent an integer of 0 to 3. R 17 represents a single bond or a divalent organic group having one or more carbon atoms. *5 represents a bonding site connected to the nitrogen atom of the imide group in the structural unit represented by formula (1) or the amide bond in the structural unit represented by formula (2).)

[12] The resin composition according to

[11] above, wherein the diamine residue (A3) has a structure represented by any one of formulas (6) to (10).

[0025]

[0026] (* indicates a bonding site connected to the nitrogen atom of the imide group in the structural unit represented by formula (1) or the amide bond in the structural unit represented by formula (2).)

[13] The resin composition according to

[11] or

[12] above, further containing a light absorber.

[14] The resin composition according to any one of

[11] to

[13] above, further containing a siloxane diamine.

[15] The resin composition according to any one of

[11] to

[14] above, further containing a crosslinking agent having at least one functional group selected from the group consisting of an epoxy group, an alkoxymethyl group, and a methylol group.

[16] A method for manufacturing a laminate with a semiconductor element, using the laminate according to any one of [1] to [9] above, and a laser-transparent substrate with a semiconductor element, comprising: a step of bringing a surface of the laser-transparent substrate with a semiconductor element mounted thereon and a surface of the laminate facing the resin film (step I), and a step of irradiating a laser beam from a surface of the laser-transparent substrate with a semiconductor element opposite to the surface with the semiconductor element mounted thereon, thereby transferring the semiconductor element to the surface of the laminate facing the resin film (step II).

[17] A method for manufacturing a semiconductor device, using the laminate with a semiconductor element according to

[10] above or a laminate with a semiconductor element obtained by the method for manufacturing a laminate with a semiconductor element according to

[16] above, and a circuit board, comprising: a step of bringing the surface of the laminate with a semiconductor element on the side on which the semiconductor element is stacked, toward the circuit board, and electrically joining the semiconductor element to a circuit of the circuit board (step III), and a step of separating the support substrate and the resin film of the laminate with semiconductor element from the semiconductor element (step IV).

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

[17] above, further comprising, before step III, a step of removing a portion of the resin film in the laminate with semiconductor element and patterning the resin film.

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

[17] or

[18] above, wherein step IV is a step using a laser peeling method.

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

[17] or

[18] above, wherein step IV is a step using a mechanical peeling method.

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

[17] or

[18] above, wherein step IV is a step using a solvent peeling method.

[22] The laminate according to any one of [1] to [9] above, wherein the resin film has a loss tangent of 0.15 or more and 0.8 or less at a frequency of 1 Hz at -30°C.

[23] The laminate according to any one of [1] to [9] above, wherein the resin film has an absorbance of 0.4 or more and 5.0 or less at a film thickness of 1.0 μm at any one of wavelengths of 248 nm, 266 nm, and 355 nm.

[24] A laminate with a semiconductor element, in which a semiconductor element is further stacked on the surface of the resin film of the laminate according to

[23] above, opposite to the support substrate side.

[25] A method for producing a laminate with a semiconductor element according to

[16] above, wherein the laminate according to

[22] or

[23] above is used instead of the laminate according to any one of [1] to [9] above.

[26] A method for manufacturing a substrate with temporarily fixed semiconductor elements, using a laminate with semiconductor elements according to

[24] above or a laminate with semiconductor elements according to

[25] above, and a substrate for temporarily fixing the semiconductor elements (hereinafter referred to as "intermediate catch substrate"), the method comprising the steps of: placing the surface of the laminate with semiconductor elements, on which the semiconductor elements are stacked, facing the intermediate catch substrate at a certain distance (Step V); and irradiating the resin film with a laser through the support substrate of the laminate with semiconductor elements to transfer the semiconductor elements to the intermediate catch substrate (Step VI).

[27] A method for manufacturing a semiconductor device, comprising the steps of placing the surface of the substrate with temporarily fixed semiconductor elements, obtained by the method for manufacturing a substrate with temporarily fixed semiconductor elements according to

[26] above, on which the semiconductor elements are stacked, facing a circuit board, and electrically bonding the semiconductor elements to a circuit on the circuit board (Step III'); and separating the support substrate and the resin film of the laminate with semiconductor elements from the semiconductor elements (Step IV').

[0027] According to the present invention, a laminate having excellent catching properties when used as a catching material for semiconductor elements transferred by a laser transfer method is provided, and by using the laminate, a method for manufacturing a semiconductor device that can mount a large number of semiconductor elements at high speed can be provided.

[0028] FIG. 1 is a schematic side view of an example of a laminate of the present invention. FIG. 1 is a schematic side view for explaining a step of transferring a semiconductor element to a laminate of the present invention. FIG. 2 is a schematic side view showing a state in which a laminate with a semiconductor element of the present invention and a circuit board are arranged opposite each other. FIG. 2 is a schematic side view for explaining a step of transferring a semiconductor element from a laminate with a semiconductor element of the present invention to an intermediate catch substrate. FIG. 3 is a diagram for explaining a conventional manufacturing method using an intermediate catch substrate. FIG. 4 is a diagram for explaining a conventional manufacturing method using an intermediate catch substrate. FIG. 5 is a diagram for explaining a conventional manufacturing method using an intermediate catch substrate. FIG. 6 is a diagram for explaining a conventional manufacturing method using an intermediate catch substrate. FIG. 7 is a diagram for explaining a conventional manufacturing method using an intermediate catch substrate. FIG. 8 is a diagram for explaining a conventional manufacturing method using an intermediate catch substrate. FIG. 9 is a diagram for explaining a second manufacturing method. FIG. 10 is a diagram for explaining a second manufacturing method. FIG. 11 is a diagram for explaining a second manufacturing method.

[0029] Hereinafter, embodiments of the present invention will be described in detail, but the present invention should not be construed as being limited by these descriptions.

[0030] [Laminate] The laminate of the present invention will be described. As shown in Fig. 1, the laminate of the present invention (hereinafter, sometimes referred to as "laminate A" for convenience) is formed by laminating a support substrate 11 and a resin film 12, and the resin film has the characteristics described below.

[0031] <Support Substrate> The material of the support substrate is not particularly limited as long as it can support a resin film, and examples of the material that can be used include a quartz substrate, a sapphire substrate, an alkali glass substrate, an alkali-free glass substrate, a borosilicate glass substrate, a silicon substrate, a ceramic substrate, a metal substrate, a semiconductor substrate, a ceramic substrate, etc. Furthermore, an organic substrate made of a material such as PET, aramid, polyester, polypropylene, or cycloolefin can also be used as the support substrate.

[0032] The thickness of the support substrate is preferably 0.1 mm to 5 mm from the viewpoint of ease of handling.

[0033] The support substrate preferably has laser transparency. Here, laser transparency refers to an absorbance of 0.1 or less at any wavelength between 200 and 1100 nm. In the process described below, it is planned to select a wavelength for the irradiated laser that results in an absorbance of 0.1 or less. The absorbance within a specific range at any wavelength between 200 and 1100 nm means, for example, that when absorbance is measured in the wavelength range of 200 to 1100 nm, the absorbance is 0.1 or less at at least one wavelength within that range. Examples of substrates having such absorbance include inorganic substrates such as quartz substrates, sapphire substrates, alkali glass substrates, non-alkali glass substrates, and borosilicate glass substrates, and organic substrates such as PET, aramid, polyester, polypropylene, and cycloolefin. The support substrate used in the laminate A does not need to be monolithic; it may be a laminate or composite of multiple materials.

[0034] <Resin Film> The laminate A has a resin film, and the resin film has a storage modulus of 0.1 MPa or more and 80 MPa or less at a frequency of 1 Hz and at −30° C.

[0035] In the laser transfer method, the semiconductor element is caught by the catch material at high speed. When the semiconductor element is transferred at such high speed, it is necessary to effectively absorb and attenuate the kinetic energy exerted on the resin film. Insufficient absorption and attenuation can cause misalignment of the semiconductor element or poor transfer. Therefore, the resin film used in the laminate A must have a storage modulus of 0.1 MPa or more and 80 MPa or less at -30°C and a frequency of 1 Hz. By having this range, a laminate with excellent catch properties can be obtained. To explain this point in more detail, a storage modulus of 0.1 MPa or more at -30°C and a frequency of 1 Hz prevents the semiconductor element from becoming embedded in the catch material when caught, and provides excellent peelability during re-transfer. Furthermore, a storage modulus of 80 MPa or less at -30°C and a frequency of 1 Hz provides excellent catch properties when receiving the semiconductor element. The storage modulus at a frequency of 1 Hz at −30° C. is preferably in the range of 0.1 MPa to 50 MPa, more preferably 0.1 MPa to 20 MPa, and particularly preferably 0.1 MPa to 10 MPa. By setting the storage modulus in this preferred range, a laminate with even better catching properties can be obtained.

[0036] Furthermore, the resin film used in the laminate A preferably has a storage modulus of 0.1 MPa or more and 5 MPa or less at 150 ° C. and a frequency of 1 Hz. Having a storage modulus of 0.1 MPa or more at 150 ° C. and a frequency of 1 Hz is preferable in that it can prevent misalignment of the semiconductor element when directly bonding the semiconductor element held on the resin film to a circuit board. Having a storage modulus of 5 MPa or less at a frequency of 1 Hz and a frequency of 150 ° C. is preferable in that it can prevent damage to the semiconductor element when directly bonding the semiconductor element held on the resin film to a circuit board. A more preferred range for the storage modulus at 150 ° C. and a frequency of 1 Hz is 0.5 MPa or more and 5 MPa or less. By setting it in this preferred range, it is possible to better prevent misalignment of the semiconductor element when directly bonding the semiconductor element held on the resin film to a circuit board.

[0037] The resin film used in the laminate A preferably has a peel strength at 25°C of 0.02 N / cm or more and 0.3 N / cm or less on the surface opposite the support substrate. The peel strength here refers to the value obtained from a 90° peel test between the surface of the resin film and a Kapton film. A specific measurement method involves pressing a 1 cm x 9 cm piece of Kapton film (manufactured by DuPont-Toray Co., Ltd., H type, thickness 25 μm) onto the surface of the resin film using a vacuum laminator at 0.6 MPa and 35°C, and then performing a peel test on the pressed Kapton tape at 25°C in a direction perpendicular to the resin film at a constant speed of 2 mm / sec using a tensile tester.

[0038] A peel strength of 0.02 N / cm or more is preferable in that it allows for stable holding of semiconductor elements when stacked on a resin film. Furthermore, a peel strength of 0.3 N / cm or less is preferable in that it allows for excellent peeling performance when retransferring the semiconductor elements. The peel strength is more preferably 0.05 N / cm or more and 0.2 N / cm or less. A peel strength of 0.05 N / cm or more allows for more stable holding of semiconductor elements, and a peel strength of 0.2 N / cm or less allows for excellent peeling performance when retransferring the semiconductor elements.

[0039] The thickness of the resin film used in the laminate A is preferably 1.0 μm or more and 30 μm or less. A resin film thickness of 1.0 μm or more is preferable in that it has excellent catching properties when receiving a semiconductor element and can reliably hold the semiconductor element. Furthermore, a resin film thickness of 30 μm or less is preferable in that it has excellent in-plane uniformity on the surface of the resin film and can hold multiple semiconductor elements over a wide area without damage or misalignment. The thickness of the resin film can be measured using a scanning electron microscope, an optical film thickness meter, a step gauge, etc.

[0040] The resin film used in the laminate A preferably has an absorbance of 0.4 or more and 5.0 or less, and more preferably 1.0 or more and 5.0 or less, at a wavelength of 200 to 1100 nm, calculated as a film thickness of 1.0 μm. An absorbance of 0.4 or more is preferable because the resin film can efficiently absorb laser energy, making it possible to use a low-energy-density laser when re-transferring a semiconductor element held in the resin film. Furthermore, an absorbance of 5.0 or less is preferable because it increases the versatility of the resin that can be used.

[0041] The wavelength range in which the absorbance of the resin film used in the laminate A, converted into a film thickness of 1.0 μm, is 0.4 or more and 5.0 or less is preferably any one or more of 248 nm, 266 nm, 308 nm, 355 nm, 532 nm, and 1064 nm out of the 200 to 1100 nm range described above. More preferably, it is any one or more of 248 nm, 266 nm, 308 nm, and 355 nm. Even more preferably, it is any one or more of 248 nm, 266 nm, and 355 nm. When the absorbance of the resin film at these wavelengths satisfies the above-mentioned range, the resin film can efficiently absorb laser energy, which is preferable.

[0042] As mentioned above, in the laser transfer method, the semiconductor element is caught by the catch material at high speed. When the semiconductor element is transferred at such high speed, it is necessary to effectively absorb and attenuate the kinetic energy exerted on the resin film. Insufficient absorption and attenuation can result in misalignment of the semiconductor element and poor transfer. Therefore, the resin film used in the laminate A must have a storage modulus of 0.1 MPa or more and 80 MPa or less at -30°C and a frequency of 1 Hz. By being within this range, a laminate with excellent catch properties can be obtained. To explain this point in more detail, a storage modulus of 0.1 MPa or more at -30°C and a frequency of 1 Hz prevents the semiconductor element from becoming embedded in the catch material when caught, and provides excellent peelability during re-transfer. Furthermore, a storage modulus of 80 MPa or less at -30°C and a frequency of 1 Hz provides excellent catch properties when capturing the semiconductor element. The storage modulus at a frequency of 1 Hz at −30° C. is preferably in the range of 0.1 MPa to 50 MPa, more preferably 0.1 MPa to 20 MPa, and particularly preferably 0.1 MPa to 10 MPa. By setting the storage modulus in this preferred range, a laminate with even better catching properties can be obtained.

[0043] The resin film used in the laminate A preferably has a loss tangent of 0.15 to 0.8, more preferably 0.15 to 0.6, and even more preferably 0.15 to 0.5 at a frequency of 1 Hz and −30° C. The loss tangent here is the ratio of the loss modulus to the storage modulus in dynamic viscoelasticity measurement, and is expressed by the following formula:

[0044] Loss tangent = loss modulus / storage modulus.

[0045] When the loss tangent is in the above-mentioned preferred range, a laminate having both catchability and releasability can be obtained. To explain this point in more detail, when the loss tangent at −30° C. and a frequency of 1 Hz is 0.15 or more, the laminate has excellent catchability when receiving a semiconductor element. Furthermore, when the loss tangent at −30° C. and a frequency of 1 Hz is 0.8 or less, the semiconductor element is prevented from becoming embedded in the catch material when receiving the semiconductor element, and the laminate has excellent releasability when retransferring.

[0046] The resin film used in laminate A contains at least one resin selected from the group consisting of polyimide, polyimide precursor (hereinafter, polyimide, polyimide precursor, and copolymers thereof may be collectively referred to as "polyimides"), polybenzoxazole, polybenzoxazole precursor (hereinafter, polybenzoxazole, polybenzoxazole precursor, and copolymers thereof may be collectively referred to as "polybenzoxazoles"), silicone resin, acrylic resin, and polyurethane. The resin film used in laminate A may contain multiple types of these resins, or may be a copolymer, for example, a copolymer of polyimides and polybenzoxazoles.

[0047] The content of the resin contained in the resin film is preferably 5 parts by weight or more and 100 parts by weight or less per 100 parts by weight of the resin film. A resin content of 5 parts by weight or more is preferable in that shrinkage does not occur when the resin film is formed, bleeding out of other components of the resin film is suppressed, and a homogeneous resin film can be formed.

[0048] <Polyimides> Polyimides are polymers having a cyclic structure of imide rings in the main chain structure. Polyimide precursors are polymers that form imide rings by dehydration ring closure, and examples thereof include polyamic acid and polyamic acid ester.

[0049] Polyimides can be obtained by reacting tetracarboxylic acids, corresponding tetracarboxylic dianhydrides, tetracarboxylic diester dichlorides, etc. with diamines, corresponding diisocyanate compounds, trimethylsilylated diamines, etc., and contain organic groups derived from the acid dianhydrides, i.e., acid dianhydride residues, and organic groups derived from the diamines, i.e., diamine residues. Polyimides can be obtained, for example, by dehydrating and cyclizing polyamic acids obtained by reacting tetracarboxylic dianhydrides with diamines in the presence or absence of a solvent, followed by heat treatment. A solvent that forms an azeotrope with water, such as m-xylene, may be added during this heat treatment. Alternatively, polyimides can be obtained by adding a ring-closing catalyst, such as a dehydrating condensing agent (e.g., carboxylic anhydride or dicyclohexylcarbodiimide) or a base (e.g., triethylamine), followed by chemical heat treatment for dehydration and cyclization. Alternatively, polyimides can be obtained by adding a weakly acidic carboxylic acid compound and then heat treatment at a low temperature of 100°C or below for dehydration and cyclization.

[0050] Examples of solvents used in polyimide polymerization include polar aprotic solvents such as N-methyl-2-pyrrolidone, γ-butyrolactone, N,N-dimethylformamide, N,N-dimethylacetamide, and dimethyl sulfoxide, ether solvents such as tetrahydrofuran, dioxane, and propylene glycol monomethyl ether, ketone solvents such as acetylacetone, methyl ethyl ketone, methyl propyl ketone, methyl butyl ketone, diisobutyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, and 2-heptanone, ester solvents such as ethyl acetate, propylene glycol monomethyl ether acetate, and ethyl lactate, and aromatic hydrocarbon solvents such as toluene and xylene. These may be used alone or in combination of two or more.

[0051] In the laminate A, the resin film is a resin film containing polyimides, and at least one of the polyimides is a polyimide having either or both of a structural unit represented by formula (1) and a structural unit represented by formula (2), and an acid dianhydride residue (X １ ) and an acid dianhydride residue (X ２ ) and diamine residues (Y １ ) and diamine residue (Y２ It is preferable that the total content of the acid dianhydride residue (A1) represented by formula (3) and the diamine residue (A2) represented by formula (4) is 40 mol % or more and 99 mol % or less relative to 100 mol % of the total of the above.

[0052]

[0053] (X １ and X ２ each independently represents a tetravalent acid dianhydride residue having 4 or more, preferably 50 or less, carbon atoms; Y １ and Y ２ R each independently represents a divalent diamine residue having 2 or more, preferably 100 or less, carbon atoms. １ and R ２ each independently represents a hydrogen atom, a hydrocarbon group having from 1 to 10 carbon atoms, an alkylsilyl group having from 1 to 10 carbon atoms, an alkali metal atom, an ammonium group, an imidazolium group, or a pyridinium group.

[0054]

[0055] (R ３ ~R ６ , R ９ ~R １２ R each independently represents an alkyl group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, a phenyl group, or a phenoxy group. ７ ~R ８ , R １３ ~R １４each independently represents an alkylene group or a phenylene group having 1 to 30 carbon atoms. Each n independently represents an integer of 15 to 60. *3a and *3b represent a bonding site connected to an imide group in the structural unit represented by formula (1), or *3a represents a bonding site connected to a carbon atom of an amide bond in the structural unit represented by formula (2), and *3b represents a bonding site connected to a carbon atom of a carboxylic acid or carboxylic acid ester in the structural unit represented by formula (2). *4 represents an imide group in the structural unit represented by formula (1) or a bonding site connected to a nitrogen atom of an amide bond in the structural unit represented by formula (2). By setting the total content of the acid dianhydride residue (A1) represented by formula (3) and the diamine residue (A2) represented by formula (4) within the above range, the storage modulus at −30° C. and a frequency of 1 Hz is appropriately adjusted, and this is preferable in that it provides excellent catching properties when catching a semiconductor element, prevents the semiconductor element from becoming embedded in the catching material when catching the semiconductor element, and provides excellent releasability when retransferring.

[0056] Acid dianhydride residue (X １ ) and an acid dianhydride residue (X ２ ) and diamine residues (Y １ ) and diamine residue (Y ２ The total content of the acid dianhydride residue (A1) represented by formula (3) and the diamine residue (A2) represented by formula (4) relative to 100 mol % of the total is more preferably 40 mol % or more and 60 mol % or less. By setting the total content of the acid dianhydride residue (A1) represented by formula (3) and the diamine residue (A2) represented by formula (4) within the above range, the storage modulus at 150°C and a frequency of 1 Hz can be appropriately adjusted, and when a semiconductor element held on a resin film is directly bonded to a circuit board, displacement of the semiconductor element can be prevented with greater accuracy.

[0057] Examples of commercially available acid dianhydrides that provide the acid dianhydride residue (A1) represented by formula (3) include X-22-168AS, X-22-168A, X-22-168B, and X-22-168-P5-B (all trade names, manufactured by Shin-Etsu Chemical Co., Ltd.), etc. These may be used alone or in combination of two or more.

[0058] The polyimides used in the present invention may contain an acid dianhydride residue other than the acid dianhydride residue (A1) represented by formula (3). Examples of acid dianhydrides that provide an acid dianhydride residue other than the acid dianhydride residue (A1) represented by formula (3) include pyromellitic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,2'dimethyl-3,3',4,4'-biphenyltetracarboxylic dianhydride, 5,5'dimethyl-3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride, and 2,2',3,3'-biphenyltetracarboxylic dianhydride. , 3,3',4,4'-diphenyl ether tetracarboxylic acid dianhydride, 2,3,3',4'-diphenyl ether tetracarboxylic acid dianhydride, 2,2',3,3'-diphenyl ether tetracarboxylic acid dianhydride, 3,3',4,4'-benzophenone tetracarboxylic acid dianhydride, 2,2',3,3'-benzophenone tetracarboxylic acid dianhydride, 2,3,3',4'-benzophenone tetracarboxylic acid dianhydride, 3,3',4,4'-diphenyl sulfone tetracarboxylic acid Acid dianhydrides, 2,3,3',4'-diphenylsulfonetetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfoxidetetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfidetetracarboxylic dianhydride, 3,3',4,4'-diphenylmethylenetetracarboxylic dianhydride, 4,4'-isopropylidenediphthalic dianhydride, 4,4'-(hexafluoroisopropylidene)diphthalic dianhydride, 3,4,9,10-perylenetetracarboxylic acid Examples of the dianhydride include residues derived from 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 3,3",4,4"-para-terphenyltetracarboxylic dianhydride, 3,3",4,4"-meta-terphenyltetracarboxylic dianhydride, 2,3,6,7-anthracenetetracarboxylic dianhydride, and 1,2,7,8-phenanthrenetetracarboxylic dianhydride. These may be used alone or in combination of two or more.

[0059] Diamines that provide the diamine residue (A2) represented by formula (4) include α,ω-bis(3-aminopropyl)polydimethylsiloxane, α,ω-bis(3-aminopropyl)polydiethylsiloxane, α,ω-bis(3-aminopropyl)polydipropylsiloxane, α,ω-bis(3-aminopropyl)polydibutylsiloxane, α,ω-bis(3-aminopropyl)polydiphenoxysiloxane, α,ω-bis(2-aminoethyl)polydimethylsiloxane, α,ω Examples of suitable diamines include α,ω-bis(2-aminoethyl)polydiphenoxysiloxane, α,ω-bis(4-aminobutyl)polydimethylsiloxane, α,ω-bis(4-aminobutyl)polydiphenoxysiloxane, α,ω-bis(5-aminopentyl)polydimethylsiloxane, α,ω-bis(5-aminopentyl)polydiphenoxysiloxane, α,ω-bis(4-aminophenyl)polydimethylsiloxane, and α,ω-bis(4-aminophenyl)polydiphenoxysiloxane. A plurality of these may be used. Note that n in formula (4) represents an average value. Examples of industrial products known as diamines that provide the diamine residue (A2) represented by formula (4) include X-22-161A, X-22-161B, KF8012, KF8008, and X-22-1660B-3 (all trade names, manufactured by Shin-Etsu Chemical Co., Ltd.).

[0060] The polyimides used in the present invention are those having an acid dianhydride residue (X １ ) and an acid dianhydride residue (X ２ ) and diamine residues (Y １ ) and diamine residue (Y ２ The content of the diamine residue (A3) represented by formula (5) relative to 100 mol % of the total of (A1, A2, A3) and (A4) is preferably 1 mol % or more and 25 mol % or less.

[0061]

[0062] (R １５ ~R １６ each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a hydroxyl group, or a halogen. k and l each independently represent an integer of 0 to 3. R １７represents a single bond or a divalent organic group having one or more carbon atoms. *5 represents the imide group in the structural unit represented by formula (1) or the bonding site connected to the nitrogen atom of the amide bond in the structural unit represented by formula (2).) Polyimides containing a diamine residue (A3) represented by formula (5) are preferred in that a pseudo-crosslinked structure is formed via hydrogen bonds, adjusting the elastic modulus, and exhibiting excellent catchability and excellent peeling performance when re-transferring a semiconductor element held in a resin film. Furthermore, in an embodiment in which the resin composition of the present invention described below contains a crosslinking agent, the phenolic hydroxyl group in the diamine residue (A3) or its adjacent carbon atom serves as a crosslinking point, allowing for more precise adjustment of the elastic modulus and solvent solubility.

[0063] In addition, the polyimides may contain an acid dianhydride residue (X １ ) and an acid dianhydride residue (X ２ ) and diamine residues (Y １ ) and diamine residue (Y ２ The diamine residue (A3) represented by formula (5) is preferably contained in an amount of 1 mol % or more relative to 100 mol % of the total of (A1, A2, A3) and (B1, B2, B3), in that excellent peeling performance can be exhibited when a semiconductor element held by a resin film is re-transferred. The diamine residue (A3) represented by formula (5) is preferably contained in an amount of 25 mol % or less relative to 100 mol % of the total of (A1, A2, B3 ...

[0064] The diamine residue (A3) contained in the polyimide resin used in the present invention preferably has a structure represented by any one of formulas (6) to (10), and more preferably has a structure represented by formula (8) or formula (10) because this can further improve solvent solubility. These may be used alone or in combination of two or more. Note that polyimide resins containing an asymmetric carbon in the structure include all optical isomers.

[0065]

[0066] (* indicates a bonding site connected to the nitrogen atom of the imide group in the structural unit represented by formula (1) or the amide bond in the structural unit represented by formula (2).) When the diamine residue (A3) represented by formula (5) has a structure represented by any one of formulas (6) to (10), a bulky structure is introduced at the bridgehead position of the diamine residue (A3), improving the solvent solubility of the resin film, and is preferable in terms of excellent wet etching properties when patterning the resin film before step III described below, excellent removability of residues after laser peeling in step IV described below, and further excellent solvent peelability.

[0067] The diamine residue (A3) represented by the formula (5) may be a diamine residue other than the structure represented by any one of formulas (6) to (10). Examples of diamines that provide diamine residues other than the structure represented by any one of formulas (6) to (10) include 4,4'-dihydroxy-3,3'-diaminodiphenyl ether, 3,3'-dihydroxy-4,4'-diaminodiphenyl ether, 4,4'-dihydroxy-3,3'-diaminodiphenylmethane, 3,3'-dihydroxy-4,4'-diaminodiphenylmethane, 4,4'-dihydroxy-3,3'-diaminobenzophenone, and 3,3'-dihydroxy-4,4'-diaminobenzophenone.

[0068] The polyimides used in the present invention may contain a diamine residue other than the diamine residue (A3) represented by formula (5). Diamines that provide diamine residues other than the diamine residue (A3) represented by formula (5) include, in addition to the diamines described in formula (4), p-phenylenediamine, m-phenylenediamine, 2,5-diaminotoluene, 2,4-diaminotoluene, 3,5-diaminobenzoic acid, 2,6-diaminobenzoic acid, 2-methoxy-1,4-phenylenediamine, 4,4'-diaminobenzanilide, 3,4'-diaminobenzanilide, 3,3'-diaminobenzanilide, and 3,3'-dimethyl-4,4'-diaminobenzanilide. fluorene, 9,9-bis(4-aminophenyl)fluorene, 9,9-bis(3-aminophenyl)fluorene, 9,9-bis(3-methyl-4-aminophenyl)fluorene, 9,9-bis(3,5-dimethyl-4-aminophenyl)fluorene, 9,9-bis(3-methoxy-4-aminophenyl)fluorene, 9,9-bis(4-aminophenyl)fluorene-4-carboxylic acid, 9,9-bis(4-aminophenyl)fluorene-4-methyl, 9,9-bis(4-aminophenyl)fluorene-4-methoxy ...carboxylic acid, 9,9-bis(4-aminophenyl)fluorene-4-carboxylic acid, 9,9-bis(4-aminophenyl)fluorene-4-carboxylic acid, 9,9-bis(4-aminophenyl)fluorene-4-carboxylic acid, 9,9-bis(4-aminophenyl)fluorene-4-carboxylic acid, 9,9-bis(4-aminophenyl)fluorene-4-carboxylic acid, 9,9-bis(4-aminophenyl)fluorene-4-carboxylic acid, 9,9-bis(4-aminophenyl)fluorene-4-carboxylic acid, 9,9-bis bis(4-aminophenyl)fluorene-4-ethyl, 9,9-bis(4-aminophenyl)fluorene-4-sulfone, 9,9-bis(4-aminophenyl)fluorene-3-carboxylic acid, 9,9-bis(4-aminophenyl)fluorene-3-methyl, 1,3-diaminocyclohexane, 2,2'-dimethylbenzidine, 3,3'-dimethylbenzidine, 3,3'-dimethoxybenzidine, 2,4-diaminopyridine, 2,6-diaminopyridine, 1,5-diaminonaphthalene, 2,7-diaminofluorene, p-amino benzylamine, m-aminobenzylamine, 4,4'-bis(4-aminophenoxy)biphenyl, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 3,3'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfide, 3,3'-diaminobenzophenone, 3,4'-diaminobenzophenone, 4,4'-Diaminobenzophenone, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 1,4-bis(3-aminophenoxy)benzene, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(3-aminophenoxy)phenyl]propane, bis[4-(4-aminophenoxy)phenyl]methane, bis[4-(3-aminophenoxy)phenyl]methane, bis[4-(4-aminophenoxy )phenyl]ether, bis[4-(3-aminophenoxy)phenyl]ether, bis[4-(4-aminophenoxy)phenyl]sulfone, bis[4-(3-aminophenoxy)phenyl]sulfone, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 1,4-diaminocyclohexane, 4,4'-methylenebis(cyclohexylamine), 3,3'-methylenebis(cyclohexylamine), 4,4'-diamino-3,3'-dimethyldicyclohexylmethane, 4,4'-diamino-3,3'-dimethyldicyclohexyl, benzidine, and the like. These may be used alone or in combination of two or more.

[0069] The polyimides used in the present invention may be end-capped with a monoamine or an acid anhydride, which is preferable in that the resin film has excellent storage stability.

[0070] When the terminals are blocked with a monoamine, the amount of monoamine residues contained in the polyimides is preferably in the range of 0.1 to 60 mol % relative to 100 mol % of all amine residues. A monoamine residue amount of 0.1 mol % or more is preferred in terms of excellent storage stability of the resin film. Furthermore, a monoamine residue amount of 60 mol % or less is preferred in terms of achieving a sufficient weight-average molecular weight.

[0071] Examples of monoamines that can be used to cap the terminals of polyimides include 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5 2-aminonaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminothiophenol, 3-aminothiophenol, and 4-aminothiophenol. These may be used alone or in combination of two or more.

[0072] When the terminals are blocked with an acid anhydride, the amount of acid anhydride residues contained in the polyimides is preferably in the range of 0.1 to 60.0 mol % relative to 100 mol % of all acid anhydride residues. Having an amount of acid anhydride residues of 0.1 mol % or more is preferred in terms of excellent storage stability of the resin film. Furthermore, having an amount of acid anhydride residues of 60 mol % or less is preferred in terms of achieving a sufficient weight-average molecular weight.

[0073] Examples of acid anhydrides that can be used to cap the ends of polyimides include phthalic anhydride, maleic anhydride, nadic anhydride, cyclohexanedicarboxylic anhydride, 3-hydroxyphthalic anhydride, etc. These may be used alone or in combination of two or more.

[0074] The polyimides used in the present invention preferably have a weight-average molecular weight of 5,000 or more and 100,000 or less. A weight-average molecular weight of 5,000 or more is preferable in that it can exhibit excellent peeling performance when re-transferring a semiconductor element held on a resin film. Furthermore, a weight-average molecular weight of 100,000 or less is preferable in that it can provide excellent solvent solubility for the resin film. The weight-average molecular weight is measured by gel permeation chromatography (GPC) and calculated in polystyrene equivalent terms.

[0075] <Polybenzoxazoles> In the present invention, polybenzoxazoles is a general term for polybenzoxazoles, polybenzoxazole precursors, and copolymers thereof, and the laminate A may contain polybenzoxazoles as its resin film.

[0076] Polybenzoxazole can be obtained by reacting a bisaminophenol compound with a dicarboxylic acid, a corresponding dicarboxylic acid chloride, a dicarboxylic acid activated ester, or the like, and preferably has a dicarboxylic acid residue and a bisaminophenol residue. For example, it can be obtained by dehydrating and cyclizing polyhydroxyamide, which is one of the polybenzoxazole precursors obtained by reacting a bisaminophenol compound with a dicarboxylic acid, through a heat treatment. Alternatively, it can be obtained by adding phosphoric anhydride, a base, a carbodiimide compound, or the like and dehydrating and cyclizing through a chemical treatment.

[0077] Examples of bisaminophenol compounds include bis(3-amino-4-hydroxyphenyl)ether, bis(3-amino-4-hydroxyphenyl)methylene, bis[N-(3-aminobenzoyl)-3-amino-4-hydroxyphenyl]sulfone, bis[N-(4-aminobenzoyl)-3-amino-4-hydroxyphenyl]sulfone, bis(3-amino-4-hydroxyphenyl)sulfone, bis(3-amino-4-hydroxyphenyl)propane, 2,2'-bis[N-(3 -aminobenzoyl)-3-amino-4-hydroxyphenyl]propane, 2,2'-bis[N-(4-aminobenzoyl)-3-amino-4-hydroxyphenyl]propane, 9,9-bis(3-amino-4-hydroxyphenyl)fluorene, 9,9-bis[N-(3-aminobenzoyl)-3-amino-4-hydroxyphenyl]fluorene, 9,9-bis[N-(4-aminobenzoyl)-3-amino-4-hydroxyphenyl]fluorene, N,N'-bis(3-aminobenzoyl) N,N'-bis(4-aminobenzoyl)-2,5-diamino-1,4-dihydroxybenzene, N,N'-bis(4-aminobenzoyl)-4,4'-diamino-3,3-dihydroxybiphenyl, N,N'-bis(3-aminobenzoyl)-3,3'-diamino-4,4-dihydroxybiphenyl, N,N'-bis(4-aminobenzoyl)-3,3'-diamino-4,4-dihydroxybiphenyl, 3,3'- Examples of such diamines include aromatic diamines such as diamino-4,4'-biphenol, bis(3-amino-4-hydroxyphenyl)methane, 1,1-bis(3-amino-4-hydroxyphenyl)ethane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, and 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, as well as compounds in which some of the hydrogen atoms in these aromatic rings or hydrocarbons have been substituted with alkyl groups or fluoroalkyl groups having 1 to 10 carbon atoms, halogen atoms, etc. These may be used alone or in combination of two or more.

[0078] Dicarboxylic acids include phthalic acid, isophthalic acid, terephthalic acid, 2,2'-biphenyldicarboxylic acid, 3,4'-biphenyldicarboxylic acid, 4,4'-biphenyldicarboxylic acid, benzophenone-2,4'-dicarboxylic acid, benzophenone-4,4'-dicarboxylic acid, 2,2-bis(4-carboxyphenyl)hexafluoropropane, 3,3'-dicarboxydiphenyl ether, 3,4'-dicarboxydiphenyl ether, and 4,4'-dicarboxydiphenyl ether. 3,3'-dicarboxydiphenylmethane, 3,4'-dicarboxydiphenylmethane, 4,4'-dicarboxydiphenylmethane, 3,3'-dicarboxydiphenyldifluoromethane, 3,4'-dicarboxydiphenyldifluoromethane, 4,4'-dicarboxydiphenyldifluoromethane, 3,3'-dicarboxydiphenylsulfone, 3,4'-dicarboxydiphenylsulfone, 4,4'-dicarboxydiphenylsulfone, 3,3'-dicarboxydiphenyl dicarboxydiphenyl sulfide, 3,4'-dicarboxydiphenyl sulfide, 4,4'-dicarboxydiphenyl sulfide, 3,3'-dicarboxydiphenyl ketone, 3,4'-dicarboxydiphenyl ketone, 4,4'-dicarboxydiphenyl ketone, 2,2-bis(3-carboxyphenyl)propane, 2,2-bis(3,4'-dicarboxyphenyl)propane, 2,2-bis(4-carboxyphenyl)propane, 2,2-bis(3-carboxyphenyl)hexafluoro Examples of suitable aromatic hydrocarbon compounds include 1,3-bis(4-carboxyphenyl)hexafluoropropane, 2,2-bis(3,4'-carboxyphenyl)hexafluoropropane, 2,2-bis(4-carboxyphenyl)hexafluoropropane, 1,3-bis(3-carboxyphenoxy)benzene, 1,4-bis(3-carboxyphenoxy)benzene, 1,3-bis(4-carboxyphenoxy)benzene, and compounds in which some of the hydrogen atoms in these aromatic rings or hydrocarbons have been substituted with alkyl groups or fluoroalkyl groups having 1 to 10 carbon atoms, halogen atoms, or the like. These compounds may be used alone or in combination of two or more.

[0079] <Silicone Resin> Silicone resin is a resin whose main component is organopolysiloxane, which has a siloxane bond as its main skeleton and an organic group having 3 to 60 carbon atoms, such as a methyl group, an ethyl group, or a phenyl group, on its side chain. Here, "main component" means that the silicone resin contains 90 parts by weight or more of the structural unit of organopolysiloxane per 100 parts by weight of the silicone resin.

[0080] Organopolysiloxanes can be obtained, for example, by reacting a cyclic siloxane with a disiloxane in the presence of tetrabutylphosphonium hydroxide siliconate. Examples of cyclic siloxanes include hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and dodecamethylcyclohexasiloxane. These may be used alone or in combination of two or more. Examples of disiloxanes include hexamethyldisiloxane, hexaethyldisiloxane, and hexaphenyldisiloxane. These may be used alone or in combination of two or more.

[0081] <Acrylic Resin> The acrylic resin is a resin whose main components are structural units derived from acrylic acid or an acrylic monomer that is a derivative thereof, and / or structural units derived from methacrylic acid or a methacrylic monomer that is a derivative thereof. Here, the term "main component" refers to a resin containing 90 parts by weight or more of structural units derived from acrylic acid or an acrylic monomer that is a derivative thereof and structural units derived from methacrylic acid or a methacrylic monomer that is a derivative thereof per 100 parts by weight of the acrylic resin.

[0082] Examples of acrylic monomers include methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, isobutyl acrylate, pentyl acrylate, hexyl acrylate, heptyl acrylate, octyl acrylate, isooctyl acrylate, 2-ethylhexyl acrylate, nonyl acrylate, isononyl acrylate, decyl acrylate, lauryl acrylate, isomyristyl acrylate, stearyl acrylate, isostearyl acrylate, cyclohexyl acrylate, isobornyl acrylate, etc. These may be used alone or in combination of two or more.

[0083] Examples of methacrylic monomers include methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, isobutyl methacrylate, pentyl methacrylate, hexyl methacrylate, heptyl methacrylate, octyl methacrylate, isooctyl methacrylate, 2-ethylhexyl methacrylate, nonyl methacrylate, isononyl methacrylate, decyl methacrylate, lauryl methacrylate, isomyristyl methacrylate, stearyl methacrylate, isostearyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, etc. These may be used alone or in combination of two or more.

[0084] <Polyurethane> In the present invention, polyurethane is a polymer mainly composed of repeating units consisting of a divalent polyisocyanate residue having 2 or more carbon atoms and a divalent polyol residue having 2 or more carbon atoms. Here, the term "main component" means that the polyurethane contains 90 parts by weight or more of repeating units consisting of a divalent polyisocyanate residue having 2 or more carbon atoms and a divalent polyol residue having 2 or more carbon atoms per 100 parts by weight of polyurethane.

[0085] Examples of polyisocyanates that provide polyisocyanate residues include aliphatic diisocyanates such as hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, and lysine diisocyanate; and fatty acids such as dicyclohexylmethane diisocyanate, isophorone diisocyanate, 1,4-cyclohexane diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated tolylene diisocyanate, and dicyclohexylmethane-4,4'-diisocyanate. Examples of the diisocyanates include cyclic diisocyanates; and aromatic diisocyanates such as tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, naphthalene diisocyanate, xylylene diisocyanate, tolidine diisocyanate, p-phenylene diisocyanate, and naphthylene diisocyanate; as well as biurets, isocyanurates, and adducts of these with trimethylolpropane. Commercially available products include, for example, Duranate (registered trademark) 24A-100, Duranate 22A-75P, Duranate TPA-100, Duranate TKA-100, Duranate P301-75E, Duranate 21S-75E, Duranate MFA-75B, Duranate MHG-80B, Duranate TUL-100, and Duranate TL A-100, Duranate TSA-100, Duranate TSS-100, Duranate TSE100, Duranate E402-80B, Duranate E405-70B, Duranate AS700-100, Duranate D101, Duranate D201, and Duranate A201H (all trade names, manufactured by Asahi Kasei Corporation). These may be used alone or in combination of two or more.

[0086] Examples of polyols that provide the polyol residue include low molecular weight polyols, polyether polyols, polyester polyols, polycarbonate polyols, etc. These may be used alone or in combination of two or more.

[0087] Examples of low molecular weight polyols include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, 1,2-propanediol, 1,3-propanediol, dipropylene glycol, tripropylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,5-pentanediol, neopentyl glycol, 1,5-hexanediol, 1,6-hexanediol, 2,5-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, and 1,11-undecanediol. Examples of the polyol include aliphatic polyols having a molecular weight of 50 or more and 300 or less, such as 1,12-dodecanediol, 2-methyl-1,3-propanediol, neopentyl glycol, 2-butyl-2-ethyl-1,3-propanediol, 3-methyl-1,5-pentanediol, 2-ethyl-1,3-hexanediol, 2-methyl-1,8-octanediol, glycerin, trimethylolpropane, ditrimethylolpropane, trimethylolpropane, and pentaerythritol; polyols having an alicyclic structure, such as cyclohexanedimethanol and hydrogenated bisphenol A; and polyols having an aromatic structure, such as bisphenol A and bisphenol F. These may be used alone or in combination of two or more.

[0088] Examples of polyether polyols include compounds obtained by addition polymerization of alkylene oxides using one or more compounds having two or more active hydrogen atoms as an initiator. Examples of compounds having two or more active hydrogen atoms include propylene glycol, trimethylene glycol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, glycerin, diglycerin, trimethylolethane, trimethylolpropane, water, and hexanetriol. Examples of alkylene oxides include propylene oxide, butylene oxide, styrene oxide, epichlorohydrin, and tetrahydrofuran. These may be used alone or in combination of two or more.

[0089] Examples of polyester polyols include polyester polyols obtained by reacting a low-molecular-weight polyol with a polycarboxylic acid; polyester polyols obtained by ring-opening polymerization of a cyclic ester compound such as ε-caprolactone; and polyester polyols obtained by copolymerizing these. The low-molecular-weight polyols used in producing polyester polyols can be the same as the low-molecular-weight polyols described above. Examples of polycarboxylic acids include aliphatic polycarboxylic acids such as succinic acid, adipic acid, sebacic acid, and dodecanedicarboxylic acid; alicyclic polycarboxylic acids such as 1,4-cyclohexanedicarboxylic acid and cyclohexanetricarboxylic acid; aromatic polycarboxylic acids such as terephthalic acid, isophthalic acid, phthalic acid, and naphthalenedicarboxylic acid; and anhydrides or esters thereof. These may be used alone or in combination of two or more.

[0090] Examples of polycarbonate polyols include esterification products of carbonate esters and polyhydric alcohols, reaction products of polyhydric alcohols and phosgene, etc. Examples of carbonate esters include aliphatic carbonates, alicyclic carbonates, and aromatic carbonates. Examples of the aliphatic carbonate include saturated aliphatic carbonates such as dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, di-n-butyl carbonate, diisobutyl carbonate, ethyl-n-butyl carbonate, and ethyl isobutyl carbonate; and unsaturated aliphatic carbonates such as ethylene carbonate, trimethylene carbonate, tetramethylene carbonate, 1,2-propylene carbonate, 1,2-butylene carbonate, 1,3-butylene carbonate, 2,3-butylene carbonate, 1,2-pentylene carbonate, 1,3-pentylene carbonate, 1,4-pentylene carbonate, 1,5-pentylene carbonate, 2,3-pentylene carbonate, and 2,4-pentylene carbonate. Examples of aromatic carbonates include diphenyl carbonate and dibenzyl carbonate. Two or more of these may be used together. Examples of polyhydric alcohols include linear or branched diols such as ethylene glycol, propylene glycol, butanediol, pentanediol, 3-methyl-1,5-pentanediol, hexanediol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, polyethylene glycol, and polypropylene glycol; alicyclic diols such as 1,4-cyclohexanedimethanol and hydrogenated bisphenol A; and trifunctional or higher polyols such as trimethylolmethane, trimethylolpropane, ditrimethylolpropane, pentaerythritol, and dipentaerythritol. These may be used alone or in combination of two or more.

[0091] The urethane resin can be polymerized by known methods. For example, a urethane resin can be obtained by polymerizing a polyisocyanate and a polyol. If necessary, a urethane-forming catalyst may be used in the presence of the urethane-forming catalyst. Examples of the urethane-forming catalyst include nitrogen-containing compounds such as triethylamine, tributylamine, benzyldibutylamine, triethylenediamine, and N-methylmorpholine; organometallic compounds such as titanium tetrabutoxide, dibutyltin oxide, dibutyltin dilaurate, tin 2-ethylcaproate, zinc naphthenate, cobalt naphthenate, zinc 2-ethylcaproate, molybdenum glycolate, potassium acetate, zinc stearate, tin octoate, dibutyltin dilaurate, and dioctyltin dineodecanoate; and inorganic compounds such as iron chloride and zinc chloride. These may be used alone or in combination of two or more.

[0092] The polymerization may be carried out in the presence of a reaction solvent, and the same reaction solvent as used in the polymerization of polyimide can be used. The reaction temperature is preferably 0 to 100°C, more preferably 40 to 90°C. The reaction time is preferably 1.0 to 120 hours, more preferably 2.0 to 30 hours.

[0093] <Light absorber> The resin film of the laminate A preferably contains a light absorber. The light absorber here refers to a compound that has absorption somewhere in the wavelength range of 200 to 1100 nm. By containing a light absorber, the absorbance at any wavelength of 200 to 1100 nm when converted into a film thickness of 1.0 μm can be adjusted to a preferred range, and good transferability can be achieved in an embodiment in which a semiconductor element is re-transferred by irradiating the resin film from the support substrate side with a laser having a wavelength that is transmitted through the support substrate.

[0094] Examples of light absorbers include Tinuvin PS, Tinuvin 99-2, Tinuvin 326, Tinuvin 328, Tinuvin 384-2, Tinuvin 400, Tinuvin 405, Tinuvin 460, Tinuvin 477, Tinuvin 479, Tinuvin 900, Tinuvin 928, and Tinuvin 1130 (all trade names, manufactured by BASF Corporation), DAINSORB T-0, DAINSORB T-7, DAINSORB T-31, DAINSORB T-52, DAINSORB T-53, DAINSORB T-84, DAINSORB P-6, and DAINSORB P-7 (all trade names, manufactured by Daiwa Chemical Industry Co., Ltd.), and Adekastab UV absorbers such as ADK STAB LA-24, ADK STAB LA-29, ADK STAB LA-31RG, ADK STAB LA-31G, ADK STAB LA-32, ADK STAB LA-36, ADK STAB LA-36RG, ADK STAB LA-46, ADK STAB LA-F70, and ADK STAB 1413 (all trade names, manufactured by ADEKA Corporation), Solvent Yellow 93, Solvent Yellow 33, Solvent Orange 60, Solvent Red 111, Solvent Red 135, Solvent Red 168, Solvent Red 207, Solvent Red 52, and Solvent Examples of the dyes, dyes and pigments include Red 179, Solvent Blue 36, Solvent Blue 94, Solvent Blue 63, Solvent Blue 104, Solvent Blue 97, Solvent Green 20, Solvent Violet 13, Solvent Violet 36 (all trade names, manufactured by Tokyo Chemical Industry Co., Ltd.), carbon black, perylene black, cyanine black, aniline black, etc. These may be used alone or in combination of two or more.

[0095] The content of the light absorbent contained in the resin film is preferably 0.1 parts by weight or more and 80 parts by weight or less per 100 parts by weight of the resin film. A content of the light absorbent of 0.1 parts by weight or more is preferred in that the absorbance of the resin film at any wavelength of 200 to 1100 nm when converted into a film thickness of 1.0 μm can be adjusted to a preferred range. A content of the light absorbent of 80 parts by weight or more is preferred in that the storage stability of the resin film is excellent.

[0096] <Siloxane diamine> The resin film included in the laminate A preferably contains siloxane diamine. The inclusion of siloxane diamine is preferable in that it provides excellent releasability when retransferring the semiconductor element held by the resin film.

[0097] Examples of siloxane diamines include α,ω-bis(3-aminopropyl)polydimethylsiloxane, α,ω-bis(3-aminopropyl)polydiethylsiloxane, α,ω-bis(3-aminopropyl)polydipropylsiloxane, α,ω-bis(3-aminopropyl)polydibutylsiloxane, α,ω-bis(3-aminopropyl)polydiphenoxysiloxane, α,ω-bis(2-aminoethyl)polydimethylsiloxane, α,ω-bis(2-amino Examples of suitable siloxane diamines include α,ω-bis(4-aminobutyl)polydiphenoxysiloxane, α,ω-bis(4-aminobutyl)polydiphenoxysiloxane, α,ω-bis(5-aminopentyl)polydimethylsiloxane, α,ω-bis(5-aminopentyl)polydiphenoxysiloxane, α,ω-bis(4-aminophenyl)polydimethylsiloxane, and α,ω-bis(4-aminophenyl)polydiphenoxysiloxane. Examples of suitable siloxane diamines include X-22-161A, X-22-161B, KF8012, KF8008, and X-22-1660B-3 (all trade names, manufactured by Shin-Etsu Chemical Co., Ltd.). These may be used alone or in combination of two or more.

[0098] The content of siloxane diamine contained in the resin film is preferably 0.05 parts by weight or more and 10 parts by weight or less per 100 parts by weight of the resin film. A siloxane diamine content of 0.05 parts by weight or more is preferable in that excellent peeling performance can be exhibited when re-transferring a semiconductor element held by the resin film. A siloxane diamine content of 10 parts by weight or less is preferable in that the semiconductor element can be stably held.

[0099] <Crosslinking Agent> The resin film included in the laminate A preferably contains a crosslinking agent. By containing a crosslinking agent, components in the resin film are crosslinked, and bleeding out of the components in the resin film is suppressed, which is preferable in that storage stability is excellent.

[0100] In the present invention, the crosslinking agent may be present in the resin film in a state before crosslinking or in a state after crosslinking. That is, in relation to the semiconductor element transfer step (Step II) described later, crosslinking may be performed in the resin film after the semiconductor element is transferred, or crosslinking may be performed in the resin film before the semiconductor element is transferred. However, at the time of the transfer step, it is desirable that the storage modulus of the resin film at a frequency of 1 Hz and −30° C. is 0.1 MPa or more and 10 MPa or less.

[0101] The crosslinking agent is preferably a crosslinking agent having at least one functional group selected from the group consisting of an epoxy group, an oxetanyl group, an alkoxymethyl group, and a methylol group, which is preferred in that the components in the resin film are efficiently crosslinked and the storage stability is excellent.

[0102] Examples of crosslinking agents having an epoxy group include, but are not limited to, bisphenol A type epoxy resins, bisphenol F type epoxy resins, epoxy group-containing silicones such as propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, and polymethyl(glycidyloxypropyl)siloxane, and dimer acid-modified epoxy resins. Specifically, Epicron 850-S, Epicron HP-4032, Epicron HP-7200, Epicron HP-820, Epicron HP-4700, Epicron EXA-4710, Epicron HP-4770, Epicron EXA-859CRP, Epicron EXA-1514, Epicron EXA-4880, Epicron EXA-4850-150, Epicron EXA-4850-1000, Epicron EXA-4816, Epicron EXA-4822 (all trade names, manufactured by DIC Corporation), and Rikaresin Examples of such an additive include BEO-60E (hereinafter referred to as "trade name," manufactured by New Japan Chemical Co., Ltd.), EP-4003S, EP-4000S (all trade names, manufactured by Adeka Corporation), jER (registered trademark)-871, jER-872, YX-4000, YX-4000H (all trade names, manufactured by Mitsubishi Chemical Corporation), Celloxide 2021P (all trade names, manufactured by Daicel Corporation), Showfree PETG, Showfree CDMGB, Showfree BATG (all trade names, manufactured by Resonac Corporation), Denacol EX-201-IM (all trade names, manufactured by Nagase ChemteX Corporation), and TEPIC-VL (all trade names, manufactured by Nissan Chemical Industries, Ltd.). These may be used alone or in combination of two or more.

[0103] Examples of crosslinking agents having an oxetanyl group include OXT-121, OXT-221, OX-SQ-H, OXT-191, PNOX-1009, RSOX (all trade names, manufactured by Toagosei Co., Ltd.), "Etanacol (registered trademark)" OXBP, and "Etanacol" OXTP (all trade names, manufactured by UBE Co., Ltd.). These may be used alone or in combination of two or more.

[0104] Examples of crosslinking agents having an alkoxymethyl group or a methylol group include DML-PC, DML-PEP, DML-OC, DML-OEP, DML-34X, DML-PTBP, DML-PCHP, DML-OCHP, DML-PFP, DML-PSBP, DML-POP, DML-MBOC, DML-MBPC, DML-MTrisPC, DML-BisOC-Z, DMLBisOCHP-Z, DML-BPC, DML-BisOC-P, DMOM-PC, DMOM-PTBP, and DMOM-MB PC, TriML-P, TriML-35XL, TML-HQ, TML-BP, TML-pp-BPF, TML-BPE, TML-BPA, TML-BPAF, TML-BPAP, TMOM-BP, TMOM-BPE, TMOM-BPA, TMOM-BPAF, TMOM-BPAP, HML-TPPHBA, HML-TPHAP, HMOM-TPPHBA, HMOM-TPHAP (all trade names, manufactured by Honshu Chemical Industry Co., Ltd.), "NIKALAC (registered trademark)" MX-290, NIKALAC MX-280, NIKALAC MX-270, NIKALAC MX-279, NIKALAC MW-100LM, NIKALAC MX-750LM (all trade names, manufactured by Sanwa Chemical Co., Ltd.), etc. These may be used alone or in combination of two or more.

[0105] The content of the crosslinking agent contained in the resin film or the content of the structural portion derived from the crosslinking agent is preferably 0.5 parts by weight or more and 30 parts by weight or less per 100 parts by weight of the resin film. A content of the crosslinking agent of 0.5 parts by weight or more is preferable in that the components in the resin film are crosslinked and bleeding out of the components in the resin film is suppressed, thereby providing excellent storage stability. A content of the crosslinking agent of 30 parts by weight or less is preferable in that the semiconductor element can be stably held.

[0106] <Curing Accelerator> The resin film provided in the laminate A may contain a curing accelerator for the purpose of accelerating crosslinking by the crosslinking agent. Examples of curing accelerators include imidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, Curazol 2E4MZ-CN, 2-phenyl-1H-imidazole, 2,4-diamino-6-[2'-ethyl-4-methylimidazolyl-(1')]-ethyl-s-triazine, and 2-methylimidazole isocyanuric acid adduct. Preferred imidazoles include Curazol (registered trademark) 2E4MZ and Curazol (registered trademark) 2E4MZ-CN (manufactured by Shikoku Chemicals Corporation). These may be used alone or in combination of two or more.

[0107] The content of the curing accelerator contained in the resin film is preferably 0.5 parts by weight or more and 2 parts by weight or less per 100 parts by weight of the resin film. A content of the curing accelerator of 0.5 parts by weight or more is preferable in that a sufficient crosslinking promoting effect can be obtained. A content of the curing accelerator of 2 parts by weight or less is preferable in that the storage stability of the resin composition before forming the resin film is excellent.

[0108] <Adhesion improver> The resin film provided in the laminate A may contain an adhesion improver. This adhesion improver refers to a component that improves the adhesion between the resin film and the substrate. The inclusion of an adhesion improver is preferable in that it improves the adhesion between the support substrate and the resin film, making it less likely for peeling to occur at the interface between the support substrate and the resin film. Examples of adhesion improvers include N-phenylaminoethyltriethoxysilane, vinyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, and p-styryltrimethoxysilane. These may be used alone or in combination of two or more.

[0109] The content of the adhesion improver contained in the resin film is preferably 0.01 parts by weight or more and 15 parts by weight or less per 100 parts by weight of the resin film. The content of the adhesion improver of 0.01 parts by weight or more is preferred in that a sufficient adhesion improving effect can be obtained. The content of the adhesion improver of 15 parts by weight or less is preferred in that the storage stability of the resin composition before forming the resin film is excellent.

[0110] [Laminate with semiconductor element] As shown in Figure 2, the laminate with semiconductor element of the present invention is one in which a semiconductor element is further laminated on the surface of the resin film of laminate A opposite to the support substrate side (hereinafter, for convenience, this laminate with semiconductor element may be referred to as "laminate B").

[0111] <Semiconductor Element> The semiconductor element used in the laminate B preferably includes an epitaxially grown crystal layer. The epitaxially grown crystal layer is preferably made of a compound semiconductor, particularly a III-V group compound semiconductor. Examples of preferred epitaxially grown crystal layers include compound semiconductors such as AlGaInAs, InGaAs, InP, InGaAsP, AlAs, InAs, GaAs, AlN, AlP, GaN, InN, and SiC. Semiconductor elements using these epitaxially grown crystal layers may contain only one type of compound semiconductor, or two or more types of compound semiconductors. They may also contain different types of semiconductors stacked together, or may contain semiconductor substrates, electrode materials, sapphire substrates, glass substrates, wiring, and the like. The size of the semiconductor element is preferably such that the maximum side is 5 μm or more and 5.0 mm or less. Furthermore, the peel strength at 25°C of the surface where the semiconductor element and the resin film contact is preferably 0.02 N / cm or more and 0.3 N / cm or less. The peel strength at 25°C of 0.02 N / cm or more is preferable in that the semiconductor element can be stably held when laminated on the resin film, and the peel strength of 0.3 N / cm or less is preferable in that excellent peeling performance can be exhibited when the semiconductor element is retransferred.

[0112] Specific examples of semiconductor elements include transistors, light-emitting diodes including micro LED chips, and laser diodes.

[0113] [Resin Composition] The resin composition of the present invention will be described.

[0114] The resin composition of the present invention is one of the resin compositions suitable for producing the resin film of the laminate of the present invention (laminate A), and is a resin composition containing a polyimide having either or both of a structural unit represented by formula (1) and a structural unit represented by formula (2) and a solvent, wherein １ ) and an acid dianhydride residue (X ２ ) and diamine residues (Y １ ) and diamine residue (Y ２ the total content of the acid dianhydride residue (A1) represented by formula (3) and the diamine residue (A2) represented by formula (4) is 40 mol % or more and 99 mol % or less, based on 100 mol % of the total of the above-mentioned diamine residues (A1) and (A2), and the content of the diamine residue (A3) represented by formula (5) is 1 mol % or more and 25 mol % or less.

[0115]

[0116] (X １ and X ２ each independently represents a tetravalent acid dianhydride residue having 4 or more, preferably 50 or less, carbon atoms; Y １ and Y ２ R each independently represents a divalent diamine residue having 2 or more, preferably 100 or less, carbon atoms. １ and R ２ each independently represents a hydrogen atom, a hydrocarbon group having from 1 to 10 carbon atoms, an alkylsilyl group having from 1 to 10 carbon atoms, an alkali metal atom, an ammonium group, an imidazolium group, or a pyridinium group.

[0117]

[0118] (R ３ ~R ６ , R ９ ~R １２ R each independently represents an alkyl group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, a phenyl group, or a phenoxy group. ７ ~R ８ , R １３ ~R １４each independently represents an alkylene group or a phenylene group having 1 to 30 carbon atoms. Each n independently represents an integer of 15 to 60. *3a and *3b represent a bonding site connected to an imide group in the structural unit represented by formula (1), or *3a represents a bonding site connected to a carbon atom of an amide bond in the structural unit represented by formula (2), and *3b represents a bonding site connected to a carbon atom of a carboxylic acid or carboxylic acid ester in the structural unit represented by formula (2). *4 represents an imide group in the structural unit represented by formula (1) or a bonding site connected to a nitrogen atom of an amide bond in the structural unit represented by formula (2).

[0119]

[0120] (R １５ ~R １６ each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a hydroxyl group, or a halogen. k and l each independently represent an integer of 0 to 3. R １７ represents a single bond or a divalent organic group having one or more carbon atoms. *5 represents an imide group in the structural unit represented by formula (1) or a bonding site connected to the nitrogen atom of an amide bond in the structural unit represented by formula (2). The polyimides contained in the resin composition of the present invention can preferably take the same form as the polyimides described in connection with laminate A, and the resin composition of the present invention can preferably contain a light absorber, a siloxane diamine, a crosslinking agent, a curing accelerator, and an adhesion improver. These preferred forms are as described in connection with the resin film provided in laminate A.

[0121] <Solvent> The resin composition of the present invention contains a solvent. Examples of the solvent include polar aprotic solvents such as N-methyl-2-pyrrolidone, γ-butyrolactone, N,N-dimethylformamide, N,N-dimethylacetamide, and dimethyl sulfoxide; ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, and dipropylene glycol dimethyl ether; acetates such as ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propyl acetate, butyl acetate, isobutyl acetate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methoxy-3-methyl-1-butyl acetate, methyl lactate, ethyl lactate, and butyl lactate; acetylacetone, methyl propyl ketone, methyl butyl ketone, methyl isobutyl ketone, cyclopentanone; Examples of suitable solvents include ketones such as ethanol, cyclohexanone, and 2-heptanone, alcohols such as butyl alcohol, isobutyl alcohol, pentanol, 4-methyl-2-pentanol, 3-methyl-2-butanol, 3-methyl-3-methoxybutanol, and diacetone alcohol, and aromatic hydrocarbons such as toluene and xylene. These may be used alone or in combination of two or more.

[0122] The content of the solvent contained in the resin composition is preferably 30 parts by weight or more and 3000 parts by weight or less per 100 parts by weight of the solid content contained in the resin composition. A content of the solvent of 30 parts by weight or more is preferable in that the components contained in the resin composition can be sufficiently dissolved and the storage stability of the resin composition is excellent. A content of the solvent of 3000 parts by weight or less is preferable in that sufficient viscosity can be obtained and the coatability when applying a thick film can be excellent.

[0123] [Method for Producing Laminate A] Next, a method for producing the laminate A will be described with reference to FIG.

[0124] The laminate A can be obtained by forming a resin film 12 on a support substrate 11. One example of a manufacturing method thereof is to apply a resin composition, in which the components of the resin film 12 are dissolved in a solvent, to the support substrate 11, dry the composition, and then heat-treat the resin film 12. Any coating method can be selected for applying the resin composition, and examples include spinner coating, spray coating, roll coating, and slit die coating. After application, the resin film is preferably dried for one minute to several tens of minutes using a heating means such as a hot plate, drying oven, or infrared radiation at a temperature in the range of 50°C to 150°C. Thereafter, if necessary, it is preferably heat-treated at a temperature in the range of 100°C to 500°C for several minutes to several hours.

[0125] [Method for Producing Laminate with Semiconductor Element] An example of a method for producing the laminate with semiconductor element (laminate B) of the present invention will be described with reference to FIG.

[0126] The laminate B is manufactured by stacking a semiconductor element on the resin film side of the laminate A.

[0127] First, a substrate on which a semiconductor element to be transferred is mounted is prepared. In this example, the substrate 21 is laser-transparent (laser-transparent substrate 200 with semiconductor element). Laser transparency is as described above. Methods for mounting semiconductor elements on a substrate include epitaxially growing a compound semiconductor on the substrate to form a compound semiconductor layer and then directly fabricating the element, and forming another layer on the substrate and then mounting the semiconductor element on top of that. Examples of such another layer include a metal thin film or a resin film. For a metal thin film, a method is to form a metal thin film on the substrate by sputtering or vapor deposition, and then mount the semiconductor element on top of the metal thin film. For a resin film, a method is to form a resin film on the substrate and then mount the semiconductor element on the resin film. Examples of resin films include films of any resin, such as polyimide resin, polybenzoxazole resin, silicone resin, acrylic resin, and urethane resin.

[0128] Next, the surface of the semiconductor element-equipped laser transmissive substrate 200 on which the semiconductor elements are mounted is opposed to the surface of the laminate A on which the resin film 12 is mounted (step I), and then a step (step II) is performed in which laser light 29 is irradiated from the surface of the semiconductor element-equipped laser transmissive substrate 200 opposite to the surface on which the semiconductor elements 22 are mounted, thereby transferring the semiconductor elements 22 to the surface of the laminate A on which the resin film 12 is mounted.

[0129] In the laminate with semiconductor element of the present invention, the semiconductor is transferred onto a resin film with excellent catching properties, so that the transferred semiconductor element has excellent positional accuracy and damage to the semiconductor element is suppressed.

[0130] <Step I> A preferred embodiment of Step I will be described with reference to an example.

[0131] When the semiconductor element-equipped laser transmissive substrate 200 and the laminate A are arranged so that the surface of the semiconductor element-equipped laser transmissive substrate 200 on which the semiconductor element 22 is mounted and the surface of the laminate A on the resin film (12) side are opposed at a certain distance, these surfaces are arranged so that they are parallel. In order to prevent misalignment due to the weight of the semiconductor element during transfer, it is preferable to arrange the semiconductor element-equipped laser transmissive substrate 200 so that it is on the upper side. The distance between the opposing surfaces can be selected depending on the size and thickness of the semiconductor element 22, and is selected in the range of several μm to several hundred μm. Furthermore, alignment marks may be provided on the semiconductor element-equipped laser transmissive substrate 200 and the laminate A for transfer alignment.

[0132] <Step II> A preferred embodiment of Step II will be described with reference to an example.

[0133] The semiconductor element 22 is irradiated with laser light from the surface of the semiconductor element-equipped laser transmissive substrate 200 and the laminate A arranged in step I, opposite to the surface on which the semiconductor element is mounted of the semiconductor element-equipped laser transmissive substrate 200. The type of laser light is a YAG laser, a YVO ４Examples of lasers include solid-state lasers such as lasers, fiber lasers, and semiconductor lasers, and gas lasers such as carbon dioxide lasers, excimer lasers, and argon lasers, and can be selected depending on the wavelength to be used. The energy density of the laser light is set to 1 mJ / cm or less from the viewpoint of stability of the energy density of the laser light. ２ The above is preferable, and from the viewpoint of preventing damage to the semiconductor element and shortening the processing time, 1000 mJ / cm ２ The following is preferred:

[0134] [Semiconductor Device and Manufacturing Method Thereof (First Manufacturing Method)] Next, a manufacturing method (first manufacturing method) of a semiconductor device of the present invention will be described with reference to Fig. 3. The semiconductor device is a device in which a plurality of semiconductor elements are electrically connected on a circuit board, and includes, for example, an integrated circuit, a TFT substrate that drives a display, a micro LED display, a photoelectric conversion device, a semiconductor communication element, an image pickup element, and an amplifier element.

[0135] In a manufacturing method (first manufacturing method) of a semiconductor device using the laminate 300 with semiconductor element (laminate B) of the present invention, first, laminate B and a circuit board 31 on which a semiconductor is to be mounted are prepared.

[0136] Next, the surface of the laminate B300 on which the semiconductor element 22 is stacked is placed opposite the circuit board 31, and the semiconductor element 22 and the circuit board 31 are electrically joined (Step III), and then a step (Step IV) is performed in which the support substrate 11 and the resin film 12 of the laminate B300 are separated from the semiconductor element 22.

[0137] <Step III> A preferred embodiment of Step III will be described with reference to an example.

[0138] First, when the surface of the laminate B300 on which the semiconductor elements are laminated is opposed to the circuit board 31, a preferable embodiment can be understood by replacing the laser-transparent substrate with semiconductor elements in the explanation of step I with laminate B and laminate A with the circuit board.

[0139] Next, a description will be given of a process for electrically bonding the semiconductor element 22 to the circuit board 31. The electrical bonding of the semiconductor element 22 to the circuit board 31 can be carried out using a bonding device such as a mounting bonder or a wafer bonder, and preferably, a thermocompression bonding method can be used.

[0140] To explain this in detail using an example, the laminate B300 is attached to the bonder head of the lamination device, and the circuit board 31 is further placed on the bonder stage, so that the surface of the laminate B300 on which the semiconductor element 22 is laminated faces the circuit surface of the circuit board 31. When facing each other, they may be directly superimposed on each other.

[0141] When using thermocompression bonding, the optimum temperature during bonding can be selected depending on the configuration of the semiconductor element and circuit board to be bonded, and is preferably 80°C or higher and 300°C or lower. A bonding temperature of 80°C or higher is preferable in that the semiconductor element and the circuit board can be reliably bonded. A bonding temperature of 300°C or lower is preferable in that the semiconductor element can be bonded without being damaged by heat. Furthermore, the pressure during bonding can be selected within a range that allows bonding without damaging the semiconductor element.

[0142] The method for manufacturing a semiconductor device according to the present invention may further include, before step III, a step of removing a portion of the resin film 12 in the laminate B and patterning the resin film 12. The patterning may be such that the resin film 12 is present only in the portion between the support substrate 11 and the semiconductor element 22, i.e., the portion where the resin film 12 and the semiconductor element 22 are stacked is independently arranged on the support substrate 11 in a cellular form. By forming such a pattern, the portion of the resin film 12 not required for holding the semiconductor element 22 can be reduced, thereby reducing the adhesion of foreign matter to the portion where the semiconductor element 22 is not held. Furthermore, when bonding the semiconductor element 22 to the circuit board 31 in step III, the resin film 12 not required for holding the semiconductor element 22 can be prevented from contacting the circuit board 31. Examples of methods for patterning the resin film 12 include dry etching or wet etching using the semiconductor element 22 as a mask.

[0143] Moreover, this step can be similarly carried out using a substrate to which a semiconductor element, which will be described later, is temporarily fixed, instead of the laminate B (step III').

[0144] <Step IV> A preferred embodiment of Step IV will be explained with reference to an example.

[0145] After the semiconductor element 22 is electrically joined to the circuit board 31, methods for separating the support substrate 11 and resin film 12 of the laminate B300 from the semiconductor element include a mechanical peeling method in which they are mechanically peeled off and removed, a laser peeling method in which a laser is irradiated from the support substrate 11 side to remove the resin film 12 by laser ablation, and a solvent peeling method in which the resin film 12 is dissolved and removed with a solvent.

[0146] In an embodiment in which removal is performed by a mechanical peeling method, the resin film in the laminate B preferably contains siloxane diamine. When the resin film contains siloxane diamine, excellent peeling performance can be exhibited.

[0147] In an embodiment in which removal is performed by a laser peeling method, it is preferable that the resin film contains a light absorbent in the laminate B. By containing a light absorbent in the resin film, the resin film can have a sufficient absorbance at any wavelength of 200 to 1100 nm when converted into a film thickness of 1.0 μm, which is preferable in that excellent peeling performance can be exhibited.

[0148] In an embodiment in which the resin film is removed by a solvent stripping method, the diamine residue (A3) represented by the formula (5) preferably has a structure represented by any one of the formulas (6) to (10). When the diamine residue (A3) represented by the formula (5) has a structure represented by any one of the formulas (6) to (10), a bulky structure is introduced into the bridgehead position of the diamine residue (A3), and the resin film has excellent solvent solubility and can exhibit excellent stripping performance.

[0149] Moreover, this step can be similarly carried out using a substrate to which a semiconductor element, which will be described later, is temporarily fixed, instead of the laminate B (step IV').

[0150] According to the method for manufacturing a semiconductor device of the present invention, damage to semiconductor elements can be reduced when the semiconductor elements are mounted on a circuit board.

[0151] [Semiconductor Device and Manufacturing Method Thereof (Second Manufacturing Method)] Next, a manufacturing method (second manufacturing method) of a semiconductor device according to the present invention will be described. Note that specific examples of the semiconductor device are as described above.

[0152] In this second manufacturing method, instead of directly electrically joining the semiconductor elements stacked on the laminate B to the circuit board, as shown in Figure 4, a substrate for temporarily fixing the semiconductor elements (hereinafter, such a substrate will be referred to as an "intermediate catch substrate") is prepared, the semiconductor elements are temporarily transferred to the intermediate catch substrate to obtain a substrate (hereinafter, such a substrate will be referred to as an "intermediate carrier") on which the semiconductor elements are temporarily fixed, and the semiconductor elements on the intermediate carrier are electrically joined to the circuit of the circuit board to obtain the semiconductor device.

[0153] The method of manufacturing a substrate to which a semiconductor element is temporarily fixed according to the present invention comprises the following steps V and VI. Step V: A step of placing the surface of the semiconductor element-attached laminate (laminate B) on which the semiconductor element is laminated, facing an intermediate catch substrate at a certain distance. Step VI: A step of irradiating a laser onto the resin film through the support substrate of laminate B to transfer the semiconductor element to the intermediate catch substrate.

[0154] Hereinafter, each of the steps V and VI will be described in detail with reference to the drawings.

[0155] <Step V> A preferred embodiment of Step V will be described.

[0156] When stack B and the intermediate catch substrate are arranged so that the surface of stack B on which the semiconductor element 22 is mounted and the receiving surface of the intermediate catch substrate face each other at a certain distance, these surfaces are arranged so that they are parallel. In order to prevent misalignment due to the weight of the semiconductor element 22 during transfer, it is preferable to arrange stack B so that it faces upward. The distance between the opposing surfaces can be selected depending on the size and thickness of the semiconductor element 22, and is selected in the range of several μm to several hundred μm. Furthermore, alignment marks may be provided on stack B and the intermediate catch substrate for transfer alignment.

[0157] <Step VI> A preferred embodiment of Step VI will be described.

[0158] Laser light is irradiated onto the semiconductor element 22 from the surface of the laminate B and the intermediate catch substrate arranged in step V, opposite to the surface on which the semiconductor element of the laminate B is mounted. The type of laser light is a YAG laser, a YVO ４ Examples of lasers include solid-state lasers such as lasers, fiber lasers, and semiconductor lasers, and gas lasers such as carbon dioxide lasers, excimer lasers, and argon lasers, and can be selected depending on the wavelength to be used. The energy density of the laser light is set to 1 mJ / cm or less from the viewpoint of stability of the energy density of the laser light. ２ The above is preferable, and from the viewpoint of preventing damage to the semiconductor element and shortening the processing time, 1000 mJ / cm ２ The following is preferred:

[0159] In carrying out step VI, in obtaining laminate B300, it is preferable that the absorbance of the resin film of laminate A at any one of wavelengths of 248 nm, 266 nm, and 355 nm, converted into a film thickness of 1.0 μm, is 0.4 or more and 5.0 or less. When the resin film at any one of wavelengths of 248 nm, 266 nm, and 355 nm, converted into a film thickness of 1.0 μm, is 0.4 or more and 5.0 or less, it is preferable in that good transferability can be achieved.

[0160] According to the second manufacturing method of the present invention, the quality unevenness of a semiconductor element array can be improved using a laser transfer method. Furthermore, when changing the pitch of an array of semiconductor elements having electrode surfaces, such as micro LED elements, the process can be shortened compared to conventional manufacturing methods. This point will be described in detail using FIGS. 5 to 16 . In the following description, a semiconductor element array refers to a large number of semiconductor elements aligned in a row. For convenience, the electrode surfaces are shown in the figures as rectangles protruding from the semiconductor element bodies. While the following description will be given using an example in which semiconductor elements having electrode surfaces are used, it goes without saying that the method can also be applied to semiconductor elements without electrode surfaces.

[0161] Generally, semiconductor element arrays obtained by epitaxially growing a compound semiconductor on a substrate to form a compound semiconductor layer and then directly fabricating the element may have uneven properties in the semiconductor elements depending on the location on the substrate (this unevenness in the properties of the semiconductor elements on the substrate may hereinafter be simply referred to as "quality unevenness"). An example of this quality unevenness is brightness unevenness in a micro LED element array. Brightness unevenness in a micro LED element array can be evaluated non-contact, non-destructively, and without mounting on a circuit board using known photoluminescence (PL) measurement.

[0162] When improving the quality unevenness by using the laser transfer method and then converting the pitch of the semiconductor element array to match the layout of the circuit board, a conventional method involves performing the laser transfer twice.

[0163] That is, in the conventional manufacturing method, as shown in Fig. 5, a first laser transfer is performed from the laser-transparent substrate 200 with semiconductor elements to the intermediate catch substrate 41. At this time, the intermediate catch substrate 41 is moved and irradiated with laser light 29, thereby obtaining an intermediate carrier 400 arranged so that the quality variations of the semiconductor elements (23, 24, 25; note that the description will be given using an example in which the properties of the semiconductor elements 23, 24, and 25 are different) within the substrate are evened out, as shown in Fig. 6. The intermediate catch substrate 41 can be any substrate, such as a glass substrate, resin substrate, or metal substrate, on which a resin film, such as polysiloxane resin, acrylic resin, or polyester resin, is formed as a catch layer for receiving the semiconductor elements. Next, as shown in FIG. 7, the intermediate carrier 400 is bonded to a laminate in which a laser-decomposable resin film 51 is formed on a laser-transparent substrate 11. As shown in FIG. 8, the intermediate catch substrate of the intermediate carrier 400 is peeled off to obtain a laser transfer carrier 500 in which semiconductor elements (23, 24, 25) are mounted on the laser-decomposable resin film 51. The resin film 51 can be selected from the resin film disclosed in WO 2022 / 210155, the adhesive layer disclosed in JP 2022-65423 A, the resin film of the present invention, and the like. Then, as shown in FIG. 9, a second laser transfer is performed from the laser transfer carrier 500 to a second intermediate catch substrate 42. At this time, by moving the second intermediate catch substrate 42 and irradiating it with laser light 29, a second intermediate carrier 600 in which the semiconductor elements (23, 24, 25) have their pitch converted to match the layout of the circuit board is obtained, as shown in FIG. 10. The second intermediate catch substrate 42 can be made of the same material as the intermediate catch substrate 41. Thereafter, as shown in Fig. 11, the second intermediate carrier 600 is bonded to the third intermediate catch substrate 43, and as shown in Fig. 12, the second intermediate catch substrate 42 of the second intermediate carrier 600 is peeled off to obtain a mounting carrier 700. The semiconductor element on the mounting carrier 700 is bonded to a circuit board to form a semiconductor device.

[0164] On the other hand, according to the second semiconductor device manufacturing method, the process of improving the quality unevenness and converting the pitch of the semiconductor element array can be shortened compared to the conventional manufacturing method. As shown in FIG. 13, first, a first laser transfer is performed from the laser-transparent substrate 200 with semiconductor elements to the laminate A100. At this time, by moving the laminate A100 and irradiating it with laser light 29, the semiconductor elements (23, 24, 25) with uneven properties within the substrate are arranged so that the quality unevenness is evened out, resulting in a laminate B300 with improved quality unevenness, as shown in FIG. 14. Next, as shown in FIG. 15, a second laser transfer is performed from the laminate B300 to the intermediate catch substrate 41. At this time, by moving the intermediate catch substrate 41 and irradiating it with laser light 29, a mounting carrier 600 is obtained in which the semiconductor elements (23, 24, 25) have their pitch converted to match the layout of the circuit board, as shown in FIG. 16. The semiconductor elements on the mounting carrier 600 are then bonded to the circuit board to form a semiconductor device. In this second semiconductor device manufacturing method, when transferring a semiconductor element having an electrode surface such as a micro LED element, in the conventional technology it was necessary to first transfer the element to a second intermediate catch substrate to obtain a mounting carrier, but since the intermediate carrier on which the semiconductor element has been transferred to the intermediate catch substrate 41 can be used as the mounting carrier, the process can be shortened.

[0165] The present invention will be described below with reference to examples, but the present invention should not be construed as being limited to these examples. First, the evaluation method will be described. Note that (1) below corresponds to the manufacturing method of laminate A, (3) and (16) correspond to the manufacturing method of laminate B, (4) and (5) correspond to the semiconductor device and its manufacturing method (first manufacturing method), and (17) corresponds to the semiconductor device and its manufacturing method (second manufacturing method).

[0166] (1) Preparation of a laminate (Laminate 1) in which a resin film is laminated on a support substrate A resin composition prepared by the method described below was applied using a spinner to a 4-inch glass substrate (Corning Eagle XG, absorbance at 355 nm: 0.01) with a thickness of 0.5 mm and an alignment mark, pre-baked on a hot plate at 120°C for 3 minutes, and further heat-treated at a predetermined temperature for a predetermined time to form a resin film on the glass substrate, thereby preparing Laminate A. The film thickness of the resin film was evaluated by cutting the laminate and examining the cross section with a scanning electron microscope (Hitachi High-Technologies Corporation, S-4800).

[0167] (2) Preparation of Laser-Transmitting Substrate with Semiconductor Elements Separately, a silicon wafer with its back surface polished was attached to dicing tape (UDC-1025MC, manufactured by Denka Corporation) and diced using a dicing device (DAD300, manufactured by DISCO Corporation) to prepare dummy chips of semiconductor elements. Each semiconductor element was 250 μm × 200 μm in size and 5 μm thick. The distance between semiconductor elements was 150 μm. Next, the dicing tape was irradiated with UV light to reduce the adhesiveness of the dicing tape, and the surrounding semiconductor elements were removed, leaving a total of 25 semiconductor elements in 10 rows × 10 columns. Separately, varnish 13 (described in Example 16) disclosed in WO 2022 / 210155 was used on a 4-inch glass substrate with a thickness of 0.5 mm and an alignment mark (Corning Eagle XG, absorbance at 355 nm is 0.01), and a laminate formed under the conditions described in Example 16 of the same WO publication was prepared, and the resin film side of the laminate was stacked facing the semiconductor element side on the dicing tape. Next, a semiconductor element was pressure-bonded onto the resin film using a vacuum laminator, and the dicing tape was peeled off to produce a laser-transparent substrate with a semiconductor element mounted thereon, with a total of 100 semiconductor elements arranged in 10 rows x 10 rows.

[0168] (3) Preparation of a laminate (laminate 2) in which a semiconductor element is laminated on the surface of the resin layer of laminate 1 opposite to the support substrate The laminate (laminate 1) prepared in (1), the laser-transmitting substrate with a semiconductor element prepared in (2), and a laser light source were arranged in this order. The laser light source had a wavelength of 355 nm and an energy density of 300 mJ / cm.２ A YAG laser (manufactured by HOYA Corporation, HSL-5500IIIIST) was used. At this time, the surface of the semiconductor element-equipped laser-transmissive substrate on which the semiconductor element was mounted and the surface of the resin film side of the laminate prepared in (1) were held parallel so that the distance between the semiconductor element surface and the resin film surface of laminate A was 50 μm. The laminate prepared in (1) and the laser-transmissive substrate with semiconductor element were aligned using their respective alignment marks. The spot size of the laser light was a square of 260 μm × 210 μm, and the positions of the laser light source and the laminate were adjusted so that one semiconductor element was positioned in the center of the laser light spot, and the laser light did not hit adjacent semiconductor elements. Thereafter, the semiconductor element placed at the laser light irradiation position was irradiated with a laser, and the semiconductor element was transferred from the laser-transmissive substrate with semiconductor element to the laminate prepared in (1), and a laminate (laminate 2) in which the semiconductor element was stacked was prepared.

[0169] (4) Thermocompression bonding of semiconductor elements to circuit boards Using the stacked semiconductor elements prepared in (3) above, thermocompression bonding was performed on a photonic integrated circuit using a known SOI (semiconductor-on-insulator) substrate as disclosed in JP-A-2017-500735 etc. UV-O was applied to the surface of the dummy chip of the semiconductor element of the stacked semiconductor element and the surface of the photonic integrated circuit. ３ After the treatment was carried out for 5 minutes to activate each surface, the semiconductor element side surface of the laminate on which the semiconductor elements were stacked was placed opposite the photonic integrated circuit surface, and they were thermocompression bonded at 150°C and 1 MPa using a chip bonder (FC-3000 manufactured by Toray Engineering Co., Ltd.).

[0170] (5) Removal of Support Substrate and Resin Film from Semiconductor Element (5)-1 Removal by Laser Peeling Method The bonded body of the photonic integrated circuit and the laminate in which the semiconductor element was stacked, prepared in (4) above, was irradiated with a 308 nm excimer laser (manufactured by Light Machinery Co., Ltd.) from the support substrate side of the laminate in which the semiconductor element was stacked, under conditions of an irradiation area of ​​2 mm × 13 mm, a frequency of 30 Hz, and a scan speed of 19.5 mm / sec, in an environment of 25 ° C. For those in which the support substrate and resin film could be peeled from the semiconductor element by irradiating the entire surface with the laser, the residue of the resin film remaining on the semiconductor element after peeling was removed by immersing it in acetone at 25 ° C. and shaking it.

[0171] (5)-2 Removal by mechanical peeling method For the laminate of the photonic integrated circuit and the semiconductor element stacked together prepared in (4) above, the support substrate and the resin film were peeled off from the semiconductor element using a debonder (TWH-008 manufactured by TAZMO Corporation) in an environment of 25°C.

[0172] (6) Evaluation of Catching Property in Laminate 2 [Catching Property 1] In (3) above, the laminate after the semiconductor elements were transferred was observed, and the number of semiconductor elements that could be confirmed to have been transferred to the laminate without damage was counted, with 95 or more being rated "A", 90 or more but less than 95 being rated "B", 80 or more but less than 90 being rated "C", and less than 80 being rated "D", with A to C being considered pass. Here, "no damage" means that no cracks, chips, cracks, etc. were observed in the semiconductor elements.

[0173] Furthermore, the position of the semiconductor element in the laminate after the semiconductor element was transferred was calculated from the alignment mark and compared with the position of the semiconductor element on the laser-transparent substrate with the semiconductor element before transfer. Among the semiconductor elements that could be transferred without damage, the one with the largest positional deviation was judged as follows: The major axis direction (250 μm direction) of the 250 μm × 200 μm semiconductor element was defined as the X direction, and the minor axis direction (200 μm direction) was defined as the Y direction. A misalignment in the range of less than ±5 μm in the X axis direction and less than ±5 μm in the Y axis direction was rated as "A." A misalignment in the range of ±10 μm or more in the X axis direction or ±10 μm or more in the Y axis direction was rated as "C." A misalignment in any other range was rated as "B," with A and B being considered acceptable. Note that A is superior to B.

[0174] (7) Evaluation of Retention of Semiconductor Elements in Laminate 2 [Retention 1] The laminate (laminate 2) on which the semiconductor elements prepared in (3) were stacked was placed in a wafer case so that it was perpendicular to the ground, i.e., so that the surface of the laminate resin layer on which the semiconductor elements were stacked was perpendicular to the ground, and stored in an environment of 25 ° C. for 10 days. Subsequently, the semiconductor on the laminate (laminate 2) on which the semiconductor elements were stacked after storage was observed under a microscope, and the number of semiconductor elements that were retained without peeling off was counted. If the number of semiconductor elements retained after storage was 95% or more of the number before storage, it was rated "A", if it was 80% or more but less than 95%, it was rated "B", and if it was less than 80%, it was rated "C", and A and B were rated as passing. Note that A is superior to B.

[0175] (8) Evaluation of damage and misalignment to semiconductor element during thermocompression bonding [Evaluation of thermocompression bonding properties] The semiconductor element of the laminate of the photonic integrated circuit and the laminate in which the semiconductor element was laminated prepared in (4) above was observed under a microscope from the side of the support substrate of the laminate in which the semiconductor element was laminated. If there was no damage, it was judged as "no damage", and if even one semiconductor element with cracks, chips, or cracks was observed, it was judged as "damage". Furthermore, the position of the semiconductor element in the laminate was calculated from the alignment mark and compared with the position of the semiconductor element before thermocompression bonding. Among the semiconductor elements that could be thermocompression bonded without damage, the one with the largest misalignment was judged as follows: The long axis direction (250 μm direction) of a 250 μm × 200 μm semiconductor element is the X axis direction, and the short axis direction (200 μm direction) is the Y axis direction. Positional deviations within the range of less than ±2 μm in the X axis direction and less than ±2 μm in the Y axis direction were rated as "A." Positional deviations within the range of ±5 μm or more in the X axis direction or ±5 μm or more in the Y axis direction were rated as "C." Positional deviations within the range between these were rated as "B," with A and B being considered acceptable. Note that A is superior to B.

[0176] (9) Evaluation of Laser Peelability After Thermocompression Bonding [Laser Peelability] In (5)-1, if the resin film did not have sufficient laser decomposability and therefore laser peeling was not possible, and the support substrate and resin film could not be removed from the semiconductor element, or if cracks, chips, or cracks occurred in the semiconductor element during laser peeling, or if there was resin film residue, the sample was rated as "B." If laser peeling was possible, and no cracks, chips, or cracks occurred in the semiconductor element during peeling, and no resin film residue remained, the sample was rated as "A," with an A being considered a pass.

[0177] (10) Evaluation of mechanical peelability after thermocompression bonding [Mechanical peelability] In (5)-2, if the number of semiconductor elements that showed no cracks, chips, fissures, or resin film residues upon peeling was 100% of the total number of semiconductor elements subjected to thermocompression bonding, it was given an "A", if it was 95% or more but less than 100%, it was given an "B", if it was 90% or more but less than 95%, it was given an "C", and if it was less than 90%, it was given an "D", with A and B being considered acceptable. Note that A is superior to B.

[0178] (11) Evaluation of storage modulus and loss tangent of resin film First, the laminate in which a resin film was laminated on a support substrate prepared in (1) above was irradiated entirely from the support substrate side with a 308 nm excimer laser (manufactured by Light Machinery Co., Ltd.) under the following conditions: irradiation area 2 mm × 13 mm, frequency 30 Hz, scan speed 19.5 mm / sec., and the resin film was separated from the support substrate. Next, the storage modulus and loss tangent of the resin film were evaluated according to the following [measurement conditions]. Measurements were performed three times using different samples, and the average values ​​were used as the storage modulus and loss tangent of the resin film. In this evaluation, the resin film was peeled off using the above method, but an equivalent method can be used as long as the resin film can be peeled off without damage. [Measurement conditions] Measuring device: DVA-200 manufactured by IT Measurement Control Co., Ltd. Measurement temperature: -50°C to 200°C Measurement frequency: 1 Hz Deformation mode: Tension Initial grip length: 1 cm Static / dynamic stress ratio: 1.7 Set strain: 0.1% Heating rate: 2°C / min.

[0179] (12) Evaluation of Peel Strength of Resin Film For the laminate in which a resin film was laminated on the support substrate prepared in (1) above, a Kapton film (H type, 25 μm thick, manufactured by DuPont-Toray Co., Ltd.) cut to 1 cm × 9 cm was attached to the surface of the resin film using a vacuum laminator at 0.6 MPa and 35 ° C., and the attached Kapton tape was peeled at a constant speed of 2 mm / sec in the direction perpendicular to the resin film using a tensile tester (FGS-VC manufactured by Nidec-Shimpo Corporation) at 25 ° C. The peel resistance at this time was measured using a digital force gauge (FGJN-5 manufactured by Nidec-Shimpo Corporation) to evaluate the peel strength of the resin film. The measurement was performed three times using different samples, and the average value was used as the peel strength as an index of adhesion.

[0180] (13) Evaluation of Solvent Solubility of Resin Film (Washability of Resin Film) The laminate in which a resin film is laminated on a support substrate prepared in (1) above was immersed in acetone at 25°C. If dissolution of the resin film was confirmed in less than 15 minutes, the solvent solubility was rated as "S", if dissolution was confirmed in 15 minutes or more but less than 30 minutes, the solvent solubility was rated as "A", if dissolution was confirmed in 30 minutes or more but less than 60 minutes, the solvent solubility was rated as "B", and if dissolution was confirmed in 60 minutes or more or if no dissolution occurred, the solvent solubility was rated as "C", with S, A and B being considered as passing. S is the best.

[0181] (14) Evaluation of absorbance of resin film The laminate A prepared in (1) above was measured for transmittance (I / I) from 200 nm to 1100 nm using an ultraviolet-visible spectrophotometer (U-2910, manufactured by Hitachi High-Tech Science Corporation). ０ I is the transmitted light intensity at a certain wavelength, I ０ is the incident light intensity at the same wavelength), were continuously measured. From these, the value at 355 nm was read, and each absorbance per 1.0 μm of film thickness was calculated using the following formula. When measuring, the same substrate as the substrate used for laminate A was used as a reference in advance, and the absorbance of the resin film was obtained by subtracting the measured value of the reference from the measured value obtained for laminate A.

[0182] Absorbance per 1.0 μm film thickness = (-log １０ (Transmittance) / (Film thickness [μm]) (15) Preparation of second laser-transmitting substrate with semiconductor element A micro-LED substrate (manufactured by EPILEDS, with alignment marks) was prepared and cut into 20 mm squares using a dicer. The micro-LEDs mounted on it are as follows. The size of the semiconductor element, the size of the protruding electrode portion, and the distance between adjacent elements were measured using a scanning electron microscope (S-4800, manufactured by Hitachi High-Tech Corporation).

[0183] Substrate for crystal growth: sapphire (thickness 0.8 mm) Type of semiconductor element: GaN Size of semiconductor element: 36 μm × 18 μm × 7.5 μm (including electrodes) Number of electrodes: two per surface Size of electrode: 10 μm × 15 μm × 2.2 μm Type of electrode: Au Distance between adjacent elements: 15 μm Next, varnish 13 (described in Example 16) disclosed in WO 2022 / 210155 was prepared on a 4-inch glass substrate with a thickness of 0.5 mm and an alignment mark (manufactured by Corning, Eagle XG, absorbance at 355 nm is 0.01), prepared under the conditions described in Example 16 of the same WO publication, and the resin film surface side of the laminate and the semiconductor element surface of the micro LED substrate were superimposed so as to be in contact, and a flip chip bonder (manufactured by Toray Engineering Co., Ltd., FC-3000WS) was bonded under pressure of 0.5 MPa, 80 ° C., and 2 minutes. Then, from the first substrate side, a 266 nm wavelength laser device (manufactured by HOYA Corporation, HSL-5500IIISUV, pulse width 5 to 7 nec, energy density 600 mJ / cm ２ ) a laser was irradiated onto the entire surface of the micro-LED substrate, and the crystal growth substrate was separated at the interface between the crystal growth substrate and the semiconductor element, thereby producing a laser-transmitting substrate with a semiconductor element.

[0184] (16) Preparation of a laminate (Laminate 2') in which a semiconductor element is laminated on the surface of the resin layer of the laminate of (1) opposite the support substrate. The laminate prepared in (1), the laser-transmitting substrate with semiconductor element prepared in (15), and the laser light source were arranged in this order. At this time, the surface of the laser-transmitting substrate with semiconductor element on which the semiconductor element is mounted and the surface of the resin film side of the laminate prepared in (1) were held parallel so that the distance between the semiconductor element surface and the resin film surface of Laminate 1 was 50 μm. The laminate prepared in (1) and the laser-transmitting substrate with semiconductor element were aligned using their respective alignment marks. The laser light spot size was a square 36 μm × 18 μm, and the positions of the laser light source and the laminate were adjusted so that one semiconductor element was positioned in the center of the laser light spot, and the laser light was not incident on adjacent semiconductor elements. Thereafter, a laser was irradiated onto the semiconductor element placed at the laser light irradiation position, and the semiconductor element was transferred from the laser-transparent substrate with the semiconductor element to the laminate prepared in (1), thereby preparing a laminate (laminate 2') on which the semiconductor element was laminated.

[0185] The laser light source has a wavelength of 355 nm and an energy density of 300 mJ / cm ２ A YAG laser (manufactured by HOYA Corporation, HSL-5500IIIIST) was used to perform laser transfer of 100 semiconductor elements.

[0186] (17) Laser transfer from laminate 2' to intermediate catch substrate PDMS (polydimethylsiloxane, see below) was diluted with toluene onto a 0.5 mm thick alkali-free glass substrate (Corning Eagle XG) with a square surface measuring 4 inches on a side. The diluted solution, adjusted to a 1:3 weight ratio of PDMS to toluene, was applied using a spinner and heated and cured on a hot plate at 120°C for 3 minutes to form a PDMS film on the glass substrate. The thickness of the PDMS film after thermal curing was measured using an optical film thickness meter (Dainippon Screen Co., Ltd., Lambda Ace, refractive index = 1.543), and an intermediate catch substrate with a PDMS film thickness of 5.0 μm was obtained.

[0187] Next, the intermediate catch substrate, the laminate 2' prepared in (16), and the laser light source were arranged in this order. At this time, the surface of the laminate 2' on which the semiconductor element was mounted and the surface of the PDMS film side of the intermediate catch substrate were held parallel so that the distance between the semiconductor element surface and the PDMS film surface of the intermediate catch substrate was 50 μm. The laminate prepared in (1) and the laser-transparent substrate with semiconductor element were aligned using their respective alignment marks. The laser light spot size was a square shape of 36 μm x 18 μm, and the positions of the laser light source and the laminate were adjusted so that one semiconductor element was positioned in the center of the laser light spot, and the laser light did not hit adjacent semiconductor elements. The semiconductor element placed at the laser light irradiation position was then irradiated with laser light, and the semiconductor element was laser-transferred from the laminate 2' to the intermediate catch substrate.

[0188] A YAG laser (HSL-5500IIIIST, manufactured by HOYA Corporation) with a wavelength of 355 nm was used as the laser light source, and 400 mJ / cm was applied to the semiconductor element placed at the laser light irradiation position. ２ , 500 mJ / cm ２ At each energy density, laser light was irradiated to all of the semiconductor elements that were not broken or turned over and were normally caught in the resin film in (16) above, and laser transfer was performed.

[0189] (18) Evaluation of Catching Property in Laminate 2' [Catching Property 2] In (16) above, the laminate 2' was observed after laser transfer, and the number of semiconductor elements that were properly caught by the resin film of the laminate 2' without being damaged or turned over was counted as properly caught semiconductor elements, and the catch yield in the laminate 2' was calculated using the formula below.

[0190] Catch yield (%) for laminate 2' = [number of semiconductor elements successfully caught by the resin film of laminate 2'] / [number of semiconductor elements to be transferred (100)]. 95% or more was rated as "A," 90% or more but less than 95% as "B," 80% or more but less than 90% as "C," and less than 80% as "D," with A to C being considered pass. A is superior to B.

[0191] When the laser-transmitting substrate with semiconductor elements was observed after being irradiated with the laser light, it was found that all 100 semiconductor elements irradiated with the laser had been released and none remained on the laser-transmitting substrate.

[0192] (19) Evaluation of Retention of Semiconductor Elements in Laminate 2' [Retention 2] The laminate (laminate 2') on which the semiconductor elements prepared in (16) were stacked was placed in a wafer case so that it was perpendicular to the ground, i.e., so that the surface of the resin layer of the laminate on which the semiconductor elements were stacked was perpendicular to the ground, and stored in an environment of 25 ° C. for 10 days. Subsequently, the semiconductor on the laminate (laminate 2') on which the semiconductor elements were stacked after storage was observed under a microscope, and the number of semiconductor elements that were retained without peeling off was counted. If the number of semiconductor elements retained after storage was 95% or more of the number before storage, it was rated "A", if it was 80% or more but less than 95%, it was rated "B", and if it was less than 80%, it was rated "C", and A and B were rated as passing. Note that A is superior to B.

[0193] (20) Evaluation of laser transferability to intermediate catch substrate [Laser transferability] (20)-1 Laser transfer yield In (17) above, the intermediate catch substrate was observed after laser transfer, and the number of semiconductor elements that were properly caught by the intermediate catch substrate without being damaged or turned over was counted, and the laser transfer yield of the resin film was calculated using the following formula. The calculated value was rounded to one decimal place to obtain an integer.

[0194] Laser transfer yield (%) = [number of semiconductor elements successfully caught on the intermediate catch substrate] / [number of semiconductor elements to be transferred] 95% or more was judged as "A", 90% or more but less than 95% as "B", 80% or more but less than 90% as "C", and less than 80% as "D". In addition, the laminate 2' after laser transfer was observed, and if even one semiconductor element was not released, it was judged as "E" regardless of the transfer yield. A to C were judged to be acceptable. Note that A is better than B.

[0195] (20)-2 Laser Transfer Accuracy Except for samples judged as "D" or "E" in the evaluation of (20)-1 above, the laser transfer accuracy was evaluated by the following method. The position of the semiconductor element on the intermediate catch substrate after the semiconductor element was transferred was calculated from the alignment mark and compared with the position of the semiconductor element on the laminate 2' before transfer, and the amount of misalignment of the center of the semiconductor element before and after transfer was calculated. The amount of misalignment was calculated only for semiconductor elements that were transferred normally, and the laser transfer accuracy was evaluated based on the average value. An average value of 0 μm or more and less than 2 μm was rated "A," 2 μm or more and less than 3 μm was rated "B," and 3 μm or more was rated "C." A and B were rated as passing. Note that A is better than B.

[0196] The names and abbreviations of the compounds used are shown below. <Acid dianhydride that provides the acid dianhydride residue (A1) represented by formula (3)> 168AS: Polysiloxane modified with maleic anhydride at both ends (average molecular weight: 1008, X-22-168AS manufactured by Shin-Etsu Chemical Co., Ltd.) <Diamine that provides the diamine residue (A2) represented by formula (4)> APPS2: α,ω-bis(3-aminopropyl)polydimethylsiloxane (average molecular weight: 1590, X22-161A manufactured by Shin-Etsu Chemical Co., Ltd.) <Diamine that provides the diamine residue (A3) represented by formula (5)> DYPI: 3,3'-diamino-4,4'-Dihydroxybiphenyl (DYPI1072, manufactured by Shanghai Da Ran Chemical Co., Ltd.) BAHF: 4,4'-dihydroxy-3,3'-diaminophenylhexafluoropropane (molecular weight: 366, manufactured by Merck Ltd.) (containing a structure represented by formula (6)) BAPA: 2,2-bis(3-amino-4-hydroxyphenyl)propane (manufactured by Tokyo Chemical Industry Co., Ltd., containing a structure represented by formula (7)) FDA: 9,9-bis(3-amino-4-hydroxyphenyl)fluorene (manufactured by Tokyo Chemical Industry Co., Ltd., containing a structure represented by formula (8)) ABPS: bis(3-amino-4-hydroxyphenyl)sulfone (manufactured by Tokyo Chemical Industry Co., Ltd., containing a structure represented by formula (9)) ABMIBK: 2,2-bis(3-amino-4-hydroxyphenyl)-4-methylpentane (containing a structure represented by formula (10)) <Others> PMDA: pyromellitic anhydride (manufactured by Daicel Corporation) PBOM: 4,4'-oxydibenzoyl-1,1'-diimidazolide PDA: p-phenylenediamine (manufactured by Tokyo Chemical Industry Co., Ltd.) APPS1: α,ω-bis(3-aminopropyl)polydimethylsiloxane (average molecular weight: 860, KF8010 manufactured by Shin-Etsu Chemical Co., Ltd.) MDI: diphenylmethane diisocyanate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) PTMG: polytetramethylene oxide (average molecular weight: 1000, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) <Solvent> CHN: cyclohexanone (manufactured by Toyo Gosei Co., Ltd.) DMAC: N,N-dimethylacetamide (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) <Light absorber> Tinuvin 477: hydroxyphenyltriazine-based ultraviolet absorber (manufactured by BASF Corporation) <Crosslinking agent> GMOM: a crosslinking agent having an alkoxymethyl group represented by the following formula (11) (manufactured by Gun-ei Chemical Co., Ltd.),

[0197]

[0198] jER-871: dimer acid modified epoxy resin (manufactured by Mitsubishi Chemical Corporation) <Silicone resin> PDMS (polydimethylsiloxane): XX-9001-02 (manufactured by Dow Toray Industries, Inc.).

[0199] [Synthesis Example 1] Synthesis of Polyimide P-1 A thermometer and a stirring rod with a stirring blade were placed in a 500 mL four-neck flask. Under a dry nitrogen stream, PDA (3.2 g, 0.04 mol) and APPS2 (190.8 g, 0.16 mol) were added to the flask and dissolved in CHN (151.2 g). Subsequently, PMDA (32.7 g, 0.20 mol) was added, and the mixture was stirred at 60 ° C. for 1 hour, and then at 140 ° C. for 4 hours to obtain a 60 mass% resin solution of polyimide P-1 (simply referred to as "P-1" in the table; the same applies below).

[0200] Synthesis Examples 2 to 30 Synthesis of Polyimides P-2 to P-19 and Polyimides P23 to P-30 Resin solutions of polyimides P-2 to P-19 and polyimides P23 to P-30 were obtained in the same manner as in Synthesis Example 1, except that the types and amounts of acid dianhydrides and diamines used were changed as shown in Table 1.

[0201] Synthesis Example 31 Synthesis of Polybenzoxazole P-31 A thermometer and a stirring rod with a stirring blade were installed in a 500 mL four-neck flask. Under a dry nitrogen stream, BAHF (5.5 g, 0.02 mol) and APPS2 (214.7 g, 0.18 mol) were added to the flask and dissolved in CHN (169.7 g). Subsequently, PBOM (34.4 g, 0.20 mol) was added, and the mixture was stirred at 60°C for 1 hour, followed by stirring at 150°C for 4 hours to obtain a 60% by mass resin solution of polybenzoxazole P-31.

[0202]

[0203] For each component (acid dianhydride component, dicarboxylic acid component, diamine component), the upper row indicates the composition ratio (mol%), and the lower row indicates the amount (g) of each component. １ ) and an acid dianhydride residue (X ２ ) and diamine residues (Y １ ) and diamine residue (Y ２ The content (unit: mol%) of the acid dianhydride residue (A1) represented by formula (3) and the diamine residue (A2) represented by formula (4) relative to the total of 100 mol% of the acid dianhydride residue (X １ ) and an acid dianhydride residue (X ２) and diamine residues (Y １ ) and diamine residue (Y ２ The content (unit: mol %) of the diamine residue (A3) represented by formula (5) relative to 100 mol % of the total of the diamine residues (A3), (A4), (A5), (A6), (A7), (A8), (A9), (B10), (B11), (B12), (B13), (B14), (B15), (B16), (B17), (B18), (B19), (B20), (

[0204] Synthesis Example 32 Synthesis of Acrylic Resin P-32 A solution of acrylic resin P-32, a 2-ethylhexyl acrylate / 2-hydroxyethyl acrylate / acrylic acid copolymer (weight ratio 94.7 / 5 / 0.3), was obtained by the method described in WO 2022 / 210155.

[0205] Synthesis Example 33 Synthesis of Polyurethane P-33 A thermometer and a stirring rod with a stirring blade were installed in a 500 mL four-neck flask. Next, under a dry nitrogen stream, DMAC (110 g) and MDI (24.78 g (99.00 mmol)) were added and stirred at 40°C. While stirring, PTMG (50.00 g (50.00 mmol)) was added and washed in with DMAC (20 g). After stirring at 80°C for 3 hours, 1,4-butanediol (4.506 g (50.00 mmol)) was added and washed in with DMAC (20 g). Stirring was continued at 80°C for 5 hours to obtain a polymerization solution of 41% by mass of polyurethane P-33.

[0206] Synthesis Examples 34 and 35 Synthesis of Polyimide P-34 and Polyimide P-35 Resin solutions of polyimide P-34 and polyimide P-35 were obtained in the same manner as in Synthesis Example 1, except that the types and amounts of acid dianhydrides and diamines used were changed as shown in Table 1.

[0207] (Examples 1 to 58, Comparative Examples 1 to 10) [Preparation Example 1] The resin solution of polyimide P-1 obtained in Synthesis Example 1 was stirred without adding any additives, and then filtered using a polytetrafluoroethylene (PTFE) filter with a pore size of 0.2 μm to prepare Resin Composition 1.

[0208] [Preparation Examples 2] to [Preparation Examples 58] Resins and additives shown in Tables 2 and 3 were used, and each component was mixed in the weight parts shown in Tables 2 and 3 relative to 100 parts by weight of the solid content of the resin solution. The mixture was then filtered using a PTFE filter with a pore size of 0.2 μm to prepare Resin Compositions 2 to 58.

[0209] The resin compositions obtained in Preparation Examples 1 to 58 were evaluated for the above-mentioned items. The evaluation results are summarized in Tables 2 and 3.

[0210]

[0211] In the resin column, the upper row indicates the resin type, and the lower row indicates the blend amount (parts by weight).

[0212]

[0213] *1: Damage to the semiconductor element was observed during thermocompression bonding, so further evaluation was not performed. *2: The semiconductor element could not be caught, so further evaluation was not performed. *3: When catching the semiconductor element, it was observed that the semiconductor element was embedded in the resin film, so further evaluation was not performed after the evaluation of catching ability.

[0214]

[0215] In the resin column, the upper row indicates the resin type, and the lower row indicates the blend amount (parts by weight).

[0216]

[0217] *4: The laser transfer yield was rated "D" or "E", so no evaluation was made. *5: The semiconductor element could not be caught, so no further evaluation was made. *6: When catching the semiconductor element, the semiconductor element was found to be embedded in the resin film, so no evaluation was made after the evaluation of catching ability.

[0218] REFERENCE SIGNS LIST 11 Support substrate 12 Resin film 100 Laminate A 21 Laser-transparent substrate 22 Semiconductor element 23, 24, 25 Semiconductor element with electrode surface 29 Laser light 200 Laser-transparent substrate with semiconductor element 300 Laminate B 31 Circuit board 41 Intermediate catch substrate 42 Second intermediate catch substrate 43 Third intermediate catch substrate 400 Intermediate carrier 51 Laser-decomposable resin film 500 Carrier for laser transfer 600 Second intermediate carrier 700 Carrier for mounting

Claims

1. A laminate comprising a support substrate and a resin film, wherein the resin film contains at least one resin selected from the group consisting of polyimide, polyimide precursor (hereinafter, polyimide, polyimide precursor, and copolymers thereof may be collectively referred to as "polyimides"), polybenzoxazole, polybenzoxazole precursor (hereinafter, polybenzoxazole, polybenzoxazole precursor, and copolymers thereof may be collectively referred to as "polybenzoxazoles"), silicone resin, acrylic resin, and polyurethane, and wherein the storage modulus of the resin film at a frequency of 1 Hz and -30°C is 0.1 MPa or more and 80 MPa or less.

2. The laminate according to claim 1, wherein the peel strength at 25°C of the surface of the resin film of the laminate opposite to the support substrate side is 0.02 N / cm or more and 0.3 N / cm or less.

3. The laminate according to claim 1 or 2, wherein the storage modulus of the resin film at 150°C and a frequency of 1 Hz is 0.1 MPa or more and 5 MPa or less.

4. The resin film is a resin film containing polyimides, at least one of which has a structural unit represented by formula (1) or a structural unit represented by formula (2), or both of which have an acid dianhydride residue (X １ ) and an acid dianhydride residue (X ２ ) and diamine residues (Y １ ) and diamine residue (Y ２ 3. The laminate according to claim 1, wherein the total content of the acid dianhydride residue (A1) represented by formula (3) and the diamine residue (A2) represented by formula (4) is 40 mol % or more and 99 mol % or less, and the content of the diamine residue (A3) represented by formula (5) is 1 mol % or more and 25 mol % or less, when the total of the acid dianhydride residue (A1) represented by formula (3) and the diamine residue (A2) represented by formula (4) is 100 mol %. (X １ and X ２ each independently represents a tetravalent acid dianhydride residue having 4 or more carbon atoms, Y １ and Y ２ R each independently represents a divalent diamine residue having two or more carbon atoms. １ and R ２ each independently represents a hydrogen atom, a hydrocarbon group having from 1 to 10 carbon atoms, an alkylsilyl group having from 1 to 10 carbon atoms, an alkali metal atom, an ammonium group, an imidazolium group, or a pyridinium group. (R ３ ~R ６ , R ９ ~R １２ R each independently represents an alkyl group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, a phenyl group, or a phenoxy group. ７ ~R ８ , R １３ ~R １４ each independently represents an alkylene group or a phenylene group having 1 to 30 carbon atoms. Each n independently represents an integer of 15 to 60. *3a and *3b represent a bonding site connected to an imide group in the structural unit represented by formula (1), or *3a represents a bonding site connected to a carbon atom of an amide bond in the structural unit represented by formula (2), and *3b represents a bonding site connected to a carbon atom of a carboxylic acid or carboxylic acid ester in the structural unit represented by formula (2). *4 represents an imide group in the structural unit represented by formula (1) or a bonding site connected to a nitrogen atom of an amide bond in the structural unit represented by formula (2). (R １５ ~R １６ each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a hydroxyl group, or a halogen. k and l each independently represent an integer of 0 to 3. R １７ represents a single bond or a divalent organic group having one or more carbon atoms. *5 represents a bonding site connecting to the nitrogen atom of the imide group in the structural unit represented by formula (1) or the amide bond in the structural unit represented by formula (2).

5. The laminate according to claim 4, wherein the diamine residue (A3) has a structure represented by any one of formulas (6) to (10). (* indicates a bonding site connected to the nitrogen atom of the imide group in the structural unit represented by formula (1) or the amide bond in the structural unit represented by formula (2).) 6. The laminate according to claim 1 or 2, wherein the resin film further contains a light absorbing agent.

7. The laminate according to claim 1 or 2, wherein the resin film further contains a siloxane diamine.

8. The laminate according to claim 1 or 2, wherein the resin film further contains a crosslinking agent having at least one functional group selected from the group consisting of an epoxy group, an alkoxymethyl group, and a methylol group.

9. The laminate according to claim 1 or 2, wherein the resin film contains a structure in which crosslinking agents having at least one functional group selected from the group consisting of epoxy groups, alkoxymethyl groups, and methylol groups are combined with each other or with other components.

10. A laminate with a semiconductor element, in which a semiconductor element is further laminated on the surface of the resin film of the laminate according to claim 1 or 2 opposite to the support substrate side.

11. A resin composition containing a polyimide having either or both of a structural unit represented by formula (1) and a structural unit represented by formula (2) and a solvent, wherein the polyimide has an acid dianhydride residue (X １ ) and an acid dianhydride residue (X ２ ) and diamine residues (Y １ ) and diamine residue (Y ２ a resin composition in which the total content of the acid dianhydride residue (A1) represented by formula (3) and the diamine residue (A2) represented by formula (4) is 40 mol % or more and 99 mol % or less, relative to 100 mol % of the total of the above-mentioned components (a) and (b), and the content of the diamine residue (A3) represented by formula (5) is 1 mol % or more and 25 mol % or less. (X １ and X ２ each independently represents a tetravalent acid dianhydride residue having 4 or more carbon atoms, Y １ and Y ２ R each independently represents a divalent diamine residue having two or more carbon atoms. １ and R ２ each independently represents a hydrogen atom, a hydrocarbon group having from 1 to 10 carbon atoms, an alkylsilyl group having from 1 to 10 carbon atoms, an alkali metal atom, an ammonium group, an imidazolium group, or a pyridinium group. (R ３ ~R ６ , R ９ ~R １２ R each independently represents an alkyl group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, a phenyl group, or a phenoxy group. ７ ~R ８ , R １３ ~R １４ each independently represents an alkylene group or a phenylene group having 1 to 30 carbon atoms. Each n independently represents an integer of 15 to 60. *3a and *3b represent a bonding site connected to an imide group in the structural unit represented by formula (1), or *3a represents a bonding site connected to a carbon atom of an amide bond in the structural unit represented by formula (2), and *3b represents a bonding site connected to a carbon atom of a carboxylic acid or carboxylic acid ester in the structural unit represented by formula (2). *4 represents an imide group in the structural unit represented by formula (1) or a bonding site connected to a nitrogen atom of an amide bond in the structural unit represented by formula (2). (R １５ ~R １６ each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a hydroxyl group, or a halogen. k and l each independently represent an integer of 0 to 3. R 17 represents a single bond or a divalent organic group having one or more carbon atoms. *5 represents a bonding site connecting to the nitrogen atom of the imide group in the structural unit represented by formula (1) or the amide bond in the structural unit represented by formula (2).

12. The resin composition according to claim 11, wherein the diamine residue (A3) has a structure represented by any one of formulas (6) to (10). (* indicates a bonding site connected to the nitrogen atom of the imide group in the structural unit represented by formula (1) or the amide bond in the structural unit represented by formula (2).) 13. The resin composition according to claim 11 or 12, further comprising a light absorber.

14. The resin composition according to claim 11 or 12, further comprising a siloxane diamine.

15. The resin composition according to claim 11 or 12, further comprising a crosslinking agent having at least one functional group selected from the group consisting of an epoxy group, an alkoxymethyl group, and a methylol group.

16. A method for producing a laminate with a semiconductor element, using the laminate according to claim 1 and a laser-transparent substrate with a semiconductor element, comprising the steps of: (i) bringing the surface of the laser-transparent substrate with a semiconductor element, on which the semiconductor element is mounted, into opposition with the surface of the laminate facing the resin film (step I); and (ii) irradiating the surface of the laser-transparent substrate with semiconductor element opposite the surface on which the semiconductor element is mounted with laser light, thereby transferring the semiconductor element to the surface of the laminate facing the resin film (step II).

17. A method for manufacturing a semiconductor device using a laminate with a semiconductor element according to claim 10 or a laminate with a semiconductor element obtained by the method for manufacturing a laminate with a semiconductor element according to claim 16, and a circuit board, the method comprising the steps of: placing the surface of the laminate with semiconductor element on which the semiconductor element is stacked facing the circuit board, and electrically joining the semiconductor element to the circuit of the circuit board (Step III); and separating the support substrate and resin film of the laminate with semiconductor element from the semiconductor element (Step IV).

18. The method for manufacturing a semiconductor device according to claim 17, further comprising the step of removing a portion of the resin film in the laminate with semiconductor element and patterning the resin film before step III.

19. The method for manufacturing a semiconductor device according to claim 17, wherein step IV is a step using a laser separation method.

20. The method for manufacturing a semiconductor device according to claim 17, wherein step IV is a step using a mechanical peeling method.

21. The method for manufacturing a semiconductor device according to claim 17, wherein step IV is a step using a solvent stripping method.

22. The laminate according to claim 1 or 2, wherein the loss tangent of the resin film at a frequency of 1 Hz and at -30°C is 0.15 or more and 0.8 or less.

23. A laminate according to claim 1 or 2, wherein the resin film has an absorbance of 0.4 or more and 5.0 or less at a wavelength of 248 nm, 266 nm or 355 nm when converted into a film thickness of 1.0 μm.

24. A laminate with a semiconductor element, in which a semiconductor element is further laminated on the surface of the resin film of the laminate according to claim 23 opposite to the support substrate side.

25. A method for producing a laminate with a semiconductor element according to claim 16, in which the laminate according to claim 23 is used instead of the laminate according to claim 1.

26. A method for manufacturing a substrate with temporarily fixed semiconductor elements, using a laminate with semiconductor elements as defined in claim 24 or a laminate with semiconductor elements as defined in claim 25, and a substrate for temporarily fixing the semiconductor elements (hereinafter referred to as an "intermediate catch substrate"), comprising the steps of: (i) placing the surface of the laminate with semiconductor elements, on which the semiconductor elements are stacked, facing the intermediate catch substrate at a fixed distance (Process V); and (ii) irradiating a laser onto the resin film through the support substrate of the laminate with semiconductor elements to transfer the semiconductor elements to the intermediate catch substrate (Process VI), in this order.

27. A method for manufacturing a semiconductor device, comprising the steps of: orienting the surface of the substrate on which semiconductor elements are laminated, obtained by the method for manufacturing a substrate on which semiconductor elements are temporarily fixed as described in claim 26, facing a circuit board; and electrically connecting the semiconductor elements to the circuit of the circuit board (Step III'); and separating the support substrate and resin film of the semiconductor element-equipped laminate from the semiconductor elements (Step IV').

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