Laminate, resin composition, and method for manufacturing semiconductor device

Abstract

Provided is a laminate that allows semiconductor elements to be transferred over a wide range of processing margins using lasers of various wavelengths, without damaging the elements or leaving behind any pasty residue. This laminate is a substrate in which a laser-transmitting substrate 1, a resin film, and a semiconductor element are laminated in the stated order. The absorbance of the resin film at a wavelength of 248 nm, 266 nm, or 355 nm expressed in terms of a film thickness of 1.0 μm us 0.4-5.0, and the adhesive strength of the resin film with respect to the semiconductor elements is 0.02-0.3 N / cm.

Description

[Technical Field]

[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 when mounting a semiconductor element by laser transfer, and a method for manufacturing a semiconductor device using the laminate. [Background technology]

[0002] Typically, elements incorporated into semiconductor devices are transferred and mounted on circuit boards using a pick-and-place method such as a flip-chip bonder. In recent years, semiconductor devices have become increasingly compact and powerful, leading to smaller and thinner elements being incorporated into them. In recent years, displays in which light-emitting diodes (LEDs), a type of semiconductor element, are arranged in each pixel have attracted attention due to their high brightness, low power consumption, and high image quality. The LEDs mounted in each pixel are called micro LEDs, and are small LEDs with sides measuring several hundred to several dozen microns. Because the above mounting method takes too much time to manufacture these micro LED displays, new methods are being considered.

[0003] One method for mounting a large number of small semiconductor elements involves placing chips from a wafer onto a circuit board using an adhesive stamp made of silicone resin or the like (Patent Documents 1 and 2). In this method, the adhesive stamp can hold multiple micro LED chips, allowing multiple chips to be placed on a circuit board in a single pick-and-place process. Another proposed method involves transferring chips from a wafer to a transfer substrate with an adhesive layer, and then transferring and mounting them onto a circuit board or the like using laser lift-off (LLO) (Patent Documents 3, 4, and 5). This method has the advantage of enabling high-speed transfer with high positional accuracy. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Special Publication No. 2017-531915 [Patent Document 2] Japanese Patent Application Publication No. 2020-129638 [Patent Document 3] Japanese Patent Publication No. 2020-188037 [Patent Document 4] Japanese Patent Application Laid-Open No. 2010-251359 [Patent Document 5] Special Publication No. 2014-515883 Summary of the Invention [Problem to be solved by the invention]

[0005] In the inventions described in Patent Documents 1 and 2, the stamp size depends on the wafer size, limiting the number of semiconductor elements that can be simultaneously transferred. Furthermore, the inventions described in Patent Documents 1 and 2 also have issues, such as the need to create stamps that match the circuit board design each time. On the other hand, the LLO method eliminates area constraints and the need to create stamps with different designs, potentially reducing costs. However, in the inventions described in Patent Documents 3 and 4, for example, the adhesive layer is removed by laser ablation, which requires the formation of a very thin adhesive layer, raising concerns about reduced yield due to poor in-plane uniformity. Furthermore, in the inventions described in Patent Documents 3 and 4, in order to avoid residues of the adhesive layer on the surface of the semiconductor element, excessive laser light must be irradiated to remove the entire adhesive layer by ablation, which creates issues such as contamination of the substrate due to the adhesive layer being scattered and damage to the semiconductor element (hereinafter, the adhesive layer residue on the surface of the semiconductor element may be referred to as glue residue, and the scattered adhesive layer residue may be referred to as debris). In Patent Document 5, by separating the adhesive layer and the laser absorption layer, transfer can be performed with low energy and damage to the semiconductor element can be reduced. However, the process is complicated because two layers are formed, and the range of laser energy that can be used to transfer with good positional accuracy is narrow, so there are issues with the processing margin to achieve practical transfer. [Means for solving the problem]

[0006] To solve the above problem, the present invention provides a laminate in which a laser-transparent substrate 1 and a resin film are laminated in this order, wherein the resin film has an absorbance of 0.4 or more and 5.0 or less at any wavelength of 200 to 1100 nm when converted into a film thickness of 1.0 μm, and further, the adhesive strength of the resin film on the side opposite to the surface where the substrate 1 and the resin film contact each other is 0.02 N / cm or more and 0.3 N / cm or less. [Effects of the Invention]

[0007] The laminate of the present invention allows transfer of semiconductor elements using lasers of various wavelengths with a wide processing margin without leaving adhesive residue or damaging the elements. [Brief explanation of the drawings]

[0008] [Figure 1] 1 is a diagram showing a method for producing a laminate 2. A laminate in which semiconductor elements are stacked may be hereinafter referred to as a laminate 2. [Figure 2] 10A and 10B are diagrams illustrating a method for producing a laminate 2 using a temporary adhesive. [Figure 3] 1A to 1C are diagrams showing a method for producing a laminate 2 using laser lift-off. [Figure 4] 10A to 10C are diagrams showing another method for producing the laminate 2 using a semiconductor substrate. [Figure 5] 2A to 2C are diagrams illustrating a step of arranging the semiconductor element surface of the laminate 2 and the substrate 2 to face each other in the method for manufacturing the semiconductor device. [Figure 6] 10 is a diagram showing a process of transferring a semiconductor element onto a substrate 2 by irradiating with laser light. DETAILED DESCRIPTION OF THE INVENTION

[0009] The laminate of the present invention is a laminate in which a laser-transmitting substrate 1 and a resin film are laminated in this order, and the resin film has an absorbance of 0.4 to 5.0 at a wavelength of 200 to 1100 nm when converted into a film thickness of 1.0 μm, and further has an adhesive strength of 0.02 N / cm to 0.3 N / cm on the side opposite to the surface where the substrate 1 and the resin film contact each other. Hereinafter, the laminate of this embodiment will be referred to as laminate 1. Laminate 1 of the present invention and laminate 2 of the present invention may also be simply referred to as the laminate of the present invention.

[0010] Each of the components constituting the laminate 1 of the present invention will be described below.

[0011] The laser-transmitting substrate 1 refers to a substrate having an absorbance of 0.1 or less at any wavelength between 200 and 1100 nm. Substrates having such absorbance include inorganic substrates such as quartz, sapphire, alkali glass, non-alkali glass, and borosilicate glass. The thickness of the substrate can be selected within a range that does not impair the absorbance, and is preferably 0.1 mm to 5.0 mm. From the viewpoint of substrate handling, the thickness of the substrate is preferably 0.3 mm or more, and from the viewpoint of availability and versatility, the thickness of the substrate is more preferably 2.0 mm or less.

[0012] The laser-transmitting substrate 1 can also be an organic substrate such as PET, aramid, polyester, polypropylene, or cycloolefin. When using an organic substrate, the thickness of the substrate can be selected within a range that does not impair the absorbance, and is preferably 0.05 mm to 3.0 mm. From the viewpoint of substrate handling, the thickness of the substrate is preferably 0.1 mm or more, and from the viewpoint of suppressing light scattering during laser irradiation, the thickness of the substrate is more preferably 1.0 mm or less.

[0013] Next, the resin film will be described.

[0014] The resin film is a film containing at least a resin, and has an absorbance of 0.4 or more and 5.0 or less at a wavelength of 200 to 1100 nm, calculated as a film thickness of 1.0 μm. The absorbance of 0.4 or more allows the resin film to absorb the irradiated laser light intensively when the laser light is irradiated from the laser-transparent substrate 1 side to the resin film side to transfer the semiconductor element to the opposing substrate. More preferably, the absorbance is 0.6 or more, allowing the laser light to be absorbed particularly near the interface between the resin film and the laser-transparent substrate 1, thereby enabling transfer with even lower energy. From the viewpoint of material design, the absorbance is preferably 5.0 or less, and more preferably 4.0 or less, allowing the use of versatile resins.

[0015] Resins contained in the resin film include, but are not limited to, resins that have absorption in the range of 200 to 1100 nm, such as polyimide, polyimide precursor, polybenzoxazole, polybenzoxazole precursor, urethane resin, novolac resin, polyhydroxystyrene, polyester resin, acrylic resin, aramid resin, polysiloxane, and polyimidesiloxane.

[0016] These resins preferably have a conjugated structure within their structure. By having the conjugated structure, the absorbance of a 200 to 1100 nm film at a 1.0 μm film thickness can be adjusted to a range of 0.4 or more and 5.0 or less. Examples of structures having a conjugated structure include aromatic structures, and among these, structures such as biphenyl, imide, benzoxazole, and benzophenone are preferred. The above absorbance can be achieved by using monomer residues having a conjugated structure in an amount of 60 mol % or more of the monomer residues relative to 100 mol % of all monomer residues. These resins may be contained alone or in combination in the resin film.

[0017] The above absorbance can also be achieved by adding an additive such as an ultraviolet absorber, dye, or pigment to the resin film. Examples of additives contained in the resin film include ultraviolet absorbers such as 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 Ltd.), 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 Co., Ltd.), Solvent Yellow 93, Solvent Yellow 33, Solvent Orange 60, Solvent Red 111, Solvent Red 135, Solvent Red 168, and Solvent Examples of suitable dyes and pigments include Red 207, Solvent Red 52, Solvent Red 179, Solvent Blue 36, Solvent Blue 94, Solvent Blue 63, Solvent Blue 104, Solvent Blue 97, Solvent Green 20, Solvent Violet 13, and Solvent Violet 36 (all trade names, manufactured by Tokyo Chemical Industry Co., Ltd.), carbon black, perylene black, cyanine black, and aniline black.

[0018] These may be contained alone or in combination in the resin film. The content of the additives to bring the absorbance within the above range is preferably 0.1 parts by weight or more per 100 parts by weight of the resin film, and from the viewpoint of stability in the varnish state before forming the laminate, is preferably 50 parts by weight or less.

[0019] The adhesive strength of the resin film on the surface opposite to the surface where the resin film contacts the substrate 1 is 0.02 N / cm or more and 0.3 N / cm or less. The adhesive strength mentioned here refers to the value obtained from a 90° peel test between the surface of the resin film and Kapton film. Specifically, the measurement method involves pressing a 1 cm x 9 cm piece of Kapton film onto the resin film using a vacuum laminator at 0.1 MPa and 25°C, and then using a tensile tester to peel the pressed Kapton tape perpendicular to the resin film at a constant speed of 2 mm / sec.

[0020] When the adhesive strength is 0.02 N / cm or more, the semiconductor element can be stably held when stacked on the resin film. Furthermore, when the adhesive strength is 0.3 N / cm or less, the semiconductor element can be transferred with a low laser light energy density during transfer. More preferably, the adhesive strength is 0.2 N / cm or less. By setting the adhesive strength within this range, adhesive residue on the semiconductor element can be suppressed when the semiconductor element is transferred by irradiating a laser from the laser-transparent substrate 1 side.

[0021] To achieve the adhesive strength of the resin film within the above range, it is preferable for the resin film to contain flexible or flexible components. Introducing flexible or flexible components lowers the glass transition temperature, thereby increasing adhesive strength. Examples of components that increase flexibility or flexibility include flexible structures derived from aliphatic or silane groups such as alkylene groups and siloxanes, flexible structures derived from ether groups such as alkylene glycols and biphenyl ethers, alicyclic structures, and flexible structures such as olefins. By including 20 mol % or more of these flexible monomer residues relative to 100 mol % of all monomer residues constituting the resin contained in the resin film, adhesive strength of 0.02 N / cm or more can be achieved. Furthermore, by including 70 mol % or less, adhesive strength of 0.3 N / cm or less can be achieved.

[0022] The resin film in the laminate of the present invention preferably contains a crosslinking agent. By adding a crosslinking agent, part of the structure is crosslinked, hardening the surface of the resin film and adjusting the adhesive strength. Furthermore, by crosslinking and hardening the surface of the resin film, the effect of suppressing adhesive residue is enhanced.

[0023] Examples of the crosslinking agent include compounds having an alkoxymethyl group or a methylol group, such as 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, Examples of such polyethersulfones include DMOM-MBPC, 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, and HMOM-TPHAP (all trade names, manufactured by Honshu Chemical Industry Co., Ltd.), and NIKALAC (registered trademark) MX-290, NIKALAC MX-280, NIKALAC MX-270, NIKALAC MX-279, NIKALAC MW-100LM, and NIKALAC MX-750LM (all trade names, manufactured by Sanwa Chemical Co., Ltd.).

[0024] It is also preferable to use a crosslinking agent having an epoxy group. Examples of compounds having an epoxy group include bisphenol A type epoxy resins, bisphenol F type epoxy resins, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, epoxy group-containing silicones such as polymethyl(glycidyloxypropyl)siloxane, and dimer acid-modified epoxy resins, but the present invention is not limited thereto. 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 Dainippon Ink and Chemicals, Inc.), Rikaresin Examples of such an agent 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), JER871, JER872, 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 Showa Denko K.K.), Denacol EX-201-IM (all trade names, manufactured by Nagase ChemteX Corporation), and TEPIC-VL (all trade names, manufactured by Nissan Chemical Industries, Ltd.).

[0025] It is also preferable to have a crosslinking agent having an oxetanyl group, and specific examples include OXT-121, OXT-221, OX-SQ-H, OXT-191, PNOX-1009, RSOX (all trade names, manufactured by Toa Gosei Co., Ltd.), "Etanacol (registered trademark)" OXBP, and "Etanacol" OXTP (all trade names, manufactured by Ube Industries, Ltd.).

[0026] Two or more types of crosslinking agents may be contained in the resin film, and preferably 1 part by weight or more per 100 parts by weight of the resin film can reduce adhesive transfer. More preferably, 5 parts by weight or more per 100 parts by weight of the resin film can be contained to achieve a high adhesive transfer suppression effect. Furthermore, the crosslinking agent is preferably contained in 300 parts by weight or less per 100 parts by weight of the resin film. Within this range, a certain degree of flexibility is maintained in the resin film, and the resin film will not break during transfer of the semiconductor element. Furthermore, from the viewpoint of storage stability in the varnish state before forming the laminate, it is more preferably 200 parts by weight or less.

[0027] In particular, when the adhesive strength of the resin itself exceeds 0.3 N / cm, the preferred content of crosslinking agent is 5 to 300 parts by weight per 100 parts by weight of the resin film. By including 5 or more parts by weight of crosslinking agent, the adhesive strength of a resin with an adhesive strength of 0.3 N / cm or more can be reduced to 0.3 N / cm or less. If the content is 300 parts by weight or less, the flexibility of the resin film is maintained. In addition, a content of 10 parts by weight or more is preferred because it also has the effect of suppressing adhesive residue, and a content of 200 parts by weight or less is preferred because it also improves storage stability.

[0028] Furthermore, a curing accelerator may be added to accelerate the curing by the crosslinking agent. Examples of the curing accelerator include imidazoles, tertiary amines or their salts, and organic boron salt compounds, among which imidazoles are preferred. Specific examples of imidazoles include imidazole, 2-methylimidazole, 2-ethylimidazole, 2-isopropylimidazole, 2-n-propylimidazole, 2-undecyl-1H-imidazole, 2-heptadecyl-1H-imidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenyl-1H-imidazole, 4-methyl-2-phenyl-1H-imidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 2-benzyl-4-methylimidazole, 2 ... 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazolium trimellitate, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2,4-di Amino-6-[2′-methylimidazolyl-(1′)]-ethyl-s-triazine, 2,4-diamino-6-[2′-undecylimidazolyl-(1′)]-ethyl-s-triazine, 2,4-diamino-6-[2′-ethyl-4-methylimidazolyl-(1′)]-ethyl-s-triazine, 2,4-diamino-6-[2′-methylimidazolyl-(1′)]-ethyl-s-triazine isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2- Examples include methylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 1-cyanoethyl-2-phenyl-4,5-di(2-cyanoethoxy)methylimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 1-benzyl-2-phenylimidazole hydrochloride, and 1-benzyl-2-phenylimidazolium trimellitate.Preferred examples of commercially available imidazoles include Curesol C17Z, Curesol 2MZ, Curesol 1B2MZ, Curesol 2E4MZ, Curesol 2E4MZ-CN, Curesol 2MZ-AZINE, and Curesol 2MZ-OK (all trade names manufactured by Shikoku Chemicals Corporation).

[0029] The preferred content of the curing accelerator in the resin film is 0.1 parts by weight or more and 5.0 parts by weight or less, based on 100 parts by weight of the resin film. This range ensures a sufficient crosslinking-accelerating effect. Furthermore, from the viewpoint of maintaining the stability of the varnish before forming the laminate, the content of the curing accelerator in the resin film is more preferably 0.5 to 2.0 parts by weight.

[0030] The resin film may further contain a silane compound as needed. By including a silane compound, the adhesion between the resin film and the laser-transparent substrate 1 can be adjusted. This prevents the resin film in the non-laser-irradiated portion from peeling off from the laser-transparent substrate 1. Specific examples of silane compounds include N-phenylaminoethyltrimethoxysilane, N-phenylaminoethyltriethoxysilane, N-phenylaminopropyltrimethoxysilane, N-phenylaminopropyltriethoxysilane, N-phenylaminobutyltrimethoxysilane, N-phenylaminobutyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrichlorosilane, vinyltris(β-methoxyethoxy)silane, 3-methacryloxypropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, and 3-methacryloxypropylmethyldiethoxysilane. The content of the silane compound is preferably 0.01 parts by weight or more and 15 parts by weight or less relative to 100 parts by weight of the resin film.

[0031] Furthermore, the resin film may contain a surfactant, if necessary, for the purpose of improving the coatability with the laser-transmitting substrate 1 during film formation and forming a resin film with a uniform thickness.

[0032] The laminate of the present invention is a laminate in which a laser-transparent substrate 1, a resin film, and a semiconductor element are laminated in this order, and the resin film has an absorbance of 0.4 or more and 5.0 or less at any wavelength of 200 to 1100 nm when converted into a film thickness of 1.0 μm, and further has an adhesive strength of 0.02 N / cm or more and 0.3 N / cm or less at the surface where the resin film contacts the semiconductor element.

[0033] The explanation of the laser-transmitting substrate 1 and the resin film in the laminate 2 is the same as that for the laminate 1.

[0034] Next, the semiconductor element of the present invention will be described.

[0035] The semiconductor element in the present invention includes semiconductors such as GaN, AlN, InN, InP, GaAs, Si, and SiC that are fabricated into an element. These semiconductor elements also include those in which different types of semiconductors are further stacked, and those in which electrode materials, sapphire substrates, glass substrates, wiring, etc. are stacked. The size of the semiconductor element is preferably 5 μm or more and 5.0 mm or less on a side. More preferably, it is 3.0 mm or less, and since the laser can be focused and irradiated with a small spot diameter, transfer with high positional accuracy is possible.

[0036] The number of semiconductor elements mounted on the laminate 2 of the present invention is 5 / cm per unit area. 2 More preferably, 50 particles / cm 2 That's all. By increasing the number of semiconductor elements beyond this, the effect of improving throughput by using laser transfer becomes greater. In addition, since the laser can be accurately irradiated onto each semiconductor element, it is possible to achieve a density of 500,000 elements / cm. 2 Preferably, it is equal to or less than 100,000 particles / cm, and more preferably, it is equal to or less than 100,000 particles / cm. 2 The following is preferred:

[0037] The laminate 2 of the present invention may have another layer interposed therebetween as long as the order is laser-transparent substrate 1, resin film, and semiconductor element. However, the semiconductor element is formed directly on the resin film, and the laser-transparent substrate 1 and semiconductor element are located on the outermost surfaces of the laminate 2.

[0038] The wavelength at which the resin film of the present invention satisfies the above absorbance is preferably any one of 248 nm, 266 nm, 308 nm, 355 nm, 532 nm, and 1064 nm, and more preferably any one of 248 nm, 266 nm, and 355 nm.

[0039] The resin film preferably has an absorbance of 0.4 to 5.0 at a wavelength of 248 nm, 266 nm, 308 nm, 532 nm, or 1064 nm when converted into a film thickness of 1.0 μm, and more preferably has an absorbance of 0.4 to 5.0 at a wavelength of 248 nm, 266 nm, or 355 nm when converted into a film thickness of 1.0 μm. By ensuring that the resin's absorbance at these wavelengths falls within the above range, laser energy can be efficiently absorbed.

[0040] In the laminate of the present invention, the resin film preferably has a thickness of 0.7 μm or more and 30 μm or less. By having a thickness of 0.7 μm or more, it is possible to reduce the transfer of heat generated upon irradiation with laser light to the semiconductor element, suppress damage to the semiconductor element, and further prevent the resin film from breaking and becoming debris, which would contaminate the opposing substrate.

[0041] Furthermore, if the thickness is 30 μm or less, deformation caused by ablation of the resin film by irradiation of laser light from the laser-transparent substrate 1 side is efficiently transmitted to the interface of the semiconductor element, resulting in transfer of the semiconductor element.More preferably, the thickness is 20 μm or less, which allows the semiconductor element to be transferred to the opposing substrate with good positional accuracy.

[0042] The laminate of the present invention preferably has an indentation hardness of 2 MPa or more and 500 MPa or less, measured by pressing from the resin film side to the laser-transparent substrate 1 side. In the case of the laminate 2 having a semiconductor element laminated thereon, the indentation hardness is preferably 2 MPa or more and 500 MPa or less, measured by pressing from the resin film side to the substrate 1 side with the semiconductor element removed from the laminate 2.

[0043] Indentation hardness is a physical property that serves as an indicator when stacking semiconductor elements on a resin film. Setting the indentation hardness within an appropriate range facilitates stacking of semiconductor elements on the resin film and improves the accuracy of subsequent laser transfer. Indentation hardness can be measured using a nanoindenter. In the case of laminate 2, hardness can be measured by physically removing the semiconductor elements within the area required for hardness measurement to expose the resin surface. Methods for removing the semiconductor elements include directly removing them with tweezers or by placing a substrate or film with strong adhesive strength, such as dicing tape, on top of the semiconductor element and peeling it off. Indentation hardness is measured using a Berkovich indenter (a triangular pyramidal diamond indenter) at room temperature and in air, in an indentation load / unload test in which the resin film is pressed vertically from the surface to the laser-transparent substrate 1, and then unloaded. Measurements are performed using a continuous stiffness measurement method at a measurement frequency of 100 Hz. From the load-indentation depth diagram obtained, the indentation hardness was calculated from the value in the indentation region that was not affected by the underlying substrate.

[0044] When the semiconductor element is removed from the laminate, the indentation hardness is 2 MPa or more, so that when the semiconductor element is laminated on the resin film, the semiconductor element is not buried in the resin film even when the element is laminated by pressure bonding using a vacuum laminator, wafer bonder, or the like. Since the resin film does not adhere to the side surface of the semiconductor element, transfer is possible with a low-energy laser. Furthermore, when the indentation hardness is 500 MPa or less, the semiconductor element can be laminated without being damaged even when pressure is applied during lamination. More preferably, the indentation hardness is 300 MPa or less. When the indentation hardness is 300 MPa or less, the yield when laminating the semiconductor element on the resin film is improved.

[0045] The resin film in the laminate of the present invention preferably has a breaking elongation of 100% or more and 1000% or less. A breaking elongation of 100% or more prevents the resin film from breaking when irradiated with laser light. This suppresses the generation of debris in the resin film during transfer, preventing contamination of the opposing substrate. Furthermore, a breaking elongation of 1000% or less prevents the resin film in the non-laser-irradiated portion from being affected by the deformation of the resin film in the laser-irradiated portion and from deforming. More preferably, the breaking elongation is 200% or more and 800% or less. This range allows for a wider range in the energy density of the laser light that can be irradiated, thereby improving the processing margin.

[0046] A resin film having a breaking elongation of 100% or more and 1000% or less can be achieved by the resin contained in the resin film having a flexible structure. Examples of flexible structures include alkylene structures, siloxane structures, and alkylene glycol structures. Specifically, this can be achieved by making 20 mol % or more of the monomer residues in the resin contained in the resin film, relative to 100 mol % of all monomer residues constituting the resin, monomer residues having a flexible structure. More preferably, 30 mol % or more of the monomer residues in the resin, relative to 100 mol % of all monomer residues constituting the resin, are monomer residues having a flexible structure.

[0047] In the laminate of the present invention, the resin film preferably contains one or more resins (A) selected from the group consisting of polyimides having a structure of formula (1), polyimide precursors having a structure of formula (2), polybenzoxazoles having a structure of formula (3), polybenzoxazole precursors having a structure of formula (4), and copolymers thereof.

[0048] [ka]

[0049] In formulas (1) to (4), R 1 , R 3 , R 7 and R 9 each independently represents a tetravalent organic group having 6 to 40 carbon atoms, and R 2 , R 4 , R 6 and R 8 R each independently represents a divalent organic group having 2 to 40 carbon atoms. 5 represents a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms.

[0050] Polyimide and polybenzoxazole are resins having a cyclic structure of an imide ring or an oxazole ring within the main chain structure. Their precursors, polyimide precursors and polybenzoxazole precursors, are resins that form an imide ring or a benzoxazole ring structure by dehydration ring closure. The resin preferably contains 10 to 100,000 repeating units of the structures shown in formulas (1) to (4). Within this range, a resin film can be applied with an appropriate thickness.

[0051] Polyimides can be obtained by reacting tetracarboxylic acids, the corresponding tetracarboxylic dianhydrides, or tetracarboxylic diester dichlorides with diamines, the corresponding diisocyanates, or trimethylsilylated diamines, and contain both tetracarboxylic acid and diamine residues. For example, polyamic acids, which are polyimide precursors obtained by reacting tetracarboxylic dianhydrides with diamines, can be obtained by dehydrating and cyclizing the polyamic acid through heat treatment. A water-azeotropic solvent, such as m-xylene, can be added during this heat treatment. Alternatively, polyimides can be obtained by dehydrating and cyclizing the polyamic acid through chemical heat treatment using a ring-closing catalyst, such as a carboxylic anhydride, a dehydrating condensation agent, such as dicyclohexylcarbodiimide, or a base, such as triethylamine. Alternatively, polyimides can be obtained by adding a weakly acidic carboxylic acid compound and then heating the resulting mixture at a low temperature (below 100°C) to dehydrate and cyclize the polyamic acid.

[0052] Polybenzoxazole can be obtained by reacting a bisaminophenol compound with a dicarboxylic acid, the corresponding dicarboxylic acid chloride, or a dicarboxylic acid activated ester, and contains a dicarboxylic acid residue and a bisaminophenol residue. For example, polyhydroxyamide, a polybenzoxazole precursor obtained by reacting a bisaminophenol compound with a dicarboxylic acid, can be obtained by dehydrating and cyclizing the polyhydroxyamide through heat treatment. Alternatively, it can be obtained by adding phosphoric anhydride, a base, a carbodiimide compound, or the like and then dehydrating and cyclizing the polybenzoxazole through chemical treatment.

[0053] In formula (1) and formula (2), R 1 and R 3 (COOR 5 ) represents a tetracarboxylic acid residue. 1 or R 3 (COOR 5Examples of the tetracarboxylic acid residues constituting the tetracarboxylic acid include pyromellitic acid, 3,3',4,4'-biphenyltetracarboxylic acid, 2,3,3',4'-biphenyltetracarboxylic acid, 2,2',3,3'-biphenyltetracarboxylic acid, 3,3',4,4'-benzophenonetetracarboxylic acid, 2,2',3,3'-benzophenonetetracarboxylic acid, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane, 2,2-bis(2,3-dicarboxyphenyl)hexafluoropropane, 1,1-bis(3,4-dicarboxyphenyl)ethane, 1,1-bis(2,3-dicarboxyphenyl)ethane, Examples of the tetracarboxylic acid residue include aromatic tetracarboxylic acid residues such as bis(3,4-dicarboxyphenyl)ethane, bis(3,4-dicarboxyphenyl)methane, bis(2,3-dicarboxyphenyl)methane, bis(3,4-dicarboxyphenyl)sulfone, bis(3,4-dicarboxyphenyl)ether, 1,2,5,6-naphthalenetetracarboxylic acid, 2,3,6,7-naphthalenetetracarboxylic acid, 2,3,5,6-pyridinetetracarboxylic acid, and 3,4,9,10-perylenetetracarboxylic acid, and aliphatic tetracarboxylic acid residues such as butanetetracarboxylic acid and 1,2,3,4-cyclopentanetetracarboxylic acid. The tetracarboxylic acid residue may contain two or more of these tetracarboxylic acid residues. From the viewpoint of absorbance, aromatic tetracarboxylic acid residues are preferred.

[0054] In formula (1) and formula (2), R 2 and R 4 represents a diamine residue. 2 and R 4Examples of the diamine residue constituting the formula include hydroxyl group-containing diamine residues such as 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, bis(3-amino-4-hydroxyphenyl)sulfone, 2,2-bis(3-amino-4-hydroxyphenyl)propane, bis(3-amino-4-hydroxyphenyl)methane, bis(3-amino-4-hydroxyphenyl)ether, 3,3'-diamino-4,4'-biphenol, and 9,9-bis(3-amino-4-hydroxyphenyl)fluorene; 3-sulfone Sulfonic acid group-containing diamine residues such as 4,4'-diaminodiphenyl ether, thiol group-containing diamine residues such as dimercaptophenylenediamine, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide, 1,4-bis(4-aminophenoxy) Benzene, benzidine, m-phenylenediamine, p-phenylenediamine, 1,5-naphthalenediamine, 2,6-naphthalenediamine, bis(4-aminophenoxyphenyl)sulfone, bis(3-aminophenoxyphenyl)sulfone, bis(4-aminophenoxy)biphenyl, bis{4-(4-aminophenoxy)phenyl}ether, 2,2'-dimethyl-4,4'-diaminobiphenyl, 2,2'-diethyl-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-diethyl Examples include aromatic diamine residues such as 2,2',3,3'-tetramethyl-4,4'-diaminobiphenyl, 3,3',4,4'-tetramethyl-4,4'-diaminobiphenyl, and 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, compounds in which some of the hydrogen atoms in these aromatic rings have been substituted with alkyl or fluoroalkyl groups having 1 to 10 carbon atoms, halogen atoms, or the like, and alicyclic diamine residues such as cyclohexyldiamine and methylenebiscyclohexylamine. Two or more of these diamine residues may also be contained in combination.From the viewpoint of absorbance, it is preferable that the resin film contains aromatic diamine residues in an amount of 30 mol % or more of the total diamine residues.

[0055] In formula (2), R 5 represents a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. Examples of the organic group having 1 to 20 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a pentyl group, a hexyl group, a cyclohexyl group, an octyl group, a dodecyl group, and a phenyl group. In view of the ease of obtaining raw materials for polymerization, a methyl group and an ethyl group are preferred.

[0056] In formula (3) and formula (4), R 6 and R 8 represents a dicarboxylic acid, tricarboxylic acid or tetracarboxylic acid residue.

[0057] Examples of dicarboxylic acid residues include residues of terephthalic acid, isophthalic acid, diphenyl ether dicarboxylic acid, bis(carboxyphenyl)hexafluoropropane, biphenyl dicarboxylic acid, benzophenone dicarboxylic acid, and triphenyl dicarboxylic acid, and examples of tricarboxylic acid residues include residues of trimellitic acid, trimesic acid, diphenyl ether tricarboxylic acid, and biphenyl tricarboxylic acid. Examples of tetracarboxylic acid residues include R 1 and R 3 These are the same as the examples of the residues given above. Two or more of these may be used.

[0058] In formula (3) and formula (4), R 7 and R 9(OH)2 represents a bisaminophenol derivative residue. Specific examples of the bisaminophenol derivative residue include, but are not limited to, residues of 3,3'-diamino-4,4'-dihydroxybiphenyl, 4,4'-diamino-3,3'-dihydroxybiphenyl, bis(3-amino-4-hydroxyphenyl)propane, bis(4-amino-3-hydroxyphenyl)propane, bis(3-amino-4-hydroxyphenyl)sulfone, bis(4-amino-3-hydroxyphenyl)sulfone, 2,2-bis(3-amino-4-hydroxyphenyl)-1,1,1,3,3,3-hexafluoropropane, and 2,2-bis(4-amino-3-hydroxyphenyl)-1,1,1,3,3,3-hexafluoropropane. These compounds may be contained alone or in combination of two or more.

[0059] Furthermore, it is preferable to cap the terminals of the resins represented by formulas (1) to (4) with a monoamine, acid anhydride, acid chloride, or monocarboxylic acid having an acidic group, since this makes it possible to obtain a resin having an acidic group at the terminal of the main chain.

[0060] Preferred examples of such monoamines include 2-aminophenol, 3-aminophenol, 4-aminophenol, etc. Two or more of these may be used.

[0061] Preferred examples of such acid anhydrides, acid chlorides, and monocarboxylic acids include known compounds such as phthalic anhydride, maleic anhydride, and nadic anhydride. Di-tert-butyl dicarbonate is also preferably used as a reactive terminal. Two or more of these compounds may be used.

[0062] The resin (A) preferably has one or more structures selected from the group consisting of a dimethylsiloxane structure represented by formula (5), a diphenylsiloxane structure represented by formula (6), an alkylene glycol structure represented by formula (7), and an alkylene structure represented by formula (8).

[0063] [ka]

[0064] In formulas (5) to (8), R 10 ~R 13 each independently represents a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. l, m, and n each independently represent an integer of 4 to 40. p represents an integer of 10 to 40. o represents an integer of 1 to 16.

[0065] The resin preferably has the structures represented by formulas (5) to (8) in its structure, as this has the effect of improving the flexibility and adhesive strength of the resin film. 10 ~R 13 is R 5 This is the same as the explanation above.

[0066] Specific examples of such structures include aliphatic diamine residues, such as diamine residues containing a polyethylene oxide group, including diamine residues such as JEFFAMINE KH-511, JEFFAMINE ED-600, JEFFAMINE ED-900, JEFFAMINE ED-2003, JEFFAMINE EDR-148, JEFFAMINE EDR-176, and polyoxypropylene diamines D-200, D-400, D-2000, and D-4000 (all trade names, manufactured by HUNTSMAN Co., Ltd.), and diamine residues having a polyalkylene oxide group, including residues of Elasmer 250P, Elasmer 650P, Elasmer 1000P, and Porea SL100A (all trade names, manufactured by Kumiai Chemical Industry Co., Ltd.). Further examples of the siloxane diamine residue include residues of propylamine-terminated siloxane diamines such as LP-7100, KF-8010, KF-8012, and X22-161A (all trade names, manufactured by Shin-Etsu Chemical Co., Ltd.). Two or more of these diamine residues may be used in combination.

[0067] Furthermore, the resin (A) is more preferably a polyimidesiloxane. A polyimidesiloxane is a resin having a siloxane structure in the repeating structure of a polyimide, and the polyimidesiloxane in the present invention particularly preferably has a siloxanediamine residue represented by formula (9) in the structure.

[0068] [ka]

[0069] In formula (9), q is a natural number from 1 to 50. 14 and R 15 may be the same or different and represent an alkylene group or a phenylene group having 1 to 30 carbon atoms. 16 ~R 19 may be the same or different and represent an alkyl group having 1 to 30 carbon atoms, a phenyl group, or a phenoxy group.

[0070] Examples of the siloxane diamine residue represented by formula (9) include those derived from the following diamines: Specific examples 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, and α,ω-bis(2-aminoethyl)polydimethylsiloxane. Examples of the residue include diphenoxysiloxane, 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. The above siloxane diamine residues may be used alone or may contain two or more types. Polyimide siloxanes are characterized by high adhesive strength and high absorbance derived from polyimides, and can particularly increase absorbance at 355 nm.

[0071] In the laminate of the present invention, the resin film preferably has a 1% weight loss temperature of 300°C or higher. Here, the 1% weight loss temperature of the resin film refers to the value when the resin film is heat-treated at 250°C for 30 minutes. Even for resin films that have already been heat-treated, this can be confirmed by heat-treating the resin film at 250°C for 30 minutes. By having a 1% weight loss temperature of 300°C or higher, deterioration of the entire resin film due to heat generated during laser light irradiation can be suppressed, and the generation of debris due to deterioration of the resin film can be prevented.

[0072] To achieve a 1% weight loss temperature of 300°C or higher, it is preferable for the resin film to contain a component with high thermal stability. Specific examples of components with high thermal stability include rigid components such as aromatic rings, siloxanes with relatively high thermal stability even among flexible structures, and combinations of these. The 1% weight loss temperature can be set to 300°C or higher by ensuring that 50% or more of the monomer residues with high thermal stability, relative to 100 mol% of all monomer residues constituting the resin, are the above-mentioned monomer residues. From the perspective of versatility of the polymer, the 1% weight loss temperature is preferably 600°C or lower.

[0073] Next, the resin composition of the present invention will be described.

[0074] The resin composition of the present invention is a resin composition containing (B) a resin, (C) an ultraviolet absorber and / or a dye, and (D) a solvent, The (B) resin contains one or more selected from the group consisting of a polyimide having a structure of formula (1), a polyimide precursor having a structure of formula (2), a polybenzoxazole having a structure of formula (3), a polybenzoxazole precursor having a structure of formula (4), and copolymers thereof, and further, the polyimide having a structure of formula (1), the polyimide precursor having a structure of formula (2), the polybenzoxazole having a structure of formula (3), the polybenzoxazole precursor having a structure of formula (4), and copolymers thereof have one or more structures selected from the group consisting of a dimethylsiloxane structure represented by formula (5), a diphenylsiloxane structure represented by formula (6), an alkylene glycol structure represented by formula (7), and an alkylene structure represented by formula (8).

[0075] [ka]

[0076] In formulas (1) to (4), R 1 , R 3 , R 7 and R 9 each independently represents a tetravalent organic group having 6 to 40 carbon atoms, and R 2 , R4 , R 6 and R 8 R each independently represents a divalent organic group having 2 to 40 carbon atoms. 5 represents a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms.

[0077] [ka]

[0078] In formulas (5) to (8), R 10 ~R 13 each independently represents a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. l, m, and n each independently represent an integer of 4 to 40. p represents an integer of 10 to 40. o represents an integer of 1 to 16.

[0079] The explanation of formulas (1) to (8) in resin (B) is the same as the explanation of formulas (1) to (8) in resin (A) above.

[0080] The resin (B) in the resin composition of the present invention preferably contains a polyimide siloxane. The polyimide siloxane is a resin having a siloxane structure in the repeating structure of polyimide, and the polyimide siloxane contained in the resin (B) particularly preferably has a siloxane diamine residue represented by formula (9) in the structure.

[0081] [ka]

[0082] In formula (9), q is a natural number from 1 to 50. 14 and R 15 may be the same or different and represent an alkylene group or a phenylene group having 1 to 30 carbon atoms. 16 ~R 19 may be the same or different and represent an alkyl group having 1 to 30 carbon atoms, a phenyl group, or a phenoxy group.

[0083] The explanation of formula (9) in resin (B) is the same as the explanation of formula (9) in resin (A).

[0084] The resin composition of the present invention contains a solvent (D). Preferred examples of the solvent (D) 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; ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propyl acetate, and butyl acetate; Examples of suitable solvents include, but are not limited to, acetates such as ethyl 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, ketones such as acetylacetone, methyl propyl ketone, methyl butyl ketone, methyl isobutyl ketone, cyclopentanone, 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, aromatic hydrocarbons such as toluene and xylene, and others such as dimethyl sulfoxide and γ-butyrolactone. These may be used alone or in combination of two or more.

[0085] The preferred amount of (D) solvent to be added is 30 to 3,000 parts by weight per 100 parts by weight of (B) resin, and is preferably adjusted within a range that results in a thick viscosity that facilitates film formation when producing a resin film from the resin composition.

[0086] The resin composition contains (C) an ultraviolet absorber and / or a dye, which facilitates control of the absorbance of (B) the resin, making it possible to use lasers of various wavelengths when transferring a semiconductor element.

[0087] Examples of the component (C) contained in the resin film include the same ultraviolet absorbers and pigments as those exemplified for the resin (A) described above, and these may be contained alone or in combination in the resin film.

[0088] In particular, it is preferable that component (C) contains one or more compounds selected from the group consisting of benzotriazole-based compounds, triazine-based compounds, benzophenone-based compounds, and benzoate-based compounds. These compounds have high heat resistance, which can suppress the generation of debris during laser irradiation. Furthermore, they have absorption properties for wavelengths in the 200-300 nm range, facilitating the transfer of semiconductor elements using lasers with relatively short wavelengths in the 200-300 nm range. With lasers in this wavelength range, the laser energy absorbed by component (C) can also contribute to the decomposition of resin (B), making it possible to transfer semiconductor elements with lower energy levels, which is preferable.

[0089] In the resin composition of the present invention, the (C) component is preferably 10 to 50 parts by weight per 100 parts by weight of the (B) resin. If the (C) component is 10 parts by weight or more per 100 parts by weight of the (B) resin, even if the (B) resin itself has low absorbance, the semiconductor element can be transferred when laser-transferring the semiconductor element in a subsequent process. Furthermore, if the content of the (C) component is 50 parts by weight or less per 100 parts by weight of the (B) resin, separation or precipitation of the (C) component in the resin composition can be prevented. Furthermore, it is more preferable that the (C) component be 30 parts by weight or less per 100 parts by weight of the (B) resin. This prevents the generation of foreign matter on the surface of the resin film when the resin composition is applied to prepare a resin film and prevents the (C) component from precipitating on the surface of the applied film when the resin film is stored.

[0090] The resin composition of the present invention preferably further contains (E) a crosslinking agent. By containing a crosslinking agent, when a resin film is produced, the surface of the resin film is crosslinked and strengthened. This reduces adhesive residue on the semiconductor element when the semiconductor element is laser-transferred in a subsequent process. Furthermore, improved film strength can suppress breakage of the resin film due to laser irradiation, reducing debris.

[0091] As a preferred example of the (E) crosslinking agent, the same crosslinking agents as those listed in the description of the resin (A) can be used. The crosslinking agent is preferably a compound having at least one group selected from the group consisting of an epoxy group, an oxetanyl group, an alkoxymethyl group, and a methylol group. By using such a crosslinking agent, it is possible to obtain a resin composition that can form a high-strength resin film without impairing the storage stability of the resin composition.

[0092] Two or more types of (E) crosslinking agents may be contained in the resin composition. The preferred content of (E) crosslinking agent is 0.5 to 30 parts by weight per 100 parts by weight of (B) resin. When 0.5 parts by weight or more of (E) crosslinking agent is contained per 100 parts by weight of (B) resin, the surface of the resin film formed from the resin composition is crosslinked, thereby reducing adhesive residue on the semiconductor element when the semiconductor element is laser-transferred in a subsequent process. Furthermore, when the content is 30 parts by weight or less, the flexibility of the resin film formed from the resin composition is maintained, which has the effect of making it easier to hold the semiconductor element.

[0093] The present invention relates to a laminate in which a laser-transmitting substrate 1, a resin film containing the above-mentioned resin composition, and a semiconductor element are laminated in this order. By forming the laminate into a state in which a semiconductor element is laminated, it can be used as a laminate for manufacturing a semiconductor device, as described below, in the same way as the above-mentioned laminate 2.

[0094] Next, a method for producing the laminate of the present invention will be described.

[0095] The laminate 1 can be produced by forming a resin film on a laser-transparent substrate 1. An example of a method for producing the laminate 1 will be described. A varnish, in which the components of the resin film are dissolved in a solvent, is applied to the laser-transparent substrate 1, followed by heat curing to produce a resin film. When producing a resin film by coating, any coating method can be selected, including spin coating using a spinner, spray coating, roll coating, and slit die coating. The coated resin film is preferably dried at 50°C to 150°C for 1 minute to several tens of minutes using a hot plate, drying oven, infrared radiation, or the like. Thereafter, if necessary, the resin film is further cured by heating at 100°C to 500°C for several minutes to several hours. The thickness of the resin film at this stage is preferably 0.7 μm to 30 μm. The thickness can be measured using a scanning electron microscope, an optical film thickness gauge, a step gauge, or the like.

[0096] Next, an example of a method for stacking semiconductor elements to produce the stacked body 2 will be described with reference to the drawings.

[0097] FIG. 1 shows a method for producing laminate 2 (120). The semiconductor element (14) is directly arranged on the resin film (12) of laminate 1 (110), which is formed by laminating a resin film (12) on a laser-transparent substrate 1 (11), and laminated by pressing using a pressure-bonding device (41) such as a vacuum laminator, wafer bonder, or press. Alternatively, as shown in FIG. 2, a semiconductor element temporary bonding substrate (130) is prepared in which the semiconductor element (14) is temporarily bonded to another support (15) via a temporary adhesive (16). The semiconductor element (14) on the temporary adhesive (16) is then superimposed on the resin film (12) surface of laminate 1 (110) and pressed using the pressure-bonding device (41). The temporary adhesive (16) and support (15) are then removed from the semiconductor element (13), and laminate 2 (120) can be produced. Furthermore, as shown in FIG. 3, a semiconductor element-mounted substrate (140) in which semiconductor elements (14) are directly formed on a crystal growth substrate (17) such as sapphire is stacked with the semiconductor element (14) surface facing the resin film (12) surface, and pressure-bonded using the above-mentioned device (41). Thereafter, a laser (31) is irradiated from the crystal growth substrate (17) side to perform laser lift-off of the semiconductor elements (14) from the crystal growth substrate (17) to the laminate (110) side. The pressure applied when stacking the semiconductor elements can be optimized depending on the adhesive strength of the resin film and is selected from the range of 0.05 MPa to 5.0 MPa. A pressure of 2.0 MPa or less is preferred to avoid damage to the semiconductor elements and suppress embedding in the resin film. Furthermore, when stacking the semiconductor elements, pressure can be applied while heating as needed. Heating increases the flexibility of the resin film, allowing the semiconductor elements to be pressure-bonded at a lower pressure.

[0098] Furthermore, by providing alignment marks on the laminate in advance, it becomes easier to adjust the transfer position in subsequent operations.

[0099] Another method for producing the laminate 2 will now be described with reference to Figure 4. A semiconductor substrate (18) in a state before being singulated is attached to another support (15) via a temporary adhesive (16). A resin film varnish is then applied to the semiconductor substrate (18) before being singulated and cured by heating. In this state, the laser-transparent substrate 1 and the support with the resin film are bonded face-to-face. The support (15) and the temporary adhesive (16) adjacent to the support (15) are peeled and removed, and the semiconductor substrate (18) is then singulated to form semiconductor elements (14), thereby producing the laminate 2 (120).

[0100] A laminate corresponding to the laminate 2 can also be produced from a resin composition in the same manner.

[0101] Next, a method for manufacturing a semiconductor device will be described.

[0102] The method for manufacturing a semiconductor device of the present invention is a method for manufacturing a semiconductor device using the laminate 2, and includes a step of placing the semiconductor element surface of the laminate 2 opposite to a substrate 2, and a subsequent step of irradiating laser light from the laser-transparent substrate 1 side of the laminate 2 to transfer the semiconductor element to the substrate 2.

[0103] The process of facing the semiconductor element surface of the laminate 2 to the substrate 2 will be described with reference to the drawings. Figure 5 shows a method for manufacturing a semiconductor element device.

[0104] The semiconductor element surface refers to the surface of the laminate 2 (120) on which the semiconductor element (14) is located.

[0105] For the laminate 2 (120) and substrate 2 (21) created by the method described above, the surface of the laminate 2 (120) holding the semiconductor element (14) is placed opposite the substrate 2 (21), and the substrate is fixed so that the laminate 2 (120) and substrate 2 (21) are parallel. To prevent misalignment due to the weight of the semiconductor element (14) during transfer, the facing laminate 2 (120) and substrate 2 (21) are arranged with the laminate 2 (120) facing upward. The laminate 2 and substrate 2 are placed at a fixed distance, and the distance between the semiconductor element surface and substrate 2 can be selected depending on the size and thickness of the semiconductor element, and is selected in the range of several μm to several hundred μm.

[0106] Any substrate can be used for the substrate 2, such as a glass substrate, a resin substrate, a metal substrate, or a circuit board on which wiring has already been formed. An adhesive layer may also be provided to hold the semiconductor element after transfer. The adhesive layer can be made of an adhesive material such as polysiloxane resin, acrylic resin, polyester resin, ACF resin, conductive silver paste, or the resin film of the present invention. The thickness of the adhesive layer is selected within a range of 0.5 μm to 100 μm depending on the size of the semiconductor element and the distance between the semiconductor element and the substrate 2.

[0107] Furthermore, for the purpose of transfer alignment, there may also be an alignment mark on the substrate 2 side.

[0108] Next, the process of transferring the semiconductor element to the substrate 2 by irradiating the laminate 2 with laser light from the laser-transparent substrate 1 side will be described with reference to the drawings. An example of the transfer process is shown in 6a of Fig. 6.

[0109] In the laminate 2 (120) and substrate 2 (21) arranged by the method described above, laser light (31) is irradiated onto the semiconductor element from the laser-transparent substrate 1 (11) side of the laminate 2 (120) through the laser-transparent substrate 1 (11). The type of laser light can be selected based on the wavelength used, including solid-state lasers such as YAG lasers, YVO4 lasers, fiber lasers, and semiconductor lasers, as well as gas lasers such as carbon dioxide lasers, excimer lasers, and argon lasers. The beam shape of the irradiated laser light is not limited, and the laser spot size can be smaller than the size of the semiconductor element. However, the laser spot size must be such that the laser light does not hit semiconductor elements adjacent to the semiconductor element to be transferred. Furthermore, if the spot size of the laser light is large enough to hit adjacent semiconductor elements, it is also possible to irradiate the laser (31) through a photomask (41), as shown in FIG. 6b. The laser light can be selected with any energy density. From the viewpoint of the stability of the energy density of the laser light, the energy density of the laser light is set to 1 mJ / cm. 2 The above is preferable, and from the viewpoint of preventing damage to semiconductor elements and shortening the processing time, 1000 mJ / cm 2 More preferably, the energy density of the laser beam is 10 mJ / cm or less. 2 More than 500mJ / cm 2 The following is the result.

[0110] By using the laminate 2 of the present invention, transfer is possible even with low energy, and further, even when the energy density of the laser light is changed, the influence on positional accuracy, debris, and adhesive residue can be reduced. The energy density of the irradiated laser light may have output unevenness, and in order to reduce the influence of output unevenness on transferability, it is preferable that the laminate 2 has the same level of transferability regardless of the energy density of the laser light. The range of energy densities of laser light that has the same level of transferability is 30 mJ / cm. 2 It is more preferable to have a margin of 50 μm / cm or more, and from the viewpoint of practicality, 2 The above is particularly preferred.

[0111] It is also possible to heat the substrate 2 when transferring the semiconductor elements. In particular, if an adhesive layer is formed on the substrate 2, the retention of the transferred semiconductor elements is improved. When heating the substrate 2, it is preferable to heat the substrate 2 to a temperature of 100°C or less, as this prevents warping of the substrate 2 due to heat and allows for transfer with high positional accuracy.

[0112] The transfer of the semiconductor elements is performed while adjusting the position to match the actual mounting location of the semiconductor elements in the semiconductor device to be fabricated. For example, when fabricating an LED substrate, the LED elements are transferred while shifting the pitch to match the LED pixel size and RGB arrangement. Next, the substrate 2 with the transferred LED elements and the circuit board are placed face to face and pressure-bonded to the circuit board, thereby fabricating a circuit board with mounted LED elements. When transfer is performed using the laminate of the present invention, transfer can be performed with high positional accuracy, so the semiconductor elements can be transferred without misalignment from the circuit on the board to which they will ultimately be mounted, reducing mounting defects caused by misalignment.

[0113] The laser beam preferably has a wavelength of 248 nm, 266 nm, 308 nm, 355 nm, 532 nm, or 1064 nm, and more preferably has a wavelength at which the resin film has an absorbance of 0.4 or more. Use of such laser beams can reduce damage to semiconductor elements.

[0114] In the semiconductor device manufacturing method of the present invention, the laser light preferably has a wavelength of 248 nm, 266 nm, or 355 nm, which allows accurate transfer of even minute semiconductor elements such as μLEDs. As the 248 nm, 266 nm, or 355 nm laser light, an excimer laser or a YAG laser is particularly preferred.

[0115] Furthermore, in the method for manufacturing a semiconductor device of the present invention, the substrate 2 is preferably a circuit substrate. If the substrate 2 is a circuit substrate, the substrate transferred by the above method can be directly fabricated into a semiconductor device. This eliminates concerns about misalignment due to handling of the substrate after transfer, and further improves positional accuracy. Known circuit substrates such as TFT substrates and printed wiring boards can be used.

[0116] The present invention will be specifically described below based on examples. [Example]

[0117] The present invention will be described below with reference to examples, but the present invention is not limited to these examples. First, the evaluation methods used in each example and comparative example will be described.

[0118] (1) How to create a laminate A resin film varnish prepared by the method described below was applied 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 using a spinner, pre-baked on a hot plate at 120°C for 3 minutes, and then heated and cured at a specified temperature for a specified time, thereby producing a resin film on the glass substrate and Laminate 1.

[0119] The thickness of the resin film was confirmed by cutting the laminate and observing the cross section with a scanning electron microscope (S-4800, manufactured by Hitachi High-Technologies Corporation).

[0120] Separately, a silicon wafer was polished on the back side to a thickness of 100 μm. Dicing tape (UDC-1025MC, manufactured by Denka Co., Ltd.) was attached to the wafer, and the wafer was processed into 100 μm x 200 μm pieces using a dicing machine (DAD300, manufactured by Disco Co., Ltd.) to produce dummy chips for semiconductor elements. The distance between chips was 150 μm, and the number of dummy chips per unit area was 1100 chips / cm. 2 It was.

[0121] The dicing tape was irradiated with UV light to reduce the adhesiveness of the dicing tape. The surrounding dummy chips were removed with tweezers, leaving 100 chips arranged in 10 columns and 10 rows. The dummy chips on the dicing tape were placed on the resin film side of the aforementioned glass substrate / resin film laminate, with the chip surface facing the resin film. The dummy chips were then pressed onto the resin film using a vacuum laminator. The dicing tape was then peeled off to produce Laminate 2. The surfaces of the dummy chips stacked on the resin film were visually observed with an optical microscope, and the number of chips that could be stacked on the resin film and those that could be stacked without damage were counted. The results are shown in Tables 3 to 6.

[0122] (2) Measurement of resin film absorbance The resin film varnish was applied to a quartz substrate in the same manner as in (1) above, prebaked, and heat-cured to prepare a quartz substrate with a resin film for absorbance measurement. The film thickness was also measured in the same manner. The absorbance was continuously measured from 200 nm to 1100 nm using a UV-visible spectrophotometer (Hitachi, Ltd., U-2910). The values ​​at 248 nm, 266 nm, 308 nm, 355 nm, 532 nm, and 1064 nm were read, and the respective absorbance values ​​per μm were calculated using the following equation: Absorbance per 1 μm = Actual absorbance obtained in measurement / Measured film thickness (μm) (3) Measurement of adhesive strength of resin film (3)-1 Measurement of adhesive strength of the surface of the resin film of the laminate 1 For the laminate 1 prepared by the above method, a Kapton film cut into a 1 cm x 9 cm strip was pressure-bonded to the surface of the resin film using a vacuum laminator at 0.1 MPa and 25°C. The sample was placed in a tensile tester (Nidec-Shimpo Corporation, FGS-VC), and the pressure-bonded Kapton film was peeled off in the vertical direction at a constant speed of 2 mm / sec. The peel strength at this time was measured using a digital force gauge (Nidec-Shimpo Corporation, FGJN-5). The measurement was performed three times using different samples, and the average value was taken as the adhesive strength.

[0123] (3)-2 Measurement of adhesive strength between the resin film of the laminate 2 and the semiconductor element In the laminate 2 prepared by the above-mentioned method, dicing tape (UDC-1025MC) was attached to the dummy chip surface and then peeled off to remove the dummy chip from the resin film. Kapton film was pressed onto the surface of the resin film from which the dummy chip had been peeled off in the same manner as in (3)-1, and the adhesive strength was measured in the same manner as in (3)-1.

[0124] (4) Indentation hardness measurement The indentation hardness was measured using a nanoindenter (Triboindenter TI950, manufactured by Hysitron).

[0125] Using the same method as in the measurement of adhesive strength of the resin film in (3) above, the dummy chip was peeled off from the laminate 2 to prepare a sample with the resin film exposed, which was then cut into a size of 10 mm x 10 mm.

[0126] The prepared sample was fixed to a dedicated sample fixing stand using adhesive (Aron Alpha quick-acting multi-purpose, manufactured by Toagosei Co., Ltd.), and then pressed into the glass substrate 1 from the surface of the resin film using a Berkovich indenter (a triangular pyramidal diamond indenter), and the indentation hardness was measured using an indentation load / unload test in which the load was removed. The measurement conditions are as follows: [Measurement conditions] Measurement environment: 25±2℃, atmospheric air Measurement frequency: 100Hz Measurement method: Continuous stiffness measurement method From the load-indentation depth diagram obtained, the indentation hardness was calculated from the value of the indentation region that was not affected by the underlying substrate.

[0127] (5) Film thickness measurement The laminate 2 was cut, and the cross section was observed with a scanning electron microscope (S-4800, manufactured by Hitachi High-Technologies Corporation), and the thickness of the resin film was measured.

[0128] (6) Measurement of breaking elongation A resin film varnish was applied to copper foil using a bar coater, prebaked on a hot plate at 120°C for 3 minutes, and then heat-cured at the temperature and time shown in Table 2 below, producing a 10 μm-thick resin film on the copper foil. The resulting resin film-laminated copper foil was then completely etched with a ferric chloride solution to obtain a resin film monolayer. The resulting monolayer was cut into 1.5 cm wide, 2 cm long strips to prepare samples for elongation measurement. The samples were stretched at a room temperature of 23.0°C and a humidity of 45.0% RH at a tensile speed of 50 mm / min using a Tensilon RTM-100 (manufactured by Orientec Co., Ltd.) to measure the breaking elongation at room temperature of 23.0°C. Ten strips were measured per specimen, and the average of the top five points for each result was calculated.

[0129] (7) Measurement of thermal decomposition temperature A single resin film used in measuring elongation was heat-treated at 250°C for 30 minutes, and then approximately 15 mg was placed in an aluminum standard container and measured using a thermogravimetric analyzer (Shimadzu Corporation, TGA-50). The measurement conditions were to hold the film at 120°C for 30 minutes, then raise the temperature to 500°C at a rate of 5°C / min. The temperature at which the weight decreased by 1% was read from the obtained weight loss curve, and this temperature was defined as the 1% weight loss temperature.

[0130] (8) Semiconductor chip transfer test (8)-1 Preparation of opposing substrate for transfer Polydimethylsiloxane was diluted with toluene to a 4-inch alkali-free glass substrate (Corning Eagle XG) with a 0.5 mm thickness and equipped with an alignment mark. The diluted solution was adjusted to a weight ratio of 1:9, and applied using a spinner. The solution was then heated and cured on a hot plate at 120°C for 3 minutes to form an adhesive layer on the glass substrate. The thickness of the adhesive layer after heat curing was measured using an optical film thickness meter (Dainippon Screen, Lambda Ace, refractive index = 1.543), and an opposing substrate with an adhesive layer thickness of 20 μm was prepared.

[0131] (8)-2 Transfer of semiconductor elements Next, the laser light source, the laminate 2 prepared by the above-mentioned method, and the opposing substrate were arranged in this order. At this time, the surface of the laminate 2 on which the dummy chip was held and the surface on which the adhesive layer of the opposing substrate was formed were held facing each other so that the distance between the dummy chip surface and the adhesive layer surface was 50 μm. The laminate 2 and the opposing substrate were aligned using their respective alignment marks. The laser light spot size was a square 120 μm × 220 μm, and the positions of the laser light source and the laminate were adjusted so that one dummy chip was positioned in the center of the laser light spot, while the laser light did not hit adjacent dummy chips.

[0132] A dummy chip placed at the laser light irradiation position is irradiated with laser light of wavelengths 355 nm, 266 nm, 248 nm, 532 nm or 1064 nm at 150 mJ / cm 2 ~400mJ / cm 2 Between 50mJ / cm 2 The irradiation was carried out while changing the energy density step by step. At each energy density, a transfer test was carried out on three dummy chips.

[0133] (8)-3 Evaluation of transferability The opposing substrate was observed after irradiation with the laser light, and the number of dummy chips among the three that could be confirmed to have been transferred to substrate 2 was counted. The dummy chips transferred to the opposing substrate were also checked under a microscope, and at each laser light energy density, if no chip damage was observed, it was evaluated as no chip damage, and if even one chip with a crack, chipping, or fracture was observed, it was evaluated as chip damage.

[0134] (8)-4 Evaluation of position accuracy The position of the semiconductor element on the opposing substrate after transfer was calculated from the alignment marks on the opposing substrate and compared with the position on the laminate 2. Three chips were transferred at each laser light energy density, and the positional accuracy of the chip with the greatest positional deviation was judged as follows: If the positional deviation was within the range of less than ±5 μm in the X-axis direction and less than ±5 μm in the Y-axis direction, the positional accuracy was rated A; if the range was ±10 μm or more in the X-axis direction or ±10 μm or more in the Y-axis direction, the positional accuracy was rated C; and if the deviation was within any range in between, the positional accuracy was rated B.

[0135] (8)-5 Evaluation of adhesive residue After irradiation with laser light, the transferred chips were observed without being washed, and the area of ​​adhesive residue on the resin film on the contact surface with the resin film of the dummy chip was confirmed. The surface area of ​​the contact surface with the resin film per chip was taken as 100%, and the average area of ​​adhesive residue on the contact surface with the resin film for chips that were successfully transferred at each energy density was calculated. As a result, when the average adhesive residue area was 0% or more but less than 1%, it was rated as adhesive residue A, when it was 1% or more but less than 30%, it was rated as adhesive residue B, and when it was 30% or more, it was rated as adhesive residue C.

[0136] (8)-6 Debris evaluation After laser light irradiation, the opposing substrate was observed without being cleaned, and the number of foreign particles of 1 μm or larger observed on the surface of the adhesive layer around the transferred dummy chip was counted. At each energy density, the average number of chips that were successfully transferred was calculated, and if there were fewer than 10 pieces, the debris was rated A, if there were 10 to 50 pieces, the debris was rated B, and if there were 50 pieces or more, the debris was rated C. In addition, if debris larger than 50 μm was included, it was rated C regardless of the number of pieces.

[0137] (8)-7 Evaluation of processing margin In the evaluations of (8)-3 to (8)-6 above, among the cases where three dummy chips could be transferred to the substrate 2, those in which the evaluations of no chip damage, transfer position accuracy, adhesive residue, and debris were A or B were determined to be good transfers at that energy density, and the range of energy densities in which good transfers could be performed was evaluated.2 If it is above this, the processing margin is A, 50 mJ / cm 2 More than 100mJ / cm 2 If the processing margin is less than B, 50 mJ / cm 2 If it is less than this, the processing margin is set to C.

[0138] (9) Method for measuring the solid content of a resin solution Approximately 1 g of the resin solution produced by the method described below was weighed into an aluminum cup, placed on a hot plate at 120°C, and heated for 3 minutes, then heated to 250°C and heated for 30 minutes after reaching 250°C. The weight of the resin remaining after heating was measured, and the solid content was calculated using the following formula. Solid content (wt%) = weight of resin after heating (g) / weight of resin solution before heating (g) × 100.

[0139] The abbreviations for the acid dianhydrides, diamines, additives and solvents shown in the following Preparation Examples are as follows: PMDA: Pyromellitic anhydride (manufactured by Daicel Corporation) BPDA: 3,3',4,4'-biphenyltetracarboxylic anhydride (Mitsubishi Chemical Corporation) BTDA: 3,3',4,4'-benzophenonetetracarboxylic anhydride (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) DIBOC: di-tert-butyl dicarbonate (Tokyo Chemical Industry Co., Ltd.) PA: Phthalic anhydride (Tokyo Chemical Industry Co., Ltd.) PDA: p-phenylenediamine (Tokyo Chemical Industry Co., Ltd.) BAHF: 4,4'-dihydroxy-3,3'-diaminophenylhexafluoropropane (manufactured by Merck Ltd.) APPS2: α,ω-bis(3-aminopropyl)polydimethylsiloxane (average molecular weight: 860, q=9 (average value)) (manufactured by Shin-Etsu Chemical Co., Ltd.) APPS3: α,ω-bis(3-aminopropyl)polydimethylsiloxane (average molecular weight: 1600, q=19 (average value)) (manufactured by Shin-Etsu Chemical Co., Ltd.) Elastomer 650P: Polytetramethylene oxide-di-p-aminobenzoate (molecular weight: 888, manufactured by Kumiai Chemical Industry Co., Ltd.) Elastomer 1000P: Polytetramethylene oxide-di-p-aminobenzoate (molecular weight: 1238, manufactured by Kumiai Chemical Industry Co., Ltd.) NMP: 2-methyl-1-pyrrolidone (Mitsubishi Chemical Corporation) DMIB: N,N-dimethylisobutyramide (Mitsubishi Chemical Corporation) CHN: Cyclohexanone (manufactured by Toyo Gosei Co., Ltd.) PETG: Pentaerythritol-based epoxy resin (manufactured by Showa Denko K.K.) 2E4MZ: 2-ethyl-4-methylimidazole (manufactured by Shikoku Chemicals Corporation) Tinuvin 477: Hydroxyphenyltriazine UV absorber (manufactured by BASF Ltd.) 100LM: A crosslinking agent having an alkoxymethyl group represented by the following structure (manufactured by Sanwa Chemical Co., Ltd.)

[0140] [ka]

[0141] Production Example 1 (Polymerization of Resin Contained in Resin Film) A reactor equipped with a thermometer, dry nitrogen inlet, a heating / cooling system using hot and cold water, and a stirrer was charged with 11.79 g (0.109 mol) of PDA and 195.8 g of DMIB and dissolved. A solution of 0.48 g (2.19 mmol) of DIBOC and 26.1 g of DMIB was added dropwise with stirring and the mixture was stirred at 40 °C for 1 hour. Next, 12.87 g (0.437 mol) of BPDA and 13.05 g of DMIB were added and the mixture was stirred at 60 °C for 30 minutes. Subsequently, 13.83 g (0.063 mol) of PMDA and 13.05 g of DMIB were added and the mixture was stirred at 60 °C for 4 hours to obtain a polyimide precursor PAA-1 solution with a solids content of 13 wt%. The aromatic ring structure in PAA-1 accounted for 99.5 mol% of the total monomer residues (100 mol%). PAA-1 is a resin having the structure of formula (2).

[0142] Production Example 2 (Polymerization of Resin Contained in Resin Film) A reactor equipped with a thermometer, dry nitrogen inlet, a heating / cooling system using hot and cold water, and a stirrer was charged with 27.80 g (0.033 mol) of APPS2 and 129.4 g of NMP at 40 °C and dissolved. 8.25 g (0.076 mol) of PDA and 16.17 g of NMP were then added and dissolved. Next, 15.87 g (0.054 mol) of BPDA and 17.39 g (0.054 mol) of BTDA were added along with 16.17 g of NMP. The reaction was allowed to proceed at 60 °C for 4 hours, yielding a polyimide precursor PAA-2 solution with a solids content of 30 wt%. The aromatic ring structure in PAA-2 constituted 84.9 mol% of the total monomer residues (100 mol%). PAA-2 is a resin having the structure of formula (2) and formula (5).

[0143] Production Example 3 (Polymerization of Resin Contained in Resin Film) A reactor equipped with a thermometer, dry nitrogen inlet, hot and cold water heating and cooling system, and a stirrer was charged with 344.0 g (0.40 mol) of APPS2, 37.50 g (0.025 mol) of APPS3, and 27.47 g (0.075 mol) of BAHF along with 481.4 g of CHN. After dissolving, 14.81 g (0.10 mol) of PA and 20.00 g of CHN were added and stirred at 60 °C for 15 minutes. Next, 97.61 g (0.45 mol) of PMDA and 20.00 g of CHN were added and stirred at 60 °C for 1 hour. The temperature was then raised to 145 °C and the reaction was continued for 4 hours, yielding a 50 wt% solids solution of polyimidesiloxane PIS-1. PIS-1 is a resin having the structure of formula (1) and formula (5).

[0144] Production Example 4 (Polymerization of Resin Contained in Resin Film) A reactor equipped with a thermometer, dry nitrogen inlet, a heating / cooling system using hot and cold water, and a stirrer was charged with 39.04 g (0.033 mol) of Elastomer 650P and 131.69 g of NMP at 40 °C and dissolved. To this was added 8.25 g (0.076 mol) of PDA and 16.42 g of NMP and dissolved. Next, 15.87 g (0.054 mol) of BPDA and 17.39 g (0.054 mol) of BTDA were added along with 16.42 g of NMP. The reaction was allowed to proceed at 60 °C for 4 hours, yielding a polyimide precursor PAA-3 solution with a solids content of 30 wt%. The aromatic ring structure in PAA-3 constituted 84.9 mol% of the total monomer residues (100 mol%). PAA-3 is a resin having the structure of formula (2) and formula (7).

[0145] Production Example 5 (Polymerization of Resin Contained in Resin Film) In a reactor equipped with a thermometer, dry nitrogen inlet, heating and cooling system using hot and cold water, and a stirrer, 134.94 g (0.109 mol) of Elastomer 1000P and 353.23 g of NMP were charged and dissolved at 40 °C. Next, 15.87 g (0.054 mol) of BPDA and 17.39 g (0.054 mol) of BTDA were added along with 39.25 g of NMP. The reaction was allowed to proceed at 60 °C for 4 hours, yielding a polyimide precursor PAA-4 solution with a solids content of 30 wt%. The aromatic ring structure of PAA-4 constituted 50.0 mol% of the total monomer residues (100 mol%). PAA-4 is a resin having the structure of formula (2) and formula (7).

[0146] Production Example 6 (Polymerization of Resin Contained in Resin Film) A reactor equipped with a thermometer, dry nitrogen inlet, a heating / cooling system using hot and cold water, and a stirrer was charged with 11.79 g (0.109 mol) of PDA and 204.1 g of DMIB and dissolved. A solution of 1.90 g (8.72 mmol) of DIBOC and 27.2 g of DMIB was added dropwise with stirring and stirred at 40 °C for 1 hour. Next, 12.83 g (0.0.44 mol) of BPDA and 13.61 g of DMIB were added and stirred at 60 °C for 30 minutes. Subsequently, 14.15 g (0.065 mol) of PMDA and 13.61 g of DMIB were added and stirred at 60 °C for 4 hours to obtain a polyimide precursor PAA-5 solution with a solids content of 13 wt%. The aromatic ring structure in PAA-5 accounts for 96.3 mol% of the total monomer residues (100 mol%). PAA-5 is a resin having the structure of formula (2).

[0147] Production Example 7 (Polymerization of Resin Contained in Resin Film) A reactor equipped with a thermometer, dry nitrogen inlet, a heating / cooling system using hot and cold water, and a stirrer was charged with 27.80 g (0.033 mol) of APPS2 and 128.1 g of NMP at 40 °C and dissolved. 8.25 g (0.076 mol) of PDA and 16.01 g of NMP were then added and dissolved. Next, 15.55 g (0.053 mol) of BPDA and 17.03 g (0.053 mol) of BTDA were added along with 16.01 g of NMP. The reaction was allowed to proceed at 60 °C for 4 hours, yielding a polyimide precursor PAA-6 solution with a solids content of 30 wt%. The aromatic ring structure in PAA-6 constituted 84.5 mol% of the total monomer residues (100 mol%). PAA-6 is a resin having the structure of formula (2) and formula (5).

[0148] Production Example 8 (Synthesis of Acrylic Polymer (P-1)) Using the method described in the literature (Japanese Patent No. 3120476, Example 1), a methyl methacrylate / methacrylic acid / styrene copolymer (weight ratio 30 / 40 / 30) was synthesized, and then 40 parts by weight of glycidyl methacrylate was added. The copolymer was then reprecipitated in purified water, filtered, and dried to obtain an acrylic polymer (P-1) powder with an average molecular weight (Mw) of 40,000 and an acid value of 110 (mgKOH / g).

[0149] Production Example 9 (Preparation of Carbon Black Dispersion) 400 g of carbon black (TPX1291; CABOT) was added to a tank with 187.5 g of a 40 wt% solution of acrylic polymer (P-1) in propylene glycol monomethyl ether acetate, 62.5 g of a polymer dispersant (BYK21116; BYK-Chemie), and 890 g of propylene glycol monoethyl ether acetate. The mixture was stirred for 1 hour using a homomixer (Tokushu Kika Co., Ltd.) to obtain a preliminary dispersion. The preliminary dispersion was then fed to an Ultra Apex Mill (Kotobuki Industries Co., Ltd.) equipped with a centrifugal separator filled to 70% with 0.10 mm diameter zirconia beads (Toray Industries, Ltd.). The mixture was dispersed at a rotation speed of 8 m / s for 2 hours to obtain carbon black pigment dispersion Bk-2 with a solids concentration of 25 wt% and a pigment / resin (weight ratio) of 80 / 20. Examples 1-24 and Comparative Examples 1-2 The resin solutions obtained in Production Examples 1 to 7 were mixed and stirred with the carbon black dispersion obtained in Production Example 9, additives, and solvents according to the details in Tables 1 and 2 to prepare varnishes for resin films. The varnishes were filtered through a PTFE filter with a pore size of 0.2 μm. Laminates were prepared using these varnishes using the method described above. Details of the prepared laminates and various evaluation results are summarized in Tables 3 to 9.

[0150] [Table 1]

[0151] [Table 2]

[0152] [Table 3]

[0153] [Table 4]

[0154] [Table 5]

[0155] [Table 6]

[0156] [Table 7]

[0157] [Table 8]

[0158] [Table 9] [Explanation of symbols]

[0159] 11 Laser-transparent substrate 1 12 Resin film 14 Semiconductor elements 15 Support 16 Temporary adhesive 17 Crystal growth substrate 18 Semiconductor substrate 21 Substrate 2 31 Laser 41 Crimping device 51 Photomask 110 laminate 1 120 Laminate 2 130 Substrate to which semiconductor element is temporarily attached 140 Substrate with semiconductor element

Claims

1. A laminate in which a laser-transmitting substrate 1 and a resin film are laminated in this order, the resin film has an absorbance of 0.4 or more and 5.0 or less at a wavelength of 200 to 1100 nm when converted into a film thickness of 1.0 μm, Furthermore, the adhesive strength of the surface of the resin film opposite to the surface where the substrate 1 and the resin film are in contact is 0.02 N / cm or more and 0.3 N / cm or less, The resin film has a thickness of 0.7 μm or more and 30 μm or less.

2. A laminate in which a laser-transmitting substrate 1, a resin film, and a semiconductor element are laminated in this order, the resin film has an absorbance of 0.4 or more and 5.0 or less at a wavelength of 200 to 1100 nm when converted into a film thickness of 1.0 μm, Furthermore, the adhesive strength of the surface where the resin film contacts the semiconductor element is 0.02 N / cm or more and 0.3 N / cm or less, The resin film has a thickness of 0.7 μm or more and 30 μm or less.

3. A laminate in which a laser-transparent substrate 1 and a resin film are laminated in this order, the resin film has an absorbance of 0.4 or more and 5.0 or less at a wavelength of 200 to 1100 nm when converted into a film thickness of 1.0 μm, Furthermore, the adhesive strength of the surface of the resin film opposite to the surface where the substrate 1 and the resin film are in contact is 0.02 N / cm or more and 0.3 N / cm or less, The laminate has an indentation hardness of 2 MPa or more and 500 MPa or less, as measured by indenting from the resin film side to the laser-transparent substrate 1 side.

4. A laminate in which a laser-transparent substrate 1 and a resin film are laminated in this order, the resin film has an absorbance of 0.4 or more and 5.0 or less at a wavelength of 200 to 1100 nm when converted into a film thickness of 1.0 μm, Furthermore, the adhesive strength of the surface of the resin film opposite to the surface where the substrate 1 and the resin film are in contact is 0.02 N / cm or more and 0.3 N / cm or less, the resin film contains one or more resins (A) selected from the group consisting of polyimides having a structure of formula (1), polyimide precursors having a structure of formula (2), polybenzoxazoles having a structure of formula (3), polybenzoxazole precursors having a structure of formula (4), and copolymers thereof; 【Chemistry 1】 (In formulas (1) to (4), R 1 , R 3 , R 7 and R 9 each independently represent a tetravalent organic group having 6 to 40 carbon atoms, R 2 , R 4 , R 6 and R 8 each independently represent a divalent organic group having 2 to 40 carbon atoms, and R 5 represents a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms.) A laminate, wherein the resin (A) has one or more structures selected from the group consisting of a dimethylsiloxane structure represented by formula (5), a diphenylsiloxane structure represented by formula (6), an alkylene glycol structure represented by formula (7), and an alkylene structure represented by formula (8). 【Chemistry 2】 (In formulas (5) to (8), R 10 to R 13 each independently represent a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. l, m, and n each independently represent an integer of 4 to 40. p represents an integer of 10 to 40. o represents an integer of 1 to 16.)

5. A laminate in which a laser-transmitting substrate 1 and a resin film are laminated in this order, the resin film has an absorbance of 0.4 or more and 5.0 or less at a wavelength of 200 to 1100 nm when converted into a film thickness of 1.0 μm, Furthermore, the adhesive strength of the surface of the resin film opposite to the surface where the substrate 1 and the resin film are in contact is 0.02 N / cm or more and 0.3 N / cm or less, The laminate, wherein the resin film contains a crosslinking agent.

6. A laminate in which a laser-transparent substrate 1 and a resin film are laminated in this order, the resin film has an absorbance of 0.4 or more and 5.0 or less at a wavelength of 200 to 1100 nm when converted into a film thickness of 1.0 μm, Furthermore, the adhesive strength of the surface of the resin film opposite to the surface where the substrate 1 and the resin film are in contact is 0.02 N / cm or more and 0.3 N / cm or less, The resin film has a 1% weight loss temperature of 300°C or higher.

7. (B) a resin, (C) an ultraviolet absorber; (D) a composition comprising a solvent, the (B) resin contains one or more selected from the group consisting of a polyimide having a structure of formula (1), a polyimide precursor having a structure of formula (2), a polybenzoxazole having a structure of formula (3), a polybenzoxazole precursor having a structure of formula (4), and copolymers thereof; Furthermore, the polyimide having the structure of formula (1), the polyimide precursor having the structure of formula (2), the polybenzoxazole having the structure of formula (3), the polybenzoxazole precursor having the structure of formula (4), and their copolymers have one or more structures selected from the group consisting of a dimethylsiloxane structure represented by formula (5), a diphenylsiloxane structure represented by formula (6), an alkylene glycol structure represented by formula (7), and an alkylene structure represented by formula (8), 【Transformation 3】 (In formulas (1) to (4), R 1 , R 3 , R 7 and R 9 each independently represent a tetravalent organic group having 6 to 40 carbon atoms, R 2 , R 4 , R 6 and R 8 each independently represent a divalent organic group having 2 to 40 carbon atoms, and R 5 represents a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms.) 【Chemistry 4】 (In formulas (5) to (8), R 10 to R 13 each independently represent a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. l, m, and n each independently represent an integer of 4 to 40. p represents an integer of 10 to 40. o represents an integer of 1 to 16.) The resin composition, wherein the component (C) contains one or more compounds selected from the group consisting of benzotriazole-based compounds, triazine-based compounds, benzophenone-based compounds, and benzoate-based compounds.

8. (B) a resin, (C) an ultraviolet absorber; (D) a composition comprising a solvent, the (B) resin contains one or more selected from the group consisting of a polyimide having a structure of formula (1), a polyimide precursor having a structure of formula (2), a polybenzoxazole having a structure of formula (3), a polybenzoxazole precursor having a structure of formula (4), and copolymers thereof; Furthermore, the polyimide having the structure of formula (1), the polyimide precursor having the structure of formula (2), the polybenzoxazole having the structure of formula (3), the polybenzoxazole precursor having the structure of formula (4), and their copolymers have one or more structures selected from the group consisting of a dimethylsiloxane structure represented by formula (5), a diphenylsiloxane structure represented by formula (6), an alkylene glycol structure represented by formula (7), and an alkylene structure represented by formula (8), 【Transformation 5】 (In formulas (1) to (4), R 1 , R 3 , R 7 and R 9 each independently represent a tetravalent organic group having 6 to 40 carbon atoms, R 2 , R 4 , R 6 and R 8 each independently represent a divalent organic group having 2 to 40 carbon atoms, and R 5 represents a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms.) 【Transformation 6】 (In formulas (5) to (8), R 10 to R 13 each independently represent a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. l, m, and n each independently represent an integer of 4 to 40. p represents an integer of 10 to 40. o represents an integer of 1 to 16.) A resin composition comprising 10 to 50 parts by weight of the (C) component relative to 100 parts by weight of the (B) resin.

9. (B) a resin, (C) an ultraviolet absorber; (D) a composition comprising a solvent, the (B) resin contains one or more selected from the group consisting of a polyimide having a structure of formula (1), a polyimide precursor having a structure of formula (2), a polybenzoxazole having a structure of formula (3), a polybenzoxazole precursor having a structure of formula (4), and copolymers thereof; Furthermore, the polyimide having the structure of formula (1), the polyimide precursor having the structure of formula (2), the polybenzoxazole having the structure of formula (3), the polybenzoxazole precursor having the structure of formula (4), and their copolymers have one or more structures selected from the group consisting of a dimethylsiloxane structure represented by formula (5), a diphenylsiloxane structure represented by formula (6), an alkylene glycol structure represented by formula (7), and an alkylene structure represented by formula (8), 【Transformation 7】 (In formulas (1) to (4), R 1 , R 3 , R 7 and R 9 each independently represent a tetravalent organic group having 6 to 40 carbon atoms, R 2 , R 4 , R 6 and R 8 each independently represent a divalent organic group having 2 to 40 carbon atoms, and R 5 represents a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms.) 【Transformation 8】 (In formulas (5) to (8), R 10 to R 13 each independently represent a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. l, m, and n each independently represent an integer of 4 to 40. p represents an integer of 10 to 40. o represents an integer of 1 to 16.) The resin composition further comprises (E) a crosslinking agent.

10. A substrate 1 having laser transparency; (B) a resin; (C) an ultraviolet absorber; (D) a composition comprising a solvent, the (B) resin contains one or more selected from the group consisting of a polyimide having a structure of formula (1), a polyimide precursor having a structure of formula (2), a polybenzoxazole having a structure of formula (3), a polybenzoxazole precursor having a structure of formula (4), and copolymers thereof; Furthermore, a laminate in which a semiconductor element and a resin film containing a resin composition having one or more structures selected from the group consisting of a polyimide having the structure of formula (1), a polyimide precursor having the structure of formula (2), a polybenzoxazole having the structure of formula (3), a polybenzoxazole precursor having the structure of formula (4), and a copolymer thereof, and a dimethylsiloxane structure represented by formula (5), a diphenylsiloxane structure represented by formula (6), an alkylene glycol structure represented by formula (7), and an alkylene structure represented by formula (8) are laminated in this order. 【Chemistry 9】 (In formulas (1) to (4), R 1 , R 3 , R 7 and R 9 each independently represent a tetravalent organic group having 6 to 40 carbon atoms, R 2 , R 4 , R 6 and R 8 each independently represent a divalent organic group having 2 to 40 carbon atoms, and R 5 represents a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms.) 【Chemistry 10】 (In formulas (5) to (8), R 10 to R 13 each independently represent a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. l, m, and n each independently represent an integer of 4 to 40. p represents an integer of 10 to 40. o represents an integer of 1 to 16.) 11. A method for manufacturing a semiconductor device using the laminate according to claim 2 or 10, comprising: a step of placing a semiconductor element surface of the laminate and a substrate 2 opposite each other; The method for manufacturing a semiconductor device further comprises a step of irradiating the laminate with laser light from the laser-transparent substrate 1 side to transfer the semiconductor element to the substrate 2.

12. A method for manufacturing a semiconductor device as described in claim 11, wherein the laser light has a wavelength of either 248 nm, 266 nm, or 355 nm.

13. A method for manufacturing a semiconductor device as described in Claim 11, wherein the substrate 2 is a circuit board.

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