Manufacturing methods of multilayers and semiconductor devices

Abstract

This invention provides a laminate in which the transfer of semiconductor devices using laser light of various wavelengths can be carried out with a wide processing margin without residue or damage to the device. The laminate is a laminate in which a laser-transparent substrate 1, a resin film 1, and a resin film 2 are sequentially laminated. The resin film 1 has an absorbance of 0.4 or more and 5.0 or less at any wavelength from 200 nm to 1100 nm when the film thickness is 1.0 μm. The adhesion strength of the surface of the resin film 2 opposite to the resin film 1 side satisfies 0.02 N / cm or more and 0.3 N / cm or less.

Description

Technical Field

[0001] This invention relates to a multilayer and a method for manufacturing a semiconductor device. More specifically, it relates to a multilayer suitable for use when mounting semiconductor elements by laser transfer, and a method for manufacturing a semiconductor device using the multilayer. Prior Technology

[0002] Typically, components incorporated into semiconductor devices are transferred and mounted onto circuit boards or similar substrates using pick-and-place methods such as flip chip bonders. In recent years, semiconductor devices have seen continuous advancements in performance and miniaturization, leading to the miniaturization and thinning of components incorporated within them, while the number of components mounted is gradually increasing. Recently, displays that arrange light-emitting diodes (LEDs), a type of semiconductor component, into individual pixels have attracted attention due to their high brightness, low power consumption, and high image quality. The LEDs mounted in each pixel are called microLEDs, and are very small, ranging from a few hundred micrometers to tens of micrometers in size. The current mounting method is too time-consuming in manufacturing these microLED displays, therefore new methods are being researched.

[0003] One method for mounting a large number of small semiconductor components is to use an adhesive mold made of silicone resin or the like to place wafers onto a circuit board (Patent Document 1, Patent Document 2). In this method, the adhesive mold can hold multiple micro-LED wafers, thus allowing a large number of wafers to be placed onto the circuit board in a single pick-and-place step. Another method has been proposed whereby, after transferring wafers from a wafer to a transfer substrate having an adhesive layer, they are transferred and mounted onto a circuit board or the like using laser lift-off (LLO) (Patent Document 3, Patent Document 4, Patent Document 5). This method has the advantages of good positional accuracy and high-speed transfer capability. [Existing Technical Documents] [Patent Literature]

[0004] [Patent Document 1] Japanese Patent Publication No. 2017-531915 [Patent Document 2] Japanese Patent Application Publication No. 2020-129638 [Patent Document 3] Japanese Patent Application Publication No. 2020-188037 [Patent Document 4] Japanese Patent Application Publication No. 2010-251359 [Patent Document 5] Japanese Patent Publication No. 2014-515883 Summary of the Invention

[0005] [The problem that the invention aims to solve]

[0006] In the inventions described in Patent Documents 1 and 2, the size of the die depends on the wafer size, thus limiting the number of semiconductor devices that can be transferred simultaneously. Furthermore, the inventions described in Patent Documents 1 and 2 present the challenge of needing to fabricate a die each time that matches the circuit board design. On the other hand, in the LLO method, there are no area constraints or the need to fabricate dies with different designs, which promises further cost reduction. However, in inventions such as those described in Patent Documents 3 and 4, the adhesive layer is removed by laser ablation, but this requires forming a very thin adhesive layer, raising concerns about reduced yield due to deterioration in in-plane uniformity. Furthermore, in the inventions described in Patent Documents 3 and 4, to avoid residues of the adhesive layer on the surface of the semiconductor device and the adhesive layer scattering due to etching, thus contaminating the substrate, excessive laser light is required, and the adhesive layer is completely removed by etching. This presents the problem of damage such as semiconductor device breakage (hereafter, residues of the adhesive layer on the surface of the semiconductor device are sometimes referred to as residual adhesive, and scattered residues of the adhesive layer are referred to as debris). In Patent Document 5, by separating the adhesive layer from the laser absorption layer, transfer can be performed with low energy, and damage to the semiconductor device can be reduced. However, the energy range of the laser that can be transferred well is narrow, and the transferability changes with the laser intensity, which presents a problem in terms of processing margin when realizing practical transfer. [Methods for solving problems]

[0007] The present invention that solves the aforementioned problem is a laminate, which is a laminate in which a laser-transparent substrate 1, a resin film 1, and a resin film 2 are sequentially laminated. The absorbance of the resin film 1 at any wavelength from 200 nm to 1100 nm, when converted to a film thickness of 1.0 μm, is 0.4 or more and 5.0 or less. The adhesion strength of the surface of the resin film 2 opposite to the resin film 1 is 0.02 N / cm or more and 0.3 N / cm or less. [The effects of the invention]

[0008] According to the laminate of the present invention, the transfer of semiconductor devices using laser light of various wavelengths can be carried out with a wide processing margin without leaving any residue or damaging the device. Simple Explanation of the Diagram

[0009] Figure 1 is a diagram illustrating the fabrication method of the laminate 2. Hereinafter, the laminate containing semiconductor devices will sometimes be referred to as laminate 2. Figure 2 is a diagram illustrating the method of manufacturing the laminate 2 using a temporary adhesive. Figure 3 is a diagram illustrating the method of fabricating the laminate 2 using laser ablation. Figure 4 is a diagram illustrating another method of fabricating the multilayer 2 using a semiconductor substrate. Figure 5 is a diagram illustrating the step in a semiconductor device manufacturing method in which the semiconductor element surface of the laminate 2 faces the substrate 2. Figures 6a and 6b illustrate the steps of irradiating with laser light and transferring semiconductor elements onto substrate 2. Implementation

[0010] The laminate of the present invention is a laminate in which a laser-transparent substrate 1, a resin film 1, and a resin film 2 are sequentially laminated. The resin film 1 has an absorbance of 0.4 or more and 5.0 or less at any wavelength from 200 nm to 1100 nm when the film thickness is 1.0 μm. The adhesion strength of the surface of the resin film 2 opposite to that of the resin film 1 is 0.02 N / cm or more and 0.3 N / cm or less. Hereinafter, the laminate of this form will be referred to as laminate 1. Laminate 1 and laminate 2 of the present invention are sometimes simply referred to as laminates of the present invention.

[0011] The following describes each component of the laminate 1 of the present invention.

[0012] The term "laser-transmitting substrate 1" refers to a substrate with an absorbance of 0.1 or less at any wavelength from at least 200 nm to 1100 nm. Examples of substrates with this absorbance include inorganic substrates such as quartz, sapphire, alkali glass, alkali-free 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 processing, it is preferably 0.3 mm or more, and from the viewpoint of obtaining versatility, it is more preferably 2.0 mm or less.

[0013] The laser-transmitting substrate 1 can also be made of polyethylene terephthalate (PET) or organic substrates such as polyarylamide, polyester, polypropylene, and cycloolefins. When using an organic substrate, the thickness can be selected within a range that does not impair the absorbance, preferably from 0.05 mm to 3.0 mm. From the viewpoint of substrate processing, a thickness of 0.1 mm or more is preferred, and from the perspective of suppressing light scattering during laser irradiation, a thickness of 1.0 mm or less is more preferable.

[0014] Next, the resin film 1 will be described.

[0015] The resin film 1 is a film containing at least resin, and has an absorbance of 0.4 or more and 5.0 or less when converted to a film thickness of 1.0 μm at any wavelength from 200 nm to 1100 nm. With an absorbance of 0.4 or more, when laser light is irradiated from the laser-transmitting substrate 1 side to the resin film 1 side and a semiconductor element is transferred to the opposing substrate, the irradiated laser light can be concentratedly absorbed in the resin film 1. Furthermore, it is preferable that the absorbance is 0.6 or more, so that laser light can be absorbed, especially near the outermost surface of the resin film 1, thus enabling the transfer using laser light with lower energy density. From a material design perspective, it is preferable that the absorbance is 5.0 or less, and from the perspective of using a versatile resin, it is preferable that it is 4.0 or less.

[0016] The resins contained in the resin membrane 1 may include, but are not limited to, polyimide, polyimide precursor, polybenzoxazole, polybenzoxazole precursor, urethane resin, phenolic varnish resin, polyhydroxystyrene, polyester resin, acrylic resin, polyarylamine resin, etc., which have absorption at any wavelength in the range of 200 nm to 1100 nm.

[0017] These resins preferably have a conjugated structure. By having a conjugated structure, the absorbance at wavelengths of 200 nm to 1100 nm (equivalent to a film thickness of 1.0 μm) can be adjusted to a range of 0.4 or higher and 5.0 or lower. Examples of structures with a conjugated structure include aromatic structures, with preferred structures being biphenyl, imidin, benzoxazole, benzophenone, etc. By defining at least 60 mol% of the monomer residues in the resin film 1 as having a conjugated structure relative to 100 mol% of all monomer residues contained in the resin, the range of absorbance can be adjusted. These resins may be contained in the resin film 1 as a single type or multiple types.

[0018] The aforementioned absorbance can also be achieved by using additives such as ultraviolet absorbers, pigments, dyes, and dyes. Examples of additives contained in resin film 1 include: Tinuvin PS, Tinuvin 99-2, Tinuvin 326, Tinuvin 328, Tinuvin 384-2, Tinuvin 400, Tinuvin 405, Tinuvin 460, Tinuvin 477, Tinuvin 479, Tinuvin 900, Tinuvin 928, and Tinuvin (…). Tinuvin 1130 (the above are trade names, manufactured by BASF), DAINSORB T-0, DAINSORB T-7, DAINSORB T-31, DAINSORB T-52, DAINSORB T-53, DAINSORB T-84, DAINSORB P-6, DAINSORB P-7 (the above are trade names, manufactured by Daiwa Chemical Co., Ltd.) and other UV absorbers; Solvent Yellow Solvent Yellow (93), Solvent Yellow (33), Solvent Orange (60), Solvent Red (111), Solvent Red (135), Solvent Red (168), Solvent 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), Solvent... Violet 36 (the above are trade names, manufactured by Tokyo Kasei Corporation) and other pigments; diammonium-based near-infrared absorbers, ammonium-based near-infrared absorbers, anthraquinone-based near-infrared absorbers, phthalocyanine-based near-infrared absorbers, nickel complex-based near-infrared absorbers, polymethyl-based near-infrared absorbers, diphenylmethane-based near-infrared absorbers, triphenylmethane-based near-infrared absorbers and other infrared absorbers; carbon black, perylene black, anthocyanin black, aniline black and other pigments, etc.

[0019] These additives may be present in the resin film 1 individually or in multiple forms. The content of the additives used to set the absorbance to the stated range is preferably 0.1 parts by weight or more relative to 100 parts by weight of the resin film 1 of the present invention, and preferably 50 parts by weight or less from the viewpoint of stability in the clear varnish state before the formation of the laminate.

[0020] The resin film 1 may contain silane compounds as needed. By containing silane compounds, the adhesion between the resin film 1 and the laser-transparent substrate 1 can be adjusted. This prevents the resin film 1 in areas not irradiated by laser light 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, 3-methacryloxypropylmethyldiethoxysilane, etc. 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 1 of the present invention.

[0021] In addition, for the purpose of forming a resin film 1 with a uniform film thickness by improving the coating properties with the laser-transmitting substrate 1 during film formation, the resin film 1 may also contain a surfactant as needed.

[0022] The wavelength at which the resin film 1 satisfies the absorbance requirement is preferably any one of 248 nm, 266 nm, 308 nm, 355 nm, 532 nm, and 1064 nm. The absorbance of the resin film 1 at any one of the wavelengths 248 nm, 266 nm, 308 nm, 355 nm, 532 nm, and 1064 nm, converted to a film thickness of 1.0 μm, is preferably 0.4 or higher and 5.0 or lower.

[0023] The wavelength at which the resin film 1 satisfies the absorbance is preferably any one of 248 nm, 266 nm, and 355 nm. The absorbance of the resin film 1 at any wavelength of 248 nm, 266 nm, and 355 nm, converted to a film thickness of 1.0 μm, is preferably 0.4 or higher and 5.0 or lower. By ensuring that the absorbance of the resin film 1 meets the aforementioned range at these wavelengths, laser energy can be absorbed efficiently and effectively.

[0024] Next, the resin film 2 of the present invention will be described.

[0025] The adhesive strength of the surface of resin film 2 opposite to that of resin film 1 is 0.02 N / cm or more and 0.3 N / cm or less. The adhesive strength listed here refers to the value obtained from a 90° peel test of the surface of resin film 2 opposite to that of resin film 1 and the Kapton film. Specifically, the test method involves pressing a Kapton film cut to 1 cm × 9 cm onto the surface of resin film 2 (opposite to resin film 1) of the laminate 1 using a vacuum laminator at 0.1 MPa and 25°C. The pressed Kapton film is then peeled off using a tensile testing machine at a constant speed of 2 mm / s in a direction perpendicular to resin film 2.

[0026] With an adhesion strength of 0.02 N / cm or higher, the semiconductor element can be stably maintained when deposited on the resin film 2. Furthermore, with an adhesion strength of 0.3 N / cm or lower, the semiconductor element can be transferred using low-energy-density laser light during transfer. Preferably, the adhesion strength is 0.2 N / cm or lower. By setting it to this range, residual adhesive on the semiconductor element can be suppressed when laser light is irradiated from the laser-transmittable substrate 1 side and the semiconductor element is transferred.

[0027] The resin film 2 contains at least resin. To achieve the desired adhesive strength within the specified range, it is preferable that the resin film 2 contains a flexible or pliable component. Introducing a flexible or pliable component lowers the glass transfer temperature, thereby increasing the adhesive strength. Examples of components that enhance flexibility or pliability include: flexible structures derived from aliphatic or silane groups such as alkylene groups and siloxanes; flexible structures derived from ether groups such as alkyl glycols or biphenyl ethers; alicyclic structures; and pliable structures such as alkenes. By containing 20 mol% or more of monomer residues with these flexible structures relative to 100 mol% of all monomer residues constituting the resin in the resin film 2, the adhesive strength can be set to 0.02 N / cm or higher. Furthermore, by containing 70 mol% or less of monomer residues with these flexible structures relative to 100 mol% of all monomer residues constituting the resin in the resin film 2, the adhesive strength can be set to 0.3 N / cm or lower.

[0028] The resin contained in the resin film 2, within the range that satisfies the adhesion strength, may include: polyimide, polyimide precursor, polybenzoxazole, polybenzoxazole precursor, urethane resin, phenolic varnish resin, polyester resin, acrylic resin, polyhydroxystyrene, polysiloxane, polyimidesiloxane, etc., but is not limited to these.

[0029] The resin film 2 in the laminate of the present invention preferably contains a crosslinking agent. By containing a crosslinking agent, a portion of the structure is crosslinked, the surface of the resin film 2 hardens, and the adhesion strength can be adjusted. Furthermore, the surface of the resin film 2 becomes stronger due to crosslinking, thereby improving the residue suppression effect.

[0030] Examples of crosslinking agents, as compounds having alkoxymethyl or hydroxymethyl groups, include: DML-PC, DML-PEP, DML-OC, DML-OEP, DML-34X, DML-PTBP, DML-PCHP, DML-OCHP, DML-PFP, DML-PSBP, DML-POP, DML-MBOC, DML-MBPC, DML-MTrisPC, DML-BisOC-Z, DMLBisOCHP-Z, DML-BPC, DML-BisOC-P, DMOM-PC, DMOM-PTBP, 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, HMOM-TPHAP (the above are trade names, manufactured by Honshu Chemical Industry Co., Ltd.), "NIKALAC (registered trademark)" MX-290, NIKALAC MX-280, NIKALAC MX-270, NIKALAC MX-279, NIKALAC MW-100LM, NIKALAC MX-750LM (the above are trade names, manufactured by Sanwa Chemical Co., Ltd.).

[0031] Furthermore, it is also preferable to use a crosslinking agent containing epoxy groups. Examples of epoxy-containing compounds include: bisphenol A type epoxy resin, bisphenol F type epoxy resin, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, polymethyl (glycidyloxypropyl)siloxane, and other epoxy-containing silicones and dimer acid-modified epoxy resins, but the present invention is not limited to these. Specifically, examples include: Epiclon 850-S, Epiclon HP-4032, Epiclon HP-7200, Epiclon HP-820, Epiclon HP-4700, Epiclon EXA-4710, Epiclon HP-4770, and Epiclon EXA-859C. RP, Epiclon EXA-1514, Epiclon EXA-4880, Epiclon EXA-4850-150, Epiclon EXA-4850-1000, Epiclon EXA-4816, Epiclon EXA-4822 (the above are trade names, manufactured by Dai Nippon Ink & Chemical Co., Ltd.), physical and chemical resins (Rika) resin) BEO-60E (the above are product names, manufactured by Shin Nippon Rika (stock)), EP-4003S, EP-4000S (the above are product names, manufactured by ADEKA (stock)), JER871, JER872, YX-4000, YX-4000H (the above are product names, manufactured by Mitsubishi Chemical (stock)), Celloxide 2021P (the above are product names, manufactured by Daicel (stock)), Shofree PETG, Shofree CDMGB, Shofree BATG (the above are product names, manufactured by Showa Denko (stock)), Denacol EX-201-IM (the above are product names, manufactured by Nagase ChemteX (stock)), TEPIC-VL (the above are product names, manufactured by Nissan Chemical (stock)), etc.

[0032] Alternatively, it is also preferable to use a crosslinking agent containing an oxocyclic butyl group. Specific examples include: OXT-121, OXT-221, OX-SQ-H, OXT-191, PNOX-1009, RSOX (the above are trade names, manufactured by Toa Synthetic), "Eternacoll" OXBP (registered trademark), "Eternacoll" OXTP (the above are trade names, manufactured by Ube Industries, Ltd.), etc.

[0033] Two or more crosslinking agents may be contained in the resin film 2. It is preferable that the crosslinking agent contains at least 1 part by weight per 100 parts by weight of the resin film 2 to reduce residue. More preferably, it contains at least 5 parts by weight per 100 parts by weight of the resin film 2, thereby achieving a high residue suppression effect. Furthermore, it is preferable that the crosslinking agent contains 300 parts by weight or less per 100 parts by weight of the resin film 2. Within this range, the resin film 2 maintains its flexibility and will not crack during the transfer of semiconductor devices. Furthermore, from the viewpoint of preservation stability in the varnish state before the formation of the laminate, it is more preferable to contain 200 parts by weight or less. In particular, when the adhesion strength of the resin itself exceeds 0.3 N / cm, the preferred content of the crosslinking agent is 5 parts by weight or more and 300 parts by weight or less per 100 parts by weight of the resin film 2. By containing at least 5 parts by weight of crosslinking agent, the adhesion strength of the resin with an adhesion strength of 0.3 N / cm or more can be set to 0.3 N / cm or less. If the amount is 300 parts by weight or less, the flexibility of the resin film 2 is maintained. Furthermore, in terms of achieving the effect of suppressing residual adhesive, it is preferable to have 10 parts by weight or more, and in terms of improving storage stability, it is preferable to have 200 parts by weight or less.

[0034] In addition, a curing accelerator may be included to promote curing using the crosslinking agent. Examples of curing accelerators include imidazoles, tertiary amines or their salts, and organoboron salts, with imidazoles being 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, and 1-benzyl-2-methylimidazole. 1-Cyanoethyl-2-methylimidazolium, 1-Cyanoethyl-2-ethyl-4-methylimidazolium, 1-Cyanoethyl-2-undecaprolimidazole, 1-Cyanoethyl-2-phenylimidazolium, 1-Cyanoethyl-2-ethyl-4-methylimidazolium trimellitate, 1-Cyanoethyl-2-undecaprolimidazole trimellitate, 1-Cyanoethyl-2-phenylimidazolium trimellitate, 2,4-diamino-6-[ 2'-Methylimidazolyl-(1')]-ethyl-triazine, 2,4-diamino-6-[2'-undecapitolimidazolyl-(1')]-ethyl-triazine, 2,4-diamino-6-[2'-ethyl-4-methylimidazolyl-(1')]-ethyl-triazine, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-triazine isocyanuric acid adduct, 2-phenylimidazolyl isocyanuric acid adduct Acid adducts, 2-methylimidazolium isocyanuric acid adducts, 2-phenyl-4,5-dihydroxymethylimidazolium, 2-phenyl-4-methyl-5-hydroxymethylimidazolium, 1-cyanoethyl-2-phenyl-4,5-di(2-cyanoethoxy)methylimidazolium, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 1-benzyl-2-phenylimidazolium hydrochloride, 1-benzyl-2-phenylimidazolium trimellitate, etc. In addition, if we were to list some of the better imidazole products available on the market, we could include curezol C17Z, curezol 2MZ, curezol 1B2MZ, curezol 2E4MZ, curezol 2E4MZ-CN, curezol 2MZ-AZINE, and curezol 2MZ-OK (all of which are trade names manufactured by Shikoku Chemical Industry Co., Ltd.).

[0035] The preferred content of the curing accelerator in the resin film 2, relative to 100 parts by weight, is 0.1 parts by weight or more and 5.0 parts by weight or less. Within this range, a sufficient crosslinking promotion effect can be obtained. Furthermore, from the viewpoint of maintaining stability in the varnish state before the formation of the laminate, it is even more preferably 0.5 parts by weight to 2.0 parts by weight.

[0036] If the lamination sequence of the laminate of the present invention is a laser-transparent substrate 1, a resin film 1, and a resin film 2, other layers may also be present in between. The laser-transparent substrate 1 and the resin film 2 are located on the outermost surface of the laminate.

[0037] The laminate of the present invention is a laminate in which a laser-transparent substrate 1, a resin film 1, a resin film 2, and a semiconductor element are sequentially laminated. The absorbance of the resin film 1 at any wavelength from 200 nm to 1100 nm, when converted to a film thickness of 1.0 μm, is 0.4 or more and 5.0 or less. The adhesion strength of the surface where the resin film 2 is in contact with the semiconductor element is 0.02 N / cm or more and 0.3 N / cm or less.

[0038] The descriptions of the laser-transmittable substrate 1, resin film 1, and resin film 2 in the laminate 2 are the same as those in the laminate 1.

[0039] Next, the semiconductor element in this invention will be described.

[0040] The semiconductor element in this invention can be exemplified by being a device formed by incorporating semiconductors such as GaN, AlN, InN, InP, GaAs, Si, and SiC. These semiconductor elements further include: elements with layers of different types of semiconductors, or elements with layers of electrode materials, sapphire substrates or glass substrates, wiring, etc. The size of the semiconductor element is preferably 5 μm or more and 5.0 mm or less on one side. More preferably, it is 3.0 mm or less, which allows for focusing of laser light and reducing the spot diameter for irradiation, thus enabling transfer with good positional accuracy.

[0041] The number of semiconductor elements mounted on the multilayer 2 of the present invention is preferably 5 or more per unit area, and more preferably 50 or more per unit area. By setting the number of semiconductor elements to this number or more, the effect of increasing throughput by utilizing laser transfer is greater. In addition, in terms of accurately irradiating each semiconductor element with laser light, it is preferably 500,000 or less per unit area, and more preferably 100,000 or less per unit area.

[0042] If the stacking sequence of the stack 2 of the present invention is a laser-transparent substrate 1, a resin film 1, a resin film 2, and a semiconductor element, other layers may also be present in between. The semiconductor element is formed directly above the resin film 2, and the laser-transparent substrate 1 and the semiconductor element are located on the outermost surface of the stack.

[0043] Regarding the laminate of the present invention, the indentation hardness H2, measured by pressing from the resin film 2 side to the substrate 1 side, is 2 MPa or more and 500 MPa or less, and when the indentation hardness measured by pressing from the resin film 1 side to the substrate 1 side in the state where the resin film 2 has been removed from the laminate is set as H1, it is preferable that H1>H2.

[0044] In the case of laminate 2, with the semiconductor element removed from laminate 2, the indentation hardness H2, measured by pressing from the resin film 2 side to the substrate 1 side, is 2 MPa or more and 500 MPa or less. Preferably, when H1 is set as the indentation hardness measured by pressing from the resin film 1 side to the laser-transparent substrate 1 side with the semiconductor element and resin film 2 removed from laminate 2, H1 > H2. Indentation hardness is a physical property that serves as an indicator when semiconductor elements are deposited on the resin film 2. By setting it to an appropriate range, semiconductor elements can be easily deposited on the resin film 2, improving the accuracy of subsequent transfer of semiconductor elements using laser irradiation.

[0045] The indentation hardness H2 can be measured using a nano indenter. In the case of the laminate 2, the semiconductor element within the range required for hardness measurement can be physically removed from the laminate 2, exposing the surface of the resin film 2 for measurement. Methods for removing the semiconductor element include: direct removal using tweezers, or peeling off a substrate or film with strong adhesion, such as dicing tape, onto the surface of the semiconductor element. The indentation hardness is measured using an indentation load / unload test. In this test, a Berkovich indenter (triangular pyramidal diamond indenter) is used, and the sample is pressed from the surface of the resin film 2 towards the resin film 1 at room temperature and atmospheric conditions, followed by unloading. A continuous rigidity measurement method is used, with a measurement frequency of 100 Hz. The indentation hardness can be calculated from the obtained load-indentation depth graph using the value of the indentation area without the influence of the substrate.

[0046] The indentation hardness H1 is measured under the following conditions: the resin film 2 is removed from the laminate 1 by dry etching, exposing the surface of the resin film 1. In the case of the laminate 2, the measurement is performed under the following conditions: the semiconductor element is physically removed using the aforementioned method, and then the resin film 2 is removed by dry etching, exposing the surface of the resin film 1. Regarding the dry etching of the resin film 2, dry etching is performed beforehand at a location different from the measurement site, the etching rate of the resin film 2 is calculated, and the removal of the resin film 2 is based on this result. Subsequently, the composition of the resin film surface is analyzed by attenuated total reflectance-infrared spectroscopy (ATR-IR), and the removal of the resin film 2 is confirmed by the undetectable composition of the resin film 2. The indentation hardness H1, like the indentation hardness H2, can be measured using a nano-indenter. The conditions for measuring the nano-indenter when measuring the indentation hardness H1 are the same as those for measuring the indentation hardness H2.

[0047] Since the indentation hardness H2, measured by pressing from the resin film 2 side towards the substrate 1 side, is 2 MPa or higher, the semiconductor device will not be buried in the resin film 2 when it is deposited on the resin film 2, even when using bonding devices such as vacuum laminators or wafer bonders. Because the resin film 2 is not attached to the side of the semiconductor device, transfer can be performed using low-energy-density laser light. Furthermore, since the indentation hardness H2 is 500 MPa or less, even when pressure is applied during semiconductor device deposition, the semiconductor device can be deposited without damage. Preferably, the indentation hardness H2 is 300 MPa or less. By having an indentation hardness H2 of 300 MPa or less, the yield when depositing semiconductor devices on the resin film 2 is improved.

[0048] Furthermore, when comparing the indentation hardness H1 and the indentation hardness H2, by satisfying H1>H2, the interface between the resin film 1 and the resin film 2 is uniformly maintained when the semiconductor element is pressed onto the resin film 2, and the positional accuracy during laser transfer becomes better.

[0049] Regarding the laminate of the present invention, when the thickness of the resin film 1 is set to t1 (μm) and the thickness of the resin film 2 is set to t2 (μm), it is preferable that (t1+t2) is 1.0 μm or more and 30 μm or less, and t1 / t2 is 0.1 or more and 5.0 or less. By having (t1+t2) of 1.0 μm or more, the heat transfer to the semiconductor element generated during laser irradiation is reduced, thus suppressing damage to the semiconductor element. Furthermore, by having (t1+t2) of 30 μm or less, the deformation efficiency caused by the erosion of the resin film 1 by laser irradiation from the laser-transmitting substrate 1 side is well transferred to the interface between the resin film 2 and the semiconductor element, resulting in the transfer of the semiconductor element. Moreover, it is preferable that (t1+t2) is 20 μm or less, thereby enabling the semiconductor element to be transferred to the opposing substrate with good positional accuracy.

[0050] Furthermore, t1 / t2 is preferably 0.1 or higher and 5.0 or lower. If t1 / t2 is 0.1 or higher, when laser light is irradiated from the laser-transmitting substrate 1 side, the energy generated by the erosion of the resin film 1 reaches the interface with the semiconductor device without attenuation in the resin film 2, thereby enabling the transfer of the semiconductor device. Furthermore, if t1 / t2 is 5.0 or lower, the breakage of the resin film 2 caused by the energy generated by the erosion of the resin film 1 by laser light irradiation can be suppressed. As a result, the situation where a portion of the resin film 1 or resin film 2 splashes as debris onto the opposing substrate and contaminates the substrate can be prevented. More preferably, t1 / t2 is 0.3 or higher and 3.0 or lower.

[0051] The elongation at break of the resin film 1 in the laminate of the present invention is preferably 2.0% or more and 30% or less. By having an elongation at break of 2.0% or more, it is possible to prevent the resin film 1 from peeling off from the adjacent substrate or film due to impacts other than laser irradiation.

[0052] Furthermore, if the elongation at break of resin film 1 is less than 30%, then during laser irradiation, resin film 1 breaks at the interface between the irradiated and unirradiated portions, thus allowing accurate transfer of semiconductor elements only in the irradiated portion. The transfer of semiconductor elements using laser irradiation typically follows this mechanism: at the interface between a laser-transparent substrate and a laser-absorbing layer, the laser-absorbing layer is etched, and the semiconductor element is transferred by the pressure of the resulting decomposition gas. In the laminate of the present invention, in addition to the aforementioned effects, the laser-irradiated portion of resin film 1 breaks and falls onto resin film 2. Therefore, the impact of the falling broken resin film 1 can also be utilized as energy for semiconductor element transfer, improving positional accuracy. Furthermore, transfer can be performed even using low-energy laser irradiation, thereby significantly increasing processing margin.

[0053] The resin film 1 preferably has an elongation at break of 5% or more and 25% or less. If the elongation at break of the resin film 1 is 5% or more, the possibility of the resin film 1 peeling off due to reasons other than laser irradiation is further reduced, thus making storage or transportation in the laminated state easier. In addition, if the elongation at break of the resin film 1 is 25% or less, transfer can also be performed using lower energy, which is even better.

[0054] For the resin to achieve the stated condition of elongation at break of resin film 1, it is preferable that the resin contained in resin film 1 has a rigid structure. A rigid structure is preferably one having an aromatic ring, a condensation ring, an olefin, or an alkyl group having about 1 to 3 carbon atoms. Among these, the rigid structure is preferably an aromatic ring or a condensation ring without compromising absorbance. A rigid structure is less prone to elongation, therefore the elongation at break can be set to 30% or less. Furthermore, since it is a robust structure, the elongation at break can be set to 2% or more. Specifically, the elongation at break can be set within the stated range by having 50 mol% or more of the monomer residues with a rigid structure relative to 100 mol% of all monomer residues constituting the resin contained in resin film 1.

[0055] Furthermore, during resin polymerization, the elongation at break of the resin film 1 can be adjusted to a range of 2.0% or more and 30% or less by adjusting the monomer ratio and molecular weight. For example, when polyimide is used in the resin film 1, during polymerization, the ratio of the diamine used as a monomer to the dianhydride is shifted from equal amounts, and a difference is imparted for polymerization in a manner such as 98 moles:100 moles, thereby reducing the molecular weight of the resin. Generally, by reducing the molecular weight of the resin, the entanglement between molecules decreases, thus reducing the elongation at break. For resins with an elongation at break of 30% or more, the elongation at break can be set to 30% or less by reducing the molecular weight using the aforementioned method. On the other hand, for resins with an elongation at break of less than 2%, the elongation at break can be set to 2% or more by increasing the molecular weight. A preferred range for the molecular weight of the resin is 1,000 to 100,000 by weight average molecular weight.

[0056] When forming the resin film 1, the packing state of the resin is controlled by heat treatment, thereby enabling the film's elongation at break to be within the aforementioned range. In structures containing aromatic rings, examples include packing of aromatic rings on their planes; in structures containing alkyl chains, examples include packing of alkyl chains on their planes. For instance, when the resin contained in the resin film 1 is a polyimide containing aromatic rings, and the heat treatment temperature is below 200°C, the packing of the aromatic rings in the resin is insufficient, resulting in a lower elongation at break. On the other hand, by setting the heat treatment temperature above 200°C within a certain range of the resin's heat resistance, the elongation at break can be improved. Furthermore, compared to curing in an inert gas environment, curing in air results in a lower elongation at break. By combining these film-forming methods, in addition to the resin structure, the elongation at break within the aforementioned range can be achieved.

[0057] Regarding the laminate of the present invention, the indentation hardness H1, measured by pressing from the resin film 1 side to the substrate 1 side, is preferably 50 MPa or more and 1000 MPa or less. When the indentation hardness H1 is within this range, the resin film 1 is easier to break when irradiated with laser light, thus improving transferability.

[0058] To achieve the desired indentation hardness H1 within this range, it can be achieved by including at least 50 mol% of monomer residues with aromatic rings in the resin contained in the resin film 1, relative to 100 mol% of all monomer residues constituting the resin. Furthermore, like the elongation, the indentation hardness H1 varies depending on the packing properties of the resin, and therefore can also be adjusted by changing the curing temperature during the formation of the resin film 1. Specifically, by keeping the heat treatment temperature of the resin film 1 below 200°C, the indentation hardness H1 decreases; if the heat treatment temperature is above 200°C, the indentation hardness H1 increases. The optimal temperature and adjustable hardness range can be varied depending on the type of resin. For example, if the resin film 1 contains polyamide, the conversion from polyamide to amide occurs within the range of 180°C to 300°C, thus changing the packing properties of the film and adjusting the hardness accordingly. Furthermore, by adding a crosslinking agent, the membrane also crosslinks, thereby increasing its hardness. Therefore, resins with low hardness can be adjusted by combining them with crosslinking agents.

[0059] The preferred range for the indentation hardness H1, measured by pressing from the resin film 1 side to the substrate 1 side, is 80 MPa to 800 MPa. By setting it within this range, the positional accuracy of the element transferred by laser irradiation can be further improved.

[0060] The elongation at break of the resin film 2 in the laminate of the present invention is preferably 100% or more and 1000% or less. In the present invention, the resin film 2, in addition to its function of holding the semiconductor element, also has the function of catching the resin film 1 that has broken due to laser irradiation during the transfer step, and using this force to peel the semiconductor element off the surface of the resin film 2 for transfer. Because the elongation at break of the resin film 2 is 100% or more, even if the broken resin film 1 is caught, the resin film 2 will not break. This suppresses the generation of debris from the resin film 1 and resin film 2 during transfer, preventing contamination of the opposing substrate. Furthermore, because the elongation at break of the resin film 2 is 1000% or less, it prevents the resin film 2 in the unirradiated portion from being stretched and deformed when the resin film 2 in the irradiated portion deforms. Preferably, it is 200% or more and 800% or less. By setting it within this range, the energy density of the irradiable laser light can be widened, resulting in improved processing margin.

[0061] To achieve this property in the resin film 2, it is preferable that the resin contained in the resin film 2 has a flexible structure. Examples of flexible structures include alkyl groups, siloxanes, and alkyldiols. Specifically, this is achieved by including at least 20 mol% of the monomer residues in the resin film 2 that have a flexible structure relative to 100 mol% of all monomer residues constituting the resin. More preferably, at least 30 mol% of the monomer residues that have a flexible structure relative to 100 mol% of all monomer residues constituting the resin.

[0062] The laminate of the present invention is preferably a resin film 1 containing one or more of 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 copolymers thereof.

[0063] [Chemistry 1]

[0064] In equations (1) to (4), R1, R3, R7 and R9 independently represent tetravalent organic groups with 6 to 40 carbon atoms, and R2, R4, R6 and R8 independently represent divalent organic groups with 2 to 40 carbon atoms. R5 represents a hydrogen atom or a monovalent organic group with 1 to 20 carbon atoms.

[0065] Polyimide and polybenzoxazole are resins with cyclic structures having amide rings or oxazole rings within their main chain structure. Furthermore, the polyimide precursor and polybenzoxazole precursor, as precursors to these resins, are resins that form amide ring and oxazole ring structures by dehydration and ring closure. The structures represented by formulas (1) to (4) are preferably contained in the resin in the form of repeating units of 10 to 100,000 units. Within this range, a resin film 1 can be coated with an appropriate film thickness.

[0066] Polyimides can be obtained by reacting a tetracarboxylic acid or its corresponding tetracarboxylic dianhydride, tetracarboxylic acid diester dichloride, etc., with a diamine or its corresponding diisocyanate compound, trimethylsilylated diamine, etc., and thus possessing both tetracarboxylic acid residues and diamine residues. For example, polyamide, obtained by reacting tetracarboxylic dianhydride with a diamine, can be obtained by dehydration and ring-closure of polyamide precursors using heat treatment. During this heat treatment, a solvent that azeotropically reacts with water, such as m-xylene, can also be added. Alternatively, dehydration and ring-closure can be achieved by adding a dehydration condensing agent such as a carboxylic anhydride or dicyclohexylcarbodiimide, or a ring-closure catalyst such as a base, such as triethylamine, and then performing a chemithermal treatment. Alternatively, dehydration and ring-closure can be achieved by adding a weakly acidic carboxylic acid compound and performing a heat treatment at a low temperature below 100°C.

[0067] Polybenzoxazole can be obtained by reacting a diaminophenol compound with a dicarboxylic acid or its corresponding chloride, reactive ester, etc., and contains both dicarboxylic acid residues and diaminophenol residues. For example, it can be obtained by dehydrating and ring-closing polyhydroxyamide, which is obtained by reacting a diaminophenol compound with a dicarboxylic acid, using heat treatment. Alternatively, it can be obtained by adding phosphoric anhydride, a base, a carbodiimide compound, etc., and then using chemical treatment to dehydrate and ring-close it.

[0068] In formulas (1) and (2), R1 and R3 (COOR 5) represent tetracarboxylic acid residues. Examples of tetracarboxylic acid residues constituting R1 or R3 (COOR 5) 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, The formulation may contain aromatic tetracarboxylic acid residues such as 1-bis(2,3-dicarboxyphenyl)ethane, bis(3,4-dicarboxyphenyl)methane, bis(2,3-dicarboxyphenyl)methane, 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, or aliphatic tetracarboxylic acid residues such as butanetetracarboxylic acid and 1,2,3,4-cyclopentanetetracarboxylic acid. Alternatively, it may contain residues of two or more of these tetracarboxylic acids. From the viewpoint of absorbance, aromatic tetracarboxylic acid residues are preferred.

[0069] In formulas (1) and (2), R2 and R4 represent diamine residues. Examples of diamine residues constituting R2 or R4 include: 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, bis(3-amino-4-hydroxyphenyl) benzox, 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, 9,9-bis(3-amino-4-hydroxyphenyl)fluorene, etc., containing hydroxyl groups, 3-sulfonic acid-4, Diamine residues containing sulfonic acid groups, such as 4'-diaminodiphenyl ether; diamine residues containing thiol groups, such as dimercaptophenyldiamine; 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide, 1,4-bis(4-aminophenoxy) Benzene, benzidine, m-phenylenediamine, p-phenylenediamine, 1,5-naphthylenediamine, 2,6-naphthylenediamine, bis(4-aminophenoxyphenyl) guanidine, bis(3-aminophenoxyphenyl) guanidine, 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-4, Compounds consisting of aromatic diamine residues such as 4'-diaminobiphenyl, 2,2',3,3'-tetramethyl-4,4'-diaminobiphenyl, 3,3',4,4'-tetramethyl-4,4'-diaminobiphenyl, and 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, or compounds in which a portion of the hydrogen atom of the aromatic ring is substituted by an alkyl or fluoroalkyl group having 1 to 10 carbon atoms, a halogen atom, etc., as well as alicyclic diamine residues such as cyclohexyldiamine and methylenebiscyclohexylamine.Alternatively, aliphatic diamine residues can also be used. For example, examples of diamine residues containing polyoxyethylene alkyl groups include: Jeffamine KH-511, Jeffamine ED-600, Jeffamine ED-900, Jeffamine ED-2003, Jeffamine EDR-148, Jeffamine EDR-176, and polyoxyethylene propyl. Diamine residues such as D-200, D-400, D-2000, and D-4000 (trade names, manufactured by Huntsman Corporation) can be used as diamine residues having polyepoxyalkyl groups. Examples of diamine residues include residues from Elasmer 250P, Elasmer 650P, Elasmer 1000P, and Porea SL100A (trade names, manufactured by Kumiai Chemical Industry Corporation). Furthermore, siloxane diamine residues can also be used, such as residues from propylamine-terminated siloxane diamines like LP-7100, KF-8010, KF-8012, and X-22-161A (trade names, manufactured by Shin-Etsu Chemical Co., Ltd.). Additionally, combinations containing two or more of these diamine residues can also be used. From the viewpoint of absorbance, it is preferable that the resin membrane 1 contains at least 30 mol% of the total diamine residues of the resin membrane 1, which are aromatic diamine residues.

[0070] In formula (2), R5 represents a hydrogen atom or a monovalent organic group with 1 to 20 carbon atoms. Organic groups with 1 to 20 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, pentyl, hexyl, cyclohexyl, octyl, dodecyl, phenyl, etc. Methyl and ethyl are preferred in terms of the ease of obtaining the raw materials for polymerization.

[0071] In formulas (3) and (4), R6 and R8 represent dicarboxylic acid residues, tricarboxylic acid residues, or tetracarboxylic acid residues.

[0072] 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. Examples of tricarboxylic acid residues include residues of trimellitic acid, pyromellitic acid, diphenyl ether tricarboxylic acid, and biphenyl tricarboxylic acid. Examples of tetracarboxylic acid residues are the same as those listed as examples of R1 and R3. Two or more of these residues may be present.

[0073] In formulas (3) and (4), R7 and R9(OH)2 represent residues of the diaminophenol derivative. Specific examples of residues of the diaminophenol derivative include 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) guanidine, bis(4-amino-3-hydroxyphenyl) guanidine, 2,2-bis(3-amino-4-hydroxyphenyl)-1,1,1,3,3,3-hexafluoropropane, 2,2-bis(4-amino-3-hydroxyphenyl)-1,1,1,3,3,3-hexafluoropropane, etc., but are not limited to these. These compounds may contain only one residue, or may contain two or more residues in combination.

[0074] In addition, it is preferable to seal the ends of the resins represented by formulas (1) to (4) by using monoamines, anhydrides, chloroacetic acid, or monocarboxylic acids with acidic groups, as this can result in resins with acidic groups at the ends of the main chain.

[0075] Preferred examples of such monoamines include 2-aminophenol, 3-aminophenol, and 4-aminophenol. Two or more of these may be used.

[0076] Furthermore, preferred examples of such anhydrides, chlorohydrins, and monocarboxylic acids include phthalic anhydride, maleic anhydride, and nadic anhydride, among others. Additionally, di-tert-butyl dicarbonate is also preferred as a reactive terminator. Two or more of these may be used.

[0077] In the laminate of the present invention, the resin contained in the resin film 2 is preferably a structure having one or more of the following structures selected from the group consisting of a dimethylsiloxane structure represented by formula (5), a diphenylsiloxane structure represented by formula (6), an alkyldiol structure represented by formula (7), and an alkylene structure represented by formula (8).

[0078] [Chemistry 2]

[0079] In equations (5) to (8), R10 to R13 independently represent hydrogen atoms or monovalent organic groups with 1 to 20 carbon atoms. l, m, and n independently represent integers from 4 to 40. p represents integers from 10 to 40. o represents integers from 1 to 16.

[0080] By having the structures represented by formulas (5) to (8) in the resin structure, the resin film 2 has the effect of improved flexibility and adhesion strength, which is better. The descriptions of R10 to R13 are the same as those of R5.

[0081] Specifically, regarding aliphatic diamine residues, examples of diamine residues containing polyoxyethylene alkyl groups include: Jeffamine KH-511, Jeffamine ED-600, Jeffamine ED-900, Jeffamine ED-2003, Jeffamine EDR-148, Jeffamine EDR-176, and polyoxyethylene alkyl groups. The diamine residues of propyl diamines such as D-200, D-400, D-2000, and D-4000 (trade names, manufactured by Huntsman Corporation) can be used as diamine residues having polyepoxyalkyl groups. Examples of such residues include those from Elasmer 250P, Elasmer 650P, Elasmer 1000P, and Porea SL100A (trade names, manufactured by Kumiai Chemical Industry Corporation). Furthermore, as siloxane diamine residues, examples of siloxane diamines ending in propylamine include residues from LP-7100, KF-8010, KF-8012, and X-22-161A (trade names, manufactured by Shin-Etsu Chemical Co., Ltd.). Additionally, two or more of these diamine residues can be used in combination.

[0082] The laminate of the present invention is preferably a resin contained in the resin film 2 that is a polyimide silicate. Polyimide silicate is a resin having a silicate structure in the repeating structure of polyimide, and the polyimide silicate in the present invention is particularly preferably having silicate diamine residues represented by formula (9) in its structure.

[0083] [Chemistry 3]

[0084] In formula (9), q is a natural number from 1 to 50. R14 and R15 may be the same or different, representing alkyl or phenyl groups with 1 to 30 carbon atoms. R16 to R19 may be the same or different, representing alkyl, phenyl or phenoxy groups with 1 to 30 carbon atoms.

[0085] Examples of siloxane diamine residues represented by formula (9) include: α,ω-bis(3-aminopropyl)polydimethylsiloxane, α,ω-bis(3-aminopropyl)polydiethylsiloxane, α,ω-bis(3-aminopropyl)polydipropylsiloxane, α,ω-bis(3-aminopropyl)polydibutylsiloxane, α,ω-bis(3-aminopropyl)polydiphenoxysiloxane, α,ω-bis(2-aminoethyl)polydimethylsiloxane, α,ω -Residues of bis(2-aminoethyl)polydiphenoxysiloxane, α,ω-bis(4-aminobutyl)polydimethylsiloxane, α,ω-bis(4-aminobutyl)polydiphenoxysiloxane, α,ω-bis(5-aminopentyl)polydimethylsiloxane, α,ω-bis(5-aminopentyl)polydiphenoxysiloxane, α,ω-bis(4-aminophenyl)polydimethylsiloxane, α,ω-bis(4-aminophenyl)polydiphenoxysiloxane, etc. The siloxane diamine may be used alone or in combination with two or more.

[0086] The laminate of the present invention preferably has a 1% weight loss temperature of 300°C or higher for the resin film 2. Here, the 1% weight loss temperature of the resin film 2 refers to a value obtained by heat-treating the resin film 2 at 250°C for 30 minutes. Confirmation can also be made based on the resin film 2 having undergone heat treatment at 250°C for 30 minutes. By setting the 1% weight loss temperature to 300°C or higher, the degradation of the resin film 2 itself caused by heat generated during laser irradiation can be suppressed, and the generation of debris caused by the degradation of the resin film 2 can be prevented. To set the 1% weight loss temperature to 300°C or higher, it is preferable that the resin film 2 contains components with high thermal stability. Specifically, components with high thermal stability refer to rigid components such as aromatic rings, silicones with relatively high thermal stability in flexible structures, or combinations thereof. By ensuring that at least 50% of the monomer residues in the resin comprising the resin film 2 are high-thermal-stability monomer residues (100 moles or more), the 1% weight loss temperature can be set to 300°C or higher. From the viewpoint of polymer versatility, the 1% weight loss temperature is preferably 600°C or lower.

[0087] Next, the method for manufacturing the laminate of the present invention will be described.

[0088] The laminate 1 can be obtained by sequentially forming a resin film 1 and a resin film 2 on a laser-transparent substrate 1. An example of a method for manufacturing the laminate 1 is described below. A varnish, in which the components of the resin film 1 are dissolved in a solvent, is coated onto the laser-transparent substrate 1, and then heated and cured to form the resin film 1. Then, a varnish for the resin film 2 is coated onto the resin film 1 using the same method, and the substrate is heated and cured to form the resin film 2. When using a coating method to manufacture the resin film 1 and the resin film 2, any coating method can be selected, such as spin coating using a rotary device, spray coating, roller coating, or slot die coating. Preferably, the coated resin film 1 and resin film 2 are dried at a temperature between 50°C and 150°C for 1 minute to several tens of minutes using a heating plate, drying oven, or infrared radiation. Then, as needed, they are heated and cured at a temperature between 100°C and 500°C for several minutes to several hours.

[0089] The thickness of resin membrane 1 is selected between 0.1 μm and 25 μm. Similarly, the thickness of resin membrane 2 is selected between 0.2 μm and 27 μm. The membrane thickness can be measured using a scanning electron microscope, an optical thickness gauge, or a step gauge.

[0090] Other layers can also be formed between the laser-transparent substrate 1 and the resin film 1, and between the resin film 1 and the resin film 2. When other layers are formed between the laser-transparent substrate 1 and the resin film 1, the film is formed on the laser-transparent substrate 1 before the resin film 1 is formed. Alternatively, when other layers are formed between the resin film 1 and the resin film 2, the other layers can be formed on the formed resin film 1, and then the resin film 2 can be formed.

[0091] Next, an example of a method for stacking semiconductor elements on stack 1 and forming stack 2 will be described.

[0092] Figure 1 shows a method for fabricating a laminate 2 (120). Semiconductor elements (14) are directly arranged on the resin film 2 (13) of a laminate 1 (110) obtained by laminating resin film 1 (12) and resin film 2 (13) in sequence on a laser-transparent substrate 1 (11). The laminate is then formed by pressing using a vacuum laminator, wafer bonder, or pressing machine (41). Alternatively, as shown in Figure 2, a semiconductor element temporary bonding substrate (130) is prepared, on which semiconductor elements (14) are temporarily bonded via a temporary adhesive (16) on another support (15). The semiconductor elements (14) on the temporary adhesive (16) are aligned with the surface of the resin film 2 (13) of the laminate 1 (110), and the laminate is formed using the pressing device (41). Afterward, the temporary adhesive (16) and the support (15) are removed, and the laminate 2 (120) is fabricated. Furthermore, the following methods can be used: As shown in FIG3, a substrate (140) with a semiconductor element (14) formed directly on a sapphire or other crystal growth substrate (17) is overlapped with the surface of the semiconductor element (14) facing the surface of the resin film 2 (13) of the stack 1 (110) using the aforementioned device (41); thereafter, laser light (31) is irradiated from the crystal growth substrate (17) side, and the semiconductor element (14) is laser-peeled from the crystal growth substrate (17) to the stack 1 (110) side. The pressure during semiconductor element stacking can be selected according to the adhesion strength of the resin film 2, and is selected in the range of 0.05 MPa to 5.0 MPa. In terms of avoiding damage to the semiconductor element and suppressing burial into the resin film 2, it is preferable to be 2.0 MPa or less. In addition, when stacking semiconductor elements, pressure can also be applied while heating is performed as needed. Heating reduces the elastic modulus of the resin film 2, thereby allowing the semiconductor device to be pressed together with lower pressure.

[0093] In addition, by pre-marking alignment marks on the laminate, it becomes easier to adjust the transfer position in subsequent operations.

[0094] Next, another method for fabricating the multilayer 2 will be described using FIG4. A semiconductor substrate (18) is bonded to another support (15) via a temporary adhesive (16) before monolithization. Then, a varnish of resin film 2 is applied to the semiconductor substrate (18) before monolithization, and heat-cured to form resin film 2 (13). Then, resin film 1 (12) is formed on a laser-transparent substrate 1 (11). The resin film 1 (12) side on the laser-transparent substrate 1 (11) and the resin film 2 (13) side on the semiconductor substrate (18) are pressed together face-to-face using the aforementioned apparatus (41). The support (15) and the temporary adhesive (16) are peeled off and removed, and then the semiconductor substrate (18) is monolithized to form a semiconductor element (14), thereby fabricating the multilayer 2 (120).

[0095] Next, the manufacturing method of the semiconductor device will be explained.

[0096] The semiconductor device manufacturing method of the present invention is as follows: a semiconductor device manufacturing method using the stacked body 2, the method comprising: a step of making the semiconductor element surface of the stacked body 2 face the substrate 2; and then, irradiating laser light from the laser-transmittable substrate 1 side of the stacked body 2 to transfer the semiconductor element to the substrate 2.

[0097] The steps of aligning the semiconductor element surface of the laminate 2 with the substrate 2 are illustrated using diagrams.

[0098] Figure 5 illustrates a method for manufacturing a semiconductor device. The term "semiconductor element surface" refers to the surface of the laminate 2 (120) in which a semiconductor element (14) exists.

[0099] The semiconductor element face of the laminate 2 (120) fabricated using the method is placed face-to-face with the substrate 2 (21), and the substrate is fixed in a manner where the laminate 2 (120) and the substrate 2 (21) are parallel. To prevent the semiconductor element (14) from shifting due to its own weight during transfer, the face-to-face laminate 2 (120) and the substrate 2 (21) are arranged with the laminate 2 (120) on top. The laminate 2 (120) and the substrate 2 (21) are arranged with a certain interval, the interval between the semiconductor element face and the substrate 2 can be selected according to the size and thickness of the semiconductor element, and is selected in the range of a few micrometers to several hundred micrometers.

[0100] The substrate 2 can be any substrate, such as a glass substrate, resin substrate, metal substrate, or circuit board with pre-formed wiring. Additionally, an adhesive layer may be provided to hold the transferred semiconductor device. The adhesive layer can be made of adhesive materials such as polysiloxane resin, acrylic resin, polyester resin, anisotropic conductive film (ACF) resin, conductive paste, or the resin film 2 of this invention. The thickness of the adhesive layer is in the range of 0.5 μm to 100 μm, selected according to the size of the semiconductor device or the distance between the semiconductor device and the substrate 2.

[0101] In addition, alignment marks may also be present on the second side of the substrate in order to align the transfer position.

[0102] Next, the steps of irradiating the laser light from the laser-transmittible substrate 1 side of the stacked body 2 and transferring the semiconductor element to the substrate 2 will be described using diagrams.

[0103] An example of the transfer step is shown in Figure 6a. In the laminate 2 (120) and substrate 2 (21) configured using the method described above, laser light (31) is irradiated onto the semiconductor element (14) via the laser-transmittable substrate 1 (11) side of the laminate 2 (120). Examples of laser light types include solid-state lasers such as yttrium aluminum garnet (YAG) lasers, YVO4 lasers, fiber lasers, and semiconductor lasers, as well as gas lasers such as CO2 lasers, excimer lasers, and argon lasers, which can be selected according to the wavelength used. The shape of the laser beam used for irradiation is not limited, and the laser spot size can be smaller than the size of the semiconductor element. The laser light is designed to avoid irradiating semiconductor elements adjacent to the semiconductor element to be transferred. In addition, when the size of the laser spot is the same as the size of the semiconductor element adjacent to the semiconductor element that is being irradiated, as shown in Figure 6b, the laser light (31) can also be irradiated through the photomask (51).

[0104] The laser light can have any energy density. Regarding the energy density of the laser light, from the viewpoint of stability, it is preferably 1 mJ / cm² or higher; from the viewpoint of preventing damage to semiconductor devices and shortening processing time, it is preferably 1000 mJ / cm² or lower. More preferably, the laser light energy density is 10 mJ / cm² or higher and 500 mJ / cm² or lower.

[0105] By using the laminate 2 of the present invention, transfer can be performed even at low energy levels, and the impact on positional accuracy or debris and residue can be reduced even when the energy density of the laser light is changed. Sometimes, the energy density of the irradiating laser light is uneven. To reduce the impact of this unevenness on transferability, it is preferable that the laminate 2 has the same degree of transferability regardless of the laser light energy density. The range of laser light energy densities that provides the same degree of transferability is preferably 30 mJ / cm² or higher, and from a practical point of view, it is particularly preferably 50 μm / cm² or higher.

[0106] Furthermore, the substrate 2 can be heated during the transfer of semiconductor elements. In particular, when an adhesive layer is formed on the substrate 2, the retention of the transferred semiconductor elements is improved. When heating the substrate 2, the temperature is preferably below 100°C to prevent heat-induced warping of the substrate 2 and to ensure good positional accuracy during transfer.

[0107] The transfer of semiconductor components is performed simultaneously with adjusting their positions according to the actual mounting locations of the semiconductor components in the semiconductor device to be manufactured. For example, in the case of manufacturing an LED substrate, the spacing of the LED components is staggered according to the pixel size and red-green-blue (RGB) configuration of the LEDs, and the transfer is performed simultaneously. Next, the substrate 2 with the transferred LED components is brought face-to-face with the circuit board and pressed onto the circuit board, thereby manufacturing a circuit board on which the LED components are mounted. When using the laminate of the present invention for transfer, transfer can be performed with high positional accuracy, so semiconductor components can be transferred without offset from the circuit of the final mounted substrate, reducing mounting defects caused by positional misalignment.

[0108] In the method for manufacturing the semiconductor device of the present invention, it is preferable that the laser light has a wavelength of any one of 248 nm, 266 nm, 308 nm, 355 nm, 532 nm, and 1064 nm, and particularly preferably that the absorbance of the resin film 1 is 0.4 or higher. By using these laser lights, damage to semiconductor elements can be reduced. The laser light is more preferably any one of 248 nm, 266 nm, and 355 nm, which also allows for the accurate transfer of tiny semiconductor elements such as μLEDs. As laser light of 248 nm, 266 nm, 308 nm, 355 nm, 532 nm, and 1064 nm, excimer lasers, YAG lasers, and infrared (IR) lasers are particularly preferred.

[0109] Furthermore, in the semiconductor device manufacturing method of the present invention, the substrate 2 is preferably a circuit board. If the substrate 2 is a circuit board, the substrate transferred using the method can be directly incorporated into a semiconductor device. There is no need to worry about positional shifts caused by the operation of the transferred substrate, and positional accuracy can be further improved. As the circuit board, known substrates such as thin-film transistor (TFT) substrates or printed wiring substrates can be used.

[0110] The present invention will now be described in detail based on embodiments. [Example]

[0111] The present invention will now be illustrated by examples, but the invention is not limited to these examples. First, the evaluation methods in each example and comparative example will be described.

[0112] (1) Method for preparing laminated bodies On a 4-inch glass substrate (manufactured by Corning, Eagle XG, absorbance at 355 nm of 0.01) with alignment marks and a thickness of 0.5 mm, or a 4-inch synthetic quartz substrate (manufactured by Taishin Manufacturing Co., Ltd., absorbance at 266 nm of 0.01) with alignment marks and a thickness of 0.5 mm, a varnish for resin film 1 prepared by the method described later is applied using a spin coater. The substrate is then pre-baked at 120°C for 3 minutes using a heating plate, and then further heated and hardened at a specified temperature and time to form resin film 1 on the glass substrate or synthetic quartz substrate.

[0113] Then, similarly, a varnish for the resin film 2 prepared by the method described later is applied using a spin coater, and the film is pre-baked at 120°C for 3 minutes using a heating plate, and then heated and hardened at a specified temperature and time, thereby creating a laminate 1 on a glass substrate or synthetic quartz substrate on which the resin film 1 and the resin film 2 are sequentially deposited.

[0114] The film thicknesses of resin film 1 and resin film 2 were confirmed by cutting the laminate and observing the cross-section using a scanning electron microscope (manufactured by Hitachi High-Technologies, S-4800).

[0115] Separately, silicon wafers with a back-grinding process to a thickness of 100 μm were attached to a dicing tape (Denka, UDC-1025MC) and processed into 100 μm × 200 μm dimensions using a dicing device (Disco, DAD300) to create virtual wafers of semiconductor devices. The distance between the wafers was 150 μm, resulting in 1100 virtual wafers per unit area / cm².

[0116] The dicing tape was irradiated with ultraviolet light (UV light) to reduce its adhesion. One hundred virtual wafers remained in a 10x10 row x 10 column configuration, and the surrounding virtual wafers were removed using tweezers. The virtual wafers on the dicing tape were overlapped on the resin film 2 side of the laminate 1 with their wafer faces facing each other. Next, the virtual wafers were pressed onto the resin film 2 using a vacuum laminator. The dicing tape was then peeled off to fabricate the laminate 2. The surface of the virtual wafers laminated on the resin film 2 was visually observed using an optical microscope, and the number of successfully laminated wafers on the resin film 2 and the number of undamaged successfully laminated wafers were measured. The results are recorded in Tables 2 and 3.

[0117] (2) Measurement of absorbance of resin film 1 Using the same method as described in (1), resin film 1 was coated onto a quartz substrate with varnish, pre-baked, and heat-cured to produce a quartz substrate with resin film 1 for absorbance measurement. The film thickness was also measured in the same manner. The absorbance from 200 nm to 1100 nm was continuously measured using a UV-Vis spectrophotometer (manufactured by Hitachi, Ltd., U-2910). The absorbance at 248 nm, 266 nm, 308 nm, 355 nm, 532 nm, and 1064 nm was read, and the absorbance per 1 μm was calculated according to the following formula. Absorbance per 1 μm = Actual absorbance obtained during measurement / Measurement film thickness (μm).

[0118] (3) Determination of the adhesion strength of the surface of resin film 2 opposite to that of resin film 1 (3)-1 Determination of the adhesion strength of the surface of the resin film 2 in the laminate 1 that is opposite to the side of the resin film 1. On the surface of the resin film 2 of the laminate 1 prepared by the method described above, opposite to the side of the resin film 1, a Kapton film cut into strips of 1 cm × 9 cm was pressed using a vacuum laminator at 0.1 MPa and 25°C. The sample was placed on a tensile testing machine (manufactured by NIDEC Shimpo, FGS-VC) and the pressed Kapton film was peeled off vertically at a constant speed of 2 mm / s. The peel strength was measured using a digital force gauge (manufactured by NIDEC Shimpo, FGJN-5). Three measurements were performed with different samples, and the average value was taken as the adhesion strength.

[0119] (3)-2 Determination of the adhesion strength of the surface of the resin film 2 in the laminate 2 that is opposite to the resin film 1 side. A dicing tape (UDC-1025MC) is attached to the surface of the virtual wafer deposited on the resin film 2 of the laminate 2 prepared by the method described above, and then peeled off, thereby removing the virtual wafer from the resin film 2. A Kapton film is pressed onto the surface of the resin film 2 from which the virtual wafer has been removed using the same method as in (3)-1, and the adhesion strength is measured using the same method as in (3)-1.

[0120] (4) Determination of indentation hardness H1 and indentation hardness H2 Indentation hardness H1 and indentation hardness H2 were measured using a nano indenter (manufactured by Hysitron, Triboindenter TI950).

[0121] In the case of laminate 1, laminate 1 is cut into 10 mm × 10 mm pieces to prepare a test sample. In the case of laminate 2, using the same method as the determination of the adhesion strength of resin film 2 described in (3), a virtual wafer is peeled off from the laminate to prepare a sample exposing resin film 2, and then cut into 10 mm × 10 mm pieces.

[0122] The prepared sample was fixed on a dedicated sample holder using an adhesive (manufactured by Dong-A Synthetic Co., Ltd., Aron Alpha fast-acting multi-purpose). The indentation hardness H2 was determined by an indentation load / unload test. In the test, a Berkovich indenter (triangular pyramidal diamond indenter) was used to press the sample from the surface of the resin film 2 toward the resin film 1, and then unloaded.

[0123] The indentation hardness H1 was measured after the semiconductor element had been removed from the laminate 2 using the aforementioned method, and then the surface of the resin film 1 was exposed after the resin film 2 had been removed by dry etching. During the etching of the resin film 2, O2 gas was used, and dry etching was performed beforehand at a location different from the measurement site to calculate the etching rate of the resin film 2. Based on this result, the etching time of the resin film 2 was determined, and etching was performed. Subsequently, the composition of the resin film surface was analyzed using ATR-IR (manufactured by BRUKER, INVENIOS), and the removal of the resin film 2 was confirmed by the absence of detectable components in the resin film 2.

[0124] For the sample from which the resin film 2 has been removed using the method described above, it is similarly cut into 10 mm × 10 mm pieces, and the indentation hardness H1 is determined by an indentation load / unload test. In the test, the resin film 1 is pressed into the substrate 1 with laser permeability from the surface of the resin film 1 and then unloaded. [Measurement Conditions] The environment during the measurement was 25±2℃, atmospheric. Measurement frequency: 100 Hz Measurement method: Continuous rigidity measurement method. Based on the obtained load-indentation depth diagram, the indentation hardness H1 and indentation hardness H2 are calculated using the values ​​of the indentation region in the range without the influence of the substrate.

[0125] (5) Measurement of film thickness The stacked body 2 was cut open, and the cross-section was observed using a scanning electron microscope (manufactured by Hitachi High-Technologies, S-4800) to measure t1 (μm) and t2 (μm).

[0126] (6) Determination of elongation at break Resin film 1 and resin film 2 were coated onto copper foil using a rod coater with varnish. The coating was pre-baked at 120°C for 3 minutes using a heating plate, and then heat-cured at the temperatures and times shown in Table 2 below, resulting in a 10 μm thick resin film 1 on the copper foil. Next, the copper foil of the laminated copper foil containing resin film 1 and resin film 2 was etched using a ferric chloride solution to obtain single films of resin film 1 and resin film 2. The obtained single films were cut into strips 1.5 cm wide and 2 cm long to prepare samples for elongation measurement. For the samples, a Tensilon RTM-100 (manufactured by Orientec) was used to stretch the samples at 23.0°C and 45.0%RH at a stretching speed of 50 mm / min, and the elongation at break was measured at 23.0°C. For one subject, 10 strips were measured, and the average of the first 5 results was calculated.

[0127] (7) Determination of thermal decomposition temperature The single film of resin film 2 used in the elongation determination was heat-treated at 250°C for 30 minutes, and then approximately 15 mg was placed in an aluminum standard container for measurement using a thermogravimetric analyzer (Shimadzu Corporation, TGA-50). The measurement conditions were: holding at 120°C for 30 minutes, then increasing 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 reduction curve and set as the 1% weight reduction temperature.

[0128] (8) Transfer test of semiconductor wafers (8)-1 Fabrication of a transfer substrate On a 0.5 mm thick 4-inch alkali-free glass substrate (Corning Eagle XG) with alignment marks, a diluent prepared by diluting polydimethylsiloxane with toluene at a weight ratio of 1:9 was applied using a spin coater. The substrate was then heated and cured at 120°C for 3 minutes using a heating plate to form an adhesive layer. The thickness of the heat-cured adhesive layer was measured using an optical thickness gauge (Dai Nippon Mesh, Lambda ace, refractive index = 1.543), resulting in a 20 μm thick substrate.

[0129] (8)-2 Transfer of semiconductor components Next, the laser light source, the laminate 2 fabricated using the described method, and the opposing substrate are arranged sequentially. At this time, the surface of the laminate holding the virtual wafer and the surface of the opposing substrate with the adhesive layer formed are held face-to-face with a 50 μm gap between the virtual wafer surface and the adhesive layer surface. The laminate and the opposing substrate are aligned using their respective alignment marks. The laser beam spot size is adjusted to a 120 μm × 220 μm square using a slit, and the positions of the laser light source and the laminate are adjusted such that a virtual wafer is positioned at the center of the laser beam spot, thereby preventing the laser beam from illuminating adjacent virtual wafers.

[0130] For a virtual wafer positioned at the laser irradiation location, laser light with wavelengths of 248 nm, 266 nm, 208 nm, 355 nm, 536 nm, or 1064 nm was simultaneously irradiated at energy densities ranging from 150 mJ / cm² to 400 mJ / cm², varying in 50 mJ / cm² increments. Transfer experiments were conducted on three virtual wafers at each energy density.

[0131] (8)-3 Evaluation of transferability The opposing substrates were observed after laser irradiation, and the number of virtual wafers that could be confirmed to have been transferred to substrate 2 was measured out of the three virtual wafers. In addition, the virtual wafers transferred to the opposing substrates were confirmed using a microscope. Among the energy densities of each laser beam, a case in which no wafer was damaged was evaluated as no wafer damage, and a case in which even one wafer with a crack, notch, or fissure was observed was evaluated as wafer damage.

[0132] (8)-4 Evaluation of Position Accuracy The positions of the semiconductor elements on the opposing substrate after transfer are calculated based on the alignment marks on the opposing substrate and compared with the positions in the stack 2. For the wafer with the largest positional deviation during the transfer process in units of 3 at each energy density, the positional accuracy is determined as follows: If the positional deviation is less than ±5 μm in the X-axis direction and less than ±5 μm in the Y-axis direction, the positional accuracy is set to A; if the positional deviation is greater than ±10 μm in the X-axis direction or greater than ±10 μm in the Y-axis direction, the positional accuracy is set to C; and if the deviation is in between, the positional accuracy is set to B.

[0133] (8)-5 Evaluation of residual adhesive The transferred wafers were not cleaned after laser irradiation. Instead, they were observed using an optical microscope. The area of ​​residual adhesive on either resin film 1 or resin film 2 at the contact surface between the virtual wafer and resin film 2 was confirmed. The average area of ​​residual adhesive on the contact surface between the transferred wafers and resin film 2 was calculated at each energy density, with the surface area of ​​the contact surface of each wafer with resin film 2 set to 100%. As a result, if the average residual adhesive area was 0% or more and less than 1%, the residual adhesive was designated as A; if it was 1% or more and less than 30%, the residual adhesive was designated as B; and if it was 30% or more, the residual adhesive was designated as C.

[0134] (8)-6 Evaluation of debris The opposing substrates after laser irradiation are not cleaned. Optical microscopy is used to observe and measure foreign matter larger than 1 μm observed on the surface of the adhesive layer surrounding the transferred virtual wafer. At various energy densities, the average value of the transferred wafer is calculated. If there are fewer than 10 pieces, the debris is designated A; if there are 10 to 50 pieces, the debris is designated B; and if there are more than 50 pieces, the debris is designated C. Furthermore, if there are debris larger than 50 μm, regardless of the number of pieces, it is designated C.

[0135] (8)-7 Evaluation of processing margin For the evaluations in (8)-3 to (8)-6, if the three virtual wafers can be transferred to the wafers of the substrate 2 without wafer breakage, and the evaluation of the transfer position accuracy, residual adhesive, and debris is A or B, it is judged that the transfer is good at that energy density, and the range of energy densities that can be transferred well is evaluated. If the energy range is 100 mJ / cm2 or higher, the processing margin is set to A; if it is 50 mJ / cm2 or higher but less than 100 mJ / cm2, the processing margin is set to B; if it is less than 50 mJ / cm2, the processing margin is set to C.

[0136] (9) Method for determining the solid content of resin solutions Approximately 1 g of the resin solution prepared using the method described later was measured into an aluminum cup, placed on a heating plate at 120°C, and heated for 3 minutes. The temperature was then increased to 250°C and heated for 30 minutes after reaching 250°C. The weight of the resin residue after heating was measured, and the solid content was calculated using the following formula. Solid content (weight %) = weight of the heated resin (g) / weight of the resin solution before heating (g) × 100.

[0137] The abbreviated names of the acid dianhydrides, diamines, additives, and solvents shown in the following manufacturing examples are as follows. PMDA: Pyromellitic anhydride (manufactured by Daicel Inc.) BPDA: 3,3',4,4'-Biphenyltetracarboxylic anhydride (manufactured by Mitsubishi Chemical Co., Ltd.) BTDA: 3,3',4,4'-benzophenone tetracarboxylic anhydride (manufactured by Fujifilm and Hikari Pure Chemicals Co., Ltd.) DIBOC: Di-tert-butyl dicarbonate (manufactured by Tokyo Chemical Industry Co., Ltd.) PA: Phthalic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) PDA: p-Phenylenediamine (manufactured by Tokyo Chemical Industries, Ltd.) BAHF: 4,4'-Dihydroxy-3,3'-Diaminophenylhexafluoropropane (manufactured by Merck). 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)) (manufactured by Shin-Etsu Chemical Co., Ltd.) NMP: 2-Methyl-1-pyrrolidone (manufactured by Mitsubishi Chemical Co., Ltd.) DMIB: N,N-Dimethylisobutylamide (manufactured by Mitsubishi Chemical Co., Ltd.) CHN: Cyclohexanone (manufactured by Toyo Synthetic Industries, Ltd.) TPX1291: Carbon Black (manufactured by Cabot) BYK21116: Polymer dispersant (manufactured by BYK-Chemie) JER871: Dimer acid modified epoxy resin (manufactured by Mitsubishi Chemical Co., Ltd.) PETG: Pentaerythritol-based skeletal epoxy resin (manufactured by Showa Denko Co., Ltd.) 2E4MZ: 2-Ethyl-4-methylimidazole (manufactured by Shikoku Chemical Industries, Ltd.) 100LM: The following structure represents a crosslinking agent containing an alkoxymethyl group (manufactured by Sanwa Chemical Co., Ltd.).

[0138] [Chemistry 4]

[0139] Manufacturing Example 1 (Polymerization of the resin contained in resin film 1) In a reactor equipped with a thermometer, a dry nitrogen inlet, a heating / cooling device using warm / cooling water, and a stirrer, 11.82 g (0.109 mol) of PDA and 195.8 g of DMIB were added and dissolved. While stirring, a solution of 0.48 g (2.19 mmol) of DIBOC and 26.1 g of DMIB was added dropwise, 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 solid content of 13% by weight. The monomer residues with aromatic ring structures in PAA-1 are 99.5 mol% of all monomer residues per 100 mol%. PAA-1 is a resin having the structure of formula (2).

[0140] Manufacturing Example 2 (Polymerization of the resin contained in resin film 1) In a reactor equipped with a thermometer, a dry nitrogen inlet, a heating / cooling device using warm / cooling water, and a stirrer, 127.5 g (0.150 mol) of APPS2 and 866 g of NMP were added and dissolved at 40°C. Then, 37.85 g (0.350 mol) of PDA and 113.5 g of NMP were added and dissolved. Next, 73.56 g (0.250 mol) of BPDA, 95.06 g (0.295 mol) of BTDA, and 223.5 g of NMP were added together. The reaction was carried out at 60°C for 4 hours to obtain a polyimide precursor PAA-2 solution with a solid content of 25% by weight. The monomer residues with aromatic ring structures in PAA-2 were 85 mol% of all monomer residues per 100 mol%. PAA-2 is a resin having the structures of formulas (2) and (5).

[0141] Manufacturing Example 3 (Polymerization of the resin contained in resin film 2) In a reactor equipped with a thermometer, a dry nitrogen inlet, a heating / cooling device using warm / cooling water, and a stirrer, 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 were added along with 481.4 g of CHN and dissolved. Then, 14.81 g (0.10 mol) of PA and 20.00 g of CHN were added, and the mixture was stirred at 60°C for 15 minutes. Subsequently, 97.61 g (0.45 mol) of PMDA and 20.00 g of CHN were added, and the mixture was stirred at 60°C for 1 hour. The temperature was then raised to 145°C and reacted for 4 hours to obtain a polyimide silicate PIS-1 solution with a solid content of 50% by weight. The monomer residues in PIS-1 with a soft structure are 43 mol% of all monomer residues per 100 mol%. PIS-1 is a resin having the structures of formula (1) and formula (5).

[0142] Manufacturing Example 4 (Polymerization of the resin contained in resin film 2) In a reactor equipped with a thermometer, a dry nitrogen inlet, a heating / cooling device using warm / cooling water, and a stirrer, 254.56 g (0.296 mol) of APPS2, 28.68 g (0.019 mol) of APPS3, and 20.33 g (0.056 mol) of BAHF were added along with 310.56 g of CHN and dissolved. Then, 16.44 g (0.111 mol) of PA and 38.82 g of CHN were added, and the mixture was stirred at 60°C for 15 minutes. Subsequently, 68.20 g (0.312 mol) of PMDA and 38.82 g of CHN were added, and the mixture was stirred at 60°C for 1 hour. The temperature was then raised to 145°C and reacted for 4 hours to obtain a polyimide silicate PIS-2 solution with a solid content of 50% by weight. The monomer residues with a soft structure in PIS-2 are 40 mol% of all monomer residues per 100 mol%. PIS-2 is a resin having the structures of formula (1) and formula (5). Manufacturing Example 5 (Polymerization of the resin contained in resin film 2) In a reactor equipped with a thermometer, a dry nitrogen inlet, a heating / cooling device using warm / cooling water, and a stirrer, 39.04 g (0.033 mol) of elasmer 650P and 131.69 g of NMP were added and dissolved at 40°C. Then, 8.25 g (0.076 mol) of PDA and 16.42 g of NMP were added and dissolved. Next, 15.87 g (0.054 mol) of BPDA, 17.39 g (0.054 mol) of BTDA, and 16.42 g of NMP were added together. The reaction was carried out at 60°C for 4 hours to obtain a polyimide precursor PAA-3 solution with a solid content of 30% by weight. The monomer residues with aromatic ring structures in PAA-3 were 84.9 mol% of all monomer residues per 100 mol%. PAA-3 is a resin having the structures of formula (2) and formula (7).

[0143] Manufacturing Example 6 (Preparation of carbon black dispersion contained in resin membrane 1) Using the method described in the literature (Japanese Patent No. 3120476), a methyl methacrylate / methacrylic acid / styrene copolymer (weight ratio 30 / 40 / 30) was synthesized, followed by the addition of 40 parts by weight of glycidyl methacrylate. The mixture was then subjected to reprecipitation with purified water, filtration, and drying 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). In a tank, 187.5 g of a 40% by weight solution of propylene glycol monomethyl ether acetate of acrylic resin (P-1), 62.5 g of a polymeric dispersant (BYK21116; manufactured by BYK-Chemie, Inc.), and 890 g of propylene glycol monoethyl ether acetate were added to 400 g of TPX1291. The mixture was stirred for 1 hour using a homogenizer (manufactured by Special Machinery) to obtain a pre-dispersion liquid 1. Subsequently, pre-dispersion liquid 2 was supplied to an Ultra Apex Mill (manufactured by Kosei Kogyo) containing a centrifugal separator filled with 70% 0.10 mm ϕ zirconia beads (manufactured by Toray) and dispersed at a rotation speed of 8 m / s for 2 hours to obtain carbon black pigment dispersion Bk-1 with a solid content concentration of 25% by weight and a pigment / resin (weight ratio) of 80 / 20.

[0144] Examples 1 to 23, Comparative Examples 1 to 2 In the resin solutions obtained in Manufacturing Examples 1 to 5, the carbon black dispersion or additives and solvent obtained in Manufacturing Example 6 were mixed and stirred according to Table 1 to prepare varnishes for resin membrane 1 and resin membrane 2. The varnishes were filtered using a polytetrafluoroethylene (PTFE) filter with a pore size of 0.2 μm. Using these varnishes, laminates were prepared using the method described above. Details of the prepared laminates and various evaluation results are summarized in Tables 2 to 5.

[0145] [Table 1] [Table 1] use Varnish Name resin solution additive solvent type weight The resin contains Specific structure type weight type weight type weight type weight Resin film 1 Forming Varnish 1-1 PAA-1 3.85 g Equation (2) - - - NMP 6.15 g varnish 1-2 PAA-2 6.00 g Equation (2) Equation (5) - - - NMP 4.00 g Varnish 1-3 PAA-2 10.00 g Equation (2) Equation (5) - - - - Varnish 1-4 PAA-1 6.73 g Equation (2) Bk-1 0.50 g - - NMP 2.77 g Resin film 2 Forming Varnish 2-1 PIS-1 3.28 g Equation (1) Equation (5) JER871 0.33 g 100LM 0.02 g 2E4MZ 0.02 g CHN 6.36 g varnish 2-2 PIS-2 3.58 g Equation (1) Equation (5) JER871 0.18 g 100LM 0.02 g 2E4MZ 0.02 g CHN 6.21 g 2-3 varnishes PIS-2 7.14 g Equation (1) Equation (5) JER871 0.36 g 100LM 0.04 g 2E4MZ 0.04 g CHN 2.43 g varnish 2-4 PIS-2 7.14 g Equation (1) Equation (5) PETG 0.36 g 100LM 0.04 g 2E4MZ 0.04 g CHN 2.43 g varnish 2-5 PIS-2 6.84 g Equation (1) Equation (5) PETG 0.51 g 100LM 0.03 g 2E4MZ 0.03 g CHN 2.58 g Varnish 2-6 PIS-2 8.00 g Equation (1) Equation (5) - - - CHN 2.00 g Varnish 2-7 PAA-3 5.00 g Equation (2) Equation (7) - - - NMP 5.00 g Varnish 2-8 PAA-3 5.00 g Equation (2) Equation (7) - - - NMP 5.00 g

[0146] [Table 2-1] [Table 2-1] Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Laser-transmitting substrate 1 type - Alkali-free glass Alkali-free glass Alkali-free glass Alkali-free glass Alkali-free glass Alkali-free glass Resin film 1 physical properties Varnish - varnish 1-2 varnish 1-2 Varnish 1-1 Varnish 1-3 varnish 1-2 Varnish 1-3 Film forming conditions ℃ / minute 180 / 30 180 / 30 180 / 30 180 / 30 180 / 30 180 / 30 Absorbance at 248 nm / μm - 2.45 2.45 4.53 2.45 2.45 2.45 Absorbance at 266 nm / μm - 2.09 2.09 4.79 2.09 2.09 2.09 Absorbance at 308 nm / μm - 2.61 2.61 3.59 2.61 2.61 2.61 Absorbance at 355 nm / μm - 1.68 1.68 1.90 1.68 1.68 1.68 Absorbance at 532 nm / μm - 0.00 0.00 0.05 0.00 0.00 0.00 Absorbance of 1064 nm / μm - 0.00 0.00 0.03 0.00 0.00 0.00 Elongation at break % 1.5 1.5 1.8 1.5 1.5 1.5 t1 μm 2.0 2.0 30.0 30.0 0.3 10.0 Resin film 2 physical properties Varnish - varnish 2-4 2-3 varnishes varnish 2-2 varnish 2-2 varnish 2-2 2-3 varnishes Film forming conditions ℃ / minute 180 / 10 180 / 10 18.0 180 / 10 180 / 10 180 / 10 Elongation at break % 1,050 1,200 1,200 1,200 1,200 1,200 t2 μm 30 30 0.5 5.0 1.0 15 1% weight reduction in temperature ℃ 287 285 285 285 285 285 laminated body physical properties The resin film 2 in the laminate 1 is on the side opposite to the resin film 1. Adhesion strength on the opposite side surface N / cm 0.03 0.28 0.06 0.07 0.07 0.09 The resin film 2 in the laminate 2 is on the side opposite to the resin film 1. Adhesion strength on the opposite side surface N / cm 0.03 0.28 0.06 0.07 0.07 0.09 Indentation hardness H1 MPa 3.8 3.8 330 3.8 3.8 3.8 Indentation hardness H2 MPa 1.8 1.4 290 2.0 2.6 2.1 Does H1 > H2? conform to conform to conform to conform to conform to conform to (t1+t2) μm 32 32 31 35 1.3 25 t1 / t2 - 0.07 0.07 60 6.0 0.30 0.67 chip Layering results Number of stacked wafers indivual 88 100 95 98 98 99 In the stacked wafer Number of undamaged chips indivual 88 100 93 98 98 99

[0147] [Table 2-2] [Table 2-2] Example 7 Example 8 Example 9 Example 10 Example 11 Example 12 Laser-transmitting substrate 1 type - Alkali-free glass Alkali-free glass Alkali-free glass Alkali-free glass Alkali-free glass Alkali-free glass Resin film 1 physical properties Varnish - varnish 1-2 varnish 1-2 Varnish 1-1 Varnish 1-1 Varnish 1-1 Varnish 1-1 Film forming conditions ℃ / minute 180 / 30 180 / 30 500 / 60 (Under nitrogen atmosphere) 250 / 30 500 / 10 (Under nitrogen atmosphere) 250 / 30 Absorbance at 248 nm / μm - 2.45 2.45 4.53 4.49 4.49 4.53 Absorbance at 266 nm / μm - 2.09 2.09 4.79 4.81 4.66 4.79 Absorbance at 308 nm / μm - 2.61 2.61 3.59 3.65 3.46 3.59 Absorbance at 355 nm / μm - 1.68 1.68 1.90 1.92 1.83 1.90 Absorbance at 532 nm / μm - 0.00 0.00 0.05 0.06 0.04 0.05 Absorbance of 1064 nm / μm - 0.00 0.00 0.03 0.03 0.03 0.03 Elongation at break % 1.5 1.5 28 12 3.0 10 t1 μm 2.0 2.0 2.0 2.0 2.0 2.0 Resin film 2 physical properties Varnish - varnish 2-2 varnish 2-2 varnish 2-2 varnish 2-2 varnish 2-2 varnish 2-2 Film forming conditions ℃ / minute 180 / 10 180 / 10 180 / 10 180 / 10 180 / 10 180 / 10 Elongation at break % 1,200 1,200 1,200 1,200 1,200 1,200 t2 μm 5.0 0.5 5.0 5.0 5.0 5.0 1% weight reduction in temperature ℃ 285 285 285 285 285 285 laminated body physical properties The resin film 2 in the laminate 1 is on the side opposite to the resin film 1. Adhesion strength on the opposite side surface N / cm 0.07 0.05 0.07 0.07 0.07 0.07 The resin film 2 in the laminate 2 is on the side opposite to the resin film 1. Adhesion strength on the opposite side surface N / cm 0.07 0.05 0.07 0.07 0.07 0.07 Indentation hardness H1 MPa 3.8 3.8 1,150 600 950 56 Indentation hardness H2 MPa 2.0 2.3 2.0 2.0 2.0 2.0 Does H1 > H2? conform to conform to conform to conform to conform to conform to (t1+t2) μm 7.0 2.5 7.0 7.0 7.0 7.0 t1 / t2 - 0.40 4.0 0.40 0.40 0.40 0.40 chip Layering results Number of stacked wafers indivual 98 95 98 99 95 98 In the stacked wafer Number of undamaged chips indivual 98 95 98 98 95 98

[0148] [Table 3-1] [Table 3-1] Example 13 Example 14 Example 15 Example 16 Example 17 Example 18 Example 19 Laser-transmitting substrate 1 type - Alkali-free glass Alkali-free glass Alkali-free glass Alkali-free glass Alkali-free glass Alkali-free glass quartz Resin film 1 physical properties Varnish - Varnish 1-1 Varnish 1-1 Varnish 1-1 Varnish 1-1 Varnish 1-1 Varnish 1-1 Varnish 1-1 Film forming conditions ℃ / minute 250 / 30 250 / 30 250 / 30 250 / 30 250 / 30 250 / 30 250 / 30 Absorbance at 248 nm / μm - 4.53 4.53 4.53 4.53 4.53 4.53 4.53 Absorbance at 266 nm / μm - 4.79 4.79 4.79 4.79 4.79 4.79 4.79 Absorbance at 308 nm / μm - 3.59 3.59 3.59 3.59 3.59 3.59 3.59 Absorbance at 355 nm / μm - 1.90 1.90 1.90 1.90 1.90 1.90 1.90 Absorbance at 532 nm / μm - 0.05 0.05 0.05 0.05 0.05 0.05 0.05 Absorbance of 1064 nm / μm - 0.03 0.03 0.03 0.03 0.03 0.03 0.03 Elongation at break % 10 10 10 10 10 10 10 t1 μm 2.0 2.0 2.0 2.0 2.0 5.0 2.0 Resin film 2 physical properties Varnish - Varnish 2-7 Varnish 2-7 Varnish 2-1 varnish 2-4 Varnish 2-1 Varnish 2-1 Varnish 2-1 Film forming conditions ℃ / minute 180 / 10 250 / 10 180 / 10 180 / 10 225 / 10 225 / 10 225 / 10 Elongation at break % 80 120 550 900 500 500 500 t2 μm 5.0 5.0 5.0 5.0 5.0 5.0 5.0 1% weight reduction in temperature ℃ 285 285 285 290 369 369 369 laminated body physical properties The resin film 2 in the laminate 1 is on the side opposite to the resin film 1. Adhesion strength on the opposite side surface N / cm 0.03 0.03 0.06 0.04 0.06 0.06 0.06 The resin film 2 in the laminate 2 is on the side opposite to the resin film 1. Adhesion strength on the opposite side surface N / cm 0.03 0.03 0.06 0.04 0.06 0.06 0.06 Indentation hardness H1 MPa 330 330 330 330 330 330 330 Indentation hardness H2 MPa 16 43 2.2 2.1 2.3 2.3 2.3 Does H1 > H2? conform to conform to conform to conform to conform to conform to conform to (t1+t2) μm 7.0 7.0 7.0 7.0 7.0 10 7.0 t1 / t2 - 0.40 0.40 0.40 0.40 0.40 1.0 0.40 chip Layering results Number of stacked wafers indivual 90 90 96 97 97 97 96 In the stacked wafer Number of undamaged chips indivual 90 88 96 97 97 97 96

[0149] [Table 3-2] [Table 3-2] Example 20 Example 21 Example 22 Example 23 Comparative Example 1 Comparative Example 2 Laser-transmitting substrate 1 type - quartz quartz Alkali-free glass Alkali-free glass Alkali-free glass Alkali-free glass Resin film 1 physical properties Varnish - Varnish 1-1 Varnish 1-1 Varnish 1-4 Varnish 1-4 varnish 1-2 varnish 1-2 Film forming conditions ℃ / minute 250 / 30 250 / 30 250 / 30 250 / 30 180 / 30 180 / 30 Absorbance at 248 nm / μm - 4.53 4.53 5.10 5.10 2.45 2.45 Absorbance at 266 nm / μm - 4.79 4.79 5.33 5.33 2.09 2.09 Absorbance at 308 nm / μm - 3.59 3.59 4.42 4.42 2.61 2.61 Absorbance at 355 nm / μm - 1.90 1.90 2.19 2.19 1.68 1.68 Absorbance at 532 nm / μm - 0.05 0.05 0.46 0.46 0.00 0.00 Absorbance of 1064 nm / μm - 0.03 0.03 0.42 0.42 0.00 0.00 Elongation at break % 10 10 10 10 1.5 1.5 t1 μm 2.0 2.0 2.0 2.0 2.0 2.0 Resin film 2 physical properties Varnish - Varnish 2-1 Varnish 2-1 Varnish 2-1 Varnish 2-1 varnish 2-5 Varnish 2-6 Film forming conditions ℃ / minute 225 / 10 225 / 10 225 / 10 225 / 10 180 / 10 180 / 10 Elongation at break % 500 500 500 500 1,020 1,500 t2 μm 5.0 5.0 5.0 5.0 30 30 1% weight reduction in temperature ℃ 369 369 369 369 280 290 laminated body physical properties The resin film 2 in the laminate 1 is on the side opposite to the resin film 1. Adhesion strength on the opposite side surface N / cm 0.06 0.06 0.08 0.08 0.01 0.36 The resin film 2 in the laminate 2 is on the side opposite to the resin film 1. Adhesion strength on the opposite side surface N / cm 0.06 0.06 0.08 0.08 0.01 0.36 Indentation hardness H1 MPa 330 330 330 330 3.8 3.8 Indentation hardness H2 MPa 2.3 2.3 2.2 2.3 1.6 0.5 Does H1 > H2? conform to conform to conform to conform to conform to conform to (t1+t2) μm 7.0 7.0 7.0 7.0 32 32 t1 / t2 - 0.40 0.40 0.40 0.40 0.07 0.07 chip Layering results Number of stacked wafers indivual 97 98 98 99 0 100 In the stacked wafer Number of undamaged chips indivual 96 97 97 99 0 100

[0150] [Table 4-1] [Table 4-1] Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 chip Transfer result wavelength of laser light nm 355 355 355 355 355 355 Laser light irradiation Energy density (mJ / cm 2) 150 Number of transfer chips 1 0 1 2 2 2 chip damage none No rating none none none none Position accuracy C C C B C Residual glue B C C C B Debris B B B B B 200 Number of transfer chips 2 1 2 2 3 3 chip damage none none none none none none Position accuracy C C B B A A Residual glue B B B B B B Debris B B B B B B 250 Number of transfer chips 3 3 3 3 3 3 chip damage none none none none none none Position accuracy B A B B A A Residual glue B B B B B B Debris B B B B B B 300 Number of transfer chips 3 3 3 3 3 3 chip damage none none none none none none Position accuracy B B B B A A Residual glue B B B B B B Debris B B B B B B 350 Number of transfer chips 3 3 3 3 3 3 chip damage none none none none none none Position accuracy B B B B A A Residual glue B C B B B B Debris C C C B B B 400 Number of transfer chips 3 3 3 3 3 3 chip damage have have have have have none Position accuracy B B B B A A Residual glue B C C C B B Debris C C C C C B Processing margin mJ / cm 2 250~300 250~300 200~300 200~350 200~350 200~400 evaluate B B A A A A

[0151] [Table 4-2] [Table 4-2] Example 7 Example 8 Example 9 Example 10 Example 11 Example 12 chip Transfer result wavelength of laser light nm 355 355 355 355 355 355 Laser light irradiation Energy density (mJ / cm 2) 150 Number of transfer chips 2 2 3 3 3 3 chip damage none none none none none none Position accuracy B B B B B B Residual glue A A A A A A Debris A A A A A A 200 Number of transfer chips 3 3 3 3 3 3 chip damage none none none none none none Position accuracy A B B A A A Residual glue B A B A B B Debris B B B A B B 250 Number of transfer chips 3 3 3 3 3 3 chip damage none none none none none none Position accuracy B B A A A A Residual glue B B B B B B Debris B B B B B B 300 Number of transfer chips 3 3 3 3 3 3 chip damage none none none none none none Position accuracy B B A A A A Residual glue B B B B B B Debris B B B B B B 350 Number of transfer chips 3 3 3 3 3 3 chip damage none none none none none none Position accuracy A A A A A A Residual glue B B B A B B Debris B A B B B B 400 Number of transfer chips 3 3 3 3 3 3 chip damage none none none none none none Position accuracy A A A A A A Residual glue B A B B A B Debris B B B B B B Processing margin mJ / cm 2 150~400 150~400 150~400 150~400 150~400 150~400 evaluate A A A A A A

[0152] [Table 5-1] [Table 5-1] Example 13 Example 14 Example 15 Example 16 Example 17 Example 18 Example 19 chip Transfer result wavelength of laser light nm 355 355 355 355 355 355 266 Laser light irradiation Energy density (mJ / cm 2) 150 Number of transfer chips 3 3 3 3 3 3 3 chip damage none none none none none none none Position accuracy B B B B A A A Residual glue A A A A A A A Debris A A A A A A A 200 Number of transfer chips 3 3 3 3 3 3 3 chip damage none none none none none none none Position accuracy A A A A A A A Residual glue A A A A A A A Debris A A A A A A A 250 Number of transfer chips 3 3 3 3 3 3 3 chip damage none none none none none none none Position accuracy A A A A A A A Residual glue A A A A A A A Debris A A A A A A A 300 Number of transfer chips 3 3 3 3 3 3 3 chip damage none none none none none none none Position accuracy A A A A A A A Residual glue A A A A A A A Debris B A A A A A A 350 Number of transfer chips 3 3 3 3 3 3 3 chip damage none none none none none none none Position accuracy A A A A A A A Residual glue A A A A A A A Debris B B B B A A A 400 Number of transfer chips 3 3 3 3 3 3 3 chip damage none none none none none none none Position accuracy A A A A A A A Residual glue B B B B A A A Debris C B B B A A A Processing margin mJ / cm 2 150~350 150~400 150~400 150~400 150~400 150~400 150~400 evaluate A A A A A A A

[0153] [Table 5-2] [Table 5-2] Example 20 Example 21 Example 22 Example 23 Comparative Example 1 Comparative Example 2 chip Transfer result wavelength of laser light nm 248 308 532 1,064 355 355 Laser light irradiation Energy density (mJ / cm 2) 150 Number of transfer chips 3 3 3 3 Unable to be applied to resin film 2 The multilayer wafer was therefore not evaluated. 0 chip damage none none none none Unable to transfer Therefore, no evaluation was given. Position accuracy A A B B Residual glue A B A A Debris A A A A 200 Number of transfer chips 3 3 3 3 0 chip damage none none none none Unable to transfer Therefore, no evaluation was given. Position accuracy A A B B Residual glue A A A A Debris A A A A 250 Number of transfer chips 3 3 3 3 0 chip damage none none none none Unable to transfer Therefore, no evaluation was given. Position accuracy A A B B Residual glue A A A A Debris A A A A 300 Number of transfer chips 3 3 3 3 0 chip damage none none none none Unable to transfer Therefore, no evaluation was given. Position accuracy A A A B Residual glue A A A A Debris A A A A 350 Number of transfer chips 3 3 3 3 0 chip damage none none none none Unable to transfer Therefore, no evaluation was given. Position accuracy A A A A Residual glue A A A A Debris B A A A 400 Number of transfer chips 3 3 3 3 1 chip damage none none none none have Position accuracy A A A A C Residual glue A B A A C Debris B A A A C Processing margin mJ / cm 2 150~400 150~400 150~400 150~400 No rating <50 evaluate A A A A C C

[0154] 11: Substrate 1 with laser transmittance 12: Resin film 1 13: Resin film 2 14: Semiconductor components 15: Support 16: Temporary adhesive 17: Substrate for crystal growth 18: Semiconductor substrate 21:Substrate 2 31: Laser light 41: Crimping device 51: Light Mask 110: Laminated body 1 120: Laminated body 2 130: Temporary bonding of semiconductor components to substrate 140: Substrate with semiconductor components

Claims

1. A laminate comprising a laser-transmittable substrate 1, a resin film 1, and a resin film 2 sequentially laminated thereon, wherein the absorbance of the resin film 1 at any wavelength from 200 nm to 1100 nm, when converted to a film thickness of 1.0 μm, is 0.4 or more and 5.0 or less, and the adhesion strength obtained by a 90° peel test of the surface of the resin film 2 opposite to the resin film 1 with a Kapton film satisfies 0.02 N / cm or more and 0.3 N / cm or less.

2. A laminate comprising, sequentially stacked, a laser-transparent substrate 1, a resin film 1, a resin film 2, and a semiconductor element, wherein the absorbance of the resin film 1 at any wavelength from 200 nm to 1100 nm, when converted to a film thickness of 1.0 μm, is 0.4 or more and 5.0 or less, and the adhesion strength of the surface of the resin film 2 in contact with the semiconductor element is 0.02 N / cm or more and 0.3 N / cm or less.

3. The laminate as claimed in claim 1 or claim 2, wherein the absorbance of the resin film 1 at any wavelength of 248 nm, 266 nm, 308 nm, 355 nm, 532 nm and 1064 nm, when converted to a film thickness of 1.0 μm, is 0.4 or more and 5.0 or less.

4. The laminate as claimed in claim 3, wherein the absorbance of the resin film 1 at any wavelength of 248 nm, 266 nm and 355 nm, when converted to a film thickness of 1.0 μm, is 0.4 or more and 5.0 or less.

5. The laminate as claimed in claim 1 or claim 2, wherein the indentation hardness H2, measured by pressing from the resin film 2 side to the substrate 1 side, is 2 MPa or more and 500 MPa or less, and satisfies H1 > H2 relative to the indentation hardness H1 measured by pressing from the resin film 1 side to the substrate 1 side in the state after the resin film 2 has been removed from the laminate.

6. The laminate as claimed in claim 1 or claim 2, wherein when the thickness of the resin film 1 is set to t1 (μm) and the thickness of the resin film 2 is set to t2 (μm), (t1+t2) is 1.0 μm or more and 30 μm or less, and t1 / t2 is 0.1 or more and 5.0 or less.

7. The laminate as claimed in claim 1 or claim 2, wherein the elongation at break of the resin film 1 is 2.0% or more and 30% or less.

8. The laminate as claimed in claim 1 or claim 2, wherein the indentation hardness H1, measured by pressing from the resin film 1 side to the substrate 1 side, is 50 MPa or more and 1000 MPa or less.

9. The laminate as claimed in claim 1 or claim 2, wherein the elongation at break of the resin film 2 is 100% or more and 1000% or less.

10. The laminate as claimed in claim 1 or claim 2, wherein the resin film 1 contains one or more of 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 copolymers thereof, wherein in formulas (1) to (4), R1, R3, R7 and R9 each independently represent a tetravalent organic group having 6 to 40 carbon atoms, R2, R4, R6 and R8 each independently represent a divalent organic group having 2 to 40 carbon atoms, and R5 represents a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms.

11. The laminate as claimed in claim 1 or claim 2, wherein the resin contained in the resin film 2 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 alkyldiol structure represented by formula (7), and an alkylene structure represented by formula (8), wherein in formulas (5) to (8), R10 to R13 independently represent hydrogen atoms or monovalent organic groups having 1 to 20 carbon atoms; l, m, and n independently represent integers from 4 to 40; p represents integers from 10 to 40; and o represents integers from 1 to 16.

12. The laminate as claimed in claim 1 or claim 2, wherein the resin contained in the resin film 2 is polyimide silicate.

13. The laminate as claimed in claim 1 or claim 2, wherein the resin film 2 contains a crosslinking agent.

14. The laminate as claimed in claim 1 or claim 2, wherein the temperature at which 1% weight reduction of the resin film 2 occurs is above 300°C.

15. A method for manufacturing a semiconductor device using a multilayer as described in claim 2, the method comprising: a step of positioning the semiconductor element face of the multilayer facing a substrate 2; and a step of irradiating the multilayer with laser light from a laser-transmittable substrate 1 side to transfer the semiconductor element onto the substrate 2.

16. A method of manufacturing a semiconductor device as claimed in claim 15, wherein the laser light has a wavelength of any one of 248 nm, 266 nm, 308 nm, 355 nm, 532 nm and 1064 nm.

17. A method of manufacturing a semiconductor device as claimed in claim 15 or claim 16, wherein the substrate 2 is a circuit substrate.

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