Laser release layer material and method of making and use thereof

Abstract

The application provides a laser release layer material and a preparation method and application thereof. The laser release layer material comprises the following components in parts by weight: 10-30 parts of a thermoplastic resin, 0.5-4 parts of inorganic nanoparticles and 0.5-4 parts of a light response filler. The UV-vis transmittance of the light response filler is 0.001%-10%. The laser release layer material is prepared by designing the material of the laser release layer, further using the thermoplastic resin, cooperating with the inorganic nanoparticles and the light response filler with a specific UV absorption value. The laser release layer material has excellent performance. After the laser release layer prepared from the laser release layer material is debonded, the laser release layer material remaining on the wafer surface can be cleaned together with the adhesive layer, the production efficiency is accelerated, and the types of cleaning agents are reduced.

Description

Technical Field

[0001] This invention belongs to the field of laser emission materials technology, specifically relating to a laser emission layer material, its preparation method, and its application. Background Technology

[0002] The processing of semiconductor wafers (hereinafter referred to as wafers) usually involves multiple steps, so it is necessary to switch and transfer the wafer between different processing steps. Generally speaking, the wafer needs to be picked up and attached by a carrier and then moved. After the steps are completed, the wafer needs to be separated from the carrier.

[0003] In existing processes, a release layer is typically placed between the carrier and the wafer. When necessary, the release layer can soften and dissociate under light of a corresponding wavelength, allowing the carrier and wafer to be quickly separated by external force. The separated wafer is then transferred to a blue film material that provides some support to the wafer and prevent damage. Finally, a cleaning agent is used to remove any remaining release layer and adhesive layer material from the wafer surface, completing the wafer transfer.

[0004] Currently, most of the adhesive layer materials used in wafer transfer processes are low-polarity resins, while the release layer materials are polar resin systems. This makes cleaning the adhesive layer materials and release layer materials after debonding very complicated, requiring the use of solvents with different polarities. The polar solvents used to clean the release layer residue can corrode the blue film supporting the wafer, causing it to lose its supporting function and resulting in wafer damage, which in turn leads to a decrease in wafer yield.

[0005] Therefore, how to provide a release layer material that can be used in conjunction with polar blue film, so that the release layer residue and adhesive layer material remaining on the wafer surface after debonding can be cleaned and removed simultaneously without damaging the supporting blue film, thereby accelerating production efficiency and reducing the types of cleaning agents used, has become an urgent technical problem to be solved. Summary of the Invention

[0006] To address the shortcomings of existing technologies, the present invention aims to provide a laser emission layer material, its preparation method, and its applications. This invention designs the laser emission layer material and, through the use of thermoplastic resin, combines it with inorganic nanoparticles and photoresponsive fillers with specific UV absorption values ​​to prepare a high-performance laser emission layer material. After debonding, the laser emission layer material remaining on the wafer surface can be cleaned along with the adhesive layer, accelerating production efficiency, reducing the types of cleaning agents used, and without damaging the supporting blue film.

[0007] To achieve this objective, the present invention adopts the following technical solution:

[0008] In a first aspect, the present invention provides a laser emission layer material, the laser emission layer material comprising the following components in parts by weight:

[0009] 10-30 parts thermoplastic resin, 0.5-4 parts inorganic nanoparticles, and 0.5-4 parts photoresponsive filler;

[0010] The UV-vis transmittance of the photoresponsive filler is 0.001%-10%.

[0011] This invention designs the laser-emitting layer material and further utilizes thermoplastic resin in conjunction with inorganic nanoparticles and photoresponsive fillers with specific UV absorption values ​​to prepare a high-performance laser-emitting layer material with photosensitive properties. This allows the laser-emitting layer prepared from this material to absorb laser light of a specific wavelength for debonding. Furthermore, the laser-emitting layer material remaining on the wafer surface after debonding can be cleaned together with the adhesive layer, accelerating production efficiency, reducing the types of cleaning agents used, and without damaging the supporting blue film.

[0012] In this invention, inorganic nanoparticles serve as the supporting material, facilitating the debonding of bond pairs. The photoresponsive filler undergoes changes upon exposure to light, absorbing the irradiated light. Light absorption leads to the degradation of the laser-emitting layer, causing it to lose its strength or adhesion after exposure to light. This degradation is caused by factors such as energy absorption, decomposition (exothermic or non-exothermic), cross-linking, configurational changes, dissociation of functional groups (and accompanying separation), layer hardening, degassing, shrinkage, or swelling.

[0013] In this invention, inorganic nanoparticles provide support for the laser emission layer; photoresponsive fillers enable the laser emission layer to have photoresponsive properties; the combined use of inorganic nanoparticles and photoresponsive fillers allows the laser emission layer to absorb laser light of a specific wavelength for debonding.

[0014] In this invention, a laser-emitting layer material with excellent comprehensive performance was prepared by controlling the amounts of inorganic nanoparticles and photoresponsive fillers within specific ranges. If the amount of inorganic nanoparticles is too small, the laser-emitting layer will have a photoresponse during debonding, but it will not be able to debond smoothly; if the amount of photoresponsive filler is too small, the photoresponsibility of the laser-emitting layer will be poor, and it will not be able to debond; if the amounts of inorganic nanoparticles and photoresponsive fillers are too large, it will be difficult to form a uniform film, and it will be difficult to prepare a usable laser-emitting layer.

[0015] In this invention, the weight percentage of thermoplastic resin in the laser release layer material can be 10 parts, 12 parts, 14 parts, 16 parts, 18 parts, 20 parts, 22 parts, 24 parts, 26 parts, 28 parts, or 30 parts, etc.

[0016] The weight percentage of inorganic nanoparticles in the laser emission layer material can be 0.5 parts, 0.8 parts, 1 part, 1.2 parts, 1.5 parts, 1.8 parts, 2 parts, 2.3 parts, 2.5 parts, 2.7 parts, 3 parts, 3.3 parts, 3.6 parts, 3.8 parts, or 4 parts, etc.

[0017] The weight percentage of the photoresponsive filler in the laser emission layer material can be 0.5 parts, 0.8 parts, 1 part, 1.2 parts, 1.5 parts, 1.8 parts, 2 parts, 2.3 parts, 2.5 parts, 2.7 parts, 3 parts, 3.3 parts, 3.6 parts, 3.8 parts, or 4 parts, etc.

[0018] The UV-vis transmittance of the photoresponsive filler is 0.001%-10%, for example, it can be 0.001%, 0.01%, 0.1%, 0.5%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9% or 10%, etc.

[0019] The method for testing the UV-vis transmittance of the photoresponsive filler is as follows: the UV-vis transmittance of the photoresponsive filler is tested using a UV-vis spectrophotometer.

[0020] The following are preferred technical solutions of the present invention, but are not intended to limit the technical solutions provided by the present invention. The purpose and beneficial effects of the present invention can be better achieved and realized through the following preferred technical solutions.

[0021] As a preferred embodiment of the present invention, the thermoplastic resin is selected from any one or a combination of at least two of the following: block copolymers containing styrene structural units, petroleum resins, or maleimide resins.

[0022] Preferably, the thermoplastic resin is selected from a combination of block copolymers containing styrene structural units and maleimide resins.

[0023] Preferably, the mass ratio of the block copolymer containing styrene structural units to the maleimide resin is (1-4):1, for example, it can be 1:1, 1.2:1, 1.5:1, 1.8:1, 2:1, 2.2:1, 2.5:1, 2.7:1, 3:1, 3.3:1, 3.6:1, 3.8:1 or 4:1, etc.

[0024] In this invention, the comprehensive performance of the laser release layer material is further optimized by selecting a combination of block copolymer containing styrene structural units and maleimide resin as the thermoplastic resin and controlling the mass ratio of the two within a specific range.

[0025] As a preferred embodiment of the present invention, the mass percentage of styrene structural units in the block copolymer containing styrene structural units is 10-60% (e.g., it can be 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, or 60%, etc.), preferably 15-50%.

[0026] Preferably, the number average molecular weight of the block copolymer containing styrene structural units is 30,000-450,000 (e.g., 30,000, 40,000, 60,000, 80,000, 100,000, 150,000, 200,000, 250,000, 300,000, 350,000, or 450,000, etc.), and more preferably 30,000-150,000.

[0027] Preferably, the raw materials for preparing the styrene unit in the block copolymer containing styrene structural units include substituted or unsubstituted styrene monomers, wherein the substituents are selected from at least one of alkyl groups selected from C1-C5 (e.g., C1, C2, C3, C3 or C5), alkoxy groups selected from C1-C5 (e.g., C1, C2, C3, C3 or C5), alkyl groups substituted with alkoxy groups selected from C1-C5 (e.g., C1, C2, C3, C3 or C5), acetoxy groups, or carboxyl groups.

[0028] Preferably, the block copolymer containing styrene structural units includes a triblock copolymer containing styrene structural units.

[0029] It should be noted that the present invention does not make any special selection of the specific triblock copolymer containing styrene structural units. Triblock copolymers containing styrene structural units that meet the above conditions are applicable, including but not limited to: polystyrene-poly(ethylene / propylene) block copolymer (SEP), styrene-isoprene-styrene block copolymer (SIS), styrene-butadiene-styrene block copolymer (SBS), styrene-butadiene-butene-styrene block copolymer (SBBS), styrene-ethylene-butene-styrene block copolymer (SEBS), styrene-ethylene-propylene-styrene block copolymer, styrene-isoprene-styrene block copolymer (SEPS), styrene-ethylene-ethylene-propylene-styrene block copolymer (SEEPS), styrene-ethylene-ethylene-propylene-styrene block copolymer with reactive crosslinked styrene blocks, styrene-ethylene-butene-styrene block copolymer with reactive crosslinking, polystyrene-poly(ethylene-ethylene / propylene) block-polystyrene block copolymer (SEEPS-OH, terminal hydroxyl modified), etc.

[0030] Preferably, the block copolymer containing styrene structural units is selected from hydrogenated block copolymers prepared from styrene and conjugated dienes (such as 1,3-butadiene).

[0031] Preferably, the block copolymers containing styrene structural units include, but are not limited to: Septon (trade name) manufactured by Kuraray Co., Ltd., Hybler (trade name) manufactured by Kuraray Co., Ltd., Tuftec (trade name) manufactured by Asahi Kasei Corporation, and Dynaron (trade name) manufactured by JSR Corporation.

[0032] It should be noted that the block copolymer containing styrene structural units can be any one of the block copolymers containing styrene structural units listed above, or it can be composed of at least two of the block copolymers containing styrene structural units listed above. It is only necessary to ensure that the block copolymers containing styrene structural units used meet the requirements for the mass percentage of styrene structural units in the block copolymer, the number-average molecular weight of the block copolymer, etc.

[0033] The petroleum resin is a resin having a hydrocarbon backbone and formed by polymerizing hydrocarbon monomers. Petroleum resins include resin A and / or resin B, wherein resin A is selected from terpene resins and / or rosin resins, and resin B includes cyclic olefin polymers.

[0034] The terpene resins mentioned above include, but are not limited to: terpene resins, terpene phenolic resins, modified terpene resins, hydrogenated terpene resins, and hydrogenated terpene phenolic resins; the rosin resins mentioned above include, but are not limited to: rosin, rosin esters, hydrogenated rosin resins, hydrogenated rosin ester resins, polymerized rosin resins, polymerized rosin ester resins, and modified rosin resins.

[0035] Preferably, resin A is selected from hydrogenated terpene resin.

[0036] It should be noted that the present invention does not impose any special limitations on the softening temperature of resin A, which may include, but is not limited to, 60-220℃ (e.g., 60℃, 80℃, 100℃, 120℃, 140℃, 160℃, 180℃, 200℃, or 220℃, etc.); at the same time, the present invention does not impose any special limitations on the number-average molecular weight of resin A, which may include, but is not limited to, 200-7000 (e.g., 200, 500, 1000, 1500, 2000, 2500, 3000, 3500, 4000, 5000, 6000, or 7000, etc.).

[0037] The monomers used to prepare resin B (including cyclic olefin polymers) include substituted or unsubstituted cyclic olefin monomers. The substituents are selected from at least one of C1-C20 (e.g., C1, C2, C4, C6, C8, C10, C12, C14, C16, C18, or C20), alkyl (e.g., methyl, ethyl, propyl, butyl, ethylidene), alkenyl (e.g., vinyl), and aryl (e.g., phenyl, tolyl, naphthyl). Cyclic olefin monomers include, but are not limited to, bicyclic compounds (e.g., norbornene, norbornadiene), tricyclic compounds (e.g., dicyclopentadiene, hydroxydicyclopentadiene), tetracyclic compounds (e.g., tetracyclododecene), pentacyclic compounds (e.g., cyclopentadiene trimer), and heptacyclic compounds (e.g., tetracyclopentadiene).

[0038] Preferably, the substituted or unsubstituted cyclic olefin monomer includes any one of norbornene, tetracyclododecene, and alkyl-substituted norbornene monomers.

[0039] The monomers used to prepare the resin B (including cyclic olefin polymers) also include other monomers that can copolymerize with the substituted or unsubstituted cyclic olefin monomers described above, including, but not limited to, olefin monomers.

[0040] The olefin monomers include, but are not limited to, at least one of α-olefins such as ethylene, propylene, 1-butene, isobutene, and 1-hexene. The olefin monomers may be straight-chain or branched-chain olefin monomers.

[0041] Considering the high heat resistance (low thermal decomposition and thermogravimetric loss), the molar percentage of substituted or unsubstituted cyclic olefin monomers in the monomers for preparing resin B (including cyclic olefin polymers) is ≥5 mol% (e.g., 5 mol%, 8 mol%, 10 mol%, 15 mol%, 20 mol%, 30 mol%, 40 mol%, 50 mol%, 60 mol%, 70 mol%, 80 mol%, 90 mol%, 95 mol%, or 100 mol%, etc.), preferably ≥10 mol%, further... The preferred percentage is ≥20 mol%. Based on solubility and flexibility, the molar percentage of substituted or unsubstituted cyclic olefin monomers in the monomers used to prepare resin B (including cyclic olefin polymers) is 10-90 mol% (e.g., 10 mol%, 15 mol%, 20 mol%, 30 mol%, 40 mol%, 50 mol%, 60 mol%, 70 mol%, 80 mol%, 85 mol%, 90 mol%, 95 mol%, or 100 mol%, etc.), preferably 15-85 mol%.

[0042] It should be noted that the present invention does not impose any special restrictions on the preparation method of resin B, and commonly used preparation methods in the art are applicable.

[0043] In this invention, the cyclic olefin polymers include, but are not limited to: “TOPAS” manufactured by Polyplastics Co., Ltd., “APEL” manufactured by Mitsui Chemicals, Inc., “ZEONOR” and “ZEONEX” manufactured by Nippon, and “ARTON” manufactured by Zeon Co., Ltd. and JSR Corporation.

[0044] Preferably, the glass transition temperature of the resin B is ≥60℃ (e.g., it can be 60℃, 65℃, 70℃, 75℃, 80℃, 90℃, 100℃, 110℃ or 120℃, etc.), and more preferably ≥70℃.

[0045] In this invention, the monomers for preparing the maleimide resin include, but are not limited to: N-methylmaleimide, N-ethylmaleimide, N-n-propylmaleimide, N-isopropylmaleimide, N-n-butylmaleimide, N-isobutylmaleimide, N-sec-butylmaleimide, and maleimides having alkyl groups, such as N-tert-butylmaleimide, N-n-pentylmaleimide, N-n-hexylmaleimide, and N-n-heptyl. Maleimide, N-n-octylmaleimide, N-laurylmaleimide, N-stearylmaleimide, N-cyclopropylmaleimide, N-cyclobutylmaleimide, N-cyclopentylmaleimide, N-cyclohexylmaleimide, N-cycloheptylmaleimide, N-cyclooctylmaleimide, N-phenylmaleimide, N-m-methylphenylmaleimide, N-o-methylphenylmaleimide, N-p-methylphenylmaleimide, etc.

[0046] It should be noted that the present invention does not impose any special restrictions on the preparation method of maleimide resin, and commonly used preparation methods in the art are applicable.

[0047] As a preferred embodiment of the present invention, the average particle size of the inorganic nanoparticles is 10-200nm (for example, it can be 10nm, 20nm, 40nm, 60nm, 70nm, 80nm, 100nm, 120nm, 140nm, 160nm, 180nm or 200nm, etc.), preferably 10-100nm.

[0048] Preferably, the thermal decomposition temperature of the inorganic nanoparticles is ≥300℃, for example, it can be 300℃, 310℃, 320℃, 330℃, 340℃, 350℃, 360℃, 370℃, 380℃, 390℃ or 400℃, etc.

[0049] Preferably, the thermal decomposition temperature of the inorganic nanoparticles is ≥350℃.

[0050] Preferably, the inorganic nanoparticles include any one or a combination of at least two of the following: metal particles, metal oxide particles, metal nitride particles, metal carbide particles, or metal sulfide particles.

[0051] Preferably, the metal particles include any one or a combination of at least two of the following: gold particles, silver particles, copper particles, iron particles, palladium particles, platinum particles, nickel particles, aluminum particles, titanium particles, or chromium particles.

[0052] Preferably, the metal oxide particles include any one or a combination of at least two of the following: nickel oxide (NiO) particles, cobalt oxide (Co2O3) particles, manganese oxide (Mn2O3 or Mn3O4) particles, aluminum oxide particles, copper oxide particles, iron oxide particles, zinc oxide particles, cerium oxide particles, or silicon dioxide particles.

[0053] Preferably, the metal nitride includes titanium nitride or gallium nitride.

[0054] Preferably, the metal sulfide includes zinc sulfide or cadmium sulfide.

[0055] As a preferred embodiment of the present invention, the average particle size of the photoresponsive filler is 10-200nm (for example, it can be 10nm, 20nm, 40nm, 60nm, 80nm, 100nm, 120nm, 140nm, 160nm, 180nm or 200nm, etc.), preferably 10-100nm, and more preferably 20-100nm.

[0056] In this invention, the overall performance of the laser emission layer material is further optimized and improved by controlling the average particle size of the inorganic nanoparticles and photoresponsive fillers within a specific range. If the average particle size of both the inorganic nanoparticles and photoresponsive fillers is too small, uncontrollable agglomeration is easily formed, affecting the uniformity of the laser emission layer adhesive. If the average particle size of both the inorganic nanoparticles and photoresponsive fillers is too large, it will affect the surface roughness and internal uniformity of the film (voids are easily generated in the cross-section).

[0057] Preferably, the thermal decomposition temperature of the photoresponsive filler is ≥300℃, for example, it can be 300℃, 310℃, 320℃, 330℃, 340℃, 350℃, 360℃, 370℃, 380℃, 390℃ or 400℃, etc.

[0058] Preferably, the thermal decomposition temperature of the photoresponsive filler is ≥350℃.

[0059] Preferably, the photoresponsive filler comprises carbon nanoparticles and / or organic nanoparticles.

[0060] Preferably, the carbon nanoparticles include any one or a combination of at least two of the following: carbon black particles, diamond particles, fullerene particles, diamond-like carbon particles, and carbon nanotubes.

[0061] Preferably, the organic nanoparticles include pigments, and more preferably any one or a combination of at least two of the following: azo pigments, phthalocyanine pigments, quinacridone pigments, indole pigments, cyanine pigments, fullerene pigments, polycyclic aromatic pigments, or polyacetylene pigments.

[0062] As a preferred embodiment of the present invention, the laser emission layer material further includes additives.

[0063] Preferably, the additives include any one or a combination of at least two of the following: antioxidants, dispersants, plasticizers, adhesives, stabilizers, colorants, heat inhibitors, surfactants, or additive resins.

[0064] It should be noted that the present invention does not impose any special restrictions on the amount of additives in the laser emission layer material, and they can be added according to actual needs. The weight parts of the additives in the laser emission layer material are exemplary, including but not limited to: 0.1-2 parts, for example, 0.1 parts, 0.2 parts, 0.4 parts, 0.6 parts, 0.8 parts, 1 part, 1.2 parts, 1.4 parts, 1.6 parts, 1.8 parts, or 2 parts, etc.

[0065] Preferably, the laser emission layer material further includes a solvent.

[0066] It should be noted that this invention does not impose any special restrictions on the amount of solvent used in the laser emission layer material; it can be added according to actual needs. In this invention, the sum of the weight parts of all components in the laser emission layer material is 100 parts.

[0067] Preferably, the solvent is selected from any one or a combination of at least two of the following: straight-chain or branched hydrocarbon compounds of C4-C15 (e.g., C4, C6, C8, C10, C12, or C15); cyclic hydrocarbon compounds of C4-C15 (e.g., C4, C6, C8, C10, C12, or C15); terpene solvents; lactone solvents; ketone solvents; alcohol solvents; ester solvents; and ether solvents.

[0068] The C4-C15 straight-chain or branched hydrocarbon compounds include any one or a combination of at least two of the following: hexane, heptane, octane, nonane, methyl octane, decane, undecane, dodecane, and tridecane.

[0069] The C4-C15 cyclic hydrocarbon compounds include any one or a combination of at least two of cyclohexane, cycloheptane, cyclooctane, naphthalene, decahydronaphthalene, and tetrahydronaphthalene.

[0070] The terpene solvents include any one or a combination of at least two of the following: p-menthol, o-menthol, m-menthol, diphenylmethane, 1,4-terpinene, 1,8-terpinene, borneol, norborneol, pinane, tsane, carene, longleafene, geraniol, nerol, linalool, citral, citronellol, menthol, isomenthene, neomenthene, α-terpineol, β-terpineol, γ-terpineol, terpinene-1-ol, terpinene-4-ol, dihydroterpineyl acetate, 1,4-cineole, 1,8-cineole, borneol, camphene, fentanyl, carene, camphor, D-limonene, L-limonene, and dipentene.

[0071] The lactone solvents include γ-butyrolactone.

[0072] The ketone solvents include any one or a combination of at least two of acetone, methyl ethyl ketone, cyclohexanone, methyl n-pentyl ketone, methyl isopentyl ketone, and 2-heptanone.

[0073] The alcohol solvents include any one or a combination of at least two of ethylene glycol, diethylene glycol, propylene glycol, and dipropylene glycol.

[0074] The ester solvents include any one or a combination of at least two of the following: ethylene glycol monoacetate, diethylene glycol monoacetate, propylene glycol monoacetate, dipropylene glycol monoacetate, methyl lactate, ethyl lactate (EL), methyl acetate, ethyl acetate, butyl acetate, methoxybutyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, and ethyl ethoxypropionate.

[0075] The ether solvents include any one or a combination of at least two of the following: monomethyl ether, monoethyl ether, monopropyl ether, monobutyl ether, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), dioxane, anisole, ethyl benzyl ether, cresol methyl ether, diphenyl ether, dibenzyl ether, phenethyl ether, and butylphenyl ether.

[0076] In a second aspect, the present invention provides a method for preparing a laser-emitting layer material as described in the first aspect, the method comprising the following steps:

[0077] The components of the laser emission layer material are mixed to obtain the laser emission layer material.

[0078] As a preferred embodiment of the present invention, the mixture further includes a post-processing step.

[0079] The post-processing methods include grinding and filtering.

[0080] Preferably, after the grinding, the D90 particle size of the mixture is 50-1000nm (e.g., it can be 50nm, 100nm, 200nm, 300nm, 400nm, 500nm, 600nm, 700nm, 800nm, 900nm or 1000nm, etc.), and after the filtration, the D90 particle size of the obtained laser emission layer material is 50-800nm ​​(e.g., it can be 50nm, 100nm, 200nm, 300nm, 400nm, 500nm, 600nm, 700nm or 800nm, etc.).

[0081] Thirdly, the present invention provides an application of the laser emission layer material as described in the first aspect, wherein the laser emission layer material is used in the fabrication of semiconductor devices.

[0082] Compared with the prior art, the present invention has the following beneficial effects:

[0083] (1) This invention designs the material of the laser emission layer and further utilizes thermoplastic resin in combination with inorganic nanoparticles and photoresponsive fillers with specific UV absorption values ​​to prepare a high-performance laser emission layer material with photosensitive properties. This allows the laser emission layer prepared from this material to absorb laser light of a specific wavelength for debonding. Furthermore, the laser emission layer material remaining on the wafer surface after debonding can be cleaned together with the adhesive layer, accelerating production efficiency, reducing the types of cleaning agents used, and not damaging the supporting blue film.

[0084] (2) The present invention further optimizes the comprehensive performance of the laser release layer material by selecting a combination of block copolymer containing styrene structural units and maleimide resin as thermoplastic resin and controlling the mass ratio of the two within a specific range.

[0085] (3) In this invention, by controlling the average particle size of inorganic nanoparticles and photoresponsive fillers within a specific range, the overall performance of the laser release layer material is further optimized and improved. Attached Figure Description

[0086] Figure 1 This is a top view photograph of the bonded pairs prepared from the laser-emitting layer material provided in Embodiment 1 of the present invention, with the uppermost layer being a glass substrate;

[0087] Figure 2 This is a schematic cross-sectional view of the bonding pairs prepared from the laser-emitting layer material provided in Embodiment 1 of the present invention.

[0088] Wherein, 1-glass substrate, 2-laser release layer, 3-adhesive layer, 4-silicon wafer;

[0089] Figure 3These are photographs of the bonded pairs obtained from the laser-released layer material provided in Embodiment 1 of the present invention after laser debonding of the glass substrate;

[0090] Figure 4 This is a photograph of a silicon wafer after laser debonding of the bonding pairs prepared by the laser-emitting layer material provided in Embodiment 1 of the present invention.

[0091] Figure 5 The image shows a silicon wafer after the bonding pairs prepared by the laser release layer material provided in Embodiment 1 of this invention have been laser debonded and then cleaned in Remover 3 cleaning agent. Detailed Implementation

[0092] The technical solution of the present invention will be further described below with reference to the accompanying drawings and specific embodiments. Those skilled in the art should understand that the embodiments described are merely illustrative of the present invention and should not be considered as specific limitations thereof.

[0093] The sources of some components in the following examples and comparative examples are shown in Table 1 below:

[0094] Table 1

[0095]

[0096]

[0097] Examples 1-11, Comparative Examples 1-4

[0098] Examples 1-11 and Comparative Examples 1-4 each provide a laser emission layer material and its preparation method. The specific composition of the laser emission layer material is shown in Tables 2-3 below.

[0099] The laser emission layer material is prepared as follows:

[0100] The components of the laser emission layer material were mixed evenly and ground. After grinding, the D90 particle size of the mixture was 400 nm. After filtration, a laser emission layer material with a D90 particle size of 380 nm was obtained.

[0101] Table 2

[0102]

[0103] Table 3

[0104]

[0105]

[0106] The performance of the laser emission layer materials provided in the above embodiments and comparative examples was tested, and the specific test methods are as follows:

[0107] (1) Film formation: Using a spin coater, the spin coating parameters were set to 900 rpm @ 30 s. The laser release layer material was spin-coated on one side of the glass substrate and then baked. The spin coating thickness was 1500 nm. The baking parameters were 110 ℃ @ 5 min and 220 ℃ @ 7 min. Then the film surface was observed using an optical microscope.

[0108] (2) Bonding: After spin-coating the laser emission layer material on one side of the glass substrate, the substrate was baked (the spin-coating thickness was 1500 nm, and the baking parameters were 110℃@5 min and 220℃@7 min) to obtain the laser emission layer; an adhesive was spin-coated on the other side of the silicon wafer (the adhesive was purchased from Shenzhen Huaxun Semiconductor Materials Co., Ltd., grade TB4180, and the spin-coating thickness was 50 μm) to obtain the adhesive layer.

[0109] The laser-released layer and the adhesive layer are placed opposite each other and bonded using a bonding machine (bonding parameters 215℃@10min, bonding pressure 5000N) to obtain a bond pair. The bonding is then observed to see if the bond can be formed and whether the bond pair has any defects.

[0110] (3) Debonding: The above bond pairs were debonded using a 355nm laser with a laser energy of 400-700mJ / cm. 2 Observe whether the bond pairs separate.

[0111] (4) Cleanability: Using Remover 3 cleaning agent from Huaxun Semiconductor Materials Co., Ltd., the debonded silicon wafer was immersed in Remover 3 cleaning agent for 3 minutes at 25°C, and then the surface was rinsed. The residual laser release layer and adhesive layer on the surface of the silicon wafer were observed. If there was no residue, it was recorded as "easy to clean"; if there was residue, it was recorded as "difficult to clean".

[0112] (5) Modulus of thermoplastic resin in laser release layer material: The modulus of thermoplastic resin in laser release layer material was tested using an Anton Paar 302e rheometer at a temperature of 260℃-150℃.

[0113] The top view and cross-sectional structural diagram of the bond pair prepared by the laser emitting layer material provided in Embodiment 1 of the present invention are shown below. Figure 1 , Figure 2 As shown. By Figure 1 and Figure 2 It can be seen that the bonding pairs were successfully prepared using the laser-emitting layer material provided in Example 1.

[0114] The bonding pairs prepared from the laser-emitting layer material provided in Embodiment 1 of this invention are subjected to laser debonding and cleaning, and then the glass substrate and silicon wafer are as follows: Figure 3 and Figure 4 As shown. By Figure 3 and Figure 4 It can be seen that after laser debonding, there is little residual laser-emitting layer material on the surface of the glass substrate, and most of the laser-emitting layer material and the adhesive layer remain on one side of the silicon wafer.

[0115] Figure 5 This is the silicon wafer obtained after cleaning the debonded silicon wafer using Remover 3 cleaning agent. Figure 5 It can be seen that the laser release layer material remaining on the silicon wafer surface after debonding can be cleaned together with the adhesive layer, which speeds up production efficiency and reduces the types of cleaning agents used.

[0116] The performance test results are detailed in Table 4 below:

[0117] Table 4

[0118]

[0119]

[0120] As described above, this invention, through the design of the laser emission layer material and the further use of thermoplastic resin, combined with inorganic nanoparticles and photoresponsive fillers with specific UV absorption values, prepares a high-performance laser emission layer material with photosensitive properties. This allows the laser emission layer prepared from this material to absorb laser light of specific wavelengths for debonding. Furthermore, the laser emission layer material remaining on the wafer surface after debonding can be cleaned together with the adhesive layer, accelerating production efficiency, reducing the types of cleaning agents used, and without damaging the supporting blue film.

[0121] The thermoplastic resin in the laser emitting layer material provided by this invention has a modulus of 6530-33930 Pa·s (215℃). When bonding pairs are prepared using this laser emitting layer material, the film-forming properties are good, successful bonding is achieved without defects, and stress-free separation is possible during debonding. After debonding, the laser emitting layer material remaining on the wafer surface can be cleaned together with the adhesive layer.

[0122] As can be seen from Examples 1 and 4-8, this invention further optimizes the overall performance of the laser emission layer material and improves its heat resistance by selecting a combination of block copolymers containing styrene structural units and maleimide resin as the thermoplastic resin and controlling the mass ratio of the two within a specific range. In the preparation of bonding pairs, this laser emission layer material can successfully prepare bonding pairs in a single bonding process without defects.

[0123] As can be seen from Examples 1, 9-11, and Comparative Example 2, in this invention, by controlling the average particle size of the inorganic nanoparticles and photoresponsive fillers within a specific range, the overall performance of the laser emission layer material is further optimized and improved. When bonding pairs are prepared using this laser emission layer material, the laser emission layer material can form a uniform film without cracks or pitting.

[0124] As can be seen from the contents of Example 1, Comparative Example 1, and Comparative Examples 3-4, the present invention uses thermoplastic resin in combination with inorganic nanoparticles with specific UV absorption values ​​and photoresponsive fillers to prepare a laser emission layer material with excellent photosensitive properties.

[0125] In summary, this invention, through the design of the laser emission layer material, has prepared a high-performance laser emission layer material with excellent photosensitive properties. This allows the laser emission layer prepared from this material to absorb laser light of a specific wavelength for debonding. Furthermore, the laser emission layer material remaining on the wafer surface after debonding can be cleaned together with the adhesive layer, accelerating production efficiency, reducing the types of cleaning agents used, and without damaging the supporting blue film.

[0126] The applicant declares that the detailed process flow of this invention is illustrated by the above embodiments, but this invention is not limited to the above detailed process flow, that is, it does not mean that this invention must rely on the above detailed process flow to be implemented. Those skilled in the art should understand that any improvements to this invention, equivalent substitutions of raw materials for the product of this invention, addition of auxiliary components, and selection of specific methods, etc., all fall within the protection scope and disclosure scope of this invention.

Claims

1. A laser-emitting layer material, characterized in that, The laser emission layer material comprises the following components in parts by weight: 10-30 parts thermoplastic resin, 0.5-4 parts inorganic nanoparticles, and 0.5-4 parts photoresponsive filler; The UV-vis transmittance of the photoresponsive filler is 0.001%-10%; The thermoplastic resin is selected from any one or a combination of at least two of the following: block copolymers containing styrene structural units, petroleum resins, or maleimide resins. The inorganic nanoparticles include any one or a combination of at least two of the following: metal particles, metal oxide particles, metal nitride particles, metal carbide particles, or metal sulfide particles. The average particle size of the inorganic nanoparticles is 10-200 nm. The photoresponsive filler includes carbon nanoparticles and / or organic nanoparticles; The carbon nanoparticles include any one or a combination of at least two of the following: carbon black particles, diamond particles, fullerene particles, diamond-like carbon particles, and carbon nanotubes. The organic nanoparticles are any one or a combination of at least two of the following: azo pigments, phthalocyanine pigments, quinacridone pigments, indole pigments, cyanine pigments, quinacridone pigments, indole pigments, cyanine pigments, fullerene pigments, polycyclic aromatic pigments, or polyacetylene pigments.

2. The laser emission layer material according to claim 1, characterized in that, The thermoplastic resin is selected from a combination of block copolymers containing styrene structural units and maleimide resins.

3. The laser emission layer material according to claim 2, characterized in that, The mass ratio of the block copolymer containing styrene structural units to the maleimide resin is (1-4):

1.

4. The laser emission layer material according to claim 1, characterized in that, The block copolymer containing styrene structural units has a styrene structural unit mass percentage of 10-60%.

5. The laser emission layer material according to claim 4, characterized in that, The block copolymer containing styrene structural units has a styrene structural unit mass percentage of 15-50%.

6. The laser emission layer material according to claim 1, characterized in that, The number-average molecular weight of the block copolymer containing styrene structural units is 30,000-450,000.

7. The laser-emitting layer material according to claim 6, characterized in that, The number-average molecular weight of the block copolymer containing styrene structural units is 30,000-150,000.

8. The laser emission layer material according to claim 1, characterized in that, The petroleum resin includes any one or a combination of at least two of terpene resins, rosin resins, or cyclic olefin polymers.

9. The laser emission layer material according to claim 1, characterized in that, The inorganic nanoparticles have an average particle size of 10-100 nm.

10. The laser emission layer material according to claim 1, characterized in that, The inorganic nanoparticles have a thermal decomposition temperature ≥300℃.

11. The laser emission layer material according to claim 10, characterized in that, The inorganic nanoparticles have a thermal decomposition temperature ≥350℃.

12. The laser emission layer material according to claim 1, characterized in that, The metal particles include any one or a combination of at least two of the following: gold particles, silver particles, copper particles, iron particles, palladium particles, platinum particles, nickel particles, aluminum particles, titanium particles, or chromium particles.

13. The laser emission layer material according to claim 1, characterized in that, The metal oxide particles include any one or a combination of at least two of nickel oxide particles, cobalt oxide particles, manganese oxide particles, aluminum oxide particles, copper oxide particles, iron oxide particles, zinc oxide particles, or cerium oxide particles.

14. The laser emission layer material according to claim 1, characterized in that, The metal nitrides include titanium nitride or gallium nitride.

15. The laser-emitting layer material according to claim 1, characterized in that, The metal sulfides include zinc sulfide or cadmium sulfide.

16. The laser emission layer material according to claim 1, characterized in that, The average particle size of the photoresponsive filler is 10-200 nm.

17. The laser-emitting layer material according to claim 16, characterized in that, The average particle size of the photoresponsive filler is 10-100 nm.

18. The laser-emitting layer material according to claim 17, characterized in that, The average particle size of the photoresponsive filler is 20-100 nm.

19. The laser emission layer material according to claim 1, characterized in that, The thermal decomposition temperature of the photoresponsive filler is ≥300℃.

20. The laser emission layer material according to claim 19, characterized in that, The thermal decomposition temperature of the photoresponsive filler is ≥350℃.

21. The laser emission layer material according to claim 1, characterized in that, The laser emission layer material also includes additives.

22. The laser emission layer material according to claim 21, characterized in that, The additives include any one or a combination of at least two of the following: antioxidants, dispersants, plasticizers, adhesives, stabilizers, colorants, heat inhibitors, surfactants, or additives.

23. The laser emission layer material according to claim 1, characterized in that, The laser emission layer material also includes a solvent.

24. A method for preparing a laser-emitting layer material as described in any one of claims 1-23, characterized in that, The preparation method includes the following steps: The components of the laser emission layer material are mixed to obtain the laser emission layer material.

25. The preparation method according to claim 24, characterized in that, The mixing process also includes a post-processing step. The post-processing methods include grinding and filtering.

26. An application of the laser-emitting layer material as described in any one of claims 1-23, characterized in that, The laser emission layer material is used in the fabrication of semiconductor devices.

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