Composite viscous film cleaning sheet and preparation process thereof

Abstract

The invention relates to the technical field of semiconductor manufacturing, in particular to a composite viscous film cleaning sheet and a preparation process thereof. The composite viscous film cleaning sheet comprises a release layer, a viscous cleaning layer and an antistatic layer which are arranged in sequence, and the viscous cleaning layer comprises the following components in parts by mass: 80-92 parts of a bonding composition, 0.5-0.8 part of a stabilizer, 0.3-0.6 part of a cross-linking agent and 0.2-0.4 part of a plasticizer; the bonding composition is prepared from epoxy modified polysiloxane, modified polyamide and a supramolecular polymer. In order to effectively remove the foreign matters on the surface of the wafer chuck, optimize the cleaning effect and improve the cleaning efficiency, the foreign matters on the surface of the wafer chuck can be effectively removed, and the cleaning effect is optimized and the cleaning efficiency is improved; the device can be directly attached to the surface of the chuck for cleaning, the downtime of equipment is shortened, and the surface of the chuck cannot be abraded.

Description

Technical Field

[0001] This application relates to the field of semiconductor manufacturing technology, specifically to a composite adhesive thin film cleaning sheet and its preparation process. Background Technology

[0002] In the semiconductor manufacturing industry, wafer chucks, as key components for carrying and fixing wafers, play a decisive role in product yield due to their surface cleanliness. As chip manufacturing processes continue to advance towards higher precision and performance, the cleanliness requirements for wafer chuck surfaces are becoming increasingly stringent. If impurities such as microparticles adhere to the chuck surface, they can cause deviations in pattern transfer during critical processes such as photolithography, etching, and ion implantation, leading to functional defects such as short circuits and open circuits in the chip. This severely reduces product yield and increases production costs.

[0003] Currently, traditional wafer chuck cleaning technologies have many drawbacks. For example, manual cleaning using lint-free cloths combined with process alcohol is not only inefficient but also fails to thoroughly remove tiny particles. Furthermore, frequent contact with chemical reagents poses a health risk to operators. While some automated cleaning equipment, such as existing mechanical grinding, can remove some stubborn stains, it easily generates new particles during the grinding process, causing secondary contamination. This method also causes some wear on the chuck surface, shortening its lifespan. In addition, most cleaning technologies require stopping the machine and opening the reaction chamber during operation. This process is not only time-consuming, typically requiring 6-8 hours of downtime for a single cleaning, severely impacting equipment production efficiency, but also introduces more contaminants due to the reaction chamber's contact with the external environment. Summary of the Invention

[0004] In order to effectively remove foreign matter from the surface of wafer chucks, optimize the cleaning effect and improve the cleaning efficiency, this application provides a composite adhesive film cleaning sheet and its preparation process.

[0005] In a first aspect, this application provides a composite adhesive film cleaning sheet, which adopts the following technical solution: A composite adhesive film cleaning sheet includes a release layer, an adhesive cleaning layer, and an antistatic layer arranged sequentially. The adhesive cleaning layer comprises the following components in parts by weight: 80-92 parts of an adhesive composition, 0.5-0.8 parts of a stabilizer, 0.3-0.6 parts of a crosslinking agent, and 0.2-0.4 parts of a plasticizer. The adhesive composition includes epoxy-modified polysiloxane, modified polyamide, and supramolecular polymer.

[0006] By adopting the above technical solution, the composite adhesive film cleaning sheet, with its sequentially arranged release layer, adhesive cleaning layer, and antistatic layer structure, and the adhesive cleaning layer containing components such as adhesive composition, stabilizer, crosslinking agent, and plasticizer, can effectively adsorb various impurities such as metal silicides, metals, and metal oxides. The cleaning effect is significantly different from traditional acid washing methods. After removing the release layer protection, it can be directly attached to the chuck surface for cleaning, reducing equipment downtime, effectively removing foreign matter from the wafer chuck surface, optimizing the cleaning effect and improving cleaning efficiency. It adsorbs and removes various impurities such as metal silicides, metals, and metal oxides without causing wear on the chuck surface, thereby extending the chuck's service life.

[0007] In the viscous cleaning layer, the polysiloxane backbone of the epoxy-modified polysiloxane is flexible and can adapt to the tiny unevenness of the wafer surface, with good adhesion and capture of particulate impurities in the gaps. It has an excellent removal effect, especially on silicide impurities. Furthermore, the polar groups of the modified polyamide can generate affinity with the polar sites on the wafer surface, further enhancing the adhesion and improving the capture ability of polar impurities. Moreover, the amide bond can combine with organic residues such as grease on the wafer surface through hydrogen bonds, efficiently adsorbing organic impurities. The hyperbranched structure of the supramolecular polymer provides a large number of terminal sites, which can simultaneously adsorb polar organic impurities and tiny particles, and can remove trace amounts of precious metal impurities that are difficult for epoxy-modified polysiloxane and modified polyamide to adsorb. The interaction between epoxy-modified polysiloxane and modified polyamide improves mechanical properties and enhances tensile strength. Simultaneously, the low surface energy of polysiloxane prevents residue buildup. Hyperbranched multifunctional groups synergistically expand the adsorption range, while the flexible structure ensures adhesion, collectively endowing the composite film with excellent cleaning performance. The adhesive composition forms a three-dimensional cross-linked network through active functional groups. The hyperbranched structure of the supramolecular polymer acts as a stress-dispersing agent, preventing localized fractures and imparting elasticity and toughness to the film, preventing brittle fracture. Furthermore, through interaction with the antistatic layer, the cleaning sheet effectively adsorbs impurities without tearing, removing strongly adsorbed particles and organic matter from the surface after film removal, removing the surface oxide layer, ensuring the cleanliness of the wafer surface, and achieving the removal of the metal film layer on the replica wafer surface. This achieves a synergistic effect of strong adsorption, easy peeling, and no residue, effectively solving problems such as particle aggregation at wafer edges and excessive metal ions, reducing wafer surface roughness and the number of surface particles, thereby effectively reducing the number of defects in production and improving the finished product yield.

[0008] In one specific implementation, the preparation process of the supramolecular polymer includes: sequentially adding benzaldehyde, isophorone diisocyanate and acrylic acid to dichloromethane; stirring evenly under nitrogen protection; heating to 40-50°C; reacting for 2-3 hours to obtain a hyperbranched mixture; adding acrylonitrile and 3-mercaptopropyltrimethoxysilane to the hyperbranched mixture; and reacting at 60-70°C for 4-6 hours to obtain a thiol-based supramolecular polymer.

[0009] Preferably, the optimal mass ratio of acrylonitrile to 3-mercaptopropyltrimethoxysilane is 1:(3-5).

[0010] By employing the above technical solution, a hyperbranched core structure is formed through the reaction of benzaldehyde, isophorone diisocyanate, and acrylic acid. Acrylonitrile and 3-mercaptopropyltrimethoxysilane are then introduced for functional modification, introducing nitrile and thiol groups to provide numerous active sites, enhancing both polar adsorption and chemical bonding capabilities. The hyperbranched structure also provides a large number of physical entanglement points, improving elongation at break and tear resistance. Furthermore, the nitrile groups enhance the adsorption of fluoride particles, while the thiol groups effectively adsorb and destroy contaminants such as copper oxide and alumina layers, and have a cleaning adsorption effect on polar organic impurities and metal particle contaminants. However, excessive acrylonitrile content, while slightly improving the adsorption capacity for fluoride particles, disrupts the interfacial forces with the siloxane, reducing the cohesiveness of the composite system and significantly decreasing the film's flexibility, elongation at break, and tear resistance.

[0011] In one specific implementation, the preparation steps of the modified polyamide include: adding polyamide to xylene, heating to 80-90°C under nitrogen protection and stirring to dissolve, adding 1,2-diaminoethane and triethylamine, heating to 110-120°C and refluxing for 4-6 hours, and then filtering and drying to obtain the modified polyamide.

[0012] The mass ratio of the epoxy-modified polysiloxane, modified polyamide, and supramolecular polymer is (3-5):2:(1-3).

[0013] By employing the above technical solution, when the epoxy-modified polysiloxane, modified polyamide, and supramolecular polymer in the bonding composition are within their respective strong ranges, the epoxy groups can react with the amino groups of the modified polyamide, imparting a certain elasticity and toughness to the film, enhancing its adhesion and bonding properties. Furthermore, a cross-linked network structure is formed with the active functional groups of the supramolecular polymer. The hyperbranched structure of the supramolecular polymer acts as nodes to disperse stress, preventing localized breakage. Upon peeling, all layers detach synchronously without any fragment residue, achieving complete peeling. Moreover, the thiol groups can react with the partially hydrolyzed silanol groups of the polysiloxane, forming Si-S bonds that further improve interfacial adhesion. Additionally, the adsorption force of numerous active functional groups on the cross-linked network structure on impurities, through coordination bonds, hydrogen bonds, etc., is stronger than the binding force of impurities to the wafer surface. Therefore, only impurities are removed upon peeling, and no adhesive layer residue remains on the wafer surface after cleaning, meeting the requirements for high-precision cleaning. Insufficient epoxy-modified polysiloxane content may lead to insufficient polysiloxane segment content, resulting in reduced flexibility and poor adhesion. This makes it difficult to effectively remove tiny impurities on the wafer surface, and the reduction in the number of particles on the wafer surface is not significant. A decrease in supramolecular polymer content not only reduces the removal rate of stubborn oxide films but also leads to a decrease in the overall mechanical properties of the composite film, resulting in reduced tear resistance. This makes it easier to tear and leave impurities, increasing the number of particles on the wafer surface and ultimately reducing the cleaning rate, failing to meet high-precision cleaning requirements.

[0014] The antistatic layer comprises 5-8 parts of modified carbon nanotubes, 32-48 parts of ethylene-vinyl acetate copolymer, and 4-6 parts of tributyl citrate.

[0015] The modified carbon nanotubes are silane-grafted modified carbon nanotubes.

[0016] By adopting the above technical solution, silane grafting modification of carbon nanotubes can improve their dispersibility in ethylene-vinyl acetate copolymers. Furthermore, it forms a continuous conductive network through π-bond conjugation, reducing surface resistance and interfacial tension, providing flexibility and interfacial adhesion. Tributyl citrate ensures the film maintains flexibility at room temperature. Silane grafting modification of carbon nanotubes enables hydrogen bonding interactions between modified polysiloxanes and modified polyamides, resulting in a thermodynamically compatible interface between the antistatic layer and the adhesive cleaning layer. This enhances intermolecular bonding, stabilizes the molecular structure, and strengthens the overall network structure stability. It ensures seamless adhesion during cleaning, prevents secondary contamination from electrostatic adsorption, and guarantees the integrity of the bond.

[0017] In a second aspect, this application provides a preparation process for a composite adhesive film cleaning sheet, which adopts the following technical solution: The preparation process of the composite adhesive film cleaning sheet includes the following steps: (1) Mix epoxy modified polysiloxane, modified polyamide and supramolecular polymer in proportion, then add stabilizer, crosslinking agent and plasticizer, stir at 70-80℃ for 30-45min, distill under reduced pressure to obtain prepolymer, and melt extrude a film with a thickness of 50-60μm using a twin-screw extruder; (2) Add the antistatic layer component in proportion to the extruder and melt blend at 140-150℃, and extrude and cast into a film with a thickness of 20-30μm; (3) After hot pressing the release layer, adhesive cleaning layer and antistatic layer together, cure at room temperature for 18-24h to obtain the composite adhesive film cleaning sheet.

[0018] The hot-pressing composite temperature is 110-120℃, and the pressure is 0.3-0.5MPa.

[0019] In summary, this application has the following beneficial effects: 1. The composite adhesive film cleaning sheet features a release layer, an adhesive cleaning layer, and an antistatic layer arranged sequentially. The adhesive cleaning layer contains a binder composition, stabilizer, crosslinking agent, plasticizer, and other components. This effectively adsorbs various impurities such as metal silicides, metals, and metal oxides. The cleaning effect is significantly different from traditional acid washing methods. After removing the release layer, the sheet can be directly applied to the chuck surface for cleaning, reducing equipment downtime, effectively removing foreign matter from the wafer chuck surface, optimizing the cleaning effect and improving cleaning efficiency. It adsorbs and removes various impurities such as metal silicides, metals, and metal oxides without causing wear on the chuck surface, thereby extending the chuck's service life. The bonding composition can form a three-dimensional cross-linked network through active functional groups. The hyperbranched structure of the supramolecular polymer acts as a stress disperser, avoiding local fractures and giving the film a certain degree of elasticity and toughness, thus preventing brittle fractures. Furthermore, through interaction with the antistatic layer, the cleaning sheet can effectively adsorb impurities without being easily torn. It can remove strongly adsorbed particles and organic matter from the surface after the film is peeled off, remove the surface oxide layer, ensure the cleanliness of the wafer surface, and achieve the removal of the metal film layer on the surface of the replica wafer, thereby improving the yield of the finished product.

[0020] 2. The introduction of nitrile and thiol groups into the hyperbranched structure provides numerous active sites, enhancing both polar adsorption and chemical bonding capabilities. The hyperbranched structure also provides abundant physical entanglement points, improving elongation at break and tear resistance. Furthermore, the nitrile groups enhance the adsorption of fluoride particles, while the thiol groups effectively adsorb and destroy contaminants such as copper oxide and alumina layers, and exhibit a cleaning adsorption effect on polar organic impurities and metal particle contaminants. Excessive acrylonitrile content, while slightly improving the adsorption capacity for fluoride particles, disrupts the interfacial forces with siloxanes, reducing the cohesiveness of the composite system and significantly decreasing the film's flexibility, elongation at break, and tear resistance.

[0021] 3. Silane grafting modification of carbon nanotubes improves their dispersibility in ethylene-vinyl acetate copolymers. It also forms a continuous conductive network through π-bond conjugation, reducing surface resistance and interfacial tension, providing flexibility and interfacial adhesion. Tributyl citrate ensures the film maintains flexibility at room temperature. Silane grafting modification of carbon nanotubes enables hydrogen bonding interactions between modified polysiloxanes and modified polyamides, creating a thermodynamically compatible interface between the antistatic layer and the adhesive cleaning layer. This enhances intermolecular bonding, stabilizes the molecular structure, and strengthens the overall network structure stability. It ensures seamless adhesion during cleaning, prevents secondary contamination from electrostatic adsorption, and guarantees complete bonding. Detailed Implementation

[0022] The present application will be further described in detail below with reference to the embodiments.

[0023] Some of the raw materials used in the preparation examples and embodiments: epoxy-modified polysiloxane (IOTA105); polyamide (S14142), purchased from Shanghai Yuanye Biotechnology Co., Ltd.; ethylene-vinyl acetate copolymer, purchased from Guangdong Yuanfeng Chemical Reagent Co., Ltd.; multi-walled carbon nanotubes, purchased from Xianfeng Nano; concentrated nitric acid (65wt%); concentrated sulfuric acid (98wt%); PET film (model: S10; the stabilizer is hindered phenolic antioxidant 1010; the crosslinking agent is dicumyl peroxide; the plasticizer is dioctyl phthalate.

[0024] Unless otherwise specified, all raw materials used in the examples and comparative examples are commercially available products.

[0025] Preparation Example 1 Preparation of supramolecular polymers: 50g benzaldehyde, 44g isophorone diisocyanate and 36g acrylic acid were added sequentially to 250g dichloromethane. Under nitrogen protection, the mixture was stirred at 300rpm until homogeneous, then heated to 45℃ and reacted for 3h to obtain a hyperbranched mixture. 12g acrylonitrile and 42g 3-mercaptopropyltrimethoxysilane were added to the hyperbranched mixture and reacted at 65℃ for 5h. The mixture was washed with methanol, filtered, and vacuum dried at 60℃ for 12h to obtain a thiol-based supramolecular polymer.

[0026] Preparation Example 2 Preparation of supramolecular polymers: 50g benzaldehyde, 44g isophorone diisocyanate and 36g acrylic acid were added sequentially to 250g dichloromethane. Under nitrogen protection, the mixture was stirred at 300rpm until homogeneous, then heated to 45℃ and reacted for 3h to obtain a hyperbranched mixture. 18g acrylonitrile and 36g 3-mercaptopropyltrimethoxysilane were added to the hyperbranched mixture and reacted at 65℃ for 5h. The mixture was washed with methanol, filtered, and vacuum dried at 60℃ for 12h to obtain a thiol-based supramolecular polymer.

[0027] Preparation Example 3 Preparation of modified polyamide: 10g of polyamide was added to 60ml of xylene, heated to 90℃ under nitrogen protection and stirred to dissolve, 1.5g of 1,2-diaminoethane and 0.5g of triethylamine were added, the mixture was heated to 120℃ and refluxed for 6h, cooled to room temperature, filtered, washed 3 times with acetone, and dried under vacuum at 80℃ for 12h to obtain modified polyamide.

[0028] Preparation Example 4 Preparation of modified carbon nanotubes: 10g of carbon nanotubes were added to a mixed solution of concentrated nitric acid and concentrated sulfuric acid (volume ratio 1:3) in 200ml, sonicated at 60℃ for 4h, refluxed for 6h, cooled to room temperature, and filtered to obtain carboxylated carbon nanotubes; 5g of carboxylated carbon nanotubes were added to 100ml of DMF, along with 2g of 3-aminopropyltriethoxysilane and 0.1g of 4-dimethylaminopyridine, reacted at 100℃ for 12h, filtered, washed three times with ethanol, and vacuum dried at 80℃ for 12h to obtain modified carbon nanotubes.

[0029] Example 1 A composite adhesive film cleaning sheet includes a release layer, an adhesive cleaning layer, and an antistatic layer arranged sequentially. The adhesive cleaning layer comprises the following components: 85g of an adhesive composition, 0.6g of a stabilizer, 0.4g of a crosslinking agent, and 0.3g of a plasticizer. The antistatic layer comprises 6g of modified carbon nanotubes obtained in Preparation Example 4, 42g of ethylene-vinyl acetate copolymer, and 8g of tributyl citrate. The release layer is a PET film. The adhesive composition is an epoxy-modified polysiloxane, a modified polyamide obtained in Preparation Example 3, and a supramolecular polymer obtained in Preparation Example 1, with a mass ratio of 4:2:1.8. The preparation process includes (1) mixing epoxy-modified polysiloxane, modified polyamide obtained in Preparation Example 3, and supramolecular polymer obtained in Preparation Example 1 in proportion, heating to 120°C, stirring and mixing at 200 rpm for 1 h, then adding stabilizer, crosslinking agent, and plasticizer, cooling to 80°C and stirring for 30 min, vacuum distillation to obtain prepolymer, and melt extruding a 60 μm thick film at 140°C using a twin-screw extruder; (2) adding antistatic layer components in proportion to an extruder and melt-blending at 140°C, with a screw speed of 150 rpm, extruding and granulating, and casting into a 30 μm thick film; (3) hot-pressing the release layer, adhesive cleaning layer, and antistatic layer at 120°C and a pressure of 0.5 MPa, and then curing at room temperature for 18 h to obtain a composite adhesive film cleaning sheet.

[0030] Example 2 A composite adhesive film cleaning sheet includes a release layer, an adhesive cleaning layer, and an antistatic layer arranged sequentially. The adhesive cleaning layer comprises the following components: 85g of an adhesive composition, 0.6g of a stabilizer, 0.4g of a crosslinking agent, and 0.3g of a plasticizer. The antistatic layer comprises 6g of modified carbon nanotubes obtained in Preparation Example 4, 42g of ethylene-vinyl acetate copolymer, and 8g of tributyl citrate. The release layer is a PET film. The adhesive composition consists of epoxy-modified polysiloxane, modified polyamide obtained in Preparation Example 3, and supramolecular polymer obtained in Preparation Example 1, in a mass ratio of 2:2:3.8. The preparation process includes (1) mixing epoxy-modified polysiloxane, modified polyamide obtained in Preparation Example 3, and supramolecular polymer obtained in Preparation Example 1 in proportion, heating to 120°C, stirring and mixing at 200 rpm for 1 h, then adding stabilizer, crosslinking agent, and plasticizer, cooling to 80°C and stirring for 30 min, vacuum distillation to obtain prepolymer, and melt extruding a 60 μm thick film at 140°C using a twin-screw extruder; (2) adding antistatic layer components in proportion to an extruder and melt-blending at 140°C, with a screw speed of 150 rpm, extruding and granulating, and casting into a 30 μm thick film; (3) hot-pressing the release layer, adhesive cleaning layer, and antistatic layer at 120°C and a pressure of 0.5 MPa, and then curing at room temperature for 18 h to obtain a composite adhesive film cleaning sheet.

[0031] Example 3 A composite adhesive film cleaning sheet includes a release layer, an adhesive cleaning layer, and an antistatic layer arranged sequentially. The adhesive cleaning layer comprises the following components: 85g of an adhesive composition, 0.6g of a stabilizer, 0.4g of a crosslinking agent, and 0.3g of a plasticizer. The antistatic layer comprises 6g of modified carbon nanotubes obtained in Preparation Example 4, 42g of ethylene-vinyl acetate copolymer, and 8g of tributyl citrate. The release layer is a PET film. The adhesive composition is an epoxy-modified polysiloxane, a modified polyamide obtained in Preparation Example 3, and a supramolecular polymer obtained in Preparation Example 1, with a mass ratio of 5:2:0.8. The preparation process includes (1) mixing epoxy-modified polysiloxane, modified polyamide obtained in Preparation Example 3, and supramolecular polymer obtained in Preparation Example 1 in proportion, heating to 120°C, stirring and mixing at 200 rpm for 1 h, then adding stabilizer, crosslinking agent, and plasticizer, cooling to 80°C and stirring for 30 min, vacuum distillation to obtain prepolymer, and melt extruding a 60 μm thick film at 140°C using a twin-screw extruder; (2) adding antistatic layer components in proportion to an extruder and melt-blending at 140°C, with a screw speed of 150 rpm, extruding and granulating, and casting into a 30 μm thick film; (3) hot-pressing the release layer, adhesive cleaning layer, and antistatic layer at 120°C and a pressure of 0.5 MPa, and then curing at room temperature for 18 h to obtain a composite adhesive film cleaning sheet.

[0032] Example 4 A composite adhesive film cleaning sheet includes a release layer, an adhesive cleaning layer, and an antistatic layer arranged sequentially. The adhesive cleaning layer comprises the following components: 85g of an adhesive composition, 0.6g of a stabilizer, 0.4g of a crosslinking agent, and 0.3g of a plasticizer. The antistatic layer comprises 6g of modified carbon nanotubes obtained in Preparation Example 4, 42g of ethylene-vinyl acetate copolymer, and 8g of tributyl citrate. The release layer is a PET film. The adhesive composition is an epoxy-modified polysiloxane, a modified polyamide obtained in Preparation Example 3, and a supramolecular polymer obtained in Preparation Example 2, with a mass ratio of 4:2:1.8. The preparation process includes (1) mixing epoxy-modified polysiloxane, modified polyamide obtained in Preparation Example 3, and supramolecular polymer obtained in Preparation Example 2 in proportion, heating to 120°C, stirring and mixing at 200 rpm for 1 h, then adding stabilizer, crosslinking agent, and plasticizer, cooling to 80°C and stirring for 30 min, vacuum distillation to obtain prepolymer, and melt extruding a 60 μm thick film at 140°C using a twin-screw extruder; (2) adding antistatic layer components in proportion to an extruder and melt-blending at 140°C, with a screw speed of 150 rpm, extruding and granulating, and casting into a 30 μm thick film; (3) hot-pressing the release layer, adhesive cleaning layer, and antistatic layer at 120°C and a pressure of 0.5 MPa, and then curing at room temperature for 18 h to obtain a composite adhesive film cleaning sheet.

[0033] Example 5 A composite adhesive film cleaning sheet includes a release layer, an adhesive cleaning layer, and an antistatic layer arranged sequentially. The adhesive cleaning layer comprises the following components: 85g of an adhesive composition, 0.6g of a stabilizer, 0.4g of a crosslinking agent, and 0.3g of a plasticizer. The antistatic layer comprises 12g of modified carbon nanotubes obtained in Preparation Example 4, 36g of ethylene-vinyl acetate copolymer, and 8g of tributyl citrate. The release layer is a PET film. The adhesive composition consists of epoxy-modified polysiloxane, modified polyamide obtained in Preparation Example 3, and supramolecular polymer obtained in Preparation Example 1, in a mass ratio of 4:2:1.8. The preparation process includes (1) mixing epoxy-modified polysiloxane, modified polyamide obtained in Preparation Example 3, and supramolecular polymer obtained in Preparation Example 1 in proportion, heating to 120°C, stirring and mixing at 200 rpm for 1 h, then adding stabilizer, crosslinking agent, and plasticizer, cooling to 80°C and stirring for 30 min, vacuum distillation to obtain prepolymer, and melt extruding a 60 μm thick film at 140°C using a twin-screw extruder; (2) adding antistatic layer components in proportion to an extruder and melt-blending at 140°C, with a screw speed of 150 rpm, extruding and granulating, and casting into a 30 μm thick film; (3) hot-pressing the release layer, adhesive cleaning layer, and antistatic layer at 120°C and a pressure of 0.5 MPa, and then curing at room temperature for 18 h to obtain a composite adhesive film cleaning sheet.

[0034] Example 6 A composite adhesive film cleaning sheet includes a release layer, an adhesive cleaning layer, and an antistatic layer arranged sequentially. The adhesive cleaning layer comprises the following components: 85g of an adhesive composition, 0.6g of a stabilizer, 0.4g of a crosslinking agent, and 0.3g of a plasticizer. The antistatic layer comprises 3g of modified carbon nanotubes obtained in Preparation Example 4, 45g of ethylene-vinyl acetate copolymer, and 8g of tributyl citrate. The release layer is a PET film. The adhesive composition is an epoxy-modified polysiloxane, a modified polyamide obtained in Preparation Example 3, and a supramolecular polymer obtained in Preparation Example 1, with a mass ratio of 4:2:1.8. The preparation process includes (1) mixing epoxy-modified polysiloxane, modified polyamide obtained in Preparation Example 3, and supramolecular polymer obtained in Preparation Example 1 in proportion, heating to 120°C, stirring and mixing at 200 rpm for 1 h, then adding stabilizer, crosslinking agent, and plasticizer, cooling to 80°C and stirring for 30 min, vacuum distillation to obtain prepolymer, and melt extruding a 60 μm thick film at 140°C using a twin-screw extruder; (2) adding antistatic layer components in proportion to an extruder and melt-blending at 140°C, with a screw speed of 150 rpm, extruding and granulating, and casting into a 30 μm thick film; (3) hot-pressing the release layer, adhesive cleaning layer, and antistatic layer at 120°C and a pressure of 0.5 MPa, and then curing at room temperature for 18 h to obtain a composite adhesive film cleaning sheet.

[0035] Example 7 A composite adhesive film cleaning sheet includes a release layer, an adhesive cleaning layer, and an antistatic layer arranged sequentially. The adhesive cleaning layer comprises 85g of an adhesive composition, 0.6g of a stabilizer, 0.4g of a crosslinking agent, and 0.3g of a plasticizer. The antistatic layer comprises 6g of carbon nanotubes, 42g of ethylene-vinyl acetate copolymer, and 8g of tributyl citrate. The release layer is a PET film. The adhesive composition is an epoxy-modified polysiloxane, a modified polyamide prepared in Preparation Example 3, and a supramolecular polymer prepared in Preparation Example 1, with a mass ratio of 4:2:1.8. The preparation process includes (1) mixing epoxy-modified polysiloxane, modified polyamide obtained in Preparation Example 3, and supramolecular polymer obtained in Preparation Example 1 in proportion, heating to 120°C, stirring and mixing at 200 rpm for 1 h, then adding stabilizer, crosslinking agent, and plasticizer, cooling to 80°C and stirring for 30 min, vacuum distillation to obtain prepolymer, and melt extruding a 60 μm thick film at 140°C using a twin-screw extruder; (2) adding antistatic layer components in proportion to an extruder and melt-blending at 140°C, with a screw speed of 150 rpm, extruding and granulating, and casting into a 30 μm thick film; (3) hot-pressing the release layer, adhesive cleaning layer, and antistatic layer at 120°C and a pressure of 0.5 MPa, and then curing at room temperature for 18 h to obtain a composite adhesive film cleaning sheet.

[0036] Comparative Example 1 A composite adhesive film cleaning sheet includes a release layer, an adhesive cleaning layer, and an antistatic layer arranged sequentially. The adhesive cleaning layer comprises the following components: 85g of an adhesive composition, 0.6g of a stabilizer, 0.4g of a crosslinking agent, and 0.3g of a plasticizer. The antistatic layer comprises 6g of modified carbon nanotubes obtained in Preparation Example 4, 42g of ethylene-vinyl acetate copolymer, and 8g of tributyl citrate. The release layer is a PET film. The adhesive composition consists of epoxy-modified polysiloxane, polyamide, and supramolecular polymer obtained in Preparation Example 1, in a mass ratio of 4:2:1.8. The preparation process includes (1) mixing epoxy-modified polysiloxane, polyamide, and supramolecular polymer prepared in Preparation Example 1 in proportion, heating to 120°C, stirring and mixing at 200 rpm for 1 h, then adding stabilizer, crosslinking agent, and plasticizer, cooling to 80°C and stirring for 30 min, distilling under reduced pressure to obtain prepolymer, and then melting and extruding a film with a thickness of 60 μm at 140°C using a twin-screw extruder; (2) adding the antistatic layer components in proportion to the extruder and melting and blending at 140°C, with the screw speed at 150 rpm, extruding and granulating, and casting into a film with a thickness of 30 μm; (3) hot-pressing the release layer, adhesive cleaning layer, and antistatic layer at 120°C and a pressure of 0.5 MPa, and then curing at room temperature for 18 h to obtain a composite adhesive film cleaning sheet.

[0037] Comparative Example 2 A composite adhesive film cleaning sheet includes a release layer, an adhesive cleaning layer, and an antistatic layer arranged sequentially. The adhesive cleaning layer comprises the following components: 85g of an adhesive composition, 0.6g of a stabilizer, 0.4g of a crosslinking agent, and 0.3g of a plasticizer. The antistatic layer comprises 6g of modified carbon nanotubes obtained in Preparation Example 4, 42g of ethylene-vinyl acetate copolymer, and 8g of tributyl citrate. The release layer is a PET film. The adhesive composition consists of epoxy-modified polysiloxane and modified polyamide obtained in Preparation Example 3, with a mass ratio of 5.8:2. The preparation process includes (1) mixing epoxy-modified polysiloxane and modified polyamide prepared in Preparation Example 3 in proportion, heating to 120°C, stirring and mixing at 200 rpm for 1 h, then adding stabilizer, crosslinking agent and plasticizer, cooling to 80°C and stirring for 30 min, distilling under reduced pressure to obtain prepolymer, and melt-extruding a film with a thickness of 60 μm at 140°C using a twin-screw extruder; (2) adding antistatic layer components in proportion to an extruder and melt-blending at 140°C, with a screw speed of 150 rpm, extruding and granulating, and casting into a film with a thickness of 30 μm; (3) hot-pressing the release layer, adhesive cleaning layer and antistatic layer at 120°C and a pressure of 0.5 MPa, and then curing at room temperature for 18 h to obtain a composite adhesive film cleaning sheet.

[0038] Comparative Example 3 A composite adhesive film cleaning sheet includes a release layer, an adhesive cleaning layer, and an antistatic layer arranged sequentially. The adhesive cleaning layer comprises the following components: 85g of an adhesive composition, 0.6g of a stabilizer, 0.4g of a crosslinking agent, and 0.3g of a plasticizer. The antistatic layer comprises 6g of modified carbon nanotubes obtained in Preparation Example 4, 42g of ethylene-vinyl acetate copolymer, and 8g of tributyl citrate. The release layer is a PET film. The adhesive composition consists of epoxy-modified polysiloxane and supramolecular polymer obtained in Preparation Example 1 in a mass ratio of 6:1.8. The preparation process includes (1) mixing epoxy-modified polysiloxane and supramolecular polymer prepared in Example 1 according to the proportion, heating to 120°C, stirring and mixing at 200 rpm for 1 h, then adding stabilizer, crosslinking agent and plasticizer, cooling to 80°C and stirring for 30 min, vacuum distillation to obtain prepolymer, and melt extruding a film with a thickness of 60 μm at 140°C using a twin-screw extruder; (2) adding antistatic layer components according to the proportion to an extruder and melt blending at 140°C, with a screw speed of 150 rpm, extruding and granulating, and casting into a film with a thickness of 30 μm; (3) hot-pressing the release layer, adhesive cleaning layer and antistatic layer at 120°C and a pressure of 0.5 MPa, and then curing at room temperature for 18 h to obtain a composite adhesive film cleaning sheet.

[0039] Comparative Example 4 A composite adhesive film cleaning sheet includes a release layer and an adhesive cleaning layer arranged sequentially. The adhesive cleaning layer includes the following components: 85g of an adhesive composition, 0.6g of a stabilizer, 0.4g of a crosslinking agent, and 0.3g of a plasticizer. The release layer is a PET film. The adhesive composition is an epoxy-modified polysiloxane, a modified polyamide prepared in Preparation Example 3, and a supramolecular polymer prepared in Preparation Example 1, with a mass ratio of 4:2:1.8. The preparation process includes (1) mixing epoxy-modified polysiloxane, modified polyamide obtained in Preparation Example 3, and supramolecular polymer obtained in Preparation Example 1 in proportion, heating to 120°C, stirring and mixing at 200 rpm for 1 h, then adding stabilizer, crosslinking agent, and plasticizer, cooling to 80°C and stirring for 30 min, vacuum distillation to obtain prepolymer, and melt extruding a 60 μm thick film at 140°C using a twin-screw extruder; (2) hot-pressing the release layer and adhesive cleaning layer at 120°C and 0.5 MPa, and then curing at room temperature for 18 h to obtain a composite adhesive film cleaning sheet.

[0040] Performance testing The performance of the composite adhesive film cleaning sheets prepared in Examples 1-7 and Comparative Examples 1-4 was tested using the following methods: Tensile strength test: Refer to national standard GB / T1040.2-2022 "Determination of tensile properties of plastics - Part 2: Test conditions for molded and extruded plastics" Surface particle count: The particle count on the wafer surface before and after processing was detected using a Sigma 500 scanning electron microscope. Areas with high particle density were randomly selected within the initial magnification of 2000x and magnified to 20000x to facilitate observation of the surface particle count; performance is shown in Table 1. Table 1 Performance Test Results Tensile strength / MPa Number of surface particles / Example 1 58 0 Example 2 54 2 Example 3 46 4 Example 4 51 3 Example 5 57 3 Example 6 51 4 Example 7 56 5 Comparative Example 1 45 7 Comparative Example 2 36 24 Comparative Example 3 40 17 Comparative Example 4 32 23 As shown in Table 1, compared with Comparative Examples 1-4 and Examples 1-4, the adhesive composition can form a three-dimensional cross-linked network through active functional groups. The hyperbranched structure of the supramolecular polymer acts as a stress disperser, avoiding local fracture and imparting a certain degree of elasticity and toughness to the film, preventing brittle fracture. Too low an epoxy-modified polysiloxane content may lead to insufficient polysiloxane chain segment content, resulting in reduced flexibility and poor adhesion. This makes it difficult to effectively remove tiny impurities on the wafer surface, and the reduction in the number of particles on the wafer surface is not significant. A decrease in supramolecular polymer content not only reduces the removal rate of oxide films containing difficult-to-remove impurities but also leads to a decrease in the overall mechanical properties of the composite film, resulting in decreased tear resistance, making it easier to tear and leaving impurities. This increases the number of particles on the wafer surface, actually reducing the cleaning rate. Furthermore, compared to Example 1, in the test of Comparative Example 2, the composite adhesive film was torn and adhered to the substrate surface, leaving more surface particles.

[0041] Compared with Examples 5-7, the applicant found that the interaction between the silane grafting modification of the carbon nanotube surface and the ethylene-vinyl acetate copolymer not only improves the density of the antistatic layer, but also further increases the interfacial compatibility between the antistatic layer and the adhesive cleaning layer, thereby greatly increasing the overall mechanical properties of the material, making it more adherent to the substrate, and thus adsorbing and bonding microparticles, ensuring that the entire bond is intact during cleaning without lifting edges, preventing secondary pollution caused by electrostatic adsorption and ensuring the integrity of the bond.

[0042] The above are all preferred embodiments of this application and are not intended to limit the scope of protection of this application. Therefore, all equivalent changes made to the structure, shape and principle of this application should be covered within the scope of protection of this application.

Claims

1. A composite adhesive film cleaning sheet, characterized in that: The product comprises a release layer, an adhesive cleaning layer, and an antistatic layer arranged sequentially. The adhesive cleaning layer comprises the following components in parts by weight: 80-92 parts of adhesive composition, 0.5-0.8 parts of stabilizer, 0.3-0.6 parts of crosslinking agent, and 0.2-0.4 parts of plasticizer. The adhesive composition comprises epoxy-modified polysiloxane, modified polyamide, and supramolecular polymer.

2. The composite adhesive film cleaning sheet according to claim 1, characterized in that: The preparation process of the supramolecular polymer includes: adding benzaldehyde, isophorone diisocyanate and acrylic acid sequentially to dichloromethane, stirring evenly under nitrogen protection, heating to 40-50℃, reacting for 2-3 hours to obtain a hyperbranched mixture, adding acrylonitrile and 3-mercaptopropyltrimethoxysilane to the hyperbranched mixture, and reacting at 60-70℃ for 4-6 hours to obtain a thiol-based supramolecular polymer.

3. The composite adhesive film cleaning sheet according to claim 1, characterized in that: The preparation steps of the modified polyamide include: adding polyamide to xylene, heating to 80-90℃ under nitrogen protection and stirring to dissolve, adding 1,2-diaminoethane and triethylamine, heating to 110-120℃ and refluxing for 4-6 hours, filtering and drying to obtain the modified polyamide.

4. The composite adhesive film cleaning sheet according to claim 1, characterized in that: The mass ratio of the epoxy-modified polysiloxane, modified polyamide, and supramolecular polymer is (3-5):2:(1-3).

5. The composite adhesive film cleaning sheet according to claim 1, characterized in that: The antistatic layer comprises 5-8 parts of modified carbon nanotubes, 32-48 parts of ethylene-vinyl acetate copolymer, and 4-6 parts of tributyl citrate.

6. The composite adhesive film cleaning sheet according to claim 5, characterized in that: The modified carbon nanotubes are silane-grafted modified carbon nanotubes.

7. The preparation process of the composite adhesive film cleaning sheet according to any one of claims 1-6, characterized in that, Includes the following steps: (1) Mix epoxy-modified polysiloxane, modified polyamide and supramolecular polymer in proportion, then add stabilizer, crosslinking agent and plasticizer, stir at 70-80℃ for 30-45min, distill under reduced pressure to obtain prepolymer, and melt extrude a film with a thickness of 50-60μm using a twin-screw extruder; (2) Add the antistatic layer components in proportion to the extruder and melt blend at 140-150℃, then extrude and cast into a film with a thickness of 20-30μm; (3) After hot pressing the release layer, adhesive cleaning layer and antistatic layer together, cure at room temperature for 18-24h to obtain composite adhesive film cleaning sheet.

8. The preparation process of the composite adhesive film cleaning sheet according to claim 7, characterized in that: The hot-pressing composite temperature is 110-120℃, and the pressure is 0.3-0.5MPa.