Polyether ether ketone membrane for high temperature equipment of semiconductor industry and method for manufacturing the same

Abstract

The application relates to the technical field of polyether ether ketone film processing, in particular to a polyether ether ketone film for high-temperature equipment in the semiconductor industry and a preparation method thereof, which is prepared from the following raw materials in parts by weight: polyether ether ketone resin 100 parts, two-dimensional boron nitride nanosheet 2-5 parts, low-molecular-weight PEEK copolymer 5-8 parts, perfluoropolyether silane coupling agent 1-3 parts, high-temperature-resistant antioxidant 1-2 parts and nucleating agent 0.1-0.3 parts. The two problems of thickness uniformity control and high-temperature thermal aging are solved synchronously through the above-mentioned formula, so that the polyether ether ketone film has both precise forming capacity and long-term thermal stability.

Description

Technical Field

[0001] This application relates to the field of polyetheretherketone (PEEK) film processing technology, and more specifically, to a PEEK film for high-temperature equipment in the semiconductor industry and a method for preparing the same. Background Technology

[0002] As semiconductor manufacturing processes advance towards 5nm and below, the high-temperature processes involved in wafer fabrication have significantly increased, typically requiring processing in a vacuum or inert atmosphere at 250-400℃. Such high-temperature equipment places extremely stringent comprehensive requirements on functional film materials: First, thermal stability, ensuring a glass transition temperature above 140℃, and preventing softening or deformation during long-term use above 260℃, while also matching the coefficient of thermal expansion with silicon-based materials to avoid wafer warping due to thermal stress; Second, chemical inertness, resisting corrosion from highly corrosive process gases such as halogens and ammonia, as well as acidic cleaning agents, without releasing metal ions or organic contaminants; Third, electrical insulation reliability, maintaining high breakdown field strength and low dielectric loss to prevent dielectric breakdown under high-voltage radio frequency environments; Fourth, precision forming capability, with thickness tolerance controlled within ±2μm and surface roughness Ra≤50nm to meet the assembly and stripping requirements of micro / nano-scale devices.

[0003] Polyetheretherketone (PEEK), a fully aromatic semi-crystalline polymer, possesses unique comprehensive properties due to its alternating benzene ring-ketone group structure in its molecular backbone, making it a preferred matrix for high-performance engineering plastic films. PEEK films exhibit a glass transition temperature of 143-162℃, a melting point of approximately 340℃, and a load heat distortion temperature as high as 316℃. They can be used continuously for over 5000 hours at 260℃ while retaining over 85% of their elastic modulus. Their dimensional stability under high temperature and humidity conditions is superior to that of polyimide films. In terms of chemical stability, PEEK is inert to most organic solvents, acids, alkalis, and process gases, except for concentrated sulfuric acid. After washing with ultrapure water, the amount of metal ion precipitation can be controlled to <10 ppb, meeting wafer-level cleanliness requirements.

[0004] Currently, polyetheretherketone (PEEK) films have achieved initial commercial applications in semiconductor manufacturing equipment. In chemical mechanical polishing (CMP) equipment, PEEK films are used as liners for wafer retaining rings. Utilizing their high wear resistance and low particle shedding characteristics, they significantly improve the uniformity of wafer edge planarization compared to traditional polyphenylene sulfide (PPS) materials, extending their service life. In wafer transport systems, PEEK films serve as an isolation layer for the end effector of vacuum robotic arms, allowing for continuous operation for over 1000 hours in a 300°C vacuum chamber without pyrolysis or deformation, effectively preventing contamination between the wafer and metal components.

[0005] However, the large-scale application of polyetheretherketone (PEEK) films in high-temperature semiconductor equipment still faces the following challenges: First, controlling film thickness uniformity is difficult. Extrusion casting methods, due to high melt viscosity and uneven cooling gradients, often result in thickness tolerances exceeding ±5μm in the width direction, making it difficult to meet the stringent ±2μm uniformity requirements of 12-inch wafer equipment. Second, the high-temperature thermo-oxidative aging mechanism is unclear. During long-term service at temperatures above 260℃, PEEK films experience surface microcracks due to molecular chain oxidation and breakage. These technical problems limit the widespread application of PEEK films in advanced process semiconductor equipment, necessitating the development of PEEK films that balance precision molding and long-term stability. Summary of the Invention

[0006] To address the aforementioned technical problems, this application provides a polyetheretherketone (PEEK) film for high-temperature equipment in the semiconductor industry and a method for preparing the same.

[0007] In a first aspect, this application provides a polyetheretherketone (PEEK) film for high-temperature equipment in the semiconductor industry, employing the following technical solution: A polyetheretherketone (PEEK) film for use in high-temperature equipment in the semiconductor industry is prepared from the following raw materials in parts by weight: 100 parts of polyetheretherketone resin 2-5 parts of two-dimensional boron nitride nanosheets 5-8 parts of low molecular weight PEEK copolymer 1-3 parts of perfluoropolyether silane coupling agent 1-2 parts of high-temperature resistant antioxidant Nucleating agent 0.1-0.3 parts.

[0008] By adopting the above technical solutions, low molecular weight PEEK copolymers can effectively reduce the overall melt viscosity and improve melt flowability, making polyetheretherketone resin easier to spread during the casting process, thereby suppressing thickness fluctuations caused by viscosity inhomogeneity. Two-dimensional boron nitride nanosheets have ultra-high in-plane thermal conductivity. When they are uniformly dispersed in polyetheretherketone resin, they can form an efficient heat conduction network in the transverse direction of the film, significantly homogenizing the temperature gradient during the cooling stage and avoiding thickness deviations caused by uneven local cooling. Perfluoropolyether silane coupling agent improves the interfacial compatibility between boron nitride and polyetheretherketone resin through chemical bonding, prevents nanofiller agglomeration, ensures the uniformity of thermal field control, and enhances the overall structural density of the film. Through the synergistic effect of the three raw materials, the film thickness tolerance can be controlled from more than ±5μm in the traditional range to within ±2μm, meeting the precision molding requirements of advanced process equipment.

[0009] High-temperature resistant antioxidants can efficiently capture alkyl and peroxide free radicals in the early stages of oxidation of polyetheretherketone (PEEK) resin molecules, blocking autocatalytic oxidation chain reactions and fundamentally inhibiting molecular chain breakage. Two-dimensional boron nitride nanosheets possess excellent sheet-like structures, forming a physical barrier layer on the film surface, reducing oxygen permeation rates, decreasing the concentration of oxidizing reactants, and delaying the thermo-oxidative aging process. Nucleating agents can refine the spherulite size of PEEK resin, forming a more complete crystalline network structure, limiting the diffusion path of oxidation reactions into amorphous regions, and simultaneously improving dimensional stability at high temperatures. The synergistic use of these three agents significantly extends the service life of PEEK films used in high-temperature equipment in the semiconductor industry.

[0010] Preferably, the low molecular weight PEEK copolymer has a melt flow rate of 30-50 g / 10 min at 380°C and 5 kg, and its number average molecular weight is 20,000-30,000 g / mol.

[0011] By adopting the above technical solutions and optimizing the parameters of the low molecular weight PEEK copolymer, the melt viscosity of the system is further reduced, effectively improving the melt flowability and spreadability. This makes it easier for the melt to be evenly distributed in the width direction of the die during the extrusion casting process, thereby effectively suppressing the thickness fluctuation caused by viscosity inhomogeneity. Combined with the thermal conductivity regulation effect of the two-dimensional boron nitride nanosheets, the thickness tolerance in the width direction can be precisely controlled from more than ±5μm in the traditional direction to within ±2μm, meeting the stringent requirements of 12-inch wafer equipment for precision forming. At the same time, the low molecular weight component can still maintain good compatibility and interfacial bonding with the matrix resin after forming, ensuring that the overall mechanical properties of the film are not damaged.

[0012] Preferably, the two-dimensional boron nitride nanosheets are pretreated by the following method: Two-dimensional boron nitride nanosheets were dispersed in NaOH solution, ultrasonically treated in a water bath at 70-80℃ for 3-4 hours, centrifuged and washed until pH=7, and then freeze-dried under vacuum to obtain pretreated two-dimensional boron nitride nanosheets.

[0013] By employing the above technical solution, active functional groups such as hydroxyl groups can be controllably introduced into the surface of two-dimensional boron nitride nanosheets through ultrasonic treatment in a NaOH solution, enhancing their surface reactivity and polarity. After centrifugal washing and vacuum freeze-drying, the nanosheets have a pure surface and intact structure. This pretreatment enables stronger chemical bonding between boron nitride, perfluoropolyether silane coupling agent, and polyether ether ketone resin, effectively suppressing the agglomeration of nanofillers during melt processing. This achieves uniform dispersion of two-dimensional boron nitride in polyether ether ketone resin and the construction of a stable thermally conductive network, thereby ensuring the uniformity of lateral thermal conduction of the film, synergistically improving the thickness tolerance control capability to within ±2μm, and enhancing the interfacial bonding strength and stress transfer efficiency, ultimately improving the mechanical strength, thermo-oxidative aging resistance, and long-term service reliability of the film.

[0014] Preferably, the two-dimensional boron nitride nanosheets have an aspect ratio of 500-800 and a sheet thickness of 1-10 nm.

[0015] By adopting the above technical solutions and optimizing the aspect ratio and thickness of the two-dimensional boron nitride nanosheets, it is beneficial to form a continuous and efficient thermally conductive network in polyetheretherketone resin, homogenize the lateral temperature gradient during the melt cooling stage, and precisely control the thickness tolerance in the width direction within ±2μm. At the same time, the ultrathin sheet structure gives it a large specific surface area, which can form a dense physical barrier on the film surface, effectively blocking oxygen penetration, reducing the high-temperature thermo-oxidative aging rate, and delaying the initiation of surface microcracks under 260℃ conditions. In addition, the high-rigidity sheet structure achieves efficient stress transfer through strong interfacial interaction, which improves the elastic modulus of the composite film and has a high fracture strength retention rate, fully meeting the stringent requirements of 12-inch wafer processing equipment for precision forming and long-term stability.

[0016] Preferably, the polyetheretherketone resin has a metal ion content of less than 5 ppb and an initial moisture content of less than 0.1%.

[0017] By adopting the above technical solutions, the risk of wafer contamination can be reduced by more than 50% at the source, ensuring that the amount of metal ions released during high-temperature processes above 260°C is always below the wafer-level cleanliness threshold, thus avoiding fatal contamination of advanced process devices at 5nm and below. At the same time, the ultra-low initial moisture content reduces the hygroscopic expansion effect of the film in a vacuum or inert atmosphere high-temperature environment to a negligible level, and improves the stability of the coefficient of thermal expansion by more than 30%, effectively suppressing dimensional fluctuations and interfacial stress caused by moisture escape. Combined with the thermal conductivity regulation effect of two-dimensional boron nitride, the thickness tolerance can be precisely controlled within ±2μm.

[0018] Preferably, the high-temperature resistant antioxidant is a compound of hindered phenolic primary antioxidant and thioether secondary antioxidant, with a weight ratio of 1:(0.6-1.5).

[0019] By adopting the above technical solution, the hindered phenolic main antioxidant efficiently captures alkyl free radicals and peroxide free radicals, blocking the oxidation chain reaction of polyether ether ketone resin molecules. At the same time, the thioether auxiliary antioxidant decomposes hydrogen peroxide and regenerates the main antioxidant, forming a synergistic effect mechanism. The optimized ratio of 1:(0.6-1.5) can ensure that the two complement each other without antagonism, which prolongs the oxidation induction period of the composite film at 260℃ by more than 3 times, significantly inhibits the initiation of surface microcracks caused by molecular chain breakage, and increases the elastic modulus retention rate to more than 95%, thereby achieving long-term stable service of more than 5,000 hours in the high-temperature semiconductor process.

[0020] Preferably, the perfluoropolyether silane coupling agent is perfluoropolyether trimethoxysilane, and the molecular weight of its perfluoropolyether segment is 1000-3000 g / mol.

[0021] By adopting the above technical solution and optimizing its molecular weight, an interface layer with moderate thickness and optimized reactivity can be formed on the surface of two-dimensional boron nitride. Its trimethoxysilyl groups are efficiently bonded to the hydroxyl groups on the surface of boron nitride, while the perfluoropolyether segments effectively prevent the aggregation of nanosheets through steric hindrance, achieving uniform dispersion in polyetheretherketone resin. At the same time, this molecular weight range ensures sufficient chain length to provide flexible shielding and chemical inertness to resist corrosive gases, while avoiding migration difficulties and decreased reactivity caused by excessively high molecular weight. This synergistically improves the interfacial bonding strength, ensures efficient stress transfer between the matrix and the filler, and meets the comprehensive requirements of semiconductor high-temperature processes for interface stability, precision molding, and long-term service.

[0022] Preferably, the nucleating agent is nano-titanium oxide and / or arylphosphonate.

[0023] By adopting the above technical solution, the molecular chains of polyetheretherketone resin are effectively promoted to rapidly nucleate and crystallize during the cooling process, refining the spherulite size to below 5μm and forming a denser crystalline network. At the same time, the dimensional stability at a high temperature of 260℃ is improved, avoiding warping of 12-inch wafers. Furthermore, the uniform and refined crystalline structure can effectively prevent the oxidation reaction from spreading to the amorphous region during thermo-oxidative aging. Together with the physical barrier constructed by two-dimensional boron nitride, the initiation time of microcracks on the film surface is delayed to more than 5000 hours, and the surface smoothness and gloss are improved, reducing particle shedding and contamination, and meeting the wafer-level cleanliness requirements.

[0024] Secondly, this application provides a method for preparing a polyetheretherketone (PEEK) film for high-temperature equipment in the semiconductor industry, employing the following technical solution: A method for preparing a polyetheretherketone (PEEK) film for high-temperature equipment in the semiconductor industry includes the following preparation steps: S1. Stir the polyether ether ketone resin and low molecular weight PEEK copolymer at low speed, then add the high temperature resistant antioxidant and nucleating agent in sequence and stir. Slowly add the two-dimensional boron nitride nanosheets and perfluoropolyether silane coupling agent, and then mix at high speed to obtain a mixture. S2. Add the mixture to a twin-screw mixer for melt mixing and granulation to obtain polyetheretherketone granules; S3. Clean the carrier membrane, then melt the polyether ether ketone particles and coat them onto the surface of the carrier membrane. Then, perform biaxial stretching, orientation setting, and cooling to obtain a polyether ether ketone membrane for use in high-temperature equipment in the semiconductor industry.

[0025] By adopting the above technical solutions, stepwise mixing and twin-screw internal mixing can achieve uniform dispersion and full exfoliation of two-dimensional boron nitride in high-viscosity polyether ether ketone resin melt, effectively overcoming the problem of nanofiller agglomeration; melt coating combined with biaxial stretching orientation allows molecular chains and nanosheets to be optimally aligned, improving lateral thermal conductivity uniformity, precisely controlling thickness tolerance within ±2μm, and increasing elastic modulus; the orientation-fixing and locking structure significantly suppresses the initiation of microcracks caused by 260℃ thermo-oxidative aging, with a service life exceeding 5000 hours, fully meeting the requirements of 12-inch wafer processing equipment for precision forming and long-term stability.

[0026] Preferably, in the twin-screw internal mixer, the temperature of zone one is 320-330℃, the temperature of zone two is 340-350℃, the temperature of zone three is 360-365℃, the temperature of zone four is 370-375℃, the temperature of zone five is 370-375℃, the temperature of zone six is ​​365-370℃, the temperature of zone seven is 360-365℃, and the temperature of the die head is 355-360℃. The screw speed is 200-250 rpm; The screw length-to-diameter ratio is 35-40:1; By adopting the above technical solution, it is possible to ensure that the polyetheretherketone resin is fully plasticized and does not degrade in the melting zone, while providing sufficient shear force and residence time to achieve full peeling and uniform dispersion of two-dimensional boron nitride nanosheets in the high-viscosity melt, effectively inhibiting the agglomeration of nanofillers; the die temperature of 355-360℃ is slightly lower than the melting zone temperature, which can ensure the melt strength and discharge stability, and finally obtain composite particles with uniform dispersion and good flowability, laying the structural foundation for subsequent precision coating and molding.

[0027] Preferably, the melting temperature in step S3 is 370-375℃, and the coating speed is 0.5-2 m / min.

[0028] By adopting the above technical solution, it is possible to ensure that the polyetheretherketone resin is fully melted and the two-dimensional boron nitride is uniformly dispersed, while avoiding overheating. An appropriate coating speed provides sufficient melt spreading and venting time, and the cooling rate is synergistically controlled to ensure that the melt forms a film smoothly on the carrier film surface, accurately controlling the thickness tolerance within ±2μm and the surface roughness Ra≤50nm. This balances precision molding and production efficiency, meeting the stringent requirements of 12-inch wafer equipment for film uniformity and batch stability.

[0029] Preferably, the biaxial stretching temperature is 160-170℃, the longitudinal stretching ratio is 1.8-2.0 times, and the transverse stretching ratio is 1.8-2.0 times; The orientation setting temperature is 320-330℃, and the time is 30-45 seconds.

[0030] By adopting the above technical solution, the biaxial stretching temperature of 160-170℃ is in the optimal range of high elasticity. Combined with a balanced stretching ratio of 1.8-2.0 times, the polyetheretherketone resin molecular chains and two-dimensional boron nitride nanosheets are simultaneously oriented to construct an isotropic thermally conductive network, and the thickness tolerance is precisely controlled within ±2μm. The orientation setting temperature of 320-330℃ and the time of 30-45 seconds can fully relax the internal stress and lock the orientation structure, improve the high-temperature dimensional stability of the film, inhibit the initiation of microcracks caused by 260℃ thermo-oxidative aging, improve the elastic modulus retention rate, and achieve a fracture strength of over 120 MPa, fully meeting the stringent requirements of 12-inch wafer equipment for precision forming and long-term stability.

[0031] In summary, this application has the following beneficial effects: 1. This application improves fluidity by reducing melt viscosity with low molecular weight PEEK copolymer, homogenizes the cooling gradient by constructing an in-plane heat conduction network with two-dimensional boron nitride nanosheets, and strengthens interfacial compatibility and prevents agglomeration with perfluoropolyether silane coupling agent. The three work together to precisely control the film thickness tolerance from more than ±5μm in the traditional range to within ±2μm, meeting the assembly requirements of 12-inch wafer equipment.

[0032] 2. The high-temperature resistant antioxidant in this application efficiently captures free radicals and blocks the oxidation chain reaction; the two-dimensional boron nitride nanosheets form a physical barrier layer to slow down oxygen penetration; and the nucleating agent refines the spherulite structure to limit the oxidation diffusion path. The three work together to inhibit molecular chain breakage and microcrack initiation in environments above 260°C, thereby extending the service life of the polyetheretherketone membrane. Detailed Implementation Example

[0033] The polyetheretherketone resin in this application has a metal ion content of less than 5 ppb and an initial moisture content of less than 0.1%, and is Victrex™ PEEK 90G from Vigus.

[0034] Example 1

[0035] A polyetheretherketone (PEEK) film for use in high-temperature equipment in the semiconductor industry is prepared by the following method: S1. Stir 1000g of polyether ether ketone resin and 50g of low molecular weight PEEK copolymer at a low speed of 80 rpm. Then add 10g of high temperature resistant antioxidant and 1g of nucleating agent in sequence and stir. Slowly add 20g of two-dimensional boron nitride nanosheets and 10g of perfluoropolyether silane coupling agent and mix at a high speed of 400 rpm to obtain a mixture. The low molecular weight PEEK copolymer has a melt flow rate of 30 g / 10 min at 380 °C and 5 kg, and its number average molecular weight is 20000 g / mol. The two-dimensional boron nitride nanosheets have an aspect ratio of 500 and a sheet thickness of 1 nm. The high-temperature resistant antioxidant is a compound of hindered phenolic primary antioxidant (β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate n-octadecyl alcohol ester) and thioether auxiliary antioxidant (TD-P), with a weight ratio of 1:0.6. The perfluoropolyether silane coupling agent is perfluoropolyether trimethoxysilane, and the molecular weight of its perfluoropolyether segment is 1000 g / mol. The nucleating agent is nano-titanium oxide with an average particle size of 10 nm; S2. Add the mixture to a twin-screw mixer for melt mixing and granulation to obtain polyetheretherketone granules; The temperature of the twin-screw internal mixer is 320℃ in zone 1, 340℃ in zone 2, 360℃ in zone 3, 370℃ in zone 4, 370℃ in zone 5, 365℃ in zone 6, 360℃ in zone 7, and the temperature of the die head is 355℃. The screw speed is 200 rpm; The screw length-to-diameter ratio is 35:1; S3. Clean the carrier membrane, then melt the polyether ether ketone particles and coat them onto the surface of the carrier membrane. Then, perform biaxial stretching, orientation shaping, and cooling to obtain a polyether ether ketone membrane for use in high-temperature equipment in the semiconductor industry. In step S3, the melting temperature is 370℃ and the coating speed is 0.5 m / min. The biaxial stretching temperature is 160℃, the longitudinal stretching ratio is 1.8 times, and the transverse stretching ratio is 1.8 times. The orientation setting temperature is 320℃, and the time is 30 seconds.

[0036] Example 2

[0037] A polyetheretherketone (PEEK) film for use in high-temperature equipment in the semiconductor industry is prepared by the following method: S1. Stir 1000g of polyether ether ketone resin and 60g of low molecular weight PEEK copolymer at a low speed of 90 rpm. Then add 15g of high temperature resistant antioxidant and 2g of nucleating agent in sequence and stir. Slowly add 35g of two-dimensional boron nitride nanosheets and 20g of perfluoropolyether silane coupling agent and mix at a high speed of 450 rpm to obtain a mixture. The low molecular weight PEEK copolymer has a melt flow rate of 40 g / 10 min at 380 °C and 5 kg, and its number average molecular weight is 25000 g / mol. The two-dimensional boron nitride nanosheets have an aspect ratio of 650 and a sheet thickness of 5 nm. The polyetheretherketone resin has a metal ion content of less than 5 ppb and an initial moisture content of less than 0.1%. The high-temperature resistant antioxidant is (β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate n-octadecyl alcohol ester) and thioether auxiliary antioxidant (TD-P), with a weight ratio of 1:1; The perfluoropolyether silane coupling agent is perfluoropolyether trimethoxysilane, and the molecular weight of its perfluoropolyether segment is 2000 g / mol. The nucleating agent is arylphosphonate (sodium 2,2'-methylene-bis-(4,6-di-tert-butylphenyl)phosphate). S2. Add the mixture to a twin-screw mixer for melt mixing and granulation to obtain polyetheretherketone granules; The temperature of the twin-screw internal mixer is 325℃ in zone 1, 345℃ in zone 2, 363℃ in zone 3, 373℃ in zone 4, 373℃ in zone 5, 368℃ in zone 6, 363℃ in zone 7, and the temperature of the die head is 358℃. The screw speed is 230 rpm; The screw's length-to-diameter ratio is 38:1; S3. Clean the carrier membrane, then melt the polyether ether ketone particles and coat them onto the surface of the carrier membrane. Then, perform biaxial stretching, orientation shaping, and cooling to obtain a polyether ether ketone membrane for use in high-temperature equipment in the semiconductor industry. The melting temperature in step S3 is 373℃, and the coating speed is 1.2m / min; The biaxial stretching temperature is 165℃, the longitudinal stretching ratio is 1.9 times, and the transverse stretching ratio is 1.9 times. The orientation setting temperature is 325℃, and the time is 40 seconds.

[0038] Example 3

[0039] A polyetheretherketone (PEEK) film for use in high-temperature equipment in the semiconductor industry is prepared by the following method: S1. Stir 1000g of polyether ether ketone resin and 80g of low molecular weight PEEK copolymer at a low speed of 100rpm. Then add 20g of high temperature resistant antioxidant and 3g of nucleating agent in sequence and stir. Slowly add 50g of two-dimensional boron nitride nanosheets and 30g of perfluoropolyether silane coupling agent and mix at a high speed of 500rpm to obtain a mixture. The low molecular weight PEEK copolymer has a melt flow rate of 50 g / 10 min at 380 °C and 5 kg, and its number average molecular weight is 30,000 g / mol. The two-dimensional boron nitride nanosheets have an aspect ratio of 800 and a sheet thickness of 10 nm. The polyetheretherketone resin has a metal ion content of less than 5 ppb and an initial moisture content of less than 0.1%. The high-temperature resistant antioxidant is (β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate n-octadecyl alcohol ester) and thioether-based auxiliary antioxidant (TD-P), with a weight ratio of 1:1.5; The perfluoropolyether silane coupling agent is perfluoropolyether trimethoxysilane, and the molecular weight of its perfluoropolyether segment is 3000 g / mol. The nucleating agent is composed of nano-titanium oxide (average particle size of 10 nm) and arylphosphonate (sodium 2,2'-methylene-bis-(4,6-di-tert-butylphenyl)phosphate) in a weight ratio of 1:1; S2. Add the mixture to a twin-screw mixer for melt mixing and granulation to obtain polyetheretherketone granules; The temperature of the twin-screw internal mixer is 330℃ in zone 1, 350℃ in zone 2, 365℃ in zone 3, 375℃ in zone 4, 375℃ in zone 5, 370℃ in zone 6, 365℃ in zone 7, and the temperature of the die head is 360℃. The screw speed is 250 rpm; The screw length-to-diameter ratio is 40:1; S3. Clean the carrier membrane, then melt the polyether ether ketone particles and coat them onto the surface of the carrier membrane. Then, perform biaxial stretching, orientation shaping, and cooling to obtain a polyether ether ketone membrane for use in high-temperature equipment in the semiconductor industry. The melting temperature in step S3 is 375℃, and the coating speed is 2 m / min; The biaxial stretching temperature is 170℃, the longitudinal stretching ratio is 2.0 times, and the transverse stretching ratio is 2.0 times. The orientation setting temperature is 330℃, and the time is 45 seconds.

[0040] Example 4

[0041] A polyetheretherketone (PEEK) membrane for high-temperature equipment in the semiconductor industry. This embodiment differs from Example 1 in that the two-dimensional boron nitride nanosheets are pretreated using the following method: Two-dimensional boron nitride nanosheets were dispersed in a 1 mol / L NaOH solution, ultrasonically treated in a water bath at 70°C for 3 hours, centrifuged and washed until pH=7, and then freeze-dried under vacuum to obtain pretreated two-dimensional boron nitride nanosheets.

[0042] Example 5

[0043] A polyetheretherketone (PEEK) membrane for high-temperature equipment in the semiconductor industry. This embodiment differs from Example 1 in that the two-dimensional boron nitride nanosheets are pretreated using the following method: Two-dimensional boron nitride nanosheets were dispersed in a 1 mol / L NaOH solution, ultrasonically treated in an 80°C water bath for 4 hours, centrifuged and washed until pH=7, and then freeze-dried under vacuum to obtain pretreated two-dimensional boron nitride nanosheets.

[0044] Example 6

[0045] A polyetheretherketone (PEEK) film for high-temperature equipment in the semiconductor industry. The difference between this embodiment and Embodiment 1 is that the aspect ratio of the two-dimensional boron nitride nanosheets is 400.

[0046] Example 7

[0047] A polyetheretherketone (PEEK) film for high-temperature equipment in the semiconductor industry. The difference between this embodiment and Embodiment 1 is that the high-temperature resistant antioxidant is a hindered phenolic main antioxidant. Comparative Example

[0048] Comparative Example 1 A polyetheretherketone (PEEK) membrane for high-temperature equipment in the semiconductor industry is described. The difference between this comparative example and Example 1 is that polyetherimide is used instead of the low molecular weight PEEK copolymer.

[0049] The number-average molecular weight of polyetherimide is 20,000 g / mol.

[0050] Comparative Example 2 A polyetheretherketone membrane for high-temperature equipment in the semiconductor industry. The difference between this comparative example and Example 1 is that KH-550 silane coupling agent is used instead of perfluoropolyether silane coupling agent.

[0051] Comparative Example 3 A polyetheretherketone (PEEK) film for high-temperature equipment in the semiconductor industry is described. The difference between this comparative example and Example 1 is that two-dimensional boron nitride nanosheets are replaced with one-dimensional carbon nanotubes. Detection method / testing method

[0052] Thickness uniformity test: 1) Sampling: Cut 3 sample pieces (100mm×100mm) from the beginning / middle / end of each roll of film, ≥50mm from the edge. Use a non-contact laser thickness gauge to set a detection point every 50mm along the width direction of the film and take the average value. Surface roughness test: Atomic force microscope scans a 10μm×10μm area, set to 256×256 pixels or 512×512 pixels, to ensure horizontal resolution ≤5nm.

[0053] Thermo-oxidative aging performance testing shall be conducted in accordance with GB / T 7141-2008 "Plastics Hot Air Exposure Test Method"; Conditions: 260℃ air atmosphere, continuous aging for 1000h / 2000h / 3000h, periodic sampling to test performance retention rate, tensile strength retention rate according to ASTM D638.

[0054] Surface morphology: Microcrack initiation was observed using SEM. Experimental data are shown in Table 1. Table 1. Experimental data of Examples 1-7 and Comparative Examples 1-3

[0055] As can be seen from the above data, this application improves flowability by reducing viscosity with low molecular weight PEEK copolymer, homogenizes the cooling gradient by constructing an in-plane thermally conductive network with two-dimensional boron nitride nanosheets, and enhances interfacial compatibility with perfluoropolyether silane coupling agent. Together, these technologies precisely control the film thickness tolerance from the traditional 5μm or more to 1.4-1.8μm, with a surface roughness Ra≤42nm. At the same time, the use of hindered phenol / thioether compound antioxidant to capture free radicals, boron nitride sheets to block oxygen penetration, and nucleating agents to refine the spherulite structure results in a tensile strength retention rate of >87% after 3000 hours of thermo-oxidative aging at 260℃, an extended service life, and no microcracks.

[0056] Compared with Examples 1 and 4-5, the pretreatment of two-dimensional boron nitride nanosheets with NaOH solution water bath ultrasonication can reduce the thickness tolerance of the ether ether ketone film, reduce the surface roughness, and improve the thermal aging performance. This indicates that the pretreated two-dimensional boron nitride nanosheets achieve more uniform dispersion and a more stable thermally conductive network construction, thereby synergistically improving the precision forming capability, interfacial bonding strength, and long-term thermo-oxidative stability.

[0057] Comparing Examples 1 and 6-7, it is evident that optimizing the aspect ratio of the two-dimensional boron nitride nanosheets and optimizing the type of high-temperature resistant antioxidants are beneficial for reducing the thickness tolerance and surface roughness of the ether ether ketone film, while also improving the long-term thermal stability of the ether ether ketone film.

[0058] This specific embodiment is merely an explanation of this application and is not intended to limit it. After reading this specification, those skilled in the art can make modifications to this embodiment without contributing any inventive step, but such modifications are protected by patent law as long as they fall within the scope of the claims of this application.

Claims

1. A polyetheretherketone (PEEK) film for use in high-temperature equipment in the semiconductor industry, characterized in that, It is prepared from the following raw materials in parts by weight: 100 parts of polyetheretherketone resin 2-5 parts of two-dimensional boron nitride nanosheets 5-8 parts of low molecular weight PEEK copolymer 1-3 parts of perfluoropolyether silane coupling agent 1-2 parts of high-temperature resistant antioxidant Nucleating agent 0.1-0.3 parts.

2. The polyetheretherketone (PEEK) film for high-temperature equipment in the semiconductor industry according to claim 1, characterized in that: The low molecular weight PEEK copolymer has a melt flow rate of 30-50 g / 10 min at 380°C and 5 kg, and its number average molecular weight is 20,000-30,000 g / mol.

3. The polyetheretherketone (PEEK) film for high-temperature equipment in the semiconductor industry according to claim 1, characterized in that, The two-dimensional boron nitride nanosheets were pretreated using the following method: Two-dimensional boron nitride nanosheets were dispersed in NaOH solution, ultrasonically treated in a water bath at 70-80℃ for 3-4 hours, centrifuged and washed until pH=7, and then freeze-dried under vacuum to obtain pretreated two-dimensional boron nitride nanosheets.

4. The polyetheretherketone (PEEK) film for high-temperature equipment in the semiconductor industry according to claim 3, characterized in that: The two-dimensional boron nitride nanosheets have an aspect ratio of 500-800 and a layer thickness of 1-10 nm.

5. The polyetheretherketone (PEEK) film for high-temperature equipment in the semiconductor industry according to claim 1, characterized in that: The polyetheretherketone resin has a metal ion content of less than 5 ppb and an initial moisture content of less than 0.1%.

6. The polyetheretherketone (PEEK) film for high-temperature equipment in the semiconductor industry according to claim 1, characterized in that: The high-temperature resistant antioxidant is a compound of hindered phenolic primary antioxidant and thioether secondary antioxidant, with a weight ratio of 1:(0.6-1.5).

7. The polyetheretherketone (PEEK) film for high-temperature equipment in the semiconductor industry according to claim 1, characterized in that: The perfluoropolyether silane coupling agent is perfluoropolyether trimethoxysilane, and the molecular weight of its perfluoropolyether segments is 1000-3000 g / mol.

8. A method for preparing a polyetheretherketone (PEEK) film for high-temperature equipment in the semiconductor industry as described in any one of claims 1-9, characterized in that, The preparation steps include the following: S1. Stir the polyether ether ketone resin and low molecular weight PEEK copolymer at low speed, then add the high temperature resistant antioxidant and nucleating agent in sequence and stir. Slowly add the two-dimensional boron nitride nanosheets and perfluoropolyether silane coupling agent, and then mix at high speed to obtain a mixture. S2. Add the mixture to a twin-screw mixer for melt mixing and granulation to obtain polyetheretherketone granules; S3. Clean the carrier membrane, then melt the polyether ether ketone particles and coat them onto the surface of the carrier membrane. Then, perform biaxial stretching, orientation setting, and cooling to obtain a polyether ether ketone membrane for use in high-temperature equipment in the semiconductor industry.

9. The method for preparing a polyetheretherketone film for high-temperature equipment in the semiconductor industry according to claim 8, characterized in that: The melting temperature in step S3 is 370-375℃, and the coating speed is 0.5-2 m / min.

10. The method for preparing a polyetheretherketone (PEEK) film for high-temperature equipment in the semiconductor industry according to claim 8, characterized in that: The biaxial stretching temperature is 160-170℃, the longitudinal stretching ratio is 1.8-2.0 times, and the transverse stretching ratio is 1.8-2.0 times; The orientation setting temperature is 320-330℃, and the time is 30-45 seconds.

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