A semiconductor sealing ring material and its preparation method and application

Abstract

The present invention relates to the field of semiconductor material technology, and in particular to a semiconductor sealing ring material and a preparation method and application thereof. The semiconductor sealing ring material includes the following raw materials of components in parts by weight: 100-120 parts of perfluoroether rubber, 1-5 parts of soluble polytetrafluoroethylene, 5-8 parts of fumed silica, 1-2 parts of boron nitride, 1-2 parts of a cross-linking agent, and 0.2-0.5 parts of a co-cross-linking agent. The formula of the present invention does not contain inorganic compounds containing metal ions, and the filler used has high purity and has the advantage of low metal ion content. Inorganic fillers inevitably contain trace amounts of metal ion impurities. The present invention, when using a small amount of inorganic fillers, not only ensures that the comprehensive properties such as hardness, tensile strength, elongation at break, and compression set are good.

Description

Technical Field

[0001] The present invention relates to the technical field of semiconductor materials, and in particular to a semiconductor sealing ring material and a preparation method and application thereof. Background Art

[0002] Due to the restrictions imposed by developed countries on my country's integrated circuit manufacturing industry, the self-sufficiency rate of semiconductor equipment parts is low. Except for a few parts such as quartz and sleeve rings, the self-sufficiency rate of most parts is less than 10%. Among them, the sealing ring materials used in semiconductor equipment, such as O-ring, are monopolized by large foreign chemical companies. Due to the difficulty of semiconductor technology, the requirements for sealing ring materials are extremely high, so semiconductor sealing rings with excellent performance are increasingly attracting attention.

[0003] Perfluoroether rubber (FFKM) is mainly composed of tetrafluoroethylene and perfluoroalkyl vinyl ether as main monomers, and is copolymerized with a small amount of cross-linkable third monomer. It has significant chemical resistance, high temperature steam resistance, low release and precipitation, and plasma resistance, and is particularly suitable for semiconductor, aerospace, medical and other industries. CN116769266 B discloses a semiconductor perfluoro seal ring. In order to ensure the physical and mechanical properties, a large amount of inorganic compounds containing metal ions are introduced into the formula system. The precipitation of metal ions will affect the wafer processing. At the same time, its compression permanent deformation is greater than 25%, which can only be applied to non-core semiconductor equipment parts with low metal cleanliness requirements and lax sealing. Therefore, the semiconductor seal ring has the characteristics of plasma etching resistance, low metal ion content, compression permanent deformation ≤25%, and resistance to high temperature of 300°C, which can be used in more stringent semiconductor processing technology while ensuring the physical and mechanical properties of hardness (Shao A) 72±3, tensile strength ≥15MPa, and elongation at break ≥140%. Summary of the invention

[0004] In view of the above-mentioned shortcomings of the prior art, the object of the present invention is to provide a semiconductor sealing ring material and a preparation method and application thereof, so as to obtain a semiconductor sealing material with excellent comprehensive performance.

[0005] To achieve the above-mentioned purpose and other related purposes, the present invention provides a semiconductor sealing ring material, comprising the following raw materials in parts by weight: 100-120 parts of perfluoroether rubber, 1-5 parts of soluble polytetrafluoroethylene, 5-8 parts of alkaline fumed silica, 1-2 parts of flaky boron nitride, 1-2 parts of a crosslinking agent, and 0.2-0.5 parts of a co-crosslinking agent.

[0006] The present invention also provides a method for preparing the semiconductor sealing ring material as described above, comprising the following steps:

[0007] 1) uniformly mixing perfluoroether rubber, soluble polytetrafluoroethylene, alkaline fumed silica and flake boron nitride to obtain a masterbatch;

[0008] 2) adding a crosslinking agent and a crosslinking agent to the masterbatch obtained in step 1), vulcanizing the masterbatch to obtain a sulfur product, and storing the product for future use;

[0009] 3) The sulfur product after being parked in step 2) is subjected to secondary sulfurization, and then water-grinded and dried to obtain a semiconductor sealing ring material.

[0010] The present invention also provides a use of the semiconductor sealing ring material as described above in the field of semiconductor processing.

[0011] The present invention also provides a semiconductor sealing ring, which is prepared from the semiconductor sealing ring material as described above.

[0012] As described above, the semiconductor sealing ring material of the present invention has the following beneficial effects:

[0013] The semiconductor perfluoro sealing ring material of the present invention does not contain inorganic compounds of metal ions in the formula, and the filler used is of high purity, with the advantage of low metal ion content. Inorganic fillers will inevitably contain trace amounts of metal ion impurities. The present invention, under the condition of using a small amount of inorganic fillers, not only ensures the physical and mechanical properties of hardness (Shore A) 72±3, tensile strength ≥15MPa, and elongation at break ≥140%, but also ensures a good sealing effect with compression permanent deformation ≤25%. At the same time, good physical and mechanical properties can still be guaranteed under 300°C hot air aging conditions, with hardness (Shore A) change: ±3; tensile strength and elongation at break performance change rate <20%. At the same time, in O2 and CH4 plasma etching, the weight change rate of the sealing ring material after the precipitation of particulate matter is less than 5%, which is completely applicable to semiconductor processing with more stringent environmental requirements. BRIEF DESCRIPTION OF THE DRAWINGS

[0014] Figure 1 It is a schematic diagram of the structure of the flake boron nitride used in the semiconductor perfluoro sealing ring material of the present invention. DETAILED DESCRIPTION

[0015] The following describes in detail a semiconductor sealing ring material and a preparation method and application implementation method thereof.

[0016] "Scope" disclosed in the present application is limited in the form of lower limit and upper limit, and a given range is limited by selecting a lower limit and an upper limit, and the selected lower limit and upper limit define the boundary of a special range. The scope limited in this way can be including end values ​​or not including end values, and can be arbitrarily combined, that is, any lower limit can be combined with any upper limit to form a scope. For example, if the scope of 60-120 and 80-110 is listed for a specific parameter, it is understood that the scope of 60-110 and 80-120 is also expected. In addition, if the minimum range values ​​1 and 2 are listed, and if the maximum range values ​​3, 4 and 5 are listed, the following scope can be all expected: 1-3, 1-4, 1-5, 2-3, 2-4 and 2-5. In the present application, unless otherwise specified, the numerical range "ab" represents the abbreviation of any real number combination between a and b, wherein a and b are real numbers. For example, the numerical range "0-5" means that all real numbers between "0-5" are listed in this document, and "0-5" is just an abbreviation of these numerical combinations. In addition, when a parameter is expressed as an integer ≥ 2, it is equivalent to disclosing that the parameter is, for example, an integer of 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, etc.

[0017] Unless otherwise specified, all embodiments and optional embodiments of the present application can be combined with each other to form a new technical solution.

[0018] After a lot of experimental exploration, the applicant has selected a reinforcement system of resin, white carbon black, and inorganic nitride, which has the advantages of high purity and no or only a small amount of metal compounds. The nano-scale silicon nitride used in this application not only acts as a cross-linking agent, but can also be intercalated in the flake boron nitride in the reinforcement system, and can be cross-linked and interpenetrated in the flake structure, so that the polymer and the flake boron nitride are more tightly combined.

[0019] The present invention, under the condition of using a small amount of inorganic filler, not only ensures the physical and mechanical properties of hardness (Shore A) 72±3, tensile strength ≥15MPa, elongation at break ≥140%, but also ensures good sealing effect with compression permanent deformation ≤25%. At the same time, it can still ensure good physical and mechanical properties under 300℃ hot air aging conditions, hardness (Shore A) change: ±3; tensile strength and elongation at break performance change rate <20%. At the same time, in O2 and CH4 plasma etching, the weight change rate of the sealing ring material after the precipitation of particles is less than 5%, which is completely applicable to semiconductor processing with more stringent environment. And on this basis, the present invention is completed.

[0020] Semiconductor sealing ring materials

[0021] The first aspect of the present invention provides a semiconductor sealing ring material, comprising perfluoroether rubber, soluble polytetrafluoroethylene, alkaline fumed silica, flaky boron nitride, a crosslinking agent, and a co-crosslinking agent.

[0022] The semiconductor sealing ring material provided by the present invention comprises: 100-120 parts of perfluoroether rubber. Optionally, the perfluoroether rubber is 100-105 parts, 105-110 parts, 110-115 parts or 115-120 parts.

[0023] The perfluoroether rubber is a nitrile vulcanization system. The Mooney viscosity ML1+10, 121°C is 30-80. Optionally, the Mooney viscosity ML1+10, 121°C is 30-50, 50-80, 30-40, 40-50, 50-60, 60-70 or 70-80, etc. The size of the Mooney viscosity is determined by the molecular weight and molecular weight distribution of the elastomer, which can reflect the difficulty of processing the elastomer. The Mooney viscosity range of the elastomer used in this application has good fluidity during the processing and molding process, is suitable for the manufacture of sealing rings, and has higher production efficiency.

[0024] In a preferred embodiment of the present invention, the perfluoroether rubber is obtained by copolymerization of tetrafluoroethylene (TFE), perfluoroalkyl vinyl ether (PAVE), and nitrile-containing vulcanization site monomer (CN-CSM). In a preferred embodiment of the present invention, the molar ratio of TFE / PAVE / CN-CSM is 60-70:30-40:0.2-3. The general formula of perfluoroalkyl vinyl ether is R f1 OCF = CF2, where R f1 =CF3(CF2) x , x is an integer of 1 to 3. In a preferred embodiment of the present invention, x is 1, a perfluoroalkyl vinyl ether, such as perfluoromethyl vinyl ether (PMVE).

[0025] The general formula of the nitrile-containing sulfur-site monomer is CF2=CFOR f2 (CF2) n -CN, where R f2 =(CF2CF(CF3)O) m , m is an integer of 0-5; n is an integer of 1-3. In a preferred embodiment of the present invention, n is 1 and m is 2, and the nitrile-containing sulfurization site monomer is such as perfluoro-8-cyano-5-methyl-3,6-dioxa-1-octene (8-CNVE).

[0026] The semiconductor sealing ring material provided by the present invention comprises 1-5 parts of soluble polytetrafluoroethylene, and optionally, 1-3 parts, 3-5 parts, 1-2 parts, 2-3 parts, 3-4 parts or 4-5 parts of soluble polytetrafluoroethylene.

[0027] The zero shear viscosity [η] of the soluble polytetrafluoroethylene is 3500-3800 Pas at 350° C. Optionally, the zero shear viscosity [η] of the soluble polytetrafluoroethylene is 3500-3600 Pas, 3600-3700 Pas or 3700-3800 Pas at 350° C.

[0028] The soluble polytetrafluoroethylene used in the present invention is also called tetrafluoroethylene (TFE)-perfluoroalkoxy vinyl ether (PAVE) copolymer, abbreviated as PFA. The soluble polytetrafluoroethylene with this weight and zero shear viscosity can be dispersed more evenly in the elastomer, and is easy to form a "sea-island" structure, which is beneficial to reinforcement. Beyond this range, the fluidity of the soluble polytetrafluoroethylene is limited, and the plasticity increases, which affects the elasticity of the vulcanized rubber.

[0029] The semiconductor sealing ring material provided by the present invention comprises 5-8 parts of fumed silica, and optionally, 5-6 parts, 6-7 parts or 7-8 parts of fumed silica.

[0030] In a preferred embodiment of the present invention, the BET surface area of ​​basic fumed silica is ≥30 m 2 / g, pH>7, SiO2 content ≥99.8%. Optionally, the BET surface area of ​​fumed silica is 30 to 140 m 2 / g, pH is 8-12.

[0031] The advantage of using alkaline fumed silica within the above weight range is that in the nitrile-based vulcanization system, since -CN is a nitrogen-containing compound, alkaline fillers are helpful for vulcanization. As a conventional reinforcing material, fumed silica can improve hardness, tensile strength, elongation at break, reduce permanent compression set and other advantages. After O2 and CH4 etching, the weight change of the precipitated particles can meet the requirements. When the amount of alkaline fumed silica exceeds 8 parts, although the tensile strength increases, the elongation at break decreases significantly and cannot meet the use requirements. When the amount of alkaline fumed silica is less than 5 parts, the disadvantage is that it is easy to agglomerate, resulting in performance degradation.

[0032] The semiconductor sealing ring material provided by the present invention comprises 1-2 parts of boron nitride. Optionally, the boron nitride is 1-1.5 parts or 1.5-2 parts.

[0033] The structure of the boron nitride is a sheet structure, and the purity of the boron nitride is ≥99.8%. The boron nitride is a sheet boron nitride. The present invention has unexpectedly found through research that different silicon nitride structures also affect the physical and mechanical properties of the O-ring. When using cubic silicon nitride and spherical silicon nitride, the tensile strength and elongation at break cannot meet the use requirements. When using sheet boron nitride, the sheet boron nitride mainly has a reinforcing effect, and can meet the performance requirements of hardness, tensile strength, elongation at break, permanent compression deformation, etc. At the same time, after O2 and CH4 etching, the weight change of the precipitated particles can meet the requirements.

[0034] Furthermore, the amount of flaky boron nitride used is 1-2 parts. Too much will adsorb nano-scale silicon nitride and affect the cross-linking effect of silicon nitride.

[0035] The semiconductor sealing ring material provided by the present invention comprises 1-2 parts of a crosslinking agent. Optionally, the crosslinking agent is 1-1.5 parts or 1.5-2 parts.

[0036] Furthermore, the cross-linking agent is one or both of silicon nitride and carbon nitride.

[0037] Furthermore, the silicon nitride has a flaky crystal structure and a purity of ≥98%. The silicon nitride has a nanostructure, such as α-phase silicon nitride, and another example has a particle size of 30nm to 100nm, and another example has a particle size of 50nm.

[0038] In the semiconductor sealing ring material provided by the present invention, the auxiliary cross-linking agent is a carbamate, and one or two of tert-butyl carbamate (t-BCM), methyl carbamate, etc. can be selected.

[0039] The properties of the semiconductor sealing ring material of the present invention are any one or more of the following:

[0040] a) Hardness (Shore A): 72±3;

[0041] b) Tensile strength ≥15MPa;

[0042] c) Elongation at break ≥ 140%;

[0043] d) Compression set ≤ 25%;

[0044] e) Weight change rate after O2 etching ≤ 5%;

[0045] f) Weight change rate after CH4 etching ≤5%;

[0046] g) Change in hardness (Shore A) after 72h@300℃ hot air aging: ±3;

[0047] h) After 72h@300℃ hot air aging, the change rate of tensile strength is less than 20%;

[0048] i) After 72h@300℃ hot air aging, the change in elongation at break is less than 20%.

[0049] Preparation method of semiconductor sealing ring material

[0050] A second aspect of the present invention provides a method for preparing the semiconductor sealing ring material as described above, comprising the following steps:

[0051] 1) uniformly mixing perfluoroether rubber, soluble polytetrafluoroethylene, fumed silica and flake boron nitride to obtain a masterbatch;

[0052] 2) adding a crosslinking agent and a crosslinking agent to the masterbatch obtained in step 1), vulcanizing the masterbatch to obtain a sulfur product, and storing the product for future use;

[0053] 3) The sulfur product after being parked in step 2) is subjected to secondary sulfurization, and then water-grinded and dried to obtain a semiconductor sealing ring material.

[0054] In the method for preparing the semiconductor sealing ring material of the present invention, in step 1), the soluble polytetrafluoroethylene, fumed silica, and flake boron nitride are mixed in an internal mixer at 80-100° C. Optionally, the mixing is carried out at 80-90° C., 90-100° C., 80-85° C., 85-90° C., 90-95° C., or 95-100° C. In a preferred embodiment of the present invention, the mixing temperature is 80° C.

[0055] In step 1) of the present invention, after the mixing is uniform, the mixture needs to be discharged at 90-110°C to an open mixer for tableting, and left for more than 16 hours to obtain a masterbatch. The discharge temperature can be 90-100°C, 100-110°C, 90-95°C, 95-100°C, 100-105°C or 105-110°C. In a preferred embodiment of the present invention, the discharge temperature is 95°C.

[0056] In step 1) of the present invention, the parking time is greater than 16 hours.

[0057] In the preparation method of the semiconductor sealing ring material of the present invention, in step 2), the masterbatch needs to be thin-passed on the open mill before adding the auxiliary cross-linking agent and the cross-linking agent. After the thin pass, the left and right cutters are cut 2 to 4 times, 2 to 3 times or 3 to 4 times respectively, and the roll speed of the open mill is adjusted to 12 to 14 r / min, 12 to 13 r / min or 13 to 14 r / min for the front roll, 14 to 16 r / min, 14 to 15 r / min or 15 to 16 r / min for the rear roll, and then the roll distance is adjusted to 0.5 to 0.8 mm, 0.5 to 0.6 mm, 0.6 to 0.7 mm or 0.7 to 0.8 mm before adding the auxiliary cross-linking agent and the cross-linking agent. In a preferred embodiment of the present invention, after the thin pass, the left and right cutters are cut 3 times respectively, the roll speed of the open mill is adjusted to 12 r / min for the front roll, 14 r / min for the rear roll, and then the roll distance is adjusted to 0.6 mm before adding the auxiliary cross-linking agent and the cross-linking agent.

[0058] In step 2) of the present invention, after adding the auxiliary cross-linking agent and the cross-linking agent, the triangular package is formed at a roller distance of 0.3 to 0.5 mm, for example, the roller distance is 0.3 to 0.4 mm or 0.4 to 0.5 mm. In a preferred embodiment of the present invention, the triangular package is formed at a roller distance of 0.4 mm. The number of triangular packages is 15 to 20 times, for example, 15 to 16 times, 16 to 17 times, 17 to 18 times, 18 to 19 times or 19 to 20 times. In a preferred embodiment of the present invention, the number of triangular packages is 20 times.

[0059] In step 2) of the present invention, the plate vulcanization temperature is 180-190° C., for example, 180-185° C. or 185-190° C. In a preferred embodiment of the present invention, the plate vulcanization temperature is 180° C.

[0060] In step 2) of the present invention, the plate vulcanization pressure is 10-15 MPa, for example, 10-11 MPa, 11-12 MPa, 12-13 MPa, 13-14 MPa or 14-15 MPa. In a preferred embodiment of the present invention, the plate vulcanization pressure is 11 MPa.

[0061] In step 2) of the present invention, the plate vulcanization time is 15-20 minutes, for example, 15 to 18 minutes or 18 to 20 minutes. In a preferred embodiment of the present invention, the plate vulcanization time is 15 minutes.

[0062] In step 2) of the present invention, the parking time is 16 to 20 hours, for example, 16 to 17 hours, 17 to 18 hours, 18 to 19 hours or 19 to 20 hours.

[0063] In the method for preparing semiconductor sealing ring material of the present invention, in step 3), the secondary vulcanization temperature is 250-290° C., for example, 250-270° C., 250-260° C., 260-270° C., 270-280° C. or 280-290° C. In a preferred embodiment of the present invention, the secondary vulcanization temperature is 290° C.

[0064] In step 3) of the present invention, the secondary vulcanization time is 16-20 hours, for example 16-18 hours, 18-20 hours, 16-17 hours, 17-18 hours, 18-19 hours or 19-20 hours. In a preferred embodiment of the present invention, the secondary vulcanization time is 16 hours.

[0065] The preparation process of the semiconductor sealing ring material of the present invention is carried out in a dust-free workshop of Class 1000 or below. Semiconductor components have relatively high requirements for product cleanliness. In ordinary processing workshops, there will be a large amount of impurities such as dust and bacteria, which affect the sealing ring's resistance to etching gas. The semiconductor sealing ring material prepared by the present invention is prepared in a dust-free workshop of Class 1000, which ensures the product's excellent resistance to etching gas.

[0066] use

[0067] A third aspect of the present invention provides a use of the semiconductor sealing ring material as described above in the field of semiconductor processing.

[0068] A fourth aspect of the present invention provides a semiconductor sealing ring, which is prepared from the semiconductor sealing ring material as described above.

[0069] In the following examples, the reagents, materials and instruments used are all commercially available unless otherwise specified.

[0070] The manufacturer of nitrile vulcanization system perfluoroether rubber is SOLVAY, brand PFR1055B.

[0071] Silicon nitride (α phase, 50 nm) was purchased from Admas, CAS No. 12033-89-5.

[0072] Boron nitride (hexagonal, 150 nm) was purchased from Admas, CAS No. 10043-11-5.

[0073] Boron nitride (flake, 10μm) was purchased from Shenzhen Fangda New Materials Co., Ltd., CAS No. 10043-11-5.

[0074] Boron nitride (spherical, 75 μm) was purchased from Shenzhen Fangda New Materials Co., Ltd., CAS No. 10043-11-5.

[0075] Soluble polytetrafluoroethylene, brand MJ-102, purchased from Mitsui DuPont, CAS No. 26655-00-5.

[0076] Basic fumed silica, brand NA50H, purchased from Evonik, CAS No. 199876-44-3.

[0077] Acidic fumed silica, brand R972, purchased from Evonik, CAS No. 68611-44-9.

[0078] The manufacturer of tert-butyl carbamate was Admas Company, CAS No. 4248-19-5.

[0079] Example 1

[0080] This embodiment provides a semiconductor sealing ring material, and the preparation method thereof includes the following steps:

[0081] 1) In a Class 1000 dust-free workshop, 100 parts of PFR1055B perfluoroether rubber were added to an internal mixer at 80°C. After the rubber compound was stabilized, 5 parts of MJ-102 soluble polytetrafluoroethylene, 5 parts of NA50H alkaline fumed silica, and 1 part of 10μm flake boron nitride were added to the internal mixer. After mixing evenly, the mixture was discharged at a temperature of 95°C. The mixture was pressed on an open mixer and left for 18 hours to obtain a masterbatch.

[0082] 2) The masterbatch obtained in step 1) is thin-passed on an open mill, with the left and right cutters each cutting 3 times, the roller speed is 12r / min for the front roller and 14r / min for the rear roller, the roller spacing is adjusted to 0.6mm, 2 parts of silicon nitride (α phase, 50nm) cross-linking agent and 0.2 parts of t-BCM co-cross-linking agent are added in sequence, and triangle packages are made 20 times at a roller spacing of 0.4mm, and sheets are produced; the flat plate is vulcanized in a Class 1000 dust-free workshop, the vulcanization temperature is 180°C, the vulcanization pressure is 11MPa, and the vulcanization time is 15min. The sulfur product obtained after the flat plate vulcanization is parked for 16h for standby use;

[0083] 3) placing the product of step 2) in a drying oven for secondary vulcanization at a vulcanization temperature of 290° C. for 16 h, and drying the product after disulfurization by water milling to obtain a semiconductor sealing ring material.

[0084] Example 2

[0085] This embodiment provides a semiconductor sealing ring material, and the preparation method thereof includes the following steps:

[0086] 1) In a Class 1000 dust-free workshop, 100 parts of PFR1055B perfluoroether rubber were added to an internal mixer at 80°C. After the rubber compound was stabilized, 5 parts of MJ-102 soluble polytetrafluoroethylene, 5 parts of NA50H alkaline fumed silica, and 2 parts of 10μm flake boron nitride were added to the internal mixer. After mixing evenly, the mixture was discharged at a temperature of 95°C. The mixture was pressed on an open mixer and left for 18 hours to obtain a masterbatch.

[0087] 2) The masterbatch obtained in step 1) is thin-passed on an open mill, with the left and right cutters each cutting 3 times, the roller speed is 12r / min for the front roller and 14r / min for the rear roller, the roller spacing is adjusted to 0.6mm, 2 parts of silicon nitride (α phase, 50nm) cross-linking agent and 0.2 parts of t-BCM co-cross-linking agent are added in sequence, and triangle packages are made 20 times at a roller spacing of 0.4mm, and sheets are produced; the flat plate is vulcanized in a Class 1000 dust-free workshop, the vulcanization temperature is 180°C, the vulcanization pressure is 11MPa, and the vulcanization time is 15min. The sulfur product obtained after the flat plate vulcanization is parked for 16h for standby use;

[0088] 3) placing the product of step 2) in a drying oven for secondary vulcanization at a vulcanization temperature of 290° C. for 16 h, and drying the product after disulfurization by water milling to obtain a semiconductor sealing ring material.

[0089] Example 3

[0090] This embodiment provides a semiconductor sealing ring material, and the preparation method thereof includes the following steps:

[0091] 1) In a Class 1000 dust-free workshop, 100 parts of PFR1055B perfluoroether rubber were added to an internal mixer at 80°C. After the rubber compound was stabilized, 5 parts of MJ-102 soluble polytetrafluoroethylene, 8 parts of NA50H alkaline fumed silica, and 2 parts of 10μm flake boron nitride were added to the internal mixer. After mixing evenly, the mixture was discharged at a temperature of 95°C. The mixture was pressed on an open mixer and left for 18 hours to obtain a masterbatch.

[0092] 2) The masterbatch obtained in step 1) is thin-passed on an open mill, with the left and right cutters each cutting 3 times, the roller speed is 12r / min for the front roller and 14r / min for the rear roller, the roller spacing is adjusted to 0.6mm, 2 parts of silicon nitride (α phase, 50nm) cross-linking agent and 0.2 parts of t-BCM co-cross-linking agent are added in sequence, and triangle packages are made 20 times at a roller spacing of 0.4mm, and sheets are produced; the flat plate is vulcanized in a Class 1000 dust-free workshop, the vulcanization temperature is 180°C, the vulcanization pressure is 11MPa, and the vulcanization time is 15min. The sulfur product obtained after the flat plate vulcanization is parked for 16h for standby use;

[0093] 3) placing the product of step 2) in a drying oven for secondary vulcanization at a vulcanization temperature of 290° C. for 16 h, and drying the product after disulfurization by water milling to obtain a semiconductor sealing ring material.

[0094] Example 4

[0095] This embodiment provides a semiconductor sealing ring material, and the preparation method thereof includes the following steps:

[0096] 1) In a Class 1000 dust-free workshop, 100 parts of PFR1055B perfluoroether rubber were added to an internal mixer at 80°C. After the rubber compound was stabilized, 1 part of MJ-102 soluble polytetrafluoroethylene, 8 parts of NA50H alkaline fumed silica, and 1 part of 10μm flake boron nitride were added to the internal mixer. After mixing evenly, the mixture was discharged at a temperature of 95°C. The mixture was pressed on an open mixer and left for 18 hours to obtain a masterbatch.

[0097] 2) The masterbatch obtained in step 1) is thin-passed on an open mill, with the left and right cutters each cutting 3 times, the roller speed is 12r / min for the front roller and 14r / min for the rear roller, the roller spacing is adjusted to 0.6mm, 2 parts of silicon nitride (α phase, 50nm) cross-linking agent and 0.2 parts of t-BCM co-cross-linking agent are added in sequence, and triangle packages are made 20 times at a roller spacing of 0.4mm, and sheets are produced; the flat plate is vulcanized in a Class 1000 dust-free workshop, the vulcanization temperature is 180°C, the vulcanization pressure is 11MPa, and the vulcanization time is 15min. The sulfur product obtained after the flat plate vulcanization is parked for 16h for standby use;

[0098] 3) placing the product of step 2) in a drying oven for secondary vulcanization at a vulcanization temperature of 290° C. for 16 h, and drying the product after disulfurization by water milling to obtain a semiconductor sealing ring material.

[0099] Example 5

[0100] This embodiment provides a semiconductor sealing ring material, and the preparation method thereof includes the following steps:

[0101] 1) In a Class 1000 dust-free workshop, 100 parts of PFR1055B perfluoroether rubber were added to an internal mixer at 80°C. After the rubber compound was stable, 3 parts of MJ-102 soluble polytetrafluoroethylene, 5 parts of NA50H alkaline fumed silica, and 2 parts of 10μm flake boron nitride were added to the internal mixer. After mixing evenly, the mixture was discharged at a temperature of 95°C. The mixture was pressed on an open mixer and left for 18 hours to obtain a masterbatch.

[0102] 2) The masterbatch obtained in step 1) is thin-passed on an open mill, with the left and right cutters each cutting 3 times, the roller speed is 12r / min for the front roller and 14r / min for the rear roller, the roller spacing is adjusted to 0.6mm, 2 parts of silicon nitride (α phase, 50nm) cross-linking agent and 0.2 parts of t-BCM co-cross-linking agent are added in sequence, and triangle packages are made 20 times at a roller spacing of 0.4mm, and sheets are produced; the flat plate is vulcanized in a Class 1000 dust-free workshop, the vulcanization temperature is 180°C, the vulcanization pressure is 11MPa, and the vulcanization time is 15min. The sulfur product obtained after the flat plate vulcanization is parked for 16h for standby use;

[0103] 3) placing the product of step 2) in a drying oven for secondary vulcanization at a vulcanization temperature of 290° C. for 16 h, and drying the product after disulfurization by water milling to obtain a semiconductor sealing ring material.

[0104] Comparative Example 1

[0105] This comparative example provides a semiconductor sealing ring material, and the preparation method thereof comprises the following steps:

[0106] 1) In a Class 1000 dust-free workshop, 100 parts of PFR1055B perfluoroether rubber were added to an internal mixer at 80°C. After the rubber compound was stabilized, 5 parts of MJ-102 soluble polytetrafluoroethylene, 5 parts of acidic fumed silica R972, and 2 parts of 10μm flake boron nitride were added to the internal mixer. After mixing evenly, the mixture was discharged at a temperature of 95°C. The mixture was pressed on an open mixer and left for 18 hours to obtain a masterbatch.

[0107] 2) The masterbatch obtained in step 1) is thin-passed on an open mill, with the left and right cutters each cutting 3 times, the roller speed is 12r / min for the front roller and 14r / min for the rear roller, the roller spacing is adjusted to 0.6mm, 2 parts of silicon nitride (α phase, 50nm) cross-linking agent and 0.2 parts of t-BCM co-cross-linking agent are added in sequence, and triangle packages are made 20 times at a roller spacing of 0.4mm, and sheets are produced; the flat plate is vulcanized in a Class 1000 dust-free workshop, the vulcanization temperature is 180°C, the vulcanization pressure is 11MPa, and the vulcanization time is 15min. The sulfur product obtained after the flat plate vulcanization is parked for 16h for standby use;

[0108] 3) placing the product of step 2) in a drying oven for secondary vulcanization at a vulcanization temperature of 290° C. for 16 h, and drying the product after disulfurization by water milling to obtain a semiconductor sealing ring material.

[0109] Comparative Example 2

[0110] This comparative example provides a semiconductor sealing ring material, and the preparation method thereof comprises the following steps:

[0111] 1) In a Class 1000 dust-free workshop, 100 parts of PFR1055B perfluoroether rubber were added to an internal mixer at 80°C. After the rubber compound was stabilized, 5 parts of MJ-102 soluble polytetrafluoroethylene, 5 parts of NA50H alkaline fumed silica, and 2 parts of 150nm cubic boron nitride were added to the internal mixer. After mixing evenly, the mixture was discharged at a temperature of 95°C. The mixture was pressed on an open mixer and left for 18 hours to obtain a masterbatch.

[0112] 2) The masterbatch obtained in step 1) is thin-passed on an open mill, with the left and right cutters each cutting 3 times, the roller speed is 12r / min for the front roller and 14r / min for the rear roller, the roller spacing is adjusted to 0.6mm, 2 parts of silicon nitride (α phase, 50nm) cross-linking agent and 0.2 parts of t-BCM co-cross-linking agent are added in sequence, and triangle packages are made 20 times at a roller spacing of 0.4mm, and sheets are produced; the flat plate is vulcanized in a Class 1000 dust-free workshop, the vulcanization temperature is 180°C, the vulcanization pressure is 11MPa, and the vulcanization time is 15min. The sulfur product obtained after the flat plate vulcanization is parked for 16h for standby use;

[0113] 3) placing the product of step 2) in a drying oven for secondary vulcanization at a vulcanization temperature of 290° C. for 16 h, and drying the product after disulfurization by water milling to obtain a semiconductor sealing ring material.

[0114] Comparative Example 3

[0115] 1) In a Class 1000 dust-free workshop, 100 parts of PFR1055B perfluoroether rubber were added to an internal mixer at 80°C. After the rubber compound was stabilized, 5 parts of MJ-102 soluble polytetrafluoroethylene, 5 parts of NA50H alkaline fumed silica, and 2 parts of 75μm spherical boron nitride were added to the internal mixer. After mixing evenly, the mixture was discharged at a temperature of 95°C. The mixture was pressed on an open mixer and left for 18 hours to obtain a masterbatch.

[0116] 2) The masterbatch obtained in step 1) is thin-passed on an open mill, with the left and right cutters each cutting 3 times, the roller speed is 12r / min for the front roller and 14r / min for the rear roller, the roller spacing is adjusted to 0.6mm, 2 parts of silicon nitride (α phase, 50nm) cross-linking agent and 0.2 parts of t-BCM co-cross-linking agent are added in sequence, and triangle packages are made 20 times at a roller spacing of 0.4mm, and sheets are produced; the flat plate is vulcanized in a Class 1000 dust-free workshop, the vulcanization temperature is 180°C, the vulcanization pressure is 11MPa, and the vulcanization time is 15min. The sulfur product obtained after the flat plate vulcanization is parked for 16h for standby use;

[0117] 3) placing the product of step 2) in a drying oven for secondary vulcanization at a vulcanization temperature of 290° C. for 16 h, and drying the product after disulfurization by water milling to obtain a semiconductor sealing ring material.

[0118] Comparative Example 4

[0119] This comparative example provides a semiconductor sealing ring material, and the preparation method thereof comprises the following steps:

[0120] 1) In a Class 1000 dust-free workshop, 100 parts of PFR1055B perfluoroether rubber were added to an internal mixer at 80°C. After the rubber compound was stabilized, 5 parts of MJ-102 soluble polytetrafluoroethylene, 10 parts of NA50H alkaline fumed silica, and 2 parts of 10μm flake boron nitride were added to the internal mixer. After mixing evenly, the mixture was discharged at a temperature of 95°C. The mixture was pressed on an open mixer and left for 18 hours to obtain a masterbatch.

[0121] 2) The masterbatch obtained in step 1) is thin-passed on an open mill, with the left and right cutters each cutting 3 times, the roller speed is 12r / min for the front roller and 14r / min for the rear roller, the roller spacing is adjusted to 0.6mm, 2 parts of silicon nitride (α phase, 50nm) cross-linking agent and 0.2 parts of t-BCM co-cross-linking agent are added in sequence, and triangle packages are made 20 times at a roller spacing of 0.4mm, and sheets are produced; the flat plate is vulcanized in a Class 1000 dust-free workshop, the vulcanization temperature is 180°C, the vulcanization pressure is 11MPa, and the vulcanization time is 15min. The sulfur product obtained after the flat plate vulcanization is parked for 16h for standby use;

[0122] 3) placing the product of step 2) in a drying oven for secondary vulcanization at a vulcanization temperature of 290° C. for 16 h, and drying the product after disulfurization by water milling to obtain a semiconductor sealing ring material.

[0123] Comparative Example 5

[0124] This comparative example provides a semiconductor sealing ring material, and the preparation method thereof comprises the following steps:

[0125] 1) In a Class 1000 dust-free workshop, 100 parts of PFR1055B perfluoroether rubber were added to an internal mixer at 80°C. After the rubber compound was stabilized, 5 parts of MJ-102 soluble polytetrafluoroethylene, 5 parts of NA50H alkaline fumed silica, and 5 parts of 10μm flake boron nitride were added to the internal mixer. After mixing evenly, the mixture was discharged at a temperature of 95°C. The mixture was pressed on an open mixer and left for 18 hours to obtain a masterbatch.

[0126] 2) The masterbatch obtained in step 1) is thin-passed on an open mill, with the left and right cutters each cutting 3 times, the roller speed is 12r / min for the front roller and 14r / min for the rear roller, the roller spacing is adjusted to 0.6mm, 2 parts of silicon nitride (α phase, 50nm) cross-linking agent and 0.2 parts of t-BCM co-cross-linking agent are added in sequence, and triangle packages are made 20 times at a roller spacing of 0.4mm, and sheets are produced; the flat plate is vulcanized in a Class 1000 dust-free workshop, the vulcanization temperature is 180°C, the vulcanization pressure is 11MPa, and the vulcanization time is 15min. The sulfur product obtained after the flat plate vulcanization is parked for 16h for standby use;

[0127] 3) placing the product of step 2) in a drying oven for secondary vulcanization at a vulcanization temperature of 290° C. for 16 h, and drying the product after disulfurization by water milling to obtain a semiconductor sealing ring material.

[0128] Comparative Example 6

[0129] This comparative example provides a semiconductor sealing ring material, and the preparation method thereof comprises the following steps:

[0130] 1) In a Class 1000 dust-free workshop, 100 parts of PFR1055B perfluoroether rubber were added to an internal mixer at 80°C. After the rubber compound was stabilized, 5 parts of MJ-102 soluble polytetrafluoroethylene, 2 parts of NA50H alkaline fumed silica, and 2 parts of 10μm flake boron nitride were added to the internal mixer. After mixing evenly, the mixture was discharged at a temperature of 95°C. The mixture was pressed on an open mixer and left for 18 hours to obtain a masterbatch.

[0131] 2) The masterbatch obtained in step 1) is thin-passed on an open mill, with the left and right cutters each cutting 3 times, the roller speed is 12r / min for the front roller and 14r / min for the rear roller, the roller spacing is adjusted to 0.6mm, 2 parts of silicon nitride (α phase, 50nm) cross-linking agent and 0.2 parts of t-BCM co-cross-linking agent are added in sequence, and triangle packages are made 20 times at a roller spacing of 0.4mm, and sheets are produced; the flat plate is vulcanized in a Class 1000 dust-free workshop, the vulcanization temperature is 180°C, the vulcanization pressure is 11MPa, and the vulcanization time is 15min. The sulfur product obtained after the flat plate vulcanization is parked for 16h for standby use;

[0132] 3) placing the product of step 2) in a drying oven for secondary vulcanization at a vulcanization temperature of 290° C. for 16 h, and drying the product after disulfurization by water milling to obtain a semiconductor sealing ring material.

[0133] As shown in Table 1, the component contents of each embodiment and comparative example are as follows:

[0134] Table 1

[0135]

[0136]

[0137] Performance Test:

[0138] The semiconductor sealing ring materials obtained in each embodiment and comparative example were subjected to performance tests, and the performance test standards and methods are as follows:

[0139] According to ASTM D2240 & D1414 Standard test method for rubber property-Durometer Hardness, test the hardness of rubber materials;

[0140] According to GB / T 528-2009 Determination of tensile stress-strain properties of vulcanized rubber or thermoplastic rubber, the tensile strength and elongation at break of rubber materials are tested; according to GB / T 528-2009 Determination of tensile stress-strain properties of vulcanized rubber or thermoplastic rubber, the tensile strength and elongation at break are tested.

[0141] The compression permanent deformation properties of rubber materials were tested according to ASTM D395-03 Standard test methods for rubber property-Compression Set; sample size: AS568-214 O-ring; test conditions: 204℃, 70h.

[0142] Plasma etching test: at a temperature of 100°C, a time of 60min, a power of 800w, and a gas flow rate of 80sccm, O2 and CH4 ion etching gases were used to calculate the weight change of the particle precipitation. The weight change was based on the following formula: Particle precipitation weight change (%) = (weight before etching - weight after etching) / weight before etching * 100.

[0143] The hot air aging performance was tested according to GB / T3512-2014 Hot air aging and heat resistance test for vulcanized rubber or thermoplastic rubber. The test conditions were: 300°C, 72h.

[0144] The properties of the semiconductor sealing ring materials of Examples 1 to 5 and Comparative Examples 1 to 6 are shown in Table 2:

[0145] Table 2

[0146]

[0147] Combined with Table 1 and Table 2, it can be seen from Example 2 and Comparative Example 1 that the tensile strength of the O-ring is lower than 15MPa when the fumed silica R972 with a pH value less than 7 is used in the system, and the tensile strength of the O-ring cannot meet the use requirements. It can be seen from Example 2 and Comparative Examples 2 and 3 that different silicon nitride structures also affect the physical and mechanical properties of the O-ring. When using cubic silicon nitride and spherical silicon nitride, the tensile strength and elongation at break cannot meet the use requirements. In Comparative Example 4, when the number of fumed silica exceeds 8 parts, although the tensile strength increases, the elongation at break decreases significantly, which cannot meet the use requirements. In Comparative Example 5, increasing the number of flake boron nitride not only reduces the elongation at break, but also fails to meet the use requirements. At the same time, boron nitride is not resistant to the bombardment of CF4 plasma, and the weight change of the precipitated particles exceeds 5%, which cannot meet the semiconductor preparation process. In Comparative Example 6, the 2 parts of alkaline fumed silica have poor reinforcement effect and cannot meet the requirement of tensile strength higher than 15MPa.

[0148] Since the perfluoroether rubber of the nitrile vulcanization system has good heat resistance, the O-rings in the embodiments can maintain good physical and mechanical properties under high temperature conditions of 300°C, with hardness (Shore A) changes of ±3, and the change rates of tensile strength and elongation at break are both <20%, and the changes in hardness are all within the prescribed range of use. At the same time, the plasma etching resistance of the O-rings in the embodiments meets the use requirements. In summary, the O-rings of the present invention can cope with more stringent use conditions, and can be fully used in semiconductor equipment sealing scenarios while ensuring that there are no metal ion compounds in the system.

[0149] In summary, the semiconductor sealing ring material of the present invention does not contain inorganic compounds of metal ions in the formula, and the filler used is of high purity, with the advantage of low metal ion content. Inorganic fillers will inevitably contain trace amounts of metal ion impurities. The present invention, under the condition of using a small amount of inorganic fillers, not only ensures the physical and mechanical properties of hardness (Shore A) 72±3, tensile strength ≥15MPa, and elongation at break ≥140%, but also ensures a good sealing effect with compression permanent deformation ≤25%. At the same time, good physical and mechanical properties can still be guaranteed under 300°C hot air aging conditions, with hardness (Shore A) changes: ±3; tensile strength and elongation at break performance change rates <20%. At the same time, in O2 and CH4 plasma etching, the weight change rate of the sealing ring material after the precipitation of particulate matter is less than 5%, which is completely applicable to semiconductor processing with more stringent environmental requirements.

[0150] The above embodiments are merely illustrative of the principles and effects of the present invention, and are not intended to limit the present invention. Anyone familiar with the art may modify or alter the above embodiments without departing from the spirit and scope of the present invention. Therefore, all equivalent modifications or alterations made by a person of ordinary skill in the art without departing from the spirit and technical concept disclosed by the present invention shall still be covered by the claims of the present invention.

Claims

1. A semiconductor sealing ring material, characterized in that: The raw materials include the following components in parts by weight: Perfluoroether rubber 100-120 parts, soluble polytetrafluoroethylene 1-5 parts, alkaline fumed silica 5-8 parts, flake boron nitride 1-2 parts, crosslinking agent 1-2 parts, co-crosslinking agent 0.2-0.5 parts; The perfluoroether rubber is a nitrile-based vulcanization system; The cross-linking agent is one or both of silicon nitride and carbon nitride, and the particle size of the silicon nitride is 30nm to 100nm.

2. The semiconductor sealing ring material according to claim 1, characterized in that: The Mooney viscosity of the perfluoroether rubber is ML1+10 at 121°C and is 30-80.

3. The semiconductor sealing ring material according to claim 1, characterized in that: The zero shear viscosity [η] of the soluble polytetrafluoroethylene is 3500-3800 Pas at 350°C.

4. The semiconductor sealing ring material according to claim 1, characterized in that: The BET surface area of ​​the basic fumed silica is ≥30 m 2 / g, PH>7, SiO2 content ≥99.8%.

5. The semiconductor sealing ring material according to claim 1, characterized in that: The purity of the flaky boron nitride is ≥99.8%.

6. The semiconductor sealing ring material according to claim 1, characterized in that: The auxiliary cross-linking agent is a carbamate, and the carbamate is one or both of tert-butyl carbamate and methyl carbamate.

7. The semiconductor sealing ring material according to any one of claims 1 to 6, characterized in that: The properties of the semiconductor sealing ring material are any one or more of the following: a) Hardness Shore A: 72±3; b) Tensile strength ≥15MPa; c) Elongation at break ≥ 140%; d) Compression set ≤ 25%; e) Weight change rate after O2 etching ≤5%; f) Weight change rate after CH4 etching ≤5%; g) Change in hardness Shore A after 72h@300℃ hot air aging: ±3; h) After 72h@300℃ hot air aging, the change rate of tensile strength is less than 20%; i) The change rate of elongation at break after 72h@300℃ hot air aging is less than 20%.

8. The method for preparing a semiconductor sealing ring material according to any one of claims 1 to 7, characterized in that: The following steps are involved: 1) Evenly mix perfluoroether rubber, soluble polytetrafluoroethylene, alkaline fumed silica and flake boron nitride to obtain a masterbatch; 2) adding a crosslinking agent and a crosslinking agent to the masterbatch obtained in step 1), vulcanizing the masterbatch to obtain a sulfur product, and storing it for standby use; 3) The sulfur product after being parked in step 2) is subjected to secondary sulfurization, and then water-grinded and dried to obtain a semiconductor sealing ring material.

9. The method for preparing a semiconductor sealing ring material according to claim 8, characterized in that: In step 1), the perfluoroether rubber, soluble polytetrafluoroethylene, alkaline fumed silica, and flake boron nitride are mixed at 80-100° C.; And / or, in step 1), after the mixing is uniform, the mixture is discharged to an open mixer at 90-110°C for tableting and left for more than 16 hours to obtain a masterbatch; And / or, in step 2), before adding the auxiliary cross-linking agent and the cross-linking agent, the masterbatch needs to be thin-passed on the open mill, and after the thin-passing, the left and right cutters are cut 2 to 4 times each, and the roll speed of the open mill is adjusted to 12 to 14 r / min for the front roll and 14 to 16 r / min for the rear roll, and then the roll distance is adjusted to 0.5 to 0.8 mm before adding the auxiliary cross-linking agent and the cross-linking agent; And / or, in step 2), the plate vulcanization temperature is 180-190°C; And / or, in step 2), the plate vulcanization pressure is 10-15 MPa; And / or, in step 2), the plate vulcanization time is 15-20min; And / or, in step 2), the parking time is 16 to 20 hours; And / or, in step 3), the secondary vulcanization is carried out in an oven; And / or, in step 3), the secondary vulcanization temperature is 250-290°C; And / or, in step 3), the secondary vulcanization time is 16-20 hours.

10. Use of the semiconductor sealing ring material according to any one of claims 1 to 7 in the field of semiconductor processing.

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