Passivated perfluoroether elastomer rubber, preparation method and application

Abstract

The invention provides passivated perfluoroether elastomer rubber as well as a preparation method and application thereof. The passivated perfluoroether elastomer rubber is prepared by sputtering an yttrium oxide passivation layer on the surface of perfluoroether elastomer rubber. The preparation method comprises the following steps: placing the perfluoroether elastomer rubber in a vacuum sputtering cavity, and carrying out sputtering treatment by adopting an yttrium target material to form an yttrium oxide passivation layer with the thickness of 10-100 nm so as to obtain passivated perfluoroether elastomer rubber; and carrying out annealing treatment on the passivated perfluoroether elastomer rubber to eliminate surface stress, and then cleaning and drying for later use. The passivated perfluoroether elastomer rubber is applied to the etching process in the semiconductor manufacturing process, the plasma etching resistance of a perfluoroether elastomer rubber product can be effectively improved by sputtering the yttrium oxide passivation layer, and meanwhile the lubricating performance of the perfluoroether elastomer rubber product is improved.

Description

Technical Field

[0001] The present application relates to the technical field of fluoroelastomer rubber, and in particular to a passivated perfluoroether elastomer rubber, a preparation method and an application thereof. Background Art

[0002] Perfluoroelastomer (PFER) is a synthetic elastomer with excellent resistance to high temperatures and chemical media. It is widely used in aerospace, petrochemical, food and pharmaceutical, and semiconductor manufacturing. However, under the extreme operating conditions of semiconductor manufacturing, such as plasma and high-energy particle environments, the surface and matrix of PFER are prone to rapid fluorine loss, resulting in a decrease in its chemical resistance and a limited service life.

[0003] Prior art processes for improving the lubricity of perfluoroether elastomers include plasma treatment to form a dense fluorocarbon layer to reduce the viscosity effect; or coating the elastomer surface with perfluoropolyether oil or silicone derivatives to form a temporary lubricating film to reduce starting friction.

[0004] The above technical solutions are all prone to damage of the surface lubricating layer during the dynamic friction process, resulting in failure and reduced service life.

[0005] For example, while plasma treatment can reduce surface energy, the fluorocarbon layer (such as silicon oxide or carbon fluoride) formed by plasma treatment only weakly bonds with the perfluoroether matrix. Applied perfluoropolyether oils (PFPE) or silicone derivatives are only physically adsorbed and easily peel under sustained shear forces. Furthermore, insufficient substrate surface pretreatment and insufficient activation of the elastomer surface result in poor coating adhesion.

[0006] Based on this, the present invention provides a new technical solution. Summary of the Invention

[0007] In view of this, the present invention provides a passivated perfluoroether elastomer rubber. The invention comprises a perfluoroether elastomer rubber, on the surface of which an yttrium trioxide passivation layer is sputtered; The thickness of the yttrium oxide passivation layer is 10-100 nm.

[0008] The present application also provides a method for preparing a passivated perfluoroether elastomer rubber, comprising: The perfluoroether elastomer rubber is placed in a vacuum sputtering chamber and sputtered using an yttrium target to form an yttrium trioxide passivation layer with a thickness of 10-100 nm to obtain a passivated perfluoroether elastomer; The passivated perfluoroether elastomer is subjected to annealing, cleaning and drying treatments in sequence.

[0009] Optionally, the vacuum degree in the vacuum sputtering chamber is ≤1×10-3 Pa.

[0010] Optionally, during the sputtering process, argon and oxygen are used as working gases, and the argon flow rate is 15-30 cm 3 / min, pressure 0.3-0.6 Pa, oxygen flow rate 45-150 cm 3 / min, pressure is 0.9-3.0 Pa.

[0011] Optionally, the sputtering temperature is 100-300°C.

[0012] Optionally, the sputtering power is 50-300 W, and the sputtering time is 5-30 min.

[0013] The present application also provides an application of a passivated perfluoroether elastomer rubber, wherein the passivated perfluoroether elastomer rubber is used in photolithography and etching processes in semiconductor manufacturing processes.

[0014] Compared with the prior art, the at least one technical solution adopted in the embodiments of this specification can achieve the following beneficial effects: The technical solution of the present application, by sputtering a yttrium trioxide passivation layer on the surface of perfluoroether elastomer rubber, utilizes the dual effects of physical shielding and chemical inertness to effectively block the penetration of plasma and other substances into the perfluoroether rubber matrix, reducing the loss rate of fluorine elements in the matrix, thereby improving the chemical resistance of the material and extending its service life; The passivation treatment transforms the sample surface from smooth to scaly, significantly increasing the microscopic surface roughness, increasing the surface area, and improving the adaptability and sealing performance of the seal under dynamic working conditions. The scaly structure of yttrium oxide formed by sputtering is compatible with the elastic properties of perfluoroether rubber, and the yttrium oxide passivation layer with a scaly structure effectively reduces the friction coefficient of the perfluoroether rubber sealing material, thereby improving the performance of the seal. The passivation treatment only affects the surface layer of the material and does not destroy the dense cross-linked structure of the perfluoroether rubber. The yttrium oxide layer has good compatibility with the matrix, maintaining the high temperature resistance and elasticity of the perfluoroether rubber itself. BRIEF DESCRIPTION OF THE DRAWINGS

[0015] In order to more clearly illustrate the technical solutions of the embodiments of the present application, the following briefly introduces the drawings required for use in the embodiments. Obviously, the drawings described below are only some embodiments of the present application. For ordinary technicians in this field, they can also refer to these attached process diagrams without paying any creative work.

[0016] Figure 1 The present invention is a schematic flow chart of a method for preparing a passivated perfluoroether elastomer rubber; Figure 2 Schematic diagram of the surface before and after passivation of Example 1; Figure 3 This is the distribution diagram of fluorine (F) and yttrium (Y) on the surface of perfluoroether rubber after passivation in Example 1. DETAILED DESCRIPTION

[0017] The embodiments of the present application are described in detail below with reference to the accompanying drawings.

[0018] The following describes the embodiments of the present application through specific examples, and those skilled in the art can easily understand other advantages and effects of the present application from the contents disclosed in this specification. Obviously, the described embodiments are only a part of the embodiments of the present application, rather than all the embodiments. The present application can also be implemented or applied through other different specific embodiments, and the details in this specification can also be modified or changed in various ways based on different viewpoints and applications without departing from the spirit of the present application. It should be noted that, in the absence of conflict, the features in the following embodiments and embodiments can be combined with each other. Based on the embodiments in the present application, all other embodiments obtained by those of ordinary skill in the art without making creative work are within the scope of protection of this application.

[0019] It should be noted that various aspects of the embodiments within the scope of the appended claims are described below. It should be apparent that the aspects described herein can be embodied in a wide variety of forms, and any specific structures and / or functions described herein are merely illustrative. Based on this application, those skilled in the art will appreciate that an aspect described herein can be implemented independently of any other aspect, and two or more of these aspects can be combined in various ways. In addition, in the following description, specific details are provided to facilitate a thorough understanding of the examples. However, those skilled in the art will understand that practice can be performed without these specific details.

[0020] The embodiment of this specification provides a passivated perfluoroether elastomer rubber: comprising a perfluoroether elastomer rubber, on the surface of which a yttrium trioxide passivation layer is sputtered; The thickness of the yttrium oxide passivation layer is 10-100 nm.

[0021] The present specification also provides a method for preparing a passivated perfluoroether elastomer rubber, comprising placing the perfluoroether elastomer rubber in a vacuum sputtering chamber and sputtering the perfluoroether elastomer rubber using a yttrium target to form a yttrium oxide passivation layer with a thickness of 10-100 nm to obtain a passivated perfluoroether elastomer; The passivated perfluoroether elastomer is subjected to annealing, cleaning and drying treatments in sequence.

[0022] The vacuum degree in the vacuum sputtering chamber is ≤1×10-3 Pa.

[0023] During the sputtering process, argon and oxygen were used as working gases, and the argon flow rate was 15-30 cm 3 / min, pressure 0.3-0.6 Pa, oxygen flow rate 45-150 cm 3 / min, pressure is 0.9-3 Pa.

[0024] The sputtering temperature is 100-300°C.

[0025] The sputtering power is 50-300 W, and the sputtering time is 5-30 min.

[0026] The embodiments of this specification also propose an application of a passivated perfluoroether elastomer rubber: the passivated perfluoroether elastomer rubber is used in an etching process in a semiconductor manufacturing process.

[0027] Unless otherwise specified, the cleaning steps in this application were performed with deionized water.

[0028] The thickness of the yttrium oxide passivation layer in the embodiment of the present application was obtained by detecting the cross section using a scanning electron microscope (SEM), model JSM 7800F, produced by JEOL, Japan.

[0029] The perfluoroether elastomer rubber used in the embodiment of the present application is specifically an O-ring with a wire diameter of 3.53 mm and an inner diameter of 40.87 mm.

[0030] Example 1 A method for preparing passivated perfluoroether elastomer rubber, comprising: The perfluoroether elastomer rubber is placed in a vacuum sputtering chamber and sputtered using an yttrium target to form an yttrium trioxide passivation layer with a thickness of 10-100 nm to obtain a passivated perfluoroether elastomer; The passivated perfluoroether elastomer is subjected to annealing, cleaning and drying treatments in sequence.

[0031] The vacuum degree in the vacuum sputtering chamber is ≤1×10 -3 Pa.

[0032] In the sputtering process, argon and oxygen were used as working gases, and the argon flow rate was 20 cm 3 / min, pressure 0.4Pa, oxygen flow rate 80 cm 3 / min, pressure is 1.6 Pa.

[0033] The sputtering temperature is 200°C.

[0034] The sputtering power was 200 W, and the sputtering time was 20 min.

[0035] The scale structure described in this application is a micron-sized flaky yttrium oxide passivation layer distributed on the surface of the perfluoroether elastomer, and there are gaps between the flaky passivation layers, such as Figure 2 As shown, it is a schematic diagram of the surface of the elastomer rubber observed under a microscope with a magnification of 100 times.

[0036] Example 2 A method for preparing passivated perfluoroether elastomer rubber, comprising: The perfluoroether elastomer rubber is placed in a vacuum sputtering chamber and sputtered using an yttrium target to form an yttrium trioxide passivation layer with a thickness of 10-100 nm to obtain a passivated perfluoroether elastomer; The passivated perfluoroether elastomer is subjected to annealing and cleaning treatments in sequence.

[0037] The vacuum degree in the vacuum sputtering chamber is ≤1×10 -3 Pa.

[0038] In the sputtering process, argon and oxygen were used as working gases, and the argon flow rate was 15 cm 3 / min, pressure 0.35 Pa, oxygen flow rate 45 cm 3 / min, pressure is 1.05 Pa.

[0039] The sputtering temperature is 180°C.

[0040] The sputtering power was 180 W, and the sputtering time was 25 min.

[0041] Example 3 A method for preparing passivated perfluoroether elastomer rubber, comprising: The perfluoroether elastomer rubber is placed in a vacuum sputtering chamber and sputtered using an yttrium target to form an yttrium trioxide passivation layer with a thickness of 10-100 nm to obtain a passivated perfluoroether elastomer; The passivated perfluoroether elastomer is subjected to annealing, cleaning and drying treatments in sequence.

[0042] The vacuum degree in the vacuum sputtering chamber is ≤1×10 -3 Pa.

[0043] During the sputtering process, argon and oxygen were used as working gases, and the argon flow rate was 25 cm 3 / min, pressure 0.5Pa, oxygen flow rate 140 cm 3 / min, pressure is 2.8 Pa.

[0044] The sputtering temperature is 270°C.

[0045] The sputtering power was 270 W, and the sputtering time was 30 min.

[0046] This application Figure 3 The scanning electron microscope used was a JSM 7800F from JEOL, Japan.

[0047] This application Figure 3 The perfluoroether elastomer rubber used is Morisz from Shanghai Senhuan New Material Technology Co., Ltd. ® 5130up.

[0048] The perfluoroether elastomer rubber sealing ring prepared in the examples of the present application has enhanced adaptability under dynamic working conditions and reduced friction coefficient due to the change in surface structure. The EDX (X-ray fluorescence spectrometry, Shimadzu EDX-8100) test results before and after passivation are shown in Table 1.

[0049] Explanation of the thickness of the yttrium oxide passivation layer: The thickness of the passivation layer of this application is at the micro-nano level, that is, the microscopic level, and the passivation object is an O-ring. Due to the existence of a certain curvature, the energy of sputtering at different positions cannot be guaranteed to be uniform, resulting in the thickness of the passivation layer at different positions cannot be guaranteed to be a uniform fixed value. Therefore, the passivation layer of this application has been measured many times, and the statistical thickness is 10-100 nm. The thickness of the passivation layer in the embodiment of this application is obtained by detecting the cross section using a scanning electron microscope.

[0050] Table 1 EDX detection results before and after passivation

[0051] Table 2 shows the surface friction coefficient (using friction coefficient meter DK-3009, Deka Precision Instrument Co., Ltd.) of perfluoroether elastomer rubber before and after passivation under the maximum force of 0.737 (N) and the mass loss rate before and after plasma etching (O2 / CF4 plasma, power 800 W, flow rate 50 / 50 cm 3 / min, vacuum degree 500 mt, plasma etching (see Senhuan Enterprise Standard Q / SMS 001-2024) test results.

[0052] Table 2 Surface friction coefficient and plasma etching results

[0053] Through Table 1, Figure 2 and Figure 3Analysis showed that the reduction in the F element content indicated that the passivation layer covered part of the perfluoroether rubber surface, or that the fluorocarbon chain broke during the sputtering process. Perfluoroether rubber (FFKM) was originally mainly composed of CF bonds. The formation of the yttrium oxide layer introduced YO bonds and YF bonds, completing the passivation of the perfluoroether rubber surface, indicating that the treatment only affected the surface layer (the thickness is usually in the nanometer to micrometer level) and did not destroy the dense cross-linked structure of the perfluoroether rubber.

[0054] The analysis in Table 2 shows that although the scaly surface of the perfluoroether rubber surface becomes rougher than the smooth surface before passivation, the friction coefficient analysis shows that the lubrication performance of the perfluoroether rubber surface after passivation is improved and the friction coefficient is reduced. The mass loss rate of the passivated perfluoroether rubber after etching is reduced to about 1 / 3 of that before passivation.

[0055] In this specification, the same or similar parts between the various embodiments can be referred to each other, and each embodiment focuses on the differences from other embodiments. In particular, for the embodiments described later, the description is relatively simple, and the relevant parts can be referred to the partial description of the previous embodiments.

[0056] The above description is merely a specific embodiment of the present application, but the scope of protection of the present application is not limited thereto. Any changes or substitutions that can be easily conceived by a person skilled in the art within the technical scope disclosed in the present application should be included in the scope of protection of the present application. Therefore, the scope of protection of the present application should be based on the scope of protection of the claims.

Claims

1. A passivated perfluoroether elastomer rubber, characterized in that: The invention comprises a perfluoroether elastomer rubber, on the surface of which an yttrium trioxide passivation layer is sputtered; The thickness of the yttrium oxide passivation layer is 10-100 nm.

2. An application of a passivated perfluoroether elastomer rubber, characterized in that: The passivated perfluoroether elastomer rubber according to claim 1 is used in the sealing field in semiconductor manufacturing processes.

3. A method for preparing a passivated perfluoroether elastomer rubber, characterized in that: The perfluoroether elastomer rubber is placed in a vacuum sputtering chamber and sputtered using an yttrium target to form an yttrium trioxide passivation layer with a thickness of 10-100 nm to obtain a passivated perfluoroether elastomer rubber; The passivated perfluoroether elastomer rubber is annealed to eliminate surface stress, and then cleaned and dried for later use.

4. The method for preparing a passivated perfluoroether elastomer rubber according to claim 3, wherein: The vacuum degree in the vacuum sputtering chamber is ≤1×10 -3 Pa.

5. The method for preparing a passivated perfluoroether elastomer rubber according to claim 3, wherein: During the sputtering process, argon and oxygen were used as working gases, and the argon flow rate was 15-30 cm 3 / min, pressure 0.3-0.6 Pa, oxygen flow rate 45-150 cm 3 / min, pressure is 0.9-3.0 Pa.

6. The method for preparing a passivated perfluoroether elastomer rubber according to claim 3, wherein: The sputtering temperature is 100-300°C.

7. The method for preparing a passivated perfluoroether elastomer rubber according to claim 3, wherein: The sputtering power is 50-300 W, and the sputtering time is 5-30 min.

Images