Passivated perfluoroether elastomer rubber, method of making and use

Abstract

The application provides a passivated perfluoroether elastomer rubber, a preparation method and application. The passivated perfluoroether elastomer rubber is a perfluoroether elastomer rubber with a yttrium trioxide passivation layer on the surface. The preparation method comprises the following steps: placing the perfluoroether elastomer rubber in a vacuum sputtering cavity, performing sputtering treatment on the perfluoroether elastomer rubber by using a yttrium target material, forming a yttrium trioxide passivation layer with a thickness of 10-100 nm, obtaining the passivated perfluoroether elastomer rubber, annealing the passivated perfluoroether elastomer rubber to eliminate surface stress, and cleaning and drying the passivated perfluoroether elastomer rubber for standby. The passivated perfluoroether elastomer rubber is applied to an etching process in a semiconductor process. By sputtering a yttrium trioxide passivation layer, the plasma etching resistance of perfluoroether elastomer rubber products can be effectively improved, and the lubricity of the perfluoroether elastomer rubber products can be improved.

Description

TECHNICAL FIELD

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

[0002] Perfluoroether rubber is a kind of synthetic elastomer, which has excellent high-temperature resistance and chemical medium resistance, and is widely used in aerospace, petrochemical industry, food and medicine, and semiconductor manufacturing fields. However, under extreme working conditions of semiconductor process, such as plasma and high-energy particle environment, the surface and matrix of perfluoroether rubber are prone to rapid loss of fluorine element, resulting in a decrease in chemical resistance and a limitation on service life.

[0003] The existing technology for improving the lubricity of perfluoroether elastomer includes forming a dense fluorocarbon layer by plasma treatment to reduce the adhesion effect, or coating a perfluoro polyether oil or a siloxane derivative on the surface of the elastomer to form a temporary lubricating film to reduce the starting friction.

[0004] In the above technical solutions, the lubricating layer on the surface is prone to damage during dynamic friction, resulting in failure and reducing the service life.

[0005] For example, although the fluorocarbon layer (such as silicon oxide or fluorocarbon) formed by plasma treatment can reduce the surface energy, the chemical bonding with the perfluoroether matrix is weak; the coated perfluoro polyether oil (PFPE) or siloxane derivative is only physically adsorbed and is prone to peeling under continuous shear force. In addition, the surface of the matrix is not pretreated enough, and the surface of the elastomer is not fully activated, resulting in poor adhesion of the coating.

[0006] Based on this, the present application provides a new technical solution. SUMMARY

[0007] Therefore, the present application provides a passivated perfluoroether elastomer rubber,

[0008] The passivated perfluoroether elastomer rubber comprises a perfluoroether elastomer rubber, and a yttrium trioxide passivation layer is sputtered on the surface of the perfluoroether elastomer rubber.

[0009] The thickness of the yttrium trioxide passivation layer is 10-100 nm.

[0010] The present application also provides a preparation method of the passivated perfluoroether elastomer rubber, comprising the following steps:

[0011] The perfluoroether elastomer rubber is placed in a vacuum sputtering chamber, and yttrium target material is used for sputtering treatment to form a yttrium trioxide passivation layer with a thickness of 10-100 nm, thereby obtaining a passivated perfluoroether elastomer.

[0012] The passivated perfluoroether elastomer is sequentially subjected to annealing, cleaning and drying treatment.

[0013] Optionally, the vacuum degree in the vacuum sputtering chamber is ≤1*10 -3 Pa.

[0014] Optionally, argon and oxygen are used as working gas in the sputtering process, the argon flow rate is 15-30 cm 3 / min, the pressure is 0.3-0.6 Pa, the oxygen flow rate is 45-150 cm 3 / min, and the pressure is 0.9-3.0 Pa.

[0015] Optionally, the sputtering temperature is 100-300 ℃.

[0016] Optionally, the sputtering power is 50-300 W, and the sputtering time is 5-30 min.

[0017] The application also provides an application of the passivated perfluoroether elastomer rubber, which is used in the photoetching and etching process in the semiconductor process.

[0018] Compared with the prior art, the above at least one technical solution adopted by the embodiments of the present application can achieve at least the following beneficial effects:

[0019] The technical solution of the present application passivates a yttrium trioxide layer on the surface of the perfluoroether elastomer rubber, and by using the dual effects of physical shielding and chemical inertness, the penetration of plasma and the like into the perfluoroether rubber matrix can be effectively blocked, and the loss rate of fluorine elements in the matrix can be reduced, thereby improving the chemical resistance of the material and prolonging the service life.

[0020] The passivation treatment changes the sample surface from smooth to scale structure, significantly improves the micro-surface roughness, increases the surface area, and improves the adaptability and sealing performance of the sealing member under dynamic working conditions.

[0021] The scale structure of yttrium oxide formed by sputtering is compatible with the elastic properties of the perfluoroether rubber, and the scale structure of the yttrium oxide passivation layer effectively reduces the friction coefficient of the perfluoroether rubber sealing material and improves the use performance of the sealing member.

[0022] The passivation treatment only affects the surface layer of the material and does not damage the dense cross-linked structure of the perfluoroether rubber, the yttrium trioxide layer has good compatibility with the matrix, and the high temperature resistance and elasticity of the perfluoroether rubber itself are maintained. BRIEF DESCRIPTION OF DRAWINGS

[0023] In order to more clearly illustrate the technical solutions of the embodiments of the present application, the following will briefly introduce the drawings needed to be used in the embodiments. Obviously, the drawings described below only illustrate some of the embodiments of the present application, and those skilled in the art can obtain other embodiments according to the drawings without any creative effort.

[0024] Figure 1 It is a flow chart schematic diagram of a preparation method of a passivated perfluoroether elastomer rubber;

[0025] Figure 2 It is a schematic diagram of the surface before and after passivation of Example 1;

[0026] Figure 3 It is a distribution diagram of fluorine (F) and yttrium (Y) on the surface of the passivated perfluoroether rubber of Example 1. DETAILED DESCRIPTION

[0027] The embodiments of the present application will be described in detail below with reference to the drawings.

[0028] The embodiments of the present application will be described in detail below with reference to the drawings.

[0029] It should be noted that the various aspects of the embodiments described below are within the scope of the appended claims. It should be apparent that the aspects described herein can be embodied in a wide variety of forms and that any specific structure and / or function described herein is merely illustrative. Based on the teachings herein one skilled in the art should appreciate that an aspect described herein can be implemented independently of any other aspects and that an aspect described herein can be implemented both as any stand-alone embodiment and as any combination of aspects.

[0030] The embodiments of the present application provide a passivated perfluoroether elastomer rubber: comprising a perfluoroether elastomer rubber, on the surface of the perfluoroether elastomer rubber, a passivation layer of yttrium trioxide is sputtered;

[0031] The thickness of the yttrium trioxide passivation layer is 10-100 nm.

[0032] The embodiment of the present specification also provides a preparation method of passivated perfluoroether elastomer rubber, comprising the following steps:

[0033] The passivated perfluoroether elastomer is sequentially subjected to annealing, cleaning and drying treatment.

[0034] The vacuum degree in the vacuum sputtering cavity is ≤1×10 -3 Pa.

[0035] In the sputtering process, argon and oxygen are used as working gas, the argon flow rate is 15-30 cm 3 / min, the pressure is 0.3-0.6 Pa, the oxygen flow rate is 45-150 cm 3 / min, and the pressure is 0.9-3 Pa.

[0036] The sputtering temperature is 100-300 ℃.

[0037] The sputtering power is 50-300 W, and the sputtering time is 5-30 min.

[0038] The embodiment of the present specification also provides an application of passivated perfluoroether elastomer rubber, wherein the passivated perfluoroether elastomer rubber is used in an etching process in a semiconductor process.

[0039] In the present application, deionized water is used for cleaning unless otherwise specified.

[0040] In the present application, the thickness of the yttrium trioxide passivation layer is obtained by scanning electron microscope detection of the cross section, and the model is JSM 7800F of Japan JEOL Company.

[0041] In the present application, the perfluoroether elastomer rubber specifically refers to an O-shaped sealing ring with a wire diameter of 3.53 mm and an inner diameter of 40.87 mm.

[0042] Example 1

[0043] A preparation method of passivated perfluoroether elastomer rubber, comprising

[0044] The perfluoroether elastomer rubber is placed in a vacuum sputtering cavity, yttrium target material is used for sputtering treatment, a yttrium trioxide passivation layer with a thickness of 10-100 nm is formed, and a passivated perfluoroether elastomer is obtained.

[0045] The passivated perfluoroether elastomer is sequentially subjected to annealing, cleaning and drying treatment.

[0046] The vacuum degree in the vacuum sputtering chamber is ≤1*10 -3 Pa.

[0047] In the sputtering process, argon and oxygen are used as working gas, the argon flow is 20 cm 3 / min, the pressure is 0.4 Pa, the oxygen flow is 80 cm 3 / min, and the pressure is 1.6 Pa.

[0048] The sputtering temperature is 200 ℃.

[0049] The sputtering power is 200 W, and the sputtering time is 20 min.

[0050] The scale structure described in the application is a micron-level flaky yttrium oxide passivation layer distributed on the surface of the perfluoroether elastomer, and gaps exist between the flaky passivation layers, as shown in Figure 2 , which is a surface schematic diagram obtained by observing the elastomer rubber under the condition of one hundred times magnification of a microscope.

[0051] Example 2

[0052] A preparation method of a passivated perfluoroether elastomer rubber, comprising

[0053] The perfluoroether elastomer rubber is placed in a vacuum sputtering chamber, and a yttrium target material is used for sputtering treatment to form a yttrium trioxide passivation layer with a thickness of 10-100 nm, thereby obtaining a passivated perfluoroether elastomer.

[0054] The passivated perfluoroether elastomer is sequentially subjected to annealing and cleaning treatment.

[0055] The vacuum degree in the vacuum sputtering chamber is ≤1*10 -3 Pa.

[0056] In the sputtering process, argon and oxygen are used as working gas, the argon flow is 15 cm 3 / min, the pressure is 0.35 Pa, the oxygen flow is 45 cm 3 / min, and the pressure is 1.05 Pa.

[0057] The sputtering temperature is 180 ℃.

[0058] The sputtering power is 180 W, and the sputtering time is 25 min.

[0059] Example 3

[0060] A preparation method of a passivated perfluoroether elastomer rubber, comprising

[0061] The perfluoroether elastomer rubber is placed in a vacuum sputtering chamber and sputtered using a yttrium target to form a yttrium oxide passivation layer with a thickness of 10-100 nm, thereby obtaining a passivated perfluoroether elastomer.

[0062] The passivated perfluoroether elastomer was subjected to annealing, cleaning and drying processes in sequence.

[0063] The vacuum level in the vacuum sputtering chamber is ≤1×10⁻⁶. -3 Pa.

[0064] Argon and oxygen are used as the working gases in the sputtering process, with an argon flow rate of 25 cm⁻¹. 3 / min, pressure 0.5Pa, oxygen flow rate 140 cm 3 / min, pressure is 2.8 Pa.

[0065] The sputtering temperature is 270 ℃.

[0066] The sputtering power is 270 W and the sputtering time is 30 min.

[0067] This application Figure 3 The scanning electron microscope used was a JSM 7800F from JEOL Corporation of Japan.

[0068] This application Figure 3 The perfluoroether elastomer rubber used is Morizz from Shanghai Senhuan New Material Technology Co., Ltd. ® 5130up.

[0069] The perfluoroether elastomer rubber seal prepared in this embodiment has enhanced adaptability under dynamic working conditions and reduced friction coefficient due to changes in its surface structure. The EDX (X-ray fluorescence spectroscopy analysis, Shimadzu EDX-8100) test results before and after passivation are shown in Table 1.

[0070] Yttrium oxide passivation layer thickness description: The passivation layer thickness in this application is at the micro-nano level, i.e., the microscopic level, and the passivation target is an O-ring. Due to its certain curvature, the sputtering energy at different positions cannot be guaranteed to be uniform, resulting in the passivation layer thickness at different positions not being guaranteed to be a uniform constant value. Therefore, the passivation layer in this application has been measured multiple times, and the statistical thickness is 10-100 nm. In the embodiments of this application, the passivation layer thickness is obtained by detecting the cross-section using a scanning electron microscope.

[0071] Table 1. EDX detection results before and after passivation

[0072]

[0073] Table 2 is the surface friction coefficient (using a friction coefficient instrument DK-3009, Deca Precision Instrument Co., Ltd.) and 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 of perfluoroether elastomer rubber before and after passivation under the action of maximum force 0.737 (N).

[0074] Table 2 Surface friction coefficient and plasma etching results

[0075]

[0076] Through Table 1, Figure 2 and Figure 3 analysis shows that the decrease of F element content indicates that the passivation layer covers part of the perfluoroether rubber surface, or the fluorocarbon chain is broken in the sputtering process. The perfluoroether rubber (FFKM) is originally mainly composed of C-F bonds, and the formation of yttrium trioxide layer introduces Y-O bonds and Y-F bonds, which completes the passivation of the perfluoroether rubber surface, indicating that the treatment only affects the surface layer (usually in nanometers to microns), without damaging the dense cross-linked structure of the perfluoroether rubber.

[0077] Through Table 2 analysis shows that although the scaly structure surface of the perfluoroether rubber after passivation becomes rougher than the smooth surface before passivation, through the friction coefficient analysis, the lubrication performance of the perfluoroether rubber surface after passivation is improved and the friction coefficient is reduced. The mass loss rate of the perfluoroether rubber after passivation after etching is reduced to about 1 / 3 of that before passivation.

[0078] In this specification, the same or similar parts between each embodiment are referred to each other, and each embodiment focuses on the difference from other embodiments. Especially, for the embodiments described later, the description is relatively simple, and the relevant part refers to the part of the foregoing embodiment.

[0079] The above is only a specific embodiment of the present application, but the protection scope of the present application is not limited to this. Any person skilled in the art can easily think of changes or replacements within the technical scope disclosed in the present application, which should be covered within the protection scope of the present application. Therefore, the protection scope of the present application should be subject to the protection scope of the claims.

Claims

1. A passivated perfluoroether elastomer rubber, characterized in that: comprising a perfluoroether elastomer rubber, a yttrium trioxide passivation layer is sputtered on the surface of the perfluoroether elastomer rubber; the thickness of the yttrium trioxide passivation layer is 10-100 nm, the scaly structure of yttrium oxide sputtered is matched with the elastic properties of the perfluoroether rubber, and the yttrium oxide passivation layer of the scaly structure effectively reduces the friction coefficient of the perfluoroether rubber sealing material and improves the performance of the sealing element; the passivated perfluoroether elastomer rubber in claim 1 is used in the sealing field in the semiconductor process.

3. A preparation method of a passivated perfluoroether elastomer rubber, characterized in that: the perfluoroether elastomer rubber is placed in a vacuum sputtering chamber, and a yttrium target is used for sputtering treatment to form a yttrium trioxide passivation layer with a thickness of 10-100 nm, thereby obtaining a passivated perfluoroether elastomer rubber; the passivated perfluoroether elastomer rubber is subjected to annealing treatment to eliminate surface stress, and then is cleaned and dried for standby use; the sputtering temperature is 100-300 ℃. the sputtering time is 5-30 min. In the sputtering process, argon and oxygen are used as working gas, argon flow is 15-30 cm 3 / min, pressure is 0.3-0.6 Pa, oxygen flow is 45-150 cm 3 / min, pressure is 0.9-3.0 Pa, sputtering power is 50-300 W.

2. Use of a perfluoroether elastomer rubber for passivation, characterized in that: ​ ​ ​ ​ In the sputtering process, argon and oxygen are used as working gas, argon flow is 15-30 cm 3 / min, pressure is 0.3-0.6 Pa, oxygen flow is 45-150 cm 3 / min, pressure is 0.9-3.0 Pa, sputtering power is 50-300 W.

4. A process for the preparation of a passivated perfluoroether elastomer rubber according to claim 3, characterized in that: The vacuum degree in the vacuum sputtering chamber is ≤1×10 -3 Pa.

5. A process for the preparation of a passivated perfluoroether elastomer rubber according to claim 3, characterized in that: ​ 6. A process for the preparation of a passivated perfluoroether elastomer rubber according to claim 3, characterized in that: ​

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