Preparation method of hydrogen-etching-resistant single-walled carbon nanotube composite protective film for extreme ultraviolet lithography mask

Abstract

The invention relates to the field of preparation of protective films of extreme ultraviolet lithography masks, in particular to a preparation method of a single-walled carbon nanotube composite protective film for a hydrogen-etching-resistant extreme ultraviolet lithography mask. Growing a single-walled carbon nanotube by using a floating catalyst chemical vapor deposition method, and preparing and assembling a single-walled carbon nanotube film by using a vapor filtration deposition method; the surface of the thin film formed by the single-walled carbon nanotube / tube bundle is coated with the hydrogen etching resistant protective layer, so that the hydrogen etching resistant capability of the protective film of the single-walled carbon nanotube base ultraviolet lithography mask plate is improved. Wherein in order to prevent film failure caused by damage to the single-walled carbon nanotubes in the compounding process, the single-walled carbon nanotube film needs to have high crystallinity, and the Raman spectrum G / D ratio of the single-walled carbon nanotube film is gt; 200). The hydrogen plasma etching resistance of the prepared single-walled carbon nanotube composite film is improved by 4-6 times compared with that of an uncompounded single-walled carbon nanotube film, and meanwhile, the single-walled carbon nanotube composite film has 13.5 nm extreme ultraviolet light transmittance exceeding 85%.

Description

Technical Field

[0001] This invention relates to the field of preparation of protective films for extreme ultraviolet (EUV) lithography masks, specifically a method for preparing a hydrogen-resistant single-walled carbon nanotube composite protective film for EUV lithography masks. Background Technology

[0002] The advent of extreme ultraviolet (EUV) lithography technology has enabled further miniaturization of circuits and significant performance improvements. The EUV transparent film used to protect the photomask from particle impact and contamination during the lithography process must possess high EUV light transmittance, excellent mechanical and thermal properties, thermal stability, and resistance to hydrogen plasma etching. The controllable structure and excellent mechanical, thermal, optical, and chemical stability of carbon nanotubes make it possible to customize carbon nanotube-based EUV lithography photomask protective films according to performance requirements. Furthermore, the extremely high intrinsic EUV transmittance and vacuum heat resistance of single-walled carbon nanotubes make them an ideal candidate material for next-generation high-power EUV lithography photomask protective films.

[0003] However, a significant challenge in using carbon nanotube films as protective films for extreme ultraviolet (EUV) lithography masks is extending their lifespan in EUV-induced hydrogen plasma environments. Lithography systems use low-pressure hydrogen as a background gas, and high-energy EUV radiation excites this hydrogen into low-density hydrogen plasma and free radicals. Ensuring the stability of carbon nanotube-based protective films under the high temperatures and hydrogen plasma etching environment introduced by high-energy EUV light remains a bottleneck issue for using carbon nanotubes as EUV lithography protective films.

[0004] Patent CN109765752A discloses a protective film for EUV lithography and its manufacturing method, using carbon nanotubes only as one of the optional materials for the reinforcing layer of the protective film, addressing the balance between mechanical strength and light transmittance. Patent CN117170178A discloses a thin film for EUV lithography masks and its manufacturing method, using Joule heating to treat the carbon nanotube layer to remove contaminants and form nanotube bundles, but it is difficult to improve resistance to hydrogen plasma etching. Patent CN1413906A discloses a method for preparing carbon nanotubes on a gold / iron composite film, but it only involves the preparation of multi-walled carbon nanotubes under a high-hydrogen atmosphere.

[0005] Carbon nanotubes can be viewed as one-dimensional tubular structures formed by rolling up graphene. Defects on their surface cause uneven distribution of surface charge, creating adsorption sites for hydrogen plasma and accelerating etching. Therefore, preparing carbon nanotubes with high crystallinity (intact wall structure) is crucial for improving the hydrogen resistance of protective films. However, carbon nanotube sp... 2The intrinsic structure of the C-C bond makes it difficult to withstand the combined effects of physical bombardment and chemical etching by high-energy hydrogen plasma.

[0006] Therefore, the key to obtaining carbon nanotube-based protective films with high resistance to hydrogen etching is how to protect carbon nanotubes from etching by hydrogen plasma, thereby extending the effectiveness and lifespan of the carbon nanotube extreme ultraviolet lithography mask protective film. Summary of the Invention

[0007] The purpose of this invention is to provide a method for preparing a hydrogen-resistant extreme ultraviolet lithography mask using a single-walled carbon nanotube composite protective film, thereby solving the key bottleneck problem that the overall performance of current carbon nanotube protective films at home and abroad cannot meet the needs of practical applications, and developing a single-walled carbon nanotube composite protective film with high strength, high extreme ultraviolet light transmittance, and high hydrogen resistance.

[0008] The technical solution of this invention is: A method for preparing a hydrogen-resistant extreme ultraviolet (EUV) lithography mask composite protective film using single-walled carbon nanotubes (SUVs) is disclosed. SUVs are grown using a floating catalyst chemical vapor deposition (CVD) method, and assembled SUV films are prepared using a vapor-phase filtration deposition (VPS). The grown SUVs exhibit extremely high crystallinity, with a Raman spectral G / D ratio > 200. The SUV film is formed by overlapping and entanglement of SUVs / tube bundles. A hydrogen-resistant protective layer is coated onto the surface of the SUV film composed of SUVs / tube bundles, thereby enhancing the hydrogen resistance of the SUV-based EUV lithography mask protective film.

[0009] The method for preparing a hydrogen-resistant extreme ultraviolet lithography mask using a single-walled carbon nanotube composite protective film combines a floating catalyst chemical vapor deposition method with a vapor phase filtration deposition method, avoiding the structural damage and impurity introduction of carbon nanotubes caused by traditional wet methods for preparing carbon nanotube films.

[0010] The method for preparing a hydrogen-resistant extreme ultraviolet lithography mask using a single-walled carbon nanotube composite protective film, wherein the single-walled carbon nanotube refers to a material that, when observed under a transmission electron microscope, consists of only a single layer of tube wall.

[0011] The method for preparing a hydrogen-resistant extreme ultraviolet lithography mask using a single-walled carbon nanotube composite protective film involves coating a hydrogen-resistant protective layer onto the surface of a highly crystalline single-walled carbon nanotube film to enhance the film's resistance to hydrogen plasma etching. The material used to coat the hydrogen-resistant protective layer is one or more of the following: elemental metals and their compounds, Si-based compounds, and two-dimensional materials.

[0012] The method for preparing a hydrogen-etch-resistant extreme ultraviolet lithography mask using a single-walled carbon nanotube composite protective film includes the following metal elements: Fe, Co, Ni, Cu, Au, Ag, Pt, Ti, Zr, W, Nb, Ru, Mo, and Al; and Si-based compounds: Si and SiO. x SiN x SiO x The value of X is in the range of 1 ≤ X ≤ 2, SiN x The value of X ranges from 0.5 to 1.33; two-dimensional materials include Mo2C and MoS2.

[0013] The method for preparing a hydrogen-resistant extreme ultraviolet lithography mask using a single-walled carbon nanotube composite protective film involves the following composite methods for the single-walled carbon nanotube film and the protective layer material: chemical vapor deposition (CVD), magnetron sputtering, atomic layer deposition (ALD), electron beam evaporation, electrodeposition, or hydrothermal assisted methods.

[0014] The method for preparing a hydrogen-resistant extreme ultraviolet lithography mask using a single-walled carbon nanotube composite protective film involves coating the surface of the single-walled carbon nanotube film with a hydrogen-resistant protective layer, using single-walled carbon nanotubes / tube bundles as a substrate, and forming a coaxial coating or a densely packed particle coating on the outer layer of the tubes / tube bundles.

[0015] The method for preparing a hydrogen-resistant extreme ultraviolet lithography mask using a single-walled carbon nanotube composite protective film allows the thickness of the protective layer to be controlled by coating conditions and process parameters.

[0016] The method for preparing a hydrogen-resistant extreme ultraviolet lithography mask using a single-walled carbon nanotube composite protective film shows that the hydrogen plasma etching resistance of the single-walled carbon nanotube composite protective film is 4 to 6 times higher than that of the uncomposite single-walled carbon nanotube film, and it has an extreme ultraviolet light transmittance of over 85% at 13.5 nm.

[0017] The design concept of this invention is: Highly crystalline single-walled carbon nanotubes (SHU) with a Raman spectral G / D ratio > 200 were grown using a floating catalyst chemical vapor deposition (CVD) method. A vapor-phase filtration deposition (VPS) method was then employed to prepare and assemble SHU films, avoiding the damage to the intrinsic structure of carbon nanotubes caused by traditional wet film formation processes. The prepared SHUs exhibit extremely high crystallinity, which not only enhances their hydrogen resistance but also provides an ideal template for subsequent coating of hydrogen-resistant protective layers.

[0018] Using highly crystalline single-walled carbon nanotube films as a substrate, a protective layer with high resistance to hydrogen plasma etching is coated on its surface to enhance the film's hydrogen resistance. By screening coating materials and optimizing the coating process, the contradiction between high hydrogen resistance and high extreme ultraviolet light transmittance is balanced, and a carbon nanotube composite film with high extreme ultraviolet light transmittance and excellent hydrogen etching resistance is finally obtained.

[0019] The advantages and beneficial effects of this invention are: 1. In order to prevent the composite process from damaging the single-walled carbon nanotubes and causing film failure, this invention uses a highly crystalline single-walled carbon nanotube film (Raman spectrum G / D ratio > 200) as a substrate and directly achieves hydrogen etching resistant protective layer coating on the ultrathin self-supporting film. The coating process does not depend on the substrate and does not damage the self-supporting structure of the film.

[0020] 2. By selecting coating materials and optimizing the coating process, this invention achieves controllable coating of hydrogen-resistant etching layers, which improves the hydrogen resistance of the film while ensuring the high extreme ultraviolet light transmittance of the film.

[0021] 3. The single-walled carbon nanotube composite film obtained by this invention has a transmittance of over 85% under extreme ultraviolet light at 13.5 nm, and its resistance to hydrogen plasma etching is 4 to 6 times higher than that of the uncomposite single-walled carbon nanotube film. This effectively solves the core bottleneck of the prior art and is suitable for the practical application requirements of EUV lithography. Attached Figure Description

[0022] Figure 1 (a) Optical photograph and (b) Raman spectrum of single-walled carbon nanotube films grown using floating catalyst chemical vapor deposition. The horizontal axis represents the Raman shift (cm). -1 The vertical axis Intensity represents the relative intensity (au).

[0023] Figure 2 Transmission electron microscopy (TEM) image of a single-walled carbon nanotube film grown using floating catalyst chemical vapor deposition.

[0024] Figure 3 Transmission electron microscopy (TEM) image of a single-walled carbon nanotube / silicon composite film prepared by magnetron sputtering for 15 minutes.

[0025] Figure 4 Transmission electron microscopy (TEM) images of single-walled carbon nanotube / silicon nitride composite films prepared by magnetron sputtering for 20 minutes.

[0026] Figure 5 Transmission electron microscopy (TEM) image of a single-walled carbon nanotube / molybdenum composite film.

[0027] Figure 6 This is a transmission electron microscope (TEM) image of a single-walled carbon nanotube / tungsten composite film. Detailed Implementation

[0028] In its specific implementation, this invention employs a floating catalyst chemical vapor deposition method to grow single-walled carbon nanotubes, a method similar to that used in previous work by our research team (Publication No.: CN110155986A). By introducing trace amounts of water during the growth process, its weak etching effect reduces the amorphous carbon residue on the surface of the grown carbon nanotubes, thereby improving the purity and crystallinity of the single-walled carbon nanotube film. The carbon nanotube film is then collected by gas-phase filtration using a porous membrane at the tail end of the reactor.

[0029] High-strength and tough single-walled carbon nanotube films were transferred onto a hollow framework to form a self-supporting structure, which was then coated with a hydrogen-resistant protective layer. The resistance of the films to hydrogen plasma etching was tested by ionizing hydrogen gas using an radio frequency power source to generate hydrogen plasma. The time to film failure in the hydrogen plasma environment was observed and recorded to evaluate its resistance to hydrogen plasma etching.

[0030] The present invention will now be described in further detail with reference to embodiments and accompanying drawings.

[0031] Example 1

[0032] In this embodiment, a method for preparing a hydrogen-resistant extreme ultraviolet lithography mask using a single-walled carbon nanotube composite protective film includes the following specific steps: (1) In this embodiment, under argon protection, the reactor temperature is first raised to 1100℃, and then hydrogen is switched as the carrier gas; the catalyst solution is injected into the tube furnace by ultrasonic atomization, and ethylene is introduced as a gaseous carbon source. A small amount of argon carries a trace amount of water to the growth process through a Mendel washing bottle, and the carbon nanotube film is collected at the tail end of the tube furnace. Figure 1 As shown in Figure a, an optical image of the collected carbon nanotube thin film is obtained. The thickness of the film can be controlled by different collection times. Figure 1 As shown in b, the thin film was transferred onto a glass slide and characterized by Raman spectroscopy; its G / D ratio was 203. Figure 2 As shown, the thin film was transferred to a copper mesh microgrid and characterized using transmission electron microscopy. The microstructure revealed that all carbon nanotubes were single-layered, i.e., single-walled carbon nanotubes. The tube walls were long and straight, exhibiting good crystallinity.

[0033] (2) A single-walled carbon nanotube (SUV) film with a transmittance of 91% at 550 nm (98% at 13.5 nm) was selected as the base film, and the film was transferred onto a stainless steel ring with a through-hole diameter of 1 cm. Since silicon has high extreme ultraviolet transmittance, it was chosen as a protective layer resistant to hydrogen plasma etching. A SUV / silicon composite film was prepared using magnetron sputtering. The stainless steel ring with the SUV film was attached to a tray and placed inside the magnetron sputtering chamber. The magnetron sputtering equipment was adjusted to radio frequency mode, and silicon was sputtered onto the film for 15 minutes to prepare a silicon-coated SUV / tube bundle composite film. The composite film maintained a high transmittance and self-supporting morphology. Figure 3 As shown, the microstructure of the single-walled carbon nanotube / silicon composite film was characterized using transmission electron microscopy. The single-walled carbon nanotubes / tube bundles have a distinct outer coating layer with a thickness of approximately 2–3 nanometers. Its extreme ultraviolet light transmittance was measured, and it showed a transmittance of 92.5% at a wavelength of 13.5 nm.

[0034] (3) Single-walled carbon nanotube / silicon composite films were treated with hydrogen plasma generated by ionizing hydrogen gas using a radio frequency power supply. The radio frequency power supply frequency was 13.56 MHz and the power was 50 W. The single-walled carbon nanotube / silicon composite films could remain intact in this environment for more than 55 minutes.

[0035] Example 2

[0036] In this embodiment, a method for preparing a hydrogen-resistant extreme ultraviolet lithography mask using a single-walled carbon nanotube composite protective film includes the following specific steps: (1) Step (1) of this embodiment is exactly the same as step (1) of embodiment 1.

[0037] (2) Step (2) of this embodiment is similar to step (2) of embodiment 1. A single-walled carbon nanotube film with a transmittance of 91% at a wavelength of 550 nm is selected. The difference is that the sputtering material is changed to silicon nitride, which also has a high extreme ultraviolet transmittance. The sputtering time is 20 minutes. Figure 4 As shown in the transmission electron microscope (TEM) image of the obtained single-walled carbon nanotube / silicon nitride composite film, the outer layer of the single-walled carbon nanotube bundles has a distinct coating layer with a thickness of approximately 5–6 nanometers. Its extreme ultraviolet (EUV) transmittance was measured, and the transmittance at a wavelength of 13.5 nm was 85.4%.

[0038] (3) Step (3) of this embodiment is the same as step (3) of embodiment 1. The single-walled carbon nanotube / silicon nitride composite film can remain intact in this environment for more than 60 minutes.

[0039] Example 3

[0040] In this embodiment, a method for preparing a hydrogen-resistant extreme ultraviolet lithography mask using a single-walled carbon nanotube composite protective film includes the following specific steps: (1) The single-walled carbon nanotube film used in this embodiment is the same as the film prepared in step (1) of Example 1.

[0041] (2) Step (2) of this embodiment is similar to step (2) of embodiment 1, except that the sputtering material is changed to molybdenum metal, because molybdenum metal also has a relatively high extreme ultraviolet transmittance. The sputtering mode is switched to DC mode, and the sputtering time is 15 minutes. Figure 5 As shown in the transmission electron microscope (TEM) image of the obtained single-walled carbon nanotube / molybdenum composite film, the outer layer of the single-walled carbon nanotube bundles has a distinct coating layer with a thickness of approximately 1–2 nanometers. Its extreme ultraviolet (EUV) transmittance was measured, and the transmittance at a wavelength of 13.5 nm was 82%.

[0042] (3) Step (3) of this embodiment is the same as step (3) of embodiment 1. The single-walled carbon nanotube / molybdenum composite film can remain intact in this environment for more than 50 minutes.

[0043] Example 4

[0044] In this embodiment, a method for preparing a hydrogen-resistant extreme ultraviolet lithography mask using a single-walled carbon nanotube composite protective film includes the following specific steps: (1) The single-walled carbon nanotube film used in this embodiment is the same as the film prepared in step (1) of Example 1.

[0045] (2) In this embodiment, an electron beam evaporation apparatus was used to coat the single-walled carbon nanotube film with molybdenum metal. The thickness of the coating layer on the outside of the tube / tube bundle was controlled to be about 1~2 nm by controlling the evaporation time. Its extreme ultraviolet light transmittance was tested, and its transmittance at a wavelength of 13.5 nm was 83%.

[0046] (3) Step (3) of this embodiment is the same as step (3) of embodiment 1. The single-walled carbon nanotube / molybdenum composite film can remain intact in this environment for more than 45 minutes.

[0047] Example 5

[0048] In this embodiment, a method for preparing a hydrogen-resistant extreme ultraviolet lithography mask using a single-walled carbon nanotube composite protective film includes the following specific steps: (1) The single-walled carbon nanotube film used in this embodiment is the same as the film prepared in step (1) of Example 1.

[0049] (2) In this embodiment, a chemical vapor deposition method was used to coat a single-walled carbon nanotube film with platinum. A platinum-containing organic compound was placed at the front end of a tube furnace, and its position was adjusted to allow it to volatilize or decompose at high temperature. The compound was then carried by argon carrier gas to the film at the rear end of the tube furnace, forming the coating. Through optimization of the coating process, a single-walled carbon nanotube / platinum composite film coated with platinum particles was obtained. Its transmittance at a wavelength of 13.5 nm was 80%.

[0050] (3) Step (3) of this embodiment is the same as step (3) of embodiment 1. The single-walled carbon nanotube / platinum composite film can remain intact in this environment for more than 40 minutes.

[0051] Comparative Example 1 In this comparative example, a method for preparing a single-walled carbon nanotube composite protective film includes the following specific steps: (1) The single-walled carbon nanotube film used in this comparative example is the film prepared in step (1) of Example 1.

[0052] (2) Step (2) of this comparative example is the same as step (3) of Example 1. The single-walled carbon nanotube film is directly transferred to a stainless steel ring and then its resistance to hydrogen plasma etching is tested. The single-walled carbon nanotube film remains intact in this environment for about 10 minutes.

[0053] This comparative example demonstrates that the introduction of a coating layer can effectively improve the hydrogen plasma etching resistance of single-walled carbon nanotube films. Compared with Examples 1 to 5, the coating layer improves the hydrogen etching resistance of single-walled carbon nanotube films by 4 to 6 times.

[0054] Comparative Example 2 In this comparative example, a method for preparing a single-walled carbon nanotube composite protective film includes the following specific steps: (1) Step (1) of this comparative example is similar to step (1) of Example 1, except that water is not introduced through a Mendel washing bottle and the growth temperature is 1000°C. The collected carbon nanotubes are also single-walled carbon nanotubes with a Raman spectrum G / D of 38.

[0055] (2) Step (2) of this comparative example is similar to step (2) of Example 1. A single-walled carbon nanotube film with a transmittance of 91% at a wavelength of 550 nm was selected as the base film, and the same magnetron sputtering conditions were used. The experiment found that after 15 minutes of magnetron sputtering, due to the ion bombardment and etching during the sputtering process, the original single-walled carbon nanotube film could not withstand 15 minutes of magnetron sputtering, resulting in film rupture and making it impossible to continue the hydrogen resistance test.

[0056] This comparative example illustrates that the high strength and toughness of single-walled carbon nanotube films due to their high crystallinity are crucial for the feasibility of introducing coatings; poor-quality single-walled carbon nanotube films have too low strength and poor impact resistance, making it difficult to coat them through post-processing.

[0057] Comparative Example 3 In this comparative example, a method for preparing a single-walled carbon nanotube composite protective film includes the following specific steps: (1) The single-walled carbon nanotube film used in this comparative example is the same as the film prepared in step (1) of Example 1.

[0058] (2) Step (2) of this comparative example is similar to step (2) of Example 1, except that the sputtering material is replaced with tungsten metal. Figure 6 As shown, when the sputtering mode was switched to DC mode and the sputtering time was 15 minutes, the obtained transmission electron microscopy (TEM) image of the single-walled carbon nanotube / tungsten composite film showed a distinct coating layer on the outer layer of the single-walled carbon nanotube bundles. The extreme ultraviolet (EUV) transmittance was tested, and its transmittance at a wavelength of 13.5 nm was only 73%. This is because metallic tungsten has a strong absorption of EUV light.

[0059] (3) Step (3) of this comparative example is the same as step (3) of Example 1. The single-walled carbon nanotube / tungsten composite film can remain intact in this environment for more than 50 minutes.

[0060] This comparative example illustrates that while introducing a coating layer can improve the hydrogen etching resistance of the film, the coating layer can also reduce the extreme ultraviolet light transmittance of the film. It is necessary to select a suitable coating material and adjust the coating thickness to achieve both high hydrogen etching resistance and high light transmittance.

[0061] The results of the examples and comparative examples show that highly crystalline single-walled carbon nanotubes (SUVs) can be grown using floating catalyst chemical vapor deposition (CVD), and assembled SUV films can be prepared using vapor phase filtration deposition (VPS). A hydrogen-resistant protective layer is coated onto the surface of the film composed of SUVs / tube bundles, thereby improving the hydrogen etching resistance of the SUV-based extreme ultraviolet (EUV) photomask protective film. The prepared SUV composite film exhibits 4–6 times greater resistance to hydrogen plasma etching compared to the uncomposite SUV film, while simultaneously possessing over 85% EUV transmittance at 13.5 nm.

[0062] Although the present invention has been described in detail above with general descriptions and specific embodiments, modifications or improvements can be made to it, which will be obvious to those skilled in the art. Therefore, all such modifications or improvements made without departing from the spirit of the present invention are within the scope of protection claimed by the present invention.

Claims

1. A method for preparing a hydrogen-resistant extreme ultraviolet lithography mask using a single-walled carbon nanotube composite protective film, characterized in that, Single-walled carbon nanotubes (SUVs) were grown using a floating catalyst chemical vapor deposition (CVD) method, and assembled SUV films were prepared using a vapor-phase filtration deposition (VPS) method. The grown SUVs exhibited extremely high crystallinity, with a Raman spectral G / D ratio > 200. The SUV films were formed by overlapping and entanglement of SUVs / tube bundles. A hydrogen-resistant protective layer was coated onto the surface of the SUV films composed of SUVs / tube bundles, thereby enhancing the hydrogen etch resistance of the SUV-based ultraviolet lithography mask protective film.

2. The method for preparing a hydrogen-resistant extreme ultraviolet lithography mask using a single-walled carbon nanotube composite protective film according to claim 1, characterized in that, The combination of floating catalyst chemical vapor deposition and vapor phase filtration deposition avoids the structural damage and impurity introduction of carbon nanotubes caused by traditional wet methods for preparing carbon nanotube films.

3. The method for preparing a hydrogen-resistant extreme ultraviolet lithography mask using a single-walled carbon nanotube composite protective film according to claim 1, characterized in that, Single-walled carbon nanotubes are those that, when observed under a transmission electron microscope, consist of only a single layer of tube wall.

4. The method for preparing a hydrogen-resistant extreme ultraviolet lithography mask using a single-walled carbon nanotube composite protective film according to claim 1, characterized in that, A hydrogen-resistant protective layer is coated on the surface of a highly crystalline single-walled carbon nanotube film to enhance the film's resistance to hydrogen plasma etching. The material used to coat the hydrogen-resistant protective layer is one or more of the following: elemental metals and their compounds, Si-based compounds, and two-dimensional materials.

5. The method for preparing a hydrogen-resistant extreme ultraviolet lithography mask using a single-walled carbon nanotube composite protective film according to claim 4, characterized in that, Metallic elements include Fe, Co, Ni, Cu, Au, Ag, Pt, Ti, Zr, W, Nb, Ru, Mo, and Al; Si-based compounds include Si and SiO. x SiN x SiO x The value of X is in the range of 1 ≤ X ≤ 2, SiN x The value of X ranges from 0.5 to 1.33; two-dimensional materials include Mo2C and MoS2.

6. The method for preparing a hydrogen-resistant extreme ultraviolet lithography mask composite protective film using single-walled carbon nanotubes according to claim 1 or 5, characterized in that, The composite methods for single-walled carbon nanotube films and protective layer materials include: chemical vapor deposition (CVD), magnetron sputtering, atomic layer deposition (ALD), electron beam evaporation, electrodeposition, or hydrothermal assisted methods.

7. The method for preparing a hydrogen-resistant extreme ultraviolet lithography mask using a single-walled carbon nanotube composite protective film according to claim 1, characterized in that, A hydrogen-resistant protective layer is coated on the surface of a single-walled carbon nanotube film. The single-walled carbon nanotube / tube bundle is used as the substrate, and a coaxial coating or a densely packed particle coating is formed on the outer layer of the tube / tube bundle.

8. The method for preparing a hydrogen-resistant extreme ultraviolet lithography mask using a single-walled carbon nanotube composite protective film according to claim 1, characterized in that, The thickness of the protective layer is controlled by coating conditions and process parameters.

9. The method for preparing a hydrogen-resistant extreme ultraviolet lithography mask using a single-walled carbon nanotube composite protective film according to claim 1, characterized in that, The hydrogen plasma etching resistance of the single-walled carbon nanotube composite protective film is 4 to 6 times higher than that of the uncomposite single-walled carbon nanotube film, and it has a transmittance of more than 85% of 13.5 nm extreme ultraviolet light.

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