Method for forming a metallic coating on a film of a HARM structure attached to a support

Abstract

A method for forming a metallic coating on a film of high aspect ratio molecular structures (HARM structures) attached to a support, the method comprising: providing an electrode comprising a film of HARM structures attached to a support, the support having a current collector; and subjecting the electrode to an electrodeposition process in an aqueous deposition bath of a metal complex and / or its salt, the electrodeposition process comprising first, at a first potential value in the range of 0.2 to 5 V, to form a metallic coating on the film of HARM structures attached to the support; and then, at a second potential value in the range of 0 to -4 V, to etch the formed metallic coating.

Description

[Technical Field]

[0001] The present disclosure relates to filters including films of high aspect ratio molecular structures (HARM structures). Another aspect of the present disclosure relates to methods of forming a metal-based coating on a film of high aspect ratio molecular structures (HARM structures) attached to a support. The present disclosure further relates to metal-based coatings on films of HARM structures attached to a support. The present disclosure further relates to uses of metal-based coatings on films of HARM structures attached to a support. [Background technology]

[0002] Electrodeposition (also called electroplating) is a process in which an electric current is used to controllably deposit a material onto a conductive surface from a solution containing ionic species. That is, electrodeposition is a process in which an electric current is used to reduce dissolved metal cations to form a coherent metal-based coating on an electrode. Electrodeposition is widely used to form a wide variety of two-dimensional and three-dimensional materials, such as coatings and films. However, there remains a need for methods of coating large areas of HARM structure films and for improved filters based on HARM structure films. Summary of the Invention

[0003] A filter is disclosed, which includes a support, a film of high aspect ratio molecular structures (HARM structures) attached to the support, and a transition metal-based coating on the film of the HARM structures, and the size of the film of the HARM structures is 10 to 200 cm. 2 The thickness of the formed transition metal coating film is 1 to 500 nm.

[0004] A method for forming a metallic coating on a film of high aspect ratio molecular structures (HARM structures) attached to a substrate is disclosed, the method comprising: - providing an electrode comprising a film of a HARM structure attached to a support, said support being provided with a current collector; - subjecting said electrode to an electrodeposition treatment in an aqueous deposition bath of metal complexes and / or salts thereof; Including, The electrodeposition treatment is - firstly, carrying out an electrodeposition process at a first potential value ranging from 0.2 to 5 V to form said metallic coating on the film of said HARM structure attached to said support; - then performing an electrodeposition process at a second potential value in the range of 0 to -4 V to etch the formed metallic coating; Includes:

[0005] Further disclosed is a metal-based coating on a film of high aspect ratio molecular structures (HARM structures) attached to a substrate, the metal-based coating being obtainable by the method as disclosed herein.

[0006] Further disclosed is the use of a metal-based coating on a film of high aspect ratio molecular structures (HARM structures) attached to a substrate, as disclosed herein, as a sensor or filter.

[0007] The accompanying drawings provide a further understanding of the above methods and substrates and are included as part of this specification, illustrate embodiments, and together with the description herein, serve to explain the above principles. [Brief explanation of the drawings]

[0008] [Figure 1a] FIG. 1a shows an example of a two-electrode system electrodeposition process. [Figure 1b] FIG. 1b shows an example of a three-electrode electrodeposition process. [Figure 2] FIG. 2 shows a TEM image of a metal-based coating on a HARM structure film, according to one embodiment. [Figure 3] FIG. 3 is a diagram schematically illustrating an example of a filter. Detailed Description of the Invention

[0009] A filter is disclosed, which includes a support, a film of high aspect ratio molecular structures (HARM structures) attached to the support, and a transition metal-based coating on the film of the HARM structures, and the size of the film of the HARM structures is 10 to 200 cm. 2 The thickness of the formed transition metal coating film is 1 to 500 nm.

[0010] A method for forming a metallic coating on a film of high aspect ratio molecular structures (HARM structures) attached to a substrate is disclosed, the method comprising: - providing an electrode comprising a film of a HARM structure attached to a support, said support being provided with a current collector; - subjecting said electrode to an electrodeposition treatment in an aqueous deposition bath of metal complexes and / or salts thereof, The electrodeposition treatment is - firstly, carrying out an electrodeposition process at a first potential value ranging from 0.2 to 5 V to form said metallic coating on the film of said HARM structure attached to said support; - then performing an electrodeposition process at a second potential value in the range of 0 to -4 V to etch the formed metallic coating; Includes:

[0011] Further disclosed is a metal-based coating on a film of high aspect ratio molecular structures (HARM structures) attached to a substrate, the metal-based coating being obtainable by the method as disclosed herein.

[0012] Further disclosed is the use of a metal-based coating on a film of a HARM structure attached to a support as disclosed herein as a sensor, filter, or pellicle, preferably in an extreme ultraviolet (EUV) device. The sensor may be an electrochemical sensor or a biosensor. The filter may be an optical filter, a debris filter, or a membrane filter. The pellicle may be an extreme ultraviolet lithography pellicle.

[0013] Electrodeposition (also known as electroplating) is the controlled deposition of a material onto a conductive surface from a solution containing ionic species using an electric current. That is, electrodeposition is a process in which an electric current is used to oxidize / reduce dissolved ionic species to form a coherent metallic coating on an electrode.

[0014] The method includes providing an electrode comprising a film of a HARM structure attached to a support, the support being provided with a current collector. During electrodeposition, the current collector can be used to collect electrons from the electrodeposition process. The current collector can typically be formed from a conductive material such as a metal. The use of the current collector provides additional benefits in the electroplating process, such as ensuring uniform deposition and controlling the deposition rate.

[0015] In the present disclosure, the electrode provided includes a film of a HARM structure attached to a support. That is, the electrode may be formed from a film of a HARM structure attached to a support. The support may also be provided with a current collector along at least a portion of the support. The current collector may be provided, for example, on at least one edge of the support. The current collector may be formed of, for example, Ag, Au, Cu, Fe, Pt, C, or any combination or mixture thereof.

[0016] The term "HARM structure" or "HARMS" is used herein, unless otherwise specified, to refer to "nanostructures," i.e., structures having one or more characteristic dimensions on the nanometer scale (approximately 100 nanometers or less). "High aspect ratio" refers to conductive structures whose dimensions in two orthogonal directions are significantly different orders of magnitude. For example, the length of a nanostructure may be tens or hundreds of times greater than its thickness and / or width. In HARM structure films, many such nanostructures are interconnected to form a network of interconnected molecules. Considered on a macroscopic scale, HARMS networks form monolithic solid materials in which the individual molecular structures are unoriented or non-oriented, i.e., substantially randomly oriented. Various types of HARM structure networks can be formed in the form of thin, transparent layers with suitable resistivities. Preferably, the HARM structures are conductive HARM structures.

[0017] Preferably, the HARM structure is a carbon nanostructure. Preferably, the carbon nanostructure comprises a carbon nanotube (CNT), a carbon nanobud (CNB), a carbon nanoribbon, or any combination thereof. Preferably, the carbon nanostructure comprises a carbon nanotube and / or a carbon nanobud. Carbon nanobuds (also called carbon nanobud molecules) have fullerene or fullerene-like molecules covalently bonded to the side of a cylindrical carbon molecule.

[0018] The substrate can be any type of substrate suitable for mounting a film of the HARM structure on, and can be made of a polymer, metal, silicon, glass, ceramic material, or any combination thereof.

[0019] The support may take a variety of forms. The support may take the form of a frame. Preferably, the support takes the form of a frame, and the HARM structure film is a free-standing HARM structure film attached to the frame. The frame may support the free-standing HARM structure film at its outer edge, so that an unsupported, standalone region is formed in the free-standing HARM structure film. Support locations may be located anywhere on the structure, as long as they provide sufficient support for the free-standing HARM structure film. For example, support locations may be located on the side of the free-standing HARM structure film, near a corner, or adjacent to each other along the side. Any larger region including multiple support points is also intended to be included in this embodiment. For example, if the frame is a continuous circle, the free-standing region exists within the circle. The frame may have any other elongated, continuous shape. Preferably, the frame is formed as a circle, square, triangle, rectangle, ellipse, or polygon.

[0020] The support may include a network structure such as a mesh or grid, which may be composed of interconnected nodes, vertices, or edges. The network structure may include cells having regular or irregular shapes. The nodes, vertices, edges, or cells of the network structure may be arranged in a regular or irregular pattern. The cells may be circular, triangular, rectangular, square, hexagonal, octagonal, or other polygonal shapes. The support may also have the form of a network structure mounted on a frame, which may be as described above.

[0021] The size of the film of the HARM structure is 0.1 to 10,000 cm 2 , or 1 to 7000 cm 2 , or 10 to 5000 cm 2, or 100 to 3000 cm 2 , or 500 to 2500 cm 2 , or 1000-2000cm 2 The size of the film of the HARM structure may be 0.1 to 1000 cm 2 , or 1 to 500 cm 2 , or 10 to 200 cm 2 , or 50-150cm 2 The inventors have surprisingly found that the method of the present disclosure makes it possible to form a metallic coating by electrodeposition on a free-standing film of a large-sized HARM structure, which was not possible before.

[0022] The inventors have surprisingly found that by performing the electrodeposition process as disclosed herein, i.e., by employing a two-step process using different potential values ​​and a predetermined potential difference, it is possible to form a metallic coating on a large-area free-standing film of HARM structures. During electrodeposition at a first potential value, all of the HARM structures on the surface of the film are covered with metal complexes deposited on the surface. During electrodeposition at a second potential value, the formed metallic coating is etched, and any defects that may exist in the metallic coating are covered with additional material to form a uniform metallic coating.

[0023] The term "etching" may be understood as referring to a process carried out during electrodeposition at the second potential value, which removes or scrapes off the thicker portions of the metallic coating formed on the film of the HARM structure due to their higher abundance. By carrying out electrodeposition at the second potential value, a uniform metallic coating may be formed.

[0024] The first potential value may be in the range of 0.2 to 5 V, or 0.3 to 3 V, or 0.5 to 2 V, or 1 to 1.5 V. The second potential value may be in the range of 0 to −4 V, or −0.1 to −3 V, or −0.3 to −2 V, or −0.5 to −1 V. The difference between the first potential value and the second potential value may be 0.2 to 9 V, or 0.4 to 6 V, or 0.8 to 4 V, or 1.5 to 2 V.

[0025] The electrodeposition process can be carried out in a two-electrode system or a three-electrode system. A two-electrode system can be understood as consisting of two electrodes (a working electrode and a counter electrode that also functions as a reference electrode). An example of a two-electrode system is disclosed in FIG. 1a. A three-electrode system can be understood as consisting of three electrodes (a working electrode, a counter electrode, and a reference electrode). The role of the reference electrode is to serve as a reference for measuring and controlling the potential of the working electrode without passing any current. An example of a three-electrode system is disclosed in FIG. 1b.

[0026] A polymer primer may be provided between the HARM structure film and the support to improve adhesion of the HARM structure film to the support and / or improve electrical conductivity. The polymer primer may be formed by using a dispersion of a halogenated and / or sulfonated polymer selected from polyvinylidene chloride (PVDC), polyvinylidene fluoride (PVDF), sulfonated tetrafluoroethylene-based fluoropolymer copolymer (Nafion), polystyrene sulfonate (PSS), or any combination thereof. Thus, the polymer primer may comprise or consist of a halogenated and / or sulfonated polymer selected from polyvinylidene chloride (PVDC), polyvinylidene fluoride (PVDF), sulfonated tetrafluoroethylene-based fluoropolymer copolymer (Nafion), polystyrene sulfonate (PSS), or any combination thereof.

[0027] The electrodeposition treatment may be carried out for 1 to 5000 seconds, or 5 to 500 seconds, or 10 to 300 seconds, or 20 to 100 seconds.

[0028] The electrodeposition at the first potential value may be carried out for 1 to 30 seconds, 30 to 300 seconds, or 300 to 5000 seconds, or 1 to 1000 seconds, 10 to 600 seconds, 20 to 200 seconds, or 30 to 150 seconds.

[0029] The electrodeposition at the second potential value may be carried out for 1 to 30 seconds, 30 to 300 seconds, or 300 to 5000 seconds, or 1 to 1000 seconds, 50 to 600 seconds, 100 to 400 seconds, or 150 to 350 seconds.

[0030] The electrodeposition treatment may be continued until the thickness of the formed metallic coating is 1 to 500 nm, or 1 to 300 nm, or 1 to 100 nm, or 1 to 50 nm, or 1 to 30 nm, or 1 to 20 nm, or 1 to 10 nm. The thickness can be measured, for example, by transmission electron microscopy (TEM), scanning electron microscopy (SEM), or any other relevant technique.

[0031] The electrode is subjected to the electrodeposition process in an aqueous deposition bath of a metal complex and / or its salt. The aqueous deposition bath does not require the use of a supporting electrolyte. Films of HARM structures, such as carbon nanotubes, are known to be highly hydrophobic, and non-aqueous deposition baths have traditionally been used. The inventors surprisingly discovered that an aqueous deposition bath can be used for the electrodeposition process. The use of an aqueous deposition bath offers additional benefits, such as environmental friendliness and safety. The use of an aqueous deposition bath also offers additional benefits, such as a high deposition rate, resulting in a rapid process. Aqueous deposition baths also provide a high conductivity ratio of HARMS to electrolyte, reducing the need for a supporting electrolyte. The addition of a supporting electrolyte to the deposition bath can potentially increase the risk of particle contamination of HARMS due to surface crystallization.

[0032] The method may include degassing the aqueous deposition tank by a vacuum cycle and / or by purging an inert gas through the aqueous deposition tank.

[0033] The metal complexes used in the aqueous deposition bath can be selected so that the resistivity of the metal-based coating formed is higher than the resistivity of the HARM structure film, which can be measured using a four-point probe, two-point probe, eddy current, or terahertz before coating.

[0034] The resistance of the combination of the metal-based coating films formed on the HARM structure film may be 10Ω to 1 kΩ, or 1 to 100 kΩ, or 100 to 1000 kΩ. The resistance of the HARM structure film is 10Ω to 10 kΩ, or 10Ω to 1 kΩ, or 20 to 500 Ω, or 30 to 350 Ω, or 40 to 250 Ω, or 50 to 200 Ω, or 60 to 150 Ω. The resistance of the combination of the metal-based coating films on the HARM structure film may be measured using a four-terminal probe, a two-terminal probe, an eddy current, or a terahertz.

[0035] The metal complex may be selected so that the resistance of the formed metal-based coating is higher than the resistance of the film of the HARM structure, which can be observed by an increase in the resistance of the formed structure after depositing a metal-based coating on the film of the HARM structure.

[0036] The expression "metal complex," as used herein, unless otherwise specified, is to be understood as referring to a compound comprising or consisting of a metal ion bound to one or more ligands. The metal ion serves as the central atom, and the ligands are typically neutral molecules or anions bound to the metal by coordinate covalent bonds. The properties of a metal complex depend on the type of metal ion and the nature of the ligands, as well as their oxidation state and coordination number.

[0037] The metal complex may be a transition metal complex. The metal complex may be a sulfur-based metal complex, an oxygen-based metal complex, or an oxygen-sulfur-based metal complex. The metal complex may be a sulfur-based transition metal complex, an oxygen-based transition metal complex, or an oxygen-sulfur-based transition metal complex. The transition metal may be selected from the group consisting of Mo, W, Cu, Zr, Ti, Nb, V, Hf, Cr, Zn, Fe, Ni, and Co. Preferably, the transition metal is Mo or W.

[0038] The metal complex may contain, in addition to a (transition) metal, sulfur, oxygen, hydrogen, carbon, nitrogen, or any combination or mixture thereof.

[0039] The metal complex is α C β H γ N δ O ε S ζ ], where: M is a transition metal ion; α is a value between 1 and 20, β, γ, δ, ε, and ζ each independently represent a value of 0 to 50.

[0040] Preferably, the metal complex is α S ζ ], [M α O ε ], [M α O ε S ζ ], [M α C β H γ Sζ ], [M α C β H γ O ζ ], or [M α C β H γ O ε S ζ ], [M α C β H γ N δ O ε S ζ ], where: M is a transition metal ion; α is a value between 1 and 20, β, γ, δ, ε, and ζ each independently represent a value of 1 to 50.

[0041] The transition metal ions may be ions of Mo, W, Cu, Zr, Ti, Nb, V, Hf, Cr, Zn, Fe, Ni, or Co.

[0042] The metal complex may be in the form of a salt, such as an ammonium salt or a sodium salt of the metal complex.

[0043] Thus, the aqueous deposition bath may be a deposition bath formed from water and a metal complex and / or a salt thereof. The aqueous deposition bath may further contain additives such as organic brighteners, throwing power enhancers, and adhesion promoters. Preferably, the aqueous deposition bath is formed from water and a metal complex and / or a salt thereof. The concentration of the metal complex in the aqueous deposition bath may be 0.001 mM to 3 M, or 0.1 mM to 1 M, or 0.2 to 500 mM, or 0.3 to 100 mM, or 0.4 to 50 mM, or 0.5 to 10 mM, or 0.6 to 5 mM, or 0.7 to 3 mM. By lowering the concentration of the metal complex in the deposition bath, it becomes easier to control the material balance and material diffusion, which further enhances the utility of controlling the uniformity of the formed film.

[0044] The formed metallic coating may be a coating of a transition metal such as a transition metal dichalcogenide, and the transition metal may be Mo, W, Cu, Zr, Ti, Nb, V, Hf, Cr, Zn, Fe, Ni, or Co.

[0045] The methods disclosed herein have the additional advantage of enabling ultrafast formation of large-area, uniform depositions on freestanding or support films of HARM structures. The methods disclosed herein can be used in a variety of applications, such as filters, preferably filters in EUV devices, EUV pellicles, electrochromic displays, and electrochemical sensors. [Example]

[0046] The above-mentioned embodiments will now be described in detail, examples of which are illustrated in the accompanying drawings.

[0047] The following description discloses some embodiments in sufficient detail to enable one skilled in the art to utilize the methods described above based on this disclosure. Not all steps are discussed in detail, as many of the steps of these embodiments will be apparent to one skilled in the art based on this specification.

[0048] Figure 1a shows an example of a two-electrode system that can be used to form a metallic coating on a film of a HARM structure attached to a support, according to one embodiment. The two-electrode system in Figure 1a consists of two electrodes: a working electrode and a counter electrode that also functions as a reference electrode.

[0049] Figure 1b shows an example of a three-electrode system that can be used to form a metal-based coating on a film of a HARM structure attached to a support, according to one embodiment. The three-electrode system in Figure 1b consists of three electrodes: a working electrode, a counter electrode, and a reference electrode. The role of the reference electrode is to serve as a reference for measuring and controlling the potential of the working electrode without passing any current.

[0050] Example 1 - Formation of a metallic coating on a film of a HARM structure attached to a support In this example, a metallic coating was formed on a HARM structure film attached to a support. An electrode was first prepared by attaching a previously prepared HARM structure film to a support provided with a current collector. The current collector in this example was an Ag conductor. The resulting electrode was then subjected to an electrodeposition process in an aqueous deposition bath formed using a metal complex salt, as described herein.

[0051] In the examples, the following materials and parameters were used:

[0052] [Table 1]

[0053] From the above results, it can be seen that the applied method can form a metallic coating on the free-standing film of the HARM structure. Furthermore, it can provide a metallic coating with a higher resistance than the resistance of the free-standing film of the HARM structure. Furthermore, from Figure 2, it can be seen that a very uniform metallic coating can be formed on the free-standing film of the HARM structure by the two-step electrodeposition process.

[0054] As an example of a filter of the present invention, Figure 3 shows a schematic representation of a filter 100. This diagram is provided for a better understanding of the filter's construction and is obviously not drawn to scale in order to show the support and HARM structure in the same view. Filter 100 includes a support 110, a HARM structure film 120 attached to support 110, and a transition metal-based coating 130 on the HARM structure film 120.

[0055] In this example, the film 120 of HARM structures includes individual HARM structures 122 (CNTs in this example). The term "transition metal-based coating on a film of HARM structures" is used herein because the film 120 of HARM structures may be produced by first obtaining the film 120 of HARM structures and then forming the transition metal-based coating 130 on the film 120, as described in "Example 1" above. This term does not exclude a configuration in which the individual HARM structures 122 are covered with the coating 130, as can be seen in FIG. 3 . Not all HARM structures 122 are necessarily completely covered with the metal-based coating 130. The coverage may depend on how closely the HARM structures 122 are arranged. For example, some HARM structures 122 may be covered and some may not, or the same individual HARM structures 122 may be completely covered (360°) in some locations but not in other locations. All of these variations are intended to be encompassed by the term "transition metal-based coating on a film of HARM structures."

[0056] It is obvious to those skilled in the art that with the advancement of technology, the basic idea can be implemented in various ways. Therefore, the embodiments of the present invention are not limited to the above examples, but instead can be modified within the scope of the claims.

[0057] The above-described embodiments may be used in combination with each other. Several embodiments may be combined to obtain further embodiments. The filters, methods, metal-based coatings on films of HARM structures attached to supports, or uses disclosed herein may include at least one of the above-described embodiments. It is understood that the above benefits and advantages may relate to one embodiment or to several embodiments. These embodiments are not limited to those that solve any or all of the above problems, or to those that have any or all of the above benefits and advantages. Furthermore, it is understood that a reference to an item refers to one or more items. As used herein, the term "comprising" is used to mean including the referenced structure or operation without excluding the presence of one or more additional structures or operations.

Claims

1. 1. A method for forming a metallic coating on a film of high aspect ratio molecular structures (HARM structures) attached to a substrate, said method comprising: - providing an electrode comprising a film of a HARM-structure attached to a support, said support being provided with a current collector; - subjecting said electrodes to an electrodeposition treatment in an aqueous deposition bath of metal complexes and / or salts thereof; Including, The electrodeposition treatment is - firstly carrying out an electrodeposition process at a first potential value ranging from 0.2 to 5 V to form said metallic coating on said HARM-structure film attached to said support; - then carrying out an electrodeposition treatment at a second potential value in the range of 0 to -4 V to etch the formed metallic coating; A method comprising:

2. 2. The method of claim 1, wherein the support has the form of a frame and the film of the HARM-structure is a free-standing film of the HARM-structure attached to the frame.

3. The size of the HARM structure film is 0.1 to 1000 cm ２ , or 1 to 500 cm ２ , or 10 to 200 cm ２ , or 50 to 150 cm ２ The method according to claim 1 or 2, wherein

4. The method according to any one of claims 1 to 3, wherein the first potential value is in the range of 0.3 to 3V, or 0.5 to 2V, or 1 to 1.5V.

5. The method according to any one of claims 1 to 4, wherein the second potential value is in the range of 0 to -4V, or -0.1 to -3V, or -0.3 to -2V, or -0.5 to -1V.

6. 6. The method according to claim 1, wherein the difference between the first potential value and the second potential value is 0.2 to 9 V, or 0.4 to 6 V, or 0.8 to 4 V, or 1.5 to 2 V.

7. 7. The method according to claim 1, wherein a polymer primer is provided between the HARM-structure film and the substrate in order to improve adhesion of the HARM-structure film to the substrate and / or to improve electrical conductivity.

8. The method of any one of claims 1 to 7, wherein the support is formed from a polymer, a metal, silicon, glass, a ceramic material, or any combination thereof.

9. 9. The method according to any one of claims 1 to 8, wherein electrodeposition at the first potential value is carried out for a period of from 1 to 1000 seconds, or from 10 to 600 seconds, or from 20 to 200 seconds, or from 30 to 150 seconds.

10. 10. The method according to any one of the preceding claims, wherein electrodeposition at the second potential value is carried out for 1 to 1000 seconds, or 50 to 600 seconds, or 100 to 400 seconds, or 150 to 350 seconds.

11. 11. The method according to claim 1, wherein the metal complex is selected so that the resistance of the formed metal-based coating is higher than the resistance of the HARM-structure film alone.

12. The method according to any one of claims 1 to 11, wherein the metal complex is a sulfur-based metal complex, an oxygen-based metal complex, or an oxygen-sulfur-based metal complex.

13. 13. The method of any one of claims 1 to 12, wherein the metal complex comprises, in addition to the metal, sulfur, oxygen, hydrogen, carbon, nitrogen, or any combination or mixture thereof.

14. The method of any one of claims 1 to 13, wherein the aqueous precipitation bath is free of supporting electrolyte.

15. 15. The method of any one of claims 1 to 14, wherein the method comprises degassing the aqueous precipitation bath by a vacuum cycle and / or by purging an inert gas through the aqueous precipitation bath.

16. The method according to any one of claims 1 to 15, wherein the electrodeposition treatment is continued until the thickness of the formed metallic coating film is 1 to 500 nm, or 1 to 300 nm, or 1 to 100 nm, or 1 to 50 nm, or 1 to 30 nm, or 1 to 20 nm, or 1 to 10 nm, or 10 to 500 nm, or 10 to 300 nm, or 10 to 100 nm, or 10 to 50 nm, or 10 to 30 nm, or 10 to 20 nm.

17. 17. The method according to any one of claims 1 to 16, wherein the resistance of the combination of the metal-based coating formed on the HARM-structure film is 10 Ω to 1 kΩ, or 1 to 100 kΩ, or 100 to 1000 kΩ.

18. 18. The method according to any one of the preceding claims, wherein the resistance of the HARM-structure film is from 10 Ω to 10 kΩ, or from 10 Ω to 1 kΩ, or from 20 to 500 Ω, or from 30 to 350 Ω, or from 40 to 250 Ω, or from 50 to 200 Ω, or from 60 to 150 Ω.

19. The method according to any one of claims 1 to 18, wherein the electrodeposition process is carried out in a two-electrode or three-electrode system.

20. A metallic coating on a film of high aspect ratio molecular structures (HARM structures) attached to a support, the metallic coating being obtainable by the method according to any one of claims 1 to 19.

21. 21. Use of a metal-based coating on a film of high aspect ratio molecular structures (HARM structures) attached to a support according to claim 20 as a sensor, filter or pellicle, preferably in an extreme ultraviolet (EUV) device.

22. 22. The use according to claim 21, wherein the sensor is an electrochemical sensor or a biosensor.

23. 23. Use according to claim 21 or 22, wherein the filter is an optical filter, a debris filter or a membrane filter, preferably in an EUV device.

24. 24. The use according to claim 21, 22 or 23, wherein the pellicle is an EUV lithography pellicle.

25. A support; a film of high aspect ratio molecular structures (HARM structures) attached to the substrate; a transition metal-based coating on the HARM-structure film, The size of the HARM structure film is 10 to 200 cm ２ and the formed transition metal-based coating film has a thickness of 1 to 500 nm.

26. 26. The filter of claim 25, which is a debris filter, an optical filter, or a combination thereof.

27. 27. The filter according to claim 25 or 26, in an EUV device, which is a debris filter, an optical filter, or a combination thereof.

28. 28. A filter according to any one of claims 25 to 27, wherein the support has the form of a frame and the HARM-structure film is a free-standing HARM-structure film attached to the frame.

29. 30. The filter of claim 28, wherein the frame supports the free-standing film of the HARM-structure at an outer edge of the frame such that an unsupported, stand-alone region of the free-standing film of the HARM-structure is formed.

30. The filter of any one of claims 25 to 29, wherein the frame is formed as a circle, a square, a triangle, a rectangle, an oval, or a polygon.

31. The filter of any one of claims 25 to 30, wherein the support is formed from a polymer, a metal, silicon, glass, a ceramic material, or any combination thereof.

32. 32. A filter according to any one of claims 25 to 31, wherein the HARM-structures are nanostructures having one or more characteristic dimensions of 100 nanometers or less, and the length of each nanostructure is tens or hundreds of times the thickness and / or width of the nanostructure.

33. A filter according to any one of claims 25 to 32, wherein said HARM-structures are carbon nanostructures.

34. 34. The filter of claim 33, wherein the carbon nanostructures comprise carbon nanotubes (CNTs), carbon nanobuds (CNBs), carbon nanoribbons, or any combination thereof.

35. A filter according to any one of claims 25 to 34, wherein a polymer primer is provided between the HARM-structure film and the support.

36. The filter according to any one of claims 25 to 35, wherein the formed transition metal-based coating has a thickness of 10 to 500 nm, or 10 to 300 nm, or 10 to 100 nm, or 10 to 50 nm, or 10 to 30 nm, or 10 to 20 nm.

37. A filter according to any one of claims 25 to 36, wherein the resistance of the formed transition metal based coating is higher than the resistance of the HARM-structure film.

38. 38. The filter of any one of claims 25 to 37, wherein the transition metal comprises Mo, W, Cu, Zr, Ti, Nb, V, Hf, Cr, Zn, Fe, Ni, or Co.

39. The filter of any one of claims 25 to 38, wherein the formed transition metal-based coating comprises a transition metal dichalcogenide.

40. A filter according to any one of claims 25 to 39, wherein the support is provided with a current collector.

41. A filter according to any one of claims 25 to 40, wherein the support is provided with a current collector along at least a portion of the support.

42. A filter according to any one of claims 25 to 41, wherein the current collector is provided on at least one edge of the support.

43. 43. A filter according to any one of claims 25 to 42, wherein the support comprises a network structure, for example a mesh or grid, optionally arranged in a frame, and wherein the cells of the mesh or grid may be circular, triangular, rectangular, square, hexagonal, octagonal or other polygonal in shape.

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