Thin film for EUV reflective mask and method for manufacturing the same

Abstract

The film for EUV photomask includes: a first layer; a second layer; and a main layer, disposed between the first layer and the second layer and including a plurality of nanotubes. At least one of the first layer or the second layer includes a two-dimensional material in which one or more two-dimensional layers are stacked. In one or more embodiments above and below, the first layer includes a first two-dimensional material and the second layer includes a second two-dimensional material. Embodiments of the present application also relate to a film for an extreme ultraviolet (EUV) reflective mask and a method for manufacturing the same.

Description

Technical Field

[0001] Embodiments of the present application relate to a thin film for an EUV reflective mask and a method for manufacturing the same. Background Art

[0002] A pellicle is a thin transparent film stretched over a frame that is glued over one side of the photomask to protect the photomask from damage, dust and / or moisture. In EUV lithography, a pellicle with high transparency, high mechanical strength and low thermal expansion in the EUV wavelength region is often required. Summary of the invention

[0003] Some embodiments of the present application provide a thin film for an extreme ultraviolet (EUV) reflective mask, comprising: a first layer; a second layer; and a main layer, arranged between the first layer and the second layer and comprising a plurality of nanotubes, wherein: at least one of the first layer or the second layer comprises a two-dimensional material in which one or more two-dimensional layers are stacked.

[0004] Other embodiments of the present application provide a thin film for an extreme ultraviolet (EUV) reflective mask, comprising: a first layer; a second layer; and a main layer disposed between the first layer and the second layer, wherein the main layer comprises a plurality of first nanotubes and a plurality of second nanotubes different from the plurality of first nanotubes.

[0005] Still other embodiments of the present application provide a method for manufacturing a thin film for an extreme ultraviolet (EUV) reflective mask, comprising: forming a nanotube layer above a supporting substrate; forming a first covering layer above the nanotube layer; forming a thin film frame above the first covering layer; cutting the nanotube layer and the first covering layer to form a cut thin film membrane; forming a second layer to completely encapsulate the nanotube layer sealed by the first layer of the cut thin film membrane using the cut thin film membrane; and forming a protective layer above the first covering layer, the second covering layer and the thin film frame. BRIEF DESCRIPTION OF THE DRAWINGS

[0006] When read in conjunction with the accompanying drawings, various aspects of the present invention can be best understood from the following detailed description. It should be noted that, in accordance with standard practice in the industry, the various components are not drawn to scale. In fact, for clarity of discussion, the size of the various components may be arbitrarily increased or reduced.

[0007] Figure 1A , Figure 1B and Figure 1C Various views of a pellicle for an EUV photomask according to an embodiment of the present invention are shown.

[0008] Figure 2A , Figure 2B , Figure 2C , Figure 2D , Figure 2E , Figure 2F and Figure 2G Various views of a web film of a pellicle for an EUV photomask according to an embodiment of the present invention are shown.

[0009] Figure 3A , Figure 3B , Figure 3C , Figure 3D , Figure 3E , Figure 3F , Figure 3G , Figure 3H , Fig. 3I and Figure 3J Various views of a web film of a pellicle for an EUV photomask according to an embodiment of the present invention are shown.

[0010] Figure 4A , Figure 4B , Figure 4C , Figure 4D , Figure 4E and Figure 4F Various views of a pellicle for an EUV photomask according to an embodiment of the present invention are shown.

[0011] Figure 5A The invention shows a manufacturing process of a network film according to an embodiment of the present invention, and Figure 5B A flow chart thereof according to an embodiment of the present invention is shown.

[0012] Figure 6 A manufacturing process of a network film according to an embodiment of the present invention is shown.

[0013] Fig. 7A and Figure 7B Shown are cross-sectional and plan (top) views of one of the various stages in fabricating a pellicle for an EUV photomask in accordance with an embodiment of the present invention.

[0014] Fig. 8A and Figure 8B Shown are cross-sectional and plan (top) views of one of the various stages in fabricating a pellicle for an EUV photomask in accordance with an embodiment of the present invention.

[0015] Fig. 9A and Fig. 9B Shown are cross-sectional and plan (top) views of one of the various stages in fabricating a pellicle for an EUV photomask in accordance with an embodiment of the present invention.

[0016] Fig. 10A and Fig. 10B Shown are cross-sectional and plan (top) views of one of the various stages in fabricating a pellicle for an EUV photomask in accordance with an embodiment of the present invention.

[0017] Fig.11A and Fig. 11B Shown are cross-sectional and plan (top) views of one of the various stages in fabricating a pellicle for an EUV photomask in accordance with an embodiment of the present invention. Fig. 11C and Fig.11D A cross-sectional view of one of the various stages for fabricating a pellicle for an EUV photomask is shown in accordance with an embodiment of the present invention.

[0018] Fig. 12A and Fig. 12B Shown are cross-sectional and plan (top) views of one of the various stages in fabricating a pellicle for an EUV photomask in accordance with an embodiment of the present invention.

[0019] Fig.13A A flowchart of a method for manufacturing a semiconductor device according to an embodiment of the present invention is shown, and Fig. 13B , Fig. 13C , Fig.13D and Fig.13E Sequential manufacturing operations of a method of fabricating a semiconductor device according to an embodiment of the present invention are shown. DETAILED DESCRIPTION

[0020] It should be understood that the following disclosure provides many different embodiments or examples for realizing different features of the present invention. Specific embodiments or examples of components and arrangements are described below to simplify the present invention. Of course, these are merely examples and are not intended to limit the present invention. For example, the size of the element is not limited to the disclosed range or value, but may depend on the process conditions and / or desired characteristics of the device. In addition, in the following description, forming a first component above or on a second component may include an embodiment in which the first component and the second component are directly contacted, and may also include an embodiment in which an additional component is formed between the first component and the second component so that the first component and the second component may not be in direct contact. For simplicity and clarity, the various components may be arbitrarily drawn in different proportions. In the accompanying drawings, some layers / components may be omitted for simplicity.

[0021] In addition, for ease of description, spatial relative terms such as "under...", "below...", "lower", "above...", "upper", etc. may be used herein to describe the relationship between one element or component and another (or other) elements or components as shown in the figure. In addition to the orientation shown in the figure, spatial relative terms are intended to include different orientations of the device in use or operation. The device can be oriented in other ways (rotated 90 degrees or in other orientations), and the spatial relative descriptors used herein can be interpreted accordingly. In addition, the term "made of..." can mean "including" or "consisting of...". In addition, in the following manufacturing process, there may be one or more additional operations between the operations described, and the order of the operations may be changed. In the present invention, the phrase "at least one of A, B and C" means any one of A, B, C, A+B, A+C, B+C or A+B+C, and does not mean one from A, one from B and one from C, unless otherwise explained. The materials, configurations, structures, operations and / or dimensions explained using one embodiment can be applied to other embodiments, and their detailed descriptions can be omitted.

[0022] EUV lithography is one of the key technologies for extending Moore's Law. However, due to wavelength scaling from 193nm (ArF) to 13.5nm, EUV light sources suffer from strong power attenuation due to environmental adsorption. Even though the stepper / scanner chamber operates under vacuum to prevent strong adsorption of EUV by gases, maintaining high EUV transmittance from the EUV light source to the wafer is still an important factor in EUV lithography.

[0023] Thin films usually require high transparency and low reflectivity. In UV or DUV lithography, thin film membranes are made of transparent resin films. However, in EUV lithography, resin-based films are not acceptable, and non-organic materials such as polysilicon, silicide or metal films are used.

[0024] Carbon nanotubes (CNTs) are one of the materials suitable for thin films used in EUV reflective photomasks because CNTs have a high EUV transmittance of more than 96.5%. In general, thin films used in EUV reflective masks require the following properties: (1) long lifetime in the hydrogen-rich radical operating environment in the EUV stepper / scanner; (2) strong mechanical strength to minimize sagging effects during vacuum pumping and exhaust operations; (3) high or perfect blocking performance for particles larger than about 20 nm (killer particles); and (4) good heat dissipation to prevent the film from being burned by EUV radiation.

[0025] In the present invention, a film for EUV photomask includes a network film having a plurality of nanotubes and a two-dimensional material layer covering the network film. Such a film has high EUV transmittance, improved mechanical strength, prevents killer particles from falling on the EUV mask and / or has improved durability.

[0026] Figure 1A , Figure 1B and Figure 1C An EUV pellicle 10 is shown mounted on an EUV reflective mask 5 according to an embodiment of the present invention. Figure 1A is the cross-sectional view in the X direction, Figure 1B is a cross-sectional view in the Y direction, and Figure 1C It is a top view (plan) diagram.

[0027] In some embodiments, the thin film 10 for EUV reflective mask includes a first cover layer 20, a second cover layer 30, and a main network film 100 disposed between the first cover layer 20 and the second cover layer 30. In some embodiments, the main network layer includes a plurality of nanomaterials, such as nanotubes and / or nanosheets. In some embodiments, a support frame 15 is attached to the first cover layer 20 to maintain the spacing between the film of the thin film and the EUV mask 5 (pattern area) when mounted on the EUV mask 5. One or both of the first cover layer 20 and the second cover layer 30 include a two-dimensional material in which one or more two-dimensional layers are stacked. Here, in some embodiments, a "two-dimensional" layer generally refers to one or more crystalline layers of an atomic matrix or network having a thickness in the range of about 0.1-5 nm.

[0028] The support frame 15 of the film is attached to the surface of the EUV photomask 5 using a suitable bonding material. In some embodiments, the bonding material is an adhesive, such as an acrylic or silicone-based glue or an AB cross-linked glue. The size of the frame structure is larger than the area of ​​the black border of the EUV photomask, so that the film not only covers the circuit pattern area of ​​the photomask, but also covers the black border.

[0029] In some embodiments, the two-dimensional materials of the first cover layer 20 and the second cover layer 30 are the same or different from each other. In some embodiments, the first cover layer includes a first two-dimensional material and the second cover layer includes a second two-dimensional material.

[0030] In some embodiments, the two-dimensional material for the first capping layer 20 and / or the second capping layer 30 includes at least one of boron nitride (BN), graphene, and / or a transition metal dichalcogenide (TMD) represented by MX2, where M = Mo, W, Pd, Pt, and / or Hf, and X = S, Se, and / or Te. In some embodiments, the TMD is one of MoS2, MoSe2, WS2, or WSe2.

[0031] In some embodiments, the total thickness of each of the first capping layer 20 and the second capping layer 30 is in a range from 0.3 nm to 3 nm, and in other embodiments, in a range from about 0.5 nm to about 1.5 nm. In some embodiments, the number of two-dimensional layers of each of the two-dimensional materials of the first capping layer and / or the second capping layer is 1 to about 20, and in other embodiments, 2 to about 10. When the thickness and / or number of the layers is greater than these ranges, the EUV transmittance of the film 10 may be reduced, and when the thickness and / or number of the layers is less than these ranges, the mechanical strength of the film may be insufficient.

[0032] In some embodiments, Figure 1A and Figure 1B As shown in , the first cover layer 20 and the second cover layer 30 are sealed at their peripheries to completely encapsulate the main web film 100. In some embodiments, the first cover layer 20 and the second cover layer 30 form a vacuum sealed structure. In some embodiments, the pressure inside the vacuum sealed structure is about 0.01Pa to about 100Pa. If the internal pressure is too high, for example, higher than the internal pressure of the EUV lithography equipment in operation, the film may rupture due to the pressure difference. In some embodiments, one or more exhaust holes are formed at the first cover layer 20 and / or the second cover layer 30.

[0033] In some embodiments, the protective layer 40 is further disposed above the first cover layer 20, the second cover layer 30 and the support frame 15. Figure 1A and Figure 1B As shown in . In some embodiments, the protective layer 40 includes at least one layer of an oxide, such as HfO2, Al2O3, ZrO2, Y2O3, or La2O3. In some embodiments, the protective layer 40 includes at least one layer of a non-oxide compound, such as B4C, YN, Si3N4, BN, NbN, RuNb, YF3, TiN, or ZrN. In some embodiments, the protective layer 40 includes at least one metal layer made of, for example, Ru, Nb, Y, Sc, Ni, Mo, W, Pt, or Bi. In some embodiments, the protective layer 40 is a single layer, and in other embodiments, two or more layers of these materials are used as the protective layer 40. In some embodiments, the thickness of the protective layer is in the range from 0.1 nm to 5 nm, and in other embodiments, in the range from about 0.2 nm to about 2.0 nm. When the thickness of the protective layer 40 is greater than these ranges, the EUV transmittance of the film 10 may be reduced, and when the thickness of the protective layer 40 is less than these ranges, the mechanical strength of the film may be insufficient.

[0034] By using a first cover layer and / or a second cover layer and / or a protective layer without holes, such as openings and / or spaces larger than about 10-20 nm, it is possible to completely block killer particles larger than about 20 nm from passing through the main web film 100 and landing on the surface of the EUV mask 5 .

[0035] Figure 2A , Figure 2B , Figure 2C , Figure 2D , Figure 2E , Figure 2F and Figure 2G Various web films of a pellicle for an EUV photomask according to an embodiment of the present invention are shown.

[0036] In some embodiments, the mesh film 100 includes a plurality of nanotubes. In some embodiments, the plurality of nanotubes are randomly arranged to form a mesh structure. In some embodiments, the diameter of each of the plurality of nanotubes is in the range of from 0.5 nm to 20 nm, and in other embodiments in the range of from about 1 nm to about 10 nm. In some embodiments, the length of each of the plurality of nanotubes is in the range of from about 0.5 μm to about 50 μm, and in other embodiments in the range of from about 1.0 μm to about 20 μm.

[0037] In some embodiments, the plurality of nanotubes are carbon nanotubes, boron nitride nanotubes and / or TMD nanotubes, wherein TMD is represented by MX2, wherein M=Mo, W, Pd, Pt and / or Hf, and X=S, Se and / or Te. In some embodiments, the plurality of nanotubes are MoS2 nanotubes, MoSe2 nanotubes, WS2 nanotubes or WSe2 nanotubes.

[0038] In some embodiments, the plurality of nanotubes comprises only one type of nanotube in terms of material and structure. In some embodiments, the plurality of nanotubes comprises nanotubes of the same material. In some embodiments, the main web film 100 comprises only single-walled nanotubes 111, such as Figure 2A In other embodiments, the main network film 100 includes only multi-walled (eg, double-walled) nanotubes 113, such as Figure 2B As shown in . The multi-walled nanotubes include an inner tube and one or more outer tubes coaxially arranged around the inner tube. In some embodiments, the outer tube is movable relative to the inner tube in the axial direction, and in other embodiments, the outer tube is fixed to the outer surface of the inner tube. In some embodiments, the diameter of each of the single-walled nanotubes is in the range from about 0.5nm to about 5nm, and in other embodiments in the range from about 1nm to about 2nm. In some embodiments, the diameter of each of the multi-walled nanotubes is in the range from about 3nm to about 20nm, and in other embodiments in the range from about 5nm to about 10nm.

[0039] In some embodiments, the plurality of nanotubes include two or more types of nanotubes in terms of material and structure. In some embodiments, the plurality of nanotubes include single-walled nanotubes made of two or more materials (a mixture of nanotubes of different materials). For example, in some embodiments, the plurality of nanotubes include a plurality of first nanotubes and a plurality of second nanotubes made of a material different from the plurality of first nanotubes, and they are all single-walled nanotubes.

[0040] In some embodiments, the main network layer 100 includes a plurality of nanotubes 111 that are single-walled nanotubes and a plurality of nanotubes 113 that are multi-walled (eg, double-walled) nanotubes. Figure 2C In some embodiments, the amount (weight) of the single-walled nanotubes 111 is greater than the amount of the multi-walled nanotubes 113. In some embodiments, the amount (weight) of the single-walled nanotubes 111 is greater than the amount of the multi-walled nanotubes 113.

[0041] In some embodiments, the plurality of single-walled nanotubes 111 are made of the same material as the plurality of multi-walled nanotubes 113. For example, the plurality of single-walled nanotubes 111 are single-walled carbon nanotubes, and the plurality of multi-walled nanotubes are multi-walled carbon nanotubes. In other embodiments, the plurality of single-walled nanotubes 111 are made of a material different from the plurality of multi-walled nanotubes 113. For example, the plurality of single-walled nanotubes 111 are single-walled TMD nanotubes, and the plurality of multi-walled nanotubes are multi-walled carbon nanotubes. In some embodiments, the plurality of nanotubes are a plurality of nanotubes made of two or more different materials (a mixture of two types of multi-walled nanotubes).

[0042] In some embodiments, the main network film 100 includes a plurality of nanotubes 111 and a plurality of sheets 121 (nanoflakes) made of a two-dimensional material in which one or more two-dimensional layers are stacked, such as Figures 2D to 2F as shown in .

[0043] In some embodiments, the two-dimensional material sheet 121 includes at least one of boron nitride (BN), graphene and / or transition metal dichalcogenide (TMD), represented by MX2, where M=Mo, W, Pd, Pt and / or Hf, and X=S, Se and / or Te. In some embodiments, TMD is one of MoS2, MoSe2, WS2 or WSe2.

[0044] In some embodiments, the thickness of the two-dimensional material sheet 121 is in the range of from 0.3 nm to 3 nm, and in other embodiments in the range of from about 0.5 nm to about 1.5 nm. In some embodiments, the number of two-dimensional layers of the two-dimensional material sheet 121 is from 1 to about 20, and in other embodiments is from 2 to about 10. When the thickness and / or number of the layers is greater than these ranges, the EUV transmittance of the film 10 may be reduced, and when the thickness and / or number of the layers is less than these ranges, the mechanical strength of the film may be insufficient.

[0045] In some embodiments, the shape of the two-dimensional material flakes 121 is random. In other embodiments, the shape of the two-dimensional material flakes 121 is triangular or hexagonal. In some embodiments, the shape of the two-dimensional material flakes 121 is a triangle formed by three atoms or a hexagon formed by six atoms. In some embodiments, the size (area) of each of the two-dimensional material flakes 121 is between about 10 nm and about 10 nm. 2 to about 10 μm 2 and in other embodiments from about 100 nm 2 to about 1 μm 2 within the range.

[0046] In some embodiments, the two-dimensional material sheet 121 is embedded in or mixed with a plurality of single-walled nanotubes 111, such as Figure 2D In some embodiments, the two-dimensional material sheet 121 is embedded in or mixed with a plurality of multi-walled nanotubes 113, such as Figure 2E In some embodiments, the two-dimensional material sheet 121 is embedded in or mixed with the plurality of single-walled nanotubes 111 and the plurality of multi-walled nanotubes 113, such as Figure 2F as shown in .

[0047] In some embodiments, the amount (weight) of the two-dimensional material flakes 121 is in the range of from about 5% to about 30%, and in other embodiments, in the range of from about 10% to about 20% relative to the total weight of the web film 100. When the amount of the two-dimensional material flakes is greater than these ranges, the EUV transmittance of the film 10 may be reduced, and when the amount of the two-dimensional material flakes is less than these ranges, the mechanical strength of the film may be insufficient.

[0048] In some embodiments, the mesh film 100 includes multi-walled nanotubes 117 each having an inner tube and one or more outer tubes, wherein the inner tube and the outer tube are made of different materials, such as Figure 2GAs shown in . In some embodiments, each multi-walled nanotube 117 includes an inner tube formed of a carbon nanotube, a boron nitride nanotube and / or a TMD nanotube and a coating as an outer tube. In some embodiments, the coating includes an oxide (such as HfO2, Al2O3, ZrO2, Y2O3 or La2O3); a non-oxide compound (such as B4C, YN, Si3N4, BN, NbN, RuNb, YF3, TiN or ZrN); and / or one of a metal (such as Ru, Nb, Y, Sc, Ni, Mo, W, Pt or Bi). In some embodiments, the coating is made of the same material as the protective layer 40.

[0049] Figure 3A , Figure 3B , Figure 3C , Figure 3D , Figure 3E , Figure 3F , Figure 3G , Figure 3H , Fig. 3I and Figure 3J Various views of a web film of a pellicle for an EUV photomask according to an embodiment of the present invention are shown. In some embodiments, the web film 100 has a single-layer structure or a multi-layer structure.

[0050] In some embodiments, the web film 100 has a single layer 110 of multiple single-walled or multi-walled nanotubes, such as Figure 3A In some embodiments, the web film 100 has two layers of different types of nanotubes 110 and 112, such as Figure 3B The thickness of layer 110 and layer 112 may be the same or different from each other. In some embodiments, the web film 100 has three layers of nanotubes 110, 112, and 114, such as Figure 3C In some embodiments, at least adjacent layers are of different types. The thicknesses of layers 110, 112, and 114 are the same or different from each other. In some embodiments, the web film 100 has a single layer 115 having a mixture of different types of nanotubes, such as Figure 3D as shown in .

[0051] In some embodiments, the network film 100 has a nanotube layer 110 and a two-dimensional sheet layer 120, such as Figure 3E and Figure 3F The thickness of layer 110 and layer 120 may be the same or different from each other. Layer 110 may be a mixed layer 115, such as Figure 3D In some embodiments, the network film 100 has a two-dimensional sheet layer 120 disposed between the first nanotube layer 110 and the second nanotube layer 112, such as Figure 3GIn some embodiments, the first nanotube layer and the second nanotube layer are of the same type or of different types. In some embodiments, the mesh film 100 has a nanotube layer 110 disposed between a first two-dimensional sheet layer 120 and a second two-dimensional sheet layer 122, such as Figure 3H In some embodiments, the first two-dimensional thin sheet layer and the second two-dimensional thin sheet layer are made of the same material or different materials. In some embodiments, the network film 100 has a nanotube layer 110, a first two-dimensional thin sheet layer 120 located above the nanotube layer 110, and a second two-dimensional thin sheet layer 122 disposed above the first two-dimensional thin sheet layer 120, as shown in FIG. Fig. 3I In some embodiments, the web film 100 has one or more nanotube layers of the same or different types and one or more two-dimensional flake layers of the same or different materials. In some embodiments, the web film 100 has a single layer 125 of a mixture of nanotubes and two-dimensional flakes, such as Figure 3J as shown in .

[0052] Figure 4A , Figure 4B , Figure 4C , Figure 4D , Figure 4E and Figure 4F Various views of a pellicle for an EUV photomask according to an embodiment of the present invention are shown.

[0053] Figure 4A and Figures 1A to 1C In some embodiments, the film does not include a protective layer, such as Figure 4B In some embodiments, the first cover layer is not used and only the second cover layer 30 is disposed above the main web film 100, as shown in FIG. Figure 4C In some embodiments, the second cover layer is not used and only the first cover layer 20 is disposed above the main web film 100, as shown in FIG. Figure 4D In some embodiments, the first cover layer is not used and only the second cover layer 30 is disposed above the main web film 100, and a protective layer 40 is formed on the second cover layer and the web film 100, thereby forming a covered web layer 119, as shown in FIG. Figure 4E In some embodiments, the second covering layer is not used and only the first covering layer 30 is disposed above the main web film 100, and a protective layer 40 is formed on the second covering layer and the web film 100, thereby forming a covering web layer 119, as shown in FIG. Figure 4F as shown in .

[0054] Figure 5A The invention shows a manufacturing process of a network film according to an embodiment of the present invention, and Figure 5B A flow chart thereof according to an embodiment of the present invention is shown.

[0055] In some embodiments, the nanotubes are dispersed in a solution, such as Figure 5A In some embodiments, the nanotubes are carbon nanotubes formed by various methods, such as arc discharge, laser ablation or chemical vapor deposition (CVD) methods. Similarly, BN nanotubes and TMD nanotubes are also formed by CVD processes. The solution is a solvent including water or an organic solvent such as sodium dodecyl sulfate (SDS). The nanotubes are one or two or more nanotubes (materials and / or wall structures).

[0056] like Figure 5A As shown in , the support film is placed between the chamber or cylinder in which the nanotube dispersion solution is disposed and the vacuum chamber. In some embodiments, the support film is an organic or inorganic porous or mesh material. In some embodiments, the support film is a woven or non-woven fabric. In some embodiments, the support film has a circular shape in which a film size or a 150 mm x 150 mm square (the size of an EUV mask) can be placed.

[0057] like Figure 5A As shown in , the pressure in the vacuum chamber is reduced so that pressure is applied to the solvent in the chamber or cylinder. Because the mesh or pore size of the support membrane is sufficiently smaller than the size of the nanotubes, the nanotubes are captured by the support membrane as the solvent passes through the support membrane. Figure 5A The support membrane with the nanotubes deposited thereon is separated by a filtration device and then dried. In some embodiments, the filtration deposition is repeated to obtain the desired thickness of the nanotube network layer, such as Figure 5B In some embodiments, after depositing the nanotubes in a solution, additional nanotubes are dispersed in the same or a new solution and the filter deposition is repeated. In other embodiments, after the nanotubes are dried, another filter deposition is performed. In the repetition, the same type of nanotubes are used in some embodiments, and different types of nanotubes are used in other embodiments.

[0058] Figure 6 1 shows a manufacturing process of a mesh membrane according to an embodiment of the present invention. When the main mesh membrane 100 includes nanotubes and two-dimensional material sheets, the filtration deposition for the nanotubes and the filtration deposition for the sheets are repeated, such as Figure 6 In some embodiments, a mixture of nanotubes and flakes is dispersed in a solvent, and filter deposition is performed to form a mixed network layer of nanotubes and two-dimensional material flakes.

[0059] A two-dimensional material layer is formed over a substrate by a CVD method, and the deposited layer is then peeled off from the substrate. In some embodiments, after peeling off the two-dimensional material layer, the layer is crushed into flakes.

[0060] Fig. 7A and FIG. 7B to FIG. 12A and Fig. 12B1 shows a cross-sectional view ("A") and a plan (top view) view ("B") of various stages of manufacturing a thin film for an EUV photomask according to an embodiment of the present invention. It should be understood that additional embodiments of the method may be 7A to 12B Additional operations are provided before, during, and after the processes shown, and some of the operations described below may be replaced or eliminated. The order of operations / processes may be interchanged.

[0061] like Figure 5A , Figure 5B or Figure 6 As shown in FIG. 1 , a main web film 100 is formed on a support film 80 by filtration deposition. The main web film 100 is then separated from the deposition device, as shown in FIG. Fig. 7A and Figure 7B Then, as Fig. 8A and Figure 8B As shown in FIG. 1 , in some embodiments, a first cover layer 20 is formed over the main web film 100 .

[0062] The first cover layer 20 (which is a two-dimensional material) is formed on the substrate by, for example, a CVD method, and then the deposited two-dimensional layer is peeled off from the substrate. Subsequently, the peeled two-dimensional layer is transferred to the main network layer 100 formed on the supporting substrate 80, as shown in FIG. Fig. 8A and Figure 8B as shown in .

[0063] In some embodiments, a TMD layer represented by MX2 is formed by CVD. In some embodiments, a MoS2 layer is formed by CVD using a source gas, such as Mo(CO)6 gas, MoCl5 gas and / or MoOCl4 gas as a Mo source; and H2S gas and / or dimethyl sulfide gas as an S source. In other embodiments, MO3 gas is sublimated from a solid MO3 or MoCl5 source and / or S gas is sublimated from a solid S source. A solid source of Mo and S is placed in a reaction chamber, and a carrier gas containing an inert gas (such as Ar, N2 and / or He) flows in the reaction chamber. The solid source is heated by sublimation to generate a gas source, and the generated gas source reacts to form MoS2 molecules. The MoS2 molecules are then deposited on a substrate. In some embodiments, the substrate is appropriately heated. In other embodiments, the entire reaction chamber is heated by induction heating. Other TMD layers may also be formed by CVD using a suitable source gas. For example, metal oxides such as WO3, PdO2, and PtO2 can be used as sublimation sources for W, Pd, and Pt, respectively, and metal compounds such as W(CO)6, WF6, WOCl4, PtCl2, and PdCl2 can also be used as metal sources. In some embodiments, the substrate on which the TMD two-dimensional layer is formed includes one of Si(110), γ-Al2O3(110), Ga2O3(010), or MgO(110). In other embodiments, a layer of hexagonal boron nitride (h-BN) or graphene is formed as a first capping layer 20 over the substrate by CVD. In some embodiments, the substrate includes one of SiC(0001), Si(111), or Ge(111).

[0064] Then, if Fig. 9A and Fig. 9B As shown in , the support frame 15 is attached to the first cover layer 20. In some embodiments, the support frame 15 is formed of one or more layers of crystalline silicon, polycrystalline silicon, silicon oxide, silicon nitride, ceramic, metal, or organic material. Fig. 9B As shown in FIG. 1 , the support frame 15 has a rectangular (including square) frame shape, which is larger than the black boundary area of ​​the EUV mask and smaller than the substrate of the EUV mask.

[0065] Next, if Fig. 10A and Fig. 10B As shown in , in some embodiments, the first cover layer 20, the main mesh film 100, and the support film 80 are cut into a rectangular shape having the same size as or slightly larger than the support frame 15, and then the support substrate 80 is separated or removed. When the support substrate 80 is made of an organic material, the support substrate 80 is removed by wet etching using an organic solvent.

[0066] In addition, if Fig.11A and Fig. 11BAs shown in , a second cover layer 30 is formed over the main web film 100. The operations for forming the second cover layer 30 (which is a two-dimensional material) are the same or similar to those for the above-mentioned first cover layer 20. In some embodiments, the first cover layer 20 and the second cover layer 30 are sealed at their peripheries to completely encapsulate the main web film 100.

[0067] In some embodiments, the second cover layer 30 has a flange portion at which the second cover layer 30 is fixed or bonded to the first cover layer 20, such as Fig. 11C In other embodiments, the second cover layer 30 is attached to the first cover layer 20 and the side of the support frame 15, such as Fig.11D as shown in .

[0068] In addition, if Fig. 12A and Fig. 12B As shown in FIG, a protective layer 40 is formed over the first cover layer 20, the second cover layer and the support frame 15. In some embodiments, the protective layer 40 is formed by CVD, physical vapor deposition (PVD) or atomic layer deposition (ALD).

[0069] Fig.13A A flow chart of a method for manufacturing a semiconductor device is shown, and Fig. 13B , Fig. 13C , Fig.13D and Fig.13E Sequential manufacturing operations of a method for making a semiconductor device according to an embodiment of the present invention are shown. A semiconductor substrate or other suitable substrate to be patterned to form an integrated circuit thereon is provided. In some embodiments, the semiconductor substrate includes silicon. Alternatively or additionally, the semiconductor substrate includes germanium, silicon germanium, or other suitable semiconductor material, such as a III-V semiconductor material. Fig.13A In S801, a target layer to be patterned is formed over a semiconductor substrate. In some embodiments, the target layer is a semiconductor substrate. In some embodiments, the target layer includes: a conductive layer, such as a metal layer or a polysilicon layer; a dielectric layer, such as silicon oxide, silicon nitride, SiON, SiOC, SiOCN, SiCN, hafnium oxide, or aluminum oxide; or a semiconductor layer, such as an epitaxially formed semiconductor layer. In some embodiments, the target layer is formed over an underlying structure, such as an isolation structure, a transistor, or a wiring. Fig.13A In S802, a photoresist layer is formed above the target layer, such as Fig. 13B In the subsequent photolithography exposure process, the photoresist layer is sensitive to radiation from the exposure source. In this embodiment, the photoresist layer is sensitive to EUV light used in the photolithography exposure process. The photoresist layer can be formed above the target layer by spin coating or other suitable techniques. The coated photoresist layer can be further baked to drive out the solvent in the photoresist layer. Fig.13AIn S803, the photoresist layer is patterned using an EUV reflective mask having the above-mentioned thin film, such as Fig. 13B As shown in . The patterning of the photoresist layer includes implementing a photolithography exposure process by an EUV exposure system using an EUV mask. During the exposure process, the integrated circuit (IC) design pattern defined on the EUV mask is imaged to the photoresist layer to form a latent pattern thereon. The patterning of the photoresist layer also includes developing the exposed photoresist layer to form a patterned photoresist layer with one or more openings. In an embodiment where the photoresist layer is a positive photoresist layer, the exposed portion of the photoresist layer is removed during the development process. The patterning of the photoresist layer may also include other process steps, such as various baking steps at different stages. For example, a post-exposure baking (PEB) process may be implemented after the photolithography exposure process and before the development process.

[0070] exist Fig.13A In S804, the target layer is patterned using the patterned photoresist layer as an etching mask, such as Fig.13D In some embodiments, patterning the target layer includes applying an etching process to the target layer using the patterned photoresist layer as an etching mask. The portions of the target layer exposed within the openings of the patterned photoresist layer are etched while protecting the remaining portions from etching. In addition, the patterned photoresist layer can be removed by wet stripping or plasma ashing, such as Fig.13E as shown in .

[0071] The film according to the embodiments of the present invention provides higher strength and thermal conductivity (dissipation) and higher EUV transmittance than conventional films. In the aforementioned embodiments, two or more types of nanotubes are used as the main web film to increase the mechanical strength of the film and obtain high EUV transmittance. In addition, the two-dimensional material layer is used as a covering layer (a first covering layer and / or a second covering layer) and / or is used with the nanotubes to increase the mechanical strength of the film. In addition, by using a two-dimensional material layer and / or a protective layer to surround the main web film, the mechanical strength of the film can be increased and high or perfect blocking properties for killing particles can be provided. In addition, in some embodiments, the use of two-dimensional materials improves heat dissipation to prevent the film from being burned by EUV radiation.

[0072] It should be understood that not all advantages are necessarily discussed herein and that no particular advantage is required for all embodiments or examples, and that other embodiments or examples may provide different advantages.

[0073] According to one aspect of the present invention, a film for an EUV photomask includes: a first layer; a second layer; and a main layer, disposed between the first layer and the second layer and including a plurality of nanotubes. At least one of the first layer or the second layer includes a two-dimensional material in which one or more two-dimensional layers are stacked. In one or more embodiments above and below, the first layer includes a first two-dimensional material and the second layer includes a second two-dimensional material. In one or more embodiments above and below, each of the first two-dimensional material and the second two-dimensional material includes at least one selected from the group consisting of boron nitride (BN), graphene, MoS2, MoSe2, WS2 and WSe2. In one or more embodiments above and below, the first two-dimensional material is different from the second two-dimensional material. In one or more embodiments above and below, the thickness of each of the first layer and the second layer is in the range from 0.3nm to 3nm. In one or more embodiments above and below, the number of one or more two-dimensional layers of each of the first two-dimensional material and the second two-dimensional material is 1 to 20. In one or more embodiments above and below, the first layer and the second layer are sealed to completely encapsulate the main layer. In one or more embodiments above and below, the film further includes a protective layer disposed above the first layer and the second layer. In one or more embodiments above and below, the protective layer includes at least one selected from the group consisting of HfO2, Al2O3, ZrO2, Y2O3 and La2O3. In one or more embodiments above and below, the protective layer includes at least one selected from the group consisting of B4C, YN, Si3N4, BN, NbN, RuNb, YF3, TiN and ZrN. In one or more embodiments above and below, the protective layer includes a metal layer made of at least one selected from the group consisting of Ru, Nb, Y, Sc, Ni, Mo, W, Pt and Bi. In one or more embodiments above and below, the thickness of the protective layer is in the range of from 0.1nm to 5nm. In one or more embodiments above and below, the diameter of each of the plurality of nanotubes is in the range of from 0.5nm to 20nm.

[0074] According to another aspect of the present invention, a film for an extreme ultraviolet (EUV) reflective mask includes: a first layer; a second layer; and a main layer, disposed between the first layer and the second layer. The main layer includes a plurality of first nanotubes and a plurality of second nanotubes different from the plurality of first nanotubes. In one or more embodiments above and below, at least one of the first layer or the second layer includes a two-dimensional material in which one or more two-dimensional layers are stacked. In one or more embodiments above and below, the plurality of first nanotubes are single-walled nanotubes and the plurality of second nanotubes are multi-walled nanotubes. In one or more embodiments above and below, the plurality of first nanotubes are made of the same material as the plurality of second nanotubes. In one or more embodiments above and below, the plurality of first nanotubes are made of a material different from the plurality of second nanotubes. In one or more embodiments above and below, each of the plurality of first nanotubes and the plurality of second nanotubes is one or more selected from the group consisting of carbon nanotubes, boron nitride nanotubes, MoS2 nanotubes, MoSe2 nanotubes, WS2 nanotubes, and WSe2 nanotubes. In one or more embodiments above and below, the plurality of first nanotubes and the plurality of second nanotubes are single-walled nanotubes. In one or more embodiments above and below, the first plurality of nanotubes and the second plurality of nanotubes are multi-walled nanotubes.In one or more embodiments above and below, the first plurality of nanotubes are single-walled nanotubes and the second plurality of nanotubes are multi-walled nanotubes.

[0075] According to another aspect of the present invention, a thin film for an extreme ultraviolet (EUV) reflective mask includes: a first layer; a second layer; and a main layer disposed between the first layer and the second layer. The main layer includes a plurality of nanotubes and a plurality of thin sheets including a two-dimensional material in which one or more two-dimensional layers are stacked. In one or more embodiments above and below, the two-dimensional material includes at least one selected from the group consisting of boron nitride (BN), graphene, MoS2, MoSe2, WS2, and WSe2. In one or more embodiments above and below, the size of each of the plurality of thin sheets is in the range of from 100 nm to 200 nm. 2 Up to 100 μm 2 In one or more embodiments above and below, the thickness of each of the plurality of flakes is in the range from 0.3 nm to 3 nm. In one or more embodiments above and below, the number of the one or more two-dimensional layers of each of the plurality of flakes is 1 to 20.

[0076] According to another aspect of the present invention, a film for an extreme ultraviolet (EUV) reflective mask includes: a first film; a support frame attached to the first film; and a main layer, disposed above the first layer and including a plurality of nanotubes. The first film includes a two-dimensional material in which one or more two-dimensional layers are stacked. In one or more embodiments above and below, the two-dimensional material of the first film includes at least one selected from the group consisting of boron nitride (BN), graphene, MoS2, MoSe2, WS2 and WSe2. In one or more embodiments above and below, the thickness of the first film is in the range from 0.3nm to 3nm. In one or more embodiments above and below, the number of one or more two-dimensional layers of the first film is 1 to 20. In one or more embodiments above and below, the first film is disposed between the support frame and the main layer. In one or more embodiments above and below, a portion of the main layer is disposed between the first film and the support frame. In one or more embodiments above and below, the film further includes a protective layer disposed above both sides of the first film. In one or more embodiments above and below, the protective layer includes at least one selected from the group consisting of HfO2, Al2O3, ZrO2, Y2O3 and La2O3. In one or more embodiments above and below, the protective layer includes at least one selected from the group consisting of B4C, YN, Si3N4, BN, NbN, RuNb, YF3, TiN and ZrN. In one or more embodiments above and below, the protective layer includes a metal layer made of at least one selected from the group consisting of Ru, Nb, Y, Sc, Ni, Mo, W, Pt and Bi. In one or more embodiments above and below, the thickness of the protective layer is in the range of from 0.1nm to 5nm. In one or more embodiments above and below, the protective layer is also formed as a plurality of nanotubes covering the main layer. In one or more embodiments above and below, the plurality of nanotubes includes a plurality of first nanotubes and a plurality of second nanotubes different from the plurality of first nanotubes. In one or more embodiments above and below, the plurality of first nanotubes are single-walled nanotubes and the plurality of second nanotubes are multi-walled nanotubes. In one or more embodiments above and below, the plurality of first nanotubes are made of the same material as the plurality of second nanotubes. In one or more embodiments above and below, the plurality of first nanotubes are made of a material different from the plurality of second nanotubes. In one or more embodiments above and below, each of the plurality of first nanotubes and the plurality of second nanotubes is one or more selected from the group consisting of carbon nanotubes, boron nitride nanotubes, MoS2 nanotubes, MoSe2 nanotubes, WS2 nanotubes and WSe2 nanotubes. In one or more embodiments above and below, the plurality of first nanotubes and the plurality of second nanotubes are single-walled nanotubes. In one or more embodiments above and below, the plurality of first nanotubes and the plurality of second nanotubes are multi-walled nanotubes.In one or more embodiments above and below, the plurality of first nanotubes are single-walled nanotubes and the plurality of second nanotubes are multi-walled nanotubes. In one or more embodiments above and below, the main layer further comprises: a plurality of flakes comprising a two-dimensional material in which one or more two-dimensional layers are stacked. In one or more embodiments above and below, the two-dimensional material comprises at least one selected from the group consisting of boron nitride (BN), graphene, MoS2, MoSe2, WS2 and WSe2. In one or more embodiments above and below, the size of each of the plurality of flakes is from 100 nm. 2 Up to 100 μm 2 In one or more embodiments above and below, the thickness of each of the plurality of flakes is in the range from 0.3 nm to 3 nm. In one or more embodiments above and below, the number of the one or more two-dimensional layers of each of the plurality of flakes is 1 to 20.

[0077] According to another aspect of the present invention, in a method for manufacturing a thin film for an extreme ultraviolet (EUV) reflective mask, a nanotube layer is formed over a supporting substrate, a first covering layer is formed over the nanotube layer, a thin film frame is attached over the first covering layer, the nanotube layer and the first covering layer are cut to form a cut thin film membrane, a second layer is formed to completely encapsulate the nanotube layer of the cut thin film membrane by using the first layer of the cut thin film membrane to seal, and a protective layer is formed over the first covering layer, the second covering layer and the thin film frame. In one or more embodiments above and below, at least one of the first covering layer or the second covering layer includes a two-dimensional material in which one or more two-dimensional layers are stacked. In one or more embodiments above and below, the first covering layer includes a first two-dimensional material and the second covering layer includes a second two-dimensional material. In one or more embodiments above and below, each of the first two-dimensional material and the second two-dimensional material includes at least one selected from the group consisting of boron nitride (BN), graphene, MoS2, MoSe2, WS2 and WSe2. In one or more embodiments above and below, the first two-dimensional material is different from the second two-dimensional material. In one or more embodiments above and below, the thickness of each of the first capping layer and the second capping layer is in the range of from 0.3 nm to 3 nm. In one or more embodiments above and below, the number of one or more two-dimensional layers of each of the first two-dimensional material and the second two-dimensional material is 1 to 20. In one or more embodiments above and below, the protective layer includes at least one selected from the group consisting of HfO2, Al2O3, ZrO2, Y2O3 and La2O3. In one or more embodiments above and below, the protective layer includes at least one selected from the group consisting of B4C, YN, Si3N4, BN, NbN, RuNb, YF3, TiN and ZrN. In one or more embodiments above and below, the protective layer includes a metal layer made of at least one selected from the group consisting of Ru, Nb, Y, Sc, Ni, Mo, W, Pt and Bi. In one or more embodiments above and below, the thickness of the protective layer is in the range of from 0.1 nm to 5 nm. In one or more embodiments above and below, the nanotube layer includes a plurality of nanotubes having a diameter in the range of from 0.5 nm to 20 nm. In one or more embodiments above and below, the plurality of nanotubes include a plurality of first nanotubes and a plurality of second nanotubes different from the plurality of first nanotubes. In one or more embodiments above and below, at least one of the first layer or the second layer includes a two-dimensional material in which one or more two-dimensional layers are stacked. In one or more embodiments above and below, the plurality of first nanotubes are single-walled nanotubes and the plurality of second nanotubes are multi-walled nanotubes. In one or more embodiments above and below, the plurality of first nanotubes are made of the same material as the plurality of second nanotubes.In one or more embodiments above and below, a plurality of first nanotubes are made of a material different from a plurality of second nanotubes. In one or more embodiments above and below, each of a plurality of first nanotubes and a plurality of second nanotubes is selected from one or more of the group consisting of carbon nanotubes, boron nitride nanotubes, MoS2 nanotubes, MoSe2 nanotubes, WS2 nanotubes and WSe2 nanotubes. In one or more embodiments above and below, a plurality of first nanotubes and a plurality of second nanotubes are single-walled nanotubes. In one or more embodiments above and below, a plurality of first nanotubes and a plurality of second nanotubes are multi-walled nanotubes. In one or more embodiments above and below, a plurality of first nanotubes are single-walled nanotubes and a plurality of second nanotubes are multi-walled nanotubes. In one or more embodiments above and below, a nanotube layer includes a plurality of nanotubes and a plurality of thin sheets of a two-dimensional material including one or more two-dimensional layers stacked therein. In one or more embodiments above and below, the two-dimensional material includes at least one selected from the group consisting of boron nitride (BN), graphene, MoS2, MoSe2, WS2 and WSe2. In one or more embodiments above and below, a size of each of the plurality of flakes is from 100 nm. 2 Up to 100 μm 2 In one or more embodiments above and below, the thickness of each of the plurality of flakes is in the range from 0.3 nm to 3 nm. In one or more embodiments above and below, the number of the one or more two-dimensional layers of each of the plurality of flakes is 1 to 20.

[0078] According to another aspect of the present invention, in a method for manufacturing an EUV film, a network structure of nanotubes is formed, a two-dimensional (2D) material layer is formed above the network structure of nanotubes, and a protective layer is formed above the network structure of nanotubes. In one or more embodiments above and below, when forming the network structure of nanotubes, a first network structure of first nanotubes is formed, and a second network structure of second nanotubes is formed above the first network structure of the first nanotubes. In one or more embodiments above and below, the first nanotube is different from the second nanotube. In one or more embodiments above and below, when forming the network structure of nanotubes, a third network structure of a 2D material sheet is formed above the first network structure of the first nanotube. In one or more embodiments above and below, the 2D material sheet is different from the first nanotube and the second nanotube. In one or more embodiments above and below, before forming the second network structure of the second nanotube above the first network structure of the first nanotube, the third network structure of the 2D material sheet is formed above the first network structure of the first nanotube. In one or more embodiments above and below, forming a third network structure of a 2D material sheet over the first network structure of the first nanotubes is after forming a second network structure of the second nanotubes over the first network structure of the first nanotubes. In one or more embodiments above and below, forming a 2D material layer over the network structure of the nanotubes is before forming a protective layer over the network structure of the nanotubes. In one or more embodiments above and below, forming a 2D material layer over the network structure of the nanotubes is after forming a protective layer over the network structure of the nanotubes.

[0079] According to another aspect of the present invention, in a method for manufacturing an EUV film, a nanostructure is formed, the nanostructure is dispersed in a solution, the nanostructure is filtered through a support membrane to form a main film, a first two-dimensional layer is formed above a first side of the main film, the support membrane is removed, and a second two-dimensional layer is formed above a second side of the main film where the support membrane is removed. In one or more embodiments above and below, the nanostructure includes nanotubes. In one or more embodiments above and below, the nanostructure also includes a thin sheet of one or more two-dimensional materials. In one or more embodiments above and below, the support membrane is porous. In one or more embodiments above and below, a support frame is attached to the first two-dimensional layer. In one or more embodiments above and below, a protective layer is formed above the first two-dimensional layer, the second two-dimensional layer, and the support frame.

[0080] The features of several embodiments or examples are summarized above so that those skilled in the art can better understand aspects of the present invention. Those skilled in the art should understand that they can easily use the present invention as a basis to design or modify other processes and structures for implementing the same purpose and / or achieving the same advantages as the embodiments or examples introduced herein. Those skilled in the art should also appreciate that this equivalent construction does not deviate from the spirit and scope of the present invention, and that they can make various changes, substitutions and modifications herein without departing from the spirit and scope of the present invention.

Claims

1. A film for an extreme ultraviolet (EUV) reflective mask, comprising: First floor; Second floor; as well as a main layer disposed between the first layer and the second layer and comprising a plurality of nanotubes and a plurality of two-dimensional material flakes made of a two-dimensional material in which one or more two-dimensional layers are stacked, wherein the two-dimensional material flakes are embedded in the plurality of nanotubes, and wherein: At least one of the first layer or the second layer includes a two-dimensional material in which one or more two-dimensional layers are stacked.

2. The film according to claim 1, wherein The first layer comprises a first two-dimensional material and the second layer comprises a second two-dimensional material.

3. The film according to claim 2, wherein Each of the first two-dimensional material and the second two-dimensional material includes at least one selected from the group consisting of boron nitride (BN), graphene, MoS 2 , MoSe 2 , WS 2 , and WSe 2 .

4. The film according to claim 3, wherein The first two-dimensional material is different from the second two-dimensional material.

5. The film according to claim 2, wherein The thickness of each of the first layer and the second layer is in the range from 0.3 nm to 3 nm.

6. The film according to claim 2, wherein The number of the one or more two-dimensional layers of each of the first two-dimensional material and the second two-dimensional material is 1 to 20.

7. The film according to claim 1, wherein The first layer and the second layer are sealed to completely enclose the primary layer.

8. The film according to claim 7, further comprising: A protective layer is disposed above the first layer and the second layer.

9. The film according to claim 8, wherein The protective layer includes at least one selected from the group consisting of HfO 2 , Al 2 O 3 , ZrO 2 , Y 2 O 3 , and La 2 O 3 .

10. The film according to claim 8, wherein The protective layer includes at least one selected from the group consisting of B4C, YN, Si3N4, BN, NbN, RuNb, YF3, TiN and ZrN.

11. The film according to claim 8, wherein The protective layer includes a metal layer made of at least one selected from the group consisting of Ru, Nb, Y, Sc, Ni, Mo, W, Pt, and Bi.

12. The film according to claim 8, wherein The thickness of the protective layer ranges from 0.1 nm to 5 nm.

13. The film according to claim 1, wherein A diameter of each of the plurality of nanotubes ranges from 0.5 nm to 20 nm.

14. A film for an extreme ultraviolet (EUV) reflective mask, comprising: First floor; Second floor; as well as a main layer, disposed between the first layer and the second layer, Wherein, the main layer includes a plurality of first nanotubes and a plurality of second nanotubes different from the plurality of first nanotubes and a plurality of two-dimensional material sheets made of a two-dimensional material in which one or more two-dimensional layers are stacked, wherein the two-dimensional material sheets are embedded in the plurality of first nanotubes and the plurality of second nanotubes.

15. The film according to claim 14, wherein The first plurality of nanotubes are single-walled nanotubes and the second plurality of nanotubes are multi-walled nanotubes.

16. The film according to claim 15, wherein The plurality of first nanotubes are made of the same material as the plurality of second nanotubes.

17. The film according to claim 14, wherein The plurality of first nanotubes are made of a different material than the plurality of second nanotubes.

18. The film according to claim 17, wherein The plurality of first nanotubes and the plurality of second nanotubes are both single-walled nanotubes.

19. A method of making a pellicle for an extreme ultraviolet (EUV) reflective mask, comprising: forming a nanotube layer over a supporting substrate; forming a first capping layer over the nanotube layer; forming a film frame over the first covering layer; cutting the nanotube layer and the first cover layer to form cut thin film membranes; forming a second cover layer to completely encapsulate the nanotube layer of the cut thin film membrane piece sealed by the first cover layer of the cut thin film membrane piece; as well as forming a protective layer over the first covering layer, the second covering layer and the film frame, The nanotube layer includes a plurality of nanotubes and a plurality of two-dimensional material sheets made of a two-dimensional material in which one or more two-dimensional layers are stacked, wherein the two-dimensional material sheets are embedded in the plurality of nanotubes.

20. The method according to claim 19, wherein: At least one of the first cover layer or the second cover layer includes a two-dimensional material in which one or more two-dimensional layers are stacked.

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