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

Abstract

A thin film for an EUV photomask includes a first layer, a second layer, and a main film disposed between the first layer and the second layer. The main film includes a plurality of coaxial nanotubes, each of the plurality of coaxial nanotubes including an inner tube and one or more outer tubes surrounding the inner tube, and two of the inner tube and the one or more outer tubes are made of different materials from each other. Embodiments of the present application also relate to a thin film for an EUV reflective mask and a method of manufacturing the same.

Description

TECHNICAL FIELD

[0001] Embodiments of the present application relate to a pellicle for an EUV reflective mask and a method of manufacturing the same. BACKGROUND

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

[0003] Some embodiments of the present application provide a pellicle for an extreme ultraviolet (EUV) reflective mask, comprising: a first layer; a second layer; and a main film disposed between the first layer and the second layer, wherein: the main film comprises a plurality of coaxial nanotubes, each of the plurality of coaxial nanotubes comprises an inner tube and one or more outer tubes surrounding the inner tube, and two of the inner tube and the one or more outer tubes are made of different materials from each other.

[0004] Some embodiments of the present application provide a pellicle for an extreme ultraviolet (EUV) reflective mask, comprising: a first layer; a support frame attached to the first layer; and a main film disposed over the first layer, wherein: the main film comprises a plurality of nanotubes, each of the plurality of nanotubes comprises an inner nanotube and first to Nth outer layers each coaxially surrounding the inner nanotube, where N is a natural number from 1 to 10.

[0005] Some embodiments of the present application provide a method of manufacturing a pellicle for an extreme ultraviolet (EUV) reflective mask, comprising: forming a nanotube layer comprising a plurality of nanotubes over a support substrate; forming a pellicle frame over the nanotube layer; separating the nanotube layer from the support substrate; and forming one or more outer tubes around each of the plurality of nanotubes as an inner nanotube, thereby forming a network film comprising a plurality of coaxial tubes each comprising the inner nanotube and the one or more outer tubes each coaxially surrounding the inner nanotube, wherein at least two of the inner nanotube and the one or more outer tubes are made of different materials from each other. BRIEF DESCRIPTION OF DRAWINGS

[0006] Various aspects of the application can be best understood from the following detailed description when read with the accompanying drawings in which: It should be noted that, in accordance with standard practice in the industry, the various elements are not drawn to scale. In fact, the dimensions of the various elements can be arbitrarily increased or decreased for the sake of clarity in the discussion.

[0007] FIG. 1A , FIG. 1B , FIG. 1C and FIG. 1DVarious views of a thin film for an EUV photomask according to embodiments of the present application are shown.

[0008] FIG. 2A , FIG. 2B , FIG. 2C and FIG. 2D Various views of a multi-walled nanotube according to embodiments of the present application are shown.

[0009] FIG. 3A , FIG. 3B and FIG. 3C Various views of a network film for a thin film for an EUV photomask according to embodiments of the present application are shown.

[0010] FIG. 4A , FIG. 4B , FIG. 4C , FIG. 4D , FIG. 4E , FIG. 4F , FIG. 4G , FIG. 4H , FIG. 4I and FIG. 4J Various views of a network film for a thin film for an EUV photomask according to embodiments of the present application are shown.

[0011] FIG. 5A A manufacturing process of a network film is shown, FIG. 5B a flowchart thereof is shown, and FIG. 5C and FIG. 5D A manufacturing process of a multi-walled nanotube according to embodiments of the present application is shown.

[0012] FIG. 6 A manufacturing process of a network film according to embodiments of the present application is shown.

[0013] FIG. 7A and FIG. 7B Cross-sectional and planar (top view) views of one of the various stages for manufacturing a thin film for an EUV photomask according to embodiments of the present application are shown.

[0014] FIG. 8A and FIG. 8B Cross-sectional and planar (top view) views of one of the various stages for manufacturing a thin film for an EUV photomask according to embodiments of the present application are shown.

[0015] FIG. 9A and FIG. 9B Cross-sectional and planar (top view) views of one of the various stages for manufacturing a thin film for an EUV photomask according to embodiments of the present application are shown.

[0016] FIG. 10A and FIG. 10BA cross-sectional view and a plan (top view) of one of the various stages for manufacturing a thin film for an EUV photomask according to an embodiment of the application is shown.

[0017] FIG. 11A and FIG. 11B A cross-sectional view and a plan (top view) of one of the various stages for manufacturing a thin film for an EUV photomask according to an embodiment of the application is shown. FIG. 11C A cross-sectional view of one of the various stages for manufacturing a thin film for an EUV photomask according to an embodiment of the application is shown. FIG. 11D A cross-sectional view of one of the various stages for manufacturing a thin film for an EUV photomask according to an embodiment of the application is shown.

[0018] FIG. 12A and FIG. 12B A cross-sectional view and a plan (top view) of one of the various stages for manufacturing a thin film for an EUV photomask according to an embodiment of the application is shown.

[0019] FIG. 13A and FIG. 13B A cross-sectional view and a plan (top view) of one of the various stages for manufacturing a thin film for an EUV photomask according to an embodiment of the application is shown.

[0020] FIG. 14A and FIG. 14B A cross-sectional view and a plan (top view) of one of the various stages for manufacturing a thin film for an EUV photomask according to an embodiment of the application is shown.

[0021] FIG. 15A , FIG. 15B and FIG. 15C A cross-sectional view of one of the various stages for manufacturing a thin film for an EUV photomask according to an embodiment of the application is shown.

[0022] FIG. 16A A cross-sectional view of one of the various stages for manufacturing a thin film for an EUV photomask according to an embodiment of the application is shown.

[0023] FIG. 16B A cross-sectional view of one of the various stages for manufacturing a thin film for an EUV photomask according to an embodiment of the application is shown.

[0024] FIG. 17A , FIG. 17B , FIG. 17C and FIG. 17D A cross-sectional view of a thin film for an EUV photomask according to an embodiment of the application is shown.

[0025] FIG. 18A , FIG. 18B、 FIG. 18C 、 FIG. 18D 、 FIG. 18E and FIG. 18F A flow chart of a process for fabricating a pellicle for an EUV photomask according to an embodiment of the present application is shown.

[0026] FIG. 19A A flow chart of a method of fabricating a semiconductor device is shown, and FIG. 19B 、 FIG. 19C 、 FIG. 19D and FIG. 19E Sequential fabrication operations of a method of fabricating a semiconductor device according to an embodiment of the present application are shown. DETAILED DESCRIPTION DETAILED DESCRIPTION

[0027] It should be understood that the following disclosure provides many different embodiments, or examples, for implementing different features of the present application. Specific embodiments or examples of components and arrangements are described below to simplify the present application. These are, of course, merely examples and are not intended to limit the application in any way. For example, the dimensions of the elements can depend on the process conditions and / or desired characteristics of the device. Moreover, in the following description, the formation of a first component over or on a second component can include embodiments where the first component is formed directly on the second component and / or embodiments where the first component is formed indirectly on the second component with one or more additional components intervening therebetween. For the purposes of this description, the term "over" or "on" includes direct or indirect positioning of one component over another. Each of the components can be formed in different sizes and shapes than shown in the drawings. In the drawings, some layers / elements can be omitted for simplicity.

[0028] In addition, spatially relative terms, such as "beneath", "below", "lower", "above", "upper" and the like, can be used herein for ease of description to describe one element or component's relationship to another element(s) or component(s) as illustrated in the figures. The spatially relative terms are intended to encompass different orientations of the device in use or operation in addition to the orientation depicted in the figures. The devices can be otherwise oriented (rotated 90 degrees or at other orientations) and the spatially relative descriptors used herein interpreted accordingly. Furthermore, the term "from" can mean "comprising" or "consisting of". Moreover, in the following manufacturing processes, there can be one or more additional operations between the operations described and the order of the operations can be changed. In this application, 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, but does not mean one from A, one from B, and one from C, unless otherwise stated. Materials, configurations, structures, operations, and / or dimensions explained using one embodiment are applicable to other embodiments, and detailed descriptions thereof can be omitted.

[0029] EUV lithography is one of the key technologies for extending Moore's law. However, due to the wavelength scaling from 193 nm (ArF) to 13.5 nm, EUV light sources suffer from strong power decay due to ambient adsorption. Even though the stepper / scanner chamber is operated under vacuum to prevent strong adsorption of gas to EUV, it is still an important factor in EUV lithography to maintain high EUV transmissivity from the EUV light source to the wafer.

[0030] Thin films generally require high transparency and low reflectivity. In UV or DUV lithography, thin films are made of transparent resin films. However, in EUV lithography, resin-based films are not acceptable, and non-organic materials, such as polycrystalline silicon, silicide, or metal films, are used.

[0031] Carbon nanotubes (CNTs) are one of the materials suitable for thin films for EUV reflective photomasks, because CNTs have high EUV transmissivity of more than 96.5%. Generally, thin films for EUV reflective masks require the following characteristics: (1) long lifetime in a hydrogen-rich radical operating environment in an EUV stepper / scanner; (2) strong mechanical strength to minimize the sag effect during vacuum pumping and exhaust operations; (3) high or perfect barrier performance against particles greater than about 20 nm (killer particles); and (4) good heat dissipation to prevent the thin film from being burned by EUV radiation.

[0032] In the present invention, a thin film for an EUV photomask includes a network film having a plurality of multi-walled nanotubes and a two-dimensional material layer covering the network film. Such a thin film has high EUV transmissivity, improved mechanical strength, prevents killer particles from falling on the EUV mask, and / or has improved durability.

[0033] FIG. 1A 、 FIG. 1B and FIG. 1C An EUV thin film 10 mounted on an EUV reflective mask 5 according to an embodiment of the present invention is shown. FIG. 1A is a cross-sectional view in the X direction, FIG. 1B is a cross-sectional view in the Y direction, and FIG. 1C is a top view (plan view).

[0034] In some embodiments, the thin film 10 for an EUV reflective mask includes a first capping layer 20, a second capping layer 30, and a main mesh film 100 disposed between the first capping layer 20 and the second capping layer 30. In some embodiments, the main mesh layer includes a plurality of multi-walled nanomaterials, such as nanotubes and / or nanosheets of two-dimensional materials. In some embodiments, a support frame 15 is attached to the main mesh film 100 and / or the first capping layer 20 to maintain a 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 capping layer 20 and the second capping layer 30 includes a two-dimensional material in which one or more two-dimensional layers are stacked. Here, in some embodiments, a "two-dimensional" layer refers to one or several crystalline layers of an atomic matrix or mesh having a thickness in the range of about 0.1-5 nm.

[0035] The support frame 15 of the thin film is attached to the surface of the EUV photomask 5 with a suitable bonding material. In some embodiments, the bonding material is an adhesive, such as an acrylic or silicon-based glue or an A-B cross-linking type glue. The frame structure is larger in size than the area of the black border of the EUV photomask, so that the thin film covers not only the circuit pattern area of the photomask but also the black border.

[0036] In some embodiments, the two-dimensional materials of the first capping layer 20 and the second capping layer 30 are the same or different from each other. In some embodiments, the first capping layer includes a first two-dimensional material and the second capping layer includes a second two-dimensional material.

[0037] 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.

[0038] In some embodiments, the total thickness of each of the first capping layer 20 and the second capping layer 30 is in the range from about 0.3 nm to about 3 nm, and in other embodiments in the range from about 0.5 nm to about 1.5 nm. In some embodiments, the number of two-dimensional layers of the two-dimensional material 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 layers is greater than these ranges, the EUV transmittance of the thin film 10 can decrease, and when the thickness and / or number of layers is less than these ranges, the mechanical strength of the thin film can be insufficient.

[0039] In some embodiments, as FIG. 1A and FIG. 1BAs shown in FIG. 1, the first cover layer 20 and the second cover layer 30 are sealed at their periphery to completely enclose the main membrane 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 0.01 Pa to about 100 Pa. If the internal pressure is too high, for example, higher than the internal pressure of an EUV lithography apparatus in operation, the membrane can be broken 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.

[0040] In some embodiments, a protective layer 40 is further disposed above the first cover layer 20, the second cover layer 30, and the support frame 15, as shown in FIG. 1. FIG. 1D In some embodiments, the protective layer 40 includes at least one layer of an oxide, such as Hf02, AI2O3, Zr02, 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 about 0.1 nm to about 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 membrane 10 can be reduced, and when the thickness of the protective layer 40 is less than these ranges, the mechanical strength of the membrane can be insufficient.

[0041] By using the first cover layer and / or the second cover layer and / or the protective layer without holes, such as openings and / or spaces greater than about 10-20 nm, it is possible to completely block killer particles greater than about 20 nm from passing through the main membrane 100 and falling on the surface of the EUV mask 5.

[0042] In some embodiments, the nanotubes in the main membrane 100 include multi-walled nanotubes, which are also referred to as coaxial nanotubes. FIG. 2A A perspective view of a multi-walled coaxial nanotube having three tubes 210, 220, and 230 is shown, and FIG. 2B a cross-sectional view thereof is shown. In some embodiments, the inner tube 210 is a carbon nanotube, and the two outer tubes 220 and 230 are boron nitride nanotubes.

[0043] The number of tubes of the multi-walled nanotube is not limited to three. In some embodiments, the multi-walled nanotube has two coaxial nanotubes, as shown in FIG. 2A, and FIG. 2Cas shown in FIG. 1, and in other embodiments, the multi-walled nanotube includes an innermost tube 210 and first through Nth nanotubes including an outermost tube 200N, where N is a natural number from 1 to about 20, as shown in FIG. 2. FIG. 2D as shown in FIG. 1. In some embodiments, N is up to 10 or up to 5. In some embodiments, at least one of the first through Nth outer layers is a nanotube coaxially surrounding the innermost nanotube 210. In some embodiments, two of the innermost nanotube 210 and the first through Nth outer layers 220, 230,... 200N are made of different materials from each other. In some embodiments, N is at least two (i.e., three or more tubes), and two of the innermost nanotube 210 and the first through Nth outer tubes 220, 230,... 200N are made of the same material. In other embodiments, three of the innermost nanotube 210 and the first through Nth outer tubes 220, 230,... 200N are made of different materials from each other.

[0044] In some embodiments, each of the nanotubes of the multi-walled nanotube is one selected from the group consisting of a carbon nanotube, a boron nitride nanotube, a transition metal dichalcogenide (TMD) nanotube, where the TMD is represented by MX2, where M is one or more of Mo, W, Pd, Pt, or Hf, and X is one or more of S, Se, or Te. In some embodiments, at least two of the tubes of the multi-walled nanotube are made of different materials from each other. In some embodiments, two adjacent layers (tubes) of the multi-walled nanotube are made of different materials from each other.

[0045] In some embodiments, the multi-walled nanotube includes three coaxial layered tubes made of different materials from each other. In other embodiments, the multi-walled nanotube includes three coaxial layered tubes, where the innermost tube (first tube) and the second tube surrounding the innermost tube are made of different materials from each other, and the third tube surrounding the second tube is made of the same material as the innermost tube or the second tube or a different material.

[0046] In some embodiments, the multi-walled nanotube includes four coaxial layered tubes each made of a different material A, B, or C. In some embodiments, the materials of the four layers from the innermost (first) tube to the fourth tube are A / B / A / A, A / B / A / B, A / B / A / C, A / B / B / A, A / B / B / B, A / B / B / C, A / B / C / A, A / B / C / B, or A / B / C / C.

[0047] In some embodiments, all of the tubes of the multi-walled nanotube are crystalline nanotubes. In other embodiments, one or more tubes are amorphous (e.g., non-crystalline) layers that encase one or more inner tubes. In some embodiments, the outermost tube is made of a layer of Hf02, AI2O3, Zr02, Y2O3, La2O3, B4C, YN, Si3N4, BN, NbN, RuNb, YF3, TiN, ZrN, Ru, Nb, Y, Sc, Ni, Mo, W, Pt, or Bi, for example. In some embodiments, the outermost layer is made of the same material as the protective layer 40.

[0048] In some embodiments, the innermost nanotube has a diameter in the range from about 0.5 nm to about 20 nm, and in other embodiments in the range from about 1 nm to about 10 nm. In some embodiments, the multi-walled nanotube has a diameter (i.e., the diameter of the outermost tube) in the range from about 3 nm to about 40 nm, and in other embodiments in the range from about 5 nm to about 20 nm. In some embodiments, the multi-walled nanotube has a length in the range from about 0.5 μιη to about 50 μιη, and in other embodiments in the range from about 1.0 μιη to about 20 μιη.

[0049] FIG. 3A 、 FIG. 3B and FIG. 3C Various mesh films 100 for thin films of EUV photomasks according to embodiments of the present application are shown.

[0050] In some embodiments, the mesh film 100 includes a plurality of multi-walled nanotubes 101. In some embodiments, the plurality of multi-walled nanotubes are randomly arranged to form a mesh structure. In some embodiments, the plurality of multi-walled nanotubes includes only one type of multi-walled nanotube in terms of material and structure (number of layers). In other embodiments, the plurality of multi-walled nanotubes includes two or more types of multi-walled nanotubes in terms of material and structure (number of layers). For example, the plurality of multi-walled nanotubes includes: a first type of multi-walled nanotube (e.g., two-walled nanotubes) and a second type of multi-walled nanotube (e.g., three-walled nanotubes); a first type of multi-walled nanotube (e.g., two-walled nanotubes of layer A and layer B) and a second type of multi-walled nanotube (e.g., two-walled nanotubes of layer A and layer C).

[0051] In some embodiments, the main mesh layer 100 includes a plurality of one or more types of multi-walled nanotubes 101 and a plurality of one or more types of single-walled nanotubes 111, as shown in FIG. 1A. FIG. 3BIn some embodiments, the amount (weight) of single-walled nanotubes 111 is less than the amount of multi-walled nanotubes 101. In some embodiments, the amount (weight) of single-walled nanotubes 111 is greater than the amount of multi-walled nanotubes 101. In some embodiments, the amount (weight) of multi-walled nanotubes 101 is at least about 20 wt% relative to the total weight of the network film 100, or in other embodiments, at least 40 wt%. When the amount of multi-walled nanotubes is less than these ranges, sufficient network film strength can not be obtained.

[0052] In some embodiments, the primary network film 100 includes a plurality of multi-walled nanotubes 101 and a plurality of flakes 121 (nanoflakes) made of a two-dimensional material stacked with one or more two-dimensional layers, as shown in FIG. 3C .

[0053] In some embodiments, the two-dimensional material flakes 121 include 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.

[0054] In some embodiments, the thickness of the two-dimensional material flakes 121 is in a range from about 0.3 nm to about 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 the two-dimensional material flakes 121 is 1 to about 20, and in other embodiments, 2 to about 10. When the thickness and / or number of layers is greater than these ranges, the EUV transmittance of the thin film 10 can decrease, and when the thickness and / or number of layers is less than these ranges, the mechanical strength of the thin film can be insufficient.

[0055] 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 certain 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 in a range from about 10 nm 2 to about 10 μm 2 , and in other embodiments, in a range from about 100 nm 2 to about 1 μm 2 . In some embodiments, the two-dimensional material flakes 121 are embedded in or mixed with the plurality of nanotubes 101.

[0056] In some embodiments, the amount (weight) of the two-dimensional material sheet 121 relative to the total weight of the network film 100 ranges from about 5 wt% to about 30 wt%, and in other embodiments it ranges from about 10 wt% to about 20 wt%. When the amount of the two-dimensional material sheet is greater than these ranges, the EUV transmittance of the film 10 may decrease, and when the amount of the two-dimensional material sheet is less than these ranges, the mechanical strength of the film may be insufficient. In some embodiments, the plurality of nanotubes are similar to FIG. 3A The multi-walled nanotubes, and in other embodiments, the multiple nanotubes are similar to FIG. 3B A mixture of single-walled nanotubes and multi-walled nanotubes.

[0057] FIG. 4A , FIG. 4B , FIG. 4C , FIG. 4D , FIG. 4E , FIG. 4F , FIG. 4G , FIG. 4H , FIG. 4I and FIG. 4J Various views of a mesh film for an EUV photomask according to an embodiment of the present invention are shown. In some embodiments, the mesh film 100 has a single-layer structure or a multi-layer structure.

[0058] In some embodiments, the network membrane 100 has a single layer 110 of multiple multi-walled nanotubes, such as FIG. 4A As shown in the figure. In some embodiments, the network membrane 100 has two layers of multi-walled nanotubes 110 and 112 of different types, such as FIG. 4B As shown in the diagram. Layers 110 and 112 may have the same or different thicknesses. In some embodiments, the network film 100 has three layers of nanotubes 110, 112, and 114, as shown in the diagram. FIG. 4C As shown in the figure. In some embodiments, at least adjacent layers are different types (e.g., materials and / or the number of walls). Layers 110, 112, and 114 have the same thickness or are different from each other. In some embodiments, a single nanotube layer is disposed between two multi-walled nanotube layers. In some embodiments, the network membrane 100 is a monolayer 115 of a mixture of different types of nanotubes, such as... FIG. 4D As shown in the image.

[0059] In some embodiments, the network film 100 has a nanotube layer 110 and a two-dimensional sheet layer 120, such as FIG. 4E and FIG. 4F As shown in the diagram. Layers 110 and 120 may have the same or different thicknesses. Layer 110 may be a hybrid layer 115, such as... FIG. 4D As shown in the figure. 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, as shown in the figure.FIG. 4G In some embodiments, the first nanotube layer and the second nanotube layer are of the same type or 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, as shown in FIG. 4H In some embodiments, the first two-dimensional sheet layer and the second two-dimensional sheet layer are made of the same material or different materials from each other. In some embodiments, the mesh film 100 has a nanotube layer 110, a first two-dimensional sheet layer 120 located above the nanotube layer 110, and a second two-dimensional sheet layer 122 disposed above the first two-dimensional sheet layer 120, as shown in FIG. 4I In some embodiments, the mesh film 100 has one or more nanotube layers of the same type or different types and one or more two-dimensional sheet layers of the same material or different materials. In some embodiments, the mesh film 100 has a single layer 125 of a mixture of nanotubes and two-dimensional sheets, as shown in FIG. 4J

[0060] FIG. 5A A manufacturing process of the mesh film is shown, and FIG. 5B A flowchart thereof according to an embodiment of the present application is shown.

[0061] In some embodiments, the nanotubes are dispersed in a solution, as shown in FIG. 5A 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 types of nanotubes (material and / or number of walls). In some embodiments, the nanotubes are single-walled nanotubes. In some embodiments, the single-walled nanotubes are carbon nanotubes formed by various methods, such as arc discharge, laser ablation, or chemical vapor deposition (CVD) methods. Similarly, single-walled BN nanotubes and single-walled TMD nanotubes are also formed by CVD processes.

[0062] As shown in FIG. 5A The support film is placed between a chamber or cylinder in which the nanotube dispersion solution is disposed and a vacuum chamber, as shown in

[0063] As shown in FIG. 5A The pressure in the vacuum chamber is reduced, such that pressure is applied to the solvent in the chamber or cylinder. Because the mesh or pore size of the support film is sufficiently small compared to the size of the nanotubes, the nanotubes are captured by the support film as the solvent passes through the support film. From FIG. 5A ​The filtration device separates and then dries the support film on which the nanotubes are deposited. In some embodiments, the filtration deposition is repeated in order to obtain a desired thickness of the nanotube network layer, as shown in FIG. 5B In some embodiments, after depositing the nanotubes in solution, other nanotubes are dispersed in the same or a new solution and the filtration deposition is repeated. In other embodiments, after the nanotubes are dried, another filtration deposition is performed. In the repetitions, in some embodiments the same type of nanotubes are used, and in other embodiments different types of nanotubes are used.

[0064] In some embodiments, the nanotubes dispersed in solution include multi-walled nanotubes. In some embodiments, the multi-walled nanotubes are formed by CVD using single-walled nanotubes as seeds, as shown in FIG. 5C In some embodiments, single-walled nanotubes formed by CVD, such as carbon nanotubes, BN nanotubes, or TMD nanotubes, are placed above the substrate. Then, a source material, such as a source gas, is provided above the substrate with the seed nanotubes. In the case of CVD for forming a MoS2 layer, in some embodiments, Mo(CO)6 gas, MoCl5 gas, and / or MoOCl4 gas are used as the Mo source, and H2S gas and / or dimethyl sulfide gas are used as the S source. In other embodiments, MoO3 gas sublimed from a solid MoO3 or MoCl5 source and / or S gas sublimed from a solid S source can be used, as shown in FIG. 5C As shown in FIG. 5C The solid sources of Mo and S are placed in a reaction chamber, and a carrier gas containing an inert gas, such as Ar, N2, and / or He, is flowed in the reaction chamber. The solid sources are heated to generate the gas sources by sublimation, and the generated gas sources react to form MoS2 molecules. The MoS2 molecules are then deposited around the seed nanotubes above the substrate. In some embodiments, the substrate is heated appropriately. In other embodiments, the entire reaction chamber is heated by induction heating. Other TMD layers can also be formed by CVD using appropriate source gases. 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.

[0065] In other embodiments, as shown in FIG. 5D The seed nanotubes are immersed in, dispersed in, or treated by one or more metal precursors, such as (NH4)WS4, WO3, (NH4)MoS4, or MoO3, and placed above the substrate, and then a sulfur-containing gas is provided above the substrate to form multi-walled nanotubes.

[0066] In other embodiments, a carbon source gas is used to form carbon nanotubes as an outer layer over BN or TMD inner nanotubes. In some embodiments, three or more coaxial nanotubes are formed by repeating the above process. In some embodiments, multi-walled nanotubes are disposed in solution, as shown in FIG. 5A In some embodiments, a mixture of single-walled nanotubes and multi-walled nanotubes are disposed in solution.

[0067] FIG. 6 A manufacturing process for a network film according to embodiments of the application is shown. When the primary network film 100 includes nanotubes and two-dimensional material platelets, a filtered deposition is repeated for the nanotubes and a filtered deposition is repeated for the platelets, as shown in FIG. 6 In some embodiments, a mixture of single-walled and / or multi-walled nanotubes and platelets are dispersed in a solvent and a filtered deposition is performed to form a mixed network layer of nanotubes and two-dimensional material platelets.

[0068] A two-dimensional material layer is formed over a substrate by a CVD method and then the deposited layer is exfoliated from the substrate. In some embodiments, after exfoliating the two-dimensional material layer, the layer is crushed into platelets.

[0069] FIG. 7A and FIG. 7B to FIG. 11A and FIG. 11B Cross-sectional (“A” figures) and planar (top view) (“B” figures) views of various stages of a process for manufacturing a thin film for an EUV photomask according to embodiments of the application are shown. It should be understood that additional operations can be provided before, during, and after the processes shown in FIG. 7A to FIG. 11B and some of the operations described below can be replaced or eliminated. The order of the operations / processes can be interchanged. Materials, configurations, methods, processes, and / or dimensions as explained with respect to the foregoing embodiments are applicable to the following embodiments and detailed descriptions thereof can be omitted.

[0070] A nanotube layer 90 is formed over the support film 80 by filtered deposition, as shown in FIG. 5A to FIG. 5D or FIG. 6 In some embodiments, the nanotube layer 90 includes only single-walled nanotubes. The nanotube layer 90 is then detached from the deposition apparatus, as shown in FIG. 7A and FIG. 7B

[0071] The support frame 15 is then attached to the nanotube layer 90, as shown in FIG. 8A and FIG. 8B In some embodiments, the support frame 15 is formed of one or more layers of crystalline silicon, polysilicon, silicon oxide, silicon nitride, ceramic, metal, or organic material. In some embodiments, the support frame 15 is formed of a material that is substantially transparent to EUV light, as shown in FIG. 8B ​As shown in FIG. 1, the support frame 15 has a rectangular (including square) frame shape, which is larger than the black border area of the EUV mask and smaller than the substrate of the EUV mask.

[0072] Next, as shown in FIG. 2, the nanotube layer 90 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. FIG. 9A and FIG. 9B As shown in FIG. 3, in some embodiments, the nanotube layer 90 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.

[0073] Then, one or more outer tubes are formed around each of the nanotubes (e.g., individual nanotubes) of the nanotube layer forming the nanotube network film 100. In some embodiments, a CVD process is performed using the nanotube layer 90 as a seed layer, similar to FIG. 5C or FIG. 5D The CVD process is repeated a desired number of times to form three or more outer tubes.

[0074] Further, as shown in FIG. 4, a first cover layer 20 and a second cover layer 30 are formed to seal the nanotube network layer 100. One or both of the first cover layer 20 and the second cover layer include a two-dimensional material. The two-dimensional material is formed on a substrate by, for example, a CVD method, and then the deposited two-dimensional layer is peeled off from the substrate. The peeled two-dimensional layer is subsequently transferred over the nanotube network layer 100. FIG. 11A and FIG. 11B

[0075] ​In some embodiments, the first and / or second capping layer comprises a two-dimensional TMD layer, where the TMD layer represented by MX2 is formed by CVD. In some embodiments, a MoS2 layer is formed by CVD using source gases 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 a S source. In other embodiments, a MoO3 gas is sublimated from a solid MoO3 or MoCl5 source and / or a S gas is sublimated from a solid S source. The solid sources of Mo and S are placed in a reaction chamber and a carrier gas containing an inert gas such as Ar, N2, and / or He is flowed in the reaction chamber. The solid sources are heated by sublimation to generate the gas sources, which react to form MoS2 molecules. The MoS2 molecules are then deposited on the substrate. In some embodiments, the substrate is heated appropriately. In other embodiments, the entire reaction chamber is heated by induction heating. Other TMD layers can also be formed by CVD using appropriate source gases. 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 comprises one of Si (101), γ-Al2O3 (101), Ga2O3 (010), or MgO (101). In other embodiments, a layer of hexagonal boron nitride (h-BN) or graphene is formed by CVD over the substrate as the first capping layer 20. In some embodiments, the substrate comprises one of SiC (0001), Si (111), or Ge (111).

[0076] In some embodiments, as shown in FIG. 1 1, a capping layer 40 is further formed over the first and second capping layers and the support frame 15 by using CVD, ALD, or any other suitable film formation method. FIG. 11C

[0077] In some embodiments, the second capping layer 30 is attached to the sides of the first capping layer 20 and the support frame 15, as shown in FIG. 1 1. FIG. 11D

[0078] FIG. 12A and FIG. 12B to FIG. 14A and FIG. 14B Cross-sectional ("A" figures) and planar (top view) ("B" figures) diagrams showing various stages of the fabrication of a thin film for an EUV photomask according to embodiments of the present application are shown in FIGS. 1 1- 1 1 1. It should be understood that for additional embodiments of the method, the stages can be performed in FIG. 12A to FIG. 14B ​​The illustrated process provides additional operations before, during, and after, and some of the operations described below can be replaced or eliminated. The order of the operations / processes can be interchanged. The materials, configurations, methods, processes, and / or dimensions as explained with respect to the foregoing embodiments apply to the following embodiments and detailed descriptions thereof can be omitted.

[0079] After forming the nanotube layer 90 over the support substrate 80, as FIG. 7A and FIG. 7B illustrated, a first cover layer 20 is formed over the nanotube layer 90, as FIG. 12A and FIG. 12B illustrated. Then, as FIG. 12A and FIG. 12B illustrated, the support frame 15 is attached to the first cover layer 20.

[0080] Next, as FIG. 13A and FIG. 13B illustrated, the first cover layer 20, nanotube layer 90, and support film 80 are cut into a rectangular shape having the same size as or slightly larger than the support frame 15, and then, in some embodiments, the support substrate 80 is separated or removed.

[0081] Then, similar to the operations explained with respect to FIG. 10A and FIG. 10B one or more outer tubes are formed over the nanotubes of the nanotube layer 90, as FIG. 14A and FIG. 14B illustrated.

[0082] Further, similar to FIG. 11A and FIG. 11B a second cover layer 30 is formed over the nanotube layer 90, as FIG. 15A illustrated. The operations for forming the second cover layer 30, which is a two-dimensional material, are the same as or similar to those for the first cover layer 20 as described above. In some embodiments, the first cover layer 20 and the second cover layer 30 are sealed at their peripheries to completely enclose the nanotube layer 90.

[0083] In some embodiments, the second cover layer 30 is attached to the sides of the first cover layer 20 and the support frame 15, as FIG. 15B illustrated. In some embodiments, the second cover layer 30 has a flange portion at which the second cover layer 30 is fixed or joined to the first cover layer 20, as FIG. 15C illustrated.

[0084] Further, similar to FIG. 11C 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).

[0085] In some embodiments, when the multi-walled nanotubes are dispersed in solution in the filter deposition operation shown in FIG. 5A or FIG. 6 In some embodiments, when the multi-walled nanotubes are dispersed in solution in the filter deposition operation shown in FIG. 16A In some embodiments, as shown in FIG. 16B In some embodiments, as shown in FIG. 7A In some embodiments, as shown in FIG. 8A , FIG. 8B , FIG. 9A , FIG. 9B , FIG. 11A and FIG. 11B (And FIG. 11C ) or FIG. 12A , FIG. 12B , FIG. 13A , FIG. 13B and FIG. 15A are explained with respect to

[0086] FIG. 17A , FIG. 17B , FIG. 17C and FIG. 17D show various views of a thin film for an EUV photomask according to embodiments of the present application. In some embodiments, no first cover layer is used and only a second cover layer 30 is disposed over the main network film 100, as shown in FIG. 17A In some embodiments, no second cover layer is used and only a first cover layer 20 is disposed over the main network film 100, as shown in FIG. 17B In some embodiments, no first cover layer is used and only a second cover layer 30 is disposed over the main network film 100, and a protective layer 40 is formed over the second cover layer and network film 100, forming a covered network layer 119, as shown in FIG. 17C In some embodiments, the protective layer is formed around each of the multi-walled nanotubes, and in other embodiments, the protective layer covers the periphery of the main network film 100. In some embodiments, no second cover layer is used and only a first cover layer 20 is disposed over the main network film 100, and a protective layer 40 is formed over the second cover layer and network film 100, forming a covered network layer 119, as shown in FIG. 17D In some embodiments, the protective layer is formed around each of the multi-walled nanotubes, and in other embodiments, the protective layer covers the periphery of the main network film 100.

[0087] FIG. 18A , FIG. 18B ,FIG. 18C , FIG. 18D , FIG. 18E and FIG. 18F A flowchart illustrating the fabrication of a thin film for an EUV photomask according to an embodiment of the present invention is shown. It should be understood that for additional embodiments of the method, [further details may be needed]. FIG. 18A to FIG. 18F Additional operations are provided before, during, and after the process frame shown, and some of the operations described below can be replaced or eliminated. The order of operations / processes can be interchanged. The materials, configurations, methods, processes, and / or dimensions explained with respect to the foregoing embodiments are applicable to the following embodiments, and their detailed descriptions may be omitted.

[0088] In some embodiments, such as FIG. 18A As shown, in box S101, a nanotube layer comprising single-walled nanotubes is formed over a supporting substrate using a filter deposition method. Then, in box S102, a thin film framework is formed over the nanotube layer. In box S103, the nanotube layer and the supporting substrate are cut into desired shapes, and in box S104, the supporting substrate is removed. In box S105, one or more outer tubes are formed around each single-walled nanotube. In box S106, one or more capping layers made of a two-dimensional material are formed to seal the multi-walled nanotube layer. In box S107, a protective layer may optionally be formed over the capping layers.

[0089] In some embodiments, such as FIG. 18B As shown, in box S201, a nanotube layer comprising single-walled nanotubes is formed over a supporting substrate using a filter deposition method. Then, in box S202, one or more outer tubes are formed around each of the single-walled nanotubes. In box S203, a thin film framework is formed over the multi-walled nanotube layer. In box S204, the multi-walled nanotube layer and the supporting substrate are cut into desired shapes, and in box S205, the supporting substrate is removed. In box S206, one or more capping layers made of a two-dimensional material are formed to seal the multi-walled nanotube layer. In box S207, a protective layer may optionally be formed over the capping layers.

[0090] In some embodiments, such as FIG. 18C As shown, in box S301, a nanotube layer comprising single-walled nanotubes is formed over a supporting substrate using a filter deposition method. Then, in box S302, a first capping layer made of a two-dimensional material is formed over the nanotube layer on the supporting substrate. In box S303, a thin film framework is formed over the first capping layer. In box S304, the nanotube layer and the supporting substrate are cut into desired shapes, and the supporting substrate is removed. In box S305, one or more outer tubes are formed around each of the single-walled nanotubes. In box S306, a second capping layer made of a two-dimensional material is formed to seal the multi-walled nanotube layer. In box S307, a protective layer may optionally be formed over the capping layer.

[0091] In some embodiments, as shown in FIG. 18D In block S401, a nanotube layer comprising single-walled nanotubes is formed over a support substrate by a filter deposition method. Then, in block S402, one or more outer tubes are formed around the single-walled nanotubes, respectively. In block S403, a first capping layer made of a two-dimensional material is formed over the nanotube layer on the support substrate. In block S404, a thin film frame is formed over the first capping layer. In block S405, the multi-walled nanotube layer and the support substrate are cut into a desired shape, and the support substrate is removed. In block S406, a second capping layer made of a two-dimensional material is formed to seal the multi-walled nanotube layer. In block S407, a protective layer is optionally formed over the capping layer.

[0092] In some embodiments, as shown in FIG. 18E In block S501, a nanotube layer comprising multi-walled nanotubes is formed over a support substrate by a filter deposition method. Then, in block S502, a thin film frame is formed over the multi-walled nanotube layer. In block S503, the multi-walled nanotube layer and the support substrate are cut into a desired shape, and in block S504, the support substrate is removed. In block S505, one or more capping layers made of a two-dimensional material are formed to seal the multi-walled nanotube layer. In block S506, a protective layer is optionally formed over the capping layer. In some embodiments, between blocks S501 and S502 and / or between blocks S504 and S505, one or more additional outer tubes are formed around the multi-walled nanotubes, respectively.

[0093] In some embodiments, as shown in FIG. 18F In block S601, a nanotube layer comprising multi-walled nanotubes is formed over a support substrate by a filter deposition method. Then, in block S602, a first capping layer is formed over the multi-walled nanotube layer on the support substrate. In block S603, a thin film frame is formed over the first capping layer. In block S604, the multi-walled nanotube layer and the support substrate are cut into a desired shape, and the support substrate is removed. In block S605, a second capping layer made of a two-dimensional material is formed to seal the multi-walled nanotube layer. In block S606, a protective layer is optionally formed over the capping layer. In some embodiments, between blocks S601 and S602 and / or between blocks S604 and S605, one or more additional outer tubes are formed around the multi-walled nanotubes, respectively.

[0094] FIG. 19A A flowchart of a method of fabricating a semiconductor device is shown, and FIG. 19B , FIG. 19C , FIG. 19D and FIG. 19EA sequential manufacturing method for fabricating a semiconductor device according to an embodiment of the present invention is illustrated. A semiconductor substrate or other suitable substrate is provided to be patterned for forming an integrated circuit thereon. In some embodiments, the semiconductor substrate comprises silicon. Optionally or additionally, the semiconductor substrate comprises germanium, silicon-germanium, or other suitable semiconductor materials, such as group III-V semiconductor materials. FIG. 19A In step S801, a target layer to be patterned is formed over a semiconductor substrate. In some embodiments, the target layer is the 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 a structure such as an isolation structure, a transistor, or wiring. FIG. 19A In S802, a photoresist layer is formed above the target layer, such as... FIG. 19B As shown in the diagram. During subsequent photolithography processes, 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 process. The photoresist layer can be formed over the target layer by spin coating or other suitable techniques. The coated photoresist layer can be further baked to remove solvent from the photoresist layer. FIG. 19A In S803, an EUV reflective mask with a thin film as described above is used to pattern a photoresist layer, such as... FIG. 19C As shown in the diagram, patterning of the photoresist layer includes performing a photolithography exposure process using an EUV exposure system with an EUV mask. During the exposure process, an integrated circuit (IC) design pattern defined on the EUV mask is imaged onto the photoresist layer to form a potential pattern thereon. Patterning of the photoresist layer also includes developing the exposed photoresist layer to form a patterned photoresist layer with one or more openings. In one embodiment where the photoresist layer is a positive photoresist layer, the exposed portions of the photoresist layer are removed during the development process. 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 performed after the photolithography exposure process and before the development process.

[0095] exist FIG. 19A In S804, a patterned photoresist layer is used as an etching mask to pattern the target layer, such as... FIG. 19D As shown in the figure. In some embodiments, patterning the target layer includes applying an etching process to the target layer using a patterned photoresist layer as an etching mask. The portion of the target layer exposed within the openings of the patterned photoresist layer is etched, while the remaining portion is protected from etching. Furthermore, the patterned photoresist layer can be removed by wet stripping or plasma ashing, as shown in the figure. FIG. 19E As shown in the image.

[0096] The thin film according to embodiments of the present application provides higher strength and thermal conductivity (dissipation) and higher EUV transmittance than conventional thin films. In the foregoing embodiments, multi-walled nanotubes are used as the main network film to increase the mechanical strength of the thin film and to obtain high EUV transmittance. Further, a two-dimensional material layer is used as a cover layer (first and / or second cover layer) and / or with the nanotubes to increase the mechanical strength of the thin film. Further, by using a two-dimensional material layer and / or a protective layer to surround the main network film, the mechanical strength of the thin film can be increased and high or perfect barrier properties against killer particles can be provided. Further, in some embodiments, the use of two-dimensional material flakes improves heat dissipation to prevent the thin film from being burned out by EUV radiation.

[0097] It should be understood that all the advantages can not be discussed here, no particular advantage is required for all embodiments or examples, and other embodiments or examples can provide different advantages.

[0098] According to one aspect of the present application, a thin film for an EUV photomask includes a first layer, a second layer, and a main film disposed between the first layer and the second layer. The main film includes a plurality of coaxial nanotubes, each of the plurality of coaxial nanotubes including an inner tube and one or more outer tubes surrounding the inner tube, and two of the inner tube and the one or more outer tubes are made of different materials from each other. In one or more embodiments above and below, each of the inner tube and the one or more outer tubes is one selected from the group consisting of a carbon nanotube, a boron nitride nanotube, a transition metal dichalcogenide (TMD) nanotube, wherein the TMD is represented by MX2, wherein M is one or more of Mo, W, Pd, Pt, or Hf, and X is one or more of S, Se, or Te. In one or more embodiments above and below, the inner tube is a carbon nanotube. In one or more embodiments above and below, each of the plurality of coaxial nanotubes includes an inner tube and one outer tube made of a different material from the inner tube. In one or more embodiments above and below, each of the plurality of coaxial nanotubes includes an inner tube and two outer tubes, all of the inner tube and the outer tubes being made of different materials from each other. In one or more embodiments above and below, each of the plurality of coaxial nanotubes includes two outer tubes made of the same material and an inner tube. In one or more embodiments above and below, the main film further includes a plurality of single-walled nanotubes.

[0099] According to another aspect of the present application, a thin film for an extreme ultraviolet (EUV) reflective mask includes a first layer, a support frame attached to the first layer, and a main film disposed above the first layer. The main film includes a plurality of nanotubes, each of the plurality of nanotubes including an inner nanotube and a first through Nth outer layer each coaxially surrounding the inner nanotube, where N is a natural number from 1 to 10. In one or more embodiments above and below, at least one of the first through Nth outer layers is a nanotube coaxially surrounding the inner nanotube. In one or more embodiments above and below, two of the inner nanotube and the first through Nth outer layers are made of different materials from each other. In one or more embodiments above and below, N is at least two, and two of the inner nanotube and the first through Nth outer layers are made of the same material. In one or more embodiments above and below, N is at least two, and three of the inner nanotube and the first through Nth outer layers are made of different materials from each other. In one or more embodiments above and below, the inner nanotube is one selected from the group consisting of a carbon nanotube, a boron nitride nanotube, a transition metal dichalcogenide (TMD) nanotube, where TMD is represented by MX2, where M is one or more of Mo, W, Pd, Pt, or Hf, and X is one or more of S, Se, or Te. In one or more embodiments above and below, each of the first through Nth outer layers is made of carbon, boron nitride, a transition metal dichalcogenide (TMD), where TMD is represented by MX2, where M is one or more of Mo, W, Pd, Pt, or Hf, and X is one or more of S, Se, or Te. In one or more embodiments above and below, the thin film further includes a protective layer. In one or more embodiments above and below, a material of the protective layer is the same as the Nth outer layer.

[0100] According to another aspect of the present application, a thin film for an extreme ultraviolet (EUV) reflective mask includes a first layer, a second layer, and a main film disposed between the first layer and the second layer. The main film includes a plurality of nanotubes, each of the nanotubes including an inner nanotube and first through Nth outer tubes each coaxially surrounding the inner nanotube, where N is a natural number from 1 to 10, and 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 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 main film further includes a plurality of nanosheets of the two-dimensional material including 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 thin 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, La2O3, B4C, YN, Si3N4, BN, NbN, RuNb, YF3, TiN, ZrN, Ru, Nb, Y, Sc, Ni, Mo, W, Pt, and Bi.

[0101] According to another aspect of the present disclosure, a thin film for an extreme ultraviolet (EUV) reflective mask includes a first layer, a support frame attached to the first layer, and a main film disposed above the first layer. The main film includes a network of a plurality of multi-walled nanotubes each having a plurality of coaxial tubes, and at least two of the plurality of coaxial tubes are made of different materials from each other. In one or more embodiments above and below, each of the plurality of coaxial tubes is one selected from the group consisting of carbon nanotubes, boron nitride nanotubes, transition metal dichalcogenide (TMD) nanotubes, wherein TMD is represented by MX2, wherein M is one or more of Mo, W, Pd, Pt, or Hf, and X is one or more of S, Se, or Te. In one or more embodiments above and below, an innermost tube of the plurality of coaxial tubes is one selected from the group consisting of carbon nanotubes, boron nitride nanotubes, transition metal dichalcogenide (TMD) nanotubes, wherein TMD is represented by MX2, wherein M is one or more of Mo, W, Pd, Pt, or Hf, and X is one or more of S, Se, or Te. In one or more embodiments above and below, each of the plurality of coaxial tubes except the innermost tube is made of carbon, boron nitride nanotubes, transition metal dichalcogenide (TMD), wherein TMD is represented by MX2, wherein M is one or more of Mo, W, Pd, Pt, or Hf, and X is one or more of S, Se, or Te. In one or more embodiments above and below, an outermost tube of the plurality of coaxial tubes is made of at least one selected from the group consisting of HfO2, Al2O3, ZrO2, Y2O3, La2O3, B4C, YN, Si3N4, BN, NbN, RuNb, YF3, TiN, ZrN, Ru, Nb, Y, Sc, Ni, Mo, W, Pt, and Bi. In one or more embodiments above and below, each of the plurality of multi-walled nanotubes has three or four coaxial tubes, and at least three of the three or four coaxial tubes are made of different materials from each other. In one or more embodiments above and below, the main film further includes a plurality of single-walled nanotubes. In one or more embodiments above and below, the first 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 two-dimensional material includes at least one selected from the group consisting of boron nitride (BN), graphene, and transition metal dichalcogenide (TMD), wherein TMD is represented by MX2, wherein M is one or more of Mo, W, Pd, Pt, or Hf, and X is one or more of S, Se, or Te. In one or more embodiments above and below, a thickness of the first layer is in a range from 0.3 nm to 3 nm. In one or more embodiments above and below, a number of the one or more two-dimensional layers of the first layer is 1 to 20. In one or more embodiments above and below, the first layer is disposed between the support frame and the main film.In one or more embodiments above and below, a portion of the main film is disposed between the first layer and the support frame. In one or more embodiments above and below, the thin film further comprises a second layer. In one or more embodiments above and below, the main film is disposed between the first layer and the second layer. In one or more embodiments above and below, the second layer comprises a two-dimensional material having one or more two-dimensional layers stacked therein. 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, and a transition metal dichalcogenide (TMD), wherein the TMD is represented by MX2, wherein M is one or more of Mo, W, Pd, Pt, or Hf, and X is one or more of S, Se, or Te. In one or more embodiments above and below, the first layer has a thickness in a range 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 the first layer is 1 to 20. In one or more embodiments above and below, the thin film further comprises a protective layer disposed over both sides of the first layer. In one or more embodiments above and below, the protective layer comprises 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 comprises 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 comprises 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 protective layer has a thickness in a range from 0.1 nm to 5 nm. In one or more embodiments above and below, the protective layer is also formed to cover the plurality of nanotubes of the main film. In one or more embodiments above and below, the material of the protective layer is the same as the material of the outermost one of the plurality of coaxial tubes. In one or more embodiments above and below, the plurality of multi-walled nanotubes comprises a plurality of first multi-walled nanotubes and a plurality of second multi-walled nanotubes different from the plurality of first multi-walled nanotubes. In one or more embodiments above and below, the number of wall layers of each of the plurality of first multi-walled nanotubes is different from the number of wall layers of each of the plurality of second multi-walled nanotubes. In one or more embodiments above and below, the number of wall layers of each of the plurality of first multi-walled nanotubes is the same as the number of wall layers of each of the plurality of second multi-walled nanotubes. In one or more embodiments above and below, a layer structure in terms of the material of each of the plurality of first multi-walled nanotubes is different from a layer structure in terms of the material of each of the plurality of second multi-walled nanotubes. In one or more embodiments above and below, the main film further comprises a plurality of flakes comprising a two-dimensional material having one or more two-dimensional layers stacked therein.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, each of the plurality of platelets has a size in a range from 10 nm. 2 to 10 pm 2 In one or more embodiments above and below, each of the plurality of platelets has a thickness in a range 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 plurality of platelets is 1 to 20.

[0102] According to another aspect of the present application, in a method of manufacturing a thin film for an extreme ultraviolet (EUV) reflective mask, a nanotube layer comprising a plurality of nanotubes is formed over a support substrate. A thin film frame is formed over the nanotube layer. The nanotube layer is separated from the support substrate. One or more outer tubes are formed around each of the plurality of nanotubes as inner nanotubes, thereby forming a network film comprising a plurality of coaxial tubes, each coaxial tube comprising an inner nanotube and one or more outer tubes each coaxially surrounding the inner nanotube. At least two of the inner nanotube and the one or more outer tubes are made of different materials from each other. In one or more embodiments above and below, at least the nanotube layer is cut into a polygonal shape after the thin film frame is formed and before the one or more outer tubes are formed. In one or more embodiments above and below, each of the plurality of coaxial tubes is one selected from the group consisting of a carbon nanotube, a boron nitride nanotube, a transition metal dichalcogenide (TMD) nanotube, wherein the TMD is represented by MX2, wherein M is one or more of Mo, W, Pd, Pt, or Hf, and X is one or more of S, Se, or Te. In one or more embodiments above and below, the inner nanotube is one selected from the group consisting of a carbon nanotube, a boron nitride nanotube, a transition metal dichalcogenide (TMD) nanotube, wherein the TMD is represented by MX2, wherein M is one or more of Mo, W, Pd, Pt, or Hf, and X is one or more of S, Se, or Te. In one or more embodiments above and below, each of the one or more outer tubes is made of carbon, boron nitride, a transition metal dichalcogenide (TMD), wherein the TMD is represented by MX2, wherein M is one or more of Mo, W, Pd, Pt, or Hf, and X is one or more of S, Se, or Te. In one or more embodiments above and below, each of the plurality of coaxial tubes has a total of three or four coaxial tubes, and at least three of the total of three or four coaxial tubes are made of different materials from each other. In one or more embodiments above and below, the network film further comprises a plurality of single-walled nanotubes.

[0103] According to another aspect of the invention, in a method of manufacturing a thin film for an extreme ultraviolet (EUV) reflective mask, a nanotube layer comprising a plurality of multi-walled nanotubes is formed, a thin film framework is formed over the nanotube layer, and a first capping layer and a second capping layer are formed such that the nanotube layer is disposed between the first capping layer and the second capping layer. The multi-walled nanotubes include inner nanotubes and one or more outer nanotubes, and at least one of the first capping layer and the second capping 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 capping layer includes a first two-dimensional material and the second capping 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 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, a protective layer is formed over the first capping layer, the second capping layer, and the thin film framework. In one or more embodiments above and below, the protective layer comprises at least one selected from the group consisting of HfO2, Al2O3, ZrO2, Y2O3, La2O3, B4C, YN, Si3N4, BN, NbN, RuNb, YF3, TiN, ZrN, Ru, Nb, Y, Sc, Ni, Mo, W, Pt, and Bi.

[0104] According to another aspect of the invention, in a method for manufacturing a thin film for an extreme ultraviolet (EUV) reflective mask, a nanotube layer comprising a plurality of nanotubes and one or more two-dimensional materials is formed over a supporting substrate; a thin film framework is formed over a first capping layer; the nanotube layer is diced to form a diced thin film; and a first capping layer and a second capping layer are formed to encapsulate the diced thin film. In one or more embodiments above and below, the nanotube layer comprises a network structure of a plurality of multi-walled coaxial nanotubes, and at least two of the plurality of multi-walled coaxial nanotubes are made of different materials from each other. In one or more embodiments above and below, each of the one or more two-dimensional materials 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 sheet is from 10 nm. 2 Up to 10μm 2In one or more embodiments above and below, the thickness of each of the plurality of sheets is in a range from 0.3 nm to 3 nm. In one or more embodiments above and below, the number of two-dimensional layers of each of the plurality of sheets is 1 to 20. In one or more embodiments above and below, each of the plurality of multi-walled coaxial nanotubes is one selected from the group consisting of carbon nanotubes, boron nitride nanotubes, transition metal dichalcogenide (TMD) nanotubes, wherein TMD is represented by MX2, wherein M is one or more of Mo, W, Pd, Pt, or Hf, and X is one or more of S, Se, or Te.

[0105] The features outlined herein are of a number of embodiments or examples, so that those skilled in the art can better understand the aspects of the present application. Those skilled in the art should appreciate that they can readily use the present application as a basis for designing or modifying other processes and structures for carrying out the same purpose and / or achieving the same advantages of the embodiments or examples introduced herein. Those skilled in the art should also realize that such equivalent constructions do not depart from the spirit and scope of the present application, and that they can make various changes, substitutions and alterations thereto without departing from the spirit and scope of the present application.

Claims

1. A thin film for use as an extreme ultraviolet reflective mask, comprising: First layer; Second layer; as well as The main membrane is disposed between the first layer and the second layer, wherein: The main membrane comprises a plurality of coaxial nanotubes, each of the plurality of coaxial nanotubes comprising an inner tube and one or more outer tubes surrounding the inner tube, and Two of the inner tube and the one or more outer tubes are made of different materials. The main film comprises multiple multi-walled nanotubes and multiple two-dimensional material sheets made of two-dimensional material stacked with one or more two-dimensional layers. The two-dimensional material sheets comprise boron nitride and / or transition metal dichalcogenides, wherein the transition metal dichalcogenides are represented by MX2, where M is Pd and / or Pt, and X is one or more of S, Se, or Te.

2. The thin film according to claim 1, wherein, Each of the inner tube and the one or more outer tubes is selected from the group consisting of carbon nanotubes, boron nitride nanotubes, and transition metal dichalcogenide nanotubes, wherein the transition metal dichalcogenide is represented by MX2, where M is one or more of Mo, W, Pd, Pt, or Hf, and X is one or more of S, Se, or Te.

3. The thin film according to claim 2, wherein, The inner tube is a carbon nanotube.

4. The film according to claim 2, wherein, Each of the plurality of coaxial nanotubes includes an inner tube and an outer tube made of a different material from the inner tube.

5. The film according to claim 2, wherein, Each of the plurality of coaxial nanotubes includes the inner tube and two outer tubes, all of which are made of different materials.

6. The thin film according to claim 2, wherein, Each of the plurality of coaxial nanotubes includes the inner tube and two outer tubes made of the same material.

7. The thin film according to claim 1, further comprising: A protective layer is disposed above the first layer and the second layer.

8. A thin film for use as an extreme ultraviolet reflective mask, comprising: First layer; Support frame, attached to the first layer; as well as The main membrane is disposed above the first layer. The main membrane comprises multiple multi-walled nanotubes, each of which includes an inner nanotube and a first to Nth outer layer coaxially surrounding the inner nanotube, where N is a natural number from 1 to 10. The main film further includes a plurality of two-dimensional material sheets made of two-dimensional material stacked with one or more two-dimensional layers, the two-dimensional material sheets including boron nitride and / or transition metal dichalcogenides, wherein the transition metal dichalcogenides are represented by MX2, where M is Pd and / or Pt, and X is one or more of S, Se or Te.

9. The thin film according to claim 8, wherein, At least one of the first to the Nth outer layers is a nanotube coaxially surrounding the inner nanotube.

10. The thin film according to claim 8, wherein, The inner nanotube and two of the first to Nth outer layers are made of different materials.

11. The thin film according to claim 10, wherein: N is at least two, and The inner nanotube and two of the first to Nth outer layers are made of the same material.

12. The thin film according to claim 8, wherein: N is at least two, and The inner nanotube and three of the first to Nth outer layers are made of different materials.

13. The thin film according to claim 8, wherein, The inner nanotube is selected from the group consisting of carbon nanotubes, boron nitride nanotubes, and transition metal dichalcogenide nanotubes, wherein the transition metal dichalcogenide is represented by MX2, where M is one or more of Mo, W, Pd, Pt, or Hf, and X is one or more of S, Se, or Te.

14. The thin film according to claim 13, wherein, Each of the first to the Nth outer layers is made of carbon, boron nitride, or a transition metal dichalcogenide, wherein the transition metal dichalcogenide is represented by MX2, where M is one or more of Mo, W, Pd, Pt, or Hf, and X is one or more of S, Se, or Te.

15. The thin film according to claim 8, further comprising: Protective layer The material of the protective layer is the same as that of the Nth outer layer.

16. A method for manufacturing a thin film for an extreme ultraviolet reflective mask, comprising: A nanotube layer comprising multiple nanotubes is formed above a supporting substrate; A thin film framework is formed above the nanotube layer; Separate the nanotube layer from the supporting substrate; as well as One or more outer tubes are formed around each of the plurality of nanotubes as inner nanotubes, thereby forming a network film comprising a plurality of coaxial tubes, each coaxial tube comprising the inner nanotube and each coaxially surrounding the inner nanotube by the one or more outer tubes. In this embodiment, at least two of the inner nanotubes and the one or more outer nanotubes are made of different materials. The network film includes multiple multi-walled nanotubes and multiple two-dimensional material sheets made of two-dimensional material stacked with one or more two-dimensional layers. The two-dimensional material sheets include boron nitride and / or transition metal dichalcogenides, wherein the transition metal dichalcogenides are represented by MX2, where M is Pd and / or Pt, and X is one or more of S, Se, or Te.

17. The method of claim 16, further comprising: After the formation of the thin film framework and before the formation of the one or more outer tubes, at least the nanotube layer is cut into a polygonal shape.

18. The method according to claim 16, wherein, Each of the plurality of coaxial tubes is selected from the group consisting of carbon nanotubes, boron nitride nanotubes, and transition metal dichalcogenide nanotubes, wherein the transition metal dichalcogenide is represented by MX2, wherein M is one or more of Mo, W, Pd, Pt, or Hf, and X is one or more of S, Se, or Te.

19. The method of claim 16, wherein, The inner nanotube is selected from the group consisting of carbon nanotubes, boron nitride nanotubes, and transition metal dichalcogenide nanotubes, wherein the transition metal dichalcogenide is represented by MX2, where M is one or more of Mo, W, Pd, Pt, or Hf, and X is one or more of S, Se, or Te.

20. The method according to claim 19, wherein, Each of the one or more outer tubes is made of carbon, boron nitride, or a transition metal disulfide, wherein the transition metal disulfide is represented by MX2, where M is one or more of Mo, W, Pd, Pt, or Hf, and X is one or more of S, Se, or Te.

Images