Pellicle for EUV lithography masks and methods of manufacturing thereof

Abstract

In a method for manufacturing a pellicle for an extreme ultraviolet (EUV) photomask, a membrane of SP2 carbon is formed, a treatment is performed on the membrane to change the surface properties of the membrane, and after the treatment, a cover layer is formed on the membrane.

Description

Technology Field

[0001] Related applications

[0002] This application claims priority to U.S. Provisional Application No. 63 / 414,256 filed October 7, 2022 and U.S. Provisional Application No. 63 / 392,777 filed July 27, 2022, the entire contents of each of which are incorporated herein by reference. Background Technology

[0003] A pellicle is a thin, transparent film extending over a frame that is adhered to one side of a photomask to protect it from damage, dust, and / or moisture. In extreme ultraviolet (EUV) lithography, pellicles with high transparency, high mechanical strength, and low or no contamination are generally required in the EUV wavelength range. EUV transmissive membranes are also used in EUV lithography devices instead of pellicles. Brief explanation of the drawing

[0004] The embodiments of the present disclosure are best understood from the following detailed description when read together with the accompanying drawings. Note that, in accordance with standard industry practice, various features are not drawn at the same scale. In practice, the dimensions of various features may be increased or decreased at will for the sake of clarity of discussion. FIGS. 1a and 1b illustrate a pellicle for an EUV photomask according to embodiments of the present disclosure. FIGS. 2a, 2b, 2c, and 2d illustrate various drawings of multi-walled nanotubes according to embodiments of the present disclosure. FIGS. 3a, 3b, 3c, 3d, and 3e illustrate diagrams of a pellicle according to some embodiments of the present disclosure. FIGS. 4a, 4b, and 4c illustrate a manufacturing process of a network membrane according to an embodiment of the present disclosure. FIG. 5a illustrates the manufacturing process of a network membrane, and FIG. 5b illustrates the flowchart according to an embodiment of the present disclosure. FIGS. 6a and 6b illustrate a cross-sectional view and a top view of one of the various stages for manufacturing a pellicle for an EUV photomask according to an embodiment of the present disclosure. FIGS. 7a and 7b illustrate a cross-sectional view and a top view of one of the various stages for manufacturing a pellicle for an EUV photomask according to an embodiment of the present disclosure. FIGS. 8a and 8b illustrate a cross-sectional view and a top view of one of the various stages for manufacturing a pellicle for an EUV photomask according to an embodiment of the present disclosure. FIGS. 9a and 9b illustrate a cross-sectional view and a top view of one of the various stages for manufacturing a pellicle for an EUV photomask according to an embodiment of the present disclosure. FIG. 10a illustrates a flowchart, and FIG. 10b and 10c illustrate operations for manufacturing a pellicle for an EUV photomask according to embodiments of the present disclosure. FIG. 11 illustrates a flowchart for manufacturing a pellicle for an EUV photomask according to embodiments of the present disclosure. FIGS. 12a and 12b illustrate cross-sectional views of various stages for manufacturing a pellicle for an EUV photomask according to an embodiment of the present disclosure. FIGS. 13a and 13b illustrate cross-sectional views of various stages for manufacturing a pellicle for an EUV photomask according to an embodiment of the present disclosure. FIGS. 14a and 14b illustrate cross-sectional views of various stages for manufacturing a pellicle for an EUV photomask according to an embodiment of the present disclosure. FIGS. 15a and 15b illustrate cross-sectional views of various stages for manufacturing a pellicle for an EUV photomask according to an embodiment of the present disclosure. FIG. 16 illustrates a cross-sectional view of one of the various stages for manufacturing a pellicle for an EUV photomask according to an embodiment of the present disclosure. FIG. 17a illustrates a flowchart of a method for manufacturing a semiconductor device, and FIG. 17b, 17c, 17d, and 17e illustrate sequential manufacturing operations of a method for manufacturing a semiconductor device according to embodiments of the present disclosure. Specific details for implementing the invention

[0005] The following disclosure provides many different embodiments or examples for implementing different features of the present invention. For the sake of simplicity of the disclosure, specific embodiments or examples of components and arrangements are described below. Of course, these are merely examples and are not intended to be limiting. For example, the dimensions of the elements are not limited to the disclosed ranges or values, but may depend on process conditions and / or desired characteristics of the device. Additionally, forming a first feature over or on a second feature in the following description may include embodiments in which the first and second features are formed in direct contact, and may also include embodiments in which an additional feature may be formed between the first and second features so that the first and second features are not in direct contact. Various features may be drawn at different scales for simplicity and clarity. In the accompanying drawings, some layers / features may be omitted for simplification.

[0006] Additionally, spatially relative terms such as "beneath," "below," "lower," "above," and "upper" may be used herein for convenience of description to describe the relationship between one element or feature and another element(s) or feature(s) as illustrated in the drawings. Spatially relative terms are intended to include other orientations of the device in use or operation in addition to the orientation illustrated in the drawings. The device may be otherwise oriented (rotated 90 degrees or in a different direction), and the spatially relative terms used herein may be interpreted similarly accordingly. Also, the term "made of" may mean either "comprising" or "consisting of." Additionally, in the following manufacturing process, there may be one or more additional operations between the described operations, and the order of the operations may be changed. In the present disclosure, the phrase “at least one of A, B, and C” means one of A, B, C, A+B, A+C, B+C, and A+B+C, and does not mean one from A, one from B, and one from C unless otherwise stated. The materials, configurations, structures, operations, and / or dimensions described in one embodiment may be applied to other embodiments, and their constrained description may be omitted.

[0007] EUV lithography is one of the key technologies for extending Moore's Law. However, due to wavelength scaling from 193 nm (ARF) to 13.5 nm, EUV light sources suffer from severe power loss due to environmental adsorption. Although stepper / scanner chambers operate under vacuum to prevent strong EUV adsorption by gases, maintaining high EUV transmittance from the EUV light source to the wafer remains a critical factor in EUV lithography.

[0008] Pellicles generally require high transparency and low reflectivity. In UV or DUV lithography, pellicle films are fabricated from transparent resin films. However, in EUV lithography, resin-based films are not permitted, and inorganic materials such as polysilicon, silicides, or metal films are used.

[0009] Carbon nanotubes (CNTs) are one of the materials suitable for pellicles for EUV reflective photomasks, because CNTs have a high EUV transmittance of over 96.5%. Generally, pellicles for EUV reflective masks require the following characteristics: (1) a long lifetime in hydrogen radical-rich operating environments in EUV steppers / scanners; (2) strong mechanical strength to minimize sagging effects during vacuum pumping and evacuation operations; (3) high or perfect blocking properties for particles larger than about 20 nm (killer particles); and (4) good heat dissipation to prevent the pellicle from burning out due to EUV radiation. Other nanotubes made of non-carbon-based materials may also be used for pellicles for EUV photomasks. In some embodiments of the present disclosure, the nanotubes are one-dimensional elongated tubes having a diameter in the range of about 0.5 nm to about 100 nm.

[0010] In the present disclosure, a pellicle for an EUV photomask comprises a network membrane having a plurality of nanotubes forming a mesh structure. Additionally, a method for treating the network membrane to remove contaminants and increase mechanical strength is also disclosed.

[0011] FIGS. 1a and 1b illustrate an EUV pellicle (10) according to an embodiment of the present disclosure. In some embodiments, the pellicle (10) for an EUV reflective mask comprises a main network membrane (100) disposed over a pellicle frame (15) and attached to the pellicle frame (15). In some embodiments, as shown in FIG. 1a, the main network membrane (100) comprises a plurality of single-walled nanotubes (100S), and in other embodiments, as shown in FIG. 1b, the main network membrane (100) comprises a plurality of multi-walled nanotubes (100M). In some embodiments, the single-walled nanotubes are carbon nanotubes, and in other embodiments, the single-walled nanotubes are nanotubes made of a non-carbon-based material. In some embodiments, the non-carbon-based material comprises at least one of boron nitride (BN), SiC, and transition metal dichalcogenide (TMDS) 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.

[0012] In some embodiments, the multi-walled nanotube is a coaxial nanotube having two or more tubes coaxially surrounding an inner tube(s). In some embodiments, the main network membrane (100) comprises only one type of nanotube (single-walled / multi-walled, or material), and in other embodiments, different types of nanotubes form the main network membrane (100).

[0013] In some embodiments, a pellicle (support) frame (15) is attached to the main network membrane (100) to maintain a space between the main network membrane of the pellicle and the EUV mask (pattern area) when mounted on the EUV mask. The pellicle frame (15) of the pellicle is attached to the surface of the EUV photomask with 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-link type glue. The size of the frame structure is larger than the area of ​​the black boundaries of the EUV photomask so that the pellicle covers the black boundaries as well as the circuit pattern area of ​​the photomask.

[0014] In some embodiments, the thickness of the network membrane (100) is in the range of about 5 nm to about 100 nm, and in other embodiments, it is in the range of about 10 nm to about 50 nm. When the thickness of the network membrane (100) is greater than this range, the EUV transmittance may be reduced, and when the thickness of the network membrane (100) is less than this range, the mechanical strength may be insufficient.

[0015] FIGS. 2a, 2b, 2C and 2d illustrate various drawings of multi-walled nanotubes according to embodiments of the present disclosure.

[0016] In some embodiments, the nanotubes within the main network membrane (100) comprise multi-walled nanotubes, also referred to as co-axial nanotubes. FIG. 2a shows a perspective view of a multi-walled co-axial nanotube having three tubes (210, 220 and 230), and FIG. 2b shows a cross-sectional view thereof. In some embodiments, the inner tube (210) is a carbon nanotube, and the two outer tubes (220, 230) are non-carbon-based nanotubes, such as boron nitride nanotubes. In some embodiments, all tubes are non-carbon-based nanotubes.

[0017] The number of tubes in the multi-walled nanotube is not limited to three. In some embodiments, the multi-walled nanotube has two coaxial nanotubes as shown in FIG. 2c, and in other embodiments, the multi-walled nanotube comprises a first to Nth nanotube comprising an innermost tube (210) and an outermost tube (200N), where N is a natural number from 1 to about 20 as shown in FIG. 2d. In some embodiments, N is at most 10 or at most 5. In some embodiments, at least one of the first to Nth outer tubes is a nanotube that coaxially surrounds the innermost nanotube (210). In some embodiments, two of the innermost nanotubes (210) and the first to Nth outer tubes (220, 230, ... 200N) are made of different materials. In some embodiments, N is at least two (i.e., three or more tubes), and two of the innermost nanotube (210) and the first to Nth outer tubes (220, 230, ... 200N) are made of the same material. In other embodiments, three of the innermost nanotube (210) and the first to Nth outer tubes (220, 230, ... 200N) are made of different materials.

[0018] In some embodiments, each of the nanotubes of the multi-walled nanotube is selected from the group consisting of carbon nanotubes; boron nitride nanotubes; and transition metal dichalcogenide (TMD) nanotubes, wherein 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. In some embodiments, two adjacent layers (tubes) of the multi-walled nanotube are made of different materials. In some embodiments, the outermost nanotube of the multi-walled nanotube is a non-carbon-based nanotube.

[0019] In some embodiments, the outermost tube or outermost layer of the multi-walled nanotube is made of at least one layer of oxide such as HfO2, Al2O3, ZrO2, Y2O3, or La2O3; at least one layer of non-oxide compound such as B4C, YN, Si3N4, BN, NbN, RuNb, YF3, TiN, SiC, or ZrN; or at least one metal layer made of, for example, Ru, Nb, Y, Sc, Ni, Mo, W, Pt, or Bi.

[0020] In some embodiments, the multi-walled nanotube comprises three coaxially layered tubes made of different materials. In other embodiments, the multi-walled nanotube comprises three coaxially layered tubes, wherein the innermost tube (first tube) and the second tube surrounding the innermost tube are made of different materials, 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. In some embodiments, one or more outer tubes are formed around the inner tube, and in other embodiments, one or more tubes are formed within the outer tube.

[0021] In some embodiments, the multi-walled nanotube comprises four coaxially layered tubes, each made of a different material (A, B, or C). In some embodiments, the materials of the four layers extend from the innermost (first) tube to the fourth tube and 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.

[0022] In some embodiments, all tubes of the multi-walled nanotube are crystalline nanotubes. In other embodiments, one or more tubes are amorphous (e.g., amorphous) layers surrounding one or more inner tubes. In some embodiments, the outermost tube is made of a layer of, for example, HfO2, Al2O3, ZrO2, Y2O3, La2O3, B4C, YN, Si3N4, BN, NbN, RuNb, YF3, TiN, ZrN, Ru, Nb, Y, Sc, Ni, Mo, W, Pt, or Bi.

[0023] In some embodiments, the diameter of the innermost nanotube is in the range of about 0.5 nm to about 20 nm, and in other embodiments, in the range of about 1 nm to about 10 nm. In some embodiments, the diameter of the multi-walled nanotube (i.e., the diameter of the outermost tube) is in the range of about 3 nm to about 40 nm, and in other embodiments, in the range of about 5 nm to about 20 nm. In some embodiments, the length of the multi-walled nanotube is in the range of about 0.5 µm to about 50 µm, and in other embodiments, in the range of about 1.0 µm to about 20 µm.

[0024] In embodiments of the present disclosure, one or more cover layers or sheets are formed on one or both sides of the membrane (100), as illustrated in FIGS. 3a through 3e. The membrane (100) comprises carbon nanotubes and / or 2D material nanotubes as described above.

[0025] In some embodiments, a first cover layer (or sheet) (520) is formed on the bottom surface of the network membrane (100) between the pellicle frame (15) and the network membrane (100), as shown in FIG. 3a. In some embodiments, a second cover layer (530) is formed on the network membrane (100) to seal the network membrane together with the first cover layer (520), as shown in FIG. 3b. In some embodiments, the first cover layer is not used, and only the second cover layer (530) is used, as shown in FIG. 3c. In some embodiments, a third cover layer (540) is placed on the second cover layer (530), as shown in FIG. 3d. In some embodiments, the first cover layer (520), the second cover layer (530), and the third cover layer (540) are formed as shown in FIG. 3e. In some embodiments, the material of the third cover layer (540) is the same as the material of the first and / or second cover layer. In some embodiments, the first, second, and third cover layers are made of different materials. In some embodiments, the thickness of the first cover layer (520) and the second cover layer (530), respectively, is in the range of about 0.5 nm to about 10 nm, and in other embodiments, is in the range of about 1 nm to about 5 nm.

[0026] In some embodiments, the first, second, and / or third cover layers are carbon, aluminum or aluminum compounds (e.g., AlF3, Al2O3, and AlN), boron or boron compounds (e.g., BN, B4C, B2O, and B6Si), silicon or silicon compounds (e.g., SiN, Si3N4, SiN2, SiZr, SiC, and SiCN), niobium or niobium compounds (e.g., NbSiN, Nb2O5, NbTiN, NbSe3, NBC, and Nb5Si3), zirconium or zirconium compounds (e.g., ZrN, ZrO2, ZrYO, ZrF4, ZrB2, and ZnSe2), yttrium or yttrium compounds (e.g., YN, Y2O3, and YF3), molybdenum or molybdenum compounds (e.g., Mo2N, Mo5Si3, Mo3Si, MoSiB, MoSi, MoC2, It is formed from Mo2B4, MoC, Mo2C, MoSe2, MoS2, MoN, and MoP), titanium or titanium compounds (e.g., TiN, TiCN, and TiS2), hafnium or hafnium compounds (e.g., HfO2, HfN, and HfF4), vanadium or vanadium compounds (e.g., VN), tungsten or tungsten compounds (e.g., WS2 and WSe2), ruthenium or ruthenium compounds (e.g., RuO2, RuIrO, Ru2Ni2, RuCu, RuPt, RuIr, and RuP), iridium or iridium compounds (e.g., IrO2), cobalt or cobalt compounds (e.g., CoP, CoSe2, and CoS2), nickel or nickel compounds (e.g., NiMo), or iron or iron compounds (e.g., Fe3C, Fe2O3, and FePO).

[0027] In some embodiments, one or both of the first cover layer (520) and the second cover layer (530) comprise a two-dimensional material in which one or more two-dimensional layers are stacked. Here, in some embodiments, "two-dimensional" layers refer to one or several crystalline layers of an atomic matrix or network having a thickness in the range of about 0.1 to 5 nm. In some embodiments, the two-dimensional materials of the first cover layer (520) and the second cover layer (530) are the same or different from each other. In some embodiments, the first cover layer (520) comprises a first two-dimensional material, and the second cover layer (530) comprises a second two-dimensional material.

[0028] In some embodiments, the two-dimensional material for the first cover layer (520) and / or the second cover layer (530) comprises at least one of boron nitride (BN), graphene, and / or transition metal dichalcogenide (TMDS) 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.

[0029] In some embodiments, the number of two-dimensional layers of each of the two-dimensional materials of the first and / or second cover layers is 1 to about 20, and in other embodiments, 2 to about 10. When the thickness and / or the number of layers is greater than these ranges, the EUV transmittance of the pellicle may be reduced, and when the thickness and / or the number of layers is less than these ranges, the mechanical strength of the pellicle may be insufficient.

[0030] In some embodiments, the third cover layer (540) comprises at least one layer of an oxide such as HfO2, Al2O3, ZrO2, Y2O3, or La2O3. In some embodiments, the third cover layer (540) comprises 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 third cover layer (540) comprises at least one metal layer made of, for example, Ru, Nb, Y, Sc, Ni, Mo, W, Pt, or Bi. In some embodiments, the third cover layer (540) is a single layer, and in other embodiments, two or more layers of these materials are used as the third cover layer (540). In some embodiments, the thickness of the third cover layer is in the range of about 0.5 nm to about 10 nm, and in other embodiments, is in the range of about 1 nm to about 5 nm. When the thickness of the third cover layer (540) is greater than this range, the EUV transmittance of the pellicle may be reduced, and when the thickness of the third cover layer (540) is smaller than this range, the mechanical strength of the pellicle may be insufficient.

[0031] In some embodiments, one or more of the second or third cover layers also completely or partially cover the sides of the pellicle frame (15), as illustrated in FIG. 3b-3e. In some embodiments, the first cover layer partially or completely covers the sides of the pellicle frame (15). In some embodiments, one or more of the first, second or third cover layers do not cover the sides of the pellicle frame.

[0032] FIGS. 4a, 4b, and 4c illustrate the fabrication of a nanotube network membrane for a pellicle according to embodiments of the present disclosure.

[0033] In some embodiments, carbon nanotubes are formed by a chemical vapor deposition (CVD) process. In some embodiments, the CVD process is performed using a vertical furnace as shown in FIG. 4a, and the synthesized nanotubes are deposited on a support membrane (80) as shown in FIG. 4b. In some embodiments, carbon nanotubes are formed from a carbon source gas (precursor) using a suitable catalyst such as Fe or Ni. Then, the network membrane (100) formed on the support membrane (80) is separated from the support membrane (80) and transferred onto a pellicle frame (15) as shown in FIG. 4c. In some embodiments, the stage or susceptor on which the support membrane (80) is placed rotates continuously or intermittently so that the synthesized nanotubes are deposited on the support membrane (80) in different or random directions (step-by-step method).

[0034] FIG. 5a illustrates the manufacturing process of a network membrane, and FIG. 5b illustrates the flowchart according to an embodiment of the present disclosure.

[0035] In some embodiments, carbon nanotubes are dispersed in a solution as shown in FIG. 5a. The solution comprises a solvent, such as water or an organic solvent, and a surfactant, such as sodium dodecyl sulfate (SDS). The nanotubes are one or more types of nanotubes (material and / or wall number). In some embodiments, carbon nanotubes are formed by various methods, such as arc discharge, laser ablation, or chemical vapor deposition (CVD).

[0036] As illustrated in FIG. 5a, a support membrane (80) is placed between a chamber or cylinder in which a nanotube dispersion solution is placed and a vacuum chamber. In some embodiments, the support membrane is an organic or inorganic porous or mesh material. In some embodiments, the support membrane is a woven or non-woven fabric. In some embodiments, the support membrane has a circular shape in which a pellicle size of 150 mm × 150 mm square (size of an EUV mask) can be placed.

[0037] As illustrated in FIG. 5a, the pressure within the vacuum chamber is reduced so that pressure is applied to the solvent within the chamber or cylinder. Since 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 while the solvent passes through it. The support membrane on which the nanotubes are deposited is separated from the filtration device of FIG. 5a and subsequently dried. In some embodiments, as illustrated in FIG. 5b, deposition by filtration is repeated to obtain the desired thickness of the nanotube network layer. In some embodiments, after the deposition of nanotubes in the solution, other nanotubes are dispersed in the same solution or a new solution, and the filtration-deposition is repeated. In other embodiments, after the nanotubes are dried, another filtration-deposition is performed. In repetitions, the same type of nanotubes is used in some embodiments, and different types of nanotubes are used in others. In some embodiments, the nanotubes dispersed in the solution include multi-walled nanotubes.

[0038] FIGS. 6a and 6b through 9a and 9b illustrate cross-sectional views ("a" figures) and top ("b" figures) of various stages for manufacturing a pellicle for an EUV photomask according to an embodiment of the present disclosure. For additional embodiments of the method, it is understood that additional operations may be provided before, during, and after the processes illustrated by FIGS. 4a through 9b, and that some of the operations described below may be replaced or removed. The order of operations / processes may be interchangeable. The materials, configurations, methods, processes, and / or dimensions described in connection with the foregoing embodiments are applicable to the following embodiments, and a detailed description thereof may be omitted.

[0039] As illustrated in FIGS. 6a and 6b, a nanotube layer (90) is formed on a support membrane (80) by one or more methods as described above. In some embodiments, the nanotube layer (90) comprises single-walled nanotubes, multi-walled nanotubes, or a mixture thereof. In some embodiments, the nanotube layer (90) comprises only single-walled nanotubes. In some embodiments, the nanotubes are carbon nanotubes.

[0040] Then, as shown in FIGS. 7a and 7b, a pellicle frame (15) is attached to a nanotube layer (90). In some embodiments, the pellicle 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, as shown in FIG. 7b, the pellicle frame (15) has a rectangular (including square) frame shape, which is larger than the black boundary region of the EUV mask and smaller than the substrate of the EUV mask.

[0041] Next, as illustrated in FIGS. 8a and 8b. In some embodiments, the nanotube layer (90) and the support membrane (80) are cut into a rectangular shape having the same size as or slightly larger than the pellicle frame (15), and then the support membrane (80) is separated or removed to form a network membrane (100). When the support membrane (80) is made of an organic material, the support membrane (80) is removed by wet etching using an organic solvent.

[0042] In some embodiments, the nanotube layer (90) is removed from the support membrane (80) as a free-standing layer before the pellicle frame (15) is attached.

[0043] As illustrated in FIGS. 3a-3e, one or more cover layers are formed on the membrane (100) during or after the operations illustrated in FIGS. 6a-8b. In some embodiments, one or more cover layers are formed on the membrane (100) together with a pellicle frame (15) as illustrated in FIGS. 8a and 8b. In other embodiments, one or more cover layers are formed on a nanotube layer (90) on a support membrane (80) as illustrated in FIGS. 6a and 6b. In some embodiments, one or more cover layers are formed on a free-standing membrane (100) as illustrated in FIGS. 9a and 9b.

[0044] In some embodiments of the present disclosure, before the first and / or second cover layer is formed, the membrane (100) (or nanotube layer (90)) undergoes physical and / or chemical surface treatment (600) to improve adhesion between the cover layer and the nanotube membrane, as illustrated in FIG. 10a, 10b and 10c. As illustrated in FIG. 10a, a plurality of nanotubes (e.g., carbon nanotubes) are formed, and a membrane having a frame or not having a frame is formed. The nanotube membrane (100) undergoes physical and / or chemical treatment (600) as shown in FIG. 10b, and then, as shown in FIG. 10c, one or more cover layers (500) corresponding to the first, second, and / or third cover layers (520, 530, 540) are formed on the nanotube membrane (100) as described above.

[0045] In some embodiments, the treatment (600) comprises chemisorption and / or physisorption to form one or more functional groups on the surface of the nanotube membrane (100). In some embodiments, the functional groups include a hydroxyl group, a sulfhydryl group, a carbonyl group, a carboxyl group, an amino group, and / or a phosphate group.

[0046] In some embodiments, the treatment (600) includes applying a solution to the membrane (100) or soaking or immersing the membrane in the solution. The solution comprises an organic or inorganic acid solution, a polymer material, or any organic material having one or more of functional groups. In some embodiments, the solution comprises HNO3, H2SO4, 5-isocyanato-isophthaloyl chloride (ICIC), dodecylamine (DDA), polycaprolactone (PCL), polyacrylic acid (PAA), polydopamine (PdoP), polyaniline (PANI), polymethyl triethyl ammonium chloride (PMTAC), poly(ethylene glycol)methyl ether methacrylate (PEGMA), polysulfobetaine methacrylate (PSBMA), 3-aminopropyl triethoxysilane (APTS), and It includes 1,3-phenylenediamine (mPDA).

[0047] In some embodiments, the treatment (600) involves gas immersion by applying one or more gases to the membrane. In some embodiments, the membrane and / or gas are heated to a temperature in the range of about 300°C to 1200°C. In other embodiments, the temperature is in the range of about 600°C to 800°C. If the temperature is too high, the membrane may be damaged, and if the temperature is too low, surface modification may be insufficient. The soaking gas comprises one or more of Ar, He, H2, Ne, N2, and NH3 without oxygen. In some embodiments, O2 is used alternatively or additionally.

[0048] In some embodiments, the treatment (600) includes plasma treatment of the membrane. The gas for the plasma comprises one or more of Ar, He, H2, Ne, N2, and NH3 without oxygen. In some embodiments, O2 is used alternatively or additionally. In some embodiments, the membrane and / or gas are heated to a temperature in the range of about 200°C to 600°C during the plasma treatment. In other embodiments, the temperature is in the range of about 300°C to 500°C. The plasma is generated as a capacitively coupled plasma, an inductively coupled plasma, an electron cyclotron plasma, a hybrid low-temperature plasma, a glow discharge plasma, or a high-pressure arc plasma. The input power of the plasma is in the range of about 1 W to about 2 kW in some embodiments.

[0049] After plasma treatment, SP 3 The amount of carbon structures (disordered or amorphous carbon) increases. In some embodiments, the membrane after plasma treatment is in the D band (1360 cm⁻¹) in Raman spectroscopy. -1 Higher peaks in the G band (1560 cm⁻¹) and higher peaks than those prior to plasma treatment -1 )(SP 2It exhibits a lower peak in (corresponding to the carbon structure). Because the surface of the nanotube membrane (100) is caused to become disordered or to have defects or defective sites, the adhesion of the cover layer (500) can be improved.

[0050] In some embodiments, after the treatment (600) is performed, one or more post-treatments are performed. In some embodiments, the post-treatment includes annealing such as no-annealing, high-speed thermal annealing, laser annealing, UV annealing, or electron beam annealing.

[0051] In some embodiments of the present disclosure, one or more seed layers are formed on the surface of a nanotube membrane before a cover layer is formed, as shown in FIG. 11 and FIG. 12a-16.

[0052] As illustrated in FIG. 11, a plurality of nanotubes (e.g., carbon nanotubes) are formed, and a membrane having a frame or not having a frame is formed. Then, one or more seed layers are formed, and then, one or more cover layers (500) corresponding to the first, second, and / or third cover layers (520, 530, 540) as described above are formed. In some embodiments, the process (600) illustrated in FIG. 10b is performed before the seed layers are formed.

[0053] In some embodiments, as illustrated in FIG. 12a or 13a, a seed layer (410 or 415) is formed on at least one surface of a nanotube membrane (100) that does not completely cover the surface. In some embodiments, the seed layer comprises a plurality of nano-grains or nano-particles (410) having a size in the range of about 5 nm to about 50 nm in the top view. In some embodiments, the seed layer comprises a plurality of sheets or islands (415) having a size in the range of about 10 nm to about 1000 nm in the top view. In some embodiments, the thickness of the seed layer is in the range of about 0.5 nm to about 10 nm, and in other embodiments, is in the range of about 1 nm to about 5 nm.

[0054] In some embodiments, the seed layers (410 or 415) cover about 40% to about 60% of the surface area of ​​the nanotube membrane (100). When the coverage is smaller than this range, the subsequently formed cover layer may not completely cover the entire surface of the nanotube membrane. When the coverage is larger than this range, the EUV transmittance of the pellicle may be reduced.

[0055] After the seed layer (410 or 415) is formed, a cover layer (500) is formed on the nanotube membrane (100) and the seed layer. Since the seed layer only partially covers the surface of the nanotube membrane, the cover layer (500) comes into contact with the surface of the nanotube membrane (100).

[0056] In some embodiments, as shown in FIGS. 14a and 14b, the seed layer comprises first nanograins (420) and second nanograins (430) made of different materials, or as shown in FIGS. 15a and 15b, the seed layer comprises a first sheet or island (425) and a second sheet or island (435) made of different materials.

[0057] In some embodiments, the seed layer comprises one or more of C, Al, B, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Cd, Hf, Ta, W, Re, Os, Ir, Pt, Au, or Rf, and compounds thereof. Compounds include oxides, nitrides, silicides, or carbides.

[0058] In some embodiments, as shown in FIG. 16, the first cover layer (520) is formed on the seed layer (410), and the nanotube membrane (100) and the second cover layer (530) are formed on the first cover layer (520) and do not come into contact with the nanotube membrane (100).

[0059] The cover layer and the seed layer may be formed directly on the membrane (100) by at least one of electron beam evaporation (deposition), ion beam deposition, sputtering, chemical vapor deposition (CVD), plasma-enhanced CVD, atomic layer deposition (ALD), plasma-enhanced ALD, metal-organic CVD (MOCVD), electroplating, and any other suitable film-forming method. In other embodiments, the cover layer formed on the dummy substrate is removed and transferred over the membrane (100).

[0060] In some embodiments, after the cover layer is formed, one or more post-treatments are performed to rearrange and / or rearrange surface atoms or to crystallize the surface or film. In some embodiments, the post-treatment includes annealing (e.g., furnace annealing, high-speed thermal annealing, laser annealing, UV annealing, or electron beam annealing) or plasma treatment.

[0061] In some embodiments, the network membrane is alternatively or in addition to carbon nanotubes SP such as graphite or graphene 2 It includes carbon structures.

[0062] FIG. 17a illustrates a flowchart of a method for manufacturing a semiconductor device, and FIG. 17b, 17c, 17d, and 17e illustrate a sequential manufacturing method for manufacturing a semiconductor device according to embodiments of the present disclosure. A semiconductor substrate or other suitable substrate to be patterned to form an integrated circuit on top is provided. In some embodiments, the semiconductor substrate comprises silicon. Alternatively or additionally, the semiconductor substrate comprises germanium; silicon germanium; or other suitable semiconductor materials such as III-V semiconductor materials. In S801 of FIG. 17a, a target layer to be patterned is formed on the semiconductor substrate. In certain embodiments, the target layer is the semiconductor substrate. In some embodiments, the target layer comprises 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 a semiconductor layer formed epitaxially. In some embodiments, the target layer is formed on a substructure such as an isolation structure, a transistor, or wiring. In S802 of FIG. 17a, a photoresist layer is formed on the target layer as shown in FIG. 17b. The photoresist layer is sensitive to radiation from an exposure source during a subsequent photolithography exposure process. In this embodiment, the photoresist layer is sensitive to EUV light used in the photolithography exposure process. The photoresist layer may be formed on the target layer by spin-on coating or other suitable techniques. The coated photoresist layer may be further baked to allow a solvent to flow into the photoresist layer. In S803 of FIG. 17a, the photoresist layer is patterned using an EUV reflective mask having the pellicle presented above, as shown in FIG. 17c. Patterning the photoresist layer involves performing a photolithography exposure process by an EUV exposure system using an EUV mask.During the exposure process, an integrated circuit (IC) design pattern defined on an EUV mask is imaged onto a photoresist layer to form a latent pattern thereon. Patterning of the photoresist layer further involves developing the exposed photoresist layer to form a patterned photoresist layer having one or more openings. In one embodiment where the photoresist layer is a positive tone photoresist layer, the exposed portions of the photoresist layer are removed during the development process. Patterning of the photoresist layer may further 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.

[0063] In S804 of FIG. 17a, the target layer is patterned using a patterned photoresist layer as an etching mask, as shown in FIG. 17d. In some embodiments, patterning the target layer involves 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 the remaining portions are protected from etching. Additionally, the patterned photoresist layer may be removed by wet stripping or plasma ashing, as shown in FIG. 17e.

[0064] In some embodiments, a network membrane containing carbon nanotubes as described above is used in an EUV transparent window, a debris catcher placed between an EUV lithography device and an EUV radiation source, or any other part of an EUV lithography device and EUV radiation, where high EUV transmittance is required.

[0065] In the aforementioned embodiments, the pellicle membrane includes one or more cover layers that reinforce the mechanical strength of the pellicle and improve the lifespan of the pellicle.

[0066] It will be understood that not all advantages are necessarily discussed in this specification, that no particular advantages are required for all embodiments or examples, and that other embodiments or examples may provide different advantages.

[0067] According to one aspect of the present disclosure, in a method for manufacturing a pellicle for an extreme ultraviolet (EUV) photomask, SP 2A carbon membrane is formed, a treatment is performed on the membrane to change the surface properties of the membrane, and after the treatment, a cover layer is formed on the membrane. In one or more of the above-described embodiments and the following embodiments, the treatment comprises applying to the membrane at least one solution selected from the group consisting of HNO3, H2SO4, 5-isocyanato-isophthaloyl chloride, dodecylamine, polycaprolactone, polyacrylic acid, polydopamine, polyaniline, polymethyl triethylammonium chloride, poly(ethylene glycol)methyl ether methacrylate, polysulfobetaine methacrylate, 3-aminopropyl triethoxysilane, and 1,3-phenylenediamine. In one or more of the above-described examples and the following examples, the treatment comprises applying at least one gas selected from the group consisting of Ar, H2, Ne, O2, N2, and NH3 to the membrane. In one or more of the above-described examples and the following examples, the treatment with the gas is performed at a temperature in the range of 300°C to 1200°C. In one or more of the above-described examples and the following examples, the treatment comprises applying plasma to the membrane. In one or more of the above-described examples and the following examples, the treatment causes the surface of the membrane to have at least one selected from the group consisting of a hydroxyl group, a sulfhydryl group, a carbonyl group, a carboxyl group, an amino group, and a phosphate group.In one or more of the above-described embodiments and the following embodiments, the cover layer is C, Al2O3, AlN, Al, B, BN, B4C, B2O3, B6Si, SiN, Si3N4, SiN2, SiZr, SiC, SiCN, NbSiN, Nb2O5, NbTiN, NbSe3, NbC, Nb5Si3, ZrN, ZrO2, ZrYO, ZrF4, ZrB2, ZnSe2, YN, Y2O3, YF3, Mo2N, Mo5Si3, Mo3Si, MoSiB, MoSi, MoC2, Mo2B4, MoC, Mo2C, MoSe2, MoS2, MoN, MoP, TiN, TiCN, TiS2, HfO2, HfN, HfF4, VN, WS2, WSe2, RuO2, RuIrO, Ru2Ni2, RuCu, RuPt, It comprises at least one layer prepared from a composition selected from the group consisting of RuIr, RuP, ZrO2, IrO2, CoP, CoSe2, CoS2, NiMo, Fe3C, Fe2O3, and FePO. In one or more of the above-described examples and the following examples, the cover layer comprises a single layer or multiple layers of a two-dimensional material. In one or more of the above-described examples and the following examples, the cover layer comprises a nano-grain structure, a nano-island structure, or a nano-particle structure. In one or more of the above-described examples and the following examples, the thickness of the cover layer is within the range of 0.5 nm to 10 nm. In one or more of the above-described examples and the following examples, the membrane comprises at least one of carbon nanotubes, graphene, and graphite.

[0068] According to another aspect of the present disclosure, in a method for manufacturing a pellicle for an extreme ultraviolet (EUV) photomask, SP 2A carbon membrane is formed, a seed layer is formed on the main surface of the membrane, and a cover layer is formed on the membrane and the seed layer. In one or more of the above-described examples and the following examples, the seed layer covers only partially the main surface of the membrane. In one or more of the above-described examples and the following examples, the seed layer covers 40% to 60% of the main surface of the membrane. In one or more of the above-described examples and the following examples, the seed layer includes a plurality of openings. In one or more of the above-described examples and the following examples, the seed layer is made of a material selected from the group consisting of C, Al, B, Sc, Ti, V, VN, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Cd, Hf, Ta, W, Re, Os, Ir, Pt, Au, Rf, and compounds thereof. In one or more of the above-described embodiments and the following embodiments, the seed layer comprises two or more different materials. In one or more of the above-described embodiments and the following embodiments, the cover layer is C, Al2O3, AlN, Al, B, BN, B4C, B2O3, B6Si, SiN, Si3N4, SiN2, SiZr, SiC, SiCN, NbSiN, Nb2O5, NbTiN, NbSe3, NbC, Nb5Si3, ZrN, ZrO2, ZrYO, ZrF4, ZrB2, ZnSe2, YN, Y2O3, YF3, Mo2N, Mo5Si3, Mo3Si, MoSiB, MoSi, MoC2, Mo2B4, MoC, Mo2C, MoSe2, MoS2, MoN, MoP, TiN, TiCN, TiS2, HfO2, HfN, HfF4, VN, WS2, WSe2, RuO2, RuIrO, Ru2Ni2, RuCu, RuPt, It includes at least one layer prepared with a composition selected from the group consisting of RuIr, RuP, ZrO2, IrO2, CoP, CoSe2, CoS2, NiMo, Fe3C, Fe2O3, and FePO.

[0069] According to another aspect of the present disclosure, in a method for manufacturing a pellicle for an extreme ultraviolet (EUV) photomask, SP 2A carbon membrane is formed, a seed layer is formed on the main surface of the membrane, a first cover layer is formed on the membrane and the seed layer, and a second cover layer is formed on the first cover layer. In one or more of the above-described examples and the following examples, the seed layer partially covers the main surface of the membrane. In one or more of the above-described examples and the following examples, the first cover layer is in contact with the membrane, and the second cover layer is separated from the membrane by the first cover layer. In one or more of the above-described examples and the following examples, the seed layer is made of a material selected from the group consisting of C, Al, B, Sc, Ti, V, VN, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Cd, Hf, Ta, W, Re, Os, Ir, Pt, Au, Rf, and compounds thereof. In one or more of the above-described embodiments and the following embodiments, the seed layer comprises two or more different materials. In one or more of the above-described embodiments and the following embodiments, the first cover layer and the second cover layer are each C, Al2O3, AlN, Al, B, BN, B4C, B2O3, B6Si, SiN, Si3N4, SiN2, SiZr, SiC, SiCN, NbSiN, Nb2O5, NbTiN, NbSe3, NbC, Nb5Si3, ZrN, ZrO2, ZrYO, ZrF4, ZrB2, ZnSe2, YN, Y2O3, YF3, Mo2N, Mo5Si3, Mo3Si, MoSiB, MoSi, MoC2, Mo2B4, MoC, Mo2C, MoSe2, MoS2, MoN, MoP, TiN, TiCN, TiS2, HfO2, HfN, HfF4, VN, WS2, WSe2, RuO2, RuIrO, Ru2Ni2, It includes at least one layer prepared with a composition selected from the group consisting of RuCu, RuPt, RuIr, RuP, ZrO2, IrO2, CoP, CoSe2, CoS2, NiMo, Fe3C, Fe2O3, and FePO.

[0070] According to another aspect of the present disclosure, a pellicle for an extreme ultraviolet (EUV) reflective mask comprises a membrane comprising a plurality of nanotubes and a first cover layer disposed on a first main surface of the membrane. The first cover layer is C, Al2O3, AlN, Al, B, BN, B4C, B2O3, B6Si, SiN, Si3N4, SiN2, SiZr, SiC, SiCN, NbSiN, Nb2O5, NbTiN, NbSe3, NbC, Nb5Si3, ZrN, ZrO2, ZrYO, ZrF4, ZrB2, ZnSe2, YN, Y2O3, YF3, Mo2N, Mo5Si3, Mo3Si, MoSiB, MoSi, MoC2, Mo2B4, MoC, Mo2C, MoSe2, MoS2, MoN, MoP, TiN, TiCN, TiS2, HfO2, HfN, HfF4, VN, WS2, WSe2, RuO2, RuIrO, Ru2Ni2, RuCu, RuPt, RuIr, RuP, It comprises at least one layer prepared from a composition selected from the group consisting of ZrO2, IrO2, CoP, CoSe2, CoS2, NiMo, Fe3C, Fe2O3, and FePO. In one or more of the above-described examples and the following examples, the pellicle further comprises a seed layer disposed on a first main surface and partially covering the first main surface of the membrane. In one or more of the above-described examples and the following examples, the seed layer is prepared from a material selected from the group consisting of C, Al, B, Sc, Ti, V, VN, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Cd, Hf, Ta, W, Re, Os, Ir, Pt, Au, Rf, and compounds thereof. In one or more of the above-described examples and the following examples, the pellicle further comprises a second cover layer disposed on a second main surface opposite the first main surface of the membrane.In one or more of the above-described embodiments and the following embodiments, the second cover layer is C, Al2O3, AlN, Al, B, BN, B4C, B2O3, B6Si, SiN, Si3N4, SiN2, SiZr, SiC, SiCN, NbSiN, Nb2O5, NbTiN, NbSe3, NbC, Nb5Si3, ZrN, ZrO2, ZrYO, ZrF4, ZrB2, ZnSe2, YN, Y2O3, YF3, Mo2N, Mo5Si3, Mo3Si, MoSiB, MoSi, MoC2, Mo2B4, MoC, Mo2C, MoSe2, MoS2, MoN, MoP, TiN, TiCN, TiS2, HfO2, HfN, HfF4, VN, WS2, WSe2, RuO2, RuIrO, Ru2Ni2, RuCu, RuPt, It comprises at least one layer prepared from a composition selected from the group consisting of RuIr, RuP, ZrO2, IrO2, CoP, CoSe2, CoS2, NiMo, Fe3C, Fe2O3, and FePO. In one or more of the above-described examples and the following examples, the first cover layer and the second cover layer are prepared from the same material. In one or more of the above-described examples and the following examples, the pellicle further comprises a third cover layer disposed on a second main surface opposite to the first main surface of the membrane.In one or more of the above-described embodiments and the following embodiments, the third cover layer is C, Al2O3, AlN, Al, B, BN, B4C, B2O3, B6Si, SiN, Si3N4, SiN2, SiZr, SiC, SiCN, NbSiN, Nb2O5, NbTiN, NbSe3, NbC, Nb5Si3, ZrN, ZrO2, ZrYO, ZrF4, ZrB2, ZnSe2, YN, Y2O3, YF3, Mo2N, Mo5Si3, Mo3Si, MoSiB, MoSi, MoC2, Mo2B4, MoC, Mo2C, MoSe2, MoS2, MoN, MoP, TiN, TiCN, TiS2, HfO2, HfN, HfF4, VN, WS2, WSe2, RuO2, RuIrO, Ru2Ni2, RuCu, RuPt, It comprises at least one layer prepared from a composition selected from the group consisting of RuIr, RuP, ZrO2, IrO2, CoP, CoSe2, CoS2, NiMo, Fe3C, Fe2O3, and FePO. In one or more of the above-described examples and the following examples, the third cover layer is prepared from the same material as either the first cover layer or the second cover layer.

[0071] According to another aspect of the present disclosure, a pellicle for an extreme ultraviolet (EUV) reflective mask comprises a membrane comprising a plurality of nanotubes, a first seed layer disposed on a first main surface of the membrane, and a first cover layer disposed on the first seed layer. The first seed layer is made of one material selected from the group consisting of C, Al, B, Sc, Ti, V, VN, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Cd, Hf, Ta, W, Re, Os, Ir, Pt, Au, Rf, and compounds thereof. The first cover layer is C, Al2O3, AlN, Al, B, BN, B4C, B2O3, B6Si, SiN, Si3N4, SiN2, SiZr, SiC, SiCN, NbSiN, Nb2O5, NbTiN, NbSe3, NbC, Nb5Si3, ZrN, ZrO2, ZrYO, ZrF4, ZrB2, ZnSe2, YN, Y2O3, YF3, Mo2N, Mo5Si3, Mo3Si, MoSiB, MoSi, MoC2, Mo2B4, MoC, Mo2C, MoSe2, MoS2, MoN, MoP, TiN, TiCN, TiS2, HfO2, HfN, HfF4, VN, WS2, WSe2, RuO2, RuIrO, Ru2Ni2, RuCu, RuPt, RuIr, RuP, It comprises at least one layer prepared from a composition selected from the group consisting of ZrO2, IrO2, CoP, CoSe2, CoS2, NiMo, Fe3C, Fe2O3, and FePO. In one or more of the above-described examples and the following examples, the first seed layer partially covers the first main surface of the membrane. In one or more of the above-described examples and the following examples, the first seed layer covers 40% to 60% of the main surface of the membrane. In one or more of the above-described examples and the following examples, the seed layer comprises a plurality of openings, and the first cover layer contacts the membrane through the plurality of openings.In one or more of the above-described embodiments and the following embodiments, the pellicle further comprises a second seed layer disposed on a second main surface opposite to the first main surface of the membrane, and a second cover layer disposed on the second seed layer. The second seed layer is made of one material selected from the group consisting of C, Al, B, Sc, Ti, V, VN, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Cd, Hf, Ta, W, Re, Os, Ir, Pt, Au, Rf, and compounds thereof. The second cover layer is C, Al2O3, AlN, Al, B, BN, B4C, B2O3, B6Si, SiN, Si3N4, SiN2, SiZr, SiC, SiCN, NbSiN, Nb2O5, NbTiN, NbSe3, NbC, Nb5Si3, ZrN, ZrO2, ZrYO, ZrF4, ZrB2, ZnSe2, YN, Y2O3, YF3, Mo2N, Mo5Si3, Mo3Si, MoSiB, MoSi, MoC2, Mo2B4, MoC, Mo2C, MoSe2, MoS2, MoN, MoP, TiN, TiCN, TiS2, HfO2, HfN, HfF4, VN, WS2, WSe2, RuO2, RuIrO, Ru2Ni2, RuCu, RuPt, RuIr, RuP, It comprises at least one layer prepared from a composition selected from the group consisting of ZrO2, IrO2, CoP, CoSe2, CoS2, NiMo, Fe3C, Fe2O3, and FePO. In one or more of the above-described examples and the following examples, the first cover layer and the second cover layer are prepared from the same material. In one or more of the above-described examples and the following examples, the pellicle further comprises a third cover layer disposed on the first cover layer.The third cover layer is C, Al2O3, AlN, Al, B, BN, B4C, B2O3, B6Si, SiN, Si3N4, SiN2, SiZr, SiC, SiCN, NbSiN, Nb2O5, NbTiN, NbSe3, NbC, Nb5Si3, ZrN, ZrO2, ZrYO, ZrF4, ZrB2, ZnSe2, YN, Y2O3, YF3, Mo2N, Mo5Si3, Mo3Si, MoSiB, MoSi, MoC2, Mo2B4, MoC, Mo2C, MoSe2, MoS2, MoN, MoP, TiN, TiCN, TiS2, HfO2, HfN, HfF4, VN, WS2, WSe2, RuO2, RuIrO, Ru2Ni2, RuCu, RuPt, RuIr, RuP, It comprises at least one layer prepared from a composition selected from the group consisting of ZrO2, IrO2, CoP, CoSe2, CoS2, NiMo, Fe3C, Fe2O3, and FePO. In one or more of the above-described examples and the following examples, the third cover layer is prepared from the same material as either the first cover layer or the second cover layer. In one or more of the above-described examples and the following examples, the pellicle further comprises a second cover layer disposed on the first cover layer.The second cover layer is C, Al2O3, AlN, Al, B, BN, B4C, B2O3, B6Si, SiN, Si3N4, SiN2, SiZr, SiC, SiCN, NbSiN, Nb2O5, NbTiN, NbSe3, NbC, Nb5Si3, ZrN, ZrO2, ZrYO, ZrF4, ZrB2, ZnSe2, YN, Y2O3, YF3, Mo2N, Mo5Si3, Mo3Si, MoSiB, MoSi, MoC2, Mo2B4, MoC, Mo2C, MoSe2, MoS2, MoN, MoP, TiN, TiCN, TiS2, HfO2, HfN, HfF4, VN, WS2, WSe2, RuO2, RuIrO, Ru2Ni2, RuCu, RuPt, RuIr, RuP, It comprises at least one layer prepared from a composition selected from the group consisting of ZrO2, IrO2, CoP, CoSe2, CoS2, NiMo, Fe3C, Fe2O3, and FePO. In one or more of the above-described examples and the following examples, the first cover layer and the second cover layer are prepared from different materials.

[0072] According to another aspect of the present disclosure, a pellicle for an extreme ultraviolet (EUV) reflective mask comprises a first layer, a second layer, and a main membrane disposed between the first layer and the second layer. The main membrane comprises a plurality of coaxial nanotubes, each 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. In one or more of the foregoing embodiments and the following embodiments, 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 (TMD) nanotubes, wherein TMD is represented as MX2, where M is one or more of Mo, W, Pd, Pt, and Hf, and X is one or more of S, Se, and TE. In one or more of the foregoing embodiments and the following embodiments, the inner tube is a carbon nanotube. In one or more of the aforementioned embodiments and the following embodiments, each of the plurality of coaxial nanotubes comprises an inner tube and one outer tube made of a material different from that of the inner tube. In one or more of the aforementioned embodiments and the following embodiments, each of the plurality of coaxial nanotubes comprises an inner tube and two outer tubes, all of which are made of different materials. In one or more of the aforementioned embodiments and the following embodiments, each of the plurality of coaxial nanotubes comprises two outer tubes and an inner tube made of the same material. In one or more of the aforementioned embodiments and the following embodiments, the main membrane further comprises a plurality of single-walled nanotubes. In one or more of the above-described embodiments and the following embodiments, at least one of the first layer or the second 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.In one or more of the above-described examples and the following examples, the EUV transmittance of the membrane is 95% to 98%.

[0073] The foregoing describes the features of various embodiments or examples to better enable those skilled in the art to understand the aspects of the present disclosure. Those skilled in the art should understand that the present disclosure can be readily used as a basis for designing or modifying other processes and structures to perform and / or achieve the same purposes or the same advantages as the embodiments or examples introduced herein. Those skilled in the art should also recognize that such equivalent configurations do not depart from the spirit and scope of the present disclosure, and that various modifications, substitutions, and changes can be made in the present disclosure without departing from the spirit and scope of the present disclosure.

[0074] Book

[0075] 1. A method for manufacturing a pellicle for an extreme ultraviolet (EUV) photomask,

[0076] SP 2 Step of forming a carbon membrane;

[0077] A step of performing a treatment on the membrane to change the surface characteristics of the membrane; and

[0078] After the above processing, a step of forming a cover layer on the membrane

[0079] A method for manufacturing a pellicle comprising

[0080] 2. The pellicle according to claim 1, wherein the treatment comprises applying to the membrane at least one solution selected from the group consisting of HNO3, H2SO4, 5-isocyanato-isophthaloyl chloride, dodecylamine, polycaprolactone, polyacrylic acid, polydopamine, polyaniline, polymethyl triethyl ammonium chloride, poly(ethylene glycol)methyl ether methacrylate, polysulfobetaine methacrylate, 3-aminopropyl triethoxysilane, and 1,3-phenylenediamine. Method of manufacturing.

[0081] 3. A method for manufacturing a pellicle according to claim 1, wherein the treatment comprises applying at least one gas selected from the group consisting of Ar, H2, Ne, O2, N2 and NH3 to the membrane.

[0082] 4. A method for manufacturing a pellicle according to paragraph 3, wherein the treatment with gas is performed at a temperature in the range of 300°C to 1200°C.

[0083] 5. A method for manufacturing a pellicle according to claim 1, wherein the treatment comprises applying plasma to the membrane.

[0084] 6. A method for producing a pellicle according to claim 1, wherein the treatment causes the surface of the membrane to have at least one selected from the group consisting of a hydroxyl group, a sulfhydryl group, a carbonyl group, a carboxyl group, an amino group, and a phosphate group.

[0085] 7. The method of claim 1, wherein the cover layer is C, Al2O3, AlN, Al, B, BN, B4C, B2O3, B6Si, SiN, Si3N4, SiN2, SiZr, SiC, SiCN, NbSiN, Nb2O5, NbTiN, NbSe3, NbC, Nb5Si3, ZrN, ZrO2, ZrYO, ZrF4, ZrB2, ZnSe2, YN, Y2O3, YF3, Mo2N, Mo5Si3, Mo3Si, MoSiB, MoSi, MoC2, Mo2B4, MoC, Mo2C, MoSe2, MoS2, MoN, MoP, TiN, TiCN, TiS2, HfO2, HfN, HfF4, VN, WS2, WSe2, RuO2, RuIrO, Ru2Ni2, RuCu, RuPt, RuIr, A method for manufacturing a pellicle comprising at least one layer prepared with a composition selected from the group consisting of RuP, ZrO2, IrO2, CoP, CoSe2, CoS2, NiMo, Fe3C, Fe2O3, and FePO.

[0086] 8. A method for manufacturing a pellicle according to claim 1, wherein the cover layer comprises a single layer or multiple layers of a two-dimensional material.

[0087] 9. A method for manufacturing a pellicle according to claim 1, wherein the cover layer comprises a nano-grain structure, a nano-island structure, or a nano-particle structure.

[0088] 10. A method for manufacturing a pellicle according to claim 1, wherein the thickness of the cover layer is within the range of 0.5 nm to 10 nm.

[0089] 11. A method for manufacturing a pellicle according to claim 1, wherein the membrane comprises at least one of carbon nanotubes, graphene, and graphite.

[0090] 12. A method for manufacturing a pellicle for an extreme ultraviolet (EUV) photomask,

[0091] SP 2 Step of forming a carbon membrane;

[0092] A step of forming a seed layer on the main surface of the above membrane; and

[0093] Step of forming a cover layer on the above membrane and the above seed layer

[0094] A method for manufacturing a pellicle comprising

[0095] 13. A method for manufacturing a pellicle according to claim 12, wherein the seed layer partially covers the main surface of the membrane.

[0096] 14. A method for manufacturing a pellicle according to claim 13, wherein the seed layer covers 40% to 60% of the main surface of the membrane.

[0097] 15. A method for manufacturing a pellicle according to claim 12, wherein the seed layer comprises a plurality of openings.

[0098] 16. A method for manufacturing a pellicle according to claim 12, wherein the seed layer is made of one material selected from the group consisting of C, Al, B, Sc, Ti, V, VN, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Cd, Hf, Ta, W, Re, Os, Ir, Pt, Au, Rf and compounds thereof.

[0099] 17. A method for manufacturing a pellicle according to claim 16, wherein the seed layer comprises two or more different materials.

[0100] 18. In claim 12, the cover layer is C, Al2O3, AlN, Al, B, BN, B4C, B2O3, B6Si, SiN, Si3N4, SiN2, SiZr, SiC, SiCN, NbSiN, Nb2O5, NbTiN, NbSe3, NbC, Nb5Si3, ZrN, ZrO2, ZrYO, ZrB2, ZnSe2, ZrF4, YN, Y2O3, YF3, Mo2N, Mo5Si3, Mo3Si, MoSiB, MoSi, MoC2, Mo2B4, MoC, Mo2C, MoSe2, MoS2, MoN, MoP, TiN, TiCN, TiS2, HfO2, HfN, HfF4, VN, WS2, WSe2, RuO2, RuIrO, Ru2Ni2, RuCu, RuPt, A method for manufacturing a pellicle comprising at least one layer prepared from a composition selected from the group consisting of RuIr, RuP, ZrO2, IrO2, CoP, CoSe2, CoS2, NiMo, Fe3C, Fe2O3, and FePO.

[0101] 19. In a pellicle for an extreme ultraviolet (EUV) reflective mask,

[0102] A membrane comprising a plurality of nanotubes; and

[0103] A first cover layer disposed on the first main surface of the above membrane

[0104] Includes,

[0105] The first cover layer is C, Al2O3, AlN, Al, B, BN, B4C, B2O3, B6Si, SiN, Si3N4, SiN2, SiZr, SiC, SiCN, NbSiN, Nb2O5, NbTiN, NbSe3, NbC, Nb5Si3, ZrN, ZrO2, ZrYO, ZrF4, ZrB2, ZnSe2, YN, Y2O3, YF3, Mo2N, Mo5Si3, Mo3Si, MoSiB, MoSi, MoC2, Mo2B4, MoC, Mo2C, MoSe2, MoS2, MoN, MoP, TiN, TiCN, TiS2, HfO2, HfN, HfF4, VN, WS2, WSe2, RuO2, RuIrO, Ru2Ni2, RuCu, RuPt, RuIr, RuP, A pellicle comprising at least one layer prepared from a composition selected from the group consisting of ZrO2, IrO2, CoP, CoSe2, CoS2, NiMo, Fe3C, Fe2O3, and FePO.

[0106] 20. In Paragraph 19,

[0107] It further includes a seed layer disposed on the first main surface of the membrane and partially covering the first main surface,

[0108] A pellicle in which the seed layer is made of one material selected from the group consisting of C, Al, B, Sc, Ti, V, VN, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Cd, Hf, Ta, W, Re, Os, Ir, Pt, Au, and Rf and compounds thereof.

Claims

Claim 1 A method for manufacturing a pellicle for an extreme ultraviolet (EUV) photomask, SP 2 A method for manufacturing a pellicle comprising the steps of: forming a carbon membrane; performing a treatment on the membrane to change the surface characteristics of the membrane, wherein the treatment causes the surface of the membrane to have at least one selected from a group consisting of a sulfhydryl group and a phosphate group; and, after the treatment, forming a seed layer on the main surface of the membrane, wherein the seed layer partially covers only the main surface of the membrane; and forming a cover layer on the membrane and the seed layer. Claim 2 In claim 1, the treatment comprises applying to the membrane at least one solution selected from the group consisting of HNO3, H2SO4, 5-isocyanato-isophthaloyl chloride, dodecylamine, polycaprolactone, polyacrylic acid, polydopamine, polyaniline, polymethyl triethyl ammonium chloride, poly(ethylene glycol)methyl ether methacrylate, polysulfobetaine methacrylate, 3-aminopropyl triethoxysilane, and 1,3-phenylenediamine to produce a pellicle. method. Claim 3 A method for manufacturing a pellicle according to claim 1, wherein the treatment comprises applying at least one gas selected from the group consisting of Ar, H2, Ne, O2, N2, and NH3 to the membrane. Claim 4 A method for manufacturing a pellicle according to claim 1, wherein the treatment comprises applying plasma to the membrane. Claim 5 delete Claim 6 The method of claim 1, wherein the cover layer is C, Al2O3, AlN, Al, B, BN, B4C, B2O3, B6Si, SiN, Si3N4, SiN2, SiZr, SiC, SiCN, NbSiN, Nb2O5, NbTiN, NbSe3, NbC, Nb5Si3, ZrN, ZrO2, ZrYO, ZrF4, ZrB2, ZnSe2, YN, Y2O3, YF3, Mo2N, Mo5Si3, Mo3Si, MoSiB, MoSi, MoC2, Mo2B4, MoC, Mo2C, MoSe2, MoS2, MoN, MoP, TiN, TiCN, TiS2, HfO2, HfN, HfF4, VN, WS2, WSe2, RuO2, RuIrO, Ru2Ni2, RuCu, RuPt, RuIr, RuP, A method for manufacturing a pellicle comprising at least one layer prepared from a composition selected from the group consisting of ZrO2, IrO2, CoP, CoSe2, CoS2, NiMo, Fe3C, Fe2O3, and FePO. Claim 7 A method for manufacturing a pellicle according to claim 1, wherein the cover layer comprises a single layer or multiple layers of a two-dimensional material. Claim 8 A method for manufacturing a pellicle according to claim 1, wherein the cover layer comprises a nano-grain structure, a nano-island structure, or a nano-particle structure. Claim 9 A method for manufacturing a pellicle for an extreme ultraviolet (EUV) photomask, SP 2 A method for manufacturing a pellicle comprising the steps of: forming a carbon membrane; forming a first seed layer and a second seed layer made of a material different from the first seed layer on the main surface of the membrane, wherein the first seed layer partially covers the main surface of the membrane; and forming a cover layer on the membrane and the first and second seed layers. Claim 10 A pellicle for an extreme ultraviolet (EUV) reflective mask, comprising: a membrane comprising a plurality of nanotubes; a first seed layer disposed on a first main surface of the membrane and a second seed layer made of a material different from the first seed layer, wherein the first seed layer partially covers only the first main surface of the membrane; and comprises a first main surface of the membrane, the first seed layer, and a first cover layer disposed on the second seed layer, wherein the first cover layer comprises C, Al2O3, AlN, Al, B, BN, B4C, B2O3, B6Si, SiN, Si3N4, SiN2, SiZr, SiC, SiCN, NbSiN, Nb2O5, NbTiN, NbSe3, NbC, Nb5Si3, ZrN, ZrO2, ZrYO, ZrF4, ZrB2, ZnSe2, YN, Y2O3, YF3, Mo2N, Mo5Si3, Mo3Si, MoSiB, MoSi, MoC2, Mo2B4, MoC, Mo2C, MoSe2, MoS2, MoN, MoP, TiN, TiCN, TiS2, HfO2, HfN, HfF4, VN, WS2, A pellicle comprising at least one layer prepared from a composition selected from the group consisting of WSe2, RuO2, RuIrO, Ru2Ni2, RuCu, RuPt, RuIr, RuP, ZrO2, IrO2, CoP, CoSe2, CoS2, NiMo, Fe3C, Fe2O3, and FePO.

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