Pellicle for reticle and method of manufacturing the same

Abstract

According to some embodiments of the present invention, a method for manufacturing an EUV protective film includes the following steps: depositing a first insulating layer on a substrate; partially removing the substrate to form an opening exposing the first insulating layer; partially removing the first insulating layer while leaving a support portion in contact with the substrate; forming a core layer on the support portion of the insulating layer, wherein the core layer includes sp2 and sp3 carbon atoms; and forming a hydrogen barrier layer on the core layer.

Description

Technical Field

[0001] The embodiments of the present invention relate to a protective film for a photomask and a method for manufacturing the same. Prior Technology

[0002] A protective film is a thin, transparent film stretched over a frame bonded to one side of a reticle to protect a pattern on the reticle from damage, dust, and / or moisture. In extreme ultraviolet (EUV) lithography, a protective film with high transparency, high mechanical strength, low thermal expansion, and resistance to hydrogen radicals in the EUV wavelength is typically required. Summary of the Invention

[0003] According to an embodiment of the present invention, a method for manufacturing a protective film includes: depositing a first insulating layer on a substrate; partially removing the substrate to form an opening exposing the first insulating layer; removing the first insulating layer through a remaining portion of the substrate to expose a portion to form a protective film boundary; forming a core layer on the protective film boundary, wherein the core layer includes sp2 bonds and sp3 bonds; and forming a hydrogen barrier layer that at least partially covers the core layer.

[0004] According to an embodiment of the present invention, a method for manufacturing a protective film includes: providing a substrate having a first surface and a second surface opposite to the first surface; forming a first hydrogen barrier layer that at least partially covers the first surface of the substrate; depositing a core layer on the first hydrogen barrier layer, wherein the core layer includes sp2 bonds and sp3 bonds; forming a second hydrogen barrier layer that at least partially covers the core layer to form a protective film; and partially removing the substrate to form a protective film boundary coupled to the protective film.

[0005] According to an embodiment of the present invention, a protective film includes: a core layer of a carbon nanostructure comprising a combination of sp2 and sp3 bonds; and a hydrogen barrier material distributed in the core layer, wherein the hydrogen barrier material comprises a transition metal selected from Group IV or Group V of the periodic table. Simple Explanation of the Diagram

[0006] [] The nature of this disclosure is better understood by reading in conjunction with the accompanying drawings. It should be noted that, according to standard industry practice, the various components are not drawn to scale. In fact, for clarity of explanation, the dimensions of the various components may be arbitrarily increased or decreased. []

[0007] Figure 1 is a schematic diagram of one of the exposure tools according to some embodiments of the present disclosure.

[0008] Figure 2 is a schematic cross-sectional view of one of the following embodiments of the present disclosure: a photomask, a protective film, and a frame for supporting the protective film on the photomask.

[0009] Figure 3 is a schematic bottom view of a protective film and a frame according to some embodiments of the present disclosure.

[0010] Figure 4 is a graph illustrating the Raman spectra of a core layer in a protective film according to some embodiments of the present disclosure.

[0011] Figure 5 is a graph illustrating the work function of various materials used in the core layer according to some embodiments of the present disclosure.

[0012] Figure 6 is a graph illustrating one variation between various transition metal nitride materials exposed to hydrogen radicals and those not exposed to hydrogen radicals according to some embodiments of the present disclosure.

[0013] Figure 7 is a schematic cross-sectional view of one of the protective films according to some embodiments of the present disclosure.

[0014] Figure 8 is a schematic cross-sectional view of one of the protective films according to some embodiments of the present disclosure.

[0015] Figure 9 is a schematic cross-sectional view of one of the protective films according to some embodiments of the present disclosure.

[0016] Figure 10 is a flowchart illustrating one method of manufacturing a protective film according to some embodiments of the present disclosure.

[0017] Figures 11 to 16 are cross-sectional views of intermediate stages of a method for manufacturing a protective film according to some embodiments of the present disclosure.

[0018] Figure 17 is a schematic diagram of one of the vertical furnaces for forming nanotubes according to some embodiments of the present disclosure.

[0019] Figure 18 is a flowchart illustrating one method of manufacturing a protective film according to some embodiments of the present disclosure.

[0020] Figures 19 and 20 are cross-sectional views of an intermediate stage of a method for manufacturing a protective film according to some embodiments of the present disclosure.

[0021] Figure 21 is a flowchart illustrating one method of manufacturing a protective film according to some embodiments of the present disclosure.

[0022] Figures 22 and 23 are cross-sectional views of an intermediate stage of a method for manufacturing a protective film according to some embodiments of the present disclosure. Implementation

[0023] The following disclosure provides numerous different embodiments or instances of various components for implementing the provided subject matter. Specific examples of components and configurations are described below to simplify this disclosure. Of course, these are merely examples and are not intended to be limiting. For example, in the following description, an embodiment in which a first component is formed above or on a second component may include instances in which the first and second components are in direct contact, and embodiments in which additional components may be formed between the first and second components such that the first and second components are not in direct contact. Furthermore, reference numerals and / or letters may be repeated in various instances of this disclosure. This repetition is for simplicity and clarity and does not in itself indicate any relationship between the various embodiments and / or configurations discussed.

[0024] Furthermore, for ease of description, spatial relative terms such as "below," "under," "down," "above," "above," and similar terms are used herein to describe the relationship between one element or component and another element or component(s) illustrated in the figures. Spatial relative terms are intended to cover different orientations of the apparatus in use or operation other than those depicted in the figures. The apparatus may be oriented in other ways (rotated 90 degrees or otherwise), and the spatial relative descriptors used herein may be interpreted accordingly.

[0025] As used herein, terms such as "first," "second," and "third" describe various elements, components, areas, layers, and / or segments, but such elements, components, areas, layers, and / or segments should not be limited by these terms. These terms are used only to distinguish one element, component, area, layer, or segment from another. Terms such as "first," "second," and "third," when used herein, do not imply a sequence, order, or importance unless explicitly indicated by the context.

[0026] While the numerical ranges and parameters described in this disclosure are approximate, the values ​​presented in specific examples are reported as precisely as possible. However, any numerical value inherently contains some error due to the normality bias necessarily found in the respective test measurements. Furthermore, as used herein, the terms "substantially," "approximately," or "about" generally mean a value or range that would be expected by a person of ordinary skill (e.g., within 10%, 5%, 1%, or 0.5% of a given value or range). Alternatively, when considered by a person of ordinary skill, the terms "substantially," "approximately," or "about" mean within one acceptable standard error of the mean. It will be understood by a person of ordinary skill that the acceptable standard error can vary depending on the technique used. Except in operational / working instances, or unless otherwise expressly specified, all ranges, quantities, values, and percentages (such as those relating to material quantities, durations, temperatures, operating conditions, ratios of quantities, and similar quantities disclosed herein) should be understood to be modified in all instances by the terms “substantially,” “approximately,” or “about.” Therefore, unless indicated to the contrary, the numerical parameters set forth in this disclosure and the accompanying claims are approximate values ​​that may vary as necessary. At a minimum, each numerical parameter should be interpreted based on the reported significant figures and by applying common rounding techniques. Ranges may be expressed herein as from one endpoint to another or between two endpoints. Unless otherwise specified, all ranges disclosed herein include endpoints.

[0027] This disclosure relates to a protective film and a method for manufacturing the same. The protective film disclosed herein is used to protect a pattern of a photomask from particulate contamination. The protective film may comprise a protective film thin film containing a core layer formed of sp2 and sp3 carbon atoms to provide superior mechanical and thermal performance compared to existing materials used in manufacturing the protective film thin film. The protective film thin film further comprises a barrier layer that at least partially covers the core layer to protect the core layer from hydrogen radicals / ions generated by extreme ultraviolet (EUV) or deep ultraviolet (DUV) radiation within a lithography tool. Therefore, the pattern of the photomask remains uncontaminated, and the service life of the protective film is extended. The barrier layer may comprise, for example, transition metal nitrides or silicon carbide (SiC), wherein the transition metal may be selected from Group IV and Group V of Period IV in the periodic table.

[0028] Figure 1 is a schematic diagram of one of the exposure tools 10 according to some embodiments of the present disclosure. Referring to Figure 1, the exposure tool 10 can be used, for example, to manufacture integrated circuits. The exposure tool 10 may include a photomask stage 110, a substrate stage 120, a radiation source 130, an illumination optics module 140, and a projection optics module 150. In some embodiments, the photomask stage 110 fixes a photomask 210 and provides accurate positioning and movement of the photomask 210 during exposure operations. The substrate stage 120 supports a substrate 220 and is movable relative to the photomask 210. In some embodiments, a photoresist layer 230 is formed on the substrate 220. The photoresist layer 230 includes a radiation-sensitive material.

[0029] Radiation source 130 is configured to generate electromagnetic radiation ER_1. Radiation source 130 can be any suitable light source, such as a DUV source or an EUV source. A DUV source can generate DUV radiation with a wavelength centered at approximately 248 nm or approximately 193 nm. An EUV source can generate EUV radiation with a wavelength centered at approximately 13.5 nm. In embodiments where the exposure tool 10 includes a DUV source or an EUV source, the illumination optical module 140 and the projection optical module 150 include various reflective optical components, such as plane mirrors and / or multiple mirrors including reflective surfaces with convex spherical, concave spherical, or non-spherical shapes.

[0030] An illumination optics module 140 can be used to guide electromagnetic radiation ER_1 generated by radiation source 130 to a photomask 210. The photomask 210 is irradiated by electromagnetic radiation ER_1, wherein a pattern 212 of the photomask 210 reflects and patternes the electromagnetic radiation ER_1 to form electromagnetic radiation ER_2, thereby carrying an image of the pattern 212 on the photomask 210. A projection optics module 150 can guide electromagnetic radiation ER_2 to a photoresist layer 230. Electromagnetic radiation ER_2 can cause a chemical conversion in a selected area of ​​the photoresist layer 230. In a subsequent development step, the selected or non-selected area can be removed from the substrate 220. In this way, the pattern 212 of the photomask 210 can be transferred to the photoresist layer 230, thus forming a patterned photoresist layer. Next, the substrate 220 can be further processed through a patterned photoresist layer (e.g., the material can be removed, deposited, doped, etc.) to form a patterned layer (corresponding to the pattern of the magnification mask 210) in or on the substrate 220.

[0031] In one embodiment employing an EUV source as radiation source 130, EUV radiation is generated, for example, by illuminating a tin (Sn) droplet with a laser to form a tin plasma. In addition to generating EUV radiation, the EUV source further generates undesirable byproducts that can damage or reduce the operational efficiency of the illumination optics module 140 and the projection optics module 150. These byproducts may include high-energy ions and scattered debris from plasma formation, such as tin atoms and / or clumps / droplets. These byproducts may deposit on the reflective optics components 160 (i.e., mirrors) of the illumination optics module 140 and the projection optics module 150. Consequently, the reflectivity of the mirrors relative to EUV radiation is degraded.

[0032] One mitigation technique for reducing or removing byproducts deposited on a microscope involves the use of hydrogen radicals / ions. For example, a hydrogen-containing gas (e.g., H₂) is introduced into a chamber for receiving an exposure tool 10. During exposure operation, EUV radiation excites molecular hydrogen to form hydrogen radicals (H*) or hydrogen ions (H⁺). Some of these hydrogen radicals / ions in the exposure tool 10 react with the byproducts to form volatile hydrides, such as tin hydride, in the gas phase (at standard temperatures and pressures within the exposure tool 10). These volatile hydrides can be at least partially removed by an exhaust device or a pump. Thus, tin contamination on the microscope is removed.

[0033] Given the good condition of the photomask 210, it can be used to reproducibly imprint hundreds or thousands of substrates 220. Although efforts are made to maintain a clean environment inside the exposure tool 10, particles can still be present. Particles landing on the photomask 210 can adversely affect the pattern 212 carried by electromagnetic radiation ER_2 and transferred to the substrate 220, leading to yield problems and quality concerns. To protect the photomask 210 from particle contamination, the pattern 212 of the photomask 210 is protected by a protective film 300. The protective film 300 advantageously provides a barrier between the pattern 212 of the photomask 210 and the environment within the exposure tool 10 to prevent particles from settling on the pattern 212 of the photomask 210.

[0034] Figure 2 is a schematic cross-sectional view of a photomask 210, a protective film 300, and a frame 240 for supporting the protective film 300 on the photomask 210 according to some embodiments of the present disclosure. Figure 3 is a schematic bottom view of the protective film 300 and the frame 240 according to some embodiments of the present disclosure. Referring to Figures 2 and 3, the photomask 210 includes a main surface 214 on which a pattern 212 is formed. In some embodiments, the frame 240 is attached to the main surface 214 of the photomask 210 and surrounds the pattern 212 on the photomask 210. The protective film 300 may be positioned on the frame 240 and may be included as a protective film 320 extending over the pattern 212 of the photomask 210 to protect the pattern 212 from contaminant particles. Therefore, any contaminants that would otherwise be deposited on the pattern 212 of the photomask 210 are blocked by the protective film 320.

[0035] From a bottom view, frame 240 may have a ring shape. For example, frame 240 may have a continuous rectangular ring shape and may surround the pattern 212 on the magnifying glass 210. Alternatively, depending on the configuration of the pattern 212 on the magnifying glass 210, frame 240 may be designed to have another suitable ring shape, such as a circle, a square, or a polygon. Frame 240 may be any material with high mechanical strength, low dust attraction tendency, and low weight. Hard plastics and materials such as aluminum or aluminum alloys may be suitable materials for frame 240. Frame 240 may be made of a material with a low coefficient of thermal expansion. For example, frame 240 comprises titanium, quartz, silicon, or other suitable materials with a low coefficient of thermal expansion. Frame 240 is secured to magnifying glass 210, for example, by an adhesive layer 250 or any other suitable fixing mechanism. Adhesive layer 250 is tolerant of electromagnetic radiation ER_1 and ER_2 provided by radiation source 130 shown in FIG. 1.

[0036] Referring again to Figure 2, the protective membrane 300 includes a protective membrane boundary 310, and the protective membrane film 320 is held in place by the protective membrane boundary 310. In some embodiments, the protective membrane boundary 310 is positioned on the frame 240 and supports the protective membrane film 320 around a peripheral portion of the protective membrane film 320. The protective membrane boundary 310 can be designed in various sizes, shapes, and configurations. In some embodiments, the protective membrane boundary 310 has a rectangular ring shape similar to that of the underlying frame 240. The protective membrane boundary 310 may at least partially overlap with the frame 240. In one embodiment, the frame 240 and the protective membrane boundary 310 have a uniform width, and the frame 240 is completely overlapped by the overlying protective membrane boundary 310 to increase a coupling area and thus increase a coupling strength between the frame 240 and the protective membrane boundary 310.

[0037] The protective film boundary 310 is configured to support the protective film 320 and may include a single material layer or multiple material layers. As shown in FIG2, the protective film boundary 310 includes a substrate layer 312 and a functional layer 314, wherein the substrate layer 312 is placed between the frame 240 and the functional layer 314. The substrate layer 312 may contain a material with good mechanical strength. The substrate layer 312 may contain an elemental semiconductor material or a compound semiconductor material. In some embodiments, the substrate layer 312 contains an elemental semiconductor material such as silicon or germanium or a compound semiconductor material such as silicon carbide, gallium arsenide, indium arsenide, or indium phosphide.

[0038] Functional layer 314 supports the protective film 320. In some embodiments, functional layer 314 is attached around a peripheral portion of the protective film 320, and thus the protective film 320 is stretched over functional layer 314. In some embodiments, the protective film 320 may be attached to functional layer 314, for example, by van der Waals force. Alternatively, the protective film 320 may be glued to functional layer 314 or attached to functional layer 314 by another fixing method. Functional layer 314 contains a dielectric material, such as an oxide. Functional layer 314 may contain silicon oxide (SiO) or silicon dioxide (SiO2). The base layer 312 of the protective film boundary 310, the functional layer 314, and the frame 240 are used to position the protective film 320 at a sufficient defocus distance from one of the patterns 212, such that any particles on the protective film 320 will be defocused during exposure operations and therefore will not be projected onto the substrate 220.

[0039] During exposure, when a protective film has low transmittance and / or high reflectance to electromagnetic radiation ER_1 and ER_2, electromagnetic radiation ER_2 may not be able to sufficiently reach the deep portion of the photoresist layer 230 (i.e., the portion near the substrate 220), and thus one or more defective exposure areas are likely to appear at the bottom of the photoresist layer 230. Therefore, the protective film 320 needs to transmit electromagnetic radiation ER_1 and ER_2 with high transmittance. In some embodiments, the protective film 320 has a transmittance of about 92% or higher in a wavelength range below about 250 nm. For example, the protective film 320 may have a transmittance between about 92% and about 94% relative to electromagnetic radiation with a wavelength of 13.5 nm. In some embodiments, the protective film 320 exhibits a reflectance of less than about 20% in a wavelength range below about 250 nm. For example, the protective film 320 may have a reflectance equal to or less than 0.05% relative to electromagnetic radiation in the EUV wavelength range. In another example, the protective film 320 has a reflectivity of less than about 0.01% relative to electromagnetic radiation with a wavelength of about 13.5 nm.

[0040] The protective film 320 further requires a high refractive index (close to 1) and a low extinction coefficient (essentially zero). The refractive index (n) determines the degree to which the path of electromagnetic radiation is bent or refracted as it enters the protective film 320. The extinction coefficient (k) refers to the amount of electromagnetic radiation absorbed by the protective film 320. Herein, the refractive index and extinction coefficient are defined relative to EUV radiation (such as 13.5 nm) used in the exposure tool 10 shown in FIG. 1. In some embodiments, the protective film 320 has a refractive index between about 0.85 and about 1. In some embodiments, the protective film 320 has an extinction coefficient between about 0 and about 0.02.

[0041] The protective film 320 may include a core layer 322, an insulating layer 326, and a hydrogen barrier layer 328. The core layer 322 is a carbon substrate with an amorphous structure, wherein sp3 bonds and sp2 bonds are present in a mixed configuration. In some embodiments, the ratio of sp2 bonds to sp3 bonds (i.e., sp2 / sp3) is between about 0.01 and about 100. A hardness and a residual stress can be controlled by changing the sp2 / sp3 ratio. As the sp3 content increases, the core layer 322 becomes harder, but more residual compressive stress may also be generated. Increasing the sp2 content reduces hardness and compressive strength, but increases the ductility of the core layer 322.

[0042] Referring to Figure 4, when the core layer 322 is analyzed by Raman spectroscopy, the peaks generally appear around 1332 cm⁻¹ and 1580 cm⁻¹. The spectrum around 1332 cm⁻¹ is called the D band, and it is a spectrum commonly observed in a sp³ mixed orbital. The spectrum around 1580 cm⁻¹ is called the G band, and it is a spectrum commonly observed in a sp² mixed orbital.

[0043] Referring again to Figures 2 and 3, the core layer 322 may comprise a plurality of nanotubes 324 randomly arranged to form a network structure. Each nanotube 324 intersects with one or more other nanotubes 324 to form a porous and interwoven structure. For example, the core layer 322 comprises interwoven carbon nanotubes with gaps 323 between them. Thus, the core layer 322 can be a porous core layer. The protective film 320 comprising carbon nanotubes 324 is a promising option with high EUV transmittance, low reflectance, and good mechanical stability.

[0044] In some embodiments, the carbon nanotube 324 may be conformally coated with an insulating layer 326. For example, the carbon nanotube 324 may be conformally oriented around one of its peripheries. The insulating layer 326 may surround and contact the carbon nanotube 324. The carbon nanotube 324 may be completely wound around the insulating layer 326. In one example, the insulating layer 326 comprises an inorganic material, such as silicon oxynitride (SiON). When the insulating layer 326 is laminated on the outer surface of the nanotube 324, oxidation of the core layer 322 is inhibited during EUV irradiation or during storage of the protective film 300.

[0045] In some embodiments, the hydrogen barrier layer 328 at least partially covers the insulating layer 326. The hydrogen barrier layer 328 on the insulating layer 326 may have a coverage in the range of about 10% to about 100% on the insulating layer 326. The hydrogen barrier layer 328 helps protect the core layer 322 from the effects of hydrogen radicals / ions, which are used to reduce or remove byproducts deposited on the mirrors of the illumination optical module 140 and the projection optical module 150. Thus, the service life of the core layer 322 and therefore the protective film 320 can be extended. The carbon-based core layer 322 can be protected by the hydrogen barrier layer from damage by hydrogen radicals / ions.

[0046] In some embodiments, the hydrogen barrier layer 328 comprises a metal nitride. The hydrogen barrier layer 328 may comprise a nitride of a transition metal selected from Group IV and Group V of the periodic table. For example, the hydrogen barrier layer 328 is made of or contains a transition metal nitride of a metallic element such as titanium (Ti), vanadium (V), zirconium (Zr), hafnium (Hf), niobium (Nb), or tantalum (Ta). The hydrogen barrier layer 328 may comprise oxygen, nitrogen, and a transition metal.

[0047] Figure 5 is a graph illustrating the work function of various materials used in the core layer according to some embodiments of the present disclosure. The various materials shown in Figure 5 include transition metal nitrides. These transition metal nitrides include titanium nitride (TiN), vanadium nitride (VN), zirconium nitride (ZrN), hafnium nitride (HfN), niobium nitride (NbN), and tantalum nitride (TaN). Transition metal nitrides are in a metastable state and tend to combine with oxygen under ambient conditions to form transition metal oxynitrides on a surface. As can be seen in Figure 5, for transition metal nitrides containing metals selected from Group IV and Group V of the periodic table, oxidation leads to an increase in the work function.

[0048] In one embodiment, a transition metal with a low work function is more reactive and therefore more likely to react with hydrogen radicals (compared to nitrogen or oxygen) to form a non-volatile byproduct. Therefore, the consumption of hydrogen radical-induced reactions can be limited to the vicinity of the material's surface. On the other hand, a transition metal with a high work function is less reactive and less likely to react with hydrogen, and therefore hydrogen radicals can more easily react with oxygen or nitrogen atoms near the material's surface to form water (H₂O) or ammonia (NH₃), which are volatile byproducts. Therefore, the consumption of hydrogen radical-induced reactions can penetrate into the hydrogen barrier layer 328 rather than stopping at the surface, thereby corroding the entire hydrogen barrier layer 328. Herein, a low work function can refer to a work function equal to or less than a first threshold voltage TR1, and a high work function can refer to a work function greater than the first threshold voltage TR1. Therefore, in some embodiments, TiN, VN, ZrN, and HfN are selected to form the hydrogen barrier layer 238. In one instance, the first critical voltage could be approximately 4.6 eV.

[0049] Figure 6 is a graph illustrating the changes in oxygen and nitrogen content of transition metal nitrides after exposure to hydrogen radicals according to some embodiments of the present disclosure. As can be seen in Figure 6, a positive value (greater than zero) indicates an increase in change, and a negative value (less than zero) indicates a decrease in change. Slight denitrification occurs in TiN and VN, with a slight decrease in transition metal oxide content. In one embodiment, the reduction in TiN and VN caused by hydrogen radicals is approximately 2 nm. Significant denitrification occurs in ZrN and HfN, with an increase in transition metal oxide content. Denitrification also occurs in NbN and TaN, but the increase in transition metal oxide content is less than that for ZrN and HfN, and greater than that for TiN and VN. Therefore, TiN and VN can be selected to form the hydrogen barrier layer 238. Thus, the hydrogen barrier layer 238 comprises a transition metal from Group IV or Group V of Period IV of the periodic table.

[0050] Figure 7 is a schematic cross-sectional view of a sheath 300A according to some embodiments of the present disclosure. Referring to Figure 7, in some embodiments, the sheath 300A includes a sheath boundary 330 and a sheath film 332 coupled to the sheath boundary 330. The sheath boundary 330 supports the sheath film 332 around a peripheral portion of the sheath film 332. The sheath boundary 330 may have a tapered structure. For example, the width of the sheath boundary 330 gradually decreases at increasing distances from the sheath film 332. The sheath boundary 330 may be made of silicon wafers or another type of wafer.

[0051] In some embodiments, the protective film 332 includes a first hydrogen barrier layer 334, a first coating layer 336, a core layer 338, a second coating layer 340, and a second hydrogen barrier layer 342 sequentially disposed on the protective film boundary 330. The core layer 338 may have a lower surface 3382 and an upper surface 3384 opposite to the lower surface 3382, wherein the lower surface 3382 is positioned closer to the protective film boundary 330 than the upper surface 3384. The core layer 338 is a carbon substrate with an amorphous structure, wherein sp3 bonds and sp2 bonds are present in a mixed configuration. In some embodiments, the core layer 338 includes a network of carbon nanotubes configured in a mixed configuration. For example, the core layer 338 is a porous layer comprising interwoven carbon nanotubes with gaps between them.

[0052] In some embodiments, at least one of the first hydrogen barrier layer 334 and the second hydrogen barrier layer 342 further comprises an element 344 selected from the group consisting of silicon (Si), carbon (C), phosphorus (P), aluminum (Al), and niobium (Nb). Element 344 may help increase the mechanical strength of the first hydrogen barrier layer 334. In some embodiments, the atomic percentage of element 344 in the first hydrogen barrier layer 334 is between about 0.01 atomic% and about 10 atomic%. For example, the atomic percentage of element 344 in the first hydrogen barrier layer 334 is in the range of about 0.01 atomic% to about 4 atomic%.

[0053] In some embodiments, a first cladding layer 336 is disposed on the lower surface 3382 of the core layer 338, and a second cladding layer 340 is disposed on the upper surface 3384 of the core layer 338. The first and second cladding layers 336 and 340 are used to prevent oxidation of the core layer 338 during exposure operations. The first and second cladding layers 336 and 340 may comprise the same material. An exemplary material for the first and second cladding layers 336 and 340 may comprise silicon nitride.

[0054] The first and second hydrogen barrier layers 334 and 342 help protect the core layer 338 from hydrogen radicals during exposure operations, thereby extending the service life of the protective film 332. In some embodiments, the first hydrogen barrier layer 334 at least partially covers the first coating layer 336. In one example, the first hydrogen barrier layer 334 may be placed on a peripheral portion of the first coating layer 336 and may contact the protective film boundary 330, while a central portion of the first coating layer 336 may be exposed through the protective film boundary 330. The first hydrogen barrier layer 334 may have a first coverage of between about 10% and about 100% on the first coating layer 336. A first hydrogen barrier layer 334 with about 100% first coverage may cover the entire first coating layer 336. A first hydrogen barrier layer 334 with less than 100% first coverage may partially cover the first coating layer 336. Therefore, one or more portions of the first coating layer 336 may be exposed through the first hydrogen barrier layer 334.

[0055] A second hydrogen barrier layer 342 is disposed, for example, on a second coating layer 340. The second hydrogen barrier layer 342 may have a second coverage of about 10% to about 100% on the second coating layer 340. The second coverage may be the same as or different from the first coverage. In some embodiments, the first and second hydrogen barrier layers 334 and 342 comprise a transition metal from Group IV or Group V of Period IV of the periodic table. For example, the first and second hydrogen barrier layers 334 and 342 comprise titanium or vanadium. The first and second hydrogen barrier layers 334 may further comprise oxygen and nitrogen. In some embodiments, the atomic percentage of the transition metal in the first and second hydrogen barrier layers 334 and 342 is between about 25 atomic% and about 50 atomic%, the atomic percentage of oxygen in the first and second hydrogen barrier layers 334 and 342 is between about 25 atomic% and about 50 atomic%, and the atomic percentage of hydrogen in the first and second hydrogen barrier layers 334 and 342 is between about 0% and about 25%.

[0056] Figure 8 is a schematic cross-sectional view of a sheath 300B according to some embodiments of the present disclosure. Referring to Figure 8, in some embodiments, the sheath 300B includes a sheath boundary 350 and a sheath film 356 coupled to the sheath boundary 350. The sheath boundary 350 includes a substrate layer 352 and a functional layer 354 stacked on the substrate layer 352. The substrate layer 352 includes a material with good mechanical strength, such as a silicon wafer. In some embodiments, the functional layer 354 supports the sheath film 356 around a peripheral portion of the sheath film 356. The functional layer 354 may be made of a dielectric material comprising an oxide. For example, the functional layer 354 comprises silicon oxide. The functional layer 354 can be used to facilitate adhesion of the sheath film 356 to the sheath boundary 350.

[0057] In some embodiments, the protective film 356 comprises a network of nanotubes 3562 and a hydrogen barrier material 358 doped within the nanotubes 3562. The nanotubes 3562 are randomly arranged to form a porous film. The nanotubes 3562 may have an amorphous structure, wherein sp3 and sp2 bonds are present in a mixed configuration. For example, the protective film 356 comprises interwoven nanotubes 3562 with interspersed spaces 3564. In some embodiments, the hydrogen barrier material 358 comprises a transition metal nitride. The transition metal may be selected from Group IV and Group V of Period IV of the periodic table. For example, the hydrogen barrier material 358 comprises titanium or vanadium.

[0058] Figure 9 is a schematic cross-sectional view of a sheath 300C according to some embodiments of the present disclosure. Referring to Figure 9, in some embodiments, the sheath 300C includes a sheath boundary 360 and a sheath film 362 connected to the sheath boundary 360. The sheath boundary 360 supports the sheath film 362 around a peripheral portion of the sheath film 362. The sheath boundary 360 may be formed from a portion of a substrate (such as a substrate made of silicon wafer).

[0059] In some embodiments, the protective film 362 includes a first hydrogen barrier layer 364, a first coating layer 366, a core layer 368, a second coating layer 370, and a second hydrogen barrier layer 372 sequentially stacked above the protective film boundary 360. The first hydrogen barrier layer 364 may include a peripheral portion in contact with the protective film boundary 360. In some embodiments, the first hydrogen barrier layer 364 includes a carbide, such as silicon carbide (SiC).

[0060] In some embodiments, the first hydrogen barrier layer 364 at least partially covers the first cover layer 366. In one example, the first hydrogen barrier layer 364 may cover the entire lower surface of the first cover layer 366. In another example, one or more portions of the first cover layer 366 are exposed through the first hydrogen barrier layer 364. Several exposed portions of the first cover layer 366 may be covered by or exposed through a sheath boundary 360. The first cover layer 366 is made of an insulating material such as an oxide. An exemplary material of the first cover layer 366 may comprise silicon nitride. In some embodiments, the first hydrogen barrier layer 364 has a thickness T1 less than one thickness T2 of the first cover layer 366.

[0061] In some embodiments, the core layer 368 is a carbon base layer. For example, the core layer 368 is a planar layer formed of diamond-like carbon (DLC). Diamond-like carbon has an intermediate crystalline structure between diamond and graphite. The core layer 368 has an amorphous structure in which sp3 bonds and sp2 bonds are present in a mixed configuration. In some embodiments, the core layer 368 may have a thickness T3 greater than the thickness T2 of the first overlay layer 366.

[0062] In some embodiments, a second cladding layer 370 is disposed on the core layer 368. The second cladding layer 370 may comprise the same material as the first cladding layer 366 (i.e., silicon dioxide). The second cladding layer 370 may have the same thickness as the first cladding layer 366. The first and second cladding layers 366 and 370 are used to prevent oxidation of the core layer 368 during exposure operations.

[0063] The second hydrogen barrier layer 372 at least partially covers the second coating layer 370. In one embodiment, the second hydrogen barrier layer 372 has a substantially uniform thickness T4, such that the second hydrogen barrier layer 372 can have approximately 100% coverage. In another embodiment, the second hydrogen barrier layer 372 has a non-uniform thickness T4, and one or more portions of the second coating layer 370 are exposed through the second hydrogen barrier layer 372. In this embodiment, the second hydrogen barrier layer 372 has less than 100% coverage. The coverage of the first hydrogen barrier layer 364 on the first coating layer 366 may be the same as or different from the coverage of the second hydrogen barrier layer 372 on the second coating layer 370. In some embodiments, the second hydrogen barrier layer 372 comprises a material that is the same as one of the materials of the first hydrogen barrier layer 364 (i.e., silicon carbide). The first and second hydrogen barrier layers 364 and 372 help protect the core layer 368 from hydrogen free radicals during exposure operations, thereby extending the service life of the protective film 362.

[0064] Figure 10 is a flowchart illustrating a method 500 for manufacturing a protective film 300 according to some embodiments of the present disclosure. Figures 11 to 16 are cross-sectional views of intermediate stages of the method 500 for manufacturing a protective film 300 according to some embodiments of the present disclosure. In the following description, the manufacturing stages shown in Figures 11 to 16 are discussed with reference to the process steps shown in Figure 10. It should be understood that additional steps may be provided before, during, and after the steps shown in Figure 10, and some steps described below may be replaced or eliminated for additional embodiments of method 500. The order of steps may be changed.

[0065] Referring to FIG11, a substrate 302 is provided according to step S510 in FIG10. The substrate 302 may be a semiconductor substrate. In one embodiment, the substrate 302 is a bulk silicon substrate. In an alternative embodiment, the substrate 302 comprises an elemental semiconductor such as germanium, or a compound semiconductor such as silicon germanium, silicon carbide, gallium arsenide, indium arsenide, and indium phosphide. The substrate 302 may have an upper surface 3022 and a lower surface 3024 opposite to the upper surface 3022.

[0066] Referring again to FIG. 11, according to step S520 in FIG. 10, a functional layer 304 is formed on the upper surface 3022 of the substrate 302. In some embodiments, the functional layer 304 allows a subsequent layer to be formed over the substrate 302. The functional layer 304 may comprise a dielectric material, such as an oxide. In some embodiments, the functional layer 304 is formed by performing a thermal oxidation operation; therefore, the functional layer 304 comprises a material provided by the substrate 302. In an alternative embodiment, the functional layer 304 is placed over the entire upper surface 3022 of the substrate 302. The functional layer 304 may be formed to cover the upper surface 3022 of the substrate 302 by a chemical vapor deposition (CVD) operation (such as a plasma-enhanced CVD (PECVD) operation or a low-pressure CVD (LPCVD) operation). The functional layer 304 formed by thermally grown oxide can provide a high-quality semiconductor / dielectric interface for the final structure.

[0067] Subsequently, a sacrificial layer 610 is deposited on the lower surface 3024 of the substrate 302. The sacrificial layer 610 may comprise a dielectric material, such as a nitride. In one embodiment, the sacrificial layer 610 comprises silicon nitride. The sacrificial layer 610 may be formed by a PECVD operation or an LPCVD operation to cover the entire lower surface 3024 of the substrate 302. The material of the sacrificial layer 610 is not limited to the examples described herein, but may comprise various suitable materials resistant to subsequent etching operations. By way of example, the sacrificial layer 610 may comprise silicon oxynitride, silicon carbonitride, the like, or combinations thereof.

[0068] After the sacrificial layer 610 is fully formed, a photoresist mask layer 612 is formed on the sacrificial layer 610. The photoresist mask layer 612 can be used to pattern the sacrificial layer 610. In some embodiments, the photoresist mask layer 612 includes an opening 614 to expose a region of the sacrificial layer 610. For example, the photoresist mask layer 612 is formed to expose a central portion of the sacrificial layer 610 and cover a peripheral portion of the sacrificial layer 610. Forming the photoresist mask layer 612 may include forming a blanket-like photoresist layer on the sacrificial layer 610 and patterning the blanket-like photoresist layer using a lithography operation. In some embodiments, the blanket-like photoresist layer is a radiation-sensitive layer. For example, the photoresist mask layer 612 may be sensitive to DUV or EUV radiation. The lithography operation for patterning the blanket-like photoresist layer includes DUV or EUV lithography. The shape of one of the openings 614 can be adjusted as needed. In one embodiment, the opening 614 has a rectangular shape from a plan view.

[0069] Referring to FIG12, according to step S530 in FIG10, the sacrificial layer 610 is patterned to form a hard mask layer 616 on the lower surface 3024 of the substrate 302. In some embodiments, the hard mask layer 616 is formed using an etching operation. The mask layer 616 may be etched through an opening 614 to form a via 618 in the mask layer 616. The mask layer 616 is etched until a region of the substrate 302 is exposed. The etching operation may include a wet etching, a dry etching, a combination thereof, or the like. After the hard mask layer 616 is formed, the photoresist mask layer 612 is removed, for example, in an ashing and / or wet stripping operation.

[0070] Referring to FIG13, according to step S540 in FIG10, at least one removal operation is performed to partially remove the substrate 302 and the functional layer 304. Different etchants selected for specific materials of the substrate 302 and the functional layer 304 are used to remove portions of the substrate 302 and the functional layer 304 not covered by the hard masking layer through multiple etching steps. In some embodiments, the substrate 302 and the functional layer 304 are anisotropically etched by a plasma-based etching operation (such as reactive ion etching (RIE) or similar). The masking layer 616 is used to confine a high-energy plasma etching to a desired pattern within one of the vias 618.

[0071] After etching substrate 302, a central portion of substrate 302 is removed, while a peripheral portion of substrate 302 remains intact. Hereinafter, the peripheral portion of substrate 302 is referred to as a remaining substrate 312. Additionally, a portion of the functional layer 304 exposed by the remaining substrate 312 is removed, while a remaining functional layer 314 remains substantially intact. From a bottom view, the remaining substrate 312 and the remaining functional layer 314 can form a protective film boundary 310 having an annular shape.

[0072] Referring to Figure 14, according to step S550 in Figure 10, a core layer 322 is formed on the remaining functional layer 314. The core layer 322 may be a carbon substrate containing either sp2 or sp3 hybrid carbon. In some embodiments, the core layer 322 includes a network of carbon nanotubes 324. The carbon nanotubes 324 are configured in an irregular or random configuration such that the carbon nanotubes 324 can intersect each other to form gap spaces 323 between them.

[0073] In some embodiments, carbon nanotubes 324 are formed by a CVD operation. For example, the CVD operation for forming carbon nanotubes 324 is performed using a vertical furnace as shown in FIG. 17. Referring to FIG. 17, the vertical furnace can be configured to continuously produce carbon nanotubes 324 and includes a tubular chamber 410, a carbon source 412, a catalyst source 414, a feedstock source 416, a collector 418, and one or more heating elements 420. The tubular chamber 410 defines a reaction zone for forming carbon nanotubes 324. The tubular chamber 410 includes an upper portion 4102 and a lower portion 4104 opposite to the upper portion 4102. The carbon source 412 is used to supply a carbon precursor to the tubular chamber 410, and the catalyst source 414 is used to supply a catalyst to the tubular chamber 410. The feed source 416 can supply a carrier gas flow (e.g., nitride gas) to the tubular chamber 410 at a predetermined rate.

[0074] In some embodiments, a carbon precursor, a catalyst, and a carrier gas are introduced from the upper portion 4102 of the tubular chamber 410 into the reaction zone. A heating element 420 may be positioned around and configured to heat the tubular chamber 410, thereby causing the carbon precursor to evaporate. In some embodiments, carbon nanotubes 324 are synthesized in the reaction zone, and aggregates of the carbon nanotubes 324 and the carrier gas descend to the lower portion 4104 of the tubular chamber 410. The aggregates of the carbon nanotubes 324 are wound to form a network structure. The aggregates of the carbon nanotubes 324 may be collected, for example, by means of a collector 418, at the lower portion 4104 of the tubular chamber 410.

[0075] Referring to Figure 15, according to step S560 in Figure 10, an insulating layer 326 is deposited on the core layer 322. In some embodiments, the carbon nanotube 324 may be coated with the insulating layer 326. The insulating layer 326 may comprise silicon nitride. The insulating layer 326 may be formed or deposited by a CVD operation, a physical vapor deposition (PVD) operation, an atomic layer deposition (ALD) operation, or another suitable deposition operation.

[0076] Referring to Figure 16, according to step S570 in Figure 10, a hydrogen barrier layer 328 is deposited to at least partially cover the insulating layer 326. The hydrogen barrier layer 328 may contain a material layer that resists hydrogen free radicals. The hydrogen barrier layer 328 contains a transition metal selected from Group IV and Group V of Period IV of the periodic table. For example, the hydrogen barrier layer 328 contains titanium or vanadium. The hydrogen barrier layer 328 may have a coverage of about 10% to about 100% on the insulating layer 326. The coverage of the hydrogen barrier layer 328 on the insulating layer 326 can be determined based on DUV or EUV transmittance. A protective film containing an insulating layer 326 completely covered by the hydrogen barrier layer 328 may have lower transmittance performance than a protective film containing an insulating layer 326 only partially covered by the hydrogen barrier layer 328. The hydrogen barrier layer 328 can be formed or deposited by a CVD operation, a PVD operation, an ALD operation, or another suitable deposition operation. After the hydrogen barrier layer 328 is fully formed, the hard mask layer 616 is removed by any suitable technique (such as wet etching). Thus, the protective film 300 is fully formed. As illustrated in FIG16, the protective film 300 includes an insulating layer 326 completely covered by the hydrogen barrier layer 328, while the insulating layer 326 illustrated in FIG2 and FIG3 is partially covered by the hydrogen barrier layer 328.

[0077] Figure 18 is a flowchart illustrating a method 700 for manufacturing a protective film 300A according to some embodiments of the present disclosure. Figures 19 and 20 are cross-sectional views of intermediate stages of the method 700 for manufacturing a protective film 300A according to some embodiments of the present disclosure. In the following description, the manufacturing stages shown in Figures 19 and 20 are discussed with reference to the process steps shown in Figure 18. It should be understood that additional steps may be provided before, during, and after the steps shown in Figure 18, and some steps described below may be replaced or eliminated for additional embodiments of method 700. The order of steps may be changed.

[0078] Referring to FIG19, a substrate 302 is provided according to step S710 in FIG18. The substrate 302 includes an upper surface 3022 and a lower surface 3024 opposite to the upper surface 3022. The substrate 302 may be a portion of a semiconductor wafer (e.g., a silicon wafer). The substrate 302 may be composed of any semiconductor material, including but not limited to a silicon-containing semiconductor material, a germanium-containing semiconductor material, or any combination thereof.

[0079] Subsequently, according to step S720 in FIG18, a first hydrogen barrier layer 334 is formed on the upper surface 3022 of the substrate 302. The first hydrogen barrier layer 334 may be deposited to at least partially cover the upper surface 3022 of the substrate 302. In one example, the first hydrogen barrier layer 334 may have a uniform thickness to cover the entire upper surface 3022 of the substrate 302. In another embodiment, the first hydrogen barrier layer 334 on the upper surface 3022 of the substrate 302 may have a non-uniform thickness, and one or more regions of the upper surface 3022 of the substrate 302 may be exposed through the first hydrogen barrier layer 334. The uniformity of the first hydrogen barrier layer 334 may vary depending on a deposition duration. For example, a longer deposition duration may be required to adequately cover the upper surface 3022 of the substrate 302, which may result in the first hydrogen barrier layer 334 having a substantially uniform thickness. In some embodiments, the first hydrogen barrier layer 334 comprises oxygen, hydrogen, and a transition metal selected from Group IV and Group V of Period IV in the periodic table. The first hydrogen barrier layer 334 is formed by CVD, PVD, ALD, and / or other suitable methods.

[0080] After depositing the first hydrogen barrier layer 334, an implantation operation can be performed according to step S730 in FIG18 to implant dopant 335 into the first hydrogen barrier layer 334. Dopant 335 may be selected from the group consisting of silicon, carbon, boron, phosphorus, aluminum and niobium. In some embodiments, the atomic percentage of dopant 335 in the first hydrogen barrier layer 334 is between about 0.01 atomic% and about 10 atomic%.

[0081] Method 700 continues to step S740, wherein a first cladding layer 336 is deposited to cover at least a portion of the first hydrogen barrier layer 334. The first cladding layer 336 may cover one or more regions of the first hydrogen barrier layer 334 and the upper surface 3022 of the substrate 302 exposed through the first hydrogen barrier layer 334. The first cladding layer 336 is made of a dielectric material comprising oxides and nitrides. In one example, the first cladding layer 336 comprises silicon oxynitride. The first cladding layer 336 is formed by CVD, PVD, ALD and / or other suitable methods.

[0082] Subsequently, according to step S750 in Figure 18, a core layer 338 is formed on the first coating layer 336. The core layer 338 may contain a plurality of nanotubes that intersect each other to form a network. The core layer 338 may be formed by one of the CVD operations described above.

[0083] Method 700 continues to step S760, wherein a second cladding layer 340 is deposited on the core layer 338. In some embodiments, the second cladding layer 340 covers the entire surface of the core layer 338. The second cladding layer 340 may comprise a dielectric material, such as oxide nitride. The first and second cladding layers 336 and 340 comprise the same material. The second cladding layer 340 is formed by CVD, PVD, ALD and / or other suitable methods.

[0084] Subsequently, according to step S770 in FIG18, a second hydrogen barrier layer 342 is formed on the second coating layer 340. The second hydrogen barrier layer 342 may be deposited to at least partially cover one surface 3402 of the second coating layer 340. The second hydrogen barrier layer 342 may have a uniform or non-uniform thickness. In one example, when the second hydrogen barrier layer 342 has a non-uniform thickness, one or more regions of the second coating layer 340 may be exposed through the second hydrogen barrier layer 342. The first and second hydrogen barrier layers 334 and 342 may be made of the same material. The second hydrogen barrier layer 342 is formed by CVD, PVD, ALD and / or other suitable methods.

[0085] After the second hydrogen barrier layer 342 is formed, an implantation operation is performed according to step S772 in FIG18 to implant dopant 343 into the second hydrogen barrier layer 342. The dopant 343 in the second hydrogen barrier layer 342 may be the same as or different from the dopant 335 in the first hydrogen barrier layer 334.

[0086] Subsequently, a sacrificial layer 610 is deposited on the lower surface 3024 of the substrate 302. The sacrificial layer 610 may comprise a dielectric material, such as a nitride. The sacrificial layer 610 may be formed by a PECVD operation or an LPCVD operation to cover the entire lower surface 3024 of the substrate 302. After the sacrificial layer 610 is fully formed, a photoresist mask layer 612 is formed on the sacrificial layer 610. The photoresist mask layer 612 may be used to pattern the sacrificial layer 610. In some embodiments, the photoresist mask layer 612 includes an opening 614 to expose a region of the sacrificial layer 610.

[0087] Referring to FIG. 20, according to step S780 in FIG. 18, the sacrificial layer 610 is patterned to form a hard mask layer 616 on the lower surface 3024 of the substrate 302. In some embodiments, the hard mask layer 616 is formed using an etching operation. The hard mask layer 616 may be etched through opening 614 to form a via 618 in the hard mask layer 616. The hard mask layer 616 is etched until a region of the substrate 302 is exposed. The etching operation may include a wet etching, a dry etching, a combination thereof, or similar. After the hard mask layer 616 is formed, for example, the photoresist mask layer 612 is removed in an ashing and / or wet stripping operation.

[0088] Subsequently, according to step S790 in FIG18, at least one removal operation is performed to partially remove the substrate 302. Thus, the protective film 300A shown in FIG7 is fully formed. In some embodiments, an etching operation removes a central portion of the substrate 302 not covered by the hard masking layer 616. After the etching operation, a portion of the first hydrogen barrier layer 334 is exposed. The hard masking layer 616 is then removed using any suitable technique, such as wet etching.

[0089] Figure 21 is a flowchart illustrating one method 800 for manufacturing a protective film 300B according to some embodiments of the present disclosure. Figures 22 and 23 are cross-sectional views of intermediate stages of the method 800 for manufacturing a protective film 300B according to some embodiments of the present disclosure. In the following description, the manufacturing stages shown in Figures 22 and 23 are discussed with reference to the process steps shown in Figure 21. It should be understood that additional steps may be provided before, during, and after the steps shown in Figure 21, and some steps described below may be replaced or eliminated for additional embodiments of method 800. The order of steps may be changed.

[0090] Referring to FIG22, a substrate 302 is provided according to step S810 in FIG21. In some embodiments, substrate 302 is a semiconductor substrate. For example, substrate 302 may be a silicon substrate. Substrate 302 includes an upper surface 3022 and a lower surface 3024 opposite to the upper surface 3022.

[0091] Referring again to FIG. 22, according to step S820 in FIG. 21, a first hydrogen barrier layer 364 is deposited on at least a portion of the upper surface 3022 of the substrate 302. In some embodiments, the first hydrogen barrier layer 364 comprises silicon carbide. The first hydrogen barrier layer 364 may be formed by CVD, PVD, ALD and / or other suitable methods.

[0092] Subsequently, according to step S830 in FIG21, a first coating layer 366 is deposited on the first hydrogen barrier layer 364. In some embodiments, the first coating layer 366 comprises a dielectric material, such as an oxide. For example, the first coating layer 366 may comprise silicon dioxide.

[0093] Method 800 continues to step S840, wherein a core layer 368 is deposited on the first coating layer 366. The core layer 368 may contain sp2 and sp3 carbon atoms. In some embodiments, the core layer 368 comprises carbon atoms bonded to each other by a mixture of sp3 orbitals and carbon atoms bonded to each other by a mixture of sp2 orbitals. For example, the core layer 368 may contain diamond-like carbon (DLC). The core layer 368 may be formed by CVD, PVD, or ALD.

[0094] After the core layer 368 is fully formed, a second cladding layer 370 is deposited on the core layer 368 according to step S850 in Figure 21. The second cladding layer 370 may have the same material as the first cladding layer 366.

[0095] Method 800 then proceeds to step S860, wherein a second hydrogen barrier layer 372 is deposited on the second coating layer 370. In some embodiments, the second hydrogen barrier layer 372 comprises a dielectric material. For example, the second hydrogen barrier layer 372 may have a material that is the same as that of the first hydrogen barrier layer 364.

[0096] After the second hydrogen barrier layer 372 is fully formed, a sacrificial layer 610 is deposited on the lower surface 3024 of the substrate 302. The sacrificial layer 610 may contain a dielectric material, such as a nitride. In one embodiment, the sacrificial layer 610 contains silicon nitride. After forming the sacrificial layer 610, a photoresist mask layer 612 is formed on the sacrificial layer 610. The photoresist mask layer 612 is formed on the sacrificial layer 610 by a photolithography operation comprising the steps of: applying a photoresist layer; exposing the photoresist layer through a photomask; and developing the exposed photoresist layer to form an opening 614 in a region of the exposed sacrificial layer 610.

[0097] Referring to FIG. 23, according to step S870 in FIG. 21, the sacrificial layer 610 is patterned to form a hard mask layer 616 on the lower surface 3024 of the substrate 302. In some embodiments, the hard mask layer 616 is formed using an etching operation. The hard mask layer 616 may be etched through opening 614 to form a via 618 in the hard mask layer 616. The hard mask layer 616 is etched until a region of the substrate 302 is exposed. The etching operation may include a wet etching, a dry etching, a combination thereof, or similar. After the hard mask layer 616 is formed, for example, the photoresist mask layer 612 is removed in an ashing and / or wet stripping operation.

[0098] Subsequently, according to step S880 in FIG21, the substrate 302 is partially removed to expose a portion of the first hydrogen barrier layer 364. Thus, the protective film 300C shown in FIG9 is fully formed. Next, according to step S890 in FIG21, the hard mask layer 616 is removed using any suitable method.

[0099] According to some embodiments of the present disclosure, a method for manufacturing a protective film includes the following steps: depositing a first insulating layer on a substrate; partially removing the substrate to form an opening exposing the first insulating layer; partially removing the first insulating layer to expose a portion through a remaining substrate to form a protective film boundary; forming a core layer on the protective film boundary, wherein the core layer includes sp2 and sp3 carbon atoms; and forming a hydrogen barrier layer that at least partially covers the core layer, such that a protective film thin film is formed on the protective film boundary.

[0100] According to some embodiments disclosed herein, a method for manufacturing a protective film includes the following steps: providing a substrate having a first surface and a second surface opposite to the first surface; forming a first hydrogen barrier layer that at least partially covers the first surface of the substrate; depositing a core layer on the first hydrogen barrier layer, wherein the core layer includes sp2 bonds and sp3 bonds; forming a second hydrogen barrier layer that at least partially covers the core layer to form a protective film; and partially removing the substrate to form a protective film boundary coupled to the protective film.

[0101] According to some embodiments of the present disclosure, a protective film includes a core layer and a hydrogen barrier material; the core layer includes a carbon nanostructure comprising a combination of sp2 and sp3 bonds; and the hydrogen barrier material is distributed in the core layer, wherein the hydrogen barrier material includes a transition metal selected from Group IV or Group V of the periodic table.

[0102] The foregoing overview of the features of several embodiments enables those skilled in the art to better understand the nature of this disclosure. Those skilled in the art should understand that they can readily use this disclosure as a basis for designing or modifying other procedures and structures for implementing the embodiments described herein and / or achieving the same benefits. Those skilled in the art should also recognize that such equivalent constructions do not depart from the spirit and scope of this disclosure, and that various changes, substitutions, and modifications can be made herein without departing from the spirit and scope of this disclosure.

[0103] 10: Exposure Tools 110: Reduction Mask Stage 120: Substrate stage 130: Radiation source 140: Illumination Optical Module 150: Projection Optical Module 160: Reflective optical components 210: Reduction Mask 212: Pattern 214: Main Surface 220:Substrate 230: Photoresist layer 240: Frame 250: Adhesive layer 300: Protective Film 300A: Protective Film 300B: Protective Film 300C: Protective Film 302:Substrate 304: Functional Layer 310: Protective film boundary 312: Substrate / Remaining substrate 314: Functional Layer 320: Protective film 322: Core Layer 323: Gap space 324: Carbon Nanotubes 326: Insulation layer 328: Hydrogen barrier layer 330: Protective film boundary 332: Protective film 334: First hydrogen barrier layer 335: Dopant 336: First coating layer 338: Core Layer 340: Second coating layer 342: Second hydrogen barrier layer 343: Dopant 344: Element 350: Protective film boundary 352: Basal layer 354: Functional Layer 356: Protective film 358: Hydrogen Barrier Materials 360: Protective Film Boundary 362: Protective Film 364: First Hydrogen Barrier Layer 366: First coating layer 368: Core Layer 370: Second coating layer 372: Second hydrogen barrier layer 410: Tubular chamber 412: Carbon source 414: Catalyst Source 416: Source of raw materials 418: Collector 420: Heating component 500: Methods 610: Sacrifice Layer 612: Photoresist masking layer 614: Opening 616: Hard mask layer 618: Through hole 700: Method 800: Method 3022: Top surface 3024: Lower surface 3382: Lower surface 3384: Upper surface 3562: Nanotube 3564: Gap space 4102: Upper Part 4104: Lower Part ER_1: Electromagnetic radiation ER_2: Electromagnetic radiation S510: Steps S520: Steps S530: Steps S540: Steps S550: Steps S560: Steps S570: Steps S710: Steps S720: Steps S730: Steps S740: Steps S750: Steps S760: Steps S770: Steps S772: Steps S780: Steps S790: Steps S810: Steps S820: Steps S830: Steps S840: Steps S850: Steps S860: Steps S870: Steps S880: Steps S890: Steps T1: Thickness T2: Thickness T3: Thickness T4: Thickness

Claims

1. A method for manufacturing a protective film, comprising: A first insulating layer is deposited on a substrate; Partial removal of the substrate to form an opening that exposes one of the first insulating layers; The first insulating layer is removed to expose a portion of the substrate to form a protective film boundary; a core layer is formed on the protective film boundary, wherein the core layer includes sp2 and sp3 bonds; a second insulating layer is deposited on the core layer; and a hydrogen barrier layer is formed, which at least partially covers the core layer, wherein the second insulating layer is located between the carbon nanotubes of the core layer and the hydrogen barrier layer.

2. The method of claim 1, wherein the coverage of the hydrogen barrier layer on the core layer is between about 10% and about 100%.

3. The method of claim 1, wherein the hydrogen barrier layer comprises a transition metal selected from Group IV and Group V of the periodic table.

4. The method of claim 3, wherein the transition metal is selected from period IV of the periodic table.

5. A method for manufacturing a protective film, comprising: A substrate is provided having a first surface and a second surface opposite to the first surface; A first hydrogen barrier layer is formed, at least partially covering one of the first surfaces of the substrate; a core layer is deposited on the first hydrogen barrier layer, wherein the core layer includes sp2 and sp3 bonds; a second hydrogen barrier layer is formed, at least partially covering the core layer, to form a protective film; a first insulating layer is deposited between the core layer and either the first or second hydrogen barrier layer, wherein the first insulating layer is distributed between the carbon nanotubes of the core layer and the first or second hydrogen barrier layer; and the substrate is partially removed to form a protective film boundary coupled to the protective film.

6. The method of claim 5, wherein the core layer comprises diamond-like carbon (DLC), and the first and second hydrogen barrier layers comprise: A membrane is applied to the core layer; and a passivation film placed on the coating film, wherein the coating film and the passivation film include silicon-containing dielectric materials.

7. The method of claim 5, wherein the core layer comprises a carbon nanotube (CNT) material, the method further comprising: A second insulating layer is deposited between the core layer and the other of the first hydrogen barrier layer or the second hydrogen barrier layer, wherein the second insulating layer is distributed between the carbon nanotube of the core layer and the other, wherein the coverage of one of the first and second hydrogen barrier layers is between about 10% and about 100%, wherein the first and second hydrogen barrier layers comprise a transition metal of group IV or group V in period IV of the periodic table.

8. The method of claim 5, further comprising: The hydrogen barrier layer is doped with a dopant selected from one of the groups consisting of silicon, carbon, boron, phosphorus, aluminum and niobium.

9. A protective film, comprising: A core layer, which comprises a combination of carbon nanostructures and either sp2 or sp3 bonds; A hydrogen barrier material is distributed in the core layer, wherein the hydrogen barrier material includes a transition metal selected from Group IV or Group V of the periodic table; and an insulating layer is distributed between the carbon nanotubes of the core layer and the hydrogen barrier material.

10. The protective film of claim 9, wherein the hydrogen barrier material further comprises oxygen and hydrogen.

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