Notice of Pre-AIA or AIA Status
The present application, filed on or after March 16, 2013, is being examined under the first inventor to file provisions of the AIA .
The response of the applicant has been read and given careful consideration. The amendment to the specification is approved. The rejections based upon Chao et al. 20230205073 or Le et al. 20230161261 are withdrawn based upon the statement of common ownership. Rejection of the previous office action, not repeated below are withdrawn. Responses to arguments of the applicant are presented after the first rejection they are directed to.
The following is a quotation of the first paragraph of 35 U.S.C. 112(a):
(a) IN GENERAL.—The specification shall contain a written description of the invention, and of the manner and process of making and using it, in such full, clear, concise, and exact terms as to enable any person skilled in the art to which it pertains, or with which it is most nearly connected, to make and use the same, and shall set forth the best mode contemplated by the inventor or joint inventor of carrying out the invention.
The following is a quotation of the first paragraph of pre-AIA 35 U.S.C. 112:
The specification shall contain a written description of the invention, and of the manner and process of making and using it, in such full, clear, concise, and exact terms as to enable any person skilled in the art to which it pertains, or with which it is most nearly connected, to make and use the same, and shall set forth the best mode contemplated by the inventor of carrying out his invention.
Claims 8-15 are rejected under 35 U.S.C. 112(a) or 35 U.S.C. 112 (pre-AIA ), first paragraph, as failing to comply with the written description requirement. The claim(s) contains subject matter which was not described in the specification in such a way as to reasonably convey to one skilled in the relevant art that the inventor or a joint inventor, or for applications subject to pre-AIA 35 U.S.C. 112, the inventor(s), at the time the application was filed, had possession of the claimed invention.
The specification as filed does not support the solvent treatment to form a “seamless graphitic structure”. This bonding is taught as the result of joule heating (see the prepub of thof the instant application at [0051].
In claim 10, the first nanotube material can only be carbon as the bonds in claim 8 are graphitic.
In the event the determination of the status of the application as subject to AIA 35 U.S.C. 102 and 103 (or as subject to pre-AIA 35 U.S.C. 102 and 103) is incorrect, any correction of the statutory basis (i.e., changing from AIA to pre-AIA ) for the rejection will not be considered a new ground of rejection if the prior art relied upon, and the rationale supporting the rejection, would be the same under either status.
The following is a quotation of the appropriate paragraphs of 35 U.S.C. 102 that form the basis for the rejections under this section made in this Office action:
A person shall be entitled to a patent unless –
(a)(1) the claimed invention was patented, described in a printed publication, or in public use, on sale, or otherwise available to the public before the effective filing date of the claimed invention.
(a)(2) the claimed invention was described in a patent issued under section 151, or in an application for patent published or deemed published under section 122(b), in which the patent or application, as the case may be, names another inventor and was effectively filed before the effective filing date of the claimed invention.
The following is a quotation of 35 U.S.C. 103 which forms the basis for all obviousness rejections set forth in this Office action:
A patent for a claimed invention may not be obtained, notwithstanding that the claimed invention is not identically disclosed as set forth in section 102, if the differences between the claimed invention and the prior art are such that the claimed invention as a whole would have been obvious before the effective filing date of the claimed invention to a person having ordinary skill in the art to which the claimed invention pertains. Patentability shall not be negated by the manner in which the invention was made.
Claims 1-10 and 13-20 are rejected under 35 U.S.C. 103 as being unpatentable over Timmermans et al. WO 2023117853, in view of Timmermans et al. 20180329291.
Timmermans et al. WO 2023117853 in figure 4 shows SEM images of mostly continuous ALD coatings on a film of DWCNTs pre-treated with UV-ozone. The left and pre-coated by e-beam evaporation. Fig. 5 shows by way of example SEM images of two types of mostly continuous coatings (left and center view) and a partial coating (right view)
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The film may be formed by a network of overlapping/crossing bundles of CNTs. At least some of the CNT bundles of the film may be mutually bonded (i.e. at overlaps I crossings). A “CNT bundle” as used herein refers to a number of aligned and intertwined CNTs (which may be single-, double- or multi-walled). The CNTs of a bundle may further be bonded to each other by Van der Waals-type bonding. The bonding between CNTs of crossing bundles may be of a Van der Waals-type or of a cross-linking type (e.g. covalently cross-linked) (3/13-20).
An average number of CNTs per bundle of at least 5 may contribute to an improved mechanical stability of the pellicle membrane, as well as an improved expected lifetime by enabling the pellicle membrane to withstand an increased number of cycles or amount of time in the hydrogen environment typical for EUVL scanners (2/21-25).
The presence of SWCNTs and/or DWCNTs may contribute to favorable structural and optical properties (e.g. high EUV transmission and low scattering). The MWCNTs may contribute to an increased heat dissipation. Since thermal emissivity is dependent on the size and shape of the object, the heat dissipation of the MWCNTs may be expected to exceed the heat dissipation of the SWCNTs or DWCNTs. The greater wall count of MWCNTs may further contribute to an increased lifetime of the pellicle membrane. Providing the MWCNTs in minority (by weight%) may further ensure that the target areal density range and CNT per bundle range is not exceeded (4/13-22).
A coating may make the CNT membrane less sensitive to exposure to the hydrogen plasma in the scanner atmosphere. This may enable an acceptable lifetime also for pellicle membranes with lower average bundle count and diameter, and lower CNT wall count, such that flare still may be controlled.
According to embodiments of a coated pellicle membrane, a coating of the pellicle membrane may comprise a coating material selected from the group of Al, B, C, Hf, La, Mo, Nb, Ru, Si, Ti, Y, or Zr; or carbides, nitrides, oxides or fluorides thereof, as well as their combinations (e.g. yttrium aluminum oxide, ZrAIOx, yttria-stabilized zirconia, YSZ, yttrium oxyfluoride, YOF).
According to embodiments, the coating may further comprise a seed material selected from the group of: C, Zr, Zr.sub.xO.sub.y, ZrN, Hf, Hf.sub.xO.sub.y, HfN, B, B4C, BN, Y, Y.sub.xO.sub.y, YN, YF.sub.Z, YOF, La, LaN, SiC, SiN, Ti, TiN, W, Be, Au, Ru, Al, Al.sub.xO.sub.y, Mo, MoN, Sr, Nb, Sc, Ca, Ni, Ni-P, Ni-B, Cu, Ag, and wherein the seed material forms a seed layer on the film of CNT bundles and the coating material forms an outer coating layer on the seed layer. These materials may provide a seeding function for a broad class of materials which may be deposited by ALD and which may form an outer coating with sufficient reliability and EUV transmission. Advantageously, the seed material and the coating material may be selected from the group of: Y seed material and Y.sub.xO.sub.y, YF.sub.Z, YOF coating materials, Zr or Zr oxide seed material and Zr.sub.xO.sub.y coating materials; B or B oxide seed material and Zr.sub.xO.sub.y coating material, Hf.sub.xO.sub.y coating material or Al.sub.xO.sub.y coating material; B4C seed material and Zr.sub.xO.sub.y coating material, Hf.sub.xO.sub.y coating material or Al.sub.xO.sub.y coating material; Zr or Zr.sub.xO.sub.y seed material and Al.sub.xO.sub.y coating material; Zr seed material and ZrAIO.sub.x coating material; Al.sub.xO.sub.y seed material and Y.sub.xO.sub.y, YF.sub.Z, Zr.sub.xO.sub.y or Hf.sub.xO.sub.y coating materials; Mo seed material and Zr.sub.xO.sub.y coating material (6/4-7/2).
Pre-treatment (or functionalization) of the CNT membrane, for example oxidation via UV-ozone exposure or anneal in a specific atmosphere, could also be applied prior to the coating with or without a seed layer. The membrane 10 (which may be coated) and the border 16 are assembled with a pellicle frame 18 (as indicated by step S14) to form the pellicle 20. The border 16 may be attached to the frame 18 for instance by an adhesive, by cold-welding or by some mechanical fixation structures such as clamps. The frame 18 may for instance be formed by Si, SiN, SiO2 or quartz. However other materials are also possible, such as metal, plastic or ceramic materials. It is also an option to omit a border and instead directly assemble the membrane 12 with the pellicle frame 18, for instance by directly attaching the membrane 12 to the frame 18 using an adhesive (9/29-10/9).
Tables III-VII exemplify 10-21 DWCNT/bundle, 3-12 MWCNT/bundles and 26 mixed CNTs/bundle
In the solvent-based approach, CNTs (e.g. synthesized using arc discharge, laser ablation or CVD) may be dispersed in a liquid solvent, such as water with an addition of a surfactant, and after bundling in liquid phase, be collected via vacuum filtration on e.g. a filtration membrane. The CNT film may subsequently be transferred to a border (e.g. the border 16). The types of CNTs forming the bundles (e.g. single- or mixed-type bundles) may be determined by the composition of CNTs in the dispersion (13/10-16).
Step S12 indicates an optional step of coating the film 12 to form a coated membrane 10. As will be disclosed in greater detail below, the coating process may comprise a pre-coating step and a subsequent second coating step to form a coated membrane having a coating 14 with a degree of coverage and uniformity desirable for ELIVL applications. However, a coating process omitting a pre-coating step is also possible. The coating 14 may as shown be formed on one or both sides 12a, 12b of the film 12 (9/15-21)
Timmermans et al. 20180329291 teaches pressing uncoated carbon nanotubes or carbon nanotube bundles with a pressure of 10-30 GPa to facilitate bonding between overlapping CNTs The bonding will take place directly between the CNTs 110 of the CNT film 104. Direct bonds, for instance co-valent bonds, may form between carbon atoms of overlapping CNTs of the CNT film 104 [0068]. The membrane can be formed of MWCNTs [0070]. To further facilitate the formation of the bonds, the CNT pellicle membrane 102 and the pellicle frame 202 may be heated while being pressed against each other. The CNT pellicle membrane 102 and the pellicle frame 202 may for example be heated to a temperature within the range of 200 to 500° C. while applying the pressure. In an example embodiment, the CNT pellicle membrane 102 and the pellicle frame 202 may be heated to a temperature below 300° C. while applying the pressure [0085,0067]. A coating is formed on the CNT pellicle membrane 102. The coating may be formed on the CNT pellicle membrane 102 in a manner as described above. The coating may be formed prior to or subsequent to the pressing of the CNT film 104, also as described above [0077]. The individual CNTs 110 (or bundles 110) of the CNT film 104 may be coated with a coating, not shown. The coating may be a metal coating of Mo. The coating may at least partially cover the CNTs 110 in the sense that the individual CNTs or the bundles are partially or completely enclosed by the coating, while still forming network of partially free CNTs within the CNT film 104, as depicted in FIG. 1. In an example embodiment, a thickness of the coating on the CNTs 110 may be within the range 1 nm to 30 nm, as this may form a reliable protection of the CNTS of the CNT film 104 from process conditions during use. In other embodiments, a coating thickness in the range of 1 to 10 nm may be used to enable both a reliable protection and a sufficient transmission to EUV radiation. The coating may be formed using any suitable technique as is known in the art, for instance by physical vapor deposition (“PVD”), chemical vapor deposition (“CVD”) or atomic layer deposition (“ALD”). Other examples of suitable coatings include B, B4C, ZrN, Ru, SiC, TiN, a-C, and graphene coatings to give a few examples. In other words, coatings of the above material may equally well be used in the above example. For EUV applications, suitable coatings could include coatings which exhibit a limited absorption of extreme ultraviolet light [0060-0061]. Accordingly, the present disclosure enables a method of forming a forming a pellicle for extreme ultraviolet lithography where the so formed pellicle exhibits a relatively high mechanical strength and low EUV light absorption. EUV light may have a wavelength in the range of 1 nm to 40 nm. More specifically, the CNT pellicle membrane of the pellicle formed according to the present disclosure may be reliable fixed or mounted to the pellicle frame of the pellicle. Moreover, by bonding together the coating of the CNT pellicle membrane and the pellicle support surface a durable bond which remains strong over time may be achieved. The so formed bond may be considered as clean in the sense that it is less prone to releasing particles, species and other elements which may contaminate e.g., a EUV scanner, as compared to standard attachment procedures relying on the use of conventional adhesives [0011].
Timmermans et al. WO 2023117853 does not exemplify treating the CNT pellicle to induce direct/covalent bonding between the carbon nanotubes.
With respect to claims 1-7 and 16-20, it would have been obvious to one skilled in the art to modify the process taught with respect to figure 4 of Timmermans et al. WO 2023117853 by pressing the uncoated DWCNTs as taught by Timmermans et al. 20180329291 at [0068,0070] to form a pellicle with high mechanical strength due to the bonding as taught at [0011] of Timmermans et al. 20180329291, noting the direction to covalent bonding between CNTs of crossing bundles of a cross-linking type (e.g. covalently cross-linked) (3/13-20) of Timmermans et al. WO 2023117853 and then forming the ZrO2 ALD coating and attaching the pellicle to the frame as taught by Timmermans et al. 20180329291. The ZrO2, is the second nanotube material.
With respect to claims 1-8 and 15-20, it would have been obvious to one skilled in the art to modify the process taught with respect to figure 4 of Timmermans et al. WO 2023117853 by pressing the uncoated DWCNTs while heating to below 300 degrees C as taught by Timmermans et al. 20180329291 at [0068,0070] to form a pellicle with high mechanical strength due to the bonding as taught at [0011] of Timmermans et al. 20180329291, noting the direction to covalent bonding between CNTs of crossing bundles of a cross-linking type (e.g. covalently cross-linked) (3/13-20) of Timmermans et al. WO 2023117853 and then forming the ZrO2 ALD coating and attaching the pellicle to the frame as taught by Timmermans et al. 20180329291. The ZrO2, is the second nanotube material.
With respect to claims 1-8,10,13 and 15-20, it would have been obvious to one skilled in the art to modify the process taught with respect to figure 4 of Timmermans et al. WO 2023117853 by pressing the uncoated DWCNTs while heating to below 300 degrees C as taught by Timmermans et al. 20180329291 at [0068,0070] to form a pellicle with high mechanical strength due to the bonding as taught at [0011] of Timmermans et al. 20180329291, noting the direction to covalent bonding between CNTs of crossing bundles of a cross-linking type (e.g. covalently cross-linked) (3/13-20) of Timmermans et al. WO 2023117853 and then forming a Zr.sub.xO.sub.y, or SiC ALD coating as taught at (6/4-7/2) of Timmermans et al. WO 2023117853 and attaching the pellicle to the frame as taught by Timmermans et al. 20180329291. The first monolayer of the coatings is the second nanotube material and the second or subsequent monolayers are considered the third nanotube material.
With respect to claims 1-10 and 13-20, it would have been obvious to one skilled in the art to modify the process taught with respect to figure 4 of Timmermans et al. WO 2023117853 by pressing the uncoated DWCNTs while heating to below 300 degrees C as taught by Timmermans et al. 20180329291 at [0068,0070] to form a pellicle with high mechanical strength due to the bonding as taught at [0011] of Timmermans et al. 20180329291, noting the direction to covalent bonding between CNTs of crossing bundles of a cross-linking type (e.g. covalently cross-linked) (3/13-20) of Timmermans et al. WO 2023117853 and then forming a BN ALD coating as taught at (6/4-7/2) of Timmermans et al. WO 2023117853 and attaching the pellicle to the frame as taught by Timmermans et al. 20180329291. The first monolayer of the BN coating is the second nanotube material and the second or subsequent BN monolayer are considered the third nanotube material.
Claims 1-20 are rejected under 35 U.S.C. 103 as being unpatentable over Timmermans et al. WO 2023117853, in view of Timmermans et al. 20180329291, further in view of Nam et al. KR 20180103775.
Nam et al. KR 20180103775 (machine translation attached) teaches the formation of carbon nanotubes using iron (Fe), cobalt (Co), nickel (Ni) and the like catalyst metal are first formed as a layer to have proper thickness on the SOI substrate. According to the present disclosure, a radio frequency (RF) magnetron sputtering method is used in forming an iron (Fe) layer to have a proper thickness. Then, the substrate with the catalyst metal put into a reaction furnace of a thermal CVD system and subjected to a thermal process. Then, the carbon nano tube is grown at high temperature while carbon gas is injected into the reaction furnace after forming the catalyst metal into fine-sized nano particles. Even in case of using the graphene, when the reinforcement layer 110 is fabricated by the same method as that of using carbon nano tube [0053]. Further, the method further includes a step of performing a heat treatment on the pellicle after the formation of Figs. 1 and 2 (a), or after the formation of Figs. 1 and 2 (b). The heat treatment is performed at a temperature of 300 ° C to 1000 ° C using a hot plate, an electric furnace, ultraviolet (EUV), extreme ultraviolet (EUV), or rapid thermal annealing (Rapid Thermal Annealing) [0091].
The combination of Timmermans et al. WO 2023117853 and Timmermans et al. 20180329291 does not describe the use of Ni, Fe or Co catalysts, or the heating of the pellicle to 1000-1200 degrees C in a furnace.
It would have been obvious to one skilled in the art to modify the embodiments rendered obvious by the combination of Timmermans et al. WO 2023117853 and Timmermans et al. 20180329291 by using known methods for forming carbon nanotubes useful in EUV pellicles such as the Ni, Fe or cobalt based catalyst taught in Nam et al. KR 20180103775 at [0053] and then subjecting the CNT pellicle film to heating at about 1000 degrees C using a furnace based upon this being known in the art from the teachings at [0091] of Nam et al. KR 20180103775 with a reasonable expectation of forming CNTs useful in the pellicle.
Further, It would have been obvious to one skilled in the art to modify the examples taught with respect to figure 4 by forming coatings of boron nitride (BN and hBN), silicon carbide (SiC), ZrO or TiO2, with the corresponding seed layers as taught at (6/4-7/2) with a reasonable expectation of forming as useful EUV nanotube pellicle where the nanotubes are protected from hydrogen degradation, to add a surfactant to promote bundle formation as taught at (13/10-16) and/or to form a second coating over the first coating based upon the disclosed at (9/15-20).
Claims 1-20 are rejected under 35 U.S.C. 103 as being unpatentable over Hsu et al. 20220260932, in view of Timmermans et al. 20180329291 and Timmermans et al. WO 2023117853
Hsu et al. 20220260932 illustrates in figure 6B embodiments of the present disclosure, the nanotube bundle 602 is coated with or surrounded by a coating layer 604. The description of materials useful for coating layers 404 and 406 above is applicable to the materials used for coating layer 604. In the embodiment illustrated in FIG. 6B, the coating layer 604 is shown as surrounding the nanotube bundle 602 but is not covering all of the surfaces of the individual nanotubes 600a-600g. In accordance with other embodiments, coating layer 604 coats more of the surfaces of the individual nanotubes 600a and 600b than is depicted in FIG. 6B. For example, coating layer 604 can coat the surfaces of nanotubes 600a-600e and 600g that are exposed on the exterior of the nanotube bundle 602. In such embodiment, the outer surface of nanotube 600f is not coated with coating layer 604. In other embodiments, the outer surface of each of the seven nanotubes 600a-600g are coated with the material making up coating layer 604. In other embodiments, the transparent layer includes individual nanotubes that have been partially or completely coated with coating layer 604, bundled to form nanotube bundle 602 and then the nanotube bundle is coated/surrounded with an additional layer of coating material 604. In some embodiments, the coating layer 604 covers the entire surface of the nanotube upon which it resides; however, in other embodiments, the coating layer covers less than the entire surface of the nanotube upon which it resides [0070].
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is a flowchart illustrating a method in accordance with the present disclosure for forming a protective, adhesion or coating layers on transparent layer 402 or a matrix of nanotubes formed into a membrane 950. In method 1000 of FIG. 11, the transparent layer 402 or a matrix of nanotubes provided as a membrane 950, e.g., on a frame or border 952 is supported, e.g., vertically, in a chamber 954 capable of carrying out a thermal ALD or CVD process and a plasma-enhanced ALD or CVD process. The transparent layer 402 or the frame 952 is supported within chamber 942 such that they have multiple freedoms of movement. For example in the embodiment illustrated in FIG. 10, frame 950 can be rotated around a vertical axis or it can be tilted around the horizontal axis. Embodiments in accordance with the present disclosure are not limited to rotating the frame around the vertical access or tilting it around the horizontal axis. In other embodiments, the frame has freedom of movement in addition to rotation around a vertical axis or tilting around the horizontal axis. Such rotation and tilting can be implemented during a thermal process and/or a plasma-enhanced process to promotes even coating of nanotubes of the membrane 950 with a coating layer, adhesion layer or protective layer. Conditions within the chamber are maintained to promote uniform deposition of the coating layer, adhesion layer or protective layer, e.g., temperatures in the range of 500 degrees Celsius to 1200 degrees Celsius. Such temperatures are provided by providing thermal energy from the chamber walls or heaters associated with the chamber walls. Embodiments in accordance with the present disclosure for forming protective, adhesion or coating layers on a matrix of nanotubes or transparent layer 402 are not limited to utilizing thermal PVD or CVD and plasma enhanced PVD or CVD. For example, such layers can be formed using ion beam deposition techniques. The description above regarding utilizing thermal PVD or CVD and plasma enhanced PVD or CVD also applies to the use of ion beam deposition. At step 1030, a protective layer is formed on the transparent layer or nanotubes of the membrane by a thermal atomic layer deposition process. The chamber 942 illustrated in FIG. 10 is an example of a chamber where both thermal atomic layer deposition and plasma enhanced atomic layer deposition can be carried out. Method 1000 is not limited to utilizing a single chamber in which both thermal and plasma enhanced atomic layer deposition is carried out. For example, in other embodiments, the thermal deposition process can be carried out in one chamber and the plasma enhanced deposition can be carried out in another different chamber [0078]. In accordance with embodiments of the present disclosure, the carbon nanotubes are single wall nanotubes or multi-walled nanotubes. In some embodiments, the nanotubes are carbon nanotubes. The nanotubes may be oriented nanotubes or they may be non-oriented nanotubes. The nanotubes may be individual, unbundled nanotubes or the nanotubes maybe be bundled individual nanotubes. Carbon nanotubes are susceptible to degradation from exposure to hydrogen gas or oxygen gas, such as the type employed during operation or maintenance of a photolithography system [0065]
Hsu et al. 20220260932 does not exemplify and embodiment where bundles of multiwalled nanotubes bonded or coated to form a pellicle membrane attached to a frame.
It would have been obvious to one skilled in the art to modify the embodiment of figures 6B of Hsu et al. 20220260932 by using the multiwalled nanotubes taught at [0065] of Hsu et al. 20220260932 as the nanotubes to form the pellicle membrane, by heating and pressing the MWCNTs as taught by Timmermans et al. 20180329291 to improve the strength of the pellicle, coating the result with ALD coating of ZrxOy, SiC, or BN as taught by Timmermans et al. WO 2023117853 and mounting it on a frame as discussed at [0078] of Hsu et al. 20220260932 with a reasonable expectation of forming a useful EUV pellicle.
Claims 1-20 are rejected under 35 U.S.C. 103 as being unpatentable over Timmermans et al. WO 2023117853, in view of Timmermans et al. 20180329291 and Nam et al. KR 20180103775, further in view of Hsu et al. 20220244634.
Hsu et al. 20220244634 describes a plurality of individual nanotubes 214 form a bundle (i.e., a string or rope-like structure). As a result, the porous thin film 212 includes a network of a plurality of bundles of nanotubes 214. A nanotube bundle may include, for example, 2-20 individual nanotubes 214. In a nanotube bundle, individual nanotubes 214 may be aligned and joined along their longitudinal directions. Nanotubes 214 of a bundle may also be joined end-to-end such that the length of the nanotube bundle is greater than the length of the individual nanotubes. The nanotubes 214 may typically be joined by van der Waals forces [0023]. In some embodiments, the nanotube core 214A is formed of a carbon nanotube, including both single wall carbon nanotube (SWCNT) and multiwall carbon nanotube (MWCNT) [0026]. The nanotube shell 214B includes a material having high resistance to oxidation and chemicals. The nanotube shell 214B thus helps to protect the nanotube core 214A from the attack by UV or EUV light and ionized gases that come in contact with the nanotube shell 214B, e.g., H+ gas. The nanotube shell 214B also serves as a thermal conductive layer which promotes the transfer of the thermal energy from the nanotube core 214A to the environment around the pellicle membrane 210. In some embodiments, the nanotube shell 214B includes a low extinction coefficient material to ensure sufficient transmission of UV or EUV light. In some embodiments, the shell material (i.e., second material) may have an extinction coefficient less than or equal to 0.02. In some embodiments, the shell material allows for the transmission of 80% or more, 85% or more, 90% or more, 95% or more of the radiation to the photomask. In some embodiments, the nanotube shell 214B may include boron nitride (BN), boron (B), boron carbide (B4C), boron carbon nitride (BCN), silicon nitride (SiN), silicon carbide (SiC), silicon boron nitride (SiBN), or silicon boron carbide (BC). In some embodiments, the nanotube shell 214B is formed of a single wall boron nitride nanotube (BNNT). In some other embodiments, the nanotube shell 214B is formed of a multiwall BNNT. The thickness of the nanotube shell 214B is controlled so that the nanotube shell 214B does not degrade the transparence of the pellicle membrane 210 to UV or EUV light while providing a reliable protection to the nanotube core 214A. In some embodiments, the nanotube shell 214B may have a thickness ranging from about 1 nm to about 10 nm. If the thickness of the nanotube shell 214B is too small, sufficient protection to the nanotube core 214A from attack by UV or EUV radiation or chemicals is not sufficient, in some instances. If the thickness of the nanotube shell 214B is too great, the transparence of the pellicle membrane 210 is degraded, in some instances. In some embodiments, the nanotube shell 214 has a thickness of 5 nm with a variation of 10% or less. In some embodiments, the nanotubes 214 may be formed by growth of one or more nanotubes of a first material inside of a nanotube template of a second material. The nanotube template of the second material acts as an encapsulating shell in which the confined second material can be restructured into at least one nanotube of the first material. The dimension of the nanotube core 214A thus is restricted by the dimension of the nanotube shell 214B. In some embodiments, the nanotube shell 214B is formed by plasma arc discharge, laser vaporization, ball-milling, laser ablation, or thermal plasma jet. The coalescence of molecules of the first material into the nanotube core inside the nanotube shell 214B may be achieved by electron beam irradiation or heat treatment [0027-0028]
In some embodiments, the nanotubes 214 may alternatively be formed by coating a nanotube core 214A with a shell material. In some embodiments, the nanotube core 214A may be formed by plasma arc discharge, laser vaporization, ball-milling, laser ablation, or thermal plasma jet. The deposition of the shell material that provides the nanotube shell 214B may be performed using a deposition process such as, for example, ion bean deposition, chemical vapor deposition (CVD), plasma enhanced chemical vapor deposition (PECVD), physical vapor deposition (PVD), or atomic layer deposition (ALD). During the deposition, the stage may be rotated or titled to ensure conformal and uniform deposition of the shell material onto the nanotube core 214A. In some embodiments and when the nanotube shell 214B includes BN, the BN shell can be formed by CVD by flowing boron (e.g., boron oxide B.sub.2O.sub.3 or boric acid H.sub.3BO.sub.3) and nitrogen (e.g., nitrogen N.sub.2, ammonia NH.sub.3, or urea CO(NH.sub.2).sub.2) precursors into a reaction chamber. In some other embodiments, the BN shell can be formed by CVD by flowing boron trihalides (boron trichloride BCl.sub.3 or boron trifluoride BF.sub.3) with N.sub.2 or NH.sub.3, diborane B.sub.2H.sub.6 with NH.sub.3, and single source precursors such as borazine B.sub.3H.sub.6N.sub.3 or ammonia borane H.sub.3NBH.sub.3. In some embodiments, the CVD may be performed at a temperature ranging from about 500° C. to about 1200 [0029]. In some embodiments, the porous thin film 212 may be formed by first forming a suspension of nanotubes 214 in a liquid medium. In some embodiments, the suspension is formed by adding nanotubes 214 into the liquid medium under mixing conditions. The mixture is then sonicated to ensure the nanotubes 214 are well dispersed in the liquid medium. The liquid medium is a non-solvent liquid medium that is non-reactive with the nanotubes 214 and in which the nanotubes 214 are virtually insoluble. The liquid medium also has a low boiling point so that the liquid medium can be easily and quickly removed, facilitating drying of the continuous nanotube network subsequently formed. Examples of suitable non-solvent liquid medium that can be used to make the nanotube suspension include, but are not limited to, water, volatile organic liquids such as acetone, ethanol, methanol, n-hexane, ether, acetonitrile, chloroform, DMF, and mixtures thereof. In some embodiments, the suspension is formed by dispersing nanotubes 214 into water. In some embodiments, the suspension may also include a surfactant to maintain the suspension and/or other chemical agents to facilitate nanotube network formation or dewatering. For example, Triton X-100 and dodecylbenzenesulfonic acid sodium salt may be used. However, sometimes, a surfactant may not be needed if the nanotube 214 can form a stable suspension in the liquid medium without it The concentration of nanotubes 214 in the suspension is controlled to facilitate dispersion and minimize agglomeration of nanotubes 214. In some embodiments, the concentration of nanotubes 214 in the suspension is less than 500 mg/L. In some embodiments, the concentration of nanotubes 214 in the suspension is from about 25 mg/L to about 150 mg/L. In some embodiments, the concentration of nanotubes 214 in the suspension is from about 40 mg/L to about 100 mg/L [0030-0032]. Referring to FIGS. 1 and 2D, the method proceeds to operation 108, in which an assembly of the pellicle membrane 210 and the pellicle border 220 is attached to a pellicle frame 230, in accordance with some embodiments. FIG. 2D is a cross-sectional view of the mask pellicle system 200 of FIG. 2C after attaching the assembly of the pellicle membrane 210 and the pellicle border 220 to the pellicle frame 230, in accordance with some embodiments.
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In addition to the basis above, it would have been obvious to one skilled int eh art to modify the pellicle or processes of forming them rendered obvious by the combination of Timmermans et al. WO 2023117853, Timmermans et al. 20180329291 and Nam et al. KR 20180103775 by using other protective coatings known in the art, such as the hexagonal BN of BNN\T taught by Hsu et al. 20220244634 with a reasonable expectation of forming a useful pellicle.
Claims 1-10 and 16-20 are rejected under 35 U.S.C. 103 as being unpatentable over Knisley et al. 20240248391, in view of Timmermans et al. WO 2023117853 and Timmermans et al. 20180329291
Knisley et al. 20240248391 teaches a carbon nanotube bundle comprises individual carbon nanotubes aligned along a predominant direction to form bundles. In some embodiments, the individual carbon nanotubes comprise or consist of single-walled carbon nanotubes. In some embodiments, the individual nanotubes comprise or consist of multi-walled carbon nanotubes. Such carbon nanotube bundles can form spontaneously during manufacture of carbon nanotube sheets or membranes, such as those available from Canatu, Vantaa, Finland. The carbon nanotube membrane may contain up to 1 atomic percent iron, which may comprise nanoparticles of iron [0033]. Knisley et al. teaches exposing the CNT membrane to a first gas and exposing the CNT membrane to a gas at 312 to form a nucleation layer at 314. Next, a protective material layer is deposited on the CNT membrane, which bonds to the nucleation layer. It was determined that the nucleation layer formation was instrumental in forming a protective layer that met one or more of the requirements described herein. For example, the protective material layer on the nucleation layer exhibits greater than 90% transmission of 13.5 nm EUV light. In some embodiments, the EUV pellicle exhibits greater than 91%, 92%, 93%, 94%, 95%, 96% or 97%. The protective coating of one or more embodiments does not degrade transmission of EUV light through the EUV pellicle at 13.5 nm more than 3% compared to an uncoated EUV pellicle. The protective coating of some embodiments provides high resistance to hydrogen plasma to protect the CNT membrane from EUV-active and EUV chamber cleaning processes. The coating of one or more embodiments remains pliable and reduces sag of the CNT membrane. According to some embodiments, the protective coated CNT membrane survives temperatures exceeding 1200° C., and the protective coating enhances emissivity of the CNT membrane. Emissivity at EUV wavelengths such as 13.5 nm refers to the ability of the CNT membrane to withstand a rapid heating and cooling process in the EUV lithography system. In one or more embodiments, the protective coating is conformal, and the protective coating minimizes process-induced damage to the CNT membrane [0034]. The protective material layer according to one or more embodiments comprises a material selected from the group consisting of molybdenum (Al), aluminum nitride (AlN), aluminum oxide (Al.sub.2O.sub.3), boron carbide (B.sub.4C), boron nitride (BN), molybdenum (Mo), molybdenum silicide (MoSi.sub.2), molybdenum carbide (MoC, Mo.sub.2C), ruthenium (Ru), ruthenium niobium alloy (RuNb), ruthenium oxide (RuO, RUO.sub.2), tantalum nitride (TaN), tantalum (Ta), yttrium nitride (YN), zirconium boride (ZrB.sub.2), zirconium silicide (ZrSi.sub.2), and silicon carbide (SiC). Each of the aforementioned coatings have high transmission at 13.5 nm. Materials with low emissivity are also desired, so that the EUV pellicle is able to withstand fast heating and cooling processes encountered in an system or tool or scanner as shown in FIG. 2. In specific embodiments, a Mo coating having a thickness of less than 4 nm provides high transmission and low emissivity at 13.5 nm. A B.sub.4C having a thickness of less than 4 nm provides high transmission and low emissivity at 13.5 nm. A BN coating having a thickness of less than 3 nm provides high transmission and low emissivity at 13.5 nm. A MoSi coating having a thickness of less than 3 nm provides high transmission and low emissivity at 13.5 nm. A SiN coating having a thickness of less than 2 nm provides high transmission and low emissivity at 13.5 nm. A Ru coating having a thickness of less than 2 nm provides high transmission and low emissivity at 13.5 nm. A MoC coating having a thickness of less than 4 nm provides high transmission and low emissivity at 13.5 nm. Each of these coatings has a minimum thickness of 0.1 nm. In some embodiments, a monolayer of Al.sub.2O.sub.3 can be utilized. In addition, each of these coatings provides protection to the CNT membrane during EUV processes [0037-0038]. The thin membrane is mounted on a frame and fixed to the photomask [0004].
Knisley et al. 20240248391 does not exemplify an embodiment where the bundles of multiwalled nanotubes are coated with a protective coating and then attached to a frame.
It would have been obvious to modify teachings of by forming the shells over bundles of oriented multiwalled nanotubes as taught at [0033] of Knisley et al. 20240248391 by heating and pressing the MWCNTs as taught by Timmermans et al. 20180329291 to improve the strength of the pellicle, coating the result with ALD coating of ZrxOy, SiC, or BN as taught by Timmermans et al. WO 2023117853 and mounting the resulting pellicle membrane on a frame as in [0004] of Knisley et al. 20240248391
The nonstatutory double patenting rejection is based on a judicially created doctrine grounded in public policy (a policy reflected in the statute) so as to prevent the unjustified or improper timewise extension of the “right to exclude” granted by a patent and to prevent possible harassment by multiple assignees. A nonstatutory double patenting rejection is appropriate where the conflicting claims are not identical, but at least one examined application claim is not patentably distinct from the reference claim(s) because the examined application claim is either anticipated by, or would have been obvious over, the reference claim(s). See, e.g., In re Berg, 140 F.3d 1428, 46 USPQ2d 1226 (Fed. Cir. 1998); In re Goodman, 11 F.3d 1046, 29 USPQ2d 2010 (Fed. Cir. 1993); In re Longi, 759 F.2d 887, 225 USPQ 645 (Fed. Cir. 1985); In re Van Ornum, 686 F.2d 937, 214 USPQ 761 (CCPA 1982); In re Vogel, 422 F.2d 438, 164 USPQ 619 (CCPA 1970); In re Thorington, 418 F.2d 528, 163 USPQ 644 (CCPA 1969).
A timely filed terminal disclaimer in compliance with 37 CFR 1.321(c) or 1.321(d) may be used to overcome an actual or provisional rejection based on nonstatutory double patenting provided the reference application or patent either is shown to be commonly owned with the examined application, or claims an invention made as a result of activities undertaken within the scope of a joint research agreement. See MPEP § 717.02 for applications subject to examination under the first inventor to file provisions of the AIA as explained in MPEP § 2159. See MPEP § 2146 et seq. for applications not subject to examination under the first inventor to file provisions of the AIA . A terminal disclaimer must be signed in compliance with 37 CFR 1.321(b).
The filing of a terminal disclaimer by itself is not a complete reply to a nonstatutory double patenting (NSDP) rejection. A complete reply requires that the terminal disclaimer be accompanied by a reply requesting reconsideration of the prior Office action. Even where the NSDP rejection is provisional the reply must be complete. See MPEP § 804, subsection I.B.1. For a reply to a non-final Office action, see 37 CFR 1.111(a). For a reply to final Office action, see 37 CFR 1.113(c). A request for reconsideration while not provided for in 37 CFR 1.113(c) may be filed after final for consideration. See MPEP §§ 706.07(e) and 714.13.
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Claims 16-20 are rejected on the ground of nonstatutory double patenting as being unpatentable over claims 1-20 of U.S. Patent No. 12153339, in view of Timmermans et al. 20180329291.
Claim 1 recites: A pellicle, comprising: a pellicle membrane including at least one porous film, the at least one porous film including a network of a plurality of nanotubes, at least one nanotube of the plurality of nanotubes including a core nanotube and a shell nanotube surrounding the core nanotube, wherein the core nanotube comprises a carbon nanotube or a bundle of a plurality of carbon nanotubes, and wherein the shell nanotube includes a compound selected from the group consisting of boron carbon nitride, silicon boron nitride and silicon boron carbide; a pellicle border attached to the pellicle membrane along a peripheral region of the pellicle membrane; and a pellicle frame attached to the pellicle border.
Claim 2 recites: The pellicle of claim 1, wherein the carbon nanotube comprises a single wall carbon nanotube or a multiwall carbon nanotube.
It would have been obvious to forming the pellicle with the core nanotube being a bundle as in claim 1 of the multiwalled nanotubes recited in claim 2, heating the CNTs to form a stronger pellicle as taught by Timmermans et al. 20180329291 coating it with a BN shell and mounted on a frame.
Claims 16-20 are rejected on the ground of nonstatutory double patenting as being unpatentable over claims 1-20 of U.S. Patent No. 12346020, in view of Timmermans et al. WO 2023117853 and Timmermans et al. 20180329291
Claim 7: recites A device comprising: a mask having a patterned surface; a pellicle frame coupled to the mask with a first adhesive layer; and a pellicle membrane having an external surface and an internal surface, the pellicle membrane coupled to the pellicle frame with a second adhesive layer, the pellicle membrane including a matrix of a plurality of nanotube bundles and a first coating layer on the external surface and a second coating layer on the internal surface, and each nanotube bundle of the plurality of nanotube bundles includes a third coating layer on the nanotube bundle, each of the plurality of nanotube bundles including nanotubes consisting of carbon atoms, nanotube bundles including nanotubes of carbon atoms and nitrogen atoms and nanotube bundles including nanotubes of carbon atoms and silicon atoms, wherein the first, second and third coating layers independently comprise a material selected from the group consisting of niobium monosilicide (NbSi), niobium silicide (NbSi.sub.2), niobium silicon nitride (NbSiN), niobium titanium nitride (NbTi.sub.xN.sub.y), molybdenum silicon nitride (MoSi.sub.xN.sub.y), yttrium fluoride (YF), titanium carbon nitride (TiC.sub.xN.sub.y), and hafnium fluoride (HfF.sub.4).
It would have been obvious to one skilled in the art to form the bundles of carbon nanotubes of the claims of multiwalled nanotubes based upon the teachings that carbon nanotubes can refer to single walled, double walled or multiwalled nanotubes in Timmermans et al. WO 2023117853 and heating the CNTs to form a stronger pellicle as taught by Timmermans et al. 20180329291 before providing the protective coating with a reasonable expectation of forming a useful pellicle.
Applicant's amendment necessitated the new ground(s) of rejection presented in this Office action. Accordingly, THIS ACTION IS MADE FINAL. See MPEP § 706.07(a). Applicant is reminded of the extension of time policy as set forth in 37 CFR 1.136(a).
A shortened statutory period for reply to this final action is set to expire THREE MONTHS from the mailing date of this action. In the event a first reply is filed within TWO MONTHS of the mailing date of this final action and the advisory action is not mailed until after the end of the THREE-MONTH shortened statutory period, then the shortened statutory period will expire on the date the advisory action is mailed, and any nonprovisional extension fee (37 CFR 1.17(a)) pursuant to 37 CFR 1.136(a) will be calculated from the mailing date of the advisory action. In no event, however, will the statutory period for reply expire later than SIX MONTHS from the mailing date of this final action.
Any inquiry concerning this communication or earlier communications from the examiner should be directed to Martin J Angebranndt whose telephone number is (571)272-1378. The examiner can normally be reached 7-3:30 pm EST.
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MARTIN J. ANGEBRANNDT
Primary Examiner
Art Unit 1737
/MARTIN J ANGEBRANNDT/Primary Examiner, Art Unit 1737 February 10, 2026