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 .
This application has been assigned to a new examiner. Rejections of the previous action not repeated below are withdrawn based upon the amendment and arguments of the applicant. Response to the arguments are presented after the first rejection they are directed to.
The following is a quotation of 35 U.S.C. 112(b):
(b) CONCLUSION.—The specification shall conclude with one or more claims particularly pointing out and distinctly claiming the subject matter which the inventor or a joint inventor regards as the invention.
The following is a quotation of 35 U.S.C. 112 (pre-AIA ), second paragraph:
The specification shall conclude with one or more claims particularly pointing out and distinctly claiming the subject matter which the applicant regards as his invention.
Claims 30 and 40-47 are rejected under 35 U.S.C. 112(b) or 35 U.S.C. 112 (pre-AIA ), second paragraph, as being indefinite for failing to particularly point out and distinctly claim the subject matter which the inventor or a joint inventor (or for applications subject to pre-AIA 35 U.S.C. 112, the applicant), regards as the invention.
In claims 41, the metal nitride layer should be - - on a core of the pellicle - - , rather than “at the core of the pellicle”
Claim 44 should be dependent upon claims 43 and refer to ruthenium, moplybde4num, boron or zirconium, rather than metals broadly. (the formation of silicides of Ru, Mo, B and Zr is the function of the nitride layer)
Claims 30 and 40 do not make sense as the core layer recited in the independent claims is carbon nanotubes, not a silicon based material (the specification does not seem to support the combination)
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 41,42,46-47 are rejected under 35 U.S.C. 102(a)(2) as being fully anticipated by Kurganova et al.. WO 2019025082.
Kurganova et al.. WO 2019025082 describes a methods of coating a graphene film held in a pellicle frame with hexagonal boron nitride (h-BN) [00015-0016]. This is facilitated by exposing the graphene film to ammonia borane while heating the pellicle to a temperature where the ammonia borane breaks down [00065]. The h-BN can be one or more layers thick [00045-00046].
This reference is accorded its priority date of 08/03/2017.
The applicant argued that Nikipelov et al. did not teach the nitride of Mo, Ru, B, Ti or Ta.
Kurganova teaches h-BN
Claims 41,42 and 44-47 are rejected under 35 U.S.C. 102(a)(1) as anticipated by Ohkubo et al. TW 201631199
Ohkubo et al. TW 201631199 (machine translation attached) teaches the pellicle film is not limited to a single layer, and may have a laminated structure. For example, a three-layer laminated structure of a first tantalum nitride layer, a polygermanium layer, and a second tantalum nitride layer. When the pellicle film has a three-layered structure of a first tantalum nitride layer, a polysilicon layer, and a second tantalum nitride layer, tantalum nitride can be formed to be 1 nm or more and 5 nm or less, and polycrystalline germanium can be formed to 30 nm or more and 60. Below nm, tantalum nitride can be formed to be 1 nm or more and 5 nm or less. More preferably, the tantalum nitride is formed to be 1.5 nm or more and 3 nm or less, the polycrystalline germanium is formed to be 30 nm or more and 50 nm or less, and the tantalum nitride is formed to be 1.5 nm or more and 3 nm or less [0037]. 7(a) and 7(b) are schematic views showing a state in which the pellicle film 202 is formed on the substrate 200. In the present embodiment, first, a 5 nm tantalum nitride 204 is formed by a CVD method (Chemical Vapor Deposition) on a 725 μm thick, 8 inch germanium wafer 200, and a 60 nm polysilicon 206 is formed thereon. And 5 nm of tantalum nitride 208 is formed thereon, thereby forming a pellicle film 202 (S201) [0070].
At some point during the deposition of the second TaN layer, that layer has a thickness of less than 1.5 nm.
The applicant argued that Nikipelov et al. did not teach the nitride of Mo, Ru, B, Ti or Ta.
Ohkubo et al. TW 201631199 teaches TaN
Claims 41,42 and 45-47 are rejected under 35 U.S.C. 102(a)(1) as anticipated by Singh 20130250260.
Singh 20130250260 teaches with respect to figure 1B, a pellicle with a h-BN layer as 16A and 16B [0027].
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FIG. 1D depicts another illustrative example of a pellicle 100 that is comprised of the low-absorption material layer 12 and five layers of h-BN (16A-16E). In this embodiment, two layers of h-BN (16A and 16C) are positioned above the low-absorption material layer 12 while the three layers of h-BN (16B, 16D and 16E) are formed below the low-absorption material layer 12. Of course the use of the letter designations (e.g., A-E) for the layers of graphene 14 and the h-BN layers 16 in all of the various embodiments disclosed herein should not be understood to imply any particular order of manufacture or arrangement. The graphene and/or h-BN layers may also be symmetrically positioned about the low-absorption material layer 12, e.g., 2-10 layers on each side of the low-absorption material layer 12 [0032]. FIG. 1F depicts an illustrative example of a pellicle 100 that is comprised of mixed layers of graphene 14 and h-BN 16. More specifically, in this illustrative embodiment, the pellicle is comprised of three layers of graphene (14A, 14B and 14C) and two layers of h-BN 16 (16A, 16B). In this example, the layer of h-BN 16A is sandwiched between the layers of graphene 14A, 14C. Also in this example, the layer of graphene 14A contacts the upper surface of the low-absorption material layer 12, while the layer of h-BN 16B contacts the lower surface of the low-absorption material layer 12 [0034]
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At some point during the deposition of the h-BN layer, that layer has a thickness of less than 1.5 nm.
The applicant argued that Nikipelov et al. did not teach the nitride of Mo, Ru, B, Ti or Ta.
Singh 20130250260 teaches h-BN
Claims 41-42 and 45-47 are rejected under 35 U.S.C. 102(a)(1) as anticipated by Peter et al. WO 2017067813.
Peter et al. WO 2017067813 teaches with respect to figure 44, the formation a capping layers (402,404) on the graphene core (2) where the capping layer can be Ru, Mo, B, MoSi.sub.2, h-BN (hexagonal boron nitride), Hf0.sub.2, Zr0.sub.2, Y.sub.20.sub.3, Nb.sub.20.sub.5, La.sub.20 , and A1.sub.20.sub.3, although other high k dielectric materials could be used [00202]. The capping layer 402,404 protects the at least one graphene layer 2 from chemical attack by radical species such as hydrogen, oxygen and hydroxyl radical species. Such radical species are likely to be present during scanning conditions and may cause degradation of the freestanding membrane 14 in the absence of the capping layer 402,404. The inventors have performed experiments demonstrating for example the effects of exposure of graphite to a flux of hydrogen (H*) radicals. After 28 hours exposure in a hydrogen radical generator the number of holes seen in secondary electron images (SEM) was significantly greater than prior to the exposure [00201]. The capping layers can be formed by PVD, CVD or ALD. ALD is useful for forming very thin layers on the order of nm thicknesses[00203]. Figure 45 shows adhesion layers formed between the graphene layer (2) and capping layers (402,404), which can be formed by providing hydrophilic groups and reducing the sp2 bonded carbon content [00204-000205].
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In an embodiment, the method of manufacturing a pellicle is adapted so that the freestanding membrane 14 comprises a sequence of layers having different chemical compositions, wherein the sequence comprises the at least one graphene layer 2 and at least one layer of a two-dimensional material other than graphene 700. Example arrangements are depicted in Figures 71-73. A broad class of two-dimensional materials are available. When provided as a single layer, two-dimensional materials are sometimes referred to as 2D topological materials or single layer materials, and comprise a single layer of atoms. Layered combinations of different 2D materials are sometimes referred to as van der Waals heterostructures. Examples of 2D materials include graphene, graphyne, borophene, silicene, stanene, phosphorene, molybdenite, graphane, h-BN (hexagonal boron nitride), germanane, MXenes and transition metal dichalcogenides, including for example MoS.sub.2, MoSe.sub.2 and WSe.sub.2 [00222-00223]. thirdly, the one or more layers of a two-dimensional material other than graphene can improve the thermal properties of the freestanding membrane 14. The improvement may comprise reducing a heat load on the freestanding membrane 14 during use, for example by improving DUV emission characteristics. h-BN is particularly well suited to this application. h-BN has a bandgap of about 6 eV, which allows DUV emission. h-BN is also chemically inert and thermally stable up to 1500 K. Furthermore, there is a good atomic lattice match between h-BN and other two-dimensional materials (including graphene), which favors epitaxial growth of stacks including graphene starting from a two- dimensional material such as h-BN [00227]
At some point during the deposition of the h-BN layer, that layer has a thickness of less than 1.5 nm.
The applicant argued that Nikipelov et al. did not teach the nitride of Mo, Ru, B, Ti or Ta.
Peter et al. WO 2017067813 teaches h-BN
Claims 41,42 and 44-47 are rejected under 35 U.S.C. 103 as being unpatentable over Ohkubo et al. TW 201631199.
Ohkubo et al. TW 201631199 does not exemplify an embodiment where the nitride is less than 1.5 nm thick.
It would have been obvious to one skilled in the art to modify the TaN/Ge/TaN or TaN/Si/TaN pellicles by forming the TaN layer to be between 1.0 and 1.5 nm with a reasonable expectation of forming a useful pellicle based upon the disclosure of 1-5 nm as useful thicknesses at [0037]
Claims 41,43 and 45-47 are rejected under 35 U.S.C. 103 as being unpatentable over Jeon et al. 20180284599.
Jeon et al. 20180284599 teaches with respect to figure 1, the a carbon based pellicle membrane (112) provided with chemical enhancement layers to make the pellicle resistant to hydrogen plasma. each of the chemical enhancement layers 114 and 116 may be a boron (B)-based material, a silicon (Si)-based material, or a 5th period transition metal. The boron (B)-based material may include at least one selected from elemental boron, B.sub.4C, a boron oxide, and a boron nitride. The silicon (Si)-based material may include at least one selected from a silicon oxide, a silicon nitride, and a silicon oxynitride. The 5th period transition metal may be at least one selected from ruthenium (Ru), zirconium (Zr), and molybdenum (Mo) [0041-0043]. In some example embodiments, the carbon-based main layer 112 may include graphene, graphite, and/or carbon nanotubes (CNTs). The CNTs may include single wall CNTs (SWCNTs) and/or multi-wall CNTs (MWCNTs). However, example embodiments are not limited thereto [0039]. In FIG. 2, the two intermixing layers IMa and IMb are shown as having the same width, but widths of the intermixing layers IMa and IMb may be different from each other. For example, the pellicle membrane 110 may have an asymmetrical concentration profile with respect to the center line CL. In some example embodiments, the first intermixing layer IMa may be thicker than the second intermixing layer IMb. In other example embodiments, the first intermixing layer IMa may be thinner than the second intermixing layer IMb [0052]. The thicknesses of the first chemical enhancement layers 114 and 114m and the second chemical enhancement layers 116 and 116m may be in a range of about 1 nm to about 10 nm [0068]. Referring to FIGS. 3 and 4, the first chemical enhancement layer 114 and the second chemical enhancement layer 116 may be each formed of two layers 114a, 114b, 116a, and 116b. Here, an example of the first chemical enhancement layer 114 and the second chemical enhancement layer 116 being chemical enhancement layers of a boron-based material will be described [0054]
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Jeon et al. 20180284599 does not exemplify a pellicle where a boron nitride layer is present.
With respect to claims 41,46 and 47, it would have been obvious to one skilled in the art to form the pellicle of figures 1 or 2 where the protective layers 114 and/or 116 are formed of boron nitride with a reasonable expectation of forming a useful pellicle based upon the disclosure at [0041-0043].
With respect to claims 41 and 45-47, it would have been obvious to one skilled in the art to form the pellicle of figures 1 or 2 where one protective layers 114 and/or 116 is formed of boron nitride and the other is formed of boron, boron carbide, a silicon (Si)-based material, or a 5th period transition metal with a reasonable expectation of forming a useful pellicle based upon the disclosure at [0041-0043].
With respect to claims 41,43 and 45-47, it would have been obvious to one skilled in the art to form the pellicle of figures 1 or 2 where the protective layers 114b and/or 116b are formed of boron nitride and protective layers 114 and/or 116a are formed of elemental boron, ruthenium (Ru), zirconium (Zr), or molybdenum (Mo) with a reasonable expectation of forming a useful pellicle based upon the disclosure at [0041-0043].
The applicant argued that Nikipelov et al. did not teach the nitride of Mo, Ru, B, Ti or Ta.
Jeon et al. 20180284599 teaches BN.
Claims 41 and 43-47 are rejected under 35 U.S.C. 103 as being unpatentable over Chui et al. 20170090278.
Chui et al. 20170090278 teaches with respect to figure 1, a pellicle including a linear layer (104), a layered material (106) and a cap layer. The linear layer and the cap layer can be the same or different and are selected form silicon, silicon oxide, silicon nitride, silicon carbide, ruthenium, lanthanum, molybdenum or combinations of these. The layered layer (106) can be graphene, boron nitride, a transition metal dichalcogenide ore the like [0049-0051].
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Chui et al. 20170090278 does not exemplify a pellicle where a boron nitride layer is present.
With respect to claims 41 and 45-47, it would have been obvious to one skilled in the art to form the pellicle of figure 1B where layer (106) is formed of boron nitride with a reasonable expectation of forming a useful pellicle based upon the disclosure at [0049-0051].
With respect to claims 41 and 43-47, it would have been obvious to one skilled in the art to form the pellicle of figure 1B where layer (104) is silicon, layer (106) is formed of boron nitride and layer (108) is ruthenium or molybdenum with a reasonable expectation of forming a useful pellicle based upon the disclosure at [0049-0051].
The applicant argued that Nikipelov et al. did not teach the nitride of Mo, Ru, B, Ti or Ta.
Chui et al. 20170090278 teaches BN.
Claims 21,22,24,29,30,31,35-38 and 40-49 are rejected under 35 U.S.C. 103 as being unpatentable over Gallagher et al. 20180329289.
Gallagher et al. 20180329289 teaches coating over carbon nanotubes which may include bonding between coatings formed on CNTs [0018]. The coating can be a conformal coating with a thickness of 1-30 nm [0026-0027]. The coatings may be of a materials selected from B, B4C, ZrN, Mo, Ru, SiC, TiN or a-C or combination of these. The coating may be of multiple layers of the materials of the group. Further, the coating may protect the CNTs of the membrane from the potentially adverse process environments during its use as a pellicle in EUV lithography, for instance during hydrogen plasma cleaning processes. Moreover, by forming a coating the free-standing CNT pellicle membrane being formed may exhibit a low absorption of extreme ultraviolet light, rendering the membrane suitable for EUV applications [0028]
Gallagher et al. 20180329289 does not exemplify a pellicle with a nitride layer or a pellicle with a 0.1-6 nm nitride layer and overlying metals capping layer.
With respect to claims 41,42,44 and 46-47, It would have been obvious to one skilled in the art to form CNT pellicle with a TiN coating to protect the pellicle form being etched when used in EUV based upon the teachings at [0028]. This applies to claim 42 as the TiN coating will be less than 1.5 nm during its deposition.
With respect to claims 41,42,44 and 46-47, It would have been obvious to one skilled in the art to form CNT pellicle with a 1 to 1.5 nm TiN coating to protect the pellicle form being etched when used in EUV based upon the teachings at [0028].
With respect to claims 41 and 43-47, It would have been obvious to one skilled in the art to form CNT pellicle with a TiN coating, followed by a Mo, B or Ru coating to protect the pellicle form being etched when used in EUV based upon the teachings at [0028], noting the disclosure of the use of multiple layers.
With respect to claims 21,22,24,29-31,35-38 and 40-49, It would have been obvious to one skilled in the art to form CNT pellicle with a 1-1.5 nm TiN coating, followed by a Mo, B or Ru coating to protect the pellicle form being etched when used in EUV based upon the teachings at [0028], noting the disclosure of the use of multiple layers.
With respect to claims 21,22,24,29-31,35-38 and 40-49, It would have been obvious to one skilled in the art to form CNT pellicle with a 1-1.5 nm TiN coating, followed by two layers of Mo, B or Ru coating to protect the pellicle form being etched when used in EUV based upon the teachings at [0028], noting the disclosure of the use of multiple layers.
With respect to claims 30,40 and 44, the nitride layers inherently act as a barrier to reaction, but the claims do not recite a silicon layer.
The applicant argued that Nikipelov et al. did not teach the nitride of Mo, Ru, B, Ti or Ta.
Gallagher et al. 20180329289 teaches TiN. Gallagher et al. also teaches multiple coatings and carbon nanotubes.
Claims 21,22,24,29,30,31,35-38 and 40-49 are rejected under 35 U.S.C. 103 as being unpatentable over Shin et al. 20180259844.
Shin et al. 20180259844 teaches carbon based pellicle membranes which include passivation members. The carbon based material may include at least one of graphene, nanocrystalline graphene, reduced graphene oxide (rGO), carbon nanotube (CNT), fullerene, or amorphous carbon. The defects of the carbon-based material may include at least one of a grain boundary, a vacancy, an sp3 carbon (C) atom, an oxygen (O) atom, or a nitrogen (N) atom [0011-0013]. the passivation layer may include a first passivation layer and a second passivation layer. The first passivation layer may be between the frame and the pellicle membrane. The second passivation layer may be on top of the pellicle membrane and the frame. In some example embodiments, the inorganic material may include at least one of Mo, Ti, Ru, MoO.sub.x, TiN, SiN.sub.x, Ge, ZrSi.sub.2, or a transition metal chalcogenide [0023-0028,0045-0046]. The defects, at least one selected from an oxygen (O) atom, a nitrogen (N) atom, and a hydrogen (H) atom. In the case of synthesizing the CNT, acid treatment may be performed in a refining process after synthesis, and defects may be generated by the acid treatment. Since such defects of the carbon-based material have good reactivity, the protection provided by the passivation member may be advantageous in limiting and/or preventing degeneration and degradation. The passivation members PS11 and PS22 may include the same material or may include at least one different material from each other [0114]. FIGS. 13A to 13E are merely examples and other types of defects may also be present. For example, the defects may include a nitrogen (N) atom. In this case, the nitrogen atom may be bonded to the sp3 carbon in the form of NH.sub.2. In other words, in FIG. 13A, NH.sub.2 instead of OH may be bonded to the sp3 carbon. At least two of the nitrogen atom and the various types of defects described with reference to FIGS. 13A to 13E may be included in one nanocrystalline graphene or one crystal grain. Also, defects other than the above-described defects may be present. Defects of the nanocrystalline graphene may include at least one selected from an sp3 carbon atom, an oxygen atom, a nitrogen atom, and a carbon vacancy. Herein, the oxygen atom may be the oxygen atom included in OH of FIG. 13A, the oxygen atom of FIG. 13B, or the oxygen atom included in COOH of FIG. 13D, or may also be present in various forms. The nitrogen atom may be included in the form of, for example, NH.sub.2, or may also be included in various forms [0125-0126]. In a case where the nanocrystalline graphene includes nitrogen (N), an amount (content) of nitrogen (N) in the nanocrystalline graphene may be in a range of about 1 at % to about 30 at %. For example, an amount of nitrogen (N) in the nanocrystalline graphene may be in a range of about 1 at % to about 20 at % [0127].
Shin et al. 20180259844 does not exemplify a pellicle with a nitride layer.
With respect to claims 41-47, it would have been obvious to one skilled in the art to form a pellicle with a graphene, or fullerene, amorphous carbon or carbon nanotube core as taught at to introduce nitrogen containing defects as taught at [0011-0013] with a concentration of nitrogen defects being 1-30 at% as taught at [0127], followed by the formation of Mo or Ti passivation layers. The nitrogen on the surface is held to react with the Mo or Ti to form nitrides of these.
With respect to claims 21,24,29-31,35-37,40-49, it would have been obvious to one skilled in the art to form a pellicle with a carbon nanotube core as taught at to introduce nitrogen containing defects as taught at [0011-0013] with a concentration of nitrogen defects being 1-30 at% as taught at [0127], followed by the formation of Mo passivation layers. The nitrogen on the surface is held to react with the Mo to form nitrides of these.
With respect to claims 21,24,29-31,35-37,40 and 48-49, it would have been obvious to one skilled in the art to form a pellicle with a carbon nanotube core as taught at to introduce nitrogen containing defects as taught at [0011-0013] with a concentration of nitrogen defects being 1-30 at% as taught at [0127], followed by the formation of Ru passivation layers. The nitrogen on the surface is held to react with the Ru to form nitrides of these.
With respect to claims 21,22,24,30-31,35-37,40-42 and 44-48, it would have been obvious to one skilled in the art to form a pellicle with a carbon nanotube core as taught at to introduce nitrogen containing defects as taught at [0011-0013] with a concentration of nitrogen defects being 1-30 at% as taught at [0127], followed by the formation of Ti passivation layers. The nitrogen on the surface is held to react with the Ti to form nitrides of these.
The applicant argued that Nikipelov et al. did not teach the nitride of Mo, Ru, B, Ti or Ta.
Shin et al. 20180259844 teaches TiN formed in situ. Shin et al. 20180259844 also teaches multiple coatings and carbon nanotubes.
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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If attempts to reach the examiner by telephone are unsuccessful, the examiner’s supervisor, Mark F Huff can be reached at 571-272-1385. The fax phone number for the organization where this application or proceeding is assigned is 571-273-8300.
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MARTIN J. ANGEBRANNDT
Primary Examiner
Art Unit 1737
/MARTIN J ANGEBRANNDT/Primary Examiner, Art Unit 1737 January 22, 2026