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 .
Status of the Claims
Claims 1, 2, 4-10, 16, 19, 22, 23, 26, and 27 are pending and rejected. Claims 29-31 and 34 are withdrawn. Claims 3, 11-15, 17-18, 20-21, 24-25, 28, 32-33, and 35-49 are cancelled. Claim 1 is amended.
Continued Examination Under 37 CFR 1.114
A request for continued examination under 37 CFR 1.114, including the fee set forth in 37 CFR 1.17(e), was filed in this application after final rejection. Since this application is eligible for continued examination under 37 CFR 1.114, and the fee set forth in 37 CFR 1.17(e) has been timely paid, the finality of the previous Office action has been withdrawn pursuant to 37 CFR 1.114. Applicant's submission filed on 11/24/2025 has been entered.
Claim Rejections - 35 USC § 103
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.
The factual inquiries for establishing a background for determining obviousness under 35 U.S.C. 103 are summarized as follows:
1. Determining the scope and contents of the prior art.
2. Ascertaining the differences between the prior art and the claims at issue.
3. Resolving the level of ordinary skill in the pertinent art.
4. Considering objective evidence present in the application indicating obviousness or nonobviousness.
This application currently names joint inventors. In considering patentability of the claims the examiner presumes that the subject matter of the various claims was commonly owned as of the effective filing date of the claimed invention(s) absent any evidence to the contrary. Applicant is advised of the obligation under 37 CFR 1.56 to point out the inventor and effective filing dates of each claim that was not commonly owned as of the effective filing date of the later invention in order for the examiner to consider the applicability of 35 U.S.C. 102(b)(2)(C) for any potential 35 U.S.C. 102(a)(2) prior art against the later invention.
Claims 1, 2, 4-10, 16, 19, 22-23, and 26-27 are rejected under 35 U.S.C. 103 as being unpatentable over Losego, US 2020/0325295 A1 in view of Shevchenko, US 2019/0017166 A1, Pinnau, WO 2020/222138 A1, and Palazzotto, US 2013/0229194 A1.
Regarding claims 1, 10, 16, 19, and 22, Losego teaches a process for forming an inorganic porous coating on a substrate (a method of making a hybrid membrane, 0107-0108, where the hybrid membrane comprises a microporous polymer and an atomic scale inorganic material dispersed throughout the microporous polymer within the continuous pore phase, 0078, where the hybrid membrane can comprise a film, 0102, where they are formed on substrate such as support membranes or silicon wafers, 0161 and 0176, and they have a surface area of 200 m2/g, 1800 m2-/g or more, 0095, further indicating that it will be porous or have a degree of porosity due to the high surface area, and also where they teach burning out the PIM-1 skeleton of the membrane to provide a residual microporous metal oxide structure, 0147, further indicate providing an inorganic porous coating on a substrate), comprising:
forming a polymer template having a plurality of pores comprising applying a thin film of a polymer of intrinsic microporosity on the substrate (where the membranes comprising a microporous polymer are formed as films, 0078 and 0102, and where PIM-1 thin films are formed by spin coating onto support membranes, 0161, or silicon wafers, 0176, where microporous polymers include polymers of intrinsic microporosity or PIMs, 0082, such that the PIM will be formed on a substrate to provide a polymer template having a plurality of pores); and
performing an infiltration cycle comprising:
infiltrating the pores of the polymer template with a first vapor comprising a coating precursor material, wherein the coating precursor material is a precursor for forming an inorganic coating material and the coating precursor material binds to functional groups of the polymer template (where the microporous polymer is infiltrated with the inorganic material using vapor phase infiltration using a precursor material that reacts to form the inorganic material such that it is considered to be a coating precursor material, 0108-0109, where the precursors form an adduct with the PIM-1, 0147 and Fig. 22, such that it will bind to functional groups of the polymer template, i.e., PIM-1), and
infiltrating the pores of the polymer template having the coating precursor material bound thereto with a second vapor comprising a precursor reactant, wherein the bound coating material precursor reacts with the precursor reactant to form the inorganic coating material arranged to form the porous inorganic coating (where the membrane impregnated with the precursor is exposed to a reactant, thereby forming the inorganic material, 0109, where since the precursor and the reactant result in the formation of the inorganic coating, the bound precursor is understood to react with the reactant to provide the inorganic material).
They further teach burning out the PIM-1 skeleton of the hybrid membrane to provide a microporous metal oxide structure (0147 and Fig. 27). They teach annealing an AlOx/PIM-1 hybrid hollow fiber membrane in air at 900°C, where heat treating in air combusts the polymer and leaves just and AlOx nanoporous structure (0032). They teach optimizing hybrid membrane performance by controlling the amount of metal oxide loading to balance the trade-off between chemical stability and loss of porosity (0150). They teach that the inorganic material can comprise alumina, titania, zinc oxide, etc. (0086). Losego teaches using the membranes for a variety of applications such as sensing, gas storage, etc. (0168), where hybrid membranes can be used for gas storage devices, sorbents, catalysis, sensors, and separations (0179). Therefore, Losego indicates that a variety of applications can be desirable for the membranes.
They do not teach removing the polymer when the structure is formed as a film, that the substrate has a coating, or forming multi-layered coatings.
Shevchenko teaches a method for forming a low refractive index layer on a substrate (abstract). They teach that the method includes (a) applying a block copolymer layer on a substrate, the block copolymer including a polar polymeric block and a non-polar polymeric block; (b) swelling the block copolymer layer with a solvent to increase the block copolymer layer thickness; (c) depositing a metal oxide or metalloid oxide layer on a polar polymeric block of the block copolymer layer; and (d) removing the block copolymer layer from the substrate, thereby forming a porous metal oxide or metalloid oxide layer on the substrate (abstract). They teach that the antireflective coated substrate comprises (a) a transparent material substrate, (b) a first porous metal oxide or metalloid oxide layer on the transparent material substrate, and (c) a second porous metal oxide or metalloid oxide layer above the first porous metal oxide or metalloid oxide layer as an outer layer for the antireflective coated substrate (0009). They teach depositing the metal oxide or metalloid oxide by any method that allows the metal oxide or metalloid oxide or precursors of the metal oxide or metalloid oxide to infiltrate the porosities of the polar polymeric block of the block copolymer (0036). They teach that suitable methods include ALD (0037). They teach that the metal oxide or metalloid oxide layer comprises a metal oxide or metalloid oxide selected from the group consisting of alumina, titanium dioxide, zinc oxide, and combinations thereof (0038). They teach that after the metal oxide or metalloid oxide layer is deposited, the block copolymer can be removed to provide a porous metal oxide or metalloid oxide layer on the substrate (0043). They teach that the formed porous metal oxide or metalloid oxide layer can have thickness ranging from 10-1000 nm with a porosity ranging from 10 to 90% (0044-0045 and Table 1). They teach forming a graded-index antireflective layer by performing steps (a) to (d) at least twice in succession to form at least two porous metal oxide or metalloid oxide layers having different index of refraction values (0052). They teach that each second and subsequent porous metal oxide or metalloid oxide layer can be selected to have different thickness and/or index of refraction values (0052). Therefore, Shevchenko teaches forming a graded antireflective coating by forming multiple porous metal oxide or metalloid oxide layers on a substrate.
Pinnau teaches method of fabricating thin film composite carbon molecular sieve membranes by exposing a polymer layer to a vapor-phase metal-organic precursor under vapor phase infiltration conditions such that the vapor phase metal organic precursor diffuses into the polymer layer and reacts with a functional group of the polymer to form an inorganic-organic complex; exposing the polymer layer to a vapor-phase co-reactant under vapor phase infiltration conditions such that the vapor phase co-reactant diffuses into the polymer layer ad oxidizes the organic-inorganic complex to form a metal oxide; and subjecting the polymer layer to inert-atmosphere or vacuum pyrolysis (abstract). They teach that the thin film composite carbon molecular sieve membranes are supported on a substrate (0006). They teach that exemplary polymeric precursors include polymers of intrinsic microporosity (0028). They teach that other polymer precursors include block interpolymers (0033). They teach that the polymer layer can be supported on a substrate (0034). They teach that metal-containing precursors include trimethyl aluminum, diethyl zinc, titanium isopropoxide, titanium tetrachloride, etc. (0035). They teach exposing the polymer layer or polymeric precursor to one or more vapor phase co-reactants such as water (0037). They teach that the metal oxides are dispersed on a molecular level, allowing the formation of thin films, and the weight or volume fraction of the metal oxides can be controlled, permitting the microporosity of the resulting membrane to be modulated (0018). Therefore, Pinnau teaches forming porous films by vapor phase infiltrating inorganic material into either a block polymer or a PIM.
Palazzotto teaches a sensor element that includes an absorptive dielectric layer comprising a polymer of intrinsic microporosity (abstract). They teach that the PIM comprises a porosity of at least about 10%, at least about 20%, or at least about 30% and at most about 90% (0041).
From the teachings of Shevchenko, Pinnau, and Palazzotto, it would have been obvious to a person having ordinary skill in the art before the effective filing date of the claimed invention to have modified the process of Losego to have formed multi-layered coatings to provide an antireflective coating on a substrate so as to extend their method to additional products because Losego provides a process of forming porous inorganic materials on a substrate, where the PIM can be removed so as to provide a porous inorganic structure, Shevchenko teaches that it is desirable to form multilayered porous inorganic coatings by infiltrating polymers with inorganic materials such as those of Losego, and Pinnau teaches that PIMs and block copolymers can be used as alternatives in a vapor phase infiltration process where the polymer is subsequently pyrolyzed for forming a porous film such that it will be expected to provide the desirable and predictable result of forming an antireflective coating comprising multiple porous inorganic layers resulting from the removal of the PIM. Further, it would have been obvious to a person having ordinary skill in the art before the effective filing date of the claimed invention to have optimized the porosity of the inorganic coating so as to provide a porosity within the range of claim 10 so that after removal of the PIM layer the resulting porous inorganic film has a porosity in the range of 10-90% because Shevchenko teaches that such a porosity is desirable in the antireflective coating, Palazzotto teaches that PIM materials have a porosity in the range of 10-90%, Losego teaches balancing the metal oxide coating with the loss of porosity (indicating that increasing the metal oxide amount will reduce the porosity), and Pinnau teaches teach that the weight or volume fraction of metal oxides incorporated into the polymer can be controlled, permitting the microporosity of the resulting membrane to be modulated such that by providing a PIM porosity and the amount of inorganic incorporated into the PIM it will be expected to provide a suitable inorganic film for forming the antireflective coating. Therefore, the porosity will be optimized to be within the range of claim 10. According to MPEP 2144.05 II A, “ [W]here the general conditions of a claim are disclosed in the prior art, it is not inventive to discover the optimum or workable ranges by routine experimentation.” In re Aller, 220 F.2d 454, 456, 105 USPQ 233, 235 (CCPA 1955).
Further, when forming the second layer, the substrate will comprise a preexisting coating layer in the form the first porous coating layer as required by claim 16. Further, the process will result in forming the multi-layer coating of claims 19 and 22, where a first porous inorganic coating is formed using the process of claim 1 and repeating the process to form two or more additional coating layers on the first coating layer.
Additionally, since Shevchenko teaches removing the polymer layer, it would have been obvious to a person having ordinary skill in the art before the effective filing date of the claimed invention to have also removed the PIM after performing the infiltration to have provided the porous inorganic layer so as to form the antireflective coating as suggested by Shevchenko.
As to removing the PIM, as noted above Losego teaches heating an AlOx/PIM-1 hybrid membrane in air to remove the polymer, where heating in air combusts the polymer and just leaves the AlOx nanoporous structure (0032).
Shevchenko teaches annealing under air flow to remove the polymer (0066).
From the teachings of Losego and Shevchenko, it would have been obvious to a person having ordinary skill in the art before the effective filing date of the claimed invention to have annealed or heated the polymer/inorganic structure under air flow because Losego teaches heating in air to remove the polymer and Shevchenko teaches annealing (heating) in air flow to remove a polymer such that it will be expected to provide a suitable method of removing the polymer to provide the porous inorganic structure as desired.
Regarding claims 2 and 8, Losego in view of Shevchenko, Pinnau, and Palazzotto suggest the process of clam 1. Losego further teaches pre-treating the microporous polymer prior to performing the vapor phase infiltration by contacting the microporous polymer with an alcohol such as methanol, ethanol, etc. (0113). They teach determining the effect of ethanol on a hybrid PIM-1 material by spin coating a PIM-1 layer on a silicon wafer, performing VPI, and immersing in ethanol (0176). They indicate that ethanol swells the control sample, but swelling is reduced in the hybrid films (0176). Therefore, the alcohol treatment is understood to act as a swelling treatment prior to VPI.
Shevchenko also teaches that the method includes (a) applying a block copolymer layer on a substrate, the block copolymer including a polar polymeric block and a non-polar polymeric block; (b) swelling the block copolymer layer with a solvent to increase the block copolymer layer thickness; (c) depositing a metal oxide or metalloid oxide layer on a polar polymeric block of the block copolymer layer; and (d) removing the block copolymer layer from the substrate, thereby forming a porous metal oxide or metalloid oxide layer on the substrate (abstract). Shevchenko teaches that swelling is a nondestructive strategy to induce and modify the porosity in block copolymer materials (0030). They teach that swelling has the effect of increasing the available space between the block copolymer molecules and thus reducing the diffusion limitation on metal oxide or metalloid oxide infiltration depth/growth (0031).
From the teachings of Losego and Shevchenko, it would have been obvious to a person having ordinary skill in the art before the effective filing date of the claimed invention to have immersed the PIM films in methanol to perform the pre-treatment because Losego teaches immersing the PIM films in ethanol (i.e., an alternative to methanol), which is indicated to swell the film and Shevchenko also teaches swelling polymer to reduce the diffusion limitation on metal oxide or metalloid infiltration depth/growth such that it will be expected to provide the solvent pre-treatment and also swell the PIM materials to increase the free volume for diffusion of the vapor phase precursor and reactant.
Regarding claim 4, Losego in view of Shevchenko, Pinnau, and Palazzotto suggest the process of clam 1. Losego further teaches performing one or more cycles of vapor phase infiltration to make the hybrid membrane, e.g., 2 or more, 3 or more, etc. (0112). They teach specific examples of performing two cycles of VPI on PIM-1 coated TEM grids (0139). Therefore, they provide an example of performing VPI for a number of cycles within the claimed range.
Shevchenko further teaches depositing the metal oxide or metalloid oxide layer by performing a plurality of deposition cycles, where a plurality of sequential infiltration synthesis cycles can be used to control the amount of metal oxide or metalloid oxide deposited (0040). They teach that the plurality of deposition cycles can include at least 2, at least 3, at least 4, or at least 5 cycles and/or up to 4, up to 6, up to 8, up to 10, up to 15, or up to 20 cycles (0040). They teach that the number of deposition cycles can be selected to control the amount of metal oxide or metalloid oxide deposited which in turn controls the porosity and index of refraction of the eventual porous metal oxide or metalloid oxide layer (0040).
From the teachings of Losego and Shevchenko, it would have been obvious to a person having ordinary skill in the art before the effective filing date of the claimed invention to have performed 2 or more and up to 20 infiltration cycles because Losego teaches performing 2 or more cycles and Shevchenko teaches performing at least 2 and up to 20 cycles of infiltration such that it is expected to provide a suitable range for forming the inorganic coating on the porous polymer for the resulting porous inorganic structure. Further, it would have been obvious to a person having ordinary skill in the art before the effective filing date of the claimed invention to have optimized the infiltration cycles to be within the claimed range because Shevchenko teaches that the number of cycles can be selected to control the amount of metal oxide or metalloid oxide deposited which in turn controls the porosity and index of refraction of the eventual porous metal oxide or metalloid oxide layer such that by optimizing the cycles it will provide the desired porosity and index of refraction.
According to MPEP 2131.03, “[W]hen, as by a recitation of ranges or otherwise, a claim covers several compositions, the claim is ‘anticipated’ if one of them is in the prior art.” Titanium Metals Corp.v. Banner, 778 F.2d 775, 227 USPQ 773 (Fed. Cir. 1985) (citing In re Petering, 301 F.2d 676, 682, 133 USPQ 275, 280 (CCPA 1962)) (emphasis in original). According to MPEP 2144.05 II A, “Generally, differences in concentration or temperature will not support the patentability of subject matter encompassed by the prior art unless there is evidence indicating such concentration or temperature is critical. “[W]here the general conditions of a claim are disclosed in the prior art, it is not inventive to discover the optimum or workable ranges by routine experimentation.” In re Aller, 220 F.2d 454, 456, 105 USPQ 233, 235 (CCPA 1955).
Regarding claim 5, Losego in view of Shevchenko, Pinnau, and Palazzotto suggest the process of clam 1. Losego further teaches that the precursor reactant is water (0109-0110). Shevchenko also teaches using water as a second precursor in the ALD process (0038).
Regarding claim 6, Losego in view of Shevchenko, Pinnau, and Palazzotto suggest the process of clam 1. Losego further teaches that the polymer of intrinsic microporosity if PIM-1 (0083), indicating that PIM-1 is a desirable PIM for forming porous inorganic structures.
Regarding claim 7, Losego in view of Shevchenko, Pinnau, and Palazzotto suggest the process of clam 1. Losego further teaches forming ~100 nm PIM-1 film by spin coating onto silicon wafers (0176).
Shevchenko teaches applying the block copolymer layer to the substrate at a thickness ranging from 10 to 1000 nm, at least 20 nm and up to 100 nm or 200 nm (0028).
From this, it would have been obvious to a person having ordinary skill in the art before the effective filing date of the claimed invention to have applied the PIM to the substrate to have a thickness in the range of from 10 to 1000 nm or at least 20 nm and up to 100 nm or 200 nm because Losego teaches applying the PIM within such a range and Shevchenko teaches that such polymer thickness ranges are suitable in forming the AR coating. Therefore, the thickness of the PIM will overlap or be within the claimed range. According to MPEP 2144.05, “in the case where the claimed ranges “overlap or lie inside ranges disclosed by the prior art” a prima facie case of obviousness exists.” According to MPEP 2131.03, “[W]hen, as by a recitation of ranges or otherwise, a claim covers several compositions, the claim is ‘anticipated’ if one of them is in the prior art.” Titanium Metals Corp.v. Banner, 778 F.2d 775, 227 USPQ 773 (Fed. Cir. 1985) (citing In re Petering, 301 F.2d 676, 682, 133 USPQ 275, 280 (CCPA 1962)) (emphasis in original).
Regarding claim 9, Losego in view of Shevchenko, Pinnau, and Palazzotto suggest the process of clam 1. Losego further teaches that the coating precursor material is TMA, DEZ, TiCl4, or titanium isopropoxide (understood to be tetraisopropoxide) (0110). They also teach that the compound can be a metal cyclopentadienyl compound or a metalloid cyclopentadienyl compound (0109-0110). They teach that the inorganic material can comprise a metal selected from the group consisting of Ti, V, Cr, Fe, Co, Ni, Zn, Zr, Mo, Ru, Rh, W, Sm, or Pb (0085).
Shevchenko also teaches using precursors such as TMA, titanium tetrachloride, titanium tetraisopropoxide, tetrakis(dimethylamido)zirconium, tris(dimethylamido)silane, nickel(II) acetylacetonate, palladium(II) hexafluoroacetylacetonate, copper bis (2,2,6,6-tetramethyl-3,5-heptanedionate, metallocenes (C5H5)2M, where M can be Cr, Fe, Co, Ni, Pb, Zr, Ru, Rh, Sm, Ti, V, Mo, W, or Zn, and half-metallocene compounds (e.g., (C5H5)M(CH3)3, where M can be Cr, Fe, Co, Ni, Pb, Zr, Ru, Rh, Sm, Ti, V, Mo, W, or Zn (0038).
From the teachings of Losego and Shevchenko, it would have been obvious to a person having ordinary skill in the art before the effective filing date of the claimed invention to have used the various precursors taught by Losego and Shevchenko (i.e., TMA, DEZ, metallocenes, etc.) because they teach that such precursors are suitable for infiltrating polymers for forming porous inorganic structures such that it will be expected to provide the metal oxide or metalloid oxide coating as desired.
Regarding claim 23, Losego in view of Shevchenko, Pinnau, and Palazzotto suggest the process of claim 22. As discussed above, Pinnau teaches that block polymers or PIMs can be used as templates for vapor phase infiltration to result in a porous layer. Shevchenko teaches using block copolymers for forming the porous inorganic layers. From this, it would have been obvious to a person having ordinary skill in the art before the effective filing date of the claimed invention to have formed a first layer using the PIMs as a template and then to have used the block copolymers of Shevchenko to form a second porous layer because both materials are indicated as being used to form porous inorganic layers such that it will provide a simple substitution for one known porous polymer template for another while being expected to provide desirable layers for the antireflective coating.
Further Shevchenko teaches forming the porous layer using the block copolymer by forming a block copolymer layer on the substrate and swelling the block copolymer with a solvent so as to provide a solvent treatment (abstract). They teach depositing the metal oxide or metalloid oxide by any method that allows the metal oxide or metalloid oxide or precursors of the metal oxide or metalloid oxide to infiltrate the porosities of the polar polymeric block of the block copolymer (0036). They teach using ALD in which gas phase chemical precursors that react with at least a portion of the block copolymer surface one at a time in a sequential, self-limiting manner, form the layer comprising the metal oxide or metalloid oxide (0037). Therefore, they provide infiltrating the pores of the block copolymer polymer templated with a coating precursor material in a vapor phase, wherein the coating precursor material is a precursor for forming an inorganic coating material (because it results in forming the metal or metalloid oxide). They teach reacting the deposited first precursor with a second precursor in a second subsequent half-cycle, thereby forming the metal or metalloid oxide layer (0039). Therefore, the pores of the block copolymer polymer template will be infiltrated with a precursor reactant in a vapor phase to react with the coating material precursor to form the inorganic coating material arrange to form the second porous inorganic coating on the first porous inorganic coating. Further, Shevchenko depicts the porous metal oxide or metalloid oxide as having tubular shape after removing the bock-copolymer layer (0014 and Fig. 1). Therefore, after removing the block copolymer layer, the second porous inorganic coating layer will be expected to have tubular shaped pores.
Regarding claim 26, Losego in view of Shevchenko, Pinnau, and Palazzotto suggest the process of claim 23. As noted above Shevchenko teaches removing the polymer before applying the next layer (0052). Therefore, it would have been obvious to a person having ordinary skill in the art before the effective filing date of the claimed invention to have also removed the PIM before applying the block copolymer layer because Shevchenko teaches it is desirable to remove the polymer prior to providing the next layer.
Regarding claim 27, Losego in view of Shevchenko, Pinnau, and Palazzotto suggest the process of claim 23. Shevchenko teaches removing the bock copolymer when providing a single layer and repeating steps (a)-(d) when providing the multi-layered structure (abstract and 0052). Therefore, the block copolymer will also be removed after performing the infiltration cycle.
Claims 1, 2, 4-10, 16, 19, 22-23, and 26-27 are rejected under 35 U.S.C. 103 as being unpatentable over Shevchenko, US 2019/0017166 A1 in view of Pinnau, WO 2020/222138 A1, Losego, US 2020/0325295 A1, and Palazzotto, US 2013/0229194 A1.
Regarding claims 1, 10, 16, 19, and 22, Shevchenko teaches a process for forming an inorganic porous coating on a substrate (a method for forming a low refractive index layer on a substrate which results in forming a porous metal oxide or metalloid oxide layer on a substrate, abstract), comprising:
forming a polymer template comprising applying a thin film of a polymer on the substrate (applying a block copolymer layer on a substrate, the block copolymer including a polar polymeric block and a non-polar polymeric block, abstract);
performing an infiltration cycle comprising:
infiltrating the polymer template with a first vapor comprising a coating precursor material, wherein the coating precursor material is a precursor for forming an inorganic coating material and the coating precursor material binds to functional groups of the polymer template (where precursors of the metal oxide or metalloid oxide infiltrate the porosities of the polar polymeric block of the block copolymer film, 0036, and where the deposition method is ALD, where gas phase chemical precursors react with at least a portion of the block copolymer surface one at a time in a sequential manner such that the first precursor molecules react with reactive sites on the block copolymer, 0037), and
infiltrating the pores of the polymer template having the coating precursor material bound thereto with a second vapor comprising a precursor reactant, wherein the bound coating material precursor reacts with the precursor reactant to form the inorganic coating material arranged to form the porous inorganic coating (where the second precursor is introduced to form the metal oxide or metalloid oxide film, 0037, where the second precursor reacts with the deposited first precursor to form the film, 0039, as noted above the precursor infiltrate the porosities of the polar block of the block copolymer film and the process is done using gas phase reactions by ALD, 0037); and
removing the polymer after performing the infiltration cycle by annealing under airflow or ozone etching, thereby leaving the inorganic porous coating on the substrate (where the block copolymer is removed to provide a porous metal oxide or metalloid oxide layer on the substrate, where the block copolymer is removed by thermal annealing, ozone treatment, or combinations thereof, 0043, where annealing is indicated as being done under air flow to remove the polymer, 0066).
Shevchenko does not teach using a polymer of intrinsic microporosity.
They teach that the formed porous metal oxide or metalloid oxide layer can have thickness ranging from 10-1000 nm with a porosity ranging from 10 to 90% (0044-0045 and Table 1). They teach forming a graded-index antireflective layer by performing steps (a) to (d) at least twice in succession to form at least two porous metal oxide or metalloid oxide layers having different index of refraction values (0052). They teach that each second and subsequent porous metal oxide or metalloid oxide layer can be selected to have different thickness and/or index of refraction values (0052). Therefore, Shevchenko teaches forming a graded antireflective coating by forming multiple porous metal oxide or metalloid oxide layers on a substrate through vapor phase infiltration and subsequent removal of the polymer.
Pinnau teaches method of fabricating thin film composite carbon molecular sieve membranes by exposing a polymer layer to a vapor-phase metal-organic precursor under vapor phase infiltration conditions such that the vapor phase metal organic precursor diffuses into the polymer layer and reacts with a functional group of the polymer to form an inorganic-organic complex; exposing the polymer layer to a vapor-phase co-reactant under vapor phase infiltration conditions such that the vapor phase co-reactant diffuses into the polymer layer ad oxidizes the organic-inorganic complex to form a metal oxide; and subjecting the polymer layer to inert-atmosphere or vacuum pyrolysis (abstract). They teach that the thin film composite carbon molecular sieve membranes are supported on a substrate (0006). They teach that exemplary polymeric precursors include polymers of intrinsic microporosity (0028). They teach that other polymer precursors include block interpolymers (0033). They teach that the polymer layer can be supported on a substrate (0034). They teach that metal-containing precursors include trimethyl aluminum, diethyl zinc, titanium isopropoxide, titanium tetrachloride, etc. (0035). They teach exposing the polymer layer or polymeric precursor to one or more vapor phase co-reactants such as water (0037). They teach that the metal oxides are dispersed on a molecular level, allowing the formation of thin films, and the weight or volume fraction of the metal oxides can be controlled, permitting the microporosity of the resulting membrane to be modulated (0018). Therefore, Pinnau teaches forming porous films by vapor phase infiltrating inorganic material into either a block polymer or a PIM.
Losego teaches a process for forming an inorganic porous coating on a substrate (a method of making a hybrid membrane, 0107-0108, where the hybrid membrane comprises a microporous polymer and an atomic scale inorganic material dispersed throughout the microporous polymer within the continuous pore phase, 0078, where the hybrid membrane can comprise a film, 0102, where they are formed on substrate such as support membranes or silicon wafers, 0161 and 0176, and they have a surface area of 200 m2/g, 1800 m2-/g or more, 0095, further indicating that it will be porous or have a degree of porosity due to the high surface area, and also where they teach burning out the PIM-1 skeleton of the membrane to provide a residual microporous metal oxide structure, 0147, further indicate providing an inorganic porous coating on a substrate), comprising:
forming a polymer template having a plurality of pores comprising applying a thin film of a polymer of intrinsic microporosity on the substrate (where the membranes comprising a microporous polymer are formed as films, 0078 and 0102, and where PIM-1 thin films are formed by spin coating onto support membranes, 0161, or silicon wafers, 0176, where microporous polymers include polymers of intrinsic microporosity or PIMs, 0082, such that the PIM will be formed on a substrate to provide a polymer template having a plurality of pores); and
performing an infiltration cycle comprising:
infiltrating the pores of the polymer template with a first vapor comprising a coating precursor material, wherein the coating precursor material is a precursor for forming an inorganic coating material and the coating precursor material binds to functional groups of the polymer template (where the microporous polymer is infiltrated with the inorganic material using vapor phase infiltration using a precursor material that reacts to form the inorganic material such that it is considered to be a coating precursor material, 0108-0109, where the precursors form an adduct with the PIM-1, 0147 and Fig. 22, such that it will bind to functional groups of the polymer template, i.e., PIM-1), and
infiltrating the pores of the polymer template having the coating precursor material bound thereto with a second vapor comprising a precursor reactant, wherein the bound coating material precursor reacts with the precursor reactant to form the inorganic coating material arranged to form the porous inorganic coating (where the membrane impregnated with the precursor is exposed to a reactant, thereby forming the inorganic material, 0109, where since the precursor and the reactant result in the formation of the inorganic coating, the bound precursor is understood to react with the reactant to provide the inorganic material).
They further teach burning out the PIM-1 skeleton of the hybrid membrane to provide a microporous metal oxide structure (0147 and Fig. 27). They teach annealing an AlOx/PIM-1 hybrid hollow fiber membrane in air at 900°C, where heat treating in air combusts the polymer and leaves just and AlOx nanoporous structure (0032). They teach optimizing hybrid membrane performance by controlling the amount of metal oxide loading to balance the trade-off between chemical stability and loss of porosity (0150). They teach that the inorganic material can comprise alumina, titania, zinc oxide, etc. (0086).
Palazzotto teaches a sensor element that includes an absorptive dielectric layer comprising a polymer of intrinsic microporosity (abstract). They teach that the PIM comprises a porosity of at least about 10%, at least about 20%, or at least about 30% and at most about 90% (0041).
From the teachings of Pinnau, Losego, and Palazzotto, it would have been obvious to a person having ordinary skill in the art before the effective filing date of the claimed invention to have modified the process of Shevchenko to have used a polymer of intrinsic microporosity as the polymer template in forming the porous metal oxide or metalloid oxide layers on the substrate because Pinnau teaches that PIMs and block copolymers can be used as alternatives in a vapor phase infiltration process where the polymer is subsequently pyrolyzed for forming a porous film, Losego provides a process of forming porous inorganic materials, where the PIM can be removed so as to provide an inorganic or metal oxide microporous structure, and Palazzotto teaches that PIM materials have a porosity in a range desired by Shevchenko such that it will be expected to provide the desirable and predictable result of providing a desirable polymer template in the process of Shevchenko for forming the porous metal oxide or metalloid oxide layer on the substrate. Further, it would have been obvious to a person having ordinary skill in the art before the effective filing date of the claimed invention to have optimized the porosity of the inorganic coating so as to provide a porosity within the range of claim 10 so that after removal of the PIM layer the resulting porous inorganic film has a porosity in the range of 10-90% because Shevchenko teaches that such a porosity is desirable in the antireflective coating, Palazzotto teaches that PIM materials have a porosity in the range of 10-90%, Losego teaches balancing the metal oxide coating with the loss of porosity (indicating that increasing the metal oxide amount will reduce the porosity), and Pinnau teaches teach that the weight or volume fraction of metal oxides incorporated into the polymer can be controlled, permitting the microporosity of the resulting membrane to be modulated such that by providing a PIM porosity and the amount of inorganic incorporated into the PIM it will be expected to provide a suitable inorganic film for forming the antireflective coating. Therefore, the porosity will be optimized to be within the range of claim 10. According to MPEP 2144.05 II A, “ [W]here the general conditions of a claim are disclosed in the prior art, it is not inventive to discover the optimum or workable ranges by routine experimentation.” In re Aller, 220 F.2d 454, 456, 105 USPQ 233, 235 (CCPA 1955).
Further, when forming the second layer as desired by Shevchenko, the substrate will comprise a preexisting coating layer in the form the first porous coating layer as required by claim 16. Further, the process will result in forming the multi-layer coating of claims 19 and 22, where a first porous inorganic coating is formed using the process of claim 1 and repeating the process to form two or more additional coating layers on the first coating layer.
Additionally, since Shevchenko teaches removing the polymer layer, it would have been obvious to a person having ordinary skill in the art before the effective filing date of the claimed invention to have also removed the PIM to have provided the porous inorganic layer so as to form the antireflective coating as suggested by Shevchenko.
As to removing the PIM, as noted above Shevchenko teaches annealing under air flow to remove the polymer or by ozone treatment (0043 and 0066).
Losego teaches heating an AlOx/PIM-1 hybrid membrane in air to remove the polymer, where heating in air combusts the polymer and just leaves the AlOx nanoporous structure (0032).
From the teachings of Shevchenko and Losego, it would have been obvious to a person having ordinary skill in the art before the effective filing date of the claimed invention to have annealed or heated the polymer/inorganic structure under air flow because Losego teaches heating in air to remove the polymer and Shevchenko teaches annealing (heating) in air flow to remove a polymer such that it will be expected to provide a suitable method of removing the polymer to provide the porous inorganic structure as desired. Alternatively, it would have been obvious to a person having ordinary skill in the art before the effective filing date of the claimed invention to have removed the PIM using ozone treatment because Shevchenko indicates that such a process is suitable for removing a polymer such that it will also be expected to be suitable for removing a PIM, so as to provide ozone etching.
Regarding claims 2 and 8, Shevchenko in view of Pinnau, Losego, and Palazzotto suggest the process of clam 1. Shevchenko further teaches that the method includes (a) applying a block copolymer layer on a substrate, the block copolymer including a polar polymeric block and a non-polar polymeric block; (b) swelling the block copolymer layer with a solvent to increase the block copolymer layer thickness; (c) depositing a metal oxide or metalloid oxide layer on a polar polymeric block of the block copolymer layer; and (d) removing the block copolymer layer from the substrate, thereby forming a porous metal oxide or metalloid oxide layer on the substrate (abstract). Shevchenko teaches that swelling is a nondestructive strategy to induce and modify the porosity in block copolymer materials (0030). They teach that swelling has the effect of increasing the available space between the block copolymer molecules and thus reducing the diffusion limitation on metal oxide or metalloid oxide infiltration depth/growth (0031).
Losego further teaches pre-treating the microporous polymer prior to performing the vapor phase infiltration by contacting the microporous polymer with an alcohol such as methanol, ethanol, etc. (0113). They teach determining the effect of ethanol on a hybrid PIM-1 material by spin coating a PIM-1 layer on a silicon wafer, performing VPI, and immersing in ethanol (0176). They indicate that ethanol swells the control sample, but swelling is reduced in the hybrid films (0176). Therefore, the alcohol treatment is understood to act as a swelling treatment prior to VPI.
From the teachings of Shevchenko and Losego, it would have been obvious to a person having ordinary skill in the art before the effective filing date of the claimed invention to have immersed the PIM films in methanol to perform the pre-treatment because Losego teaches immersing the PIM films in ethanol (i.e., an alternative to methanol), which is indicated to swell the film and Shevchenko also teaches swelling polymer to reduce the diffusion limitation on metal oxide or metalloid infiltration depth/growth such that it will be expected to provide the solvent pre-treatment and also swell the PIM materials to increase the free volume for diffusion of the vapor phase precursor and reactant.
Regarding claim 4, Shevchenko in view of Pinnau, Losego, and Palazzotto suggest the process of clam 1. Shevchenko further teaches depositing the metal oxide or metalloid oxide layer by performing a plurality of deposition cycles, where a plurality of sequential infiltration synthesis cycles can be used to control the amount of metal oxide or metalloid oxide deposited (0040). They teach that the plurality of deposition cycles can include at least 2, at least 3, at least 4, or at least 5 cycles and/or up to 4, up to 6, up to 8, up to 10, up to 15, or up to 20 cycles (0040). They teach that the number of deposition cycles can be selected to control the amount of metal oxide or metalloid oxide deposited which in turn controls the porosity and index of refraction of the eventual porous metal oxide or metalloid oxide layer (0040).
Losego further teaches performing one or more cycles of vapor phase infiltration to make the hybrid membrane, e.g., 2 or more, 3 or more, etc. (0112). They teach specific examples of performing two cycles of VPI on PIM-1 coated TEM grids (0139). Therefore, they provide an example of performing VPI for a number of cycles within the claimed range.
From the teachings of Losego and Shevchenko, it would have been obvious to a person having ordinary skill in the art before the effective filing date of the claimed invention to have performed 2 or more and up to 20 infiltration cycles because Losego teaches performing 2 or more cycles and Shevchenko teaches performing at least 2 and up to 20 cycles of infiltration such that it is expected to provide a suitable range for forming the inorganic coating on the porous polymer for the resulting porous inorganic structure. Further, it would have been obvious to a person having ordinary skill in the art before the effective filing date of the claimed invention to have optimized the infiltration cycles to be within the claimed range because Shevchenko teaches that the number of cycles can be selected to control the amount of metal oxide or metalloid oxide deposited which in turn controls the porosity and index of refraction of the eventual porous metal oxide or metalloid oxide layer such that by optimizing the cycles it will provide the desired porosity and index of refraction.
According to MPEP 2131.03, “[W]hen, as by a recitation of ranges or otherwise, a claim covers several compositions, the claim is ‘anticipated’ if one of them is in the prior art.” Titanium Metals Corp.v. Banner, 778 F.2d 775, 227 USPQ 773 (Fed. Cir. 1985) (citing In re Petering, 301 F.2d 676, 682, 133 USPQ 275, 280 (CCPA 1962)) (emphasis in original). According to MPEP 2144.05 II A, “[W]here the general conditions of a claim are disclosed in the prior art, it is not inventive to discover the optimum or workable ranges by routine experimentation.” In re Aller, 220 F.2d 454, 456, 105 USPQ 233, 235 (CCPA 1955).
Regarding claim 5, Shevchenko in view of Pinnau, Losego, and Palazzotto suggest the process of clam 1. Shevchenko further teaches using water as a second precursor in the ALD process (0038).
Losego also teaches that the precursor reactant is water (0109-0110).
Regarding claim 6, Shevchenko in view of Pinnau, Losego, and Palazzotto suggest the process of clam 1. Losego further teaches that the polymer of intrinsic microporosity if PIM-1 (0083), indicating that PIM-1 is a desirable PIM for forming porous inorganic structures. Therefore, it would have been obvious to a person having ordinary skill in the art before the effective filing date of the claimed invention to have used PIM-1 as the PIM because Losego teaches that such a PIM is desirable for the VPI process such that it will be expected to provide a suitable template for forming the porous oxide coating.
Regarding claim 7, Shevchenko in view of Pinnau, Losego, and Palazzotto suggest the process of clam 1. Shevchenko teaches applying the block copolymer layer to the substrate at a thickness ranging from 10 to 1000 nm, at least 20 nm and up to 100 nm or 200 nm (0028).
Losego further teaches forming ~100 nm PIM-1 film by spin coating onto silicon wafers (0176).
From this, it would have been obvious to a person having ordinary skill in the art before the effective filing date of the claimed invention to have applied the PIM to the substrate to have a thickness in the range of from 10 to 1000 nm or at least 20 nm and up to 100 nm or 200 nm because Losego teaches applying the PIM within such a range and Shevchenko teaches that such polymer thickness ranges are suitable in forming the AR coating. Therefore, the thickness of the PIM will overlap or be within the claimed range. According to MPEP 2144.05, “in the case where the claimed ranges “overlap or lie inside ranges disclosed by the prior art” a prima facie case of obviousness exists.” According to MPEP 2131.03, “[W]hen, as by a recitation of ranges or otherwise, a claim covers several compositions, the claim is ‘anticipated’ if one of them is in the prior art.” Titanium Metals Corp.v. Banner, 778 F.2d 775, 227 USPQ 773 (Fed. Cir. 1985) (citing In re Petering, 301 F.2d 676, 682, 133 USPQ 275, 280 (CCPA 1962)) (emphasis in original).
Regarding claim 9, Shevchenko in view of Pinnau, Losego, and Palazzotto suggest the process of clam 1. Shevchenko teaches using precursors such as TMA, titanium tetrachloride, titanium tetraisopropoxide, tetrakis(dimethylamido)zirconium, tris(dimethylamido)silane, nickel(II) acetylacetonate, palladium(II) hexafluoroacetylacetonate, copper bis (2,2,6,6-tetramethyl-3,5-heptanedionate, metallocenes (C5H5)2M, where M can be Cr, Fe, Co, Ni, Pb, Zr, Ru, Rh, Sm, Ti, V, Mo, W, or Zn, and half-metallocene compounds (e.g., (C5H5)M(CH3)3, where M can be Cr, Fe, Co, Ni, Pb, Zr, Ru, Rh, Sm, Ti, V, Mo, W, or Zn (0038).
Losego further teaches that the coating precursor material is TMA, DEZ, TiCl4, or titanium isopropoxide (understood to be tetraisopropoxide) (0110). They also teach that the compound can be a metal cyclopentadienyl compound or a metalloid cyclopentadienyl compound (0109-0110). They teach that the inorganic material can comprise a metal selected from the group consisting of Ti, V, Cr, Fe, Co, Ni, Zn, Zr, Mo, Ru, Rh, W, Sm, or Pb (0085).
From the teachings of Losego and Shevchenko, it would have been obvious to a person having ordinary skill in the art before the effective filing date of the claimed invention to have used the various precursors taught by Losego and Shevchenko (i.e., TMA, DEZ, metallocenes, etc.) because they teach that such precursors are suitable for infiltrating polymers for forming porous inorganic structures such that it will be expected to provide the metal oxide or metalloid oxide coating as desired.
Regarding claim 23, Shevchenko in view of Pinnau, Losego, and Palazzotto suggest the process of clam 22. As discussed above, Pinnau teaches that block polymers or PIMs can be used as templates for vapor phase infiltration to result in a porous layer. Shevchenko teaches using block copolymers for forming the porous inorganic layers.
From this, it would have been obvious to a person having ordinary skill in the art before the effective filing date of the claimed invention to have formed a first layer using the PIMs as a template and then to have used the block copolymers of Shevchenko to form a second porous layer because both materials are indicated as being used to form porous inorganic layers such that it will provide a simple substitution for one known porous polymer template for another while being expected to provide desirable layers for the antireflective coating.
Further Shevchenko teaches forming the porous layer using the block copolymer by forming a block copolymer layer on the substrate and swelling the block copolymer with a solvent so as to provide a solvent treatment (abstract). They teach depositing the metal oxide or metalloid oxide by any method that allows the metal oxide or metalloid oxide or precursors of the metal oxide or metalloid oxide to infiltrate the porosities of the polar polymeric block of the block copolymer (0036). They teach using ALD in which gas phase chemical precursors that react with at least a portion of the block copolymer surface one at a time in a sequential, self-limiting manner, form the layer comprising the metal oxide or metalloid oxide (0037). Therefore, they provide infiltrating the pores of the block copolymer polymer templated with a coating precursor material in a vapor phase, wherein the coating precursor material is a precursor for forming an inorganic coating material (because it results in forming the metal or metalloid oxide). They teach reacting the deposited first precursor with a second precursor in a second subsequent half-cycle, thereby forming the metal or metalloid oxide layer (0039). Therefore, the pores of the block copolymer polymer template will be infiltrated with a precursor reactant in a vapor phase to react with the coating material precursor to form the inorganic coating material arrange to form the second porous inorganic coating on the first porous inorganic coating. Further, Shevchenko depicts the porous metal oxide or metalloid oxide as having tubular shape after removing the bock-copolymer layer (0014 and Fig. 1). Therefore, after removing the block copolymer layer, the second porous inorganic coating layer will be expected to have tubular shaped pores.
Regarding claim 26, Shevchenko in view of Pinnau, Losego, and Palazzotto suggest the process of clam 23. As noted above Shevchenko teaches removing the polymer before applying the next layer (0052). Therefore, it would have been obvious to a person having ordinary skill in the art before the effective filing date of the claimed invention to have also removed the PIM before applying the block copolymer layer because Shevchenko teaches it is desirable to remove the polymer prior to providing the next layer.
Regarding claim 27, Shevchenko in view of Pinnau, Losego, and Palazzotto suggest the process of clam 23. Shevchenko teaches removing the bock copolymer when providing a single layer and repeating steps (a)-(d) when providing the multi-layered structure (abstract and 0052). Therefore, the block copolymer will also be removed after performing the infiltration cycle.
Response to Arguments
Applicant's arguments filed 11/24/2025 have been fully considered.
In light of the amendments to the claims, the rejection has been modified as indicated above.
Regarding Applicant’s argument over the combination of Losego in view of Shevchenko, Pinnau, and Palazzotto removing the PIM using the claimed method, as discussed above, Losego teaches removing the PIM by heating in air and Shevchenko also teaches removing the polymer by annealing (heating) in airflow. Therefore, Losego and Shevchenko are considered to suggest the claimed feature of removing the PIM by annealing under air flow. It is noted that Pinnau is relied upon for the indication that PIM and block copolymers can both be used for forming porous inorganic structures, suggesting that they are substitutes for one another.
Regarding Applicant’s argument that Losego and Pinnau are directed to separation membranes, it is noted that Losego teaches using the membranes for separation, however, they also indicate that PIMs can be used in a variety of applications such as sensing, gas storage, etc. (0168), where hybrid membranes can be used for gas storage devices, sorbents, catalysis, sensors, and separations (0179). Therefore, Losego is not considered to be confined to separations. Further, as noted above, they teach removing the polymer by heating in air (0032). Pinnau also teaches that using VPI to create organic-inorganic hybrids is desirable to applications such as sorbents, optics, lithography, or electronics, etc. (0060). Therefore, the references indicate that the materials can be used for other purposes. Shevchenko teaches using block copolymers for forming porous antireflective coatings, where Pinnau teaches that block copolymers and PIMs can both be used for VPI. Therefore, using the PIMs of Losego to form porous inorganic coatings for the antireflective coating of Shevchenko is expected to provide suitable coatings since Pinnau indicates that block copolymer and PIMs can both be used for VPI, Losego teaches removing the PIM to provide an inorganic structure, and Palazzotto indicates that PIMs have a porosity meeting the range desired by Shevchenko.
Further, a new rejection has been made using Shevchenko as the primary reference, where Pinnau, Losego, and Palazzotto indicate that PIMs are a suitable alternative material to block copolymers for forming porous inorganic structures.
Conclusion
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/CHRISTINA D MCCLURE/Examiner, Art Unit 1718