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 .
Response to Amendment
The amendment filed March 18th, 2026 does not place the application in condition for allowance.
The rejections over Du et al., in view of Xiao et al. in view of Nishihara et al. are maintained.
Claim Rejections - 35 USC § 103
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 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.
Claims 1, 3-7, 16-18, 49, and 52 are rejected under 35 U.S.C. 103 as being unpatentable over Du et al. “Polymeric Surface Modification of NiOX – Based Inverted Planar Perovskite Solar Cells with Enhanced Performance” in view of Xiao et al. “Solution-Processed Monolithic All-Perovskite Triple-Junction Solar Cells with Efficiency Exceeding 20%” in view of Nishihara et al. (US 2019/0006540 A1).
In view of Claim 1, Du et al. teaches a photovoltaic device (Abstract & associated Figure) comprising: a transparent conductive oxide (Abstract – FTO), a multilayer hole transport stack over the transparent conductive oxide (NiOx & PTAA over the FTO layer), the multilayer hole transport stack comprises a first hole transport layer (NiOX), and a second hole transport layer (PTAA), wherein the second hole transport layer comprises an organic hole transport material (PTAA) and the first hole transport layer comprises an inorganic hole transport material (NiOX), a perovskite absorber layer over the multilayer hole transport stack (PVK), wherein the second hole transport layer of the multilayer hole transport stack directly contacts the perovskite absorber layer (PTAA directly contacts the PVK layer).
Du et al. does not disclose that the first hole transport layer is at least two times the thickness of the second hole transport layer.
Xiao discloses a configuration where a first hole transport material that comprises nickel oxide is 80 nm and a second hole transport material that includes PTAA is 8nm, resulting in a ratio of 8:1 (Page 2821, Left Column, 3rd Paragraph). Xiao et al. discloses that this results in a configuration where the NiO layer has good conductivity and the PTAA layer increases the Voc (Page 2821, Column 2, Lines 1-7). Accordingly, it would have been obvious to one of ordinary skill in the art at the time the invention was filed to have the first hole transport layer is at least two times the thickness of the second hole transport layer in modified Du et al. multilayer hole transport stack for the advantage of having a configuration with good conductivity and increased VOC.
Du et al. does not disclose a third hole transport layer that is between the first and second hole transport layers.
Nishihara et al. discloses a hole transporting layer that can comprise a third hole transport layer (Paragraph 0079) while disclosing a double stack of nickel oxide hole transporting layers (Figs. 2-3, #3 – Paragraph 0057), and that this configuration increases the photoelectric conversion efficiency of a solar cell (Paragraph 0056). Accordingly, it would have been obvious to substitute the first hole transport layer of Du et al. with Nishihara et al. double stack of nickel oxide hole transporting layers for the advantages of increasing the photoelectric conversion efficiency of the solar cell.
The resulting combination would have a third hole transport layer of nickel oxide (Figs. 1-2, #32) with a thickness less than 10 nm (Paragraph 0077) sandwiched between the other hole transporting layer of nickel oxide and the PTAA hole transporting layer as disclosed by Du et al. that acts as an interface to the perovskite absorber.
Du et al. Abstract Figure
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In view of Claim 3, Du et al., Xiao, and Nishihara et al. are relied upon for the reasons given above in addressing Claim 1. Xiao discloses a configuration where a first hole transport material that comprises nickel oxide is 80 nm and a second hole transport material that includes PTAA is 8nm, resulting in a ratio of 8:1 (Page 2821, Left Column, 3rd Paragraph).
In view of Claim 4, Du et al., Xiao, and Nishihara et al. are relied upon for the reasons given above in addressing Claim 1. Du et al. teaches that the organic hole transport material includes PTAA (See Du et al. Abstract Figure, above).
In view of claim 5, Du et al., Xiao, and Nishihara et al. are relied upon for the reasons given above in addressing Claim 1. Du et al. teaches that the organic hole transport material includes PTAA (See Du et al. Abstract Figure, above - PTAA).
In view of Claim 6, Du et al., Xiao, and Nishihara et al. are relied upon for the reasons given above in addressing Claim 1. Du et al. teaches that the first hole transport layer includes at least one of a metal oxide (See Du et al. Abstract Figure, above - NiOx).
In view of Claim 7, Du et al., Xiao, and Nishihara et al. are relied upon for the reasons given above in addressing Claim 1. Du et al. teaches that the first hole transport layer includes at least one of nickel oxide (See Du et al. Abstract Figure, above - NiOx).
In view of Claim 16, Du et al. discloses a method of forming a perovskite photovoltaic device (Abstract & associated Figure) comprising: providing a substrate stack, the substrate stack having a transparent p-type contact layer (Abstract Figure - FTO), forming a first sublayer comprising a first hole transport material over the contact layer that comprises NiOX (Abstract Figure - NiOX – Page 16807, Left Column, Preparation of NiOx Precursor Solution and NiOx Film); forming a second sublayer comprising a second hole transport material over the first sublayer that comprises PTAA (Abstract Figure – PTAA – Page 16807, Left Column, Preparation of NiOx Precursor Solution and NiOx Film).
Du et al. teaches that the second sublayer comprising PTAA has an exposed surface that is hydrophobic (Page 16808, Left Column, Lines 6-36), and that a water contact angle on the exposed surface is between 45° to 120° (Page 16808, Left Column, Lines 7-13); and forming a perovskite absorber layer adjacent to the exposed surface of the second sublayer (Page 16807 – Device Fabrication & Page 16808, Left Column, Lines 7-16).
Du et al. does not disclose that a ratio of the thickness of the first sublayer to the thickness of the second sublayer is in a range from 2:1 to 100:1.
Xiao discloses a configuration where a first hole transport material that comprises nickel oxide is 80 nm and a second hole transport material that includes PTAA is 8nm, resulting in a ratio of 8:1 (Page 2821, Left Column, 3rd Paragraph). Xiao et al. discloses that this results in a configuration where the NiO layer has good conductivity and the PTAA layer increases the Voc (Page 2821, Column 2, Lines 1-7). Accordingly, it would have been obvious to one of ordinary skill in the art at the time the invention was filed to have the ratio of thicknesses of the first sublayer to the thickness of the second sublayer be in a ratio of 8:1 in Du et al. multilayer hole transport stack for the advantage of having a configuration with good conductivity and increased VOC.
Du et al. does not disclose a third hole transport layer that is between the first and second hole transport layers.
Nishihara et al. discloses a hole transporting layer that can comprise a third hole transport layer (Paragraph 0079) while disclosing a double stack of nickel oxide hole transporting layers (Figs. 2-3, #3 – Paragraph 0057), and that this configuration increases the photoelectric conversion efficiency of a solar cell (Paragraph 0056). Accordingly, it would have been obvious to substitute the first hole transport layer of Du et al. with Nishihara et al. double stack of nickel oxide hole transporting layers for the advantages of increasing the photoelectric conversion efficiency of the solar cell.
The resulting combination would have a third hole transport layer of nickel oxide sandwiched between the other hole transporting layer of nickel oxide and the PTAA hole transporting layer as disclosed by Du et al. that acts as an interface to the perovskite absorber.
Du et al. Abstract Figure
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In view of Claim 17, Du et al., Xiao, and Nishihara et al. are relied upon for the reasons given above in addressing Claim 16. Du et al. teaches that the step of forming the second hole transport sublayer comprises spin coating (Page 16807, Left Column – Preparation of NiOX Precursor Solution and NiOX Film). The resulting combination of Nishihara et al. would have a third hole transport layer of nickel oxide sandwiched between the other hole transporting layer of nickel oxide and the PTAA hole transporting layer as disclosed by Du et al. that acts as an interface to the perovskite absorber. The nickel oxide material in layers 31-32 that make up the first and third hole transport layers are different from one another (Paragraph 0057 – different amounts of lithium in the NiO).
In view of Claim 18, Du et al., Xiao, and Nishihara et al. are relied upon for the reasons given above in addressing Claim 16. Du et al. was relied upon to disclose that the first hole transport material comprises NiOX and the second hole transport material comprises PTAA (Abstract Figure - Page 16807, Left Column, Preparation of NiOx Precursor Solution and NiOx Film), and that the band gap of the first hole transport material is greater than a band gap of the second hole transport material (See Du et al. Abstract Figure). Xiao was relied upon to disclose a ratio of the thickness of the first sublayer to the thickness of the second sublayer is in a range from 3:1 to 10:1 (Page 2821, Left Column, 3rd Paragraph).
In view of Claim 49, Du et al., Xiao, and Nishihara et al. are relied upon for the reasons given above in addressing Claim 16. Du et al. teaches the step of forming a first sublayer comprises annealing at a temperature in a range of 200° C to 500° C (Page 16807, Left Column, Preparation of NiOx Precursor Solution and NiOx Film 300° C).
In view of Claim 52, Du et al. and Nishihara et al. are relied upon for the reasons given below in addressing Claim 50. Nishihara et al. does not disclose the second sublayer has a thickness less than 10 nm.
Xiao discloses a configuration where a first hole transport material that comprises nickel oxide is 80 nm and a second hole transport material that includes PTAA is 8nm, (Page 2821, Left Column, 3rd Paragraph). Xiao et al. discloses that this results in a configuration where the NiO layer has good conductivity and the PTAA layer increases the Voc (Page 2821, Column 2, Lines 1-7). Accordingly, it would have been obvious to one of ordinary skill in the art at the time the invention was filed to have the second sublayer with a thickness less than 10 nm in Du et al. multilayer hole transport stack for the advantage of having a configuration with good conductivity and increased VOC.
Claim 2 rejected under 35 U.S.C. 103 as being unpatentable over Du et al. “Polymeric Surface Modification of NiOX – Based Inverted Planar Perovskite Solar Cells with Enhanced Performance” in view of Xiao et al. “Solution-Processed Monolithic All-Perovskite Triple-Junction Solar Cells with Efficiency Exceeding 20%” in view of Nishihara et al. (US 2019/0006540 A1) in view of Hiraoka et al. (US 2022/0077411 A1).
In view of Claim 2, Du et al., Xiao, and Nishihara et al. are relied upon for the reasons given above in addressing Claim 1. Nishihara et al. teaches that the first hole transport layer has a thickness in a range of 1-50 nm (Paragraph 0075), but Xiao et al. does not disclose the second hole transport layer a thickness in a range of 0.3-4 nm.
Hiraoka et al. discloses that PTAA layers should have a range between 1-1000 nm and that this range ensures sufficient hole transporting properties will be exhibited and that the thickness in the above range also ensures that low resistance will be maintained and the energy of light may be highly efficiently converted to electricity (Paragraph 0113). Accordingly, it would have been obvious to one of ordinary skill in the art at the time the invention was filed to have the second hole transport layer have a thickness of 1-1000 nm for the advantages of ensuring sufficient hole transporting properties will be exhibited and that the thickness in the above range also ensures that low resistance will be maintained and the energy of light may be highly efficiently converted to electricity
Claims 50-51, and 58 are rejected under 35 U.S.C. 103 as being unpatentable over Du et al. “Polymeric Surface Modification of NiOX – Based Inverted Planar Perovskite Solar Cells with Enhanced Performance” in view of Nishihara et al. (US 2019/0006540 A1).
In view of Claim 50, Du et al. teaches a photovoltaic device (Abstract & associated Figure) comprising: a transparent conductive oxide (Abstract – FTO), a multilayer hole transport stack over the transparent conductive oxide (NiOx & PTAA over the FTO layer), the multilayer hole transport stack comprises a first sublayer comprising a first hole transport material (NiOX), and a second sublayer comprising a second hole transport material (PTAA), wherein the second hole transport layer comprises an organic hole transport material (PTAA) and the first hole transport layer comprises an inorganic hole transport material (NiOX), a perovskite absorber layer over the multilayer hole transport stack (PVK), wherein the second hole transport layer of the multilayer hole transport stack directly contacts the perovskite absorber layer (PTAA directly contacts the PVK layer).
Du et al. does not disclose a third sublayer comprising a third hole transport material disposed between the first sublayer and the second sublayer, and that the third sublayer is less than 10 nm thick.
Nishihara et al. discloses a hole transporting layer that can comprise a third hole transport layer (Paragraph 0079) while disclosing a double stack of nickel oxide hole transporting layers (Figs. 2-3, #3 – Paragraph 0057), and that this configuration increases the photoelectric conversion efficiency of a solar cell (Paragraph 0056). Accordingly, it would have been obvious to substitute the first hole transport layer of Du et al. with Nishihara et al. double stack of nickel oxide hole transporting layers for the advantages of increasing the photoelectric conversion efficiency of the solar cell.
The resulting combination would have a third hole transport layer of nickel oxide (Figs. 1-2, #32) with a thickness less than 10 nm (Paragraph 0077) sandwiched between the other hole transporting layer of nickel oxide and the PTAA hole transporting layer as disclosed by Du et al. that acts as an interface to the perovskite absorber.
Du et al. Abstract Figure
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In view of Claim 51, Du et al. and Nishihara et al. are relied upon for the reasons given above in addressing Claim 50. Nishihara et al. teaches that the first sublayer has a thickness in a range of 1-50 nm (Paragraph 0075) and that the first hole transport material comprises nickel oxide (Paragraph 0057).
In view of Claim 58, Du et al. and Nishihara et al. are relied upon for the reasons given above in addressing Claim 50. Du et al. teaches that the second hole transport material comprises PTAA (See Du et al. Abstract Figure, above, PTAA).
Claim 53 is rejected under 35 U.S.C. 103 as being unpatentable over Du et al. “Polymeric Surface Modification of NiOX – Based Inverted Planar Perovskite Solar Cells with Enhanced Performance” in view of Nishihara et al. (US 2019/0006540 A1) in view of Hao (CN-111223993-A). Hao is mapped to the English machine translation provided by the EPO.
In view of Claim 53, Du et al. and Nishihara et al. are relied upon for the reasons given below in addressing Claim 50. Du et al. teaches that the second sublayer contacts a perovskite absorber layer of the perovskite photovoltaic device (See Du et al. Abstract Figure, above, PTAA contacts PVK), while Nishihara et al. discloses that the total thickness of the first and second hole transporting sublayer are selected from 1-50 nm, and 1-10 nm, thus their total ranges from 2-60 nm in thickness. Du et al. is silent on what the thickness of the PTAA layer
Hao discloses a thickness of a PTAA layer is 10-30 nm that advantageously reduce surface defects of the film and the film is uniform and compact and still maintains excellent hole migration performance under the premise of ensuring high coverage (Page 1, Summary of the invention, starting at the 2nd paragraph through Page 2, 1st Paragraph). Accordingly, it would have been obvious to one of ordinary skill in the art at the time the invention was filed to have the thickness of the PTAA layer of Du et al. be within 10-30 nm as disclosed by Hao for the advantages of ensuring reduced surface defects of the film and the film is uniform and compact and still maintains excellent hole migration performance under the premise of ensuring high coverage.
Thus modified Du et al. total thickness of a hole transport stack would be in the range 12-90 nm, thus there are points in the range from 12-30 nm that overlap Applicant’s claimed ranged.
Claim 54 is rejected under 35 U.S.C. 103 as being unpatentable over Du et al. “Polymeric Surface Modification of NiOX – Based Inverted Planar Perovskite Solar Cells with Enhanced Performance” in view of Nishihara et al. (US 2019/0006540 A1) in view of Zhu et al. (US 2023/0260717 A1).
In view of Claim 54, Du et al. and Nishihara et al. are relied upon for the reasons given above in addressing Claim 50. Nishihara et al. teaches that the third hole transport material is NiO (Paragraph 0057) which is different from the second hole transport material disclosed by Du et al. (See Du et al. Abstract Figure, above, PTAA).
Modified Du et al. does not disclose the third hole transport material is a carbazole and comprises at least one of 2PACz, MeO-2PACz, or Me-4PACz.
Zhu et al. discloses that a third transport material can be selected from NiOX, 2PACz, and MeO-2PACz (Paragraph 0040). In regards to the limitation that the third transport material comprises MeO-2PACz or 2PACz, these materials and their functions are known in the art, and one of ordinary skill in the art could have substituted the material of Nishihara et al. for MeO-2PACz or 2PACz and the results of the substitution would have been predictable. See MPEP 2143, I, B.
Claim 55 is rejected under 35 U.S.C. 103 as being unpatentable over Du et al. “Polymeric Surface Modification of NiOX – Based Inverted Planar Perovskite Solar Cells with Enhanced Performance” in view of Nishihara et al. (US 2019/0006540 A1) in view of Lee et al. (US 2023/0371291 A1).
In view of Claim 55, Du et al. and Nishihara et al. are relied upon for the reasons given above in addressing Claim 50. Du et al. second hole transport material comprises PTAA, but does not disclose that the second sublayer comprises MeO-2PACz or 2PACz.
Lee et al. discloses that a charge transport layer can include MeO-2PACz or 2PACz, wherein these materials perform the function of extracting and transporting holes according to a bandgap relationship with a photoelectric conversion layer (Paragraph 0074). In regards to the limitation that the second sublayer comprises MeO-2PACz or 2PACz, these materials and their functions are known in the art, and one of ordinary skill in the art could have substituted the material of Lin et al. second sublayer for MeO-2PACz or 2PACz and the results of the substitution would have been predictable. See MPEP 2143, I, B.
Claims 56-57 are rejected under 35 U.S.C. 103 as being unpatentable over Du et al. “Polymeric Surface Modification of NiOX – Based Inverted Planar Perovskite Solar Cells with Enhanced Performance” in view of Nishihara et al. (US 2019/0006540 A1) in view of Lin et al. (US 2024/0196718 A1).
In view of Claims 56-57, Du et al. and Nishihara et al. are relied upon for the reasons given above in addressing Claim 50. Du et al. second hole transport material comprises PTAA, but does not disclose that the second sublayer comprises P3HT or poly TPD.
Lin et al. teaches that the second sublayer can comprises P3HT, poly-TPD, or PTAA and that these materials can include sublayers known in the art and containing different materials (Paragraph 0230 & 0235). In regards to the limitation that the second sublayer comprises P3HT or poly TPD, these materials and their functions are known in the art, and one of ordinary skill in the art could have substituted the material of Lin et al. second sublayer for MeO-2PACz or 2PACz and the results of the substitution would have been predictable. See MPEP 2143, I, B.
Response to Arguments
Applicant argues that Nishihara does not disclose three-hole transport layers and he does not disclose the composition of the third layer in each of the independent claims 1, 16, and 50. The Examiner respectfully points out to Applicant that Nishihara disclose that the hole transport layer is not limited to a two-layer structure including the first hole transport layer 31 and the second hold transport layer 32 (Paragraph 0079). Nishihara et al. discloses a hole transporting layer that can comprise a third hole transport layer (Paragraph 0079) while disclosing a double stack of nickel oxide hole transporting layers (Figs. 2-3, #3 – Paragraph 0057), and that this configuration increases the photoelectric conversion efficiency of a solar cell (Paragraph 0056). Accordingly, it would have been obvious to substitute the first hole transport layer of Du et al. with Nishihara et al. double stack of nickel oxide hole transporting layers for the advantages of increasing the photoelectric conversion efficiency of the solar cell. The resulting combination would have a third hole transport layer of nickel oxide (Figs. 1-2, #32) with a thickness less than 10 nm (Paragraph 0077) sandwiched between the other hole transporting layer of nickel oxide and the PTAA hole transporting layer as disclosed by Du et al. that acts as an interface to the perovskite absorber. Thus, the single layer of NiO of Du et al. is being substituted for the double layer of NiO as disclosed by Nishihara. Its also respectfully noted that Applicant does not claim a composition of the third layer in each of the independent claims 1, 16, and 50. Accordingly, for the reasons stated above, this argument is unpersuasive.
Conclusion
THIS ACTION IS MADE FINAL. 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.
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/DANIEL P MALLEY JR./Primary Examiner, Art Unit 1726