DETAILED ACTION
The present application, filed on or after March 16, 2013, is being examined under the first inventor to file provisions of the AIA .
This office action is in response to application filed on 11/29/2023.
Currently claims 1-15 are pending in the application.
Information Disclosure Statement
The information disclosure statement (IDS) submitted on 11/29/2023 was filed before the mailing date of the office action. The submission is in compliance with the provisions of 37 CFR 1.97. Accordingly, the information disclosure statements was considered by the examiner.
Claim Objections
Claims 1 and 15 are objected to because of the following informalities:
Regarding claim 1, in the limitation of the claim, “A method of manufacturing a solar cell, comprising …”, the underlined word “A” should be added.
Regarding claim 15, in the limitation of the claim, “A solar cell obtained or obtainable by the method of claim 1”, the underlined word “A” should be added.
Appropriate correction is required.
Claim Rejections - 35 USC § 112 (d)
The following is a quotation of 35 U.S.C. 112(d):
(d) REFERENCE IN DEPENDENT FORMS.—Subject to subsection (e), a claim in dependent form shall contain a reference to a claim previously set forth and then specify a further limitation of the subject matter claimed. A claim in dependent form shall be construed to incorporate by reference all the limitations of the claim to which it refers.
Claims 8 and 12 are rejected under 35 U.S.C. 112 (d), as being of improper dependent form for failing to further limit the subject matter of the claim upon which it depends, or for failing to include all the limitations of the claim upon which it depends.
Regarding claim 8, the limitation of the invention, “The method according to claim 7, wherein the concentration of said additive in said perovskite precursor solution is 0.1 mMol-50 mMol” does not further limit a similar limitation of claim 1, which states, “.…. providing a perovskite precursor solution comprising an additive comprising an organic phosphonic acid and/or a phosphonate salt in a concentration of between 0.1 mMol and 50 mMol….”.
Regarding claim 12, the limitation of the invention, “The method according to claim 10, wherein the concentration of said additive in said perovskite precursor solution is 0.1 mMol-50 mMol” does not further limit a similar limitation of claim 1, which states, “.…. providing a perovskite precursor solution comprising an additive comprising an organic phosphonic acid and/or a phosphonate salt in a concentration of between 0.1 mMol and 50 mMol….”.
Applicant may cancel the claims, amend the claims to place the claims in proper dependent form, rewrite the claims in independent form, or present a sufficient showing that the dependent claims complies with the statutory requirements.
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 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 of this title, 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 set forth in Graham v. John Deere Co., 383 U.S. 1, 148 USPQ 459 (1966), that are applied 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 and 14-15 are rejected under 35 U.S.C. 103 as being unpatentable over “Improved performance and stability of perovskite solar cells by crystal crosslinking with alkylphosphonic acid ω-ammonium chlorides, Xiang Li et al., Nature Chemistry, pp. 703-710, vol. 7, Aug. 17, 2015” (Li) and further in view of US 2012/0312364 A1 (Uhrich).
Regarding claim 1, Li discloses, method of manufacturing a solar cell, comprising steps of:
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providing a substrate (laser patterned glass substrate; Fig. 1 (a); page 710);
providing a first layer of transparent conductive oxide (Li discloses a fluorine-doped tin-oxide (FTO) coated glass substrate; Fig. 1 (a); page 710) on said substrate (glass substrate);
providing a first charge transport layer (TiO2 layer – bl-TiO2 and mp-TiO2; Fig. 1 (a); page 710) on said first layer of transparent conductive oxide (FTO);
providing a perovskite-based light-absorber layer (CH3NH3I and commercial PbI2 (99%, Acros Organics) for the 1.25M CH3NH3PbI3 solution; Fig. 1 (a); page 710) on said first charge transport layer (TiO2 layer);
providing a second charge transport layer (Li teaches that a spiro-MeOTAD solution was spin-coated on the perovskite layer at 4,000 r.p.m. for 30 s. The spiro-MeOTAD solution was prepared by dissolving 72.3 mg of spiro-MeOTAD in 1 ml chlorobenzene (extra dry, 99.8%, Acros Organics); Fig. 1 (a); page 710) on said perovskite-based light absorber layer (CH3NH3PbI3 solution);
providing a back contact layer (80 nm gold; Fig. 1 (a); page 710);
wherein said step of providing a perovskite-based light absorber layer (CH3NH3PbI3 solution) comprises:
providing a perovskite precursor solution comprising an additive comprising an organic phosphonic acid and/or a phosphonate salt in a concentration of between 0.1 mMol and 50 mMol (Li teaches that 1.25 M perovskite precursor solution containing 4-ABPACl was prepared as follows - CH3NH3I (1.2 mM), 0.05 mM 4-ABPACl and 1.25 mM PbI2 were dissolved in 1 ml GBL/DMF (4:6 vol/vol) mixed solvent with stirring overnight at 60 °C and then stored in a dry box (humidity <1%) at room temperature; Fig. 1 (a); page 710);
applying said perovskite precursor solution upon said first charge transport layer (Li teaches that filtrated perovskite precursor solution was coated onto the mp-TiO2/bl-TiO2/FTO substrate by a consecutive two-step spin-coating process at 1,000 and 3,000 r.p.m for 10 and 15 s, respectively; Fig. 1 (a); page 710);
annealing said perovskite layer at a temperature between 100° C and 170° C ( Li teaches that after spin-coating, the films were left to dry at room temperature in the dry box for 18 min, then annealed on a hotplate at 100 °C for 10 min; Fig. 1 (a); page 710).
But Li fails to teach explicitly, providing a second layer of transparent conductive oxide on said second charge transport layer; providing a patterned metallic contact layer on said second layer of transparent conductive oxide;
However, in analogous art, Uhrich discloses, providing a second layer of transparent conductive oxide (8; molybdenum oxide; Fig. 4; [0334]) on said second charge transport layer (6; hole transport layer; Fig. 4; [0334]);
providing a patterned metallic contact layer (9; top contact; Fig. 4; [0334]; it must be patterned to make it shorter in length in horizontal direction than molybdenum oxide 8) on said second layer of transparent conductive oxide (8);
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Therefore, it would have been obvious to one of ordinary skill in the art before the effective filing date of the claimed invention, having the teachings of Li and Uhrich before him/her, to modify the teachings of a perovskite-based solar cell as taught by Li and to include the teachings of a top-side transparent conductive oxide as taught by Uhrich since having transparent conductive oxides (TCOs) on both sides of solar cell would allow adequate collection of charge carriers (electrons and holes) while allowing sunlight to pass through the front side, and improve carrier collection on the back side, ensuring efficient current extraction and enhanced light trapping for higher power conversion. Absent this important teaching in Li, a person with ordinary skill in the art would be motivated to reach out to Uhrich while forming a perovskite-based solar cell of Li.
Regarding claim 14, Li discloses, the method according to claim 1, wherein said substrate is one of: an opaque support; a transparent support; a silicon solar cell (Li discloses a fluorine-doped tin-oxide (FTO) coated glass substrate which is characteristically transparent; Fig. 1 (a); page 710).
Regarding claim 15, Li discloses, Solar cell (pages 703 and 707) obtained or obtainable by the method of claim 1 (see rejection of claim 1).
Claim 5 is rejected under 35 U.S.C. 103 as being unpatentable over Li and Uhrich as applied to claim 1 and further in view of US 2024/0251574 A1 (Schmager).
Regarding claim 5, the combination of Li and Uhrich fails to teach explicitly, the method according to claim 1, wherein said perovskite-based light-absorber layer has a thickness between 200 nm and 2000 nm.
However, in analogous art, Schmager discloses, the method according to claim 1, wherein said perovskite-based light-absorber layer has a thickness between 200 nm and 2000 nm ([0087]). Schmager teaches a thickness between 800 nm to 10 um which overlaps the claimed thickness of between 200 nm and 2000 nm. In MPEP 2144.05 (I), it is stated that In the case where the claimed ranges "overlap or lie inside ranges disclosed by the prior art" a prima facie case of obviousness exists. In re Wertheim, 541 F.2d 257, 191 USPQ 90 (CCPA 1976); In re Woodruff, 919 F.2d 1575, 16 USPQ2d 1934 (Fed. Cir. 1990). Thus, it would have been obvious to one of ordinary skill in the art before the effective filing date of the claimed invention to use the above claimed ranges since it has been held that where the general conditions of a claim are disclosed in the prior art, discovering the optimum or working range involves only routine skill in the art. In re Aller, 105 USPQ 233 (See MPEP 2144.05 (II) (A)).
Therefore, it would have been obvious to one of ordinary skill in the art before the effective filing date of the claimed invention, having the teachings of Li, Uhrich and Schmager before him/her, to modify the teachings of a perovskite-based solar cell as taught by Li and to include the teachings of the thickness of perovskite-based layer as taught by Schmager since Li failed to teach this critical parameter. Absent this important teaching in Li, a person with ordinary skill in the art would be motivated to reach out to Schmager while forming a perovskite-based solar cell of Li.
Claims 7-8 are rejected under 35 U.S.C. 103 as being unpatentable over Li and Uhrich as applied to claim 1 and further in view of US 2022/0238807 A1 (Christensen).
Regarding claim 7, Li teaches, the method according to claim 1, wherein said perovskite precursor solution is applied directly to said first charge transport layer (Fig. 1 (a); page 710),
But the combination of Li and Uhrich fails to teach explicitly, said perovskite precursor solution comprises organic and inorganic perovskite precursors.
However, in analogous art, Christensen discloses, said perovskite precursor solution comprises organic and inorganic perovskite precursors ([0026]).
Therefore, it would have been obvious to one of ordinary skill in the art before the effective filing date of the claimed invention, having the teachings of Li, Uhrich and Christensen before him/her, to modify the teachings of a perovskite-based solar cell as taught by Li and to include the teachings of perovskite precursor solution comprising organic and inorganic perovskite precursors as taught by Christensen since having both organic and inorganic precursors has the advantage to manufacture a uniform perovskite layer at high speed on a flexible substrate ([0007]). Absent this important teaching in Li, a person with ordinary skill in the art would be motivated to reach out to Christensen while forming a perovskite-based solar cell of Li.
Regarding claim 8, Li discloses, the method according to claim 7, wherein the concentration of said additive in said perovskite precursor solution is 0.1 mMol-50 mMol (Li teaches that 1.25 M perovskite precursor solution containing 4-ABPACl was prepared as follows - CH3NH3I (1.2 mM), 0.05 mM 4-ABPACl and 1.25 mM PbI2 were dissolved in 1 ml GBL/DMF (4:6 vol/vol) mixed solvent with stirring overnight at 60 °C and then stored in a dry box (humidity <1%) at room temperature; Fig. 1 (a); page 710).
Allowable Subject Matter
Claims 2-4, 6 and 9-13 objected to as being dependent upon rejected base claims, but would be allowable if rewritten in independent forms including all of the limitations of the base claims and any intervening claims.
Regarding claim 2, the closest prior art, “Improved performance and stability of perovskite solar cells by crystal crosslinking with alkylphosphonic acid ω-ammonium chlorides, Xiang Li et al., Nature Chemistry, pp. 703-710, vol. 7, Aug. 17, 2015” (Li), in combination with US 2012/0312364 A1 (Uhrich), US 2024/0251574 A1 (Schmager) and US 2022/0238807 A1 (Christensen), fails to disclose, “the method according to claim 1, wherein said first charge transport layer is a hole selective layer comprising at least one of: 2,2′,7,7′-Tetra(N,N-di-p-tolyl)amino-9,9-spirobifluorene; 1,3,4,6-Tetra-O-acetyl-2-O-(trifluoromethanesulfonyl)-beta-D-mannopyranose; 3,6-dimethyl-9H-carbazol-9-yl)butyl]phosphonic acid; 1-[2-(3,6-dimethoxy-9H-carbazol-9-yl)ethyl]phosphonic acid; 1-[2-(9H-carbazol-9-yl)ethyl]phosphonic acid”, in combination with the additionally claimed features, as are claimed by the Applicant.
Regarding claim 3, the closest prior art, “Improved performance and stability of perovskite solar cells by crystal crosslinking with alkylphosphonic acid ω-ammonium chlorides, Xiang Li et al., Nature Chemistry, pp. 703-710, vol. 7, Aug. 17, 2015” (Li), in combination with US 2012/0312364 A1 (Uhrich), US 2024/0251574 A1 (Schmager) and US 2022/0238807 A1 (Christensen), fails to disclose, “the method according to claim 1, wherein said second charge transport layer comprises C60”, in combination with the additionally claimed features, as are claimed by the Applicant.
Regarding claim 4, the closest prior art, “Improved performance and stability of perovskite solar cells by crystal crosslinking with alkylphosphonic acid ω-ammonium chlorides, Xiang Li et al., Nature Chemistry, pp. 703-710, vol. 7, Aug. 17, 2015” (Li), in combination with US 2012/0312364 A1 (Uhrich), US 2024/0251574 A1 (Schmager) and US 2022/0238807 A1 (Christensen), fails to disclose, “the method according to claim 1, wherein said additive comprises —one or more of: 2,3,4,5,6-pentafluorobenzylphosphonic acid; benzylphosphonic acid, 4-bromobenzylphosphonic acid, 4-fluorobenzylphosphonic acid, (4-chlorophenyl)phosphonic acid, phenylphosphonic acid”, in combination with the additionally claimed features, as are claimed by the Applicant.
Regarding claim 6, the closest prior art, “Improved performance and stability of perovskite solar cells by crystal crosslinking with alkylphosphonic acid ω-ammonium chlorides, Xiang Li et al., Nature Chemistry, pp. 703-710, vol. 7, Aug. 17, 2015” (Li), in combination with US 2012/0312364 A1 (Uhrich), US 2024/0251574 A1 (Schmager) and US 2022/0238807 A1 (Christensen), fails to disclose, “the method according to claim 1, wherein said perovskite-based light absorber layer comprises (Cs,FA,MA)Pb(I,Br,Cl)3 or (Cs,FA)Pb(I,Br,Cl)3”, in combination with the additionally claimed features, as are claimed by the Applicant.
Regarding claim 9, the closest prior art, “Improved performance and stability of perovskite solar cells by crystal crosslinking with alkylphosphonic acid ω-ammonium chlorides, Xiang Li et al., Nature Chemistry, pp. 703-710, vol. 7, Aug. 17, 2015” (Li), in combination with US 2012/0312364 A1 (Uhrich), US 2024/0251574 A1 (Schmager) and US 2022/0238807 A1 (Christensen), fails to disclose, “the method according to claim 7, wherein said substrate has a roughness of less than 1 μm Ra on a surface facing said perovskite-based light absorber layer”, in combination with the additionally claimed features, as are claimed by the Applicant.
Regarding claim 10, the closest prior art, “Improved performance and stability of perovskite solar cells by crystal crosslinking with alkylphosphonic acid ω-ammonium chlorides, Xiang Li et al., Nature Chemistry, pp. 703-710, vol. 7, Aug. 17, 2015” (Li), in combination with US 2012/0312364 A1 (Uhrich), US 2024/0251574 A1 (Schmager) and US 2022/0238807 A1 (Christensen), fails to disclose, “the method according to claim 1, wherein said step of providing a perovskite-based light absorber layer comprises a step of vapor depositing a layer of CsX and/or PbX.sub.2, where X is I, Br, Cl, on said first charge transport layer followed by said step of applying said perovskite precursor solution”, in combination with the additionally claimed features, as are claimed by the Applicant.
Claims 11-13 are also objected to due to their dependence on an objected base claim.
Examiner’s Note (Additional Prior Arts)
The examiner included a few prior arts which are relevant to the disclosure.
US 2024/0373656 A1 (Wojciechowski) - A perovskite solar cell is disclosed having a stack of layers, wherein the layers are arranged in the following order: a front electrode layer, a photo-active layer with a perovskite material, and a back electrode layer with a porous carbon material having a plurality of open-through pores. The solar cell further includes a charge transport material that fills at least some of the open-through pores of the porous carbon material of the back electrode layer.
US 2024/0138163 A1 (Berry) - Methods and compositions for forming perovskite hole transport layers for use in manufacturing photovoltaic devices are described. Embodiments include using a plurality of hole transport materials to produce high-performance HTL contacts to improve performance and stability.
US 2019/0221742 A1 (Li) - A perovskite-containing film is disclosed comprising depositing one or more metal oxide layers onto a substrate. Then irradiating each metal oxide layer with a UV LED light source after deposition to sinter and/or anneal a target metal oxide in the one or more metal oxide layers without damaging the underlying substrate or perovskite material. The LED light source can be selected to emit a narrow spectral width of pulsed radiation. The radiation emitted can consist essentially of wavelengths within 20 nm of the wavelength of maximum absorbance (λ.sub.max) of the target metal oxide, that is, wavelength from UV LED can be λ.sub.max±20 nm, to achieve layer-specific annealing and sintering of metal oxide charge transport layer. The target metal oxide can include tin oxide in the electron transport layer or nickel oxide in the hole transport layer. Perovskite-containing films formed from the methods described herein are also disclosed.
Conclusion
Any inquiry concerning this communication or earlier communications from the examiner should be directed to S M SOHEL IMTIAZ whose telephone number is (408) 918-7566. The examiner can normally be reached on 8AM-5PM, M-F, PST.
If attempts to reach the examiner by telephone are unsuccessful, the examiner’s supervisor, Christine S. Kim can be reached at 571-272-8458. The fax phone number for the organization where this application or proceeding is assigned is 571-273-8300.
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/S M SOHEL IMTIAZ/Primary Patent Examiner
Art Unit 2812
01/27/2026