DETAILED ACTION
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 3/30/2026 does not place the application in condition for allowance.
The previous art rejections are withdrawn due to Applicant’s amendment.
New analysis follows.
Claim Rejections - 35 USC § 102
The text of those sections of Title 35, U.S. Code not included in this action can be found in a prior Office action.
Claim(s) 1, 2, 5, 6, and 12 is/are rejected under 35 U.S.C. 102(a)(1) as being anticipated by “Synergistic effects of thiocyanate additive and cesium cations on improving the performance and initial illumination stability of efficient perovskite solar cells” to Wang (included in Applicant’s 3/30/2026 IDS).
Regarding claims 1, and 2, Wang teaches a perovskite precursor material, comprising a precursor substrate and doping ions (Experimental: Precursor preparation on p. 2439: “We first made individual MA0.7FA0.3PbI3 and CsPbI3 precursors by dissolving mixed FAI, MAI, PbI2 and Pb(SCN)2 powders and mixed CsI, PbI2 and Pb(SCN)2 powders in mixed N-N-dimethylformamide (DMF) and dimethyl sulfoxide (DMSO) solvents, respectively, and then mixed these precursors in the desirable volume ratios to form (MA0.7FA-0.3PbI3)1-x(CsPbI3)x precursors”; also see Introduction for explanation of abbreviations), wherein the precursor substrate comprises a material having a chemical formula MX (FAI, MAI, CsI), M comprises organic amine cations (FA+, MA+), cesium ions (Cs+), and X comprises halogen ions (I-), wherein the doping ions comprise acid radical ions (SCN-).
The proportion of doping ions is represented as a molar percentage of PbI2 (2%, also see first paragraph underneath Results and discussion on p. 2436) that has been substituted with Pb(SCN)2. The composition of the perovskite precursor material is recited as Csx(MA0.7FA0.3)1-xPbI3. Therefore, one mole of the unsubstituted precursor material has x Cs ions (each ion having a molar mass of 132.9 g/mol), (1-x)*0.7 MA (methylammonium) ions (32.07 g/mol), (1-x)*0.3 FA (formamidinium) ions (45.07 g/mol), 1 Pb ion (207.2 g/mol), and 3 iodide ions (126.9 g/mol). Substituting 0.02 moles of Pb(SCN)2 in for 0.02 moles of PbI2 does not change the number of Pb ions in the precursor material, but does change the number of iodide ions from 3 to (1+2*0.98)= 2.96, and introduces 2*0.2=0.04 SCN ions (58.08 g/mol). Therefore, the molar mass of the substituted precursor material, substituted with 10% Cs ions (as shown in Fig. 1(d), for instance, and discussed in Results and discussion) is 635.49 g/mol, and the mass percentage of doping thiocyanate ions is 0.37%.
Regarding claims 5 and 6, Wang teaches a preparation method for a perovskite precursor material, comprising mixing an reacting, in a first solvent (DMF), a raw material (Pb(SCN)2) for providing doping ions (SCN--) and a raw material for synthesizing a precursor substrate (Experimental: Precursor preparation on p. 2439: “We first made individual MA0.7FA0.3PbI3 and CsPbI3 precursors by dissolving mixed FAI, MAI, PbI2 and Pb(SCN)2 powders and mixed CsI, PbI2 and Pb(SCN)2 powders in mixed N-N-dimethylformamide (DMF) and dimethyl sulfoxide (DMSO) solvents, respectively, and then mixed these precursors in the desirable volume ratios to form (MA0.7FA-0.3PbI3)1-x(CsPbI3)x precursors”; also see Introduction for explanation of abbreviations), and subjecting a reacted solution to first crystallization treatment (Fabrication of solar cells: “The perovskite precursor solution was spin-coated on the ESL first at 500 rpm for 3 s… The as-prepared perovskite film was annealed on a hotplate at 65 oC for 2 minutes and then at 100 oC for 5 minutes.”; crystallization is evident from Fig. 1 and relevant discussion in Results and discussion).
The precursor substrate comprises a material having a chemical formula MX (FAI, MAI, CsI), M comprises organic amine cations (FA+, MA+), cesium ions (Cs+), and X comprises halogen ions (I-), wherein the doping ions comprise acid radical ions (SCN-).
The proportion of doping ions is represented as a molar percentage of PbI2 (2%, also see first paragraph underneath Results and discussion on p. 2436) that has been substituted with Pb(SCN)2. The composition of the perovskite precursor material is recited as Csx(MA0.7FA0.3)1-xPbI3. Therefore, one mole of the unsubstituted precursor material has x Cs ions (each ion having a molar mass of 132.9 g/mol), (1-x)*0.7 MA (methylammonium) ions (32.07 g/mol), (1-x)*0.3 FA (formamidinium) ions (45.07 g/mol), 1 Pb ion (207.2 g/mol), and 3 iodide ions (126.9 g/mol). Substituting 0.02 moles of Pb(SCN)2 in for 0.02 moles of PbI2 does not change the number of Pb ions in the precursor material, but does change the number of iodide ions from 3 to (1+2*0.98)= 2.96, and introduces 2*0.2=0.04 SCN ions (58.08 g/mol). Therefore, the molar mass of the substituted precursor material, substituted with 10% Cs ions (as shown in Fig. 1(d), for instance, and discussed in Results and discussion) is 635.49 g/mol, and the mass percentage of doping thiocyanate ions is 0.37%.
Regarding claim 12, Wang teaches a perovskite solar cell (Fabrication of solar cells on p. 2439-2440) comprising a first electrode (“FTO”), a perovskite layer “(MA0.7FA0.3PbI3)1-x(CsPbI3)x”, and a second electrode (“Au”) that are sequentially stacked, wherein the perovskite layer comprises the perovskite material according to claim 1.
Claim(s) 1-3, 5, 6, 12, and 22 is/are rejected under 35 U.S.C. 102(a)(1) as being anticipated by “Efficient perovskite solar cells by metal ion doping” to Wang II.
Regarding claims 1-3 and 22, Wang II teaches a perovskite precursor material, comprising a precursor substrate (methylammonium iodide) and doping ions (Al3+), wherein the precursor substate comprises a material having a chemical formula MX, M comprising methylammonium, an organic amine cation, and X comprises iodide, a halogen ion (Perovskite solution preparation on p. 2900), wherein the doping ions comprise group IIIA element ions, Al3+.
The doping ion, in the form of Al-acac3, is added at 3mg into 1 g of a solution comprising the precursor substrate, the solution comprising the precursor substrate at 30 wt%. The molar mass of Al is 26.98 g/mol, and the molar mass of acac is 100.12 g/mol. Therefore Al3+ forms (26.98/(3*100.12 +26.98)) ~ 8% of the weight of Al-acac3, and the mass of Al3+ added to the solution is 8%*3 mg = 0.25 mg. The mass percentage of doping ions is therefore 0.25 mg/(0.3*1000 mg + 0.25 mg)=0.08% based on a mass of the perovskite precursor material.
Regarding claims 5 and 6, Wang II teaches a preparation method for a perovskite precursor material, comprising mixing and reacting, in a first solvent (N,N-dimethylformamide), a raw material for providing doping ions (Al-acac3) and a raw material (methylammonium iodide) for synthesizing a precursor substrate (Perovskite solution preparation on p. 2900), and subjecting the reacted solution to a first crystallization treatment (Device fabrication; crystallization is evident from Fig. 1 and relevant portions of Results and discussion).
The precursor substate comprises a material having a chemical formula MX, M comprising methylammonium, an organic amine cation, and X comprises iodide, a halogen ion, wherein the doping ions comprise group IIIA element ions, Al3+.
The doping ion, in the form of Al-acac3, is added at 3mg into 1 g of a solution comprising the precursor substrate, the solution comprising the precursor substrate at 30 wt%. The molar mass of Al is 26.98 g/mol, and the molar mass of acac is 100.12 g/mol. Therefore Al3+ forms (26.98/(3*100.12 +26.98)) ~ 8% of the weight of Al-acac3, and the mass of Al3+ added to the solution is 8%*3 mg = 0.25 mg. The mass percentage of doping ions is therefore 0.25 mg/(0.3*1000 mg + 0.25 mg)=0.08% based on a mass of the perovskite precursor material.
Regarding claim 12, Wang II teaches a perovskite solar cell (Device fabrication on p. 2900) comprising a first electrode (“fluorine doped tin oxide FTO coated glass”), a perovskite layer, and a second electrode (“70 nm of silver”) that are sequentially stacked, wherein the perovskite layer comprises the perovskite material according to claim 1.
Claim(s) 1-3, 5, 6, 12, 13, and 22 is/are rejected under 35 U.S.C. 102(a)(1) as being anticipated by “Liquid metal acetate assisted preparation of high-efficiency and stable inverted perovskite solar cells” to Wu.
Regarding claims 1-3 and 13, Wu teaches a perovskite precursor material comprising a precursor substrate and doping ions, wherein the precursor substrate comprises a material (MAI) having a chemical formula MX, M comprising methylammonium, an organic amine cation, and X comprising I-, a halogen ion (Fabrication of perovskite solar cells on p. 14142), wherein the doping ions comprise Ac-, an acid radical ion.
The Ac- doping ion is added as a part of Zr(Ac)4, and the proportion of doping ion is defined with respect to a Zr/Pb ratio (Results and discussion on p. 14137). 1 mmol of PbI2 (0.461 g based on the molar mass of 461 g/mol), 1 mmol of MAI (0.159 g based on the molar mass of 159 g/mol). Therefore at a proportion of 1.2 mol% (Fig. 1), 1 mmol*0.012 = 0.012 mmol of Zr(Ac)4, corresponding to 0.012*4=0.0
48 mmol of Ac- ion (0.0113 g based on the molar mass of 59.04 g/mol) is added to the precursor substrate, which is a 0.0113/(0.461+0.159+0.0113) ~ 0.45% based on a mass of the perovskite precursor material.
Regarding claims 5 and 6, Wu teaches a preparation method for a perovskite precursor material comprising mixing and reacting, in a first solvent (DMF) a raw material for providing doping ions (Zr(Ac)4) and a raw material for synthesizing a precursor substrate, and subjecting a reacted solution to first crystallization treatment (Fabrication of perovskite solar cells on p. 14142, crystallization is evident based on Fig. 1 and the relevant text in Results and discussion).
The precursor substrate comprises a material (MAI) having a chemical formula MX, M comprising methylammonium, an organic amine cation, and X comprising I-, a halogen ion, wherein the doping ions comprise Ac-, an acid radical ion.
The Ac- doping ion is added as a part of Zr(Ac)4, and the proportion of doping ion is defined with respect to a Zr/Pb ratio (Results and discussion on p. 14137). 1 mmol of PbI2 (0.461 g based on the molar mass of 461 g/mol), 1 mmol of MAI (0.159 g based on the molar mass of 159 g/mol). Therefore at a proportion of 1.2 mol% (Fig. 1), 1 mmol*0.012 = 0.012 mmol of Zr(Ac)4, corresponding to 0.012*4=0.0
48 mmol of Ac- ion (0.0113 g based on the molar mass of 59.04 g/mol) is added to the precursor substrate, which is a 0.0113/(0.461+0.159+0.0113) ~ 0.45% based on a mass of the perovskite precursor material.
Regarding claim 12, Wu teaches a perovskite solar cell (Fabrication of perovskite solar cells on p. 14142) comprising a first electrode (“ITO substrate”), a perovskite layer, and a second electrode (“100 nm Ag”) that are sequentially stacked, wherein the perovskite layer comprises the perovskite material according to claim 1.
Claim Rejections - 35 USC § 103
The text of those sections of Title 35, U.S. Code not included in this action can be found in a prior Office action.
Claim(s) 13, 14, 18, 20, and 21 is/are rejected under 35 U.S.C. 103 as being unpatentable over Wang as applied to claim 1 above, and further in view of US 2013/0214205 to Vockic.
Regarding claims 13 and 14, Wang teaches the limitations of claim 1. While the doping ions are recited as providing added material stability (Introduction on p. 2435-2436), the ions are not recited as comprising NO3-. However, it would have been obvious as of the effective filing date of the claimed invention for a person having ordinary skill in the art to substitute NO3- for the SCN- ion taught by Wang, as Vockic teaches such a dopant is also suitable for stabilizing perovskites (claim 13, ¶0067, 0075).
As the molar mass of NO3- (62 g/mol) is quite similar to that of SCN- (58 g/mol), it would have been obvious as of the effective filing date of the claimed invention for a person having ordinary skill in the art for a skilled artisan would prepare the NO3- doping ions with a substantially similar mass percentage as the SCN- ions taught by Wang to achieve the desired stabilizing function.
Regarding claims 18 and 20, Wang teaches the limitations of claim 1. The precursor substrate comprises PbI2 (Precursor preparation on p. 2439). While the doping ions are recited as providing added material stability (Introduction on p. 2435-2436), the ions are not recited as comprising NO3-. However, it would have been obvious as of the effective filing date of the claimed invention for a person having ordinary skill in the art to substitute NO3- for the SCN- ion taught by Wang, as Vockic teaches such a dopant is also suitable for stabilizing perovskites (claim 13, ¶0067, 0075).
As the molar mass of NO3- (62 g/mol) is quite similar to that of SCN- (58 g/mol), it would have been obvious as of the effective filing date of the claimed invention for a person having ordinary skill in the art for a skilled artisan would prepare the NO3- doping ions with a substantially similar mass percentage as the SCN- ions taught by Wang to achieve the desired stabilizing function.
Regarding claim 21, Wang teaches the limitations of claim 1. The precursor substrate comprises PbI2 (Precursor preparation on p. 2439). While the doping ions are recited as providing added material stability (Introduction on p. 2435-2436), the ions are not recited as comprising F-. However, it would have been obvious as of the effective filing date of the claimed invention for a person having ordinary skill in the art to substitute F- for the SCN- ion taught by Wang, as Vockic teaches such a dopant is also suitable for stabilizing perovskites (¶0067, 0075).
In Wang, the proportion of doping ions is represented as a molar percentage of PbI2 (2%, also see first paragraph underneath Results and discussion on p. 2436) that has been substituted with Pb(SCN)2. The composition of the perovskite precursor material is recited as Csx(MA0.7FA0.3)1-xPbI3. Therefore, one mole of the unsubstituted precursor material has x Cs ions (each ion having a molar mass of 132.9 g/mol), (1-x)*0.7 MA (methylammonium) ions (32.07 g/mol), (1-x)*0.3 FA (formamidinium) ions (45.07 g/mol), 1 Pb ion (207.2 g/mol), and 3 iodide ions (126.9 g/mol). Substituting 0.02 moles of Pb(SCN)2 in for 0.02 moles of PbI2 does not change the number of Pb ions in the precursor material, but does change the number of iodide ions from 3 to (1+2*0.98)= 2.96, and introduces 2*0.2=0.04 SCN ions (58.08 g/mol). In the material of modified-Wang, 0.04 F- ions (19 g/mol) are substituted instead of 0.04 SCN- ions. Therefore, in the material of modified-Vockic, the molar mass of the substituted precursor material, substituted with 10% Cs ions (as shown in Fig. 1(d), for instance, and discussed in Results and discussion) is 633.93 g/mol, and the mass percentage of doping fluoride ions is 0.12%.
Claim(s) 8 and 9 is/are rejected under 35 U.S.C. 103 as being unpatentable over Wang, Wang II, or Wu as individually applied to claim 5 above, and further in view of US 2018/0066383 to Bakr (of record).
Regarding claim 8, the references each teach the limitations of claim 5. In the respective references, M is an organic amine cation and/or cesium ions, and X comprises halogen ions. The references do not teach that the reaction temperature for mixing and reacting, in the first solvent, the raw material for providing the doping ions and the raw material for synthesizing the precursor substrate is 0oC to 5oC. Bakr teaches that it would have been obvious as of the effective filing date of the claimed invention for a person having ordinary skill in the art to vary that temperature to achieve the desired rate of formation of the substrate (¶0078), and to accommodate the solubility of ions, which depends on temperature (¶0147).
“[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.” See In re Aller, 220 F.2d 454, 456, 105 USPQ 233, 235 (CCPA 1955). The discovery of an optimum value of a known result effective variable, without producing any new or unexpected results, is within the ambit of a person of ordinary skill in the art. See In re Boesch, 205 USPQ 215 (CCPA 1980) (see MPEP § 2144.05, II.).
Regarding claim 9, the references each teach the limitations of claim 5. The references do not teach that the reaction temperature for mixing and reacting, in the first solvent, the raw material for providing the doping ions and the raw material for synthesizing the precursor substrate is 70oC to 90oC. Bakr teaches that it would have been obvious as of the effective filing date of the claimed invention for a person having ordinary skill in the art to vary that temperature to achieve the desired rate of formation of the substrate (¶0078), and to accommodate the solubility of ions, which depends on temperature (¶0147).
“[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.” See In re Aller, 220 F.2d 454, 456, 105 USPQ 233, 235 (CCPA 1955). The discovery of an optimum value of a known result effective variable, without producing any new or unexpected results, is within the ambit of a person of ordinary skill in the art. See In re Boesch, 205 USPQ 215 (CCPA 1980) (see MPEP § 2144.05, II.).
Claim(s) 10 and 11 is/are rejected under 35 U.S.C. 103 as being unpatentable over Wu, and further in view of US 2018/0248052 to Seok.
Regarding claim 10, Wu teaches a perovskite precursor solution comprising a second solvent (DMF) and further comprising the perovskite precursor material according to claim 1 (see rejection of claim 1 above over Wu). The solution is filtered, but not referred to as a slurry.
The ordinary and customary meaning of a term may be evidenced by a variety of sources, including the words of the claims themselves, the specification, drawings, and prior art. However, the best source for determining the meaning of a claim term is the specification – the greatest clarity is obtained when the specification serves as a glossary for the claim terms. See, e.g., In re Abbott Diabetes Care Inc., 696 F.3d 1142, 1149-50, 104 USPQ2d 1337, 1342-43 (Fed. Cir. 2012). MPEP §2111.01.III. The instant specification, at paragraph [0118] on p. 19, describes the formation of a perovskite slurry as comprising dissolved elements that have been filtered. In other words, Applicant’s slurry does not specifically have solid elements. Therefore, Wu’s solution is a slurry within the broadest reasonable interpretation.
The second solvent does not comprise N-methyl-2-pyrrolidone (NMP). Seok, however, teaches that it would have been obvious as of the effective filing date of the claimed invention for a person having ordinary skill in the art to form the second solvent to comprise NMP, as such a compound is a suitable alternative to DMF (¶0249, 0326).
Regarding claim 11, Wu teaches a perovskite precursor solution comprising a second solvent (DMF) and further comprising the perovskite precursor material obtained by using the preparation method according to claim 5 (see rejection of claim 5 above over Wu). The solution is filtered, but not referred to as a slurry.
The ordinary and customary meaning of a term may be evidenced by a variety of sources, including the words of the claims themselves, the specification, drawings, and prior art. However, the best source for determining the meaning of a claim term is the specification – the greatest clarity is obtained when the specification serves as a glossary for the claim terms. See, e.g., In re Abbott Diabetes Care Inc., 696 F.3d 1142, 1149-50, 104 USPQ2d 1337, 1342-43 (Fed. Cir. 2012). MPEP §2111.01.III. The instant specification, at paragraph [0118] on p. 19, describes the formation of a perovskite slurry as comprising dissolved elements that have been filtered. In other words, Applicant’s slurry does not specifically have solid elements. Therefore, Wu’s solution is a slurry within the broadest reasonable interpretation.
The second solvent does not comprise N-methyl-2-pyrrolidone (NMP). Seok, however, teaches that it would have been obvious as of the effective filing date of the claimed invention for a person having ordinary skill in the art to form the second solvent to comprise NMP, as such a compound is a suitable alternative to DMF (¶0249, 0326).
Allowable Subject Matter
Claims 15-17 and 19 objected to as being dependent upon a rejected base claim, but would be allowable if rewritten in independent form including all of the limitations of the base claim and any intervening claims. The claims recite combinations of limitations that are not taught by or not rendered as prima facie obvious by the prior art.
Response to Arguments
Applicant’s arguments with respect to claim(s) 1-3, 5, 6, 8-14, 18, and 20-22 have been considered but are moot because the new ground of rejection does not rely on any reference applied in the prior rejection of record for any teaching or matter specifically challenged in the argument.
Regarding the claims which are rejected on 103 grounds, Applicant has presented evidence of the criticality of certain limitations.
Whether the unexpected results are the result of unexpectedly improved results or a property not taught by the prior art, the "objective evidence of nonobviousness must be commensurate in scope with the claims which the evidence is offered to support." In other words, the showing of unexpected results must be reviewed to see if the results occur over the entire claimed range. In re Clemens, 622 F.2d 1029, 1036, 206 USPQ 289, 296 (CCPA 1980). MPEP §716.02(d).
For instance, claims 13, 14, 18, 20, and 21 are rejected over a combination of references. However, the evidence is insufficient to overcome the reasoning of prima facie obviousness above, as only one data point regarding the effectiveness of NO3---- and F- ions, each at only one concentration, is presented. To establish unexpected results over a claimed range, applicants should compare a sufficient number of tests both inside and outside the claimed range to show the criticality of the claimed range. In re Hill, 284 F.2d 955, 128 USPQ 197 (CCPA 1960). MPEP §716.02(d).II.
The temperature limitations of claims 8 and 9 are not shown to be critical in the instant specification, as Comparative embodiment 2 can only be compared against materials in which the dopant is PO22-.
The examiner could not identify evidence that supported the criticality of the inclusion of NMP in the claimed slurry.
Conclusion
The prior art made of record and not relied upon is considered pertinent to applicant's disclosure. “Controlled n-doping in air-stable CsPbI2Br perovskite solar cells with a record efficiency of 16.79%”; “High tolerance to iron contamination in lead halide perovskite solar cells”.
Applicant's amendment necessitated the new ground(s) of rejection presented in this Office action. Accordingly, THIS ACTION IS MADE FINAL. See MPEP § 706.07(a). Applicant is reminded of the extension of time policy as set forth in 37 CFR 1.136(a).
A shortened statutory period for reply to this final action is set to expire THREE MONTHS from the mailing date of this action. In the event a first reply is filed within TWO MONTHS of the mailing date of this final action and the advisory action is not mailed until after the end of the THREE-MONTH shortened statutory period, then the shortened statutory period will expire on the date the advisory action is mailed, and any nonprovisional extension fee (37 CFR 1.17(a)) pursuant to 37 CFR 1.136(a) will be calculated from the mailing date of the advisory action. In no event, however, will the statutory period for reply expire later than SIX MONTHS from the mailing date of this final action.
Any inquiry concerning this communication or earlier communications from the examiner should be directed to Ryan S Cannon whose telephone number is (571)270-7186. The examiner can normally be reached M-F, 8:30am-5:30pm PST.
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Ryan S. Cannon
Primary Examiner
Art Unit 1726
/RYAN S CANNON/ Primary Examiner, Art Unit 1726
Prosecution Insights