DETAILED ACTION
Examiner’s Notes
The present application, filed on or after March 16, 2013, is being examined under the first inventor to file provisions of the AIA .
Remarks
Claims 1, 3, 16, and 22-24 are amended.
Claims 25-30 and 33-34 are withdrawn from further consideration.
Claims 1-34 are pending.
Claim Rejections - 35 USC § 112
The following is a quotation of 35 U.S.C. 112:
(b) CONCLUSION.—The specification shall conclude with one or more claims particularly pointing out and distinctly claiming the subject matter which the inventor or a joint inventor regards as the invention.
The following is a quotation of 35 U.S.C. 112 (pre-AIA ), second paragraph:
The specification shall conclude with one or more claims particularly pointing out and distinctly claiming the subject matter which the applicant regards as his invention.
Claims 1-24 and 31-32 are rejected under 35 U.S.C. 112(b) or 35 U.S.C. 112 (pre-AIA ), second paragraph, as being indefinite for failing to particularly point out and distinctly claim the subject matter which the inventor or a joint inventor, or for pre-AIA the applicant regards as the invention.
Claim 1 recites “the first metal halide component” in line 5. There is insufficient antecedent basis for this limitation in the claim. For the purpose of office action, the recitation will be treated as if it recites “the first halide component”. Appropriate correction is required.
Claim Rejections - 35 USC § 102
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 the appropriate paragraphs of 35 U.S.C. 102 that form the basis for the rejections under this section made in this Office action:
A person shall be entitled to a patent unless –
(a)(1) the claimed invention was patented, described in a printed publication, or in public use, on sale or otherwise available to the public before the effective filing date of the claimed invention.
(a)(2) the claimed invention was described in a patent issued under section 151, or in an application for patent published or deemed published under section 122(b), in which the patent or application, as the case may be, names another inventor and was effectively filed before the effective filing date of the claimed invention.
Claims 1, 4, 6-9, 11-12, 14-21, 23-24, and 32 are rejected under 35 U.S.C. 102(a)(1) as being anticipated by IGUAL-MUNOZ (Room-Temperature Vacuum Deposition of CsPbI2Br Perovskite Films from Multiple Sources and Mixed Halide Precursors).
Regarding claim 1, IGUAL-MUNOZ teaches a method for producing a perovskite material (see the Room-Temperature Vacuum Deposition of CsPbI2Br Perovskite Films for perovskite solar cells) (see Abstract, Scheme 1, Fig. 4, Experimental Section) which comprises:
i. depositing a first metal halide precursor comprising a first halide component (see depositing PbI2 from the “4-sources” in Scheme 1); and
ii. depositing a second metal halide precursor comprising a second halide component (see depositing PbBr2 from the “4-sources” in Scheme 1), wherein the second halide component in the second metal halide precursor is different from the first metal halide component (see PbI2 and PbBr2, which are different from each other) and the first and second metal halide precursors are deposited separately (see “4-sources”, which is deposited separately) (see Scheme 1); and at least one of steps iii and iv:
iii. depositing an inorganic halide precursor; and/or iv. depositing a first organic halide precursor (see depositing CsI, which is an inorganic halide precursor, which corresponding “iii. depositing an inorganic halide precursor”);
to form the perovskite material which comprises a mixed halide (see CsPbI2Br, which comprises a mixed halide); wherein steps i. and ii. are carried out by physical vapour deposition and step iii., if present, is carried out by physical vapour deposition (see “In this work, we study the properties of CsPbI2Br films prepared by thermal vacuum deposition” in P8642, which is a physical vacuum deposition).
Regarding claim 4, Applicant is directed above for a full discussion as applied to claim 1.
IGUAL-MUNOZ teaches a final annealing step (see Experimental Section: The bilayer was annealed at 140°C for 10 min).
Regarding claim 6, Applicant is directed above for a full discussion as applied to claim 1.
IGUAL-MUNOZ teaches for producing a thin film of perovskite material (see Experimental Section: The CsPbBrI2 perovskite films were fabricated).
Regarding claim 7, Applicant is directed above for a full discussion as applied to claim 1.
IGUAL-MUNOZ teaches three or more precursors are sequentially vapour deposited on a substrate (see ITO-coated glass substrates) (see Fig. 4a and Experimental Section; The precursors are sequentially vapour deposited on the ITO-coated glass substrate).
Regarding claim 8, Applicant is directed above for a full discussion as applied to claim 1.
IGUAL-MUNOZ teaches wherein step iii. is present and the deposition of the first metal halide precursor and the inorganic halide precursor is done together in a co-evaporation step (see Experimental Section: all materials were codeposited).
Regarding claim 9, Applicant is directed above for a full discussion as applied to claim 1.
IGUAL-MUNOZ teaches wherein the steps are carried out in any order (see the rejection of claim 1).
Regarding claim 11, Applicant is directed above for a full discussion as applied to claim 1.
IGUAL-MUNOZ teaches wherein the first and second metal halide precursors in steps i. and ii. independently comprise a divalent cation (see Pb2+).
Regarding claim 12, Applicant is directed above for a full discussion as applied to claim 1.
IGUAL-MUNOZ teaches wherein the first metal halide precursor has formula BX2 and wherein the second metal halide precursor has formula BX'2, wherein each B is the same or different and is selected from a metal cation (see Pb2+), and X and X' are different and are each independently selected from halide anions (see I- and Br-) (see PbI2 and PbBr2; see the rejection of claim 1).
Regarding claim 14, Applicant is directed above for a full discussion as applied to claim 1.
IGUAL-MUNOZ teaches wherein the inorganic halide precursor in step iii. has formula AX, wherein A comprises a monovalent metal cation (see Cs+) and X is a halide anion (see I-) (see CsI).
Regarding claim 15, Applicant is directed above for a full discussion as applied to claim 1.
IGUAL-MUNOZ teaches wherein the inorganic halide precursor in step iii. is selected from bromides or iodides of Cs+ (see I- of Cs+).
Regarding claims 16-19, Applicant is directed above for a full discussion as applied to claim 1.
Regarding the claimed “wherein the first, second and third organic halide precursors, where present, have formulae A'X, A"X and A"'X respectively, wherein A', A" and A"' are, independently, selected from monovalent organic cations” in claim 16, “wherein the first organic halide precursor has formula A'X wherein A' is selected from MA, FA, and EA” in claim 17, “wherein the second organic halide precursor has formula A"X where A" is selected from MA, FA, GA, EA, BzA,BA, DMA, Im, PEAS and Ac” in claim 18, and “wherein the third organic halide precursor has formula A"'X where A"' is selected from MA, FA, GA, EA, BzA,BA, DMA, Im, PEAS and Ac” in claim 19, since claims 16-19 further limit the first, second and third organic halide precursors of claim 1, which are not present, and the first, second and third organic halide precursors is not relied on for the art rejection of claim 1, the claimed limitation required by claims 16-19 is considered to be already met by IGUAL-MUNOZ.
Regarding claim 20, Applicant is directed above for a full discussion as applied to claim 1.
IGUAL-MUNOZ teaches wherein the halide components of the first and second metal halide precursors in steps i. and ii. are independently selected from iodides, chlorides, and bromides (see PbI2 and PbBr2; see the rejection of claim 1).
Regarding claim 21, Applicant is directed above for a full discussion as applied to claim 1.
IGUAL-MUNOZ teaches wherein the second metal halide precursor has a different metal component to the first metal halide precursor (IGUAL-MUNOZ, alternatively, teaches i. depositing a first metal halide precursor (see depositing PbI2 from the “4-sources” in Scheme 1), ii. depositing a second metal halide precursor (see depositing CsI from the “4-sources” in Scheme 1), iii. depositing an inorganic halide precursor (see depositing PbBr2, which is an inorganic halide precursor); Therefore, Cs is different from Pb).
Regarding claim 23, Applicant is directed above for a full discussion as applied to claim 1.
IGUAL-MUNOZ teaches wherein the process is a layer-by-layer deposition carried out one or more times in a linear sequence (see Fig. 4a; see the layer-by-layer depositions of the layers in Fig. 4a).
Regarding claim 24, Applicant is directed above for a full discussion as applied to claim 1.
IGUAL-MUNOZ teaches wherein the process is carried out one or more times to obtain a desired thickness of the perovskite in the range 50 to 2000 nm (see Experimental Section: the thickness of the films used in this study was 250 nm).
Regarding claim 32, Applicant is directed above for a full discussion as applied to claim 1.
IGUAL-MUNOZ teaches wherein the first and second metal halide precursors in steps i. and ii. are independently selected from Pb2+ and Sn2+ (see Pb2+).
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 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.
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 2-3, 5, 10, 22, and 31 are rejected under 35 U.S.C. 103 as being unpatentable over IGUAL-MUNOZ (Room-Temperature Vacuum Deposition of CsPbI2Br Perovskite Films from Multiple Sources and Mixed Halide Precursors) as applied to claim 1 above, further in view of BIDIKOUDI (Low-Toxicity Perovskite Applications in Carbon Electrode Perovskite Solar Cells—A Review).
Regarding claims 2-3, Applicant is directed above for a full discussion as applied to claim 1.
Regarding the claimed “a step v. of deposition of a second organic halide precursor which is different from the first organic halide precursor” in claim 2 and “a step vi. of deposition of a third organic halide precursor which is different from the first and second organic halide precursors” in claim 3, IGUAL-MUNOZ teaches CsPbI2Br Perovskite Films for perovskite solar cells by deposition of metal halide precursors, but does not explicitly disclose the claimed feature. However, BIDIKOUDI discloses Cs0.05(MA0.17FA0.83)0.95Pb(I0.83Br0.17)3 perovskite solar cell, which provides a high photoelectric conversion efficiency (see Table 2). It would have been obvious to one of the ordinary skill in the art before the effective filing date of the claimed invention to employ Cs0.05(MA0.17FA0.83)0.95Pb(I0.83Br0.17)3 perovskite material in the device of IGUAL-MUNOZ as taught by BIDIKOUDI, because Cs0.05(MA0.17FA0.83)0.95Pb(I0.83Br0.17)3 provides a high photoelectric conversion efficiency and because the selection of a known material based on its suitability for its intended use supports a prima facie obviousness determination (MPEP 2144). Additionally, IGUAL-MUNOZ discloses the (perovskite film) deposition was possible by increasing the number of deposition sources (hence of precursors); the superior quality can be attained by increasing the number of precursors (and hence deposition sources); Multisource vacuum deposition: all materials were codeposited; In this work, we study the properties of CsPbI2Br films prepared by thermal vacuum deposition of PbI2, PbBr2, CsI, CsBr (see Abstract, Experimental Section, P8642, and Conclusion), and BIDIKOUDI disclose MAI and FAI organic halide precursors. It would have been obvious to one of the ordinary skill in the art before the effective filing date of the claimed invention to employ deposition of MAI, FAI organic halide precursors and PbI2, PbBr2, CsI, CsBr metal halide precursors by thermal vacuum deposition for fabrication of Cs0.05(MA0.17FA0.83)0.95Pb(I0.83Br0.17)3 perovskite film in the device of IGUAL-MUNOZ, because increasing the number of precursors (and hence deposition sources) provides superior quality. Therefore, modified IGUAL-MUNOZ teaches a step v. of deposition of a second organic halide precursor which is different from the first organic halide precursor (see the MAI organic halide precursor, which is different from the first organic halide precursor which is not present) and a step vi. of deposition of a third organic halide precursor which is different from the first and second organic halide precursors (see the FAI organic halide precursor which is different from MAI organic halide precursor and the first organic halide precursor which is not present).
Regarding claim 5, Applicant is directed above for a full discussion as applied to claim 2.
Modified IGUAL-MUNOZ teaches wherein steps iv., if present, and v., if present, are carried out by physical vapour deposition (see the rejection of claim 2).
Regarding claim 10, Applicant is directed above for a full discussion as applied to claim 1.
Regarding the claimed “wherein the perovskite material comprises two or more different monovalent cations”, IGUAL-MUNOZ teaches the perovskite material comprises one monovalent cation (see Cs+ in CsPbI2Br perovskite film for perovskite solar cells), but does not explicitly disclose the claimed “two or more different monovalent cations”. However, BIDIKOUDI discloses Cs0.05(MA0.17FA0.83)0.95Pb(I0.83Br0.17)3 perovskite solar cell, which provides a high photoelectric conversion efficiency (see Table 2). It would have been obvious to one of the ordinary skill in the art before the effective filing date of the claimed invention to employ Cs0.05(MA0.17FA0.83)0.95Pb(I0.83Br0.17)3 perovskite material in the device of IGUAL-MUNOZ as taught by BIDIKOUDI, because Cs0.05(MA0.17FA0.83)0.95Pb(I0.83Br0.17)3 provides a high photoelectric conversion efficiency and because the selection of a known material based on its suitability for its intended use supports a prima facie obviousness determination (MPEP 2144). Additionally, IGUAL-MUNOZ discloses the (perovskite film) deposition was possible by increasing the number of deposition sources (hence of precursors); the superior quality can be attained by increasing the number of precursors (and hence deposition sources); Multisource vacuum deposition: all materials were codeposited; In this work, we study the properties of CsPbI2Br films prepared by thermal vacuum deposition of PbI2, PbBr2, CsI, CsBr (see Abstract, Experimental Section, P8642, and Conclusion), and BIDIKOUDI disclose MAI and FAI organic halide precursors. It would have been obvious to one of the ordinary skill in the art before the effective filing date of the claimed invention to employ deposition of MAI, FAI organic halide precursors and PbI2, PbBr2, CsI, CsBr metal halide precursors by thermal vacuum deposition for fabrication of Cs0.05(MA0.17FA0.83)0.95Pb(I0.83Br0.17)3 perovskite film in the device of IGUAL-MUNOZ, because increasing the number of precursors (and hence deposition sources) provides superior quality. Therefore, modified BIDIKOUDI teaches the perovskite material comprises two or more different monovalent cations (see Cs+, MA+, and FA+ in Cs0.05(MA0.17FA0.83)0.95Pb(I0.83Br0.17)3).
Regarding claim 22, Applicant is directed above for a full discussion as applied to claim 1.
Regarding the claimed “wherein the perovskite material has formula (I): AaA’bA’’cA’’’dBxB'1-x(XyX'1-Y)3, wherein; A is a monovalent inorganic cation; A' is a first monovalent organic cation; A" is a second monovalent organic cation; A"' is a third monovalent organic cation; wherein A, A', A" and A"' are different from each other and; B is a divalent metal cation; B' is a different divalent metal cation to B;X is a halide anion; and X' is a different halide anion to X; 0<a<1 0<b<1 0<c<1 0<d<1 a+b+c+d =1 0<x<1 and 0<y<1”, IGUAL-MUNOZ teaches CsPbI2Br Perovskite Films for perovskite solar cells by deposition of metal halide precursors, but does not explicitly disclose the claimed feature. However, BIDIKOUDI discloses Cs0.05(MA0.17FA0.83)0.95Pb(I0.83Br0.17)3 perovskite solar cell, which provides a high photoelectric conversion efficiency (see Table 2). It would have been obvious to one of the ordinary skill in the art before the effective filing date of the claimed invention to employ Cs0.05(MA0.17FA0.83)0.95Pb(I0.83Br0.17)3 perovskite material in the device of IGUAL-MUNOZ as taught by BIDIKOUDI, because Cs0.05(MA0.17FA0.83)0.95Pb(I0.83Br0.17)3 provides a high photoelectric conversion efficiency and because the selection of a known material based on its suitability for its intended use supports a prima facie obviousness determination (MPEP 2144). Additionally, IGUAL-MUNOZ discloses the (perovskite film) deposition was possible by increasing the number of deposition sources (hence of precursors); the superior quality can be attained by increasing the number of precursors (and hence deposition sources); Multisource vacuum deposition: all materials were codeposited; In this work, we study the properties of CsPbI2Br films prepared by thermal vacuum deposition of PbI2, PbBr2, CsI, CsBr (see Abstract, Experimental Section, P8642, and Conclusion), and BIDIKOUDI disclose MAI and FAI organic halide precursors. It would have been obvious to one of the ordinary skill in the art before the effective filing date of the claimed invention to employ deposition of MAI, FAI organic halide precursors and PbI2, PbBr2, CsI, CsBr metal halide precursors by thermal vacuum deposition for fabrication of Cs0.05(MA0.17FA0.83)0.95Pb(I0.83Br0.17)3 perovskite film in the device of IGUAL-MUNOZ, because increasing the number of precursors (and hence deposition sources) provides superior quality. Therefore, modified IGUAL-MUNOZ teaches wherein the perovskite material has formula (I): AaA’bA’’cA’’’dBxB'1-x(XyX'1-Y)3, wherein; A is a monovalent inorganic cation; A' is a first monovalent organic cation; A" is a second monovalent organic cation; A"' is a third monovalent organic cation; wherein all A cations A, A', A" and A"' are different from each other and; B is a divalent metal cation; B' is a different divalent metal cation to B;X is a halide anion; and X' is a different halide anion to X; 0<a<1 0<b<1 0<c<1 0<d<1 a+b+c+d =1 0<x<1 and 0<y<1 (see Cs0.05(MA0.17FA0.83)0.95Pb(I0.83Br0.17)3; A0.05(A’’0.17A’’’0.83)0.95B'1(X0.83X'0.17)3).
Regarding claim 31, Applicant is directed above for a full discussion as applied to claim 5.
Modified IGUAL-MUNOZ teaches wherein all steps are carried out by a physical vapour deposition (see the rejection of claims 2, 5).
Claim 13 is rejected under 35 U.S.C. 103 as being unpatentable over IGUAL-MUNOZ (Room-Temperature Vacuum Deposition of CsPbI2Br Perovskite Films from Multiple Sources and Mixed Halide Precursors) as applied to claim 1 above, further in view of YU (Alloy-induced phase transition and enhanced photovoltaic performance: the case of Cs3Bi2I9-xBrx perovskite solar cells).
Regarding claim 13, Applicant is directed above for a full discussion as applied to claim 1.
Regarding the claimed “wherein the first metal halide precursor has formula BX and wherein the second metal halide precursor has formula BX'3, or vice versa, wherein each B is the same or different and is a metal cation, and X and X' are different and are independently selected from halide anions”, IGUAL-MUNOZ teaches CsPbI2Br Perovskite Films for perovskite solar cells by deposition of metal halide precursors, but does not explicitly disclose the claimed feature. However, YU discloses Cs3Bi2I9-xBrx perovskite material, which provides a highly stable leadfree perovskite solar cell (see Abstract). It would have been obvious to one of the ordinary skill in the art before the effective filing date of the claimed invention to employ Cs3Bi2I9-xBrx perovskite material in the device of IGUAL-MUNOZ as taught by YU, because Cs3Bi2I9-xBrx provides a high photoelectric conversion efficiency and because the selection of a known material based on its suitability for its intended use supports a prima facie obviousness determination (MPEP 2144). Additionally, IGUAL-MUNOZ discloses the (perovskite film) deposition was possible by increasing the number of deposition sources (hence of precursors); the superior quality can be attained by increasing the number of precursors (and hence deposition sources); Multisource vacuum deposition: all materials were codeposited; In this work, we study the properties of CsPbI2Br films prepared by thermal vacuum deposition of PbI2, PbBr2, CsI, CsBr (see Abstract, Experimental Section, P8642, and Conclusion), and YU disclose CsI, BiI3, CsBr, BiBr3 metal halide precursors. It would have been obvious to one of the ordinary skill in the art before the effective filing date of the claimed invention to employ deposition of CsI, BiI3, CsBr, BiBr3 metal halide precursors by thermal vacuum deposition for fabrication of Cs3Bi2I9-xBrx perovskite film in the device of IGUAL-MUNOZ, because increasing the number of precursors (and hence deposition sources) provides superior quality. Therefore, modified IGUAL-MUNOZ teaches wherein the first metal halide precursor has formula BX (see CsI) and wherein the second metal halide precursor has formula BX'3 (BiBr3) or vice versa, wherein each B is the same or different and is a metal cation (see Cs+ and Bi3+), and X and X' are different and are independently selected from halide anions (see I- and Br-).
Response to Arguments
Applicant's arguments filed on 04/06/2026 have been fully considered, but they are not persuasive.
Regarding claim 1, Applicant’s argument regarding that the prior art does not teach or suggest “the first and second metal halide precursors are deposited separately” in the amended claim 1 in P2-P4, is not persuasive.
Scheme 1 of IGUAL-MUNOZ shows that PbI2 precursor and PbBr2 precursor, which are separate from each other, are deposited separately from each other, which corresponds to the claimed “the first and second metal halide precursors are deposited separately”. The limitation “separately” does not necessarily require “separation of the deposition steps”.
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 extension fee 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 TAE-SIK KANG whose telephone number is 571-272-3190. The examiner can normally be reached on 9:00am – 5:00pm.
If attempts to reach the examiner by telephone are unsuccessful, the examiner’s supervisor, Matthew T. Martin can be reached on 571-270-7871. The fax phone number for the organization where this application or proceeding is assigned is 571-273-8300.
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/TAE-SIK KANG/
Primary Examiner, Art Unit 1728
Prosecution Insights