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 .
DETAILED ACTION
Claims 1-7,9-14,17-18 and 21-25 of A. F. Palmstrom, et al., US 18/553,888 (10/04/2023) are pending and are under examination on merits. Claims 1-7,9-14,17-18 and 21-24 are rejected and claim 25 is objected to.
Election/Restrictions
Pursuant to the restriction requirement, Applicant elected Group I, without traverse, in the reply filed on 03/11/2026. Claims 19-20 drawn to nonelected Group II are withdrawn from consideration pursuant to 37 CFR 1.142(b). Applicant cancelled claim 8, 15-16 and 19-20, added now claims 21-25 that falls within the scope of the elected Group I, in the reply filed on 08/24/2026. The restriction requirement is maintained as FINAL.
Withdrawal Claims Rejections 35 U.S.C. 112(b)
Rejection of claim 1-18 are rejected under 35 U.S.C. 112(b) as indefinite is withdrawn in view of the instant claim 1 has been amended by deletion of the term of “substantially”.
Withdrawal Claim Rejections - 35 USC § 102
Rejection of claim 1-18 under 35 U.S.C. 102(a)(1)(a)(2) as being anticipated by V-B. Javier, et al, US 20180204682 A1(2018)(“Javier”) evidenced with M. M. Hamada, et al, 505, Nuclear Instruments and Methods in Physics Research Section A, 517-520 (2003)(“Hamada”) is withdrawn in view of the instant claim 1 has been amended with a limitation of “the separating results in a solid stream comprising the halide perovskite crystal and an effluent stream comprising the metal impurity”, which cannot be met by Javier.
Rejection of claim 1, 3-10 under 35 U.S.C. 102(a)(1)(a)(2) as being anticipated by H. J. Snaith, et al, US 20190115549A1 (2019)(“Snaith”) evidenced with M. M. Hamada, et al, 505, Nuclear Instruments and Methods in Physics Research Section A, 517-520 (2003)(“Hamada”) is withdrawn for the same reason as given above.
Withdrawal Claim Rejections – Double Patenting
Rejection of claims 1, 3-10 on the ground of nonstatutory double patenting as being unpatentable over claims 1, 15 and 19 of the U.S. Patent No. US 10,797,255B2 (2020) that has been published as US 20190115549A1 in view of V-B. Javier, et al, US 20180204682 A1 (2018)(“Javier”) as evidenced with M. M. Hamada, et al, 505, Nuclear Instruments and Methods in Physics Research Section A, 517-520 (2003)(“Hamada”) is withdrawn for the same reason as given above.
New Claim Rejections - 35 USC § 112
The following is a quotation of 35 U.S.C. 112(b):
(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.
Claim 14 is rejected under 35 U.S.C. 112(b) as being indefinite for failing to particularly point out and distinctly claim the subject matter which the inventor or a joint inventor (or for applications subject to pre-AIA 35 U.S.C. 112, the applicant), regards as the invention.
Claim 14 recites the limitation of “the applying to the mixture of at least one treatment”. There is insufficient antecedent basis for this limitation in the claim. Further, the claim recites “. . . at least one of evaporating at least a portion of the mixture, the applying to the mixture of. . .”; it is not clear what’s the relationship between the evaporation and the claimed applying treatment? Is the evaporation caused by the applying treatment or the applying treatment is an alternative of the evaporation?
New Claim Rejections - 35 USC § 102
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.
35 USC § 102 Rejection over Kadro
Claims 1-7, 9-10, 12-14 and 24 are rejected under 35 U.S.C. 102(a)(1) as being anticipated by J. M. Kadro, et al. 5.1 Scientific reports 11654 (2015)(“Kadro”) evidenced with M. M. Hamada, et al, 505, Nuclear Instruments and Methods in Physics Research Section A, 517-520 (2003)(“Hamada”).
Kadro teaches a method for preparation of CH3NH3PbI3 crystals as indicated below:
The growth solutions were prepared under nitrogen by dissolving PbI2 (99%, Sigma Aldrich) and CH3NH3I in γ-Butyrolactone (98%, Sigma Aldrich) in 1:1 molar ratio. Commercially available chemicals were used as received without further purification. Solutions of 0.3 M to 0.9 M were prepared. The solvent was added to the salts at room temperature. Tightly closed vials were heated on a conventional hotplate at 100 °C until no visible traces of undissolved salts remained. Solutions were then transferred out from the glovebox. Once the salts were completely dissolved, no visible turbidity or precipitation occurred for days for equimolar solutions and for solutions with excess of CH3NH3I. Solutions below 0.8 M concentration were found to be stable for weeks.
To grow the crystals, screw-top scintillation vials of 15 ml volume were used for solution volumes of 1.5 ml. After stabilizing the temperature of the solutions for 10 min at 100 °C, temperature of the hotplate was increased until black crystals formed at around 190 °C. To avoid boilover, the solution temperature was monitored by directly inserting a thermometer into a vial of identical dimensions with the corresponding volume of the pure solvent.
Crystals were recovered from the hot solutions and immediately dried carefully prior to storage.
Kadro at page 5 of 6, method, Crystal Growth, emphasis added.
Kadro teaches that
To assess the crystallinity of the material further, XRD patterns were collected on a finely ground powder prepared by the same process (Fig. 2). CH3NH3PbI3 has a cubic Pm
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m high temperature phase with phase transition from its I4mcm tetragonal room temperature phase occurring around 56 °C at atmospheric pressure.
Kadro at page 3 of 6, last paragraph , line 1-4. Given the cubic Pm
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m high temperature phase in the XRD patterns matches that reported by the reference cited by Kadro [reference 24. Baikie, T. et al. Synthesis and crystal chemistry of the hybrid perovskite (CH3NH3)PbI3 for solid-state sensitised solar cell applications. J. Mater. Chem. A 1, 5628 (2013)], therefore, the Kadro CH3NH3PbI3 crystals is pure.
Evidence from Hamada indicated that 99.0% commercial PbI2 comprise impurity of metals Na, K, Ag, Mn, Co, Fe, W, and Au. See Hamada at page 518, left col. 2. Materials and method, line 1-5, and Table 1 at page 519.
The Kadro method comprises:
(i). preparing a mixture by dissolving PbI2 that comprises a metal impurity at a first concentration and CH3NH3I in γ-Butyrolactone;
(ii). forming CH3NH3PbI3 crystals from PbI2 and CH3NH3I in the mixture;
(iii). separating the CH3NH3PbI3 crystals from the mixture, which results in a solid stream comprising the CH3NH3PbI3 crystals and the hot solution comprising the metal impurity, the CH3NH3PbI3 crystals contains the metal impurity at a lower concentration than the first concentration.
Which meets each and every limitation of claim 1, therefore, claim 1 is anticipated.
Claim 2 is anticipated because Per Figure 1(b), Kadro teaches that the CH3NH3PbI3 crystal is a 3D crystal. See Kadro Figure 1 (b) at page 2 of 6.
Claim 3 is anticipated because CH3NH3PbI3 is a ABX3 perovskite, wherein, A is CH3NH3, B is Pb and X is I.
Claims 4-5 are anticipated because CH3NH3PbI3 maps the Csz(FAxMA1-x) 1-zPb(Clw(IyBr1-y)1-w)3 as each of z, x and w is 0 and y is 1.
Claim 6 is anticipated because Kadro teaches that the precursors are PbI2 and CH3NH3I.
Claims 7 and 9 are anticipated because the evidence from Hamada indicated that 99.0% commercial PbI2 comprise metal K at a concentration of 3630-4038 ppm that is 0.363-0.4038%. See Hamada Table 1 at page 519.
Claim 10 is anticipated because γ-Butyrolactone is a polar solvent. See Specification example 24-25 at page 25.
Claim 12-13 are anticipated because Kadro teaches to conduct the preparation at first temperature of 100ºC and the at another temperature of 190ºC.
Claim 14 is anticipated because at least a portion of the Kadro reaction mixture is evaporated by pressure and/or electrical treatment during drying of the recovered crystals.
Claim 24 is anticipated because Kadro teaches that the diameter of the CH3NH3PbI3 crystal is 0.5 mm (500µm). Kadro at page 3 of 6, line 1 in paragraph 3 under Figure 2.
35 USC § 102 Rejection over Zhang
Claims 1-7, 9-10, 17-18 and 23 are rejected under 35 U.S.C. 102(a)(1) as being anticipated by Y. Zhang, et al, 11 ChemSusChem1813-1823(2018)(“Zhang”) evidenced with M. M. Hamada, et al, 505, Nuclear Instruments and Methods in Physics Research Section A, 517-520 (2003)(“Hamada”).
Zhang teaches a method of preparing of CH3NH3PbI3 and HC(NH2)2PbI3 Powders for high-efficiency perovskite solar cells by using inexpensive low-grade (99 %) PbI2 and methylammonium (MA) or formamidinium (FA). Zhang at abstract.
Zhang teaches that :
As illustrated in Figure 1b, MAI first dissolves in MeCN in the round-bottomed flask to produce iodide anions. Then, PbI2 is slowly added into the MeCN solution containing dissolved MAI to form the pure MAPbI3 precipitate, at which point the solution turns transparent yellow at the beginning and then a black precipitate is finally formed. Zhang at page 1815, left col. paragraph 2, line 3-9, emphasis added.
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Zhang at page 1815, left col. Figure 1(b).
Zhang teaches that:
The excess amount of MAI was washed away by MeCN during the washing process, and there-by, the synthesized MAPbI3 powders are expected to be stoichiometric (phase pure) regardless of the precursor mixing ratio. Figure 1c shows the X-ray diffraction (XRD) patterns of the resulting MAPbI3 powders; all of the peaks can be indexed to the tetragonal perovskite phase and no peaks corresponding to PbI2 or MAI are detected. This is indicative of the phase purity of the synthesized MAPbI3 powders
Zhang at page 1815, left col. the last line to right col. line 4, emphasis added.
Evidence from Hamada indicated that 99.0% commercial PbI2 comprise impurity of metals Na, K, Ag, Mn, Co, Fe, W, and Au. See Hamada at page 518, left col. 2. Materials and method, line 1-5, and Table 1 at page 519.
The Zhang method comprises:
(i). preparing a mixture by dissolving PbI2 that comprises a metal impurity at a first concentration and CH3NH3I in CH3CN;
(ii). forming CH3NH3PbI3 crystal from PbI2 and CH3NH3I in the mixture;
(iii). separating the CH3NH3PbI3 crystal from the mixture, results in a solid stream comprising CH3NH3PbI3 crystal and an effluent stream comprising the metal impurity, wherein, the CH3NH3PbI3 crystal contains the metal impurity at a lower concentration than the first concentration.
(IV). Washing the CH3NH3PbI3 crystal with CH3CN to remove any remaining portion metal impurities on the CH3NH3PbI3 powder.
The Zhang method meets each and every limitation of claim 1, therefore, claim 1 is anticipated.
Claim 2 is anticipated because Zhang teaches that the CH3NH3PbI3 crystal has tetragonal perovskite phase, therefore, it is 3D.
Claims 3-7 and 9 are anticipated for the same reason as given for the rejections over Kadro.
Claim 10 is anticipated because CH3CN is a polar solvent.
Claims 17 and 23 are anticipated because Zhang teaches to wash the isolated CH3NH3PbI3 crystal to remove any impurity including any remaining portion metal impurities on the CH3NH3PbI3 crystal.
With regards Claim 18, Zhang also synthesis MAPbI3 films from the synthesized CH3NH3PbI3 crystal. See Zhang at page 1815, right col. paragraph 2, line 2-3. Thus, the MAPbI3 films comprises MA+, Pd+ and I-, which are same as those in PdI2 and/or methylammonium, therefore, claim 18 is anticipated.
New Claim Rejections - 35 USC § 103
The following is a quotation of 35 U.S.C. 103 which forms the basis for all obviousness rejections set forth in this Office action:
A patent for a claimed invention may not be obtained, notwithstanding that the claimed invention is not identically disclosed as set forth in section 102, if the differences between the claimed invention and the prior art are such that the claimed invention as a whole would have been obvious before the effective filing date of the claimed invention to a person having ordinary skill in the art to which the claimed invention pertains. Patentability shall not be negated by the manner in which the invention was made.
The factual inquiries for establishing a background for determining obviousness under 35 U.S.C. 103 are summarized as follows:
1. Determining the scope and contents of the prior art.
2. Ascertaining the differences between the prior art and the claims at issue.
3. Resolving the level of ordinary skill in the pertinent art.
4. Considering objective evidence present in the application indicating obviousness or nonobviousness.
Claims 1, 11, 17 and 21-23 are rejected under 35 U.S.C. 103 as being unpatentable over J. M. Kadro, et al. 5.1 Scientific reports 11654 (2015)(“Kadro”) further in view of N. Guo, et al. 38.1 Journal of Semiconductors 014004 (2017) (“Guo”) evidenced with M. M. Hamada, et al, 505, Nuclear Instruments and Methods in Physics Research Section A, 517-520 (2003)(“Hamada”).
J. M. Kadro, et al. 5.1 Scientific reports 11654 (2015)(“Kadro”)
Kadro teaches that:
Since the first peer-reviewed publications of metalorgano halide perovskite based solar cells in 2009, research in materials of this family has undergone immense revival. They unite a broad range of suitable characteristics including long-range charge diffusion, high extinction coefficient as well as ease of fabrication. With solar-to-energy conversion efficiencies now exceeding 20%, some already regard them as possible competitors to the well-established silicon technology.
Kadro at page 1 of 6, line 1-5.
As mentioned above in the 102 rejection that Kadro teaches a method for preparing of CH3NH3PbI3 crystal, which meets each and every limitation of claim 1 and claim 3.
Evidence from Hamada indicated that 99.0% commercial PbI2 comprise impurity of metals Na, K, Ag, Mn, Co, Fe, W, and Au. See Hamada at page 518, left col. 2. Materials and method, line 1-5, and Table 1 at page 519.
Difference between Kadro and Claims 11, 17, 21-23
The Kadro method differs from claims 11 and 21-22 in that Kadro does not tech to provide an additive to the reaction mixture.
The Kadro method differs from claim 17 and 23 in that Kadro does not tech to further remove any remaining portion metal impurities on the CH3NH3PbI3 crystal.
N. Guo, et al. 38.1 Journal of Semiconductors 014004 (2017) (“Guo”)
Similar as Kadro, Guo also studied synthesis of CH3NH3PbI3 through relative low-purity PbI2 and CH3NH3I. Guo at Abstract.
Guo compared the XRD pattern of the 98% low quality PbI2 powder and the 99.9% high quality PbI2 and teaches that there is some lead hydroxide impurity Pb(OH)I covering on the surface of low purity PbI2 powder, which prevents PbI2 dissolve in solvent; and the Pb(OH)I can reacts with HCl to form PbCl2 to help the dissolving of the low quality PbI2. Guo at page 1, right col. line 9-24. Guo also teaches that the addition of HCl into the precursor solution would induce some Cl composition, and Cl additive could help deposition of high quality MAPbI3 perovskite. Guo at page 1, right col. line 25-27.
Obviousness Rationales of the Claims
One ordinary skill in the art would have arrived at the claimed invention before the effective filling date of the instant application in view of the teaching from Kadro, or further in view of Guo.
Claim 17 and 23 are obvious because one ordinary skill seeking high purity of CH3NH3PbI3 for solar application is motivated to modify the Kadro method by including a step washing the isolated Kadro CH3NH3PbI3 crystal with a washing liquid so that any impurity including any remaining portion metal impurities on the CH3NH3PbI3 crystal would be removed, thus arrive at a method meeting each and every limitations of claims 1, 17 and 23, therefore, claims 1, 17 and 23 are obvious..
One ordinary skill in the art seeking the Kadro CH3NH3PbI3 crystal for solar cells application is also motivated to modify the Kadro method by adding HCl in the initial reaction mixture, thus arrive at a method meeting each and every limitation of claims 1, 11 and 21-22, therefore claims 1, 11, 21-22 are obvious.
One ordinary skill in the art has a motivation to do so with a reasonable of expectation of success because Guo teaches that adding HCl can help dissolve PdI2 into organic solvent by removing of Pb(OH)I covering on the surface PbI2 powder and intruding of Cl can help deposition of high quality MAPbI3 perovskite.
Allowable Subject Matter
Claim 25 is 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.
As mentioned in the 102 rejections above that Kadro or Zhang teaches a method meeting each and every limitation of claim 1.
The Kadro or the Zhang method differs from claim 25 in that neither Kadro nor Zhang teaches to further reduce the isolated CH3NH3PbI3 particle size to the claimed 0.005 mm - 0.5 mm.
Claim 25 is not obvious because neither Kadro nor Zhang provides guidance to motivate one ordinary skill in the art to modify the prior art method by further reducing the isolated CH3NH3PbI3 particle size to 0.005 mm - 0.5 mm.
Conclusion
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.
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/FRANK S. HOU/Examiner, Art Unit 1692
/ALEXANDER R PAGANO/Primary Examiner, Art Unit 1692
