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 .
Priority
Acknowledgment is made of applicant’s claim for foreign priority under 35 U.S.C. 119 (a)-(d). The certified copy has been filed in parent Application No. IN 202221048238, filed on August 24, 2022.
Receipt is acknowledged of certified copies of papers required by 37 CFR 1.55.
Drawings
The drawings are objected to because Fig. 1 depicts purging occurring in a range of 80-120°C which is outside the range of purging (100-160°C) of claim 1b, the Fig. 1 unit cell legend is difficult to distinguish differences in shading for Cs, Pb, and Mn, and the legends and shadings for Figs. 2-5 are difficult to discern. Corrected drawing sheets in compliance with 37 CFR 1.121(d) are required in reply to the Office action to avoid abandonment of the application. Any amended replacement drawing sheet should include all of the figures appearing on the immediate prior version of the sheet, even if only one figure is being amended. The figure or figure number of an amended drawing should not be labeled as “amended.” If a drawing figure is to be canceled, the appropriate figure must be removed from the replacement sheet, and where necessary, the remaining figures must be renumbered and appropriate changes made to the brief description of the several views of the drawings for consistency. Additional replacement sheets may be necessary to show the renumbering of the remaining figures. Each drawing sheet submitted after the filing date of an application must be labeled in the top margin as either “Replacement Sheet” or “New Sheet” pursuant to 37 CFR 1.121(d). If the changes are not accepted by the examiner, the applicant will be notified and informed of any required corrective action in the next Office action. The objection to the drawings will not be held in abeyance.
Specification
The abstract of the disclosure is objected to because the last sentence is incomplete. A corrected abstract of the disclosure is required and must be presented on a separate sheet, apart from any other text. See MPEP § 608.01(b).
The disclosure is objected to because of the following informalities:- In paragraph [005], there is a phrase in line 8 "... combining octadecene, oleic acid, oleylamine, trioctyl phosphine, lead chloride, manganese chloride and nickel chloride Mixing…" which is unclear.- In paragraph [0026], the first sentence does not properly end the list between thallium and tin.- In paragraph [0037], the first sentence describes use of lead acetate “tetrahydrate” but lists formula as “Pb(II)(OAC)2.3H2O” which is “trihydrate”.
Appropriate correction is required.
Claim Objections
Claim 5 objected to because of the following informalities: the list is not properly ended between thallium and tin. Appropriate correction is required.
Claim Rejections - 35 USC § 112
The following is a quotation of the first paragraph of 35 U.S.C. 112(a):
(a) IN GENERAL.—The specification shall contain a written description of the invention, and of the manner and process of making and using it, in such full, clear, concise, and exact terms as to enable any person skilled in the art to which it pertains, or with which it is most nearly connected, to make and use the same, and shall set forth the best mode contemplated by the inventor or joint inventor of carrying out the invention.
The following is a quotation of the first paragraph of pre-AIA 35 U.S.C. 112:
The specification shall contain a written description of the invention, and of the manner and process of making and using it, in such full, clear, concise, and exact terms as to enable any person skilled in the art to which it pertains, or with which it is most nearly connected, to make and use the same, and shall set forth the best mode contemplated by the inventor of carrying out his invention.
Claim 10 rejected under 35 U.S.C. 112(a) or 35 U.S.C. 112 (pre-AIA ), first paragraph, as failing to comply with the written description requirement. The claim(s) contains subject matter which was not described in the specification in such a way as to reasonably convey to one skilled in the relevant art that the inventor or a joint inventor, or for applications subject to pre-AIA 35 U.S.C. 112, the inventor(s), at the time the application was filed, had possession of the claimed invention. In claim 10, applicant describes a process to synthesize D-doped AB11-yB2yX3 perovskite nanocrystals. The specification describes the process further comprises the preparation of those nanocrystals as well in page 8, paragraph [0024]. However, the example syntheses from pages 9-12 provide no information or evidence of preparing nanocrystals with that structure. The applicants disclose synthesizing Mn-doped double halide CsPbCl3-xBrx nanocrystals with varying Cl and Br ratios. But the applicants do not disclose how the process can be applied to prepare D-doped AB11-yB2yX3 nanocrystals with B1 and B2 metal precursors.
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.
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 1-3 and 10 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 applications subject to pre-AIA 35 U.S.C. 112, the applicant), regards as the invention.
Claim 1 is rejected under 35 U.S.C. 112(b) or 35 U.S.C. 112 (pre-AIA ), second paragraph, for being unclear in its scope. Claim 1 fails to clearly define the bounds and limits of claimed "A", "B", "D", and "X". In the field of perovskites, X is generally accepted to be a halogen such as Br, Cl, or I (or combinations thereof). For the purposes, of examining claim 1, X will be considered as any of those halogens. However, "A", "B", and "D" remain any type of metal. Claims 2-10 are rejected as being dependent on, and failing to cure the deficiencies of, rejected independent claim 1. Claim 4 attempts to cure the deficiencies for defining "A" and "B" but does not define the scope of "D". Similarly, claim 5 attempts to cure the deficiencies for defining "D" but does not define the scopes of "A" and "B".
The term “naturally” in claim 1 is a relative term which renders the claim indefinite. The term “naturally” is not defined by the claim, the specification does not provide a standard for ascertaining the requisite degree, and one of ordinary skill in the art would not be reasonably apprised of the scope of the invention. Claims 2-10 are rejected as being dependent on, and failing to cure the deficiencies of, rejected independent claim 1. Examiner notes that applicant attempts to define the scope of "naturally" in specification by disclosing that general procedure in the art required rapid quenching or cooling by water or ice bath while their process avoids use of ice or water to immediately cool solution and precipitate the crystals. In their synthesis example 3 on page 10 of specification, the applicants state the reaction flask was allowed to "cool naturally" and the "cooled reaction mixture" was processed for crystal precipitation. Such broad language does not aid in defining what is claimed for "cooling down naturally", what temperature is implied by "cooled" (i.e., room temperature, cool enough to handle by one of ordinary skill in the art, etc.), nor how long "cooling down naturally" should occur to reach such temperature. The language used is subjective. For the purposes of examination, the examiner will interpret the language as "cooling down without the use of an ice or water bath to room temperature".
Claim 2 is rejected under 35 U.S.C. 112(b) or 35 U.S.C. 112 (pre-AIA ), for being unclear in its scope. Claim 2 fails to define the scope of "ratio" between presence of "non-halide precursors A and B". In the example syntheses from pages 9-12, applicants utilize a 1:1 molar ratio between Cs2CO3 (“A” precursor) and lead acetate tetrahydrate (“B” precursor). For the purposes of examination, this ratio will be interpreted as a “molar ratio”.
Claim 3 is rejected under 35 U.S.C. 112(b) or 35 U.S.C. 112 (pre-AIA ), second paragraph, for being unclear in its scope. Claim 3 fails to clarify whether D is present in a range of 5-50 wt% to A and B as precursors during synthesis process, whether D is present in the nanocrystal composition at the wt% range to A and B, or whether D is present in that range with respect to A and with respect to B or the combination of A and B. Furthermore, in paragraph [0031] of the specification, the applicant states the D precursor (Mn) "ranges from 5 to 50 wt% with respect to A .
Claim 10 is rejected under 35 U.S.C. 112(b) or 35 U.S.C. 112 (pre-AIA ), for being unclear in its scope. Claim 10 fails to define "D" and "A". Therefore, it is unclear what the bounds or limits are for perovskites of generic formula(s) provided.
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.
Claims 1-9 are rejected under 35 U.S.C. 103 as being unpatentable over Dutta et al. ("Near-Unity Photoluminescence Quantum Efficiency for all CsPbX3 (X = Cl, Br, and I) Perovskite Nanocrystals: A Generic Synthesis Approach", Angew. Chem. Int. Ed. 2019), in view of Wang et al (U.S. PGPub 2022/0145171 A1) and in view of Xu et al. ("Efficient and Stable Luminescence from Mn2+ in Core and Core−Isocrystalline Shell CsPbCl3 Perovskite Nanocrystals", Chemistry of Materials).
Regarding claim 1, Dutta teaches the following:
In the supplementary information section 2.2 “Preparation of CsPbX3 nanocrystals”, Dutta mixes Cs2CO3 (non-halide “A” precursor), PbO (non-halide “B” precursor), octadecene (a linear alpha olefin solvent), and oleic acid (a long chain acid) into a three-necked reaction flask which is consistent with the claimed “(a) loading non-halide precursors of A, B, and D in a three-neck flask along with a long chain acid and a linear alpha olefin solvent to form a reaction mixture”, outside of loading a “D” precursor.
Further, Dutta purges the reaction mix with a flow of N2 (an inert gas) at 120°C for 30 min which is consistent with the claimed “(b) purging the reaction mixture with an inert gas at a temperature in a range of 100-160°C for 30 minutes”.
Additionally, Dutta teaches that the temperature is then increased to “desired limit” and an optimized amount of oleylamine-HX (an alkylammonium halide) is injected into the mixture. According to the second and third paragraphs of Dutta’s manuscript, the “desired limit” for temperature is a higher temperature than what is typically used by the art. Their temperature is “typically between 220°C and 260°C”. Therefore, Dutta teaches the claimed “(c) injecting an alkylammonium halide solution in the reaction mixture at a temperature” but does not specifically teach the temperature range of 80-200°C.
In the section 2.2 of the SI, Dutta further teaches that the reaction mixture is “cooled down normally after 5 min of annealing” which is consistent with the claimed “(d) annealing the reaction mixture for 5 seconds to 1 hour and cooling down naturally”. According to the second paragraph on the first page of the main text manuscript (pg 5553), Dutta’s approach “does not need the ice-bath cooling required” for most of the methods reported which matches with the interpreted meaning of the claimed “cooling down naturally”.
Finally, in section 2.2 of the SI, Dutta discloses that they add hexane and precipitate the nanocrystals using a centrifuge which matches the claimed “(e) precipitating the ABX3 nanocrystals” but does not specifically teach D-doped ABX3 nanocrystals. Although Dutta does not disclose a method of doping their nanocrystals in this manuscript, Dutta does state in the first paragraph of the manuscript that “it has been further established that doping and post-synthesis treatments with different metal/non-metal salts and specific acids helped for further increasing the PLQY.”.
Xu et al. does teach a method of preparing D-doped ABX3 nanocrystals by mixing non-halide (acetate) precursors of Cs, Pb, and Mn (dopant D) with oleic acid and oleylamine in section 2.2 under the experimental section.
Wang et al teaches in paragraph [0110] generic formula I of their perovskite quantum dot (QD): AMX3 where A is any alkali (fits Cs) or an organic such as formamidinium (FA), M is any metal cation, and X any halide. Further in paragraph [0139], Wang describes a preferred embodiment for making their perovskite QDs. They mix the first (non-halide A") precursor (here they use FA acetate as example), second precursor (non-halide "M" acetate, they use Pb) and first surface ligand (they list oleic acid which matches long chain acid of claims 1) in a solvent (e.g., 1-octadecene which matches linear alpha olefin solvent of claim 1) at elevated temperature (e.g., 50-100°C) to form reaction solution. A solution comprising the third precursor (they use oleylammonium iodide as an example) is injected into reaction solution to form QDs. They state "the reaction may be carried out at a predetermined temperature, such as a temperature of greater than about 50°C (e.g., a temperature in the range of from about 50°C to about 150°C)".
Therefore, it would have been prima facie obvious to one of ordinary skill in the art before the effective date of filing to combine the teachings of Dutta et al, Xu et al, and Wang et al by adding a dopant non-halide precursor as taught by Xu et al with the other non-halide perovskite precursors of Dutta et al and following their procedure but tailoring the injection temperature to a range disclosed by Wang et al with a predictable result of synthesizing D-doped ABX3 nanocrystals. One of ordinary skill in the art would add a dopant source in the initial precursor mixture to dope the formed perovskite to improve the PLQY. Although Dutta teaches an injection temperature typically between 220-260°C, Wang teaches that lower temperatures are suitable and can be modified depending on the precursors to synthesize the desired perovskite, thus temperature in the range of 80-200°C would have been obvious to one of ordinary skill in the art as suitable in the process of Dutta.
Regarding claim 2, Dutta, Xu, and Wang teach limitations of claim 1. In SI section 3.1, Dutta further teaches an optimization process of Cs:Pb ratios (A:B) in their synthesis citing that precursor variation has a minor impact on the phase (main text Fig. 2) of their nanocrystals but a drastic impact on PLQY (Fig. 4a). In Fig. 4a, Dutta teaches that the optimal PLQY occurs with a precursor molar ratio of 1:1 which matches the claimed “The process as claimed in claim 1, wherein the non-halide precursors A and B are present in a ratio of 1:1.”.
Regarding claim 3, Dutta, Xu, and Wang teach limitations of claim 1. Xu teaches doping Mn2+ at 5 at.% to 25 at.% relative to Pb2+. At 25 at.% relative to Pb2+, the wt% of Mn2+ is 6.6%. Xu discloses they use a 1:1 molar ratio of Cs:Pb. Therefore, the wt% of Mn2+ to Cs is 10.3%. Xu’s teachings exemplify the claimed “The process as claimed in claim 1, wherein D is present in a range of 5-50 wt.% with respect to A and B.”, where Mn is D, Cs is A, and Pb is B.
Regarding claim 4, Dutta, Xu and Wang teach the limitations of claim 1. In SI sections 2.0 and 3.0, Dutta discloses synthesis of CsPbCl3, CsPbBr3, and CsPbI3 (ABX3) which matches the claimed “The process as claimed in claim 1, wherein A is selected from cesium (Cs) and formamidinium (FA); B is lead (Pb); and X is selected from chlorine (Cl), bromine (Br) and iodine (I)” outside of FA. Wang, however, does disclose synthesis of an organo-ammonium “A” precursor. In paragraph [0083], Wang states the abbreviation “FA” is used to refer to formamidinium (NH2CH=NH2+). Further, Wang discloses in paragraph [0102] the composition of their nanocrystals follow an AMX3 formula wherein A can be an alkali or FA, M is a metal cation, and X is a halide and can be synthesized under a variety of procedures (paragraph [0135]). Therefore, it would have been prima facie obvious to one of ordinary skill in the art, before the effective filing date to substitute the Cs precursor of Dutta with an FA precursor of Wang with a predictable AMX3 perovskite result.
Regarding claim 5, Dutta, Xu, and Wang meet the limitations of claim 1. Furthermore, Xu teaches the case where D is Mn2+ which matches the claimed “The process as claimed in claim 1, wherein D is selected from manganese (Mn), nickel (Ni), cobalt (Co), iron (Fe), magnesium (Mg), beryllium (Be), calcium (Ca), strontium (Sr), barium (Ba), bismuth (Bi), antimony (Sb), cerium (Ce), samarium (Sm), europium (Eu), terbium (Tb), dysprosium (Dy), erbium (Er), ytterbium (Yb), zinc (Zn), cadmium (Cd), thallium (Tl), tin (Sn).”.
Regarding claim 6, Dutta, Xu, and Wang teach the limitations of claim 1. Dutta teaches a non-halide precursor of Cs (carbonate) and Pb (oxide). Xu teaches acetate precursors for Cs, Pb, and Mn. Therefore, they exemplify the claimed “The process as claimed in claim 1, wherein the non-halide precursor source is selected from carbonate, acetate, nitrate, acetylacetonate, oleate, undecylenate, myristate, laurate, or palmitate.”.
Regarding claim 7, Dutta, Xu, and Wang teach the limitations of claim 1. Dutta discloses loading oleic acid (OA) with the A and B precursors which matches the claimed “The process as claimed in claim 1, wherein the long chain acid is selected from oleic acid, undecylenic acid, dodecanoic acid, hexadecanoic acid, or hexadecanoic acid.”.
Regarding claim 8, Dutta, Xu, and Wang teach the limitations of claim 1. Dutta discloses use of octadecene (ODE) as their solvent which matches the claimed “The process as claimed in claim 1, wherein the linear alpha olefin solvent is selected from 1- decene, 1-dodecene, 1-tetradecene, 1-hexadecene, or 1-octadecene.”.
Regarding claim 9, Dutta, Xu, and Wang teach the limitations of claim 1. Dutta further teaches synthesis using an oleylammonium halide where the halide can be Cl, Br, or I which matches the claimed “The process as claimed in claim 1, wherein the alkylammonium halide is selected from chloride or bromide or iodide salts of octylammonium, oleylammonium, dodecylammonium, dodecylamine, dihexylammonium, dioctylammonium, didecylammonium, or dioctdecylammonium.”.
Claim 10 is rejected under 35 U.S.C. 103 as being unpatentable over Dutta and Wang as applied to claim 1 above, and further in view of Han et al (CN112480912A).
Dutta and Wang teach the limitations of claim 1.
Han discloses the process of claim 1 throughout the Implementation Column 2 section to prepare perovskites in a formula matching D-doped AB11-yB2yX3 where y = 0.5 (final composition is specifically D-doped A2B1B2X6 so generic formula elements are doubled). Han mixes non-halide precursors of Cs (A), Na (B1), In (B2), and Ag (D) with oleic acid (long chain acid) and octadecene (solvent) allowing all to purge at 105°C for 1h in N2 gas. Once mixture heats to 170-185°C, they inject a Cl (X) precursor. Therefore, Han exemplifies the claimed “The process as claimed in claim 1, wherein the process comprises preparation of D-doped AB1i-yB2yX3 perovskite nanocrystals, wherein B1 comprises silver (Ag), sodium (Na) and potassium (K); B2 comprises indium (In), bismuth (Bi) and antimony (Sb); and y = 0 to 1.”. It would have been obvious to one of ordinary skill in the art before the effective date of filing to combine the aforementioned teachings of Dutta and Wang, substituting the elemental compositions from the teachings of Han, to tailor the makeup of their perovskite nanocrystals with specific absorption and emission spectra and of specific structure.
Conclusion
The prior art made of record and not relied upon is considered pertinent to applicant's disclosure. Dutta et al (2018) provides additional synthesis parameters. Imran et al teaches benefits of using long chain amines or acids during synthesis. Yassitepe et al. teaches additional forms of alkylammonium halides that can be injected for perovskite synthesis. Pradhan provides a review on state of the art for perovskite synthesis in 2019. Zhang (US PGPub 20220085312 A1) provides evidence for synthesizing antimony-containing perovskites and bismuth-containing perovskites of formula ABX3. Both Jin et al (WO2017100950) and Zheng et al (CN110194954A) provide additional non-halide “A” and “B” precursors. Liu et al further teaches Mn-doping at relevant weight percentages with respect to Cs and Pb for perovskites.
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/NWFG/Examiner, Art Unit 1759
/MELVIN C. MAYES/Supervisory Patent Examiner, Art Unit 1759