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 .
Election/Restrictions
Applicant’s election without traverse of Group I, claims 1-19 in the reply filed on May 12, 2026, is acknowledged.
Claims 20-26 are withdrawn from further consideration pursuant to 37 CFR 1.142(b) as being drawn to a nonelected invention, there being no allowable generic or linking claim. Election was made without traverse in the reply filed on May 12, 2026.
Specification
The title of the invention is not descriptive. A new title is required that is clearly indicative of the invention to which the claims are directed.
The following title is suggested:
Method of forming a perovskite superlattice by exposing a single crystal substrate to a precursor composition having ions and molecules of which a perovskite is composed
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.
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 (i.e., changing from AIA to pre-AIA ) 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.
Claim(s) 1, 4, 6, and 12 is/are rejected under 35 U.S.C. 102(a)(1) or 102(a)(2) as being anticipated by U.S. Patent Appl. Publ. No. 2002/0124790 to Masanao Era (hereinafter “Era”).
Regarding claim 1, Era teaches method of forming a perovskite superlattice (see the Abstract, Figs. 1-10, and entire reference which teach a method of forming a perovskite superlattice), comprising:
providing a single crystal substrate (see Figs. 4 & 10 and ¶¶[0012]-[0013] which teach providing a single crystal substrate such as a Si substrate or an inorganic compound single crystal substrate); and
exposing the single crystal substrate to a precursor composition having ions and molecules therein of which a perovskite is composed to thereby form a perovskite superlattice on the single crystal substrate (see Figs. 1, 4 & 10, ¶¶[0034]-[0037], and Examples 1-2 in ¶¶[0038]-[0045] which teach preparing precursor solutions comprised of, for example, a water solution having dissolved therein an inorganic halide MX2 and an alkylamine hydrohalic acid salt as an organic ammonium molecule which constitutes a perovskite then dropping a solution formed by dissolving a non-water-soluble organic amine hydrohalic acid salt, a water-soluble organic amine hydrohalic acid salt, and an inorganic halide MX2 in an organic solvent onto the surface of the water solution followed by transferring the formed layered perovskite film to the single crystal substrate),
wherein the perovskite superlattice includes at least one series of layers having alternating inorganic slabs and organic spacers, the single crystal substrate and the inorganic slabs having lattice constants that differ from one another by less than a prescribed amount (see Figs. 4 & 10 and Examples 1-2 in ¶¶[0038]-[0045] which teach that the perovskite superlattice includes alternating layers of an inorganic halide layer and an organic ammonium layer which necessarily have lattice constants that differ from each other by a prescribed amount).
Regarding claim 4, Era teaches that the series of layers includes a first and second series of layers, the first series of layers extending in a plane that is orthogonal to the second series of layers, the first and second series of layers each including alternating inorganic slabs and organic spacers (see at least Figs. 4 & 10 and Examples 1-2 in ¶¶[0038]-[0045] which teach that the perovskite superlattice includes alternating layers of an inorganic halide layer which extends horizontally in a plane that is perpendicular to the vertical thickness of the organic ammonium layer).
Regarding claim 6, Era teaches that the perovskite superlattice is a metal halide perovskite superlattice (see at least ¶¶[0012]-[0023] which teach that the perovskite may be a metal halide perovskite having the formula A2MX4 where M is a transition metal such as Pb or Sn and X is a halogen such as Cl, Br, or I).
Regarding claim 12, Era teaches that the perovskite superlattice is formed from a metal halide perovskite with a formula of B2An-1MnX3n+1, where B = R-NH3+; A = CH3NH3+ (MA), HC(NH2)2+, Cs+, or Rb+; M = Pb2+ or Sn2+; X = Cl-, Br-, or I- (see at least ¶¶[0012]-[0023], ¶¶[0034]-[0036], and Examples 1-6 in ¶¶[0038]-[0057] which teach that the perovskite may be a metal halide perovskite having the formula A2MX4 where A is an organic ammonium molecule which, in at least some embodiments, is from an alkylamine hydrohalic acid salt such as CnH2n+1NH3X and from RNH3X, M is a transition metal such as Pb or Sn and X is a halogen such as Cl, Br, or I).
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 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 1-7, 11-13, and 15-18 is/are additionally rejected under 35 U.S.C. 103 as being unpatentable over a publication to Ziyong Cheng, et al. entitled “Layered organic-inorganic hybrid perovskites: Structure, optical properties, film preparation, patterning, and templating engineering,” CrystEngComm, Vol. 12, pp. 2646-62 (2010) (hereinafter “Cheng”) in view of a publication to Yimu Chen, et al. entitled “Strain engineering and epitaxial stabilization of halide perovskites,” Nature, Vol. 577, pp. 209-15, Jan. 9, 2020 (“Yimu”).
Regarding claim 1, Cheng teaches a method of forming a perovskite superlattice (see the Abstract, Figs. 1-20, and entire reference which teach a method of forming an organic-inorganic hybrid perovskite superlattice), comprising:
providing a substrate (see Section 3.3(b) at p. 2657 which teaches providing a fused quartz substrate); and
exposing the single crystal substrate to a precursor composition having ions and molecules therein of which a perovskite is composed to thereby form a perovskite superlattice on the single crystal substrate (see Section 3.3(b) at p. 2657 which teaches providing PbI2 and phenylethylammonium iodide (C6H5C2H4NH3I) into two crucibles and the vapor rates were controlled in order to simultaneously deposit the organic and inorganic components onto the fused quartz substrate),
wherein the perovskite superlattice includes at least one series of layers having alternating inorganic slabs and organic spacers (see at least Fig. 2 and Section 2.2 at p. 2648 which teach that the organic-inorganic hybrid perovskite is deposited as alternating layers of inorganic slabs and organic spacers).
Cheng does not teach providing a single crystal substrate or that the single crystal substrate and the inorganic slabs having lattice constants that differ from one another by less than a prescribed amount. However, in at least the Abstract, Fig. 1, and the first three paragraphs at pp. 209-210, and the Extended Data Fig. 1 Yimu teaches an analogous method of depositing epitaxial halide perovskites onto a single crystal substrate comprised of MAPbClxBr3-x by heteroepitaxial growth. This is performed in order to deposit a higher quality epitaxial layer that is substantially free of defects and grain boundaries and to facilitate strain engineering of the deposited thin film such that the growth mode and resulting properties may be carefully controlled and enhanced. Thus, a PHOSITA prior to the effective filing date of the invention would look to the teachings of Yimu and would be motivated to form the organic-inorganic hybrid perovskite superlattice of Cheng by heteroepitaxial growth onto a single crystal substrate having a different lattice constant so that the growth mode and materials properties of the resulting superlattice may be controlled by strain engineering.
Regarding claim 2, Cheng does not teach that the prescribed amount is less than 20%. However, in the Abstract, Figs. 1-2, and the paragraphs spanning pp. 209-11 Yimu teaches that a compressive strain of as high as 2.4% is induced in an a-FAPBI3 layer by performing heteroepitaxial growth onto a MAPbClxBr3-x substrate and that this has the effect of reducing the bandgap, increasing the hole mobility, and stabilizing the a-FAPBI3 phase. Thus, a PHOSITA prior to the effective filing date of the invention would look to the teachings of Yimu and would start with a single crystal substrate which strains the deposited epitaxial layer by 2.4% and would then utilize routine experimentation to determine the optimal difference in lattice constants necessary to produce a heteroepitaxial layer having the desired materials properties.
Regarding claim 3, Cheng does not teach that the prescribed amount is less than 13%. However, in the Abstract, Figs. 1-2, and the paragraphs spanning pp. 209-11 Yimu teaches that a compressive strain of as high as 2.4% is induced in an a-FAPBI3 layer by performing heteroepitaxial growth onto a MAPbClxBr3-x substrate and that this has the effect of reducing the bandgap, increasing the hole mobility, and stabilizing the a-FAPBI3 phase. Thus, a PHOSITA prior to the effective filing date of the invention would look to the teachings of Yimu and would start with a single crystal substrate which strains the deposited epitaxial layer by 2.4% and would then utilize routine experimentation to determine the optimal difference in lattice constants necessary to produce a heteroepitaxial layer having the desired materials properties.
Regarding claim 4, Cheng teaches that the series of layers includes a first and second series of layers, the first series of layers extending in a plane that is orthogonal to the second series of layers, the first and second series of layers each including alternating inorganic slabs and organic spacers (see at least Fig. 2 and Section 2.2 at pp. 2648 which teach that the series of layers includes a first inorganic slab which extends horizontally in a plane that is perpendicular to the vertical thickness of the organic spacer layer).
Regarding claim 5, Cheng and Yimu do not teach that the orthogonal series of layers provide charge carrier transport in three-dimensions. However, since the combination of Cheng and Yimu perform each and every step of the claimed process it must necessarily produce the same results, namely that the orthogonal series of layers provide charge carrier transport in three dimensions. It is axiomatic that one who performs the steps of the known process must necessarily produce all of its advantages. Mere recitation of a newly discovered function or property, that is inherently possessed by things in the prior art does not cause a claim drawn to these things to distinguish over the prior art. Therefore, the occurrence of charge carrier transport in three dimensions, if not clearly envisaged, would be reasonably expected by the skilled artisan. See Leinoff v. Louis Milona & Sons, Inc. 220 USPQ 845 (CAFC 1984). Alternatively, since each layer within the deposited organic-inorganic hybrid perovskite layer has a length, a width, and a thickness, as charge carriers such as electrons travel through the entire space defined by each layer they are necessarily travelling in three dimensions.
Regarding claim 6, Cheng teaches that the perovskite superlattice is a metal halide perovskite superlattice (see at least Section 2.3 at p. 2652 which teaches that the perovskite may have the chemical formula A2’AmMmX3m+2 where A and A’ are organic cations, M is a divalent metal cation, and X is a halide).
Regarding claim 7, Cheng teaches that the single crystal substrate includes a single crystal perovskite on which the perovskite superlattice is formed (see Fig. 1 and the third paragraph at pp. 209-10 which teach the use of what is considered as essentially a single crystal MaPbCl2Br3-x substrate; alternatively, a PHOSITA prior to the effective filing date of the invention would be motivated to utilize a single crystal substrate in order to deposit a higher quality epitaxial layer that is substantially free of defects and grain boundaries and to facilitate strain engineering of the deposited thin film).
Regarding claim 11, Cheng teaches that the precursor composition is a precursor gas (see Section 3.3(b) at p. 2657 which teaches providing PbI2 and phenylethylammonium iodide (C6H5C2H4NH3I) into two crucibles and producing a precursor gas via evaporation of the source material).
Regarding claim 12, Cheng teaches that the perovskite superlattice is formed from a metal halide perovskite with a formula of B2An-1MnX3n+1, where B = R-NH3+; A = CH3NH3+ (MA), HC(NH2)2+, Cs+, or Rb+; M = Pb2+ or Sn2+; X = Cl-, Br-, or I- (see at least Section 2.2 at p. 2648 and Section 2.3 at p. 2652 which teaches that the perovskite superlattice may be a metal halide perovskite with the chemical formula A2’AmMmX3m+2 where A and A’ are organic cations, M is a divalent metal cation, and X is a halide where, in at least some embodiments, A = R-NH3+; A’ = CH3NH3+ (MA), M is Pb2+ or Sn2+; and X = Cl-, Br-, or I-; see also pp. 209-10 of Yimu which teach that MAPbClxBr3-x is known in the art; alternatively, see infra with respect to the rejection of claim 14 in which at least ¶¶[0020]-[0025] of Kamino teach that the A cation in ABX3 may comprise one or more organic cations such as methyammonium, formamidinium, ethyl ammonia, Cs+, and Rb+ which may be adjusted to produce the desired composition and materials properties).
Regarding claim 13, Cheng teaches patterning the substrate to thereby control distribution, orientation, and morphology of the perovskite superlattice (see Fig. 18 and Section 3.3(d) which teach that the substrate and/or the hybrid perovskite are patterned in order to control the shape, distribution, and morphology as part of a process for device fabrication).
Regarding claim 15, Cheng teaches that the single crystal substrate is coated and patterned by one or more additional functional layers prior to formation of the perovskite superlattice (see Fig. 18 and Section 3.3(d) which teach that prior to film growth the substrate may be patterned by PDMS soft stamps).
Regarding claim 16, Cheng teaches that the one or more additional functional layers include at least one functional layer selected from the group consisting of an electron transport layer, a hole transport layer, an electrode layer, a dielectric layer, a reflective cavity, and a semiconductive polymer layer (see Fig. 18 and Section 3.3(d) which teach that prior to film growth the substrate may be patterned by PDMS soft stamps which may be considered as a dielectric layer as claimed since PDMS has a dielectric constant in the range of 2.32 to 2.40).
Regarding claim 17, Cheng teaches that the perovskite superlattice is doped with ions and/or molecules to change electronic and optical properties of the perovskite superlattice (see at least the first and second column on p. 2651 which teach that the electronic and optical properties may be controlled by doping with, for example, Eu2+ ions to tailor the PL quantum efficiency).
Regarding claim 18, Cheng does not teach that a lattice mismatch between the perovskite superlattice and the single crystal substrate gives rise to strain that changes electronic and optical properties of the perovskite superlattice. However, as noted supra with respect to the rejection of claim 1, in at least the Abstract, Fig. 1, and the first three paragraphs at pp. 209-210, and the Extended Data Fig. 1 Yimu teaches an analogous method of depositing epitaxial halide perovskites onto a single crystal substrate comprised of MAPbClxBr3-x by heteroepitaxial growth. This is performed in order to deposit a higher quality epitaxial layer that is substantially free of defects and grain boundaries and to facilitate strain engineering of the deposited thin film such that the growth mode and resulting properties may be carefully controlled and enhanced. Thus, a PHOSITA prior to the effective filing date of the invention would look to the teachings of Yimu and would be motivated to form the organic-inorganic hybrid perovskite superlattice of Cheng by heteroepitaxial growth onto a single crystal substrate having a different lattice constant so that the growth mode and materials properties of the resulting superlattice may be controlled by strain engineering.
Claims 8-10 is/are rejected under 35 U.S.C. 103 as being unpatentable over Cheng in view of Yimu and further in view of Chinese Patent Appl. Publ. No. CN 110112300 A to Fan, et al. (“Fan”).
Regarding claim 8, Cheng and Yimu do not teach that the precursor composition includes perovskite single crystals. However, in at least the Abstract, Figs. 1-4, and at least the Summary of the Invention Fan teaches an analogous method of depositing a perovskite thin film onto a substrate. In at least the Abstract Fan specifically teaches that the precursor solution may be formed by initially dissolving perovskite single crystals in a solvent and that this has the advantage of ensuring that there is no deviation in material purity. Thus, a PHOSITA prior to the effective filing date of the invention would look to the teachings of Fan and would be motivated to utilize perovskite single crystals as the precursor in the method of Cheng and Yimu in order to minimize the inclusion of undesired impurities.
Regarding claim 9, Cheng and Yimu do not teach that the precursor composition is a precursor solution in which the perovskite single-crystals are dissolved. However, as noted supra with respect to the rejection of claim 8, in at least the Abstract, Figs. 1-4, and at least the Summary of the Invention Fan teaches an analogous method of depositing a perovskite thin film onto a substrate. In at least the Abstract Fan specifically teaches that the precursor solution may be formed by initially dissolving perovskite single crystals in a solvent and that this has the advantage of ensuring that there is no deviation in material purity. Thus, a PHOSITA prior to the effective filing date of the invention would look to the teachings of Fan and would be motivated to utilize perovskite single crystals which are dissolved in a solvent as the precursor in the method of Cheng and Yimu in order to minimize the inclusion of undesired impurities.
Regarding claim 10, Cheng teaches that exposing the single crystal substrate to a precursor composition includes spin coating, drop coating, or solution soaking the precursor solution onto the single crystal substrate (see Section 3.3(a) at p. 2657 which teaches that the hybrid perovskite thin film can be formed by spin coating; see also Section 3.3(c) at p. 2658 which teach the use of layer-by-layer assembly in which the substrate is alternatively dipped in different solutions).
Claims 14 is/are rejected under 35 U.S.C. 103 as being unpatentable over Cheng in view of Yimu and further in view of U.S. Patent Appl. Publ. No. 2018/0174761 to Kamino, et al. (“Kamino”).
Regarding claim 14, Cheng and Yimu do not teach that the morphology of the perovskite superlattice includes an array of pyramids that serve as an antireflective structure. However, in the Abstract, Figs. 1-8, and ¶¶[0102]-[0155] Kamino teaches an analogous method of depositing perovskite thin films as part of a process for forming a photovoltaic device. In Figs. 7a-b, ¶¶[0033]-[0034], and ¶¶[0152]-[0153] Kamino specifically teaches the desirability of providing a pyramidal surface texture for light trapping and antireflection properties in perovskite-on-silicon tandem solar cells. As shown specifically in Figs. 7a-b this may include providing a substrate (220) with a textured top surface (221) for the deposition of a perovskite material (113) thereupon. Thus, a PHOSITA prior to the effective filing date of the invention would be motivated to provide a substrate having a textured top surface comprised of an array of pyramids for the growth of an organic-inorganic hybrid perovskite according to the method of Cheng and Yimu in order to improve the photoelectric efficiency of the photovoltaic devices formed thereupon.
Claims 19 is/are rejected under 35 U.S.C. 103 as being unpatentable over Cheng in view of Yimu and further in view of International Patent Appl. Publ. No. WO 2021/199045 A1 to Lioz, et al. (“Lioz”).
Regarding claim 19, Cheng teaches that the perovskite superlattice may be used for characterization and device integration (see at least Fig. 18 and Section 3.3(d) at p. 2658 which teach that the perovskite thin film may be patterned and used in the fabrication of integrated optoelectronic devices and may be characterized using fluorescent microscopy), but does not teach peeling off the perovskite superlattice from the single crystal substrate and transferring the perovskite superlattice onto another substrate. However, in Fig. 1, the General Description at pp. 2-3, and associated descriptive text Lioz teaches an analogous method of producing perovskite-based photovoltaic devices by depositing one or more perovskite thin films. In the fifth paragraph on p. 2 Lioz specifically teaches that it is preferable that the deposited perovskite layer be peelable or removable so that it can be reapplied to a different substrate to form a perovskite-based device. Thus, a PHOSITA prior to the effective filing date of the invention would be motivated to make the hybrid organic-inorganic perovskite layer produced in the method of Cheng and Yimu peelable so that it may be transferred to another substrate as part of a method of producing one or more perovskite-based devices such as a photovoltaic device.
Conclusion
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/KENNETH A BRATLAND JR/Primary Examiner, Art Unit 1714
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