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 .
Claim Status
Claims 1-15 were filed on 05/21/2024. No preliminary amendment was filed.
Claims 1-15 are currently pending and under examination.
Priority
The instant application is a national stage application of PCT/US22/80887 filed on 12/05/2022, which claims domestic benefit to U.S. provisional application no. 63/285584 filed on 12/03/2021.
Applicant’s claim for the benefit of a prior-filed application under 35 U.S.C. 119(e) is acknowledged and receipt is acknowledged of certified copies of papers required by 37 CFR 1.55.
Information Disclosure Statement
The information disclosure statement (IDS) submitted on 05/30/2024 is in compliance with the provisions of 37 CFR 1.97. Accordingly, the information disclosure statement has been considered by the examiner.
Claim Rejections - 35 USC § 112(b)
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.
Claim 9 is 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 9 recites “wherein the halogen comprises at least one of iodide, chloride, or bromide” on the first and second lines of page 2 of the instant claims. A halogen is, under its broadest reasonable interpretation, a single chemical element (such as Cl, Br, or I). The instant specification does not define the limitation “halogen” and therefore, the broadest reasonable interpretation is applied. When the broadest reasonable interpretation of the term “halogen” is applied to claim 9, the claim lacks clarity because a halogen is an element and not a mixture, a compound, or a structure that can be broken down into other chemical components. Therefore, it logically cannot comprise its own ionic species (iodide, chloride, or bromide). As a result, claim 9 is indefinite because it creates a logical contradiction that makes the boundaries of the claim unclear.
For purposes of applying prior art, claim 9 will be interpreted as “wherein the halogen is selected from at least one of iodide, chloride, or bromide.”
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 (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.
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)(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 1-3, 5, 7-9, and 11-15 are rejected under 35 U.S.C. 102(a)(2) as being anticipated by Krishna et al. (NPL, published 09/16/2021, IDS dated 05/30/2024).
Krishna et al. teaches testing the potential of 2,5-thiophenedicarboxylic acid ligand and its role in enhancing the thermal stability of perovskites using FAPbI3 rich composition of FA0.97MA0.03PbI2.91Br0.09 (FA+ = formamidinium = CH(NH2)2+; MA+ = methylammonium = CH3NH3+). Hereafter, the pristine composition (FA0.97MA0.03PbI2.91Br0.09) is referred to as the control, and perovskite coated with the ligand (FA0.97MA0.03PbI2.91Br0.09 /ligand) is referred to as the target material. Perovskite films were deposited by spin-coating onto the mesoporous TiO2 (mp-TiO2) layer by a one-step method using diethyl ether as an antisolvent, and then by spin-coating the passivating ligand on the top of the perovskite layer (see Results and Discussion section). Thiophene was chosen as an aromatic core and a carboxyl (COOH) as a functional group. The COOH contains a carbonyl group (C=O) that can coordinate Pb2+ ions and it also has a hydroxyl (–OH) group that can participate in H-bonding with FA and or I (see Molecular Design, Interactions, and Local Structure section). The crystallinity and structural properties of perovskite films were analyzed by X-ray diffraction, which is bulk sensitive, and grazing incidence X-ray diffraction, which is more surface sensitive. Both control and target films showed a well-crystallized photoactive α-phase of the 3D perovskite. The surface of both control and target perovskite films are uniform and highly crystalline with similar compact textures and grain sizes of hundreds of nanometers. In the target sample, several spots were observed with different contrast than the crystal grains and we speculate these could be the ligand molecules located in between the grains or over the grains. (see second paragraph, column 1, page 5554). Thiophene itself can act as Lewis base by lone pair donation through sulfur and has been reported to improve the property of perovskites by passivating undercoordinated lead. By linking two such COOH groups on 2 and 5 positions of thiophene moiety (2,5 thiophenedicarboxylic acid), it has been feasible to synthesize a rigid bifunctional molecule that can potentially bind between adjacent surface grains thus passivating the deleterious surface grain boundaries and suppressing the interfacial ion diffusion (see last paragraph, column 2, page 5553).
Regarding instant claim 1, Krishna et al. teaches the perovskite FA0.97MA0.03PbI2.91Br0.09, corresponding to the instant perovskite containing a halogen, and a 2,5-thiophenedicarboxylic acid ligand, corresponding to the instant capture compound. Krishna et al. further teaches thiophene was chosen as an aromatic core and a carboxyl (COOH) as a functional group. The COOH contains a carbonyl group (C=O) that can coordinate Pb2+ ions and it also has a hydroxyl (–OH) group that can participate in H-bonding with FA and/or I, corresponding to the instant capture compound being able to form a complex with the halogen.
Regarding instant claims 2, 7-9, and 15, Krishna et al. teaches the target film, corresponding to the instant composition, showed a well-crystallized photoactive α-phase of the 3D perovskite, corresponding to the instant perovskite being 3D as required by instant claims 2 and 15. Krishna et al. further teaches the perovskite in the target film is FA0.97MA0.03PbI2.91Br0.09, wherein FA (formamidinium) and MA (methyl ammonium) corresponds to the instant first cation A, as required by claims 2 and 7, Pb corresponds to the instant second cation, as required by instant claims 2 and 8, and I and Br correspond to the instant halide X, as required by instant claims 2 and 9.
Regarding instant claim 3, Krishna et al. teaches FA0.97MA0.03PbI2.91Br0.09 /ligand with the ligand being 2,5-thiophenedicarboxylic acid ligand, corresponding to the instant third cation A’, with FA0.97MA0.03, corresponding to the instant Ax wherein x = 1, Pb, corresponding to the instant B, and I2.91Br0.09, corresponding to the instant X3.
Regarding instant claims 5 and 11, Krishna et al. teaches 2,5-thiophenedicarboxylic acid ligand, corresponding to the instant third cation being a thiophene moiety.
Regarding instant claim 12, Krishna et al. teaches the surface of the target perovskite films are uniform and highly crystalline with similar compact textures and grain sizes of hundreds of nanometers, corresponding to the instant at least portion of the perovskite being in the form of a plurality of grains. Krishna et al. further teaches in the target sample, several spots were observed with different contrast than the crystal grains and we speculate these could be the ligand molecules located in between the grains or over the grains, corresponding to the instant perovskite having each grain being surrounded by a grain boundary and at least a portion of the capture compound being positioned within the grain boundary.
Regarding instant claims 13 and 14, Krishna et al. teaches perovskite films were deposited by spin-coating onto the mesoporous TiO2 (mp-TiO2) layer by a one-step method using diethyl ether as an antisolvent, and then by spin-coating the passivating ligand on the top of the perovskite layer, corresponding to the instant perovskite being in the form of a layer, as required by instant claim 13, the instant capture compound being in the form of a layer, as required by instant claim 14, and the instant capture compound being positioned adjacent to and in physical contact with the perovskite layer, as required by instant claim 14.
Claim Rejections - 35 USC § 103
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.
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 1-6 are rejected under 35 U.S.C. 103 as being unpatentable over Krishna et al. (NPL, published 09/16/2021, IDS dated 05/30/2024) in view of Avantama et al. (US20210122974, published 04/29/2021, IDS dated 05/30/2024).
The teachings of Krishna et al. were discussed above.
The teachings of Krishna et al. differ from that of the instantly claimed invention in that Krishna et al. does not teach wherein the third cation has a molecular radius between 2.000 Å and 2.900 Å, as required by instant claim 4, and wherein the capture compound comprises at least one of protonated thiourea (TUH+), protonated urea, protonated thioacetamide, protonated selenourea, protonated thiophene, protonated selenophene, or any one or more of their derivatives, as required by instant claim 6.
PNG
media_image1.png
45
163
media_image1.png
Greyscale
Avantama et al. teaches luminescent crystals and manufacturing thereof (see Title). The term “luminescent crystals” (LC) is known in the field and relates to crystals of 3-500 nm, made of semiconductor materials. Preferably, luminescent crystals are approximately isometric (such as spherical or cubic). Particles are considered approximately isometric, in case the aspect ratio ( longest: shortest direction) of all 3 orthogonal dimensions is 1-2 (see 0021). Avantama et al. teaches the compounds of formula (I) (shown below) wherein A1 represents one or more organic cations, preferably selected from the group consisting of formamidinium, ammonium, guanidinium, protonated thiourea, imidazolium, pyridinium, pyrrolidinium, M1 is optional, and if present, represents one or more alkaline metals, preferably selected from Cs, Rb, K, Na, Li, M2 represents one or more metals other than M1, preferably selected from the group consisting of Ge, Sn, Pb, Sb, and Bi, X represents one or more anions selected from the group consisting of halides and pseudohalides and sulfide, preferably: chloride, bromide, iodide, cyanide, thiocyanate, isothiocyanate and sulfide, particularly preferably one or more halides selected from the group consisting of Cl, Br, and I, a represents 1-4, b represents 1-2, c represents 3-9. The compounds of formula (I) are termed organic perovskites (see 0040 and 0056). A broad range of hybrid materials (I) comprising organic cations A1 are available following the inventive manufacturing method. Suitable organic cations may be selected from the group consisting of formamidinium cations, ammonium cations, guanidinium cations, protonated thiourea cations, imidazolium cations, pyridinium cations, pyrrolidinium cations, etc. (see 0048). The method to make compounds of formula (I) provides LCs/QDs (luminescent crystals/quantum dots) having excellent properties. First, small FWHM values are observed. Second, high luminescence quantum yields are observed (>80% for emission at around 530 nm). Accordingly, the LCs/QDs provided by the method are suited for a large number of applications in electronic and optical devices. Further, the LCs/QDs provided by the inventive method are also suited for coating (non-electronic/non-optical) articles, such as a decorative coating (see 0044).
It would have been obvious before the effective filing date of the claimed invention to modify the teachings of Krishna et al. with the teachings of Avantama et al. by substituting the MA, as taught by Krishna et al., with protonated thiourea, as taught by Avantama et al., to arrive at the instantly claimed invention. It would have been prima facie obvious for one of ordinary skill in the art to substitute MA for protonated thiourea because, as taught by Avantama et al., the produced LCs/QDs have excellent properties and are suited for a large number of applications in electronic and optical devices. One of ordinary skill in the art would have a reasonable expectation of success because both 2,5-thiophenedicarboxylic acid and protonated thiourea are taught to be ligands for perovskite systems.
Regarding instant claim 1, Krishna et al. teaches the control film perovskite FA0.97MA0.03PbI2.91Br0.09, corresponding to the instant perovskite containing a halogen. The teachings of Krishna et al. are modified by Avantama et al. by substituting MA for protonated thiourea, corresponding to the instant capture compound. While Avantama et al. does not explicitly teach that protonated thiourea is capable of forming a complex with at least one of the halogen or an anionic form of the halogen, protonated thiourea is positively charged and one of ordinary skill in the art would expect a positively charged compound to form a complex with a negatively charged compound. Therefore, the inclusion of protonated thiourea flows naturally into being able to form a complex with an anionic form of the halogen.
Regarding instant claims 2 and 3, Krishna et al. teaches the control film perovskite FA0.97MA0.03PbI2.91Br0.09, corresponding to the instant composition when modified by Avantama et al. to substitute MA for protonated thiourea (TUH+) to make FA0.97TUH+0.03PbI2.91Br0.09, showed a well-crystallized photoactive α-phase of the 3D perovskite, corresponding to the instant perovskite being 3D as required by instant claim 2. Furthermore, Avantama et al. also teaches the luminescent crystals produced have all 3 orthogonal dimensions, also corresponding to the instant perovskite having a 3D crystal structure. The modified composition, FA0.97TUH+0.03PbI2.91Br0.09, contains FA, corresponding to the instant first cation A, Pb, corresponding to the instant second cation B, I and Br, corresponding to the instant halide X, and TUH+, corresponding to the instant third cation A’, as required by instant claims 2 and 3.
Regarding instant claim 4, the modified perovskite composition of FA0.97TUH+0.03PbI2.91Br0.09, as taught by Krishna et al. and Avantama et al., contains TUH+, corresponding to the instant third cation. While Krishna et al. and Avantama et al. do not teach the molecular radius of TUH+, the molecular radius of TUH+, as evidenced by the instant specification, is 2.777 Å, corresponding to the instant third cation having a molecular radius between 2.000 and 2.9000 Å (see instant specification, page 10, line 22). A chemical composition and its properties are inseparable. Therefore, if the prior art teaches the identical chemical structure, the properties applicant discloses and/or claims are necessarily present (see MPEP 2112.01(II)).
Regarding instant claims 5 and 6, the modified perovskite composition of FA0.97TUH+0.03PbI2.91Br0.09, as taught by Krishna et al. and Avantama et al., contains TUH+, corresponding to the instant third cation comprising a thione group and comprising protonated thiourea.
Allowable Subject Matter
Claim 10 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.
Claim 10 is directed to a perovskite composition wherein the perovskite comprises CszFAyMAxTUH+(1-x-y-z)Pb1-mSnmI3-zBrz, each of x, y, and m are between zero and one, inclusively, and z is between zero and three, inclusively, and (1-x-y-z) is greater than zero.
There is no prior art that teaches a perovskite composition wherein CszFAyMAxTUH+(1-x-y-z)Pb1-mSnmI3-zBrz, each of x, y, and m are between zero and one, inclusively, and z is between zero and three, inclusively, and (1-x-y-z) is greater than zero.
The closest prior art is Krishna et al. (NPL, published 09/16/2021, IDS dated 05/30/2024).
Krishna et al. teaches control perovskite FA0.97MA0.03PbI2.91Br0.09.
Krishna et al. does not teach TUH+ in the perovskite or a perovskite with the formula CszFAyMAxTUH+(1-x-y-z)Pb1-mSnmI3-zBrz, each of x, y, and m are between zero and one, inclusively, and z is between zero and three, inclusively, and (1-x-y-z) is greater than zero.
Therefore, in order to arrive at the instantly claimed invention one of ordinary skill in the art would need to modify the perovskite FA0.97MA0.03PbI2.91Br0.09 to include TUH+ and meet the criteria of the instant formula.
Avantama et al. (US20210122974, published 04/29/2021, IDS dated 05/30/2024) teaches TUH+ as a cation for perovskites.
While one of ordinary skill in the art could substitute one the cations of FA or MA in perovskite formula taught by Krishna et al. with TUH+, which is taught by Avantama et al. to be a cation for perovskite compositions, this would not meet the criteria of the instant formula. To exemplify this, the perovskite, as taught by Krishna et al., is FA0.97MA0.03PbI2.91Br0.09 which can be modified by the teachings of Avantama et al. to substitute MA for protonated thiourea (TUH+) to make FA0.97TUH+0.03PbI2.91Br0.09. The modified perovskite corresponds to the instant formula of CszFAyMAxTUH+(1-x-y-z)Pb1-mSnmI3-zBrz in that y is 0.97, x is 0, and m is 0. However, the modified formula does not include Cs and therefore, z would need to be 0 which excludes Br from the formula. Br is present in modified formula and therefore, does not meet the formula criteria for the instant composition of claim 10. Therefore, instant claim 10 is free of prior art.
Conclusion
No claim is found allowable.
Any inquiry concerning this communication or earlier communications from the examiner should be directed to KRISTEN WEEKS BRADY whose telephone number is (571)272-5906. The examiner can normally be reached 8am-5pm.
Examiner interviews are available via telephone, in-person, and video conferencing using a USPTO supplied web-based collaboration tool. To schedule an interview, applicant is encouraged to use the USPTO Automated Interview Request (AIR) at http://www.uspto.gov/interviewpractice.
If attempts to reach the examiner by telephone are unsuccessful, the examiner’s supervisor, Scarlett Goon can be reached at (571) 272-5960. The fax phone number for the organization where this application or proceeding is assigned is 571-273-8300.
Information regarding the status of published or unpublished applications may be obtained from Patent Center. Unpublished application information in Patent Center is available to registered users. To file and manage patent submissions in Patent Center, visit: https://patentcenter.uspto.gov. Visit https://www.uspto.gov/patents/apply/patent-center for more information about Patent Center and https://www.uspto.gov/patents/docx for information about filing in DOCX format. For additional questions, contact the Electronic Business Center (EBC) at 866-217-9197 (toll-free). If you would like assistance from a USPTO Customer Service Representative, call 800-786-9199 (IN USA OR CANADA) or 571-272-1000.
/KRISTEN W BRADY/ Examiner, Art Unit 1692
/SCARLETT Y GOON/ Supervisory Patent Examiner, Art Unit 1693
Prosecution Insights