DETAILED ACTION
This is the first office action for 17/436,843, filed 9/7/2021, which is a national stage entry of PCT/GB2020/050547, filed 3/6/2020, which claims priority to UK application GB1903085.7, filed 3/7/2019, after the request for continued examination filed 2/27/2026.
Claims 1, 3-5, 7-8, 10-24 and 27-35 are pending. Claims 1, 3-5, 7-8, 10-20 and 27-35 are considered herein.
In light of the claim amendments filed 2/27/2026, the prior art rejections are withdrawn, and new grounds of rejection are presented herein.
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 .
Continued Examination Under 37 CFR 1.114
A request for continued examination under 37 CFR 1.114, including the fee set forth in 37 CFR 1.17(e), was filed in this application after final rejection. Since this application is eligible for continued examination under 37 CFR 1.114, and the fee set forth in 37 CFR 1.17(e) has been timely paid, the finality of the previous Office action has been withdrawn pursuant to 37 CFR 1.114. Applicant's submission filed on 2/27/2026 has been entered.
Additional Prior Art
The Examiner wishes to apprise the Applicant of the following reference, which is not currently applied in a rejection.
U.S. Patent Application Publication 2018/0342630 A1: This reference teaches a perovskite solar cell in which the solvent used to prepare the perovskite layer comprises hydrogen peroxide (paragraph [0053]).
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.
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, 3-4, 7-8, 10-11, 13, 18-20, 28, and 31-35 are rejected under 35 U.S.C. 103 as being unpatentable over Suzuka (U.S. Patent Application Publication 2016/0351841 A1), in view of Huang, et al. (Nanoscale 2016, 8, 18734-18739).
In reference to Claim 1, Suzuka teaches a process for forming a perovskite semiconductor layer 4 on a substrate (paragraphs [0080] and [0088], with additional details in paragraphs [0082]-[0094], shown in Fig. 1A).
Suzuka teaches that the semiconductor 4 is a layer comprising a perovskite crystalline compound (paragraph [0088]), the perovskite crystalline compound comprising one or more first cations, one or more metal cations, and one or more anions, wherein the one or more first cations comprise Cs+ (i.e. CsPbBr3, paragraph [0088]).
Suzuka teaches that the layer comprising the perovskite crystalline compound is on a substrate, wherein the substrate comprises a layer of electrode material 2 (paragraphs [0083]-[0087]) and a layer of an n-type material 3 (paragraphs [0091]-[0094]).
Suzuka does not teach that the perovskite compound of his invention is passivated, as required by Claim 1.
To solve the same problem of providing a CsPbBr3 perovskite material, Huang teaches a process in which a CsPbBr3 perovskite layer is exposed to a dichloromethane solution comprising benzoyl peroxide (“Preparation of CsPbBr3 NC modified GCE,” column 2, page 18735, and further described in Fig. 7B and paragraph 2, column 1, page 18738, through paragraph 1, column 2, page 18753).
Huang further teaches that this treatment provides the benefit of passivating the surface of the CsPbBr3 (final paragraph, column 1, page 18737).
Therefore, absent a showing of persuasive secondary considerations, it would have been obvious to one of ordinary skill in the art at the time the instant invention was filed to have subjected the CsPbBr3 layer of Suzuka to the benzoyl peroxide passivation treatment of Huang, in order to achieve the taught benefit of surface passivating the CsPbBr3.
This modification teaches the limitations of Claim 1, of a process for producing a passivated semiconductor, which comprises treating a semiconductor (CsPbBr3) with a passivating agent (benzoyl peroxide).
This modification teaches the limitations of Claim 1, wherein the semiconductor comprises a perovskite crystalline compound comprising one or more first cations (Cs+), one or more metal cations (Pb2+), and one or more anions (Br-), wherein the one or more first cations comprise Cs+.
This modification teaches the limitations of Claim 1, wherein the passivating agent comprises a compound comprising a peroxide group (i.e. benzoyl peroxide).
This modification teaches the limitations of Claim 1, wherein the semiconductor is treated with the passivating agent at a temperature of less than 100 °C.
Specifically, it appears that the disclosure of Huang teaches that the exposure is performed under ambient conditions, because Huang does not teach that the process includes any heating. However, if that is not found to be the case, the exposure must have been performed at a temperature of under 100 °C, because the benzoyl peroxide solution is in a dichloromethane solvent, and dichloromethane boils at 39.6 °C. Therefore, because the dichloromethane is taught to be present in a liquid form, the passivating agent exposure was performed below 100 °C.
This modification teaches the limitations of Claim 3, wherein the passivating agent comprises a compound of the formula R-C(O)-O-O-C(O)-R, wherein R is an aryl group.
This modification teaches the limitations of Claim 4, wherein the passivating agent comprises benzoyl peroxide.
This disclosure teaches the limitations of Claim 7, wherein the semiconductor comprises a metal halide perovskite (CsPbBr3).
This disclosure teaches the limitations of Claim 8, wherein the semiconductor (CsPbBr3) comprises a crystalline compound of formula AMX3, wherein A comprises the one or more first cations, M comprises the one or more metal cations, and wherein X comprises the one or more anions, wherein the anions comprise Br-.
This disclosure teaches the limitations of Claim 10, wherein the one or more metal cations comprise Pb2+.
This disclosure teaches the limitations of Claim 11, wherein the semiconductor (CsPbBr3) comprises a crystalline compound of formula APbzSn1-zX3, wherein z is 1.
This disclosure teaches the limitations of Claim 13, wherein treating the semiconductor with the passivating agent comprises exposing the semiconductor to a composition comprising a solvent (dichloromethane) and the passivating agent (benzoyl peroxide).
This disclosure teaches the limitations of Claim 28, wherein the one or more metal cations comprise Pb2+.
In reference to Claim 18, Huang does not teach that the semiconductor is illuminated during passivation. Therefore, this disclosure teaches that the illumination is 0 kW/m2, which lies within the ranges recited in Claim 18.
This is consistent with the instant specification, which recognizes at paragraph [0098] that the passivation may be conducted in the substantial absence of illumination or light.
In reference to Claim 19, Huang teaches that the benzoyl peroxide exposure was performed during a CV test that covered a voltage range of -1.6 V-0 V at a scan rate of 50 mV/s (Fig. 7).
Therefore, the entire scan (from -1.6 V-0 V, then from 0V- -1.6 V) covered 3.2 total volts (3200 mV), and took 64 seconds.
Therefore, Huang teaches that the semiconductor is treated with the passivating agent for less than 1 hour.
In reference to Claim 20, it is noted that Huang teaches a semiconductor composition that meets the limitations of Claims 1 and 11, and a passivation material that meets the limitations of Claims 1, 3-5, and 15.
Therefore, there is reasonable basis to conclude that the passivated semiconductor of Huang has the properties recited in Claim 20.
In reference to Claim 31, Suzuka teaches that the layer 4 comprising the perovskite crystalline compound is on a surface of the substrate, which surface comprises the layer of n-type semiconductor 3 (Fig. 1A, paragraphs [0091]-[0094]).
In reference to Claim 32, Suzuka teaches that the layer of the n-type semiconductor 3 is a compact layer (i.e. a continuous layer, Fig. 1A, paragraphs [0091]-[0094]).
In reference to Claim 33, Suzuka teaches that the layer of n-type semiconductor 3 extends along the edge of the layer 2 (Fig. 1A). This disclosure teaches that a total thickness of this region of the n-type semiconductor 3 includes the thickness of the layer 3 and the thickness of layer 2, as shown in the inset below.
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Suzuka teaches that the thickness of his layer 3 is 10 nm or less (paragraph [0093]), and the thickness of his layer 2 is 1-1000 nm (paragraph [0086]).
Therefore, the thickness of layer 3 in the area indicated in the inset above is 11-1010 nm.
This disclosure teaches the limitations of Claim 33, wherein the thickness of the layer of n-type semiconductor is from 50-500 nm.
In the case where the claimed ranges "overlap or lie inside ranges disclosed by the prior art" a prima facie case of obviousness exists. See MPEP 2144.05 I. In the instant case, the claimed range of 50-500 nm overlaps with the taught range of 11-1010 nm.
In reference to Claim 34, Suzuka teaches that the electrode material 2 comprises a transparent conducting oxide (paragraph [0084]).
In reference to Claim 35, Suzuka does not teach that the layer of n-type semiconductor necessarily comprises any of the materials recited in Claim 35.
However, he teaches that the layer of n-type semiconductor 3 may suitably comprise TiO2 (paragraph [0092]).
Therefore, absent a showing of persuasive secondary considerations, it would have been obvious to one of ordinary skill in the art at the time the instant invention was filed to have formed the layer of n-type semiconductor 3 of Suzuka from TiO2, because he teaches that this is a suitable material for this layer.
Forming the layer of n-type semiconductor 3 of Suzuka from TiO2 teaches the limitations of Claim 35, wherein the layer of n-type semiconductor comprises TiO2.
Claims 5, 14-15, and 30 are rejected under 35 U.S.C. 103 as being unpatentable over Suzuka (U.S. Patent Application Publication 2016/0351841 A1), in view of Huang, et al. (Nanoscale 2016, 8, 18734-18739), in view of Katori, et al. (U.S. Patent Application Publication 2018/0369861 A1).
In reference to Claim 5, modified Suzuka/Huang does not teach that the passivating/oxidizing agent comprises hydrogen peroxide.
As described in the rejection of Claim 1 above, Huang teaches that the passivating/oxidizing agent is benzoyl peroxide.
To solve the same problem of providing a perovskite film (paragraphs [0068]-[0070]) in which the perovskite material is exposed to an oxidizing material in solution (paragraphs [0075]-[0076]), Katori teaches that suitable oxidants include benzoyl peroxide (as in Huang) and hydrogen peroxide (paragraph [0076]), and that a suitable solvent for introducing the oxidant to the perovskite includes γ-butyrolactone (paragraph [0075]).
Therefore, absent a showing of persuasive secondary considerations, it would have been obvious to one of ordinary skill in the art at the time the instant invention was filed to have replaced benzoyl peroxide in the method of Huang with hydrogen peroxide, and to have used γ-butyrolactone as the solvent in the method of modified Suzuka/Huang, based on Katori’s disclosure that both benzoyl and hydrogen peroxides are suitable peroxides for use in oxidizing perovskite materials, and that γ-butyrolactone is a suitable vehicle for a hydrogen peroxide oxidant/perovskite mixture.
This modification teaches the limitations of Claim 5, wherein the passivating agent comprises hydrogen peroxide.
In reference to Claim 14, modified Suzuka/Huang does not teach that the solvent comprises one or more polar solvents other than water.
As described in the rejection of Claim 1 above, Huang teaches that the solvent is non-polar dichloromethane.
To solve the same problem of providing a perovskite film (paragraphs [0068]-[0070]) in which the perovskite material is exposed to an oxidizing material in solution (paragraphs [0075]-[0076]), wherein the oxidizing material is benzoyl peroxide (paragraph [0076]), Katori teaches that a suitable solvent for introducing benzoyl peroxide to the perovskite includes γ-butyrolactone (paragraph [0075]).
Therefore, absent a showing of persuasive secondary considerations, it would have been obvious to one of ordinary skill in the art at the time the instant invention was filed to have used γ-butyrolactone as the solvent in the method of Huang, based on Katori’s disclosure that γ-butyrolactone is a suitable vehicle for exposing benzoyl peroxide to a perovskite for the purposes of oxidizing the perovskite.
This modification teaches the limitations of Claim 14, wherein the solvent comprises one or more polar solvents other than water.
In reference to Claim 15, Huang teaches that the composition comprising the solvent and the passivating agent comprises a solution of the passivating agent in the solvent (Fig. 7B and paragraph 2, column 1, page 18738, through paragraph 1, column 2, page 18753).
Huang does not teach that the passivating agent is hydrogen peroxide.
To solve the same problem of providing a perovskite film (paragraphs [0068]-[0070]) in which the perovskite material is exposed to an oxidizing material in solution (paragraphs [0075]-[0076]), Katori teaches that suitable oxidants include benzoyl peroxide (as in Huang) and hydrogen peroxide (paragraph [0076]), and that a suitable solvent for introducing the oxidant to the perovskite includes γ-butyrolactone (paragraph [0075]).
Therefore, absent a showing of persuasive secondary considerations, it would have been obvious to one of ordinary skill in the art at the time the instant invention was filed to have replaced benzoyl peroxide in the method of Huang with hydrogen peroxide, and to have used γ-butyrolactone as the solvent in the method of Huang, based on Katori’s disclosure that both benzoyl and hydrogen peroxides are suitable peroxides for use in oxidizing perovskite materials, and that γ-butyrolactone is a suitable vehicle for a hydrogen peroxide oxidant/perovskite mixture.
This modification teaches the limitations of Claim 15, wherein the passivating agent comprises hydrogen peroxide.
In reference to Claim 30, Huang teaches that the oxidant concentration in the method of his invention is 5mM (Fig. 7).
Therefore, modified Huang as applied to Claim 15 (in which merely the type of peroxide, not the concentration of peroxide) is changed, further teaches the limitations of Claim 30, wherein the hydrogen peroxide concentration is 0.001-0.1 M (i.e. 0.005 M).
Claims 12 and 27 are rejected under 35 U.S.C. 103 as being unpatentable over Suzuka (U.S. Patent Application Publication 2016/0351841 A1), in view of Huang, et al. (Nanoscale 2016, 8, 18734-18739), and further in view of Zhang, et al. (Advanced Materials, 2017, 29, 1606405).
In reference to Claim 12, Suzuka does not teach that the semiconductor comprises the composition required by Claim 12.
To solve the same problem of providing a perovskite ABX3-type semiconductor, Zhang teaches that introducing a molar fraction of 0.7-0.9 formamidinium (FA) into a CsPbBr3 perovskite material allowed for tuning of the perovskite’s band gap (first paragraph, column 1, page 6). Zhang further teaches that FAxCs1-x mixed cation perovskites have desirable crystallinity, photostability, and thermal stability, making them suitable for use in photovoltaic devices (paragraph 2, column 1, page 2).
Therefore, absent a showing of persuasive secondary considerations, it would have been obvious to one of ordinary skill in the art at the time the instant invention was filed to have introduced a molar fraction of 0.7-0.9 formamidinium (FA) into the CsPbBr3 perovskite material of modified Suzuka, in order to tune the bandgap of the material, while providing desirable crystallinity, photostability, and thermal stability, based on the teachings of Zhang.
This modification teaches the limitations of Claim 12, wherein the semiconductor comprises a crystalline compound of the formula Csx(H2N-C(H)=NH2)(1-x)PbBr3, wherein x is 0.1-0.3.
In reference to Claim 27, Suzuka does not teach that the one or more first cations comprise FA or MA, as required by Claim 27.
To solve the same problem of providing a perovskite ABX3-type semiconductor, Zhang teaches that introducing a molar fraction of 0.7-0.9 formamidinium (FA) into a CsPbBr3 perovskite material allowed for tuning of the perovskite’s band gap (first paragraph, column 1, page 6). Zhang further teaches that FAxCs1-x mixed cation perovskites have desirable crystallinity, photostability, and thermal stability, making them suitable for use in photovoltaic devices (paragraph 2, column 1, page 2).
Therefore, absent a showing of persuasive secondary considerations, it would have been obvious to one of ordinary skill in the art at the time the instant invention was filed to have introduced a molar fraction of 0.7-0.9 formamidinium (FA) into the CsPbBr3 perovskite material of modified Suzuka, in order to tune the bandgap of the material, while providing desirable crystallinity, photostability, and thermal stability, based on the teachings of Zhang.
This modification teaches the limitations of Claim 27, wherein the one or more first cations comprise FA.
Claims 16-17 are rejected under 35 U.S.C. 103 as being unpatentable over Suzuka (U.S. Patent Application Publication 2016/0351841 A1), in view of Huang, et al. (Nanoscale 2016, 8, 18734-18739), and further in view of Katori, et al. (U.S. Patent Application Publication 2018/0369861 A1), and further in view of Gupta, et al. (Organic Electronics 58 (2018) 202-206).
In reference to Claim 16, Huang does not teach that the method of his invention comprises treating the semiconductor layer with a vapor comprising the passivating agent.
To solve the same problem of providing a perovskite film (paragraphs [0068]-[0070]) in which the perovskite material is exposed to an oxidizing material (paragraphs [0075]-[0076]), Katori teaches that suitable oxidants include benzoyl peroxide (as in Huang) and hydrogen peroxide (paragraph [0076]).
Therefore, absent a showing of persuasive secondary considerations, it would have been obvious to one of ordinary skill in the art at the time the instant invention was filed to have replaced benzoyl peroxide in the method of modified Suzuka with hydrogen peroxide, based on Katori’s disclosure that both benzoyl and hydrogen peroxides are suitable peroxides for use in oxidizing perovskite materials.
To solve the same problem of treating a perovskite layer (Gupta, Abstract) with hydrogen peroxide (Gupta, column 2, paragraph 2, page 205), Gupta teaches a reaction chamber in which the reactant is introduced to the perovskite layer in a vapor form (Fig. 4a).
Therefore, absent a showing of persuasive secondary considerations, it would have been obvious to one of ordinary skill in the art at the time the instant invention was filed to have used the reactor of Gupta to introduce a hydrogen peroxide vapor to the perovskite material layer of modified Suzuka, because Gupta teaches that this is a suitable way to introduce hydrogen peroxide to the surface of a perovskite material layer.
Using the reactor of Gupta to introduce a hydrogen peroxide vapor to the perovskite material layer of Huang teaches the limitations of Claim 16, wherein treating the semiconductor layer with a vapor comprising the passivating agent.
Using the reactor of Gupta to introduce a hydrogen peroxide vapor to the perovskite material layer of Huang teaches the limitations of Claim 17, wherein treating the semiconductor with the passivating agent comprises exposing the semiconductor to a vapor comprising hydrogen peroxide.
Claim 29 is rejected under 35 U.S.C. 103 as being unpatentable over Suzuka (U.S. Patent Application Publication 2016/0351841 A1), in view of Huang, et al. (Nanoscale 2016, 8, 18734-18739), and further in view of Irwin, et al. (U.S. Patent Application Publication 2015/0243444 A1).
In reference to Claim 29, modified Suzuka/Huang does not teach that the solvent comprises water and isopropanol. Instead, he teaches that the solvent comprises γ-butyrolactone, as described in the rejection of Claim 1 above.
To solve the same problem of providing an AMX3-type perovskite material, Irwin teaches that suitable process solvents for processing these types of perovskite materials include a mixture of water and isopropanol (paragraph [0115]).
Therefore, absent a showing of persuasive secondary consideration, it would have been obvious to one of ordinary skill in the art at the time the instant invention was filed to have modified the solvent of modified Suzuka/Huang to comprise a mixed solvent of isopropanol and water, because Irwin teaches that both of these solvents are suitable for use in processing an AMX3-type perovskite material.
Response to Arguments
The Applicant’s arguments regarding the prior art rejections of record have been fully considered and are persuasive. Therefore, these rejection have been withdrawn. However, upon further consideration, new grounds of rejection are made herein.
Conclusion
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/SADIE WHITE/Primary Examiner, Art Unit 1721
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