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
The claims filed on 12/07/2023 is acknowledged.
Claims 1-7 are currently pending and under examination.
Priority
The instant application claims benefit to U.S. application number 63/445,119 filed on 02/13/2023. Applicant’s claim for the benefit of a prior-filed application under 35 U.S.C. 119(e) is acknowledged.
Information Disclosure Statement
The information disclosure statements (IDS) submitted on 12/07/2023, 07/01/2024, 07/01/2024, 08/26/2024, 09/06/2024, 11/25/2024, 02/13/2025, 05/21/2025, 09/22/2025, and 03/03/2026 are in compliance with the provisions of 37 CFR 1.97. Accordingly, the information disclosure statements have been considered by the examiner.
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 is rejected under 35 U.S.C. 103 as being unpatentable over U.S. Patent No. 8,901,335 B2 (‘335, published 12/02/2014, IDS dated 07/01/2024).
‘335 teaches an organometallic compound purification and apparatus. Many semi-conducting materials are manufactured using well-established deposition technologies that employ ultrapure metalorganic (organometallic) compounds, for example, metalorganic vapor phase epitaxy, metalorganic molecular beam epitaxy, metalorganic chemical vapor deposition and atomic layer
deposition. To be useful in these processes the organometallic compounds must be free from contaminants and/or deleterious impurities. If not removed, such impurities present in the organometallic sources can cause adverse effects on the electronic and/or optoelectronic properties of electronic devices (see paragraph 3, column 1). The present invention further provides an apparatus for
continuously purifying an organometallic compound comprising: (a) a source of crude organometallic compound in a liquid phase; (b) a source of a stripping gas; (c) a stripping column having a first portion with a first inlet and a first outlet and a second portion with a second inlet and a second outlet; (d) the first inlet in fluid communication with the source of the crude organometallic compound; (e) the second inlet in fluid communication with the source of stripping gas; and (f) the second outlet being in fluid communication with a collector for purified organometallic compound; wherein a flow of the crude organometallic compound in the stripping column is opposite to a flow of the stripping gas in the stripping column. The first outlet provides an exit for the stripping gas from the stripping column (see paragraph 2, column 2 and figure below). The crude organometallic compound in the liquid-phase
enters the first portion of the stripping column through the first inlet. Any crude organometallic compound which is in the liquid-phase may be suitably employed in the present process (see paragraph 3, column 5). A wide variety of organometallic compounds may be purified by the present process. As used herein, “organometallic compound” refers to a compound having at least one metal carbon, metal-oxygen, metal-nitrogen or metal-phosphorus bond. Exemplary metal atoms include, without limitation, a Markush group including tin (see paragraph 3, column 6). As the present process removes relatively more volatile impurities, the purified organometallic compound obtained from the present process may be further purified as needed, such as to remove relatively less volatile impurities. Any conventional technique for further purification of the organometallic compound may be used, including, for example, distillation or sublimation. Such further purification techniques are well-known in the art (see paragraph 3, column 9). Furthermore, Exemplary organometallic compounds are those of the formula RM"XL (formula I), where each R is independently chosen from (C1-C20)alkyl, (C2-C20)alkenyl, (C2-C20) alkynyl, (C5-C20)aryl, (C5-C20)aryl(C1-C10)alkyl, (C1-C20)alkoxy, (C2-C10)carbalkoxy, amino, (C1-C12)alkylamino(C1-C10)alkyl, di(C1-C20)alkylamino(C1-C12)alkyl, phosphino, and a divalent ligand; each X is independently chosen from H, R, cyano, and halogen; L = a neutral ligand; a = the valence of the R group and is an integer ≥ 1; M = a Group 2 to Group 14 metal; and m = the valence of M. The “amino' groups include —NH2, (C1-C12)alkylamino, and di(C1-C12)alkylamino. Neutral ligands include, without
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limitation, CO., NO, nitrogen, amines, ethers, phosphines, alkylphosphines, arylphosphines, nitriles, alkenes, dienes, trienes, alkynes, and aromatic compounds. The above R groups may optionally be substituted by replacing one or more hydrogen atoms with one or more substituent groups, such as halogen, carbonyl, hydroxyl, cyano, amino, alkylamino, dialkylamino, and alkoxy (see last paragraph, column 6 and first paragraph, column 7). Trimethylaluminum-tripropylamine adduct was used as an example compound for Formula (I).
The teachings of ‘335 do not exemplify purifying a tin compound and including a distillation as required by instant claim 1.
Nevertheless, regarding instant claim 1, it would have been obvious for one of ordinary skill in the art to combine the teachings of ‘335 by choosing tin as the metal atom for the organometallic compound, as taught by ‘335, and further purify the organometallic compound using distillation, as taught by ‘335, to arrive at the instantly claimed invention. It would have been prima facie obvious to choose tin as a metal because ‘335 teaches a wide variety of organometallic compounds may be purified by the method and further provides a Markush group in which tin is included. One of ordinary skill in the art would have a reasonable expectation of success because the metal atoms of the Markush group have equivalent volatilities. It would have been prima facie obvious to include a distillation because ‘335 teaches the purified organometallic compound may be further purified as needed and further teaches distillation as an example of a conventional technique that can be used. One of ordinary skill in the art would have a reasonable expectation of success because distillation is a conventional purification technique.
Claims 1-4 are rejected under 35 U.S.C. 103 as being unpatentable over Powell et al. (NPL, published 08/23/2018, PTO-892) in view of U.S. Patent No. 8,901,335 B2 (‘335, published 12/02/2014, IDS dated 07/01/2024).
Powell et al. teaches phosphorus doped tin(IV) oxide (P:SnO2) films have been synthesized by an aerosol assisted chemical vapor deposition route (see Abstract). Aerosol assisted CVD relies on the ability to produce an aerosol from a solution containing a suitable metal precursor. This eliminates the need for the precursor to be volatile, with the precursor only needing to be soluble in a suitable solvent, i.e. a solvent that can be atomized to generate a mist, for synthesis to be achieved. This allows for a far larger range of precursors to be used for the synthesis of functional thin film coatings. In a typical AACVD reaction, the aerosol is carried to the reaction chamber by a carrier gas, where it passes over a heated substrate resulting in nucleation, reaction and film growth (see Introduction, paragraph 3). In a typical deposition, triethyl phosphate (0.0136 g, 7.5 mmol) was added to BuSnCl3 (0.3 g, 1.1 mmol) dissolved in methanol (20 mL) with stirring. The methanol solution was allowed to stir for ca. 10 min. Briefly, a carbon block heater comprising the lower half of the reactor was used to maintain the substrate temperature using a k-type thermocouple. Depositions were carried out on Pilkington silica-coated barrier glass (50 nm SiO2 coated on one side of float glass) in order to prevent unwanted leaching of ions from the glass into the thin film. Prior to deposition, the glass substrates were cleaned with soapy water, isopropanol and acetone and were then left to air dry. The substrate was then loaded into the reaction chamber along with a second piece of float glass suspended 8 mm above (silica barrier layer pointing down) to ensure laminar flow during deposition. An aerosol mist of the precursor solution was generated using a ‘Liquifog’ piezo ultrasonic atomizer from Johnson Matthey, which uses an operating frequency of 1.6 MHz to produce a mode droplet size of ca. 3 mm. The mist was transported into the reactor via a baffle, using compressed air, as the carrier gas, at a constant flow-rate of 1.0 L min_1. The exhaust of the reactor was vented into a fume cupboard. When the precursor solution and associated aerosol mist had been completely emptied from the bubbler, the coated substrate was cooled to below 100 °C before being removed from the reactor. Deposition temperatures were fixed at 550 °C, as below this temperature carbon contamination made the films less visibly transparent. Typical deposition times were between 30–40 min (see experimental section).
The teachings of Powell et al. differ from that of the instantly claimed invention in that Powell et al. does not teach a distillation step before or after the stripping step.
The teachings of ‘335 were discussed above.
It would have been obvious before the effective filing date of the claimed invention to combine the teachings of Powell et al. with the teachings of ‘335 by performing a distillation with the stripping step to arrive at the instantly claimed invention. It would have been prima facie obvious for one of ordinary skill in the art to distill the tin compound with the stripping method because ‘335 teaches the purified organometallic compound may be further purified as needed and further teaches distillation as an example of a conventional technique that can be used. One of ordinary skill in the art would have a reasonable expectation of success because distillation is a conventional purification technique.
Regarding instant claims 1, Powell et al. teaches dissolving BuSnCl3, corresponding to the instant formula RSnX3 wherein X is a halogen and R is a C4 group, in methanol and using a carrier gas, corresponding to the instant inert gas, to transport aerosol mist generated from the liquid tin compound and combined with the distillation as taught by ‘335.
Regarding instant claim 2, Powell et al. teaches an aerosol mist of the precursor solution was generated using a ‘Liquifog’ piezo ultrasonic atomizer, corresponding to the instant ultrasonic vibration.
Regarding instant claim 3, Powell et al. teaches carrier gas carrying the aerosol mist, corresponding to the instant step of stirring by fine bubble.
Regarding instant claim 4, Powell et al. teaches a gas flow rate of 1 L/min which can be converted to .0000167 m3/sec and further divided by the amount of solvent used in m3, 2*10-5 m3 of solvent, to reach a flow rate of 0.83 m3 (gas)/sec*m3 (liquid).
Claims 1-4 and 6-7 are rejected under 35 U.S.C. 103 as being unpatentable over Powell et al. (NPL, published 08/23/2018, PTO-892) in view of Sim et al. (US2022/0402946 A1, published 12/22/2022, IDS dated 07/01/2024).
The teachings of Powell et al. were discussed above.
The teachings of Powell et al. differ from that of the instantly claimed invention in that Powell et al. does not teach a distillation step before or after the stripping step as required by instant claim 1 and a tin compound as required by instant claims 6 and 7.
Sim et al. teaches an organotin compound of Chemical Formula 1 (shown below) and a method for forming a tin-containing thin film using the same, and more particularly, to an organo tin compound used as a precursor for thin film deposition and a method for forming a tin-containing thin film using the same (see 0002). 188.27 ml (0.466 mol) of an n-butyllithium in hexane solution and 300 ml of n - hexane were put into a 1,000 ml flask and mixed. After slowly adding 21.8 g (0.483 mol) of dimethylamine at about -50 °C , the temperature was raised to room temperature, and then the mixture was reacted while performing stirring for 5 hours. After slowly injecting 30.0 g ( 0.115 mol ) of SnCl4 at about -30 °C, the temperature was raised to room temperature, and then the mixture was reacted while performing stirring for 12 hours. After performing filtration and pressure reduction on the reaction product to remove a solvent and by-products , 27 g of Sn[N(CH3)2]4 was obtained at a yield of 80 % by performing purification under conditions of a temperature of 50 °C and a pressure of 0.3 Torr. Next, 27 g (0.091 mol) of Sn[N(CH3)2]4 obtained above and 200 ml of diethyl ether were put into a 1,000 ml flask and mixed . After slowly adding 48.05 ml (0.096 mol) of t-butyl magnesium chloride in THF at about -70 °C, the temperature was raised to room temperature, and the mixture was reacted while performing stirring for 8 hours. After performing filtration and pressure reduction on the reaction product to remove a solvent and by-products , 14 g of Sn(t-Bu)[N(CH3)2]3 was obtained at a yield of 49 % by
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performing purification under conditions of a temperature of 75 °C and a pressure of 0.2 Torr (see 0055-0056). In the method for forming a tin-containing thin film, the thin film is deposited on a substrate through a deposition process using the organo tin compound according to an embodiment of the present disclosure as a precursor. The deposition process may consist of an atomic layer deposition (ALD) process or a chemical vapor deposition (CVD) process, for example, a metal organic chemical vapor deposition (MOCVD) process. The deposition process may be carried out at 50 to 700 °C. First, the organo tin compound represented by Chemical Formula 1 is transferred onto a substrate. For example, the organo tin compound may be supplied onto the substrate by a bubbling method, a vapor phase mass flow controller method, a direct gas injection (DGI) method, a direct liquid injection (DLI) method, a liquid transfer method in which the liquid is dissolved in an organic solvent and transferred, or the like, but is not limited thereto. More specifically, the organo tin compound may be mixed with a carrier gas or dilution gas containing one or more selected from argon (Ar), nitrogen (N2), helium (He), and hydrogen (H2), and transferred onto the substrate by the bubbling method or the direct gas injection method.
Regarding instant claims 1-4, it would have been obvious before the effective filing date of the claimed invention to combine the teachings of Powell et al. with the teachings of Sim et al. by purifying the tin compound, as taught by Sim et al., and depositing the tin compounds, as taught by Powell 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 combine the deposition method, as taught by Powell et al., with the purification, as taught by Sim et al., because Sim et al. teaches the purification removes solvent and by-products. One of ordinary skill in the art would have a reasonable expectation of success because Sim et al. teaches successful examples of the purification.
Regarding instant claims 6 and 7, it would have been obvious before the effective filing date of the claimed invention to substitute the teachings of Powell et al. with the teachings of Sim et al. by substituting the BuSnCl3, as taught by Powell et al., with the compound of Chemical Formula 1, as taught by Sim et al. to arrive at the instantly claimed invention. It would have been prima facie obvious to substitute the BuSnCl3 for a compound of Chemical Formula 1 because both compounds were known in the prior art as precursors used in chemical vapor deposition processes. One of ordinary skill in the art would have a reasonable expectation of success because both compounds will produce the predictable result of a tin thin film.
Regarding instant claims 1, Powell et al. teaches dissolving BuSnCl3, corresponding to the instant formula RSnX3 wherein X is a halogen and R is a C4 group, in methanol and using a carrier gas, corresponding to the instant inert gas, to transport aerosol mist generated from the liquid tin compound and combined with the purification method, corresponding to a vacuum distillation, as taught by Sim et al.
Regarding instant claim 2, Powell et al. teaches an aerosol mist of the precursor solution was generated using a ‘Liquifog’ piezo ultrasonic atomizer, corresponding to the instant ultrasonic vibration.
Regarding instant claim 3, Powell et al. teaches carrier gas carrying the aerosol mist, corresponding to the instant step of stirring by fine bubble.
Regarding instant claim 4, Powell et al. teaches a gas flow rate of 1 L/min which can be converted to .0000167 m3/sec and further divided by the amount of solvent used in m3, 2*10-5 m3 of solvent, to reach a flow rate of 0.83 m3 (gas)/sec*m3 (liquid).
Regarding instant claim 6, Sim et al. teaches Sn(t-Bu)[N(CH3)2]3 which corresponds to the instant formula RSnX3 wherein R is an alkyl group having 4 carbon atoms and X is a dialkylamino group having 2 carbons.
Regarding instant claim 7, Sim et al. teaches Sn(t-Bu)[N(CH3)2]3 which corresponds to the instant t-butyltris(dimethylamino)tin.
Allowable Subject Matter
Instant claim 5, while objected to as depending from rejected claim 1, contains allowable subject matter. Claim 5 requires an ultrasonic output of 0.1 to 240 W per 1 L of the tin compound. The prior art does not teach, suggest, or motivate one of ordinary skill in the art to use or optimize the ultrasonic output of the purification method.
Jang et al. (US20220219158A1, published 07/14/2022, PTO-892) is the closest prior art and teaches a method of preparing an intermetallic catalyst from a precursor admixture containing tin utilizing ultrasonic waves which produces a tin oxide coating layer (see 0073). The output of the ultrasonic waves have an output of about 125 W to about 200 W based on 100 mL of the precursor admixture (see 0023). Jang et al. cannot be considered prior art over instant claim 5 because the ranges of ultrasonic output are not similar and there is no motivation, teaching, or suggestion to optimize the ultrasonic output.
Conclusion
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/KRISTEN W BRADY/ Examiner, Art Unit 1692
/SCARLETT Y GOON/ Supervisory Patent Examiner, Art Unit 1693
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