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 .
Response to Amendment
The amendments filed on July 21, 2026 have been entered. Claims 1, 3-10 and 12-13 are now pending. The amendments entered to the drawings and specification have overcome the prior objections in the Non-Final Office Action dated April 22, 2026. The amendments to the presented claims have overcome the prior objection and 103 rejections in the Non-Final Office Action dated April 22, 2026.
Drawings
The drawings were received on July 21, 2026. These drawings are acceptable.
Claim Rejections - 35 USC § 112
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 12 and 13 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 12 is indefinite as it currently depends on claim 11 which is canceled in the claims presented July 21, 2026. Claim 11 is no longer pending, thus claim 12 is indefinite. For the purposes of examination, claim 12 will be treated as being dependent upon independent claim 10.
Claim 13 is indefinite as the process of claim 1 would not produce the nanoparticles of claim 10. The nanoparticles of claim 10, as currently presented, recite a semiconductor comprising Ag, In, Ga, and S whereby an additional semiconductor is disposed on the surface comprising Ag, Ga, and S, thus a semiconductor of AIGS/AGS structure. The process of claim 1 produces semiconductors of AIGS/GaS/AGS structure and not AIGS/AGS. Thus, claim 13 is indefinite.
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, 3-10, and 12-13 are rejected under 35 U.S.C. 103 as being unpatentable over Torimoto et al (US PGPub 20230151271/WO2021182417A1) in view of Mamuye et al (US PGPub 20200399535).
Regarding claim 1, Torimoto teaches two semiconductor nanoparticle synthesis methods containing an Ag-In-Ga-S core (AIGS). One method (third step) discloses synthesis where the precursors are an Ag salt, an In salt, a compound having a Ga-S bond, a gallium halide, and an organic solvent. By using a Ga-S bond as a supply source, Torimoto discloses that it is easier to control the composition of the nanoparticle. By additionally including a gallium halide, it is easy to control particle size. This process produces semiconductor nanoparticles that exhibit band-edge emission with a high purity in a one-pot process. Furthermore, Torimoto discloses that by using a Ga-S precursor with a gallium halide precursor such as gallium ethyl xanthate (Ga(EX)3), xanthic acid remains in the resulting nanoparticles; and the gallium halide acts on the partially remaining xanthic acid to facilitate conversion into GaSx, thus forming a GaS semiconductor on the surface of the nanoparticle which inherently improves band-edge emission purity (narrower FWHM) and improves internal quantum yield. Therefore, a synthesis under this method provides “first semiconductor nanoparticles comprising a first semiconductor comprising silver (Ag), indium (In), gallium (Ga), and sulfur (S), and a second semiconductor disposed on a surface of the first semiconductor and comprising gallium (Ga) and sulfur (S);”. Although Torimoto does not perform a heat treatment of this exact first semiconductor nanoparticle with a gallium and sulfur source, Torimoto does disclose in the other synthesis method a heat treatment of AIGS core nanoparticles with a gallium and sulfur source to form a shell, thus improving band-edge emission quantum yield, purity, and FWHM. In example 1, Torimoto heat treats the AIGS cores (not formed by Ga-S precursor and gallium halide source) with gallium acetylacetonate (Ga(acac)3, gallium source) and 1,3-dimethylthiourea (sulfur source) to obtain a core-shell semiconductor particle (semiconductor composite particle). It would have been prima facie obvious to one of ordinary skill in the art, as of the effective filing date, to take the semiconductors formed by the “third step” process (examples 14-22) and heat treat with a gallium and sulfur source (second half of example 1) to improve band-edge emission quantum yield and the FWHM. Torimoto does not include Ag in this second shelling. Mamuye discloses synthesis of AIGS core nanoparticles with Ag-Ga-S (AGS) shells. Mamuye describes that the prior art of AIGS exhibit improved band-edge emission and reduced defect emissions when GaS was added as a shell, but the band-edge emission was also redshifted and some defects persisted. By adding Ag to the shell, the nanoparticles exhibit much higher quantum yields (80-99.9%), narrower FWHM, and reduced redshifting. It would have been prima facie obvious to one of ordinary skill in the art, as of the effective filing date, to add an Ag precursor to form an AGS shell and reduce redshifting while improving QY and FWHM.Furthermore, in the “fourth step” process, Torimoto discloses mixing nanoparticles with a gallium halide source (gallium chloride used in examples 15-22) and heat treating to obtain an additional semiconductor product. This “fourth step” heat treatment further improves the band-edge emission purity and the internal quantum yield (paragraph [0150]). It would have been prima facie obvious to one of ordinary skill in the art, as of the effective filing date, to take the semiconductors formed by the prior heat treatment core-shell product and heat treat an additional time with a gallium halide source to improve the band-edge emission purity and internal quantum yield. Therefore, Torimoto and Mamuye teach the claimed “A method of producing semiconductor nanoparticles, the method comprising: providing first semiconductor nanoparticles comprising a first semiconductor comprising silver (Ag), indium (In), gallium (Ga), and sulfur (S), and a second semiconductor disposed on a surface of the first semiconductor and comprising gallium (Ga) and sulfur (S); performing a first heat treatment of a first mixture comprising the first semiconductor nanoparticles, a silver (Ag) source, a gallium (Ga) source, and a sulfur (S) source, to obtain a first heat-treated product comprising semiconductor composite particles; and performing a second heat treatment of a second mixture comprising the semiconductor composite particles and a gallium halide, to obtain a second heat-treated product.”
Regarding claim 3, Torimoto and Mamuye teach the method according to claim 1 but neither disclose a ratio of Ag:semiconductor nanoparticles. Torimoto discloses the stoichiometric amount of the Group 13 element source (Ga) is preferably generated in an amount of 1 µmol to 10mmol (particularly 5 µmol to 1mmol) with respect to 10nmol of the semiconductor nanoparticles. Starting with the more preferably Ga bounds of 5 µmol to 1mmol, a ratio of Ga:nanoparticles would range from 500 to 100,000. In example 1, Torimoto utilizes 0.1mmol (100,000nmol) of Ga and 30nmol of nanoparticles (akin to the “first mixture” of claim 9). This precursor amount corresponds to a ratio of 3,333 of Ga:nanoparticles which is just outside the claimed range of 5,000 to 80,000 but would be a relevant starting point for one of ordinary skill in the art. Furthermore, in paragraph [0101], Torimoto discloses that the concentration of nanoparticles can vary between 5.0×10−7 mol/L or higher and 5.0×10−5 mol/L or lower, particularly 1.0×10−6 mol/L or higher and 1.0×10−5 mol/L or lower. Torimoto also suggests that when the ratio of particles in dispersion is excessively low, “it is difficult to recover the product by an aggregation and precipitation process using a poor solvent”. When the ratio is excessively high, “the rate of fusion of the core-forming materials through Ostwald ripening and collision is increased, and this tends to result in a broader particle size distribution”. It would have been prima facie obvious to one of ordinary skill in the art, as of the effective filing date, to experimentally modify the ratio of Ga:nanoparticles starting around 3,333 and arrive within the suggested overlapping range between 5,000 to 80,000 from the larger disclosed 500 to 100,000 using the teachings of Torimoto by avoiding excessively low ratios or excessively high ratios, thus avoiding difficulty in product recovery and broader particle size distribution, respectively. For the same reasoning, it would have been prima facie obvious to one of ordinary skill in the art, as of the effective filing date, to experimentally modify the ratio of Ag:nanoparticles using the amount of Ga as a similar starting point and the knowledge of corresponding effects of having too much or too few nanoparticles and arrive at the claimed limitation in the overlapping ranges. Therefore, Torimoto and Mamuye teach the claimed “The method of producing semiconductor nanoparticles according to claim 1, wherein a ratio of a number of moles of silver contained in the silver (Ag) source with respect to a number of moles of the first semiconductor nanoparticles contained in the first mixture is 1.0 × 103 to 1.0 × 104, and a ratio of a number of moles of gallium contained in the gallium (Ga) source with respect to the number of moles of the first semiconductor nanoparticles is 5.0 × 103 to 8.0 × 104.”.
Regarding claim 4, Torimoto and Mamuye teach the method according to claim 1 but do not disclose a molar ratio of Ag:Ga sources for the first mixture (AGS shell formation). Torimoto discloses in paragraph [0044] that the shell is composed substantially of a group 13 element (Ga) and of a group 16 element (S) where a ratio of atoms other than the group 13 and 16 elements are 10% or less. Furthermore, in paragraph [0051], Torimoto describes that when the shell is constituted of Ga-S, the shell tends to be observed darker than the core since Ga is not as heavy as Ag or In when imaged by HAADF-STEM. As described above in the rejection of claim 2, Mamuye teaches the benefits of choosing Ag as a further component in the GaS shell. To achieve an AGS shell of desired composition taught by Torimoto, Ag would be present at an amount of 10% or less with respect to Ga and S. In examples 1-7, Torimoto utilizes equimolar amounts of Ga and S to synthesize the shell. Assuming that Ga and S would remain equal, if Ag is added to its maximum allowance of 10%, then Ga and S would each be 45%, thus Ag:Ga provided at 0.222. It would have been prima facie obvious to one of ordinary skill in the art, as of the effective filing date, to choose Ag as the additional shell component as taught by Mamuye (reduce redshifting) and add in an amount as suggested by Torimoto (<10%) whereby one of ordinary skill in the art would arrive at the claimed invention. Therefore, Torimoto and Mamuye teach the claimed “The method of producing semiconductor nanoparticles according to claim 1, wherein a ratio of a number of moles of silver contained in the silver (Ag) source with respect to a number of moles of gallium contained in the gallium (Ga) source contained in the first mixture is 0.04 to 0.33”.
Regarding claim 5, Torimoto and Mamuye teach the method according to claim 1. Torimoto discloses in paragraph [0163] that the nanoparticles obtained from the “fourth step” (akin to second heat-treated product) are separated from the dispersion and undergo a purification step of the “third step” process which is disclosed in paragraphs [0145] and [0146]. Torimoto discloses that in the purification step, “an appropriate organic solvent such as an alcohol” is added to the supernatant obtained in the separation step, and the resultant is subsequently centrifuged to recover the semiconductor nanoparticles as a precipitate. The purification process specifically applied involves: adding 3 mL of hexane (organic solvent) followed by centrifugation to remove coarse particles; then 8 mL of methanol (organic solvent) was added followed by centrifugation to precipitate and remove particles having large particle size; then 12 mL of methanol was added to induce precipitation which were subsequently recovered by centrifugation. It would have been prima facie obvious to one of ordinary skill in the art, as of the effective filing date, to apply this purification step to the semiconductor nanoparticles to precipitate the particles and select for particles of certain sizes. Therefore, Torimoto and Mamuye teach the claimed “The method of producing semiconductor nanoparticles according to claim 1, the method further comprising: mixing the second heat-treated product with an organic solvent to obtain a third mixture; and performing centrifugation of the third mixture.”.
Regarding claim 6, Torimoto and Mamuye teach the method of claim 5. Torimoto does not disclose changes in quantum yield following the purification step. However, since one of ordinary skill in the art could arrive to the method of claim 5 as described above, the resulting semiconductor nanoparticle would inherently have the same claimed improvement in internal quantum yield. Therefore, Torimoto and Mamuye teach the claimed “The method of producing semiconductor nanoparticles according to claim 5, wherein a ratio of an internal quantum yield of the semiconductor nanoparticles obtained after the centrifugation with respect to an internal quantum yield of the semiconductor nanoparticles contained in the second heat-treated product is 0.7 to 1.1”.
Regarding claim 7, Torimoto and Mamuye teach the method of claim 5. Torimoto discloses use of methanol (an alcohol) as the organic solvent. Therefore, Torimoto and Mamuye teach the claimed “The method of producing semiconductor nanoparticles according to claim 5, wherein the organic solvent comprises an alcohol solvent”.
Regarding claim 8, Torimoto and Mamuye teach the method of claim 1. For shell synthesis (akin to the first heat treatment), Torimoto utilizes temperatures of 280°C (examples 1-6) and of 260°C (examples 7-8). For “fourth step” (akin to second heat treatment), Torimoto utilizes a temperature of 260°C (examples 15-22). Also refer to paragraph [0106] where Torimoto describes a preferable temperature range of 200-310°C for shell-forming (first heat treatment) and to paragraph [0157] where Torimoto describes a preferable temperature range of 200-320°C for the “fourth step” (second heat treatment). Therefore, Torimoto and Mamuye teach the claimed “The method of producing semiconductor nanoparticles according to claim 1, wherein a heat treatment temperature in the first heat treatment is 200°C to 320°C, and a heat treatment temperature in the second heat treatment is 200°C to 320°C.”
Regarding claim 9, Torimoto and Mamuye teach the method of claim 1. Torimoto in paragraph [0111] states the stoichiometric amount of the Group 13 element source (Ga) is preferably generated in an amount of 1µmol to 10mmol (particularly 5 µmol to 1mmol) with respect to 10nmol of the semiconductor nanoparticles. Starting with the more preferably Ga bounds of 5 µmol to 1mmol, a ratio of Ga:nanoparticles would range from 500 to 100,000. In example 1, Torimoto utilizes 0.1mmol (100,000nmol) of Ga and 30nmol of nanoparticles (akin to the “first mixture” of claim 9). This precursor amount corresponds to a ratio of 3,333 of Ga:nanoparticles which is just outside the claimed range of 5,000 to 60,000 but would be a relevant starting point for one of ordinary skill in the art. Furthermore, in paragraph [0101], Torimoto discloses that the concentration of nanoparticles can vary between 5.0×10−7 mol/L or higher and 5.0×10−5 mol/L or lower, particularly 1.0×10−6 mol/L or higher and 1.0×10−5 mol/L or lower. Torimoto also suggests that when the ratio of particles in dispersion is excessively low, “it is difficult to recover the product by an aggregation and precipitation process using a poor solvent”. When the ratio is excessively high, “the rate of fusion of the core-forming materials through Ostwald ripening and collision is increased, and this tends to result in a broader particle size distribution”. It would have been prima facie obvious to one of ordinary skill in the art, as of the effective filing date, to experimentally modify the ratio of Ga:nanoparticles starting around 3,333 and arrive within the suggested overlapping range between 5,000 to 60,000 from the larger disclosed 500 to 100,000 using the teachings of Torimoto by avoiding excessively low ratios or excessively high ratios, thus avoiding difficulty in product recovery and broader particle size distribution, respectively. Therefore, Torimoto and Mamuye meet the claimed “The method of producing semiconductor nanoparticles according to claim 1, wherein a ratio of a number of moles of gallium contained in the gallium (Ga) source with respect to the number of moles of the first semiconductor nanoparticles contained in the first mixture is 5.0 × 103 to 6.0 × 104.”.
Regarding claim 10, as described in the rejection of claim 1, one of ordinary skill in the art could follow the teachings of Torimoto in view of Mamuye to arrive to a method for producing semiconductor nanoparticles that would have AIGS and an additional semiconductor (shell) disposed on a surface of the semiconductor that comprises Ag, Ga, and S. From examples 15-22 (Table 4), Torimoto creates AIGS cores with an inherent GaS semiconductor disposed on the shell and further heat treated with a gallium halide resulting in “baseline” quantum yields >58% and FWHM just above 30nm (31-33nm), but the average particle size is not reported. Further, in examples 3-4 and comparative examples 1-3, the AIGS cores (without Ga-S and GaX present in precursor) with a GaS added shell display average particle sizes around 6nm (Tables 1-2). Torimoto does not include Ag in this shelling. Mamuye discloses synthesis of AIGS core nanoparticles with Ag-Ga-S (AGS) shells. Mamuye describes that the prior art of AIGS exhibit improved band-edge emission and reduced defect emissions when GaS was added as a shell, but the band-edge emission was also redshifted and some defects persisted. By adding Ag to the shell, the nanoparticles exhibit much higher quantum yields (80-99.9%), narrower FWHM, and reduced redshifting. It would have been prima facie obvious to one of ordinary skill in the art, as of the effective filing date, to add an Ag precursor to form an AGS shell and reduce redshifting while improving QY and FWHM. The produced semiconductor nanoparticles from examples 15-22 would predictably exhibit markedly improved quantum yields and narrower FWHM (<30nm) from their reported measurements and would be expected to exhibit an average particle size >7.5nm. By adding shells as described in examples 3-4 and the comparative examples 1-3, the nanoparticles would also increase in size, likely >7.5nm. Furthermore, Torimoto’s disclosed purification process removes particles having “a large particle size”, so their reported measured average is lower. Thus, arrival to such a method would produce the semiconductor nanoparticles as claimed. Therefore, Torimoto and Mamuye teach the claimed “Semiconductor nanoparticles, comprising: a semiconductor comprising silver (Ag), indium (In), gallium (Ga), and sulfur (S); and an additional semiconductor disposed on a surface of the semiconductor and comprising Ga and S, wherein the semiconductor nanoparticles have an average particle size that is 7.5 nm or larger, an internal quantum yield that is 50% or higher, and a full width at half maximum that is 30 nm or lower in an emission spectrum, and wherein the additional semiconductor further comprises silver (Ag).”.
Regarding claim 12, Torimoto and Mamuye teach the semiconductor nanoparticles according to claim 10 (claim 11 as currently recited in claim 12) but do not disclose examples of nanoparticles >10nm in average size. Similar to the line of reasoning for rejection of claim 10 whereby the nanoparticles would naturally approach sizes >7.5nm by the method, the addition of Ag to the shell would expectedly increase the baseline average size of nanoparticles as reported by Mamuye. Mamuye also discloses that the nanocrystals can be tailored in size to range between 1-15nm, enabling photoemission coverage in the entire optical spectrum to offer great versatility in color rendering (paragraph [0085]). It is well known in the art that heat treatment times and temperatures influence the resulting nanocrystal size as well, thus obvious parameters for one of ordinary skill in the art to modify in the method and arrive at the claimed invention. Therefore, Torimoto and Mamuye together teach the claimed “The semiconductor nanoparticles according to claim 11, wherein the semiconductor nanoparticles have an average particle size that is 10 nm or larger”.
Regarding claim 13, Torimoto and Mamuye teach the method according to claim 1 and semiconductor nanoparticles of claim 10. Claim 13 is a “product-by-process claim” dependent on the product of claim 10 and the method of claim 1. "[E]ven though product-by-process claims are limited by and defined by the process, determination of patentability is based on the product itself. The patentability of a product does not depend on its method of production. If the product in the product-by-process claim is the same as or obvious from a product of the prior art, the claim is unpatentable even though the prior product was made by a different process." In re Thorpe, 777 F.2d 695, 698, 227 USPQ 964, 966 (Fed. Cir. 1985) (citations omitted). Furthermore, "[b]ecause validity is determined based on the requirements of patentability, a patent is invalid if a product made by the process recited in a product-by-process claim is anticipated by or obvious from prior art products, even if those prior art products are made by different processes." Amgen Inc. v. F. Hoffmann-La Roche Ltd., 580 F.3d 1340, 1370 n. 14, 92 USPQ2d 1289, 1312, n. 14 (Fed. Cir. 2009). Regardless, Torimoto and Mamuye teach the semiconductor nanoparticles of claim 10 as well as the method of claim 1. Therefore, Torimoto and Mamuye teach the claimed “The semiconductor nanoparticles according to claim 10, wherein the semiconductor nanoparticles are produced by the method according to claim 1.”
Response to Arguments
Applicant's arguments filed July 21, 2026 have been fully considered but they are not persuasive. Applicant presents arguments towards .
Regarding claim 10, the argument presented is considered not relevant to the invention as claimed. Claim 10 presents a semiconductor comprising Ag, In, Ga, and S whereby an additional semiconductor is disposed on the surface comprising Ag, Ga, and S, thus a semiconductor of AIGS/AGS structure. The applicant presents arguments specific towards bandgap energy differences when shelling AIGS cores with a specific order of GaS then AGS, thus forming AIGS/GaS/AGS semiconductors. Since claim 10 pertains to AIGS/AGS structures, the argument presented is not relevant towards differences in bandgap energies between GaS shells and AGS shells considering a GaS shell is not present. Thus, this argument is not persuasive.
Regarding claim 1, the applicant argues that one of ordinary skill in the art would not pursue shelling an AGS layer around a GaS shell on an AIGS core surface given differences in bandgap energies. The applicant asserts that under quantum confinement principles recognized by those skilled in the art “a shell having a larger bandgap energy would be expected to be formed over a shell having a smaller bandgap energy”, further citing that GaS shells are slightly over “3 eV” whereas bandgap of AGS is in the “high 2 eV range”. Torimoto (US PGPub 20230151271/WO2021182417) states preferences when shelling semiconductors in paragraphs [0042-48]. Torimoto states that the shell “may contain a semiconductor having a larger band-gap energy than that of the cores” but does not limit shells to such qualities. Torimoto also does not teach away from semiconductors having smaller band-gap energies nor asserts any teaching/limitation that band-gap energies must be larger. Therefore, one of ordinary skill in the art would not be limited to such principles of quantum confinement.If one of ordinary skill in the art is limited to such principles, Torimoto among others show evidence that AGS can have a higher bandgap energy than GaS. For instance, Torimoto states a shell may have a band-gap energy of 2.0 eV or higher and 5.0 eV or lower. The applicant cites that GaS shells have bandgap energies over 3 eV; however, bandgap energies are not necessarily a finite value to the semiconductor. Torimoto teaches that GaS (gallium sulfide) has a band-gap energy of “about 2.5 eV or higher and 2.6 eV or lower” (paragraph [0056]). Additionally, Mouacher et al (NPL: “First-principles calculations of electronic…”) and Purohit et al (NPL: “Bandgap Engineering of AgGaS2 for Optoelectronic…”) disclose bandgap energy values of AGS semiconductors in line with the “high 2 eV range” as asserted by the applicant. Mouacher (abstract) discloses a theoretical bandgap energy of AGS of “about 2.59 eV” which is “in good accord with experimental measurements”. Purohit cites a 2.51 eV value for AGS “which is in the range desirable for applications in light-emitting diodes” and further teaches methods for modifying the bandgap. Thus, there is evidence that suggests AGS having a bandgap energy higher than that of GaS. Therefore, it would be possible to prepare AIGS/GaS/AGS semiconductors as presented in the 103 rejections above for claim 1. Thus, the argument is not persuasive.
Conclusion
THIS ACTION IS MADE FINAL. Applicant is reminded of the extension of time policy as set forth in 37 CFR 1.136(a).
A shortened statutory period for reply to this final action is set to expire THREE MONTHS from the mailing date of this action. In the event a first reply is filed within TWO MONTHS of the mailing date of this final action and the advisory action is not mailed until after the end of the THREE-MONTH shortened statutory period, then the shortened statutory period will expire on the date the advisory action is mailed, and any nonprovisional extension fee (37 CFR 1.17(a)) pursuant to 37 CFR 1.136(a) will be calculated from the mailing date of the advisory action. In no event, however, will the statutory period for reply expire later than SIX MONTHS from the mailing date of this final action.
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/NWFG/Examiner, Art Unit 1759
/MELVIN C. MAYES/Supervisory Patent Examiner, Art Unit 1759
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