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 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 2, 4, and 9 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 2 recites the term “quality” in reference to graphene that is not a term defined in the instant specification; this term is relative and therefore indefinite as it is not obvious to one of ordinary skill in the art what material property should be evaluated as quality and in which direction should the change of the value of that property be correlated with a “higher quality.”
Claim 4 recites a “predetermined value” that is an indefinite term. While reciting a predetermined value is not per se indefinite, this claim recites the predetermined value in a contingent limitation, rendering the whole claim dependent on a value whose bounds are arbitrary. Therefore one of ordinary skill in the art would not be sufficiently apprised of infringement upon this limitation: for example, if an artisan designs this invention where the energy of the laser is never increased and the artisan does not disclose a predetermined value, does this infringe on the claimed invention? See MPEP 2173.05(b)(II): “In Brummer, the Board held that a limitation in a claim to a bicycle that recited "said front and rear wheels so spaced as to give a wheelbase that is between 58 percent and 75 percent of the height of the rider that the bicycle was designed for" was indefinite because the relationship of parts was not based on any known standard for sizing a bicycle to a rider, but on a rider of unspecified build. Brummer, 12 USPQ2d at 1655.” In the instant case, the claim recites a laser wavelength that may be changed when a value is less than a threshold, that itself does not change but can be changed on a case-by-case basis. The “predetermined value” appears to be analogous to the “rider of unspecified build.”
Claim Rejections - 35 USC § 103
The following is a quotation of 35 U.S.C. 103 which forms the basis for all obviousness rejections set forth in this Office action:
A patent for a claimed invention may not be obtained, notwithstanding that the claimed invention is not identically disclosed as set forth in section 102, if the differences between the claimed invention and the prior art are such that the claimed invention as a whole would have been obvious before the effective filing date of the claimed invention to a person having ordinary skill in the art to which the claimed invention pertains. Patentability shall not be negated by the manner in which the invention was made.
The factual inquiries 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 1-15 are rejected under 35 U.S.C. 103 as being unpatentable over Ionin et al. Ultrafast femtosecond laser ablation of graphite, 2015 Laser Phys. Lett. 12 075301, in view of Zhao et al. 2022 (CN115072710A), Le et al. Ultrafast Laser Pulses Enable One-Step Graphene Patterning on Woods and Leaves for Green Electronics, Adv. Funct. Mater. 2019, 29, 1902771, Huang et al. 2022 (CN114560460A), and Lin et al. Contactless graphene conductivity mapping on a wide range of substrates with terahertz time-domain reflection spectroscopy, Sci Rep 7, 10625 (2017); referred to herein as Ionin, Zhao, Le, Huang, and Lin respectively.
Regarding claim 1, Ionin teaches a method of ablating graphite (title) comprising:
A second step of irradiating a surface of a carbon-containing material (highly oriented pyrolytic graphite, HOPG) with an infrared (IR) wave (800 nm Ti:sapphire laser pulses, p. 2 column 1) and an evaluation laser beam (frequency-doubled probe beam at 400 nm, p. 2 column 1) and detecting the IR wave from the surface (pyroelectric energy meters, p. 2 column 2, Figure 1);
A third step of irradiating a processing region of the surface with a processing laser beam to form ablated graphite in the processing region (this third step being identical to the second and fourth steps, wherein the processing laser beam in this limitation is met by the IR Ti:sapphire laser pulses at 800 nm, p. 2 column 1);
A fourth step of irradiating the processing region with the IR wave and the evaluation laser beam and detecting the IR wave from the processing region (raster-moved from laser shot to shot to expose its fresh surface spots (figure 1), p. 1 column 2-p. 2 column 1); and
A fifth step of evaluating quality of the ablated graphite in the processing region (EHP dynamics, corresponding to HOPG surface disordering, p. 4 ‘Discussion’) based on an intensity difference between the IR wave detected in the fourth step and the IR wave detected in the second step (reflectivity as dependent on laser fluence, Figure 2). Specifically, Ionin teaches that the quality of the graphite is determined by the leveling off of the reflectivity of the UV and IR pulses as a function of fluence, as captured by reflectivity curves in Figure 2, because Ionin teaches that this leveling off may indicate saturation of electronic dynamics (p. 3 column 1, ‘3.1’) at the surface of the graphite, which correlates with the non-linear yield of electrons and ions from the photo-excited surfaces, corresponding to extreme HOPG surface disordering (p. 4 column 2 ‘Discussion’), thus indicating ablation present, as opposed to the intact graphite layers which exhibit less disordering (bottom curve of Figure 4). Therefore, Figure 2 of Ionin meets the limitation of the difference in intensities indicating quality: in Ionin, the intensities are indicated by reflectivities, the steps two and four of the instant claim are repeated measurements in Figure 2 of Ionin, and the quality of the material is indicated by the plateauing at higher fluences indicating more ablation present at higher fluences.
Ionin does not teach the following limitations, required by the instant claim:
A graphene manufacturing method;
A first step of preparing a workpiece including a base material made of a resin material and a plant powder dispersed in the base material; and
A terahertz wave.
However, regarding limitations I and II, Zhao teaches a method for preparing graphene layered composite materials (0008) wherein a workpiece is prepared (Figure 1) including a base material containing cellulose (substrate, 0010) made of a precursor made of biomass, synthetic materials, or a combination (0020) and the biomass material includes lignin and the synthetic material includes phenolic resin and ABS plastic (0021), meeting the definitions of a plant material and a resin material. Zhao additionally teaches a step of irradiating a processing region of the surface (the surface of the LIG substrate, 0084) with a processing laser beam (laser, 0083) to form graphene in the processing region (0005). The disclosure of Zhao is analogous art to the claimed invention and to the disclosure of Ionin in view of Le, who teaches that ablation and LIG formation are induced in the same process of laser irradiation of carbon surfaces (Figure 2(h), Ablation depth simultaneous with LIG thickness as a function of heat accumulation).
It would be obvious to one of ordinary skill in the art to modify the invention taught by Ionin by replacing the workpiece taught by Ionin (1 mm thick, 10 mm × 10 mm wide optical-quality sample of highly oriented pyrolytic graphite, p. 1 column 2) with the workpiece taught by Zhao; one would be motivated to do so since Zhao teaches that the disclosed workpiece is easily graphitized and may contain graphite which Zhao teaches is also easily graphitized when induced by lasers (0046). Thus, one of ordinary skill in the art would have reasonable expectation of predictable performance of this modification, and would be motivated to make such a modification in order to obtain graphene on the surface of the starting material, as Zhao teaches (0061), which Zhao further teaches is advantageous because the workpiece results in LIG not falling off easily (0007).
Additionally, it would be obvious to one of ordinary skill in the art to modify the invention of Ionin and Zhao by incorporating the step of irradiating the region to produce LIG, as Zhao teaches; one would be motivated to do so in order to obtain LIG, as Zhao teaches, because Zhao teaches that graphene has unique advantageous physical properties (0002) and that laser-induced synthesis of graphene is advantageous for its low cost and lack of need for a protective atmosphere (0005).
Zhao does not explicitly teach that the plant material has a powder form, as required by the instant claim. However, Huang teaches an analogous method for preparing LIG from biocompatible materials (0011) wherein the raw material used is chitosan oligosaccharide powder (0028). It is therefore evident that the use of a plant powder for the creation of laser-induced graphene was known in the art at the time of filing of the invention. The courts have held that the combination of known elements in the prior art according to known methods to yield predictable results is prima facie obvious; see MPEP 2143(I)(A). Thus the mere combination of chitosan oligosaccharide powder with a resin material, in a manner equivalent to the combination of cellulose and lignin with a resin material as Zhao teaches (Figure 1, 0020, 0021), would have been sufficiently obvious to one of ordinary skill in the art.
Regarding limitation III, Ionin, Zhao, Le, and Huang do not teach the use of a terahertz (THz) wave.
However, Lin teaches a method of evaluating graphene by reflection based THz-time-domain spectroscopy (THz-TDS, Figure 1) wherein a THz wave is obtained by an ultrashort Ti-:sapphire laser pulse (p. 2, ‘Terahertz time-domain reflection spectroscopy’) and is irradiated on a graphene sample and collected (“reflected terahertz pulse is then collected and focused onto an unbiased photoconductive antenna,” p. 2, ‘Terahertz time-domain reflection spectroscopy’) in order to evaluate the conductivity of the graphene (Figure 2). It would be obvious to one skilled in the art to modify the invention of Ionin, Zhao, Le, and Huang by using a THz laser to conduct THz-TDS as Lin teaches; one would be motivated to do so because Lin teaches that the technique disclosed enables fast and contactless in-line monitoring of the quality of graphene (“in-line graphene quality monitoring,” p. 2 pp. 1, abstract). Therefore one skilled in the art would arrive at the claimed invention prior to the effective filing date.
Regarding claim 2, Ionin, Zhao, Le, Huang, and Lin teach the method as applied to claim 1. Ionin further teaches that at higher effective laser fluences, the IR and UV reflectivity are increased (Figure 2), thus a higher quality of ablation is evaluated since the extent of ablation is dependent on fluence (ablation thresholds are 0.2 and 0.3 J/cm^2, p. 4 column 1 ‘3.3’). It would be obvious to one skilled in the art that the teaching of Ionin would be capable of performing the function of indicating a higher quality of graphene, as required by the instant limitation. Lin additionally further teaches that the conductivity values are obtained from the intensity of the reflected THz waves (“it is expected that terahertz reflection increases with increasing graphene conductivity induced by electrical gating,” p. 5 ‘Graphene mobility’). It would therefore be obvious to one skilled in the art that the teaching of Lin would be capable of performing the function of indicating a higher quality of graphene, as required by the instant limitation.
Regarding claim 3, Ionin, Zhao, Le, Huang, and Lin teach the method as applied to claim 1. Le further teaches that the laser pulse rate affects the fluence in turn affecting temperature of the material (Figure 2(a)). It would be obvious to one skilled in the art to modify the laser pulse rate, a radiation condition, in order to control the fluence based on results obtained from the evaluation result as Ionin teaches (Figure 2); one would be motivated to do so in order to optimize the temperature of the material in order to tune the extent of graphitization, as Le teaches (“IG could achieve a lower graphitization temperature thanks to the ultrashort pulse duration, being shorter than the time required for the heat transfer to surroundings,” p. 2 column 1 pp. 2). Therefore one skilled in the art would arrive at the claimed invention before the effective filing date.
Regarding claim 4, Ionin, Zhao, Le, Huang, and Lin teach the method as applied to claim 3. Due to the claim language relying on a conditional limitation, and the disclosed art as discussed for claim 3 does not disclose an intensity difference being smaller than a predetermined value, the teachings of Ionin, Zhao, Le, Huang, and Lin are considered to meet the limitations of the instant claim.
Regarding claim 5, Ionin, Zhao, Le, Huang, and Lin teach the method as applied to claim 1. Ionin further teaches that the third and fourth step are simultaneously executed, since Ionin teaches that the irradiation occurs via the IR pump (p. 2 column 1), thus meeting the instant limitation.
Regarding claim 6, Ionin, Zhao, Le, Huang, and Lin teach the method as applied to claim 1. Ionin further teaches that the processing beam (800 nm Ti:sapphire laser pulses, p. 2 column 1) and the evaluation laser beam (frequency-doubled probe beam at 400 nm, p. 2 column 1) are emitted from the same source (Ti:sapphire source, Figure 2).
Regarding claim 7, Ionin, Zhao, Le, Huang, and Lin teach the method as applied to claim 1. Ionin further teaches that both the IR pump pulse and the UV probe pulse have a FWHM duration of about 100 femtoseconds (p. 2 column 1), thus meeting the limitations of each beam being a femtosecond laser beam.
Regarding claim 8, Ionin, Zhao, Le, Huang, and Lin teach the method as applied to claim 1. Ionin further teaches that the evaluation laser beam (UV probe beam) is temporally delayed from the processing laser beam (IR pump beam) in a manner where a zero-time delay is defined as the pump and probe pulse coinciding exactly in the sample plane (p. 2 column 1), therefore necessarily requiring that the beams are spatially configured at irradiation positions that overlap with each other, thus meeting the limitation of the instant claim. This is further illustrated in Figure 2.
Regarding claim 9, Ionin, Zhao, Le, Huang, and Lin teach the method as applied to claim 1. Ionin further teaches that the evaluation laser beam (UV probe beam) is temporally delayed from the processing laser beam (IR pump beam) (p. 2 column 1), therefore necessarily requiring that the beams are temporally configured at irradiation positions that do not coincide with each other and are away from each other, thus meeting the limitation of the instant claim.
Regarding claim 10, Ionin, Zhao, Le, Huang, and Lin teach the method as applied to claim 1. Ionin further teaches that the evaluation laser beam incident on the processing region (UV probe beam) is 50 times weaker than the processing laser beam (pump beam) incident on the processing region (p. 2 column 1), therefore teaching that the intensity is weaker, thus meeting the limitation of the instant claim.
Regarding claim 11, Ionin, Zhao, Le, Huang, and Lin teach the method as applied to claim 1. Ionin further teaches that the processing laser beam (pump beam) incident on the processing region has a wavelength of 800 nm (p. 2 column 1), and that the evaluation laser beam incident on the processing region (UV probe beam) has a wavelength of 400 nm (p. 2 column 1), thus meeting the limitation of the instant claim.
Regarding claim 12, Ionin, Zhao, Le Huang, and Lin teach the method as applied to claim 11. Le also teaches a method of forming laser-induced graphene from femtosecond laser pulses (p. 2 column 1) wherein a UV laser is used for the processing (writing) step at a wavelength of 343 nm (p. 8, column 1, ‘Experimental Section’).
It would be obvious to one of ordinary skill in the art before the effective filing date of the invention to modify the invention of Ionin, Zhao, Le, Huang, and Lin by using the UV laser beam taught by Le as a processing beam, either as a supplement to the IR beam taught by Ionin as a separate processing beam, or as a substitute for its simultaneous function as a processing beam (as discussed for claim 1). One skilled in the art would be motivated to do so because Le teaches that the UV femtosecond laser advantageously and efficiently transforms wood components to the intermediate char via high-repetition-rate-assisted carbonization, and then to LIG via photo-assisted graphitization and exfoliation, within a single step (p. 2 column 1) while minimizing ablation (“Our hypothesis was that high photon energy could localize the heat into a small area…” p. 2 column 1 pp. 2; “Our findings reveal…”, p. 2 column 1 pp. 2). One of ordinary skill in the art would therefore arrive at the claimed invention prior to the effective filing date, wherein the wavelength of the evaluation laser beam (UV beam of Ionin, 400 nm, p. 2 column 1) would be larger than the wavelength of the processing laser beam (UV beam of Le, 343 nm, p. 8 column 1).
Regarding claims 13 and 15, Ionin, Zhao, Le, Huang, and Lin teach the method as applied to claim 1. Le further teaches that the UV irradiation conditions such as writing speed and repetition rate are result-effective variables in relation to the formation of LIG (p. 8 column 2, last paragraph), and the wavelength of the beam can be traded with the repetition rate to achieve exfoliation (“the pulses can achieve higher transient intensities at low pulse energies,” p. 9 column 1, ‘Photoassisted Exfoliation’) and the resulting temperature required to achieve LIG. It would therefore be obvious to one of ordinary skill in the art to substitute the 343 nm beam taught by Le with the 400 nm beam taught by Ionin as additionally functioning as a processing laser beam, therefore meeting the instant limitation since the processing and evaluation beam would be the same; one would be motivated to do so optimize the extent of exfoliation as both Ionin (“precise ablative fs-laser machining,” p. 5 column 1) and Le (“significant material exfoliation at the beam path,” p. 9 column 1 ‘Photoassisted Exfoliation’) teach. Further, the substitution for one known element for another to obtain predictable results has been held by the courts to be prima facie obviousness (see MPEP 2143(I)(B); KSR Int'l Co. v. Teleflex Inc., 550 U.S. 398, 415-421, 82 USPQ2d 1385, 1395-97 (2007) ).
Regarding claim 14, Ionin, Zhao, Le, Huang, and Lin teach the method as applied to claim 13. Modified Ionin teaches that the 400 nm beam used as a processing and evaluation beam is ultraviolet light (p. 3, ‘3.1. IR- and UV-reflection’).
Conclusion
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/Eileen Moudou/Examiner, Art Unit 1738
/MICHAEL FORREST/Primary Examiner, Art Unit 1738
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