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 .
The amendment of October 27, 2025 has been received and entered. With the entry of the amendment, claim 20 is canceled, claims 10-11 are withdrawn and claims 1-9 and 12-19 are pending for examination.
Election/Restrictions
Applicant’s election without traverse of the species of irradiation performed during soaking, claims 1-9 and 12-20, in the reply filed on June 30, 2025 is acknowledged.
Claims 10-11 are withdrawn from further consideration pursuant to 37 CFR 1.142(b) as being drawn to a nonelected species, there being no allowable generic or linking claim. Election was made without traverse in the reply filed on June 130, 2025.
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 1-9, 12 and 13 are rejected under 35 U.S.C. 103 as being unpatentable over WO 2008/020403 (hereinafter ‘403) in view of Johnson et al (US 2010/0267238), Nakagawa et al (US 4719501), Miyata et al (US 2007/0102823) and CN 105196409 (hereinafter ‘409).
Claims 1, 2, 6, 9: ‘403 teaches a substrate processing method comprising providing a silicon substrate which would have a silicon surface of a semiconductor wafer, where the substrate with a silicon surface is soaked (dipped, immersed) in a solution with liquid heavy water (D2O) for a period of time in order to passivate the silicon surface with deuterium or a mixture of deuterium and hydrogen (note page 5, lines 5-22, page 6, line 30 to page 67, line 10, page 9, lines 20-30). It is indicated to provide the treatment at temperatures less than 90 degrees C, which would therefore include the range of up to but less than 90 degrees C (note page 9, lines 20-30). It is further described that the treatment is not limited to specifically illustrated embodiments and can be provided to various Si technology, including in SiO2 layers (note page 17, line 25 to page 10, line 5).
(A) As to specifically providing the silicon as a silicon film formed on a surface, ‘403 describes using a wafer made of silicon (note page 5, lines 5-10). However, Johnson describes that for semiconductor substrates it is conventionally known to provide a semiconductor substrate of silicon (bulk silicon wafer) or also that the substrate can be formed of a layer/film of silicon on an insulating layer, and generally have one or more layers, including polycrystalline silicon (note 0015), where overlayers can includes silicon oxide, etc. (note 0017, 0018).
Therefore, it would have been obvious to one of ordinary skill in the art before the effective filing date of the claimed invention to modify ‘403 to use as the substrate, one with a silicon film formed on the substrate with an exposed silicon surface for treatment as suggested by Johnson with an expectation of predictably acceptable results, as ‘403 teaches that the substate can be a semiconductor silicon wafer with an exposed silicon surface, and Johnson would indicate that semiconductor substates can be bulk silicon wafers or also a base substrate with a layer of silicon, that would therefore have the exposed silicon surface treated by ‘403. Furthermore, as to claim 2, it would have been obvious to one of ordinary skill in the art that the silicon film would also acceptably be a polycrystalline silicon film as desired by claim 2, with an expectation of predictably acceptable results, because Johnson indicates that polycrystalline silicon can be used as a silicon layer material on the substrate.
(B) Furthermore, as to the irradiating of the silicon film with microwaves while the substrate soaks in the liquid heavy water, where the irradiating is configured to replace S-H bonds in the silicon film with Si-D bonds in the silicon film, as noted above,’403 indicates that the treatment temperature can be in a range of up to but less than 90 degrees C (363.15 K).
Nakagawa describes how polycrystalline Si layers can be provided for making semiconductor elements (note column 1, lines 10-20), where the polycrystalline layer is provided with a hydrogen content (note column 2, lines 15-50), where the hydrogen in the silicon film can include being in the form of S-H bonds (note column 5, lines 1-30).
Miyata describes SiO2 layers as also having Si-OH and Si-H structures (note 0066—0067), and that it is desirable to replace hydrogen atoms with deuterium atoms to improve resistance to dielectric breakdown (note 0078), where a semiconductor device is being formed (note abstract). The replacement of the hydrogen atoms can be by contacting with D2, D2O with heat, thermal oxidation, for example (note 0106).
‘409 teaches how temperature can be controlled for a liquid/water containing test specimen (note the water/concrete slurry) in a container/box, where the specimen in the container is placed in a casing/container/chamber 10 and then irradiated with microwaves from generator 20 to heat the liquid/slurry/water to a controlled temperature, such as 75 degrees C (348.15 K) (note figure 1, pages 2-4, translation), where the heating is provided by intermittent generation of the microwaves (note page 3, translation).
Therefore, it would have been obvious to one of ordinary skill in the art before the effective filing date of the claimed invention to modify ‘403 in view of Johnson to provide heating the soaking substrate to the desired temperature in the claimed range of claim 6 by irradiating the silicon film with microwaves while the substrate soaks in the liquid heavy water and also well, control/configure the irradiation treatment to replace Si-H bonds in the silicon film with Si-D bonds in the silicon film as suggested by Nakagawa, Miyata and ‘409 with an expectation of predictably acceptable results since ‘403 would suggest how there can be a range of temperatures during treatment which would include heating during the treatment, and Johnson would suggest providing a polycrystalline Si film, where further layers can be provided including silicon oxide, and where Nakagawa would suggest the conventional presence of Si-H bonds in the polycrystalline Si film for a desirable Si film for semiconductor use, where Miyata would indicate the desirable Si-H bond replacement with Si-D bonds when forming a semiconductor structure, which can reduce resistance to dielectric breakdown, where the H can be replaced using D2O (heavy water) and heat, and notes use of silicon oxide films, and ‘409 would indicate how controlled heating of a water containing material (also including the concrete material acting like the substrate in the present claims of also being in the water) can be provided by putting a container of the material in a chamber and exposing to microwaves which would expose the water and substrate/silicon in the bath/water and provide heating to temperature in the claimed range, where it would be suggested to provide the irradiating during the soaking so that the controlled temperature can be provided during the heating. It would have been obvious to optimize from temperature range of ‘403 during the soaking to provide the desirable Si-H bond replacement with Si-D bonds, since Miyata indicates how heating with D2O can help desirably replace S-H bonds with Si-D bonds, with the optimizing giving temperatures within the claimed range of 320-375 K of claim 6. Note In the case where the claimed ranges "overlap or lie inside ranges disclosed by the prior art" a prima facie case of obviousness exists. In re Wertheim, 541 F.2d 257, 191 USPQ 90 (CCPA 1976). The process would also provide the features of claim 9, where the irradiating of the silicon film can occur during the soaking.
Claims 3, 4, 5, 12, 13: As to providing the irradiation by irradiating the silicon film with microwaves for a first period of time, and then stop the irradiation for a second period of time, and then again irradiating the silicon film with microwaves, as in claims 3 and 12, this would be suggested by ‘409, which describes intermittent microwave use, with a temperature sensor such that when heating temperature becomes too high after a first period of microwaving the heating is stopped, and then after a second period of being stopped, when the temperature becomes too low, the microwaves are started again (note page 3, translation). The exact number and timing of repeats/cycles of heating and stopping, for claims 4, 5 and 13, as well, would be a matter of routine experimentation for the specific articles being treated and specific solutions, and such optimization would provide the cyclic irradiation between 2 and 15 times, and claimed first periods of time and second periods of time (note "[W]here the general conditions of a claim are disclosed in the prior art, it is not inventive to discover the optimum or workable ranges by routine experimentation." In re Aller, 220 F.2d 454, 456, 105 USPQ 233, 235 (CCPA 1955)).
Claims 7, 8: Further as to performing the silicon film in a first processing chamber, and the soaking including placing the substrate on which the film is formed in a bath containing the liquid heavy water and then transferring the bath into a second processing chamber different form the first processing chamber,
Johnson suggests providing the silicon film as discussed for claim 1 above. Johnson further describes how silicon films can be provided by processes such as PECVD, LPCVD, CVD (note 0017). It would have been obvious to one of ordinary skill in the art before the effective filing date of the claimed invention to modify ‘403 in view of Johnson, Nakagawa, Miyata and ‘409 to provide the silicon film by at least one of these methods as suggested by Johnson with an expectation of predictably acceptable results as a known method for forming the desired silicon film, and additionally, when providing the silicon film by such as method, the Examiner would take Official Notice that such processes would be provided in first processing chambers to hold the gas in place, maintain pressure, etc. (as applicant has not traversed this position since the Office Action of July 25, 2025, it is understood to be agreed to). ‘409 further describes the microwave processing in a second processing chamber (as desired by claim 8) as discussed for claim 1 above, where it would be understood that these chambers would be different as providing different processing features. Furthermore, ‘409 would indicate the providing of the liquid containing material occurs outside the second chamber (the box of material is then placed in the chamber) (note page 3, translation), and therefore, it would at least have been obvious to place the substrate in a bath of the liquid (which would be indicted by ‘403 at page 6, line 30 to page 7, line 5), and then place in the second chamber for heating with an expectation of predictably acceptable results.
Claims 14-19 are rejected under 35 U.S.C. 103 as being unpatentable over WO 2008/020403 (hereinafter ‘403) in view of Johnson et al (US 2010/0267238), CN 105196409 (hereinafter ‘409), Japan 2022-039009 (hereinafter ‘009) and Miyata et al (US 2007/0102823).
Claim 14: ‘403 teaches a substrate processing method comprising providing a silicon substrate which would have a silicon surface of a semiconductor wafer, where the substrate with a silicon surface is soaked (dipped, immersed) in a solution with liquid heavy water (D2O) for a period of time in order to passivate the silicon surface with deuterium or a mixture of deuterium and hydrogen (note page 5, lines 5-22, page 6, line 30 to page 67, line 10, page 9, lines 20-30). It is indicated to provide the treatment at temperatures less than 90 degrees C, which would therefore include the range of up to but less than 90 degrees C (note page 9, lines 20-30). It is further described that the treatment is not limited to specifically illustrated embodiments and can be provided to various Si technology, including in SiO2 layers (note page 17, line 25 to page 10, line 5).
(A) As to specifically providing the silicon as a silicon film formed on a surface (first material layer), ‘403 describes using a wafer made of silicon (note page 5, lines 5-10). However, Johnson describes that for semiconductor substrates it is conventionally known to provide a semiconductor substrate of silicon (bulk silicon wafer) or also that the substrate can be formed of a layer/film of silicon on an insulating layer, and generally have one or more layers, including polycrystalline silicon (note 0015).
Therefore, it would have been obvious to one of ordinary skill in the art before the effective filing date of the claimed invention to modify ‘403 to use as the substrate, one with a silicon film formed on the substrate with an exposed silicon surface for treatment as suggested by Johnson with an expectation of predictably acceptable results, as ‘403 teaches that the substate can be a semiconductor silicon wafer with an exposed silicon surface, and Johnson would indicate that semiconductor substates can be bulk silicon wafers or also a base substrate with a layer of silicon, that would therefore have the exposed silicon surface treated by ‘403. Furthermore, it would have been obvious to one of ordinary skill in the art that the silicon film would also acceptably be a polycrystalline silicon film, with an expectation of predictably acceptable results, because Johnson indicates that polycrystalline silicon can be used as a silicon layer material on the substrate.
(B) Furthermore, as to the irradiating of the silicon film with microwaves while the substrate soaks in the liquid heavy water, and forming a second material layer form the first material layer by the irradiating, as noted above,’403 indicates that the treatment temperature can be in a range of up to but less than 90 degrees C (363.15 K). It would have been obvious to optimize from this range, giving temperatures within the range of 320-375 K (note claim 6). Note In the case where the claimed ranges "overlap or lie inside ranges disclosed by the prior art" a prima facie case of obviousness exists. In re Wertheim, 541 F.2d 257, 191 USPQ 90 (CCPA 1976).
‘409 teaches how temperature can be controlled for a liquid/water containing test specimen (note the water/concrete slurry) in a container/box, where the specimen in the container is placed in a casing/container/chamber 10 and then irradiated with microwaves from generator 20 to heat the liquid/slurry/water to a controlled temperature, such as 75 degrees C (348.15 K) (note figure 1, pages 2-4, translation), where the heating is provided by intermittent generation of the microwaves (note page 3, translation).
Therefore, it would have been obvious to one of ordinary skill in the art before the effective filing date of the claimed invention to modify ‘403 in view of Johnson to provide heating the soaking substrate to the desired optimized temperature by irradiating the silicon film with microwaves while the substrate soaks in the liquid heavy water as suggested by ‘409 with an expectation of predictably acceptable results since ‘403 would suggesting heating during the treatment, and ‘409 would indicate how controlled heating of a water containing material (also including the concrete material acting like the substrate in the present claims of also being in the water) can be provided by putting a container of the material in an chamber and exposing to microwaves which would expose the water and substrate/silicon in the bath/water and provide heating to temperature in the claimed range, where it would be suggested to provide the irradiating during the soaking so that the controlled temperature can be provided during the heating. As to forming a second material layer from the soaking/irradiation and the first and second materials, ‘403 indicates D and optionally H passivation of the surface, giving a second material layer (note page 5, line5-25).
(C) As to the compounds in the first and second material layers.
‘009 indicates that formed polycrystalline silicon can conventionally have Si-OH groups formed on the surface that are desired to be removed (note page 3, translation).
Miyata describes SiO2 layers as also having Si-OH and Si-H structures (note 0066—0067), and that it is desirable to replace hydrogen atoms with deuterium atoms to improve resistance to dielectric breakdown (note 0078), where a semiconductor device is being formed (note abstract). The replacement of the hydrogen atoms can be by contacting with D2, D2O with heat, thermal oxidation, for example (note 0106).
Therefore, it would have been obvious to one of ordinary skill in the art before the effective filing date of the claimed invention to modify ‘403 in view of Johnson and ‘409 to provide that the first crystalline polysilicon material has a first compound of SixOyHz as claimed and the treatment with the soaking provide the SiaObHcDd as claimed as suggested by ‘009 and Miyata with an expectation of predictably acceptable results since ‘403 is providing the treatment of Si with the heavy water/microwaves as claimed, and Johnson suggests the Si can be a layer of polycrystalline silicon which ‘009 indicates would conventionally have a first compound of SiOH material as claimed (where x y and z understood to meet the claimed requirements as Si, O and H would all be present, and where it would be at least predictably acceptable for the y to have a value of above zero and less than 1 with Si, O and H all present to provide a balanced stoichiometric formula) and Miyata would indicate that such material can have H groups replaced with D using D2O (heavy water) and since ‘403 is providing the same microwave/heavy water soaking as claimed, the same H replacement with D is understood to occur, giving the resulting second material layer of SiaObHcDd, where since ‘403 indicates both D and H can be present, the a, b, c and d understood to meet the claimed requirements, and where it would be at least predictably acceptable for the b to have a value of above zero and less than 1 with Si, O, H and D all present to provide a balanced stoichiometric formula.
Claim 15: it further would be suggested that z>c, since the H would be lowered by the replacement with D as discussed for claim 14 above.
Claim 16: it further would be understood that z=(c+d), x=a and y=b acceptably as the replacement is of H atoms, which would leave O and Si the same.
Claim 17: as to the Si-H and Si-OH groups, Miyata indicates that with Si-OH structures there are also Si-H structures (note 0066-0067), and this would be understood to at least predictably and acceptably also be the case with polycrystalline silicon as it also has Si-OH groups, that would thus also acceptably have at least some Si-H groups. The second layer would have Si-D groups, as H replaced with D, and at least some OH groups, acceptably if not all groups replaced. Also note the same process to give such replacement is present.
Claim 18: during the forming of the second material layer from the first material layer (that is during the soaking/irradiating), the first material layer would be irradiated with microwaves while the first material layer soaks in the liquid heavy water, since as noted for claim 14 above, microwaves would be applied to substrate/article (here including first material layer) during the soaking.
Claim 19: As to providing the irradiation by irradiating the silicon film with microwaves for a number of irradiation cycles, this would be suggested by ‘409, which describes intermittent microwave use, with a temperature sensor such that when heating temperature becomes too high after a first period of microwaving the heating is stopped, and then after a second period of being stopped, when the temperature becomes too low, the microwaves are started again (note page 3, translation). The exact number and timing of repeats/cycles of heating and stopping, as well, would be a matter of routine experimentation for the specific articles being treated and specific solutions, and such optimization would provide the cyclic irradiation according to a number of irradiation cycles (note "[W]here the general conditions of a claim are disclosed in the prior art, it is not inventive to discover the optimum or workable ranges by routine experimentation." In re Aller, 220 F.2d 454, 456, 105 USPQ 233, 235 (CCPA 1955)).
Terminal Disclaimer
The terminal disclaimer filed on October 27, 2026 disclaiming the terminal portion of any patent granted on this application which would extend beyond the expiration date of any patent granted on Application Number 18/301,347 has been reviewed and is accepted. The terminal disclaimer has been recorded.
Double Patenting
The provisional rejection of claims 1-2 on the ground of nonstatutory double patenting as being unpatentable over claims 1-20 of copending Application No. 18/301,347 (hereinafter ‘347) (reference application) is withdrawn due to the terminal disclaimer filed October 27, 2025 (note the Terminal Disclaimer section above).
The US PG Publication of ‘347 is US 2023/0349050.
Response to Arguments
Applicant's arguments filed October 27, 2025 have been fully considered.
Note the adjustment to the rejections due to the amendments to the claims, including the new reference to Nakagawa.
As to the 35 USC 103 rejections, it is argued that ‘403/Nenyei indicates the fragile nature of S-H and Si-D bonds, and that ‘403 also provides the immersion preferably at room temperature, and one would not be suggested to use microwave heating, since it would heat and also have optical/vibrational effects separate from heating, and would have no reason to believe that the hydrogen or deuterium passivation would survive this treatment, reinforced by ‘409/Ma being a cement treatment. It is argued that the present specification describes vibrational effect from the microwaves to give reaction. It is further argued that as to claim 14, the art would fail to provide y and b as greater than zero and less than 1, understanding that the ‘403 treatment would remove a native oxide layer, not give a layer with oxygen.
The Examiner has reviewed these arguments, however, the rejections above are maintained. Firstly, from reading ‘403 it is unclear where it is indicated that the bonds are particularly fragile. The reference to the bond being lost at 500+ degrees C would not teach against microwave heating at the much lower temperature range of up to 90 degrees C, as there is no indication that there would be an effect of losing the bond/hydrogen at that range. Similarly, the length of time of passivation does not indicate that microwave heating at temperatures described by ‘403 would have a bad effect. While ‘403 describes providing the soaking preferably at room temperature, it also clearly indicates that the temperature can be up to 90 degrees C (page 5). As discussed in MPEP 2123, “Disclosed examples and preferred embodiments do not constitute a teaching away from a broader disclosure or nonpreferred embodiments. In re Susi, 440 F.2d 442, 169 USPQ 423 (CCPA 1971). "A known or obvious composition does not become patentable simply because it has been described as somewhat inferior to some other product for the same use."”
As to a suggestion not to use microwaves, while they may have vibrational, etc. effects in the providing of heating, it is still a known way to provide heating to temperatures in the range of ‘403, and while ‘409 is not directed to heating specifically for the deuterium treatment, it still provides a known method of heating, where ‘403 does not provide any specific limitations of how heating provided. Applicant’s attorney argues that a POSITA would not believe the passivation would survive this treatment, etc., however, this is attorney arguments without a showing/factual evidence to rebut the use of’403 and ‘409. Note MPEP 2145(I), “Arguments presented by applicant cannot take the place of evidence in the record. See In re De Blauwe, 736 F.2d 699, 705, 222 USPQ 191, 196 (Fed. Cir. 1984); In re Schulze, 346 F.2d 600, 602, 145 USPQ 716, 718 (CCPA 1965); In re Geisler, 116 F.3d 1465, 43 USPQ2d 1362 (Fed. Cir. 1997) ("An assertion of what seems to follow from common experience is just attorney argument and not the kind of factual evidence that is required to rebut a prima facie case of obviousness.").”
Applicant’s attorney further notes the specification as apparently indicating that microwave heating gives desirable results of the Si-D bonding, and there is no indication as to what was previously understood, whether the results would be good or bad or different with other heating methods, for example, and thus there is no showing that one would not have looked to microwave heating as a known heating method for liquids.
As to claim 14, as to the y and b being real numbers greater than zero and less than 1, it is the Examiner’s position that this would be suggested by the references, where ‘009 indicates the common presence of Si-OH bonds on the Si surface. Firstly, the D2O treatment of ‘403 does not necessarily require HF or other acid to be present. Note page 5, lines 1-15, where acid not required to also be present, note page 6, line 30 to page 7, line 5, where acid not required to be present. It is not required for these to be a large amount of oxygen, just some. Therefore, secondly, even if HF present, any OH bonds that are present that also react with the D from the heavy water can also meet the claim requirements. Thirdly, the soaking with D2O would also provide the presence of oxygen during the soaking. Therefore, the rejections are maintained.
As to the provisional obviousness type double patenting rejection, this has been removed, noting the filing of the terminal disclaimer.
Conclusion
Applicant's amendment necessitated the new ground(s) of rejection presented in this Office action. Accordingly, THIS ACTION IS MADE FINAL. See MPEP § 706.07(a). 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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/KATHERINE A BAREFORD/Primary Examiner, Art Unit 1718