DETAILED ACTION
In the amendment filed on December 8, 2025, claims 1 --– 18 are pending. Claims 1, 8, 14, 17, 18 have been amended.
The text of those sections of Title 35, U.S. Code not included in this action can be found in a prior Office action.
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The rejections of the claims under 35 USC § 112 in the previous Office Action are withdrawn due to Applicant amendment.
Claim Rejections - 35 USC § 102
The rejections of the claims under 35 USC § 102 in the previous Office Action are withdrawn due to Applicant amendment.
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.
The rejections of the claims under 35 USC § 103 in the previous Office Action are withdrawn due to Applicant amendment.
Claim(s) 1, 3, 4, 6, 7, 8, 9, 10, 11, 12, 13 is/are rejected under 35 U.S.C. 103 as being unpatentable over Xue et al. WO 2021/146138 A1 (hereafter “Xue”) in view of Saha et al. US 2023/0071197A1 (hereinafter “Saha”).
Regarding claims 1, 3, 4, 6, 7, 8, 10, 11, 12, 13:
Xue is directed to inter alia a method of making a patterning structure’s underlayer, wherein the underlayer provides an increase in radiation absorptivity and/or patterning performance of patterning structure’s imaging layer (Abstract, [0005]). Xue discloses that the method of forming the underlayer comprises (claims 24, 26): providing a substrate in a processing chamber; introducing e.g. an iodine-containing precursor and/or a nitrogen-containing precursor; introducing a carbon-containing precursor (claim 25); and depositing by plasma enhanced chemical vapor deposition a hydronated carbon film on a surface of the substrate.
The deposition temperature may be between 0°C to 100°C ([0025]). The plasma power may be between 100 – 1000 W and pressure between 10 to 1000 mTorr [meeting claims 12, 13] ([0025], [0032]). Xue discloses that the result of utilizing an iodine precursor renders a carbon film doped with iodine [iodine-containing film] (claim 16). In a specific implementation, Xue discloses forming an underlayer using iodomethane ([0122]) and that iodine may be included in precursors in the form RI, such as iodine gas [I2] or hydrogen iodide [HI] ([0169]) to incorporate iodine into the film ([0180]).
Furthermore, Xue discloses that the amount of iodine present improves the generation of secondary electrons when the mask and its underlayer is exposed to radiation, which aids in patterning the overall mask ([0011], [0065]). Xue discloses that in particular embodiments, the resultant underlayer film includes a hydrogenated carbon doped with inter alia oxygen and nitrogen ([0011], [0024], [0039]). Xue further discloses that precursors for the nitrogen inclusion include nitrogen gas, ammonia, hydrazine, methylamine and ethylamine, acetonitrile, ect ([0135]). Xue also discloses that the precursors for oxygen inclusion include carbon monoxide, carbon dioxide, water oxygen, ozone and hydrogen peroxide ([0130]). Finally, alongside precursors, Xue discloses that inert gases such as argon, krypton, nitrogen and neon may be used within the process ([0046]). The precursors and process gases can be selected to provide desired film properties such as e.g. etch resistance ([0026], [0107], [0116], [0124]).
While Xue does not expressly teach an embodiment of the method uses a separate iodine-containing gas and does not expressly teach an embodiment of the method that uses nitrogen precursors, oxygen precursors or inert gases, it would have been obvious to one of ordinary skill in the art to have modified any of the express embodiments of Xue to deposit an iodine-containing film using inter alia the iodine-containing gas (e.g. iodine gas and hydrogen iodide) because Xue teaches that such precursors both increase the content of the doped iodine within the resultant film and can introduce sensitivity to radiation to the underlayer; and it would have been obvious to one of ordinary skill in the art before the effective filing date of the claimed invention to have modified an embodiment of Xue to use nitrogen precursors, oxygen precursors, and inert gases as co-reactants because Xue teaches that each coreactant can lead to desired film properties one of ordinary skill in the art would seek with a reasonable expectation of success.
Xue does not expressly teach that the iodine-containing precursor may be one of C6H5I, C6H4I2.
Saha is directed to methods of forming structures including a photoresist absorber layers/underlayers that have a relatively high extreme ultraviolet sensitivity (Abstract; [0011]). Saha discloses that iodine atom is known to enhance EUV sensitivity ([0011]). Saha discloses a method of depositing such an absorber layer by a chemical vapor deposition technique ([0030] – [0032], [0035 – [0036]) using as depicted in Fig. 1, including a step of providing precursors and reactants to form the absorber layer ([0035]). Saha discloses that that their iodine reactant can be inter alia iodobenzene [C6H5I], I2, or HI ([0052]).
Therefore, it would have been obvious to one of ordinary skill before the effective filing date of the claimed invention to have modified the method of Xue by substituting iodine gas or hydrogen iodide for any aryl iodides such as iodobenzene because, as taught by Saha, such gases are known to be suitable for the incorporation of iodine into thin films. The substitution of one known process gas for incorporating iodine into films for another yields predictable results to one of ordinary skill in the art.
Regarding claim 9:
Xue does not expressly teach that the iodine atomic concentration in the film ranges within the claimed values.
However, Xue does disclose that the level of doping from precursors affect the resultant film properties ([0026], [0107], [0124]) and that the presence of iodine in the underlayer affects the amount of secondary electrons generated upon exposure to extreme ultraviolet radiation (EUV) ([0005], [0011], [0071]). The main film that is doped with iodine may be 0-30% oxygen, 20 – 50% hydrogen and /or 30 – 70%C ([0072]), and the rate of dopant precursor (and thus available dopant to deposit into the film) may flow between 1 – 100 sccm ([0103]).
Therefore, it would have been obvious to one of ordinary skill in the art before the effective filing date to have modified the method of Xue to result in a film with an iodine atomic concentration in the claimed range as a matter of routine experimentation in order to optimize film properties. "[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).
Claim(s) 2 is/are rejected under 35 U.S.C. 103 as being unpatentable over Xue in view of Saha as applied to claims 1, 3, 4, 6, 7, 8, 9, 10, 11, 12, 13 above, and further in view of Foo et al. US 5120680 A (hereinafter “Foo”).
Regarding claim 2:
Xue discloses that a substrate bias can be applied during the deposition of the underlayer, particularly to improve the density of the underlayer formed compared to the underlayer without biasing ([0020], [0025], [0032], [0047], [0083], [0093], [0287] – [0288]; Fig. 10).
Xue does not expressly teach that the deposition of the iodine-containing film comprises a step of modifying substrate material or doping iodine into the substrate material.
In analogous arts, Foo is directed to a method of forming silicon dioxide layers onto substrates with a radio frequency plasma discharge (Abstract). Foo discloses an apparatus having a lower RF generator attached to lower electrode 20 upon which a substrate is placed (col 3 lines 10 – 60; Fig. 1). The lower RF generator induces a DC bias on the substrate during plasma processing that depends on the incident RF power provided (col 4 lines 24 – 55), which in turns affects the magnitude of bombardment from ions generated within an ignited plasma (col 5 lines 55 – 65, col 5 lines 3 – 31). Ion bombardment influences the amount of surface migration from deposition species into the substrate and the amount of erosion of any patterns that are present on the substrate due to sputtering effects [surface modification/implantation] (col 5 lines 4 – 21, col 5 lines 55 – 62, col 7 lines 5 – 30). Foo therefore discloses that bias should be controlled to allow for maximum deposition and densification (by elimination of soft spots) and uniform deposition while at the same time minimizing excessive surface damage (col 6 lines 15 – 37, col 6 lines 34 – 40).
Therefore, it would have been obvious to one of ordinary skill before the effective filing date of the claimed invention to have recognized that the iodine-containing deposition of Xue in view of Saha would entail an act of substrate material modification/implantation because of the use of bias or otherwise would have modified the method of Xue in view of Saha to have modified the substrate material in a way to maximize surface migration modifications but minimize substrate damage by controlling for an optimal substrate bias. The reason why is that Foo teaches that induced DC bias affects the uniformity and nature of film deposition, alongside that of Xue’s teaching concerning density; additionally Foo teaches that some level of doping/surface modification occurs due to ion bombardment from ions accelerated by an applied bias.
Claim(s) 14, 15 remain rejected under 35 U.S.C. 103 as being unpatentable over Mitchell et al. US 2011/0059617 (hereafter “Mitchell”) in view of Surla et al. US 2015/0371869 A1 (hereafter “‘869Surla”)
Regarding claims 14, 15:
Mitchell is directed to a method of etching high-aspect-ratio features in dielectric materials such as silicon oxide (Abstract). As a result of the etching process, an iodine-containing film of CxFyI is co-deposited (Fig. 6, 7; [0028] – [0029]). Furthermore, Mitchell describes their process as both a deposition process and an etching process ([0030]). Mitchell discloses a method of depositing the iodine containing film comprising: supplying a gas mixture of 1,3 hexafluorobutadiene, iodo-trifluoroethene [ICF3], argon and molecular oxygen [collectively a vapor] into a plasma reaction chamber ([0030]); generating a plasma from the gas mixture and exposing a substrate to the plasma of the gas mixture [step a); and depositing the iodine-containing film from the action of the plasma on the substrate [step b)] onto various substrates such as photoresist film, hard mask film, polysilicon layer and silicon oxide layer (Fig. 7). As shown in Fig. 6, on a substrate of SiO2 covered with photoresist, co-etching occurs. The process temperature may be between about 0 – 100°C ([0025], [0082]).
Mitchell does not expressly teach that the coreactant may be a nitrogen-containing molecule among those recited in present claim 14 (e.g. C4NF5).
‘869Surla is directed to methods of etching silicon-containing films (Abstract). Similar to Mitchell, ‘869Surla discloses that the process of plasma etching with fluorocarbons also deposits a polymer onto the sidewalls of produced trenches ([0004], [0164], [0174], [0192], [0203]). ‘869Surla further discloses a method comprising: introducing a vapor of a nitrogen containing etching compound into a reaction chamber containing a silicon-containing film on a substrate, wherein the nitrogen containing etching compound comprises an organofluorine compound containing a "C=N" or "C≡N" functional group; introducing an inert gas into the reaction chamber; and activating a plasma to produce an activated nitrogen containing etching compound capable of etching the silicon-containing film from the substrate ([0010]). Among the compounds that may be selected as the organofluorine compound, C3HF4N, C4F5N [i.e. C4NF5] or C5F5N may be selected ([0018], [0174], [0194] – [0195]; Fig. 8). ‘869Surla states that using chlorofluorocarbon compounds with a "C≡N" functional group improves the etch resistant polymer deposition benefits compared to pure fluorocarbon polymers, mirroring the teachings of Mitchell.
Therefore, it would have been obvious to one of ordinary skill in the art before the effective filing date of the claimed invention to have modified the method of Mitchell by including e.g. C3HF4N as an etching gas [co-reactant] and in turn deposit a polymer sidewall because ‘869Surla teaches that incorporating nitrile functionality improves the etch resistance of the resultant polymer sidewall.
Claim(s) 16 is/are rejected under 35 U.S.C. 103 as being unpatentable over Mitchell in view of ‘869Surla as applied to claims 14, 15 above, and further in view of Surla et al. US2017/0178923 A (hereafter “‘923Surla”).
Regarding claim 16:
While Mitchell discloses that the iodofluorocarbon may be C2F3I (i.e. iodotrifluoroethene), Mitchell does not expressly teach that the iodine-containing precursor may be CH3-I or C2H2F3I (i.e. iodotrifluroethylene).
‘923Surla is directed to methods for etching silicon containing films with iodine-containing gases activation of plasma and subsequent deposition of a polymer onto sidewalls created by directional etching (Abstract; [0039] – [0042]; Fig. 1B). ‘923Surla discloses that iodine-containing fluorocarbons may be used for etching/deposition [0010], including iodotrifluoroethene ([0018]) and iodotrifluroethane ([0029]).
Therefore, it would have been obvious to one of ordinary skill in the art before the effective filing date of the claimed invention to have modified the method of Mitchell by substituting the iodotrifluoroethene for iodotrifluroethane because ‘869Surla teaches that both gases are known as suitable etching/deposition gases and one of ordinary skill in the art would have been able to substitute the gases with a reasonable expectation of success. The substitution of one known etching/deposition gas for another yields predictable results to one of ordinary skill in the art.
Claim(s) 17 is/are rejected under 35 U.S.C. 103 as being unpatentable over Mitchell in view of ‘869Surla and ‘923Surla.
Regarding claim 17:
The teachings of Mitchell as applied to the rejection of claims 14 – 16 under 35 USC 102 above also apply to the present rejection, mutatis mutandis.
Mitchell does not expressly teach that the film is nitrogen-containing, and exposing the film to a nitrogen-containing molecule as recited. Mitchel also does not expressly teach that the iodine precursor is one of CH3I or C2H2F3I.
The teachings of ‘869Surla as applied to the rejection of claims 14 – 16 under 35 USC 103 above also apply to the present rejection, mutatis mutandis.
The teachings of ‘923Surla as applied to the rejection of claims 14 – 16 under 35 USC 103 above also apply to the present rejection, mutatis mutandis.
It would have been obvious to one of ordinary skill in the art before the effective filing date of the claimed invention to have modified the method of Mitchell by including e.g. C3HF4N as an etching gas [coreactant] and in turn deposit a polymer sidewall because ‘869Surla teaches that incorporating nitrile functionality improves the etch resistance of the resultant polymer sidewall.
It would have been obvious to one of ordinary skill in the art before the effective filing date of the claimed invention to have modified the method of Mitchell by substituting the iodotrifluoroethene for iodotrifluroethane because ‘869Surla teaches that both gases are known as suitable etching/deposition gases and one of ordinary skill in the art would have been able to substitute the gases with a reasonable expectation of success. The substitution of one known etching/deposition gas for another yields predictable results to one of ordinary skill in the art.
Double Patenting
The rejections of the claims under non-statutory Double Patenting in the previous Office Action are withdrawn. Applicant timely filed a Terminal Disclaimer that was accepted on December 19, 2025.
Allowable Subject Matter
Claim 5 is objected to as being dependent upon a rejected base claim, but would be allowable if rewritten in independent form including all of the limitations of the base claim and any intervening claims.
Claims 18 is allowed.
The following is a statement of reasons for the indication of allowable subject matter:
Regarding claim 5:
The prior art of record does not teach and does not reasonably suggest the recited method for depositing an iodine-containing film as recited in claim 5, and in particular does not expressly teach or reasonably suggest the combination of an iodine-containing precursor selected from the group consisting of C6H5I and C6H4I2 in combination with the listed species of nitrogen-containing molecular species in the context of the claims.
Regarding claim 18:
The prior art of record does not teach and does not reasonably suggest the recited method for depositing an iodine-containing film as recited in claim 5, and in particular does not expressly teach or reasonably suggest the combination of an iodine-containing precursor selected from the group consisting of C3I and C2H2F3I in combination with the listed species of nitrogen-containing molecular species in the context of the claims.
Response to Arguments
Applicant’s arguments, filed December 8, 2025, with respect to the rejection(s) of claim(s) 1, 3,4, 6 – 13 under 35 USC §103 over Xue in view of Oberbeck et al. US 20080283973 A1 have been fully considered and are persuasive. Therefore, the rejection has been withdrawn. However, upon further consideration, a new ground(s) of rejection is made in view of Saha.
Applicant’s arguments with respect to the claims have been considered but are moot because the arguments do not apply to any of the references being used in the current rejection.
Applicant's arguments filed December 8, 2025 have been fully considered but they are not persuasive.
Applicant’s principal arguments are:
a.) Mitchell, ‘869Surla, and ‘923Surla fails to disclose or teach "the nitrogen-containing molecule is selected from the group consisting of C5HF4N, C5F5N, C3F3N3, C4N2F4, C6F9N3, C5H2F3N, C5H2F3N, C5H2F3N, C5F3H2N, C3HF2N3, C3H2FN3, C5F7N3, C4F5N3, C5H4NI, C3F4N2, C4NF5, C5H4FN, C5F5N, NH3, N2H4, C2H8N2, CH5N3.
In response to the applicant's arguments, please consider the following comments.
a.) Contrary to Applicant’s submission, ‘869Surla teaches that the nitrogen-containing molecule may be C4F5N [i.e. C4NF5] or C5F5N may be selected ([0174], [0194] – [0195]; Fig. 8).
Conclusion
The prior art made of record and not relied upon is considered pertinent to applicant's disclosure: Murakami US 2023/0377953 A1 (hereinafter “Murakami”), particularly paragraphs [0033] – [0036] that indicate that hydrazines and ammonia are known etching gases alongside iodomethane, but are suitable for etching different materials.
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 extension fee 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 date of this final action.
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/JOSE I HERNANDEZ-KENNEY/
Primary Examiner
Art Unit 1717