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 response of the applicant has been read and given careful consideration. Claims 32-36 stand as withdrawn.. Rejections of the previous office action not repeated below are withdrawn in view of the arguments and amendment of the applicant. Responses to the arguments of the applicant are presented after the first rejection they are directed to.
Applicants have submitted very long lists of citations in their Information Disclosures for this application. The examiner notes the following passage from MPEP 2004:
"It is desirable to avoid the submission of long lists of documents if it can be avoided. Eliminate clearly irrelevant and marginally pertinent cumulative information. If a long list is submitted, highlight those documents which have been specifically brought to applicant’s attention and/or are known to be of most significance. See Penn Yan Boats, Inc. v. Sea Lark Boats, Inc., 359 F. Supp. 948, 175 USPQ 260 (S.D. Fla. 1972), aff ’d, 479 F.2d 1338, 178 USPQ 577 (5th Cir. 1973), cert. denied, 414 U.S. 874 (1974). But cf.
Molins PLC v. Textron Inc., 48 F.3d 1172, 33 USPQ2d 1823 (Fed. Cir. 1995)."
The following is a quotation of the first paragraph of 35 U.S.C. 112(a):
(a) IN GENERAL.—The specification shall contain a written description of the invention, and of the manner and process of making and using it, in such full, clear, concise, and exact terms as to enable any person skilled in the art to which it pertains, or with which it is most nearly connected, to make and use the same, and shall set forth the best mode contemplated by the inventor or joint inventor of carrying out the invention.
The following is a quotation of the first paragraph of pre-AIA 35 U.S.C. 112:
The specification shall contain a written description of the invention, and of the manner and process of making and using it, in such full, clear, concise, and exact terms as to enable any person skilled in the art to which it pertains, or with which it is most nearly connected, to make and use the same, and shall set forth the best mode contemplated by the inventor of carrying out his invention.
Claims 1-30 are rejected under 35 U.S.C. 112(a) or 35 U.S.C. 112 (pre-AIA ), first paragraph, as failing to comply with the written description requirement. The claim(s) contains subject matter which was not described in the specification in such a way as to reasonably convey to one skilled in the relevant art that the inventor or a joint inventor, or for applications subject to pre-AIA 35 U.S.C. 112, the inventor(s), at the time the application was filed, had possession of the claimed invention.
Claim 1 recites the dry development of the patterned film including a metal oxide, polymerized organometallic material and organometallic materials in the presence of the gaseous metal chelator. The specification describes the provision of the metal chelator as a wet process in combination with a solvent (see prepub at [0012,0013,0022,2203,0108,0181,0093,0101) or as a polymeric component [0019,0122,0031,0094], but does not describe the provision of a gas phase/gaseous metal chelator. Please amend the claim to remove the language requiring a gas phase/gaseous metal chelator. The specification also does not support a dry development including a gas phase/gaseous metal chelator.
The applicant argues that the text at [0107,0108,0198] support a gas-phase/gaseous metal chelating agent.
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The applicant seeks to incorporate “essential material” into the claims from the provisional application 63/199129. This is not permitted as essential subject matter may only be incorporated by reference to a US patent or US patent application publication, which patent or patent application publication does not itself incorporate such essential material by reference (MPEP 608.01(p)(I), 608.01(p)(I)(A)(2), 37 CFR 1.57(d) ). While the provisional application referred to by the applicant is public once referred to by a publication, it is not itself “published”. It may be that the applicant can correct this by adding a reference to the corresponding US patent or US published application (without removing reference to the provisional application) or may need amend the specification by inserting the relevant language relied upon by the applicant (608.01(p)(I)(A)(2).
The examiner notes that this subject matter is accorded the fling date of the WO 2022016126 (07/16/2021), rather than the filing date of the provisional application 62/705855 as the provisional application does not reference the later filed 63/199,129.
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 the appropriate paragraphs of 35 U.S.C. 102 that form the basis for the rejections under this section made in this Office action:
A person shall be entitled to a patent unless –
(a)(1) the claimed invention was patented, described in a printed publication, or in public use, on sale, or otherwise available to the public before the effective filing date of the claimed invention.
(a)(2) the claimed invention was described in a patent issued under section 151, or in an application for patent published or deemed published under section 122(b), in which the patent or application, as the case may be, names another inventor and was effectively filed before the effective filing date of the claimed invention.
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 1-4,7,17-22,24 and 27-30 are rejected under 35 U.S.C. 102(a)(1) or 35 U.S.C. 102(a)(1) as being fully anticipated by Wu et al. WO 2019217749.
Wu et al. WO 2019217749 (cited by applicant) in example 2 teaches silicon substrate having a carbon underlayer is then coated using a chemical vapor deposition (CVD) process with a isopropyl tris(dimethylamino)Tin and water to form an organometallic resist which is polymerized organometallic resist. This is exposed using EUV, post exposure baked at 180 degrees C and wet developed with 2-heptanone. The patterned resist and the underlying carbon layer is then etched using as hydrogen/oxygen plasma [0045-0047]. The post exposure bake can be 150 degrees C as in example 1 [0041-0044].
The position of the examiner is that the wet development of the resist uses heptanone which is a chelating agent and that the dry etch which follows is the recited dry development step. The examiner also holds that any remaining dimethylamino or coating solvents are also chelating agents. These will be present in the interfacial region (sidewalls) when the resist and the carbon underlayer are exposed to the hydrogen/oxygen etch. The etch will also etch any organic components in the resist and is held to be a dry development within the scope of coverage sought.
The applicant argues that the none of the references teach dry development. The references used in the current rejections describe the treatment with a liquid developer, followed by a dry etch. The dry etch is considered to be a dry development which follows the wet development in the manner described in the prepub of the instant specification at [0217] as a combined wet and dry embodiment . The applicant noted, but did not comment on the examiner’s position that the ligands and solvents are chelating agents..
The applicant argues that the chelating agents are multidentate, not monodentate. The examiner disagrees, noting that the specification describes the metal chelator as “any ligand that can bind to metal centers (e.g., transition metal centers). Non-limiting ligands include those having hydroxyl, carboxyl, amido, amino, and/or oxo moieties.” The recitation of ketones, diketones, alcohols, carboxylic acids, diacids, triacids, hydroxycarboxylic acids, etc.), amides, hydroxyamides, hydroxamic acids, lactones clearly embraces monodentate ligands among the “any ligand” discussed at [0111] of the prepub of the instant application. This description is far more relevant to the meaning of the term in the instant specification than inorganic chemistry text relied upon in the arguments. The examiner points out that 2-heptanone is a ketone and the tetramethyl ammonium cation is an amine and is paired with a hydroxy group. Wu et al. WO 2019217749 rinses with 2-heptanone after the development.
In the response of 8/12/2026, on page 11 of the response, the applicant argues that the compounds bearing hydroxyl, carboxyl, amido, amino and/or oxo moieties are not necessarily chelating agents. The applicant argues that one of ordinary skill in the art would read chelating agent as multidentate. The examiner disagrees, pointing out that the instant specification specifically describes formic acid
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as a metal chelators at [0014] or the prepub and this is clearly a monodentate. So not only would one skilled in the art recognize there are monodentate chelation agents/chelators, the instant specification expressly includes them exemplifying formic acid and listing hydroxyalkyl, hydroxyaryl, carboxylic acids [0014,0031,0114]. The current claims do not expressly or implicitly require the chelators be multidentate or polydentate and claim 9 recites formic acid, which is clearly monodentate. This teachings overlaps with the teachings of organic acids as developers at [0219,0220]. This arguments is not persuasive.
In the response of 8/12/2026, the applicant argues that the heptanone and dimethylamine are inherently not considered a chelating agent, but is unwilling to actually add definitive language to the claims to require the chelating agent to be multidentate. The examiner notes that these are present during the dry etch as reaction products generated during the etch process, although they are not added as etchants themselves.
In the response of 8/12/2026, the applicant argues that the dry etching/descumming of Wu et al. WO 2019217749 is not a development. The examiner maintains the position that the development can be a wet development in combination with a dry development. The examiner points to the instant specification at [0217] which states that “In some embodiments, dry and wet operations can be combined to provide a dry/wet process. For any of the process herein (e.g., for lithographic processes, deposition processes, EUV exposure processes, development processes, pre-treatment processes, post-application processes, etc.), various specific operation can include wet, dry, or wet and dry embodiments. For instance, wet deposition can be combined with wet development; or dry deposition can be combined with wet development. Any of these, in turn, can be combined with wet or dry pre- and post-application processes, as described herein.” Based upon this the examiner holds that the dry etch is reasonably considered part of the development step. While the etching is not purely a development step, the resist pattern is more fully defined by the etching process.
Claims 1-4,7,8,11,15-19 and 22-30 are rejected under 35 U.S.C. 102(a)(1) or 35 U.S.C. 102(a)(1) as being fully anticipated by Nakagawa et al. JP 2018017780.
Nakagawa et al. JP 2018017780 (machine translation attached, originally cited by applicant) teaches Dibutyldiacetoxytin in synthesis example 2. [0154]. Synthesis example 3 uses indium acetate [0155]. Synthesis examples 4 combines tetraisopropoxy germanium, oxalic acid and 2-propanol. [0156]. Synthesis example 6 combines tributoxy titanium stearylate, PGMEA and maleic acid [0156]. Synthesis example 7 combines zirconium tetrabutoxide with tetrahydrofuran and methacrylic acid [0159]. Synthesis example 8 combines hafnium isopropoxide and trans-2,3-dimethacrylic acid [0160]. Synthesis example 11 combines benzoic acid, zirconium isopropoxide and tin isopropoxide[0163]. In examples 1-10 and comparative examples 1-8, these were combined as in table 2 and filtered to form radiation sensitive compositions [0166-0167]. These were spin coated onto a silicon wafer previously coated with a resist underlayer (NFC HM8005), dried at 100 degrees C, exposed using vacuum UV (considered EUV, see below), post baked at 150 degrees C and developed in 2-heptanone for 1 minute and then the substrate and resist pattern are etched using a dry etching [0171-0177]. In this step, the film formed by the coating step is exposed. In some cases, this exposure is performed by irradiating radiation through a mask having a predetermined pattern through an immersion medium such as water. Examples of the radiation include visible rays, ultraviolet rays, far ultraviolet rays, vacuum ultraviolet rays (extreme ultraviolet rays (EUV); wavelength 13.5 nm), electromagnetic waves such as X-rays and γ rays, and charged particle beams such as electron rays and α rays. Can be mentioned. Among these, radiation that emits more secondary electrons from metal atoms contained in the [A] metal-containing component and the like by exposure is preferable, and EUV and electron beams are more preferable [0139]
The position of the examiner is that the wet development of the resist uses heptanone which is a chelating agent. The examiner also holds that any remaining ligands or coating solvents are also chelating agents. These will be present in the interfacial region (sidewalls) when the resist and the resist under layer are exposed to the dry etch. The etch will also etch the resist and is held to be a dry development within the scope of coverage sought..
Processes using compositions containing acids (maleic, methacrylic , benzoic acid) meet the limitations claims 8,11 and 22. Processes using compositions containing trans-2,3,dimethacrylic meet claims 8,11,15,16 and 22
In response to the arguments of 02/13/2026, Nakagawa et al. JP 2018017780 does not describe a rinsing step and oxalic acid, maleic acid, methacrylic acid, trans-2,3-dimethacrylic acid, benzoic acid and 2-heptanone are chelating agents within the meaning of the instant specification.
In addition to the basis above, the examiner points out that the carboxylic acid methacrylic acid include both a ketone and a hydroxy moiety and may be considered bidentate under the applicant’s reading. The examiner notes that the methacrylic acid is not added as an etchant, but will be in the gas phase (free or metallized) during the etch process.
Claims 1-4,7,8,10-14,17-19 and 22-30 are rejected under 35 U.S.C. 103 as being unpatentable over Hatakeyama 20120208125, in view of Thackeray et al. 5108875 or Nakagawa et al. JP 2018017780.
Hatakeyama 20120208125 teaches organic resists including metal complexes listed in table 1 or 2.
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These are coated, dried and exposed using e-beam, post baked and developed in 2.38% aqueous TMAH [0074-0079] Thereafter the resist film is developed with a developer in the form of an aqueous base solution. Suitable developers are 0.1 to 30 wt %, preferably 0.1 to 5 wt %, and more preferably 2 to 3 wt % aqueous solutions of tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide (TEAH), tetrapropylammonium hydroxide (TPAH), tetrabutylammonium hydroxide (TBAH), choline hydroxide, sodium hydroxide (NaOH), and potassium hydroxide (KOH). Other suitable developers are 0.1 to 30 wt % aqueous solutions of bases which include ammonia, methylamine, ethylamine, propylamine, n-butylamine, dimethylamine, diethylamine, dipropylamine, di-n-butylamine, trimethylamine, triethylamine, tri-n-propylamine, tri-n-butylamine, hydrazine, hydrazine hydrate, methylhydrazine, dimethylhydrazine, trimethylhydrazine, tetramethylhydrazine, ethylhydrazine, diethylhydrazine, propylhydrazine, butylhydrazine, phenylhydrazine, benzylhydrazine, phenethylhydrazine, cyclopropylhydrazine, cyclopentylhydrazine, cyclohexylhydrazine, ethylenediamine, 1,2-diaminopropane, 1,3-diaminopropane, 1,2-diamino-2-methylpropane, N-methylethylenediamine, N-ethylethylenediamine, N-isopropylethylenediamine, N-hexylethylenediamine, N-cyclohexylethylenediamine, N-octylethylenediamine, N-decylethylenediamine, N-dodecylethylenediamine, N,N-dimethylethylenediamine, N,N'-dimethylethylenediamine, N,N-diethylethylenediamine, N,N'-diethylethylenediamine, N,N'-diisopropylethylenediamine, N,N,N'-trimethylethylenediamine, diethylenetriamine, N-isopropyldiethylenetriamine, N-(2-aminoethyl)-1,3-propanediamine, triethylenetetramine, N,N'-bis(3-aminopropyl)ethylenediamine, N,N'-bis(2-eminoethyl)-1,3-propanediamine, tris(2-aminoethyl)amine, tetraethylenepentamine, pentaethylenehexamine, 2-(2-aminoethylamino)ethanol, N,N'-bis(hydroxyethyl)ethylenediamine, N-(hydroxyethyl)diethylenetriamine, N-(hydroxyethyl)triethylenetetramine, piperazine, 1-(2-aminoethyl)piperazine, 4-(2-aminoethyl)morpholine, polyethyleneimine, 1,3-diaminopropane, 1,4-diaminobutane, 1,3-diaminopentane, 1,5-diaminopentane, 2,2-dimethyl-1,3-propanediamine, hexamethylenediamine, 2-methyl-1,5-diaminopropane, 1,7-diaminoheptane, 1,8-diaminooctane, 2,2,4-trimethyl-1,6-hexanediamine, 2,4,4-trimethyl-1,6-hexanediamine, 1,9-diaminononane, 1,10-diaminodecane, 1,12-diaminododecane, N-methyl-1,3-propanediamine, N-ethyl-1,3-propanediamine, N-isopropyl-1,3-propanediamine, N,N-dimethyl-1,3-propanediamine, N,N'-dimethyl-1,3-propanediamine, N,N'-diethyl-1,3-propanediamine, N,N'-diisopropyl-1,3-propanediamine, N,N,N'-trimethyl-1,3-propanediamine, 2-butyl-2-ethyl-1,5-pentanediamine, N,N'-dimethyl-1,6-hexanediamine, 3,3'-diamino-N-methyldipropylamine, N-(3-aminopropyl)-1,3-propanediamine, spermidine, bis(hexamethylene)triamine, N,N',N''-trimethylbis(hexamethylene)triamine, 4-aminomethyl-1,8-octanediamine, N,N'-bis(3-aminopropyl)-1,3-propanediamine, spermine, 4,4'-methylenebis(cyclohexylamine), 1,2-diaminocyclohexane, 1,4-diaminocyclohexane, 1,3-cyclohexanebis(methylamine), 1,4-cyclohexanebis(methylamine), 1,2-bis(aminoethoxy)ethane, 4,9-dioxa-1,12-dodecanediamine, 4,7,10-trioxa-1,13-tridecanediamine, 1,3-diaminohydroxypropane, 4,4'-methylenedipiperidine, 4-(aminomethyl)piperidine, homopiperazine, 3-aminopyrrolidine, 4-aminopiperidine, 3-(4-aminobutyl)piperidine, polyallylamine, 1,8-diazabicyclo[5.4.0]-7-undecene (DBU), 1,5-diazabicyclo[4.3.0]-5-nonene (DBN), 1,4-diazabicyclo[2.2.2]octane (DABCO), 1,4,7-trimethyl-1,4,7-triazacyclononane, 1,5,9-trimethyl-1,5,9-triazacyclododecane, 1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane, and 4,4'-trimethylenebis(1-methylpiperidine). The development may be carried out usually for 3 seconds to 3 minutes, preferably 5 seconds to 2 minutes by conventional techniques such as dip, puddle or spray techniques. The resist film in the exposed area is not dissolved in the developer whereas the resist film in the unexposed area is dissolved. In this way, the desired negative pattern is formed on the substrate. Following development, the resist pattern is rinsed with deionized water and dried by spin drying [0063]. Resist composition comprises a metal complex of a β -diketone, where the metal is magnesium, chromium, manganese, iron, cobalt, nickel, copper, zinc, silver, cadmium, indium, tin, antimony, cesium, zirconium, or hafnium [0020].
Thackeray et al. 5108875 teaches a resist which includes an acid hydrolysable organometallic material and a photoacid generator which removes the organometallic material form the polymer or prevents it from reacting with the polymer. (2/39-57). The acid labile metals are disclosed at (3/42-4/11) and include Si, Sn, Ti, P, Ge and Zr compounds. After exposure the resist is partially wet developed to remove excess metal particles and then subjected to a dry development. This results in the clean etched resist patterns of the examples (5/19-6/5)
Hatakeyama 20120208125 does not teach the process where the resist is developed or otherwise exposed to a dry etch process.
It would have been obvious to one skilled in the art to extend the processes of Hatakeyama 20120208125 by exposing the patterned resist to a dry etch process either to clean up the wet developed pattern as in Thackeray et al. 5108875 or to pattern an underlying layer/substrate as in Nakagawa et al. JP 2018017780 with a reasonable expectation of forming a useful etched pattern. In either of this modification., the sidewalls of the resists which include solvents, developer residues and/or ligands will be etched.
In addition to the basis above, it would have been obvious to one skilled in the art to modify the processes rendered obvious by the combination of Hatakeyama 20120208125 with Thackeray et al. 5108875 or Nakagawa et al. JP 2018017780 by using other developers, such as diamines, triamines or tetraamines disclosed at [0063] and/or resists using tin or cesium as metal centers with a reasonable expectation of forming a useful pattern based upon the equivalence disclosed at [0020].
In response to the arguments of 02/13/2026, the claims are open to TMAH used in the examples of Hatakeyama 20120208125 being chelating agents, noting that this compound includes both hydroxy and amine moieties. Additionally, the use of the diamines, triamines, tetraamines disclosed at [0063] as multidentate ligands in place of the TMAH is considered obvious. The applicant argues that Thackery 5108875 is used to remove two compositions (the bulk resist and the silylated top portion of the resist). The examiner points out that the dry etch process is part of a partial development and describes the overetch of the resist and is described as etching the exposed areas cleanly. The applicant also argues that the resist compositions are different. The examiner points out that resists are used to mask etching or deposition processes in lithographic processing, so the use of etch conditions after the development is not unusual and has a clearly understood effect. Nakagawa et al. JP 2018017780 as well as the disclosure of the instant application supports this position. The rejection stands.
Claim 1-4,7,17-19 and 22-30 are rejected under 35 U.S.C. 103 as being unpatentable over Namgung et al. 20200041901.
Namgung et al. 20200041901 synthesizes a tin resist at [0125-0127]. This is coated on a silicon wafer, dried, exposed to EUV, post baked at 150 degrees C and developed in 2-heptanone [0137-0140]. A semiconductor resist composition according to an embodiment includes an organometallic compound having a structural unit represented by Chemical Formula 1 and a solvent:
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M may be selected from indium (In), tin (Sn), antimony (Sb), tellurium (Te), thallium (Tl), lead (Pb), bismuth (Bi), and polonium (Po), Ar may be a substituted or unsubstituted C6 to C30 aromatic ring group, a substituted or unsubstituted C4 to C30 heteroaromatic ring group, or a combination thereof, R may be selected from hydrogen, deuterium, a halogen, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C6 to C30 aryl group, —N(R.sup.a)(R.sup.b), and —O(R.sup.c), R.sup.a to R.sup.c may each independently be selected from hydrogen, deuterium, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, and a substituted or unsubstituted C6 to C30 aryl group, adjacent R's may be fused to form a ring, Y may be selected from hydrogen, deuterium, a halogen, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, and a substituted or unsubstituted C6 to C30 aryl group, and “*” is a linking point [0009-0017]. As described above, a developing solution used in a method of forming patterns according to an embodiment may be an organic solvent. Non-limiting examples of the organic solvent used in the method of forming patterns according to an embodiment may include for example ketones (such as cyclohexanone, methylethylketone, acetone, 2-heptanone, and/or the like), alcohols (such as 4-methyl-2-propanol, 1-butanol, isopropanol, 1-propanol, methanol, and/or the like), esters (such as propylene glycol monomethyl ester acetate, ethyl acetate, ethyl lactate, n-butyl acetate, butyrolactone, and/or the like), aromatic compounds (such as benzene, xylene, toluene, and/or the like), and combinations thereof [0117]. The etching of the thin layer 102 to form the thin layer pattern 114 may be, for example, dry etching using an etching gas and the etching gas may be, for example, CHF.sub.3, CF.sub.4, Cl.sub.2, BCl.sub.3 or a mixed gas thereof. [0122].
Namgung et al. 20200041901 does not teach the process where the resist is developed or otherwise exposed to a dry etch process.
It would have been obvious to one skilled in the art to extend the processes exemplified or rendered obvious by Namgung et al. 20200041901 by exposing the patterned resist to a dry etch process to pattern an underlying layer/substrate as taught at [0122]. Further it would have been obvious to one skilled in the art to modify the examples of Namgung et al. 20200041901 by using other metals centers, in place of the tin, such as indium (In), tin (Sn), antimony (Sb), tellurium (Te) or bismuth (Bi) with a reasonable expectation of forming a useful resist pattern based upon the equivalence established at [0009-0017]. The processes rendered obvious include development with other organic solvents such as propylene glycol monomethyl ester acetate.
Heptanone is considered a chelating agent.
Claim 1-4,7-14,17-19 and 22-30 are rejected under 35 U.S.C. 103 as being unpatentable over Jiang et al. 20200326627, in view of Thackeray et al. 5108875 or Nakagawa et al. JP 2018017780.
Jiang et al. 20200326627 in example 1 coats a tin based resist onto a wafer, dries the coating, exposes the resist to patterned EUV, post bakes and develops in the solvents of table 1
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[0070-0073].
Example 3 uses combinations of 2-heptanone and formic acid as the developer [0080-0089]. Example 4 uses a mixture of 2-heptanone and 2-ethylhexanoic acid [0090-0096]. Examples 5-7 and 11 uses a combination of either 2-heptanone or PGMEA with acetic or formic acid [0097-0107,0129-0131]. Examples 8 and 10 use mixtures of 2-heptanone and 1,6-hexanediol [0108-0118,0122-128]. Example 9 uses a mixture of 2-heptanone and water [0119-0121]. Example 12 uses a mixture of n-propanol and PGME (both alcohols) [0132-0135]. In general, selection of appropriate developer solvent compositions can be influenced by solubility parameters with respect to the coating material, both irradiated and non-irradiated, as well as developer volatility, flammability, toxicity, viscosity, and potential chemical interactions with other process material. In particular, suitable base solvents for the developer include, for example, aromatic compounds (e.g., benzene, xylenes, toluene), esters (e.g., propylene glycol monomethyl ether acetate, ethyl acetate, ethyl lactate (hydroxycarboxylic acid) , n-butyl acetate, butyrolactone), ketones (e.g., methyl ethyl ketone, acetone, 2-butanone, cyclohexanone, 2-heptanone, 2-octanone), ethers (e.g., tetrahydrofuran, dioxane, anisole), 4-methyl-2-pentanol (and other weakly polar alcohols), blends thereof, and the like. In general, the base solvents have a sum of Hansen solubility parameter δH+δP of no more than about 16.0 (J/cm.sup.3).sup.1/2. Also, the suitable solvents are generally identified in the chemical genera identified above with the caveat that all members of these groups may have the identified solubility properties, especially if they include a plurality of functional groups. In some contexts, the solvent blend can conveniently be characterized with the chemical species and their functional groups without reference to the solubility parameters. For embodiments with a blend of solvents, the developer generally comprises at least about 55 volume percent base solvent, in further embodiments from about 60 vol % to about 99.75 vol %, in additional embodiments from about 65 vol % to about 99.5 vol %, in additional embodiments from about 70 vol % to about 99.25 vol %, and in other embodiments form about 75 vol % to about 99 vol % base solvent, which can involve one or more solvent compounds with the selected solubility parameters. A person of ordinary skill in the art will recognize that additional ranges of base solvent concentrations within the explicit ranges above are contemplated and are within the present disclosure. Volume percent values are calculated based on the solvent volumes prior to blending. Volume percent values can be converted to weight percent values according to the densities, if desired. As described herein, one or more highly polar additional solvent, referred to as a polar solvent, can be added to the solvent blend to form improved developers. In some embodiments, the developer can have from 0.25 vol % to about 45 vol % polar solvent, in further embodiments from about 0.4 vol % to about 30 vol %, in additional embodiments from about 0.5 vol % to about 25 vol %, and in other embodiments form about 0.75 vol % to about 22 vol % polar solvent. In some embodiments, the polar solvent can have a sum of Hansen solubility parameter δH+δP of at least about 16.0 (J/cm.sup.3).sup.1/2. Suitable polar solvents include, for example, water, acetone, polar monohydroxyl alcohols (such as methanol, ethanol, propanol, isobutanol, pentanol, and mixtures thereof), polyhydroxyl compounds (such as ethylene glycol, propylene glycol, glycerol), pyrrolidones (such as 2-pyrrolidone, 1-ethyl-2-pyrrolidone, N-methyl-2-pyrrolidone), glycol ethers (such as ethylene glycol monomethyl ether), carboxylic acids (such as formic acid, acetic acid oxalic acid, 2-ethylhexanoic acid), diols (e.g., 1,2-hexanediol, 1,2-propanediol, 1,3-propanediol), and mixtures thereof. A person of ordinary skill in the art will recognize that additional ranges of polar solvent concentrations within the explicit ranges above are contemplated and are within the present disclosure. Water may be present in the initial solvents, and this inherent water should be taken into account in the evaluation of water content. For convenience to distinguish developers with a potentially significant contribution from water, developers can be categorized as having at least 0.1 wt % (1000ppm) or less than 0.1 wt % (1000 ppm) water, which herein can for convenience be referred to, respectively, as having water or as being water free or effectively water free. For water, a weight percent can be converted to a volume percent according to the densities to allow the calculation of a volume percent water consistent with the general discussion herein. Unless indicated otherwise, herein ppm represent parts per million by mass. In some embodiments, water is used as an additive alone in a base solvent in small quantities. Thus, in these embodiments, the developer has at least about 2000 ppm water, in further embodiments from about 2500 ppm to about 10 wt %, in some embodiments from about 3500 ppm to about 5 wt %, and in other embodiments from about 4000 ppm to about 3 wt % water. A person of ordinary skill in the art will recognize that additional composition ranges within the explicit ranges above are contemplated and are within the present disclosure [0051-0054]
Jiang et al. 20200326627 does not exemplify the process where the resist is developed or otherwise exposed to a dry etch process.
It would have been obvious to one skilled in the art to extend the processes of Jiang et al. 20200326627 by exposing the patterned resist to a dry etch process either to clean up the wet developed pattern as in Thackeray et al. 5108875 or to pattern an underlying layer/substrate as in Nakagawa et al. JP 2018017780. With a reasonable expectation of forming a useful etched pattern. In either of this modification., the sidewalls of the resists which include solvents, developer residues and/or ligands will be etched.
Further, it would have been obvious to one skilled in the art to modify the processes rendered obvious by the combination of Jiang et al. 20200326627 with Thackeray et al. 5108875 or Nakagawa et al. JP 2018017780 by using other known/common carboxylic acids, such as salicylic acid, citric acid or ascorbic acid, polyhydroxy compounds and/or using multiple chelating agents/solvents such as dibutyloxalate with a reasonable expectation of forming a useful resist pattern based upon the broad disclosure of carboxylic acids and the equivalence of these in the developer.
In response to the arguments of 2/13/2026, the organic solvent developers are considered chelating agents within the meaning of the instant specification.
Claim 1-4,7,17-19 and 22-30 are rejected under 35 U.S.C. 103 as being unpatentable over Meyers WO 2017066319, in view of Thackeray et al. 5108875 or Nakagawa et al. JP 2018017780.
Meyers WO 2017066319 in example 1 forms a tin resist composition based upon tert-butyl tris(diethylamido)tin, (tBuSn(NEt.sub.2).sub.3) (page 34-35). In example 2, this is coated on a wafer, dried, exposed using EUV, post baked and developed in 2-heptanone (pages 35-36). In addition to the primary developer composition, the developer can comprise additional components to facilitate the development process. Suitable additives include, for example, dissolved salts with cations selected from the group consisting of ammonium, d-block metal cations (hafnium, zirconium, lanthanum, or the like), f-block metal cations (cerium, lutetium or the like), p-block metal cations (aluminum, tin, or the like), alkali metals (lithium, sodium, potassium or the like), and combinations thereof, and with anions selected from the group consisting of fluoride, chloride, bromide, iodide, nitrate, sulfate, phosphate, silicate, borate, peroxide, butoxide, formate, oxalate, ethylenediamine-tetraacetic acid (EDTA), tungstate, molybdate, or the like and combinations thereof. Other potentially useful additives include, for example, molecular chelating agents, such as polyamines, alcohol amines, amino acids, carboxylic acids, or combinations thereof. If the optional additives are present, the developer can comprise no more than about 10 weight percent additive and in further embodiments no more than about 5 weight percent additive. A person of ordinary skill in the art will recognize that additional ranges of additive concentrations within the explicit ranges above are contemplated and are within the present disclosure. The additives can be selected to improve contrast, sensitivity and line width roughness. The additives in the developer can also inhibit formation and precipitation of metal oxide particles (page 30/lines 12-28). The resist can be developed with a reactive gas or liquid (abstract)
Meyers WO 2017066319 does not exemplify the process where the resist is developed or otherwise exposed to a dry etch process.
It would have been obvious to one skilled in the art to extend the processes of Meyers WO 2017066319 by exposing the patterned resist to a dry etch process either to clean up the wet developed pattern as in Thackeray et al. 5108875 or to pattern an underlying layer/substrate as in Nakagawa et al. JP 2018017780. With a reasonable expectation of forming a useful etched pattern. In either of this modification., the sidewalls of the resists which include solvents, developer residues and/or ligands will be etched.
In addition to the basis above, it would have been obvious to modify the processes rendered obvious by the combination of Meyers WO 2017066319 with Thackeray et al. 5108875 or Nakagawa et al. JP 2018017780 by adding salts including formate, oxalate, ethylenediamine-tetraacetic acid (EDTA) and/or molecular chelating agents, such as polyamines, alcohol amines, amino acids, carboxylic acids based upon the disclosure to do so at (page 30/lines 12-28).
In response to the arguments of 2/13/2026, the additives to the developers are considered chelating agents within the meaning of the instant specification.
Claims 1-4,7,8,10,17-19 and 22-30 are rejected under 35 U.S.C. 103 as being unpatentable over Hatakeyama 20120208125, in view of Thackeray et al. 5108875 or Nakagawa et al. JP 2018017780, further in view of Cilibrizzi et al. “hydroxypyridinone journey into metal chelation” Chem. Rev. Vol. 118 pp 7657-7701 (07/2018).
Cilibrizzi et al. “hydroxypyridinone journey into metal chelation” Chem. Rev. Vol. 118 pp 7657-7701 (07/2018) teaches the use of various iron chelating agents including
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It would have been obvious to one skilled in the art modify the processes rendered obvious by the combination of Hatakeyama 20120208125, in view of Thackeray et al. 5108875 or Nakagawa et al. JP 2018017780 by replacing the chelating agents used in the resist with other chelating agents known to be useful in chelating iron, such as catechol, hydroxyamate, 1,2-HOPO, acetohydroxamic acid, 1-hydroxypyridin-2-one, 1methyl-3-hydroxypyridin-2-one, 1,2-dimethyl-3--hydroxypyridin-2-one, 3,2-HOPO, 3,4-HOPO or alpha-hydroxyacids established as known chelating agents for iron in Cilibrizzi et al. “hydroxypyridinone journey into metal chelation” Chem. Rev. Vol. 118 pp 7657-7701 (07/2018).
The rejection stands for the reasons above as no further arguments were directed at this rejection.
Claims 1-4,7,8,10-14 and 17-30 are rejected under 35 U.S.C. 103 as being unpatentable over Hatakeyama 20120208125, in view of Thackeray et al. 5108875 or Nakagawa et al. JP 2018017780, further in view of Ouyang 20200133131.
Ouyang 20200133131 establishes that it is known to use CVD as to form the metallic compounds in resists [0030].
In addition to the basis above, it would have been obvious to modify the processes by using other resist deposition techniques such as the CVD process of Ouyang 20200133131 with a reasonable expectation of forming a useful resist pattern.
The rejection stands for the reasons above as no further arguments were directed at this rejection.
Claims 1-4,7,8,10,12-14,19,24,27,28 and 30 are rejected under 35 U.S.C. 102(a)(2) as being fully anticipated by Kalutarage et al. 20220002882
Kalutarage et al. 20220002882 teaches with respect to figure 3, the development of the metal oxo photoresist using a vapor phase process including a halogenating agent and a protonated ligand [0011,0039]. The protonated ligand can be an amine, which generates a volatile byproduct [0049]. Figure 5 illustrates the development process where an organic acid is used [0013,0054]. The organic acid can be a carboxylic acids bounded by the formula RCOOH, where R can be H, CH3, t-Butyl, i-propyl [0059]. This treatment is evidenced to increase etch selectivity [0060] and may be used as a cyclic etch process [0062]. Embodiments disclosed herein provide various vapor phase thermal etching processes that are executed after portions of a metal oxo photoresist are exposed with a suitable electromagnetic radiation source (e.g., an EUV source) [0022] In an embodiment, the metal oxo photoresist 262 (also referred to simply as “photoresist 262”), may be any metal oxo material system. Such material systems typically comprise a metal (e.g., Sn, Hf, Zr, etc.), oxygen, and carbon. In a particular embodiment, the photoresist 262, comprises SnOC [0025]. The photoresist 262 may be disposed over the surface of the substrate 261 using any suitable deposition process. In an embodiment, the photoresist is disposed on the surface of the substrate 261 with a wet chemistry using a spin-on process. In an alternative embodiment, the photoresist is disposed on the surface of the substrate 261 using a vapor phase process (i.e., a dry process). In a vapor phase process, a metal precursor and an oxidant may be vaporized to a vacuum chamber, with the metal precursor and the oxidant reacting to deposit a metal oxo photoresist 262 on the surface of the substrate 261. Such dry processes may be characterized as a chemical vapor deposition (CVD) process, an atomic layer deposition (ALD) process, a plasma enhanced CVD (PE-CVD) process, or a plasma enhanced ALD (PE-ALD) process [0026]. In yet another additional embodiment, the halogenating agent may be an organic halogenating agent. For example, the halogenating agent may comprise thionyl chloride (SOCl.sub.2), methanesulfonyl chloride (CH.sub.3SO.sub.2Cl), trichloromethanesulfonyl chloride (CCl.sub.3SO.sub.2Cl), 4-toluenesulfonyl chloride (tosyl chloride), oxalyl chloride (ClCOCOCl), tert-butyl hypochlorite ((CH.sub.3).sub.3COCl), N-chlorophthalimide, 1,3-dichloro-5,5-dimethylhydantoin, trimethylsilyl chloride, HCl, Cl.sub.2, PCl.sub.5, BCl.sub.3, HBr, Br.sub.2, CCl.sub.3Br, CBr.sub.4, 1,2-dibromo-1,1,2,2-tetrachloroethane (Cl.sub.2CBrCBrCl.sub.2), BBr.sub.3, PBr.sub.3, N-bromosuccinimide, N-bromoacetamide, 2-bromo-2-cyano-N,N-dimethylacetamide, 1,3-dibromo-5,5-dimethylhydantoin, 2,4,4,6-tetrabromo-2,5-cyclohexadienone, or trimethylsilyl bromide [0034]. In an embodiment, the substrate 661 may have a controlled temperature during operation 544. For example, the temperature may vary between approximately 0° C. and approximately 500° C. In a particular embodiment, the temperature may vary between approximately 50° C. and approximately 150° C. Generally, it has been shown that increased substrate temperatures provide an increase in the etch selectivity of the unexposed regions of the photoresist 662.sub.U relative to the exposed regions of the photoresist 662.sub.E [0061].
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The embodiment of figure 5 and the associated text meet the embodiment of the claimed invention where the chelator is a carboxylic acid.
With respect to claims 10 and 12-14, the claims do not require the use of a dicarbonyl, hydroxyamic acid or hydroxyketone as these are alternatives recited in claims 8.
Claims 1-4,7-14,17-21,24,25 and 27-30 are rejected under 35 U.S.C. 103 as being unpatentable over Kalutarage et al. 20220002882
Kalutarage et al. 20220002882 does not in figure 5 and the associated describe an EUV exposure, specific transition metal resists, the use of spin coating to deposit the resist or the specific carboxylic acid used.
It would have bene obvious to one skilled ion the art to modify the process taught with respect to figure 5 by using an EUV exposure taught at [0022], Sn, Hf, or Zr oxo resist materials as taught at [0025], spin coating deposition of the resist as taught at [0026] and/or carboxylic acids bounded by the formula RCOOH, where R can be H, CH3, t-Butyl, i-propyl as taught at [0059] with a reasonable expectation of forming a useful resist patter based upon the disclosure of the use of these specific materials and/or process steps.
The nonstatutory double patenting rejection is based on a judicially created doctrine grounded in public policy (a policy reflected in the statute) so as to prevent the unjustified or improper timewise extension of the “right to exclude” granted by a patent and to prevent possible harassment by multiple assignees. A nonstatutory double patenting rejection is appropriate where the conflicting claims are not identical, but at least one examined application claim is not patentably distinct from the reference claim(s) because the examined application claim is either anticipated by, or would have been obvious over, the reference claim(s). See, e.g., In re Berg, 140 F.3d 1428, 46 USPQ2d 1226 (Fed. Cir. 1998); In re Goodman, 11 F.3d 1046, 29 USPQ2d 2010 (Fed. Cir. 1993); In re Longi, 759 F.2d 887, 225 USPQ 645 (Fed. Cir. 1985); In re Van Ornum, 686 F.2d 937, 214 USPQ 761 (CCPA 1982); In re Vogel, 422 F.2d 438, 164 USPQ 619 (CCPA 1970); In re Thorington, 418 F.2d 528, 163 USPQ 644 (CCPA 1969).
A timely filed terminal disclaimer in compliance with 37 CFR 1.321(c) or 1.321(d) may be used to overcome an actual or provisional rejection based on nonstatutory double patenting provided the reference application or patent either is shown to be commonly owned with the examined application, or claims an invention made as a result of activities undertaken within the scope of a joint research agreement. See MPEP § 717.02 for applications subject to examination under the first inventor to file provisions of the AIA as explained in MPEP § 2159. See MPEP § 2146 et seq. for applications not subject to examination under the first inventor to file provisions of the AIA . A terminal disclaimer must be signed in compliance with 37 CFR 1.321(b).
The filing of a terminal disclaimer by itself is not a complete reply to a nonstatutory double patenting (NSDP) rejection. A complete reply requires that the terminal disclaimer be accompanied by a reply requesting reconsideration of the prior Office action. Even where the NSDP rejection is provisional the reply must be complete. See MPEP § 804, subsection I.B.1. For a reply to a non-final Office action, see 37 CFR 1.111(a). For a reply to final Office action, see 37 CFR 1.113(c). A request for reconsideration while not provided for in 37 CFR 1.113(c) may be filed after final for consideration. See MPEP §§ 706.07(e) and 714.13.
The USPTO Internet website contains terminal disclaimer forms which may be used. Please visit www.uspto.gov/patent/patents-forms. The actual filing date of the application in which the form is filed determines what form (e.g., PTO/SB/25, PTO/SB/26, PTO/AIA /25, or PTO/AIA /26) should be used. A web-based eTerminal Disclaimer may be filled out completely online using web-screens. An eTerminal Disclaimer that meets all requirements is auto-processed and approved immediately upon submission. For more information about eTerminal Disclaimers, refer to www.uspto.gov/patents/apply/applying-online/eterminal-disclaimer.
Claim 1-4,7,8,10-14, 17 19,24,27,28 and 30 are rejected on the ground of nonstatutory double patenting as being unpatentable over claims 1-9 of 12577466. Although the claims at issue are not identical, they are not patentably distinct from each other because the acids are inherently chelating agents.
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The position of the examiner is that the organometallic resists of the co-pending claims are inherently EUV sensitive and that treatment with a carboxylic acid in the gas/vapor phase development process meets the claims.
Claim 1-4,7,8,10-14, 17 19,24,27,28 and 30 are provisionally rejected on the ground of nonstatutory double patenting as being unpatentable over claims 21-27 of copending application 19188367 (20250250485). Although the claims at issue are not identical, they are not patentably distinct from each other because the acids are inherently chelating agents.
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The position of the examiner is that the organometallic resists of the co-pending claims are inherently EUV sensitive and that treatment with a carboxylic acid in the gas/vapor phase development process meets the claims.
The prior art made of record and not relied upon is considered pertinent to applicant's disclosure.
Weidman et al. WO 2020264556 describes bake strategies for enhancing the lithographic performance of metal containing resists. This includes treating a photoresist with a reactive gas while the resist is heated. In various embodiments, the photoresist layer includes an extreme ultraviolet (EUV) photoresist material. In some embodiments, the reactive gas species includes a gas selected from the group consisting of: water, hydrogen, oxygen, ozone, hydrogen peroxide, carbon monoxide, carbon dioxide, ammonia, nitrous oxide, nitric oxide, an alcohol, acetyl acetone, formic acid, oxalyl chloride, pyridine, a carboxylic acid, an amine, and combinations thereof. the reactive gas species may include the acetyl acetone. In these or other cases, the reactive gas species may include the formic acid. [0005-0007]. The exposure to the gasses may be part of the post application bake (PAB) or post exposure bakes (PEB) [0040].
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.
Any inquiry concerning this communication or earlier communications from the examiner should be directed to Martin J Angebranndt whose telephone number is (571)272-1378. The examiner can normally be reached 7-3:30 pm EST.
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If attempts to reach the examiner by telephone are unsuccessful, the examiner’s supervisor, Ching-Yu (Coris) Fung can be reached at 571-270-5713. The fax phone number for the organization where this application or proceeding is assigned is 571-273-8300.
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MARTIN J. ANGEBRANNDT
Primary Examiner
Art Unit 1737
/MARTIN J ANGEBRANNDT/Primary Examiner, Art Unit 1737 September 1, 2026
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