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. Rejections of the previous action not repeated below are withdrawn. The applicant has responded that the football shape is that of an American football and the drum shape is like a drumhead as is accepted in the references of record. Responses to the arguments of the applicant are presented after the first rejection they are directed to.
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 1-8 are rejected under 35 U.S.C. 103 as being unpatentable over Weidman et al. WO 2021072042
Weidman et al. WO 2021072042 in FIG.1A-1D presents reaction schemes of (A) a non-limiting first precursor (1) with water (H.sub.2O) to provide a non-limiting organotin oxide material; (B) a non-limiting film subjected to PAB in air; (C) another non-limiting film subjected to PAB under inert conditions; and (D) yet another non-limiting film subjected to PAB under carbon dioxide (CO2). FIG.2 presents a schematic diagram of a non-limiting method for making and using a resist film. FIG.3A-3D presents schematic block diagrams of non-limiting methods for making and using a resist film. [0044] FIG.4A-4B presents scanning electron microscopy (SEM) images of dry deposited films that were developed using (A) negative tone development process or (B) a positive tone development process. FIG.5 presents a series of SEM images of dry deposited films that were developed using a positive tone development process. FIG.6A-6B presents (A) non-limiting reaction schemes of a tin-based precursor having isopropyl as the EUV labile group and (B) mass spectrometry analysis showing the desorption of water, propene, and propane as a function of temperature. Water, propene, and propane are desorption products when annealed under ultrahigh vacuum (UHV). FIG.7A-7C presents data related to (A) film shrinkage under nitrogen gas (N.sub.2), as a function of post-application bake (PAB) temperature, (B) extent of film shrinkage (in percentage) for PAB (at 200°C, 250°C, or 300°C) under N.sub.2 for 1 minute or 2 minutes; and (C) infrared (IR) spectroscopy analysis of films not subjected to PAB or subjected to PAB (from 200°C to 290°C) under N.sub.2 for 2 minutes. FIG.8A-8B presents data showing remaining film after wet development with tetramethylammonium hydroxide (TMAH) for samples processed with (A) PAB under N.sub.2 for 1 minute for various temperatures and (B) PAB under N2 for 2 minutes for various temperatures. FIG.9 presents another series of SEM images of dry deposited films that were developed using a positive tone development process [0041-0049].
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Exemplified precursors includes tin. In some embodiments, the tin precursor includes SnR or SnR2 or SnR4 or R3SnSnR3, wherein each R is, independently, H, halo, optionally substituted C1-12 alkyl, optionally substituted C1-12 alkoxy, optionally substituted amino (e.g., -NR.sup.1R.sup.2), optionally substituted C2-12 alkenyl, optionally substituted C.sub.2-12 alkynyl, optionally substituted C.sub.3-8 cycloalkyl, optionally substituted aryl, cyclopentadienyl, optionally substituted bis(trialkylsilyl)amino (e.g., -N(SiR.sup.1R.sup.2R.sup.3).sub.2), optionally substituted alkanoyloxy (e.g., acetate), a diketonate (e.g., -OC(R.sup.1)-Ak-(R.sup.2)CO-), or a bidentate chelating dinitrogen (e.g., -N(R.sup.1)-Ak-N(R.sup.1)-). In particular embodiments, each R.sup.1, R.sup.2, and R.sup.3 is, independently, H or C1-12 alkyl (e.g., methyl, ethyl, isopropyl, t-butyl, or neopentyl); and Ak is optionally substituted C.sub.1-6 alkylene. In particular embodiments, each R is, independently, halo, optionally substituted C1-12 alkoxy, optionally substituted amino, optionally substituted aryl, cyclopentadienyl, or a diketonate. Non-limiting tin precursors include SnF.sub.2, SnH.sub.4, SnBr4, SnCl4, SnI4, tetramethyl tin (SnMe4), tetraethyl tin (SnEt4), trimethyl tin chloride (SnMe3Cl), dimethyl tin dichloride (SnMe2Cl2), methyl tin trichloride (SnMeCl3), tetraallyltin, tetravinyl tin, hexaphenyl ditin (IV) (Ph.sub.3Sn-SnPh.sub.3, in which Ph is phenyl), dibutyldiphenyltin (SnBu2Ph2), trimethyl(phenyl) tin (SnMe3Ph), trimethyl(phenylethynyl) tin, tricyclohexyl tin hydride, tributyl tin hydride (SnBu.sub.3H), dibutyltin diacetate (SnBu2(CH3COO)2), tin(II) acetylacetonate (Sn(acac)2), SnBu3(OEt), SnBu2(OMe)2, SnBu.sub.3(OMe), Sn(t-BuO).sub.4, Sn(n-Bu)(t-BuO).sub.3, tetrakis(dimethylamino)tin (Sn(NMe.sub.2).sub.4), tetrakis(ethylmethylamino)tin (Sn(NMeEt)4), tetrakis(diethylamino)tin(IV) (Sn(NEt2)4), (dimethylamino)trimethyl tin(IV) (Sn(Me).sub.3(NMe.sub.2), Sn(i-Pr)(NMe.sub.2).sub.3, Sn(n-Bu)(NMe.sub.2).sub.3, Sn(s-Bu)(NMe.sub.2).sub.3, Sn(i-Bu)(NMe.sub.2).sub.3, Sn(t-Bu)(NMe.sub.2).sub.3, Sn(t-Bu).sub.2(NMe.sub.2).sub.2, Sn(t- Bu)(NEt2)3, Sn(tbba), Sn(II) (1,3-bis(1,1-dimethylethyl)-4,5-dimethyl-(4R,5R)-1,3,2- diazastannolidin-2-ylidene), or bis[bis(trimethylsilyl)amino] tin (Sn[N(SiMe.sub.3).sub.2].sub.2) [0118]. Counter-reactants preferably have the ability to replace the reactive moieties, ligands, or ions (e.g., L in formulas herein) so as to link at least two metal atoms via chemical bonding. Exemplary counter-reactants include oxygen-containing counter- reactants, such as oxygen (O2), ozone (O3), water, peroxides (e.g., hydrogen peroxide), oxygen plasma, water plasma, alcohols, dihydroxy alcohols, polyhydroxy alcohols, fluorinated dihydroxy alcohol, fluorinated polyhydroxy alcohols, fluorinated glycols, formic acid, and other sources of hydroxyl moieties, as well as combinations thereof. In various embodiments, a counter-reactant reacts with the precursor by forming oxygen bridges between neighboring metal atoms [0135]. Exemplary organometallic agents include SnMeCl3, (N.sup.2,N.sup.3-di-t-butyl-butane- 2,3-diamido) tin(II) (Sn(tbba)), bis(bis(trimethylsilyl)amido) tin(II), tetrakis(dimethylamino) tin(IV) (Sn(NMe2)4), t-butyl tris(dimethylamino) tin (Sn(t- butyl)(NMe.sub.2).sub.3), i-butyl tris(dimethylamino) tin (Sn(i-Bu)(NMe.sub.2).sub.3), n-butyl tris(dimethylamino) tin (Sn(n-Bu)(NMe2)3), sec-butyl tris(dimethylamino) tin (Sn(s- Bu)(NMe.sub.2).sub.3), i-propyl(tris)dimethylamino tin (Sn(i-Pr)(NMe.sub.2).sub.3), n-propyl tris(diethylamino) tin (Sn(n-Pr)(NEt2)3), and analogous alkyl(tris)(t-butoxy) tin compounds, such as t-butyl tris(t-butoxy) tin (Sn(t-Bu)(t-BuO).sub.3). In some embodiments, the organometallic agents are partially fluorinated. Lithographic processes
A counter-reactant may be used to better remove the ligands, and multiple cycles may be repeated to ensure complete saturation of the substrate surface. The surface can then ready for the EUV-sensitive film to be deposited. One possible method is to produce a thin film of SnOx. Possible chemistries include growth of SnO2 by cycling tetrakis(dimethylamino)tin and a counter-reactant such as water or O2 plasma [0157]. These are embraced by formula II,
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wherein: M is a metal or an atom having a high EUV absorption cross-section; each R is, independently, halo, optionally substituted alkyl, optionally substituted aryl, optionally substituted amino, optionally substituted alkoxy, or L; each L is, independently, a ligand, an anionic ligand, a neutral ligand, a multidentate ligand, ion, or other moiety that is reactive with a counter-reactant, in which R and L with M, taken together, can optionally form a heterocyclyl group or in which R and L, taken together, can optionally form a heterocyclyl group; a ≥ 1; b ≥ 1; and c ≥ 1 [0105]. Other development methodologies can include use of an acidic developer (e.g., an aqueous acidic developer, non-aqueous acidic developer, or an acid developer in an organic solvent) that includes a halide (e.g., HF, HCl, or HBr), an organic acid (e.g., formic acid, acetic acid, oxalic acid, or citric acid), or an organohalide compound (e.g., such as an organofluorine compound, including trifluoroacetic acid; an organochlorine compound; an organobromine compound, or an organoiodine compound); or use of an organic developer, such as a ketone (e.g., 2-heptanone, cyclohexanone, or acetone), an ester (e.g., γ-butyrolactone or ethyl 3-ethoxypropionate (EEP)), an alcohol (e.g., isopropyl alcohol (IPA)), or an ether, such as a glycol ether (e.g., propylene glycol methyl ether (PGME) or propylene glycol methyl ether acetate (PGMEA)), as well as combinations thereof. Yet other development methodologies can include use of a deprotecting solvent. Non-limiting deprotecting solvents include an organic acid (e.g., any herein, such as oxalic acid) or include choline ([N(CH3)3CH2CH2OH].sup.+), such as choline hydroxide ([N(CH.sub.3).sub.3CH.sub.2CH.sub.2OH].sup.+ [OH].sup.−). The developer can be used in any useful concentration. In one embodiment, the developer solution includes about 0.5 wt.% to about 30 wt.% of the developer(s) in a solvent (e.g., an aqueous solvent, a non-aqueous solvent, an organic solvent, or a combination thereof), including concentrations from about 1 wt. % to about 20 wt. % and 1.1 wt. % to 10 wt. % [0173-0174]. A film (e.g., a metal oxide coating or agglomerated polymeric materials, such as via metal-oxygen-metal bond formation) may also be deposited by an ALD process. For example, the precursor(s) and optional counter-reactant are introduced at separate times, representing an ALD cycle [0154]. Performing a post-application (deposition) bake (PAB) between 100°C and 200°C or even above 200°C, such as from 100°C to 250°C or 100°C to 350°C. In another instance, the PAB can be from 180°C to 250°C or 100°C to 350°C for about 30 seconds (s) to 2 minutes (min) or from 10 s to 5 min (e.g., with ambient air, inert gas(es), or CO.sub.2) [0090]. The treatment temperature in a PAB, PEB, or PDB can be varied to tune and optimize the treatment process, for example from about 90°C to 250°C for PAB and about 170°C to 250°C or more for PEB and/or PDB [0196]. Heterocyclics include acridinyl, adenyl, alloxazinyl, azaadamantanyl, azabenzimidazolyl, azabicyclononyl, azacycloheptyl, azacyclooctyl, azacyclononyl, azahypoxanthinyl, azaindazolyl, azaindolyl, azecinyl, azepanyl, azepinyl, azetidinyl, azetyl, aziridinyl, azirinyl, azocanyl, azocinyl, azonanyl, benzimidazolyl, benzisothiazolyl, benzisoxazolyl, benzodiazepinyl, benzodiazocinyl, benzodihydrofuryl, benzodioxepinyl, benzodioxinyl, benzodioxanyl, benzodioxocinyl, benzodioxolyl, benzodithiepinyl, benzodithiinyl, benzodioxocinyl, benzofuranyl, benzophenazinyl, benzopyranonyl, benzopyranyl, benzopyrenyl, benzopyronyl, benzoquinolinyl, benzoquinolizinyl, benzothiadiazepinyl, benzothiadiazolyl, benzothiazepinyl, benzothiazocinyl, benzothiazolyl, benzothienyl, benzothiophenyl, benzothiazinonyl, benzothiazinyl, benzothiopyranyl, benzothiopyronyl, benzotriazepinyl, benzotriazinonyl, benzotriazinyl, benzotriazolyl, benzoxathiinyl, benzotrioxepinyl, benzoxadiazepinyl, benzoxathiazepinyl, benzoxathiepinyl, benzoxathiocinyl, benzoxazepinyl, benzoxazinyl, benzoxazocinyl, benzoxazolinonyl, benzoxazolinyl, benzoxazolyl, benzylsultamyl benzylsultimyl, bipyrazinyl, bipyridinyl, carbazolyl (e.g., 4H-carbazolyl), carbolinyl (e.g., β-carbolinyl), chromanonyl, chromanyl, chromenyl, cinnolinyl, coumarinyl, cytdinyl, cytosinyl, decahydroisoquinolinyl, decahydroquinolinyl, diazabicyclooctyl, diazetyl, diaziridinethionyl, diaziridinonyl, diaziridinyl, diazirinyl, dibenzisoquinolinyl, dibenzoacridinyl, dibenzocarbazolyl, dibenzofuranyl, dibenzophenazinyl, dibenzopyranonyl, dibenzopyronyl (xanthonyl), dibenzoquinoxalinyl, dibenzothiazepinyl, dibenzothiepinyl, dibenzothiophenyl, dibenzoxepinyl, dihydroazepinyl, dihydroazetyl, dihydrofuranyl, dihydrofuryl, dihydroisoquinolinyl, dihydropyranyl, dihydropyridinyl, dihydroypyridyl, dihydroquinolinyl, dihydrothienyl, dihydroindolyl, dioxanyl, dioxazinyl, dioxindolyl, dioxiranyl, dioxenyl, dioxinyl, dioxobenzofuranyl, dioxolyl, dioxotetrahydrofuranyl, dioxothiomorpholinyl, dithianyl, dithiazolyl, dithienyl, dithiinyl, furanyl, furazanyl, furoyl, furyl, guaninyl, homopiperazinyl, homopiperidinyl, hypoxanthinyl, hydantoinyl, imidazolidinyl, imidazolinyl, imidazolyl, indazolyl (e.g., 1H-indazolyl), indolenyl, indolinyl, indolizinyl, indolyl (e.g., 1H-indolyl or 3H-indolyl), isatinyl, isatyl, isobenzofuranyl, isochromanyl, isochromenyl, isoindazoyl, isoindolinyl, isoindolyl, isopyrazolonyl, isopyrazolyl, isoxazolidiniyl, isoxazolyl, isoquinolinyl, isoquinolinyl, isothiazolidinyl, isothiazolyl, morpholinyl, naphthindazolyl, naphthindolyl, naphthiridinyl, naphthopyranyl, naphthothiazolyl, naphthothioxolyl, naphthotriazolyl, naphthoxindolyl, naphthyridinyl, octahydroisoquinolinyl, oxabicycloheptyl, oxauracil, oxadiazolyl, oxazinyl, oxaziridinyl, oxazolidinyl, oxazolidonyl, oxazolinyl, oxazolonyl, oxazolyl, oxepanyl, oxetanonyl, oxetanyl, oxetyl, oxtenayl, oxindolyl, oxiranyl, oxobenzoisothiazolyl, oxochromenyl, oxoisoquinolinyl, oxoquinolinyl, oxothiolanyl, phenanthridinyl, phenanthrolinyl, phenazinyl, phenothiazinyl, phenothienyl (benzothiofuranyl), phenoxathiinyl, phenoxazinyl, phthalazinyl, phthalazonyl, phthalidyl, phthalimidinyl, piperazinyl, piperidinyl, piperidonyl (e.g., 4-piperidonyl), pteridinyl, purinyl, pyranyl, pyrazinyl, pyrazolidinyl, pyrazolinyl, pyrazolopyrimidinyl, pyrazolyl, pyridazinyl, pyridinyl, pyridopyrazinyl, pyridopyrimidinyl, pyridyl, pyrimidinyl, pyrimidyl, pyronyl, pyrrolidinyl, pyrrolidonyl (e.g., 2-pyrrolidonyl), pyrrolinyl, pyrrolizidinyl, pyrrolyl (e.g., 2H-pyrrolyl), pyrylium, quinazolinyl, quinolinyl, quinolizinyl (e.g., 4H-quinolizinyl), quinoxalinyl, quinuclidinyl, selenazinyl, selenazolyl, selenophenyl, succinimidyl, sulfolanyl, tetrahydrofuranyl, tetrahydrofuryl, tetrahydroisoquinolinyl, tetrahydroisoquinolyl, tetrahydropyridinyl, tetrahydropyridyl (piperidyl), tetrahydropyranyl, tetrahydropyronyl, tetrahydroquinolinyl, tetrahydroquinolyl, tetrahydrothienyl, tetrahydrothiophenyl, tetrazinyl, tetrazolyl, thiadiazinyl (e.g., 6H-1,2,5- thiadiazinyl or 2H,6H-1,5,2-dithiazinyl), thiadiazolyl, thianthrenyl, thianyl, thianaphthenyl, thiazepinyl, thiazinyl, thiazolidinedionyl, thiazolidinyl, thiazolyl, thienyl, thiepanyl, thiepinyl, thietanyl, thietyl, thiiranyl, thiocanyl, thiochromanonyl, thiochromanyl, thiochromenyl, thiodiazinyl, thiodiazolyl, thioindoxyl, thiomorpholinyl, thiophenyl, thiopyranyl, thiopyronyl, thiotriazolyl, thiourazolyl, thioxanyl, thioxolyl, thymidinyl, thyminyl, triazinyl, triazolyl, trithianyl, urazinyl, urazolyl, uretidinyl, uretinyl, uricyl, uridinyl, xanthenyl, xanthinyl, xanthionyl, and the like, as well as modified forms thereof (e.g., including one or more oxo and/or amino) and salts thereof. The heterocyclyl group can be substituted or unsubstituted. For example, the heterocyclyl group can be substituted with one or more substitution groups, as described herein for alkyl [0310].
Weidman et al. WO 2021072042 does not exemplify the coating and exposure process with a resist precursor of the recited formula.
With respect to claims 1 and 3--8, it would have been obvious to one skilled in the art to modify the processes of figure 3A or used in the formation of the patterns in figures 4A,4B,5 or 9 by using Sn(t-Bu).sub.2(NMe.sub.2).sub.2 disclosed as a useful resist materials at [0118,0130] and a counter-reactant such as water, hydrogen peroxide, formic acid (a carboxylic acid) or other sources of hydroxyl moieties which a counter-reactant reacts with the precursor by forming oxygen bridges between neighboring metal atoms and remove the ligands better, and multiple cycles may be repeated to ensure complete saturation of the substrate surface [0135,0157] with a reasonable expectation of forming a useful resist pattern. With respect to claim 5, the examiner holds that it least some of the clusters have a Sn6, drum-shaped structure
Alternatively with respect to claims 1--8, it would have been obvious to one skilled in the art to modify the processes of figure 3A or used in the formation of the patterns in figures 4A,4B,5 or 9 by using (N.sup.2,N.sup.3-di-t-butyl-butane- 2,3-diamido) tin(II) disclosed as a useful resist materials at [0137] and a counter-reactant such as water, hydrogen peroxide, formic acid (a carboxylic acid) or other sources of hydroxyl moieties which a counter-reactant reacts with the precursor by forming oxygen bridges between neighboring metal atoms and remove the ligands better, and multiple cycles may be repeated to ensure complete saturation of the substrate surface [0135,0157] with a reasonable expectation of forming a useful resist pattern. With respect to claim 5, the examiner holds that it least some of the clusters have a Sn6, drum-shaped structure
Alternatively with respect to claims 1 and 3--8, it would have been obvious to one skilled in the art to modify the processes of figure 3A or used in the formation of the patterns in figures 4A,4B,5 or 9 by using a precursor similar to Sn(t-Bu).sub.2(NMe.sub.2).sub.2, but where at least one of the t-butyl ligands is replaced with methyl, ethyl, isopropyl or neopentyl, phenyl, trialkylsilyl which are disclosed as equivalents at [0118] and disclosed as a useful resist materials at [0118,0130] and a counter-reactant such as water, hydrogen peroxide, formic acid (a carboxylic acid) or other sources of hydroxyl moieties which a counter-reactant reacts with the precursor by forming oxygen bridges between neighboring metal atoms and remove the ligands better, and multiple cycles may be repeated to ensure complete saturation of the substrate surface [0135,0157] with a reasonable expectation of forming a useful resist pattern. With respect to claim 5, the examiner holds that it least some of the clusters have a Sn6, drum-shaped structure
With respect to claim 8, it further, would have been obvious to coat the resist using CVD based upon the disclosure of these coating processes at [0100,0114,0154,0157] with a reasonable expectation of forming a useful resist pattern.
In the response of 5/18/2026, the applicant argues that the addition of step-wise or simultaneous of the precursor and the co-reactant renders the claims patentable. This arguments fails to appreciate that the atomic layer deposition (ALD) uses a step-wise/cyclic introduction of the reactant and precursor as discussed in the statement of rejection. The chemical vapor deposition (CVD discussed as obvious above [0100,0114,0154,0157] introduces these concurrently. The rejection stands.
Claims 1-10 are rejected under 35 U.S.C. 103 as being unpatentable over Weidman et al. WO 202107204, in view of Sharps et al., “Organotin carboxylate reagents for nanopatterning” Chemical transformations during direct-write electron beam processes”, Chem. Mater., Vol. 31, pp 4840-4850 (2019).
Weidman et al. WO 202107204 does not describe the shape of the clusters or the thickness of the resist coating.
In addition to the basis above, it would have been obvious to modify the processes rendered obvious by Weidman et al. WO 202107204 by coating the resists in known useful thicknesses, such as the 20, 60 or 70 nm thicknesses of Sharps et al., “Organotin carboxylate reagents for nanopatterning” Chemical transformations during direct-write electron beam processes”, Chem. Mater., Vol. 31, pp 4840-4850 (2019) and/or to choose appropriate ligands, amounts thereof and deposition conditions to induce the formation of hexameric (drum-shaped) Sn6 clusters in the deposited resist as taught by Sharps et al., “Organotin carboxylate reagents for nanopatterning” Chemical transformations during direct-write electron beam processes”, Chem. Mater., Vol. 31, pp 4840-4850 (2019) with a reasonable expectation of forming a useful resist pattern.
The rejection stands for the reasons above without further comment as no further arguments were directed at this rejection.
Claims 10-15 are rejected under 35 U.S.C. 103 as being unpatentable over Weidman et al. WO 2021072042, in view of Yang 20240124500
Yang 20240124500 in prophetic example 4 describes the synthesis of N,N,N′,N′,1-pentamethyl-1,2-azastannolidine-2,2-diamine, which has the structure
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[0056-0057]. Prophetic example 6 describes the synthesis of 2,2-di-tert-butoxy-1-methyl-1,2-azastannolidine, which has the structure
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[0060-0061].
It would have been obvious to modify the ALD processes of figure 3A or used in the formation of the patterns in figures 4A,4B,5 or 9 of Weidman et al. WO 2021072042 by using tin compounds such as N,N,N′,N′,1-pentamethyl-1,2-azastannolidine-2,2-diamine or 2,2-di-tert-butoxy-1-methyl-1,2-azastannolidine disclosed by Yang 20240124500 which are disclosed as a useful resist materials and within the language “ R and L with M, taken together, can optionally form a heterocyclyl group or in which R and L, taken together, can optionally form a heterocyclyl group” in Weidman et al. WO 2021072042 at [0105] and a counter-reactant such as water, hydrogen peroxide, formic acid (a carboxylic acid) or other sources of hydroxyl moieties which a counter-reactant reacts with the precursor by forming oxygen bridges between neighboring metal atoms and remove the ligands better, and multiple cycles may be repeated to ensure complete saturation of the substrate surface [0135,0157] with a reasonable expectation of forming a useful resist pattern. With respect to claim 12, the examiner holds that it least some of the clusters have a Sn12, football-shaped structure
Alternatively, it would have been obvious to modify the ALD processes of figure 3A or used in the formation of the patterns in figures 4A,4B,5 or 9 of Weidman et al. WO 2021072042 by using tin compounds similar to N,N,N′,N′,1-pentamethyl-1,2-azastannolidine-2,2-diamine or 2,2-di-tert-butoxy-1-methyl-1,2-azastannolidine disclosed by Yang 20240124500, but where the monovalent ligands are methyl, ethyl, isopropyl,. t-butyl or neopentyl, phenyl, trialkylsilylas taught in Weidman et al. WO 2021072042 where the rings are within the language “ R and L with M, taken together, can optionally form a heterocyclyl group or in which R and L, taken together, can optionally form a heterocyclyl group” in Weidman et al. WO 2021072042 at [0105] and a counter-reactant such as water, hydrogen peroxide, formic acid (a carboxylic acid) or other sources of hydroxyl moieties which a counter-reactant reacts with the precursor by forming oxygen bridges between neighboring metal atoms and remove the ligands better, and multiple cycles may be repeated to ensure complete saturation of the substrate surface [0135,0157] with a reasonable expectation of forming a useful resist pattern. With respect to claim 12, the examiner holds that it least some of the clusters have a Sn12, football-shaped structure
With respect to claim 15, it further, would have been obvious to coat the resist using CVD based upon the disclosure of these coating processes at [0100,0114,0154,0157] with a reasonable expectation of forming a useful resist pattern.
The rejection stands for the reasons above without further comment as no further arguments were directed at this rejection.
Claims 10-15 are rejected under 35 U.S.C. 103 as being unpatentable over Weidman et al. WO 2021072042, in view of Yang 20240124500, further in view of Sharps et al., “Organotin carboxylate reagents for nanopatterning” Chemical transformations during direct-write electron beam processes”, Chem. Mater., Vol. 31, pp 4840-4850 (2019).
Sharps et al., "Organotin carboxylate reagents for nanopatterning" Chemical transformations during direct-write electron beam processes", Chem. Mater., Vol. 31, pp 4840- 4850 (2019) teaches in section 2.2 the synthesis of a dodecameric n-butyloxytin acetate, which is described as having a football shaped dodecameric structure in section 2.1. Section 2.3 described the synthesis of a hexameric n-butyloxotin acetate, which is described in section 2.1 as being a hexameric drum cluster. These are spin-coated on HMDS coated silicon wafers and dried/soft-baked to form 20 nm thick coatings in section 2.4. The resultant films are exposed using a scanning electron microscope and developed in toluene to remove the unreacted material .ocr_line, .ocr_header { display:block; } (section 2.5). Coating were also formed on bare silicon wafers (section 2.6) and thicker (60-70 nm) films were baked in a tube furnace (section 2.7),
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In addition to the basis above, it would have been obvious to modify the processes rendered obvious by the combination of Weidman et al. WO 202107204 and Yang 20240124500 by choosing appropriate ligands, amounts thereof and deposition conditions to induce the formation of hexameric (drum-shaped) Sn6 clusters in the deposited resist as taught by Sharps et al., “Organotin carboxylate reagents for nanopatterning” Chemical transformations during direct-write electron beam processes”, Chem. Mater., Vol. 31, pp 4840-4850 (2019) with a reasonable expectation of forming a useful resist pattern.
The rejection stands for the reasons above without further comment as no further arguments were directed at this rejection.
The prior art made of record and not relied upon is considered pertinent to applicant's disclosure.
Singhal et al. 20200199751 claims the formation of metal oxides using atomic layer deposition in claim 1. The organometal reactant Me2Sn(NMe2)2 is the reactant in claims 5 and 18. The oxygen source can be oxygen, nitrous oxide, carbon dioxide, ozone [0042].
Hansen et al. 20230266664 exemplfies organometallic agents include SnMeCl.sub.3, (N.sup.2,N.sup.3-di-t-butyl-butane-2,3-diamido) tin(II) (Sn(tbba)), bis(bis(trimethylsilyl)amido) tin(II), tetrakis(dimethylamino) tin(IV) (Sn(NMe.sub.2).sub.4), t-butyl tris(dimethylamino) tin (Sn(t-butyl)(NMe.sub.2).sub.3), i-butyl tris(dimethylamino) tin (Sn(i-Bu)(NMe.sub.2).sub.3), i-butyl tris(dimethylamino) tin (Sn(n-Bu)(NMe.sub.2).sub.3), sec-butyl tris(dimethylamino) tin (Sn(s-Bu)(NMe.sub.2).sub.3), i-propyl(tris)dimethyl amino tin (Sn(i-Pr(NMe.sub.2).sub.3), n-propyl tris(diethylamino) tin (Sn(n-Pr)(NEt.sub.2).sub.3), and analogous alkyl(tris)(t-butoxy) tin compounds, such as t-butyl tris(t-butoxy) tin (Sn(t-Bu)(t-BuO).sub.3) [0237]
Which is bounded by
A metal-containing precursor can include a hydrocarbyl-substituted capping agent having the following formula (XII):
R.sub.nMX.sub.m (XII),
wherein M is a metal, R is a C.sub.2-10 alkyl or substituted alkyl having a beta-hydrogen, and X is a suitable leaving group upon reaction with a hydroxyl group of the exposed hydroxyl groups. In various embodiments, n=1 to 3, and m=4−n, 3−n, or 2−n, so long as m>0 (or m≥1). For example, R may be I-butyl, t-pentyl, t-hexyl, cyclohexyl, isopropyl, isobutyl, sec-butyl, in-butyl, n-pentyl, n-hexyl, or derivatives thereof having a heteroatom substituent in the beta position. Suitable heteroatoms include halogen (F, Cl, Br, or I), or oxygen (—OH or —OR). X may be dialkylamino (e.g., dimethylamino, methylethylamino, or diethylamino), alkoxy (e.g., t-butoxy, isopropoxy), halo (e.g., F, Cl, Br, or I), or another organic ligand. Examples of hydrocarbyl-substituted capping agents include t-butyltris(dimethylamino)tin (Sn(t-Bu)(NMe.sub.2).sub.3), n-butyltris(dimethylamino)tin (Sn(n-Bu)(NMe.sub.2).sub.3), t-butyltris (diethylamino)tin (Sn(t-Bu)(NEt.sub.2).sub.3), di(I-butyl)di(dimethylamino)tin (Sn(t-Bu).sub.2(NMe.sub.2).sub.2), sec-butyltris(dimethylamino)tin (Sn(s-Bu)(NMe.sub.2).sub.3), n-pentyltris(dimethylamino)tin (Sn(n-pentyl)(NMe.sub.2).sub.3), i-butyltris(dimethylamino) tin (Sn(i-Bu)(NMe.sub.2).sub.3), i-propyltris (dimethylamino)tin (Sn(i-Pr)(NMe.sub.2).sub.3), t-butyltris(t-butoxy)tin (Sn(t-Bu)(t-BuO).sub.3), n-butyl(tris(t-butoxy)tin (Sn(n-Bu)(t-BuO)), or isopropyltris(t-butoxy)tin (Sn(i-Pr)(t-BuO).sub.3). In various embodiments, a metal-containing precursor includes at least one alkyl group on each metal atom that can survive the vapor-phase reaction, while other ligands or ions coordinated to the metal atom can be replaced by the counter-reactants. Accordingly, another non-limiting metal-containing precursor includes an organometallic agent having the formula (XIII):
M.sub.aR.sub.bL.sub.c (XIII),
in which M is a metal; R is an optionally substituted alkyl ; L is a ligand, ion, or other moiety which is reactive with the counter-reactant; a≥1; b≥1; and c≥1. In particular embodiments, a=1, and b+c=4. In some embodiments, M is Sn, Te, Bi, or Sb. In particular embodiments, each L is independently amino (e.g., —NR.sup.1R.sup.2, in which each of R.sup.1 and R.sup.2 can be H or alkyl, such as any described herein), alkoxy (e.g., —OR, in which R is alkyl, such as any described herein), or halo (e.g., F, Cl, Br, or I). Exemplary agents include SnMe.sub.3Cl, SnMe.sub.2Cl.sub.2, SnMeCl.sub.3, SnMe(NMe.sub.2).sub.3, SnMe.sub.2(NMe.sub.2).sub.2, SnMe.sub.3(NMe.sub.2), and the like [0232-0233]. In yet other embodiments, said depositing further includes a counter-reactant (e.g., an oxygen-containing counter-reactant). Non-limiting counter-reactants include O.sub.2, O.sub.3, water, a peroxide, hydrogen peroxide, oxygen plasma, water plasma, an alcohol, a dihydroxy alcohol, a polyhydroxy alcohol, a fluorinated dihydroxy alcohol, a fluorinated polyhydroxy alcohol, a fluorinated glycol, formic acid, and other sources of hydroxyl moieties, as well as combinations thereof [0021]. In particular embodiments, said depositing includes chemical vapor deposition (CVD), atomic layer deposition (ALD), or molecular layer deposition (MLD [0037].
Weidman et al. WO 2020264557 teaches the deposition of tin resist using CVD or ALD [0059]. Tin precursors disclosed include A related approach involving an absorption gradient targets the use of somewhat tin-based resist films using two precursors - both with alkyl groups - but one containing one or more alkyl ligands than the other. For example, isopropyltris(dimethylamino)tin and diisopropyldi(dimethylamino)tin can be used. Initially, a flow of the diisopropyldi(dimethylamino)tin is introduced during the film deposition and the ratio is increased relative to the flow of isopropyltris(dimethylamino)tin as the film is deposited. This results in a film with a higher amount of Sn bonded to two alkyl groups on the surface relative to the bottom of the film. Figure 2A describes a graded layer SnBi to Sn (top) layer formed by the reaction with water. The reactant is isopropyl tris(dimethylamino)Tin.
Weidmen et al. WO 2022182473 teaches metal resist precursors bounded by R.sub.nMX.sub.m (IX), wherein M is a metal, R is a C.sub.2-10 alkyl or substituted alkyl having a beta-hydrogen, and X is a suitable leaving group upon reaction with a hydroxyl group of the exposed hydroxyl groups. In various embodiments, n = 1 to 3, and m = 4 - n, 3 - n, or 2 - n, so long as m > 0 (or m ≥ 1). For example, R may be t-butyl, t-pentyl, t-hexyl, cyclohexyl, isopropyl, isobutyl, sec-butyl, n-butyl, n-pentyl, n-hexyl, or derivatives thereof having a heteroatom substituent in the beta position. Suitable heteroatoms include halogen (F, Cl, Br, or I), or oxygen (-OH or -OR). X may be dialkylamino (e.g., dimethylamino, methylethylamino, or diethylamino), alkoxy (e.g., t-butoxy, isopropoxy), halo (e.g., F, Cl, Br, or I), or another organic ligand. Examples of hydrocarbyl- substituted capping agents include t-butyltris(dimethylamino)tin (Sn(t-Bu)(NMe.sub.2).sub.3), n- butyltris(dimethylamino)tin (Sn(n-Bu)(NMe.sub.2).sub.3), t-butyltris(diethylamino)tin (Sn(t-Bu)(NEt.sub.2).sub.3), di(t-butyl)di(dimethylamino)tin (Sn(t-Bu).sub.2(NMe.sub.2).sub.2), sec-butyltris(dimethylamino)tin (Sn(s- Bu)(NMe.sub.2).sub.3), n-pentyltris(dimethylamino)tin (Sn(n-pentyl)(NMe.sub.2).sub.3), z-butyltris(dimethylamino) tin (Sn(i-Bu)(NMe.sub.2).sub.3), i-propyltris(dimethylamino)tin (Sn(i-Pr)(NMe.sub.2).sub.3), t-butyltris(t-butoxy)tin (Sn(t-Bu)(t-BuO).sub.3), n-butyl(tris(t-butoxy)tin (Sn(n-Bu)(t-BuO).sub.3), or isopropyltris(t-butoxy)tin (Sn(i-Pr)(t-BuO).sub.3) [0202]. In any embodiment herein, said depositing includes providing the metal-containing precursor and/or the ligand-containing precursor in vapor form. In other embodiments, said depositing includes providing a metal-containing precursor, a ligand-containing precursor, and/or a counter-reactant in vapor form. Non-limiting deposition processes include chemical vapor deposition (CVD), as well as atomic layer deposition (ALD), molecular layer deposition (MLD), and plasma-enhanced forms thereof [0054]. Non-limiting counter-reactants include an oxygen-containing or a chalcogenide- containing precursor, as well as any described herein (e.g., an oxygen-containing counter- reactant, including oxygen (O.sub.2), ozone (O.sub.3), water, a peroxide, hydrogen peroxide, oxygen plasma, water plasma, an alcohol, a dihydroxy alcohol, a polyhydroxy alcohol, a fluorinated dihydroxy alcohol, a fluorinated polyhydroxy alcohol, a fluorinated glycol, formic acid, and other sources of hydroxyl moieties, as well as combinations thereof) [0055]
Liu et al. 20220100087 teaches n organometallic precursor for extreme ultraviolet (EUV) lithography is provided. An organometallic precursor includes a chemical formula of M.sub.aX.sub.bL.sub.c, where M is a metal, X is a multidentate aromatic ligand that includes a pyrrole-like nitrogen and a pyridine-like nitrogen, L is an extreme ultraviolet (EUV) cleavable ligand, a is between 1 and 2, b is equal to or greater than 1, and c is equal to or greater than 1.
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MARTIN J. ANGEBRANNDT
Primary Examiner
Art Unit 1737
/MARTIN J ANGEBRANNDT/Primary Examiner, Art Unit 1737 May 29, 2026
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