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 following is a quotation of 35 U.S.C. 112(b):
(b) CONCLUSION.—The specification shall conclude with one or more claims particularly pointing out and distinctly claiming the subject matter which the inventor or a joint inventor regards as the invention.
The following is a quotation of 35 U.S.C. 112 (pre-AIA ), second paragraph:
The specification shall conclude with one or more claims particularly pointing out and distinctly claiming the subject matter which the applicant regards as his invention.
Claims 1-10,12 and 16-20 are rejected under 35 U.S.C. 112(b) or 35 U.S.C. 112 (pre-AIA ), second paragraph, as being indefinite for failing to particularly point out and distinctly claim the subject matter which the inventor or a joint inventor (or for applications subject to pre-AIA 35 U.S.C. 112, the applicant), regards as the invention.
In claims 1, “dimethlybutylamine” should read - -dimethylbutylamine - -
It is not clear what a “drum-shaped structure” or a “football-shaped structure” ar.
Is the drum-shaped structure a cylinder like a snare drum or does the shape only require the shape of the head of the drum ?
Doe the football shaped structure correspond to a American style football shape or a soccer/football shape ?
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 16-20 are rejected under 35 U.S.C. 102(a)(1) as being fully anticipated 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).
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 (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),
PNG
media_image1.png
273
498
media_image1.png
Greyscale
PNG
media_image2.png
458
628
media_image2.png
Greyscale
The position of the examiner is that the exposed portions are crosslinked, which renders them insoluble in the toluene developer.
Claims 16-20 are rejected under 35 U.S.C. 102(a)(2) as being fully anticipated by Lim et al. 20230384667.
Lim et al. 20230384667 synthesizes in examples 1-11 [011-0122] drum shaped tin clusters. In examples 1-111, solutions of these are coated upon silicon wafers and dried to form, coatings which are 25 nm thick. [0126]. These are crosslinked during the thermal stability testing [0133].
Claims 16-20 are rejected under 35 U.S.C. 102(a)(1) as being fully anticipated by or, in the alternative, under 35 U.S.C. 103 as obvious over Chang et al. 20210087210.
Chang et al. 20210087210 in examples 1 and 2 synthesis hexameric tin clusters [0084-0085]. These are described as drum-like at [0046]. The process of using the resist is disclosed with respect to figure 1, where the resist is coated on a semiconductor substrate, using spin coating, spray coating, dip coating or the like to a thickness of 10-100 nm, dried at 5-105 degrees C, exposed to EUV, post baked at 50-150 degrees, and developed to leave the exposed areas (negative tone) [0060-0083].
PNG
media_image3.png
505
426
media_image3.png
Greyscale
The examiner holds that one reading the reference would immediately envision the use of the tin clusters in forming a resist, coating it on a semiconductor substrate and processing it as described at [0060-0083], thereby anticipating the claims.
Alternatively, if this position is not upheld, the examiner holds that it would have been obvious to one skilled in the art to use the synthesized tin compounds in the lithographic processes disclosed at [0060-0083] based upon this being their functionality with a reasonable expectation of forming a useful resist pattern.
Claims 16-20 are rejected under 35 U.S.C. 102(a)(1) as being fully anticipated by Meyers et al. 20160116839.
Meyers et al. 20160116839 teaches the synthesis of a hydrolysate of t-butyl Tin (tris (dimethylamino) in example 1. This hydrolysate has the structure t-BuSnO(3/2-x/2)(OH)x, where X is between 0 and 3 [0124-0126]. In example 3, the tin compound of example 1 is dissolved in methanol and evaluated using NMR and dodecamer (football shaped) clusters are formed [0130-0133]. The solution of example 3 is coated on a HDMS coated silicon wafer to a thickness of ~23 nm dried/baked at 80-100 degrees C, exposed to EUV, post baked at 100-200 degrees C, and developed in 2-heptanone [0135-0140].
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].
PNG
media_image4.png
478
217
media_image4.png
Greyscale
PNG
media_image5.png
572
257
media_image5.png
Greyscale
PNG
media_image6.png
597
217
media_image6.png
Greyscale
PNG
media_image7.png
301
427
media_image7.png
Greyscale
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,
PNG
media_image8.png
40
127
media_image8.png
Greyscale
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 ALD or CVD based upon the disclosure of these coating processes at [0100,0114,0154,0157] with a reasonable expectation of forming a useful resist pattern.
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.
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
PNG
media_image9.png
127
110
media_image9.png
Greyscale
[0056-0057]. Prophetic example 6 describes the synthesis of 2,2-di-tert-butoxy-1-methyl-1,2-azastannolidine, which has the structure
PNG
media_image10.png
102
106
media_image10.png
Greyscale
[0060-0061].
It would have been obvious to modify the 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 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
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).
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 prior art made of record and not relied upon is considered pertinent to applicant's disclosure.
Sharps et al., “Implications of a crystal structure on organotin carboxylate photoresists”, Cryst. Research Technol. Vol. 52 Articles 1700081 (7 pages) (2017) exemplifies hexameric n-butyloxotin compounds (the hexamers contain Sn6 are held to have the shape of a drum head) as illustrated in the structures shown in figure 2.
PNG
media_image11.png
397
932
media_image11.png
Greyscale
Chen 20220163889 teaches dodecameric tin clusters formed during the prebaking process [0062].
Cardineau et al. 20230100995 teaches reactants with organometallic resists including a carboxylic acid, an amide, a sulfonic acid, an alcohol, a diol, a silyl halide, a germanium halide, a tin halide, an amine, a thiol, or a mixture thereof, to form an initial pattern (3/25-29) One aspect of the invention pertains to a method for developing an organotin resist with a composition comprising a contrast enhancer, wherein said contrast enhancer can be chosen, for example, from an amine, a silyl halide, an alcohol, an amide, a sulfonic acid, a carboxylic acid, a thiol, tin halide, germanium halide, and mixtures thereof. In some embodiments, the contrast enhancer can be used in combination with gaseous acid halide, HF, HC1, HBr and/or HI, to facilitate reaction. Some water vapor may be desirable in combination with other reactants (2/2-7)
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.
Examiner interviews are available via telephone, in-person, and video conferencing using a USPTO supplied web-based collaboration tool. To schedule an interview, applicant is encouraged to use the USPTO Automated Interview Request (AIR) at http://www.uspto.gov/interviewpractice.
If attempts to reach the examiner by telephone are unsuccessful, the examiner’s supervisor, Mark F Huff can be reached at 571-272-1385. The fax phone number for the organization where this application or proceeding is assigned is 571-273-8300.
Information regarding the status of published or unpublished applications may be obtained from Patent Center. Unpublished application information in Patent Center is available to registered users. To file and manage patent submissions in Patent Center, visit: https://patentcenter.uspto.gov. Visit https://www.uspto.gov/patents/apply/patent-center for more information about Patent Center and https://www.uspto.gov/patents/docx for information about filing in DOCX format. For additional questions, contact the Electronic Business Center (EBC) at 866-217-9197 (toll-free). If you would like assistance from a USPTO Customer Service Representative, call 800-786-9199 (IN USA OR CANADA) or 571-272-1000.
MARTIN J. ANGEBRANNDT
Primary Examiner
Art Unit 1737
/MARTIN J ANGEBRANNDT/Primary Examiner, Art Unit 1737 February 11, 2026