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 applicate has been read and given careful consideration. Claims 32-36 stands as withdrawn.. Rejections of the previous office action not repeated below are withdrawn ion view of the arguments and amendment of the applicant.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.
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 1-4 and 7-30 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.
Claim 1 recites the provision of the resist and the dry etching in the presence of the metal chelator. The specification is describes the provision of the metal chelator as a wet process (see prepub at [0007,0009,0012,0013,0093,0101]). Please amend the claim to recite the provision of the chelator using a developer solution. The specification also does not seem to support a dry development alone with the chelating agent.
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.
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.
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% aquesous 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.
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 and 17-30 are rejected on the ground of nonstatutory double patenting as being unpatentable over claims 16-53 of U.S. Patent No. 11314168. Although the claims at issue are not identical, they are not patentably distinct from each other because the acids are inherently chelating agents.
Claim 32 recites: The method of claim 16, wherein the imaging layer comprises an Extreme Ultraviolet (EUV)-sensitive inorganic photoresist layer, a chemical vapor deposited (CVD) film, a spin-on film, a tin oxide film, or a tin oxide hydroxide film.
Claim 42 recites: The method of claim 40, further comprising, after said exposing: developing the organometallic imaging layer using wet development.
Claims 40 recites The method of claim 33, further comprising, after said forming: exposing the organometallic imaging layer to Extreme Ultraviolet (EUV) radiation.
Claim 39 recites The method of claim 37, wherein the organometallic imaging layer comprises organotin.
Claim 42 recites The method of claim 42, wherein the wet development is performed using an organic acid.
Claims 41 and 67 recite dry development
It would have been obvious to one skilled in the art to combine the claimed process steps including the chelating agents and the dry development with a reasonable expectation of forming a useful resist pattern
The applicant has not filed a terminal disclaimer or offered any arguments regarding the ODP rejection.
The prior art made of record and not relied upon is considered pertinent to applicant's disclosure.
Tamada et al. 20200333707 teaches resists including metal complexes and ligands..
Zi et al. 20180315617 specifically describes metal resists which include ligands/chelating agents.
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MARTIN J. ANGEBRANNDT
Primary Examiner
Art Unit 1737
/MARTIN J ANGEBRANNDT/Primary Examiner, Art Unit 1737 May 11, 2026
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