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. Rejection of the previous action not repeated below are withdrawn. 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 1,3,4,7,8,10,11 and 13 are rejected under 35 U.S.C. 102(a)(1) as being fully anticipated by Nishita et al. 20190227438.
Nishita et al. 20190227438 in synthesis example 2 forms a copolymer with the repeating units.
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In example 2, 0.058 g of tetramethoxymethylglycoluril (available from Cytec Industries Japan, product name: POWDERLINK [registered trademark] 1174) and 0.0083 g of pyridinium p-toluenesulfonate (available from Tokyo Chemical Industry Co., Ltd.) were mixed with 0.82 g of a solution containing 0.13 g of the copolymer obtained in Synthesis Example 2, and 55.64 g of propylene glycol monomethyl ether and 23.94 g of propylene glycol monomethyl ether acetate were added thereto and dissolved. Then, the mixture was filtered through a polyethylene microfilter with a pore diameter of 0.05 μm to obtain a resist underlayer film-forming composition for lithography [0038]. The resist underlayer film-forming compositions for lithography prepared in Example 1 and Example 2 were applied, using a spinner, to silicon wafers on which a SiON film was formed by vapor deposition. The wafers were placed on a hot plate and baked at 205° C. for 1 minute to form a resist underlayer film with a film thickness of 5 nm. In addition, the resist underlayer film-forming composition for lithography prepared in Comparative Example 1 was applied, using a spinner, to a silicon wafer on which a SiON film was formed by vapor deposition. The wafer was placed on a hot plate and baked at 205° C. for 1 minute to form a resist underlayer film with a film thickness of 20 nm. A commercially available photoresist solution (available from Sumitomo Chemical Co., Ltd., product name: PAR855) was applied to the resist underlayer film using a spinner and heated on a hot plate at 105° C. for 60 seconds to form a photoresist film (with a film thickness of 0.10 μm). Next, exposure was performed using a scanner manufactured by Nikon Corporation, NSR-S307E (with a wavelength of 193 nm (ArF), NA: 0.85, σ: 0.65/0.93 (Dipole)) at an optimal exposure amount through a photomask. The photomask was selected according to a resist pattern to be formed. After the exposure, a post exposure bake (PEB) was performed on a hot plate at 105° C. for 60 seconds, and after cooling, in a 60 second single paddle type process of industrial standards, developing was performed using a 0.26 N tetramethylammonium hydroxide aqueous solution as a developing solution. Through the above procedure, a resist pattern was formed. Table 1 shows results of formability of a line and space pattern (hereinafter abbreviated as L/S). When a desired L/S was formed, the result was “good. [0041-0042]. The resist underlayer film-forming composition of the present invention further includes a solvent. Examples of the solvent include propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether, propylene glycol monopropyl ether, methyl ethyl ketone, ethyl lactate, cyclohexanone, y-butyrolactone, N-methylpyrrolidone, and mixtures of two or more types selected from among such solvents. A content of the solvent is, for example, 50% by mass to 99.5% by mass, with respect to the resist underlayer film-forming composition [0029]. The resist underlayer film-forming composition of the present invention further includes an organic acid catalyst. The organic acid catalyst is a catalyst component that promotes a crosslinking reaction. Examples of the organic acid catalyst include a sulfonic acid compound and a carboxylic acid compound such as p-toluenesulfonic acid, trifluoromethanesulfonic acid, pyridinium-p-toluenesulfonate, pyridinium-p-hydroxybenzenesulfonate, salicylic acid, camphorsulfonic acid, 5-sulfosalicylic acid, 4-chlorobenzenesulfonic acid, 4-phenolsulfonic acid, methyl 4-phenolsulfonate, benzenedisulfonic acid, 1-naphthalenesulfonic acid, citric acid, benzoic acid and hydroxybenzoic acid. Such organic acid catalysts may be included alone or two or more types thereof may be included in combination. A content of the organic acid catalyst is, for example, 0.1% by mass to 20% by mass, with respect to the crosslinking agent [0028].
The resist underlayer film-forming composition of the present invention may further include a surfactant as necessary. The surfactant is an additive for improving coating properties of the resist underlayer film-forming composition with respect to a substrate. A known surfactant such as a nonionic surfactant and a fluorine-based surfactant can be used. Specific examples of the surfactant include a nonionic surfactant, for example, polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, and polyoxyethylene oleyl ether, polyoxyethylene alkylaryl ethers such as polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyoxyethylene-polyoxypropylene block copolymers, sorbitan fatty acid esters such as sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, and sorbitan tristearate, and polyoxyethylene sorbitan fatty acid esters such as polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, and polyoxyethylene sorbitan tristearate, a fluorine-based surfactant such as Eftop [registered trademark] EF301, Eftop EF303, Eftop EF352 (available from Mitsubishi Materials Electronic Chemicals Co., Ltd.), MEGAFACE [registered trademark] F171, MEGAFACE F173, MEGAFACE R-30, MEGAFACE R-40, MEGAFACE R-40-LM (available from DIC Corporation), Fluorad FC430, Fluorad FC431 (available from Sumitomo 3M Limited), AsahiGuard [registered trademark] AG710, Surflon [registered trademark] S-382, Surflon SC101, Surflon SC102, Surflon SC103, Surflon SC104, Surflon SC105, Surflon SC106 (available from Asahi Glass Co., Ltd.), and organosiloxane polymer KP341 (available from Shin-Etsu Chemical Co., Ltd.). Such surfactants may be included alone and two or more types thereof may be included in combination. When the resist underlayer film-forming composition includes a surfactant, a content of the surfactant is, for example, 0.1% by mass to 5% by mass, and preferably 0.2% by mass to 3% by mass, with respect to the copolymer [0030-0031]. A second aspect of the present invention is a method of forming a resist pattern comprising; a process of applying the resist underlayer film-forming composition for lithography of the first aspect of the present invention to a substrate and performing baking to form a resist underlayer film with a thickness of 1 nm to 25 nm; a process of applying a resist solution to the resist underlayer film and performing heating to form a resist film; a process of exposing the resist film with radiated light selected from the group consisting of a KrF excimer laser, an ArF excimer laser and an extreme ultraviolet ray through a photomask; and a process of performing development with a developing solution after the exposure [0020]
The position of the examiner is that the NH groups in the left two repeating units of the polymer used in resist 2 and the process of evaluating it are (secondary) amine functional groups bounded by the recited polar group and affinity group of the claims.
Claims 1,3,4,6-8,10,11 and 13 are rejected under 35 U.S.C. 103 as being unpatentable over Nishita et al. 20190227438.
Nishita et al. 20190227438 does not exemplify the process where the full range of solvents are used, the full range of exposure devices disclosed are used or a surfactant is included in the underlayer composition.
With respect to claims 1,3,4,7,8,10,11 and 13, it would have been obvious to one of ordinary skill in the art to modify the embodiments of example 2 by using different solvents disclosed at [0029] and/or different exposure sources disclosed at [0020] with a reasonable expectation of forming a useful resist pattern based upon the disclosed equivalence of these with the solvents and exposure apparatus of the example.
With respect to claims 1,3,4,6-8,10,11 and 13, it would have been obvious to one of ordinary skill in the art to modify the embodiments of example 2 by adding in the surfactants disclosed at [0030-0031] where the underlayer has improved coating properties with a reasonable expectation of forming a useful resist pattern based upon the disclosed equivalence of these with the solvents and exposure apparatus of the example.
Claims 1,3,4,6-8, and 10-13 are rejected under 35 U.S.C. 103 as being unpatentable over Nishita et al. 20190227438, in view of Kamimura et al. 20190258168.
Kamimura et al. 20190258168 teaches a resist which includes a metal complex (a complex of magnesium, chromium, manganese, iron, cobalt, nickel, copper, zinc, silver, cadmium, indium, tin, antimony, cesium, zirconium, hafnium, or the like; titanium, zirconium, or hafnium is preferable from the viewpoint of pattern formability) having an absorption to light such as a g-ray, a h-ray, an i-ray, KrF, ArF, EB, and EUV, and in which ligand disengagement or ligand exchange occurs in a case of being used in combination with a photoacid generator (for example, a resist material described in paragraphs 0017 to 0033, and 0037 to 0047 of JP2015-075500A, in paragraphs 0017 to 0032, and 0043 to 0044 of JP2012-185485A, paragraphs 0042 to 0051, and 0066 of US2012/0208125A, and the like) [0302]
Nishita et al. 20190227438 does not teach the use of resists including the metals recited in claims 12 or 24.
It would have been obvious to modify the embodiments exemplified or rendered obvious by the teachings of Nishita et al. 20190227438by using resist which include a complexes of chromium, iron, cobalt, nickel, tin or zirconium taught by Kamimura et al. 20190258168 with a reasonable expectation of forming a resist pattern where the sensitivity of the resist to ArF is realized as taught at [0302] of Kamimura et al. 20190258168.
Claims 1-4,7,8,10,11,13,21-24 and 26-27 are rejected under 35 U.S.C. 103 as being unpatentable over Hatakeyama et al. 20080220381.
Hatakeyama et al. 20080220381 exemplifies a polymer with the following structures.
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in synthesis examples 11 and 9.
Table 1 combines these with (thermal) acid generators AG1 (iodonium fluoroalkylsulfonic acid salt, which is also photoacid generator) and AG2 (ammonium fluoroalkyl sulfonic acid salt) , polyethylene glycol monomethyl ether (PGMEA, solvent) and in example 3 a separate crosslinking agent (CR1) (pages 27-34). The underlayer antireflection compositions are coated from solution onto a silicon wafer, baked at 200 degrees C for 60 seconds, the chemically amplified resist is coated, dried, exposed using ArF, post baked at 100 degrees C and developed in TMAH. This resist has a triphenylsulfonium photoacid generator [0297]. Other useful repeating units which enhance adhesiveness disclosed include
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(pages 15 and 18 [0063]). Useful acid generators for promoting crosslinking in the antireflection layer thermal acid generators and/or photoacid generators can be added. These include onium salts, diazomethane compounds, glyoxime compounds, bis sulfone compounds, sulfonate imides, keto sulfonic acids, disulfones, nitrobenzyl sulfonates, sulfonates and the like. These can be used alone or in admixtures [0079-0130]. Useful solvents are disclosed including any organic solvent that dissolves the base polymer, an acid generator, a crosslinker and other additives may be used. Examples of such an organic solvent may include: ketones such as cyclohexanone, methyl-2-amyl ketone; alcohols such as 3-methoxy butanol, 3-methyl-3-methoxy butanol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol; ethers such as propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, propylene glycol dimethyl ether, or diethylene glycol dimethyl ether; and esters such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethyl lactate, ethyl pyruvate, butyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, tert-butyl acetate, tert-butyl propionate, propylene glycol mono methyl ether acetate, or propylene glycol mono tert-butyl ether acetate. Above solvents may be used alone or in admixture. However, the organic solvent that may be added to the antireflection film composition according to the present invention is not restricted to the above solvents [0142]. subsequently, the method of forming the antireflection film of the present invention as a lower layer of the photoresist film (resist lower layer antireflection film) will be described. It is possible to form the resist lower layer antireflection film on the substrate by spin-coating method in the same way as in the ordinary photoresist films. After forming the resist lower layer antireflection film by the spin-coating method, it is desirable to bake for facilitating the crosslinking reaction in order to evaporate the organic solvent and prevent the mixing with the resist upper layer. A baking temperature is preferably in the range of 80 to 300.degree. C. for 10 to 300 seconds. The thickness of the resist lower layer antireflection film is appropriately selected, and is 10 to 200 nm and particularly preferably 20 to 150 nm. The film thickness exhibiting the high antireflection effect can be selected [0152]. It is preferable that the above antireflection film composition further contains one or more of an organic solvent, an acid generator and a crosslinking agent. Specific examples of the addition type crosslinker which can be used in the present invention may include: a melamine compound, a guanamine compound, a glycol uryl compound or an urea compound each substituted with at least one group selected from a methylol group, an alkoxy methyl group and an acyloxy methyl group; an epoxy compound, an isocyanate compound, an azide compound, a compound including a double bond such as an alkenyl ether group, and the like. These compounds may be used as an additive, or may be introduced into a polymer side chain as a pendant group. Moreover, a compound containing a hydroxy group may also be used as a crosslinker. The amount of the crosslinker to be added to the antireflection film composition of the present invention is preferably 5 to 50 parts (parts by mass, hereinafter, parts denote "parts by mass"), more preferably 10 to 40 parts per 100 parts of the base polymer (total resin content). When the amount is 5 parts or more, it is unlikely to cause the mixing with the resist film. When it is 50 parts or less, there is less possibility that antireflection effect is deteriorated or cracks are generated in the film after crosslinking [0072-0078]. The antireflection layer composition 3, used in the example includes
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,
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and the solvent PGMEA. The four hydroxy and three ester groups are polar groups, the CF3 groups are fluorine containing, the two -CH2OH and -CH2CH2OH groups are photoresist affinity groups and the four hydroxy groups are thermally crosslinkable, CR1 is a crosslinker and AG1 is a thermal acid generator and the process of using described at [0297] anticipates claims1,3,4,7-11 and 13 rejected under this heading.
The antireflection layer composition of comparative example 2 which is used in the examples combines
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,
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and
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(a photoacid generator which is also inherently thermal acid generator) and PGMEA (solvent). The two hydroxy and two ester groups are polar groups, the CF2 groups are fluorine containing, the -CH2CH(OH)CH2OH group is a photoresist affinity groups and the two hydroxy groups are thermally crosslinkable, CR1 is a crosslinker and PAG1 is a photoacid generator, which is inherently also a thermal acid generator, and the process of using this composition at [0297] anticipates claims 1,3,4,7-11,13,21-24 and 26-27 rejected under this heading. The curing by heating at 200 degrees C evidences the ability of the photoacid generator (PAG) to act as a thermal acid generator.
Hatakeyama et al. 20080220381 does not exemplify the recites process where the underlayer compositions include a polymer with thiol/mercaptan (SH), azide (N3), -S(=O)-, alkyne, imine, ahdehyde, acetic acid, cyanide/cyano, allene, amine, phosphine, phosphite, aniline, pyridine or pyrrole group, a composition where the polymer is combined with a crosslinking agent, thermal acid generator and a photoacid generator, a composition where the polymer is combined with a crosslinking agent, thermal acid generator and solvents other than PGMEA, or processes where the heating occurs are temperatures other than 200 degrees C.
With respect to claims 1-4 and 7, it would have been obvious to modify the process of using composition of example 3 described at [0297] by adding a cyanide/cyano group repeating unit such as any of
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into the polymer to increase the adhesiveness. In this embodiment, the affinity group is cyanide/cyano/-CN or the groups
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, the polar group are the hydroxymethyl (
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) or
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, the fluorine containing group is
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and
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with a reasonable expectation of forming a useful resist pattern, noting the equivalence of the hydroxyhexafluoropropyl moiety and the cyanide/cyano/CN as adhesive improving functional groups at [0063].
With respect to claims 8 and 10-11 and 13, it would have been obvious to modify the process of using composition of example 3 described at [0297] by adding a cyanide/cyano group repeating unit such as any of
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into the polymer to increase the adhesiveness. In this embodiment, the polar group is cyanide/cyano/-CN or the groups
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, the affinity group are the hydroxymethyl (
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) or
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, the fluorine containing group is
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and
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with a reasonable expectation of forming a useful resist pattern, noting the equivalence of the hydroxyhexafluoropropyl moiety and the cyanide/cyano/CN as adhesive improving functional groups at [0063].
With respect to claims 1-4,7,8,10,11 and 13, it would have been obvious to modify the process of using composition of example 3 described at [0297] by adding a cyanide/cyano group repeating unit such as any of
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into the polymer to increase the adhesiveness as discussed above and using other solvents, such as cyclohexanone, methyl-2-amyl ketone; alcohols such as 3-methoxy butanol, 3-methyl-3-methoxy butanol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol; ethers such as propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, propylene glycol dimethyl ether, or diethylene glycol dimethyl ether; and esters such as propylene glycol monomethyl ether acetate, ethyl lactate, ethyl pyruvate, butyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, tert-butyl acetate, tert-butyl propionate, propylene glycol mono methyl ether acetate, or propylene glycol mono tert-butyl ether acetate in place of at least a portion of the PGMEA based upon the disclosure at [0142] with a reasonable expectation of forming a useful resist pattern, noting the equivalence of the hydroxyhexafluoropropyl moiety and the cyanide/cyano/CN as adhesive improving functional groups at [0063].
With respect to claims 1-4,7,8,10,11 and 13, it would have been obvious to modify the process of using composition of example 3 described at [0297] by adding a cyanide/cyano group repeating unit such as any of
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into the polymer to increase the adhesiveness as discussed above and using other heating temperatures such as 160-250 degrees C, which is within the 80-300 degrees C range taught, in place of the 200 degrees C used with a reasonable expectation of successfully forming a resist pattern based upon the useful 80-300 degree C range taught at [0152]
With respect to claims 1-4,7,8,10,11,13,21-24 and 26-27, it would have been obvious to modify the process of using composition of example 3 described at [0297] by adding a cyanide/cyano group repeating unit such as any of
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into the polymer to increase the adhesiveness as discussed above and adding a photoacid generator, such as the onium salts, diazomethane compounds, glyoxime compounds, bis sulfone compounds, sulfonate imides, keto sulfonic acids, disulfones, nitrobenzyl sulfonates, sulfonates and the like discussed at [0079-0130] to the composition with a reasonable expectation of success based upon the disclosure that the composition can include thermal acid generators and/or photoacid generators and that the acid generators can be used alone or in admixtures to promote thermal (heat) crosslinking reactions [0079,0130].
Combination of these motivations are also considered obvious for the reasons associated with the modification identified above.
In the arguments of 2/126/2026, the applicant argues that the references do not teach the recited photoresist affinity groups (claim 1 and dependent claims) or the recited polar groups (claims 8, 21 and those dependent upon them) As indicated in the interview summary, Hatakeyama et al. teaches cyano/cyanide groups (pages 15,18 and [0063]) which produce adhesiveness. The rejection as modified stands.
Claims 1-5,7-13 and 21-27 are rejected under 35 U.S.C. 103 as being unpatentable over Hatakeyama et al. 20080220381, in view of Cardineau et al. 20210011383.
Cardineau et al. 20210011383 teaches the desire to improve the adhesion between the underlayer coating and the substrate and the overlying organometallic resist by the addition of monomeric unit which improve the adhesion [0028,0047]. The polymer composition comprises repeat units with side-chain adhesion-promoting moieties and/or end-chain adhesion-promoting moieties, where the repeat units comprise functionalized styrenes, functionalized acrylates, functionalized vinyl ketones, functionalized acrylamides, functionalized urethane acrylates, functionalized phenolic resins, and/or other functionalized vinyl or non-vinyl repeat units, where the adhesion-promoting moieties may be terminally functionalized with amine, imine, imide, oxime, carboxylic amide, carboxylic acid, thiol, thiocarboxylic acid, dithiocarboxylic acid, alcohol/hydroxy, sulfinic acid [-S(=O)-OH] , sulfonic acid, sulfonium salt, a photolabile moiety, such as sulfonium sulfonate, iodonium sulfonate, N-sulfonic imide, and/or N-sulfonic imines, and where the polymer composition has suitable film forming properties from solution. The adhesion-promoting moieties are capable of hydrogen bonding and comprise an amine, imine, imide, oxime, carboxylic amide, carboxylic acid, thiol, thiocarboxylic acid, dithiocarboxylic acid, alcohol, sulfinic acid, sulfonic acid, or sulfonium salt [0048,0058]. Disclosed organomethallic resists based upon Tin are disclosed. RzSnO(2−z/2−x/2) (OH)x where 0<x<3, 0<z≤2, x+z≤4, and R is a hydrocarbyl group forming a carbon bond with the tin atom.at [0026].
Hatakeyama et al. 20080220381 does not describe the case where the polar group and the affinity groups are different and the polar group is one of mercaptan (SH), azide (N3), -S(=O)-, alkyne, imine, aldehyde, acetic acid, cyanide/cyano, allene, amine, phosphine, phosphite, aniline, pyridine or pyrrole group and the photoresist affinity group is one of mercaptan (SH), azide (N3), -S(=O)-, alkyne, imine, ahdehyde, acetic acid, cyanide/cyano or the resist is an organometallic resist including Sn, Pd, Zr, Co, Ni, Cr, Fe, Rh or Ru.
With respect to claims 1-4,7,8,10-13,21 and 23-27, in addition to the basis above It would have been obvious to one skilled in the art to modify the processes of using the resist underlayers rendered obvious by Hatakeyama et al. 20080220381 by using an Tin based organometallic resist taught by Cardineau et al. 20210011383 at [0026] with a reasonable expectation of forming a useful resist pattern based upon the disclosed use of hydroxy/alcohol moieties to improve adhesion between the underlayer and the organometallic resist and the underlayer and the substrate in Cardineau et al. 20210011383 at [0028,0047-0048,0058].
With respect to claims 1-5,7-13 and 21-27, it would have been obvious to modify the process of using composition of example 3 described at [0297] of Hatakeyama et al. 20080220381 by adding (or replacing at least a portion of the hydroxy groups with) a cyanide/cyano group repeating unit as taught in Hatakeyama et al. 20080220381 and one of an amine, imine, thiol (SH or sulfinic acid [-S(=O)-OH] moiety taught at adhesion promoting moieties in Cardineau et al. 20210011383 at [0048,0058] and using an Tin based organometallic resist taught by Cardineau et al. 20210011383 at [0026] with a reasonable expectation of forming a useful resist pattern based upon the disclosed equivalence with hydroxy/alcohol moieties to improve adhesion between the underlayer and the organometallic resist and the underlayer and the substrate in Cardineau et al. 20210011383 at [0028,0047-0048,0058] and Hatakeyama et al. 20080220381 at [0063].
Claims 1-5,7-13 and 21-27 are rejected under 35 U.S.C. 103 as being unpatentable over Hatakeyama et al. 20080220381, in view of Cardineau et al. 20210011383 and Kamimura et al. 20190258168
The combination of Hatakeyama et al. 20080220381 and Cardineau et al. 20210011383 does not teach the use of resists including the metals recited in claims 12 or 24.
It would have been obvious to modify the embodiments exemplified or rendered obvious by the teachings of Hatakeyama et al. 20080220381 and Cardineau et al. 20210011383 by using resist which include a complexes of chromium, iron, cobalt, nickel, tin or zirconium taught by Kamimura et al. 20190258168 with a reasonable expectation of forming a resist pattern where the sensitivity of the resist to ArF is realized as taught at [0302] of Kamimura et al. 20190258168 and increase the adhesion between the underlayer and the inorganic containing resists as taught in Hatakeyama et al. 20080220381 and Cardineau et al. 20210011383 due to the polar/adhesion groups in the underlayer.
Claims 1-11,13, 21-24 and 26-27 are rejected under 35 U.S.C. 103 as being unpatentable over Nakahara et al. 20120077124.
Nakahara et al. 20120077124 teaches polymer A-5, which is a copolymer of monomers M-1, M-5, M-3 and M-7. And polymer A-6, which is a copolymers of monomers M1, M5,M3 and M8.
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[034-037].
In example 11, the polymer A-5 is combined with crosslinking agent (B-1), crosslinking catalyst (thermal acid generator, C-1) and solvents (PGME). Example 12 combines polymer A-5 is combined with crosslinking agent (B-1), crosslinking catalyst (thermal acid generator, C-1) and solvents (PGME).
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[0254-0256].
Each of the resist underlayer film-forming compositions prepared in Examples and Comparative Examples was applied to the surface of an 8-inch silicon wafer by spin coating, and baked at 205 ° C. for 60 seconds on a hot plate to form a resist underlayer having a thickness of 90 nm. A film was formed. The radiation sensitive composition (P-1) adjusted above was apply | coated by spin coating on this resist underlayer film, and it baked at 120 degree C for 60 second on the hotplate, and formed the photoresist film of 120 nm in thickness. At this time, intermixing of the resist and the anti-reflection film was not observed. The silicon wafer to which the obtained resist underlayer film forming composition and the radiation sensitive composition were apply | coated was exposed through the mask pattern using ArF excimer laser exposure apparatus (brand name "NSRS306C", the Nikon Corporation make). Thereafter, PEB was performed at 115 ° C. for 60 seconds, followed by developing at 25 ° C. for 30 seconds with a 2.38% aqueous tetramethylammonium hydroxide solution (hereinafter also referred to as “TMAH aqueous solution”), washing with water, and drying to obtain a positive type. A resist pattern was formed and the pattern collapse dimension was measured in accordance with the following evaluation method. The radiation sensitive resin composition used and the result are shown in Table 4 (Examples 33-45 and Comparative Examples 33-45) [0149-0152]. In the step (3), the resist film obtained by the step (2) is exposed by selectively applying radiation to the resist film via a photomask. Radiation used in the step (3) is appropriately selected from visible rays, ultraviolet rays, deep ultraviolet rays, X-rays, electron beams, .gamma.-rays, molecular beams, ion beams, and the like depending on the type of acid generator included in the resist composition. Among these, it is preferable to use deep ultraviolet rays. It is particularly preferable to use KrF excimer laser light (248 nm), ArF excimer laser light (193 nm), F.sub.2 excimer laser light (157 nm), Kr.sub.2 excimer laser light (147 nm), or ArKr excimer laser light (134 nm), extreme ultraviolet rays (e.g., 13.5 nm), or the like [0120]. Repeating unit 2-1 has the structure
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and
R4 represents a hydrogen atom, a halogen atom, a methyl group, or a trifluoromethyl group, R6 represents an alkyl group having 1 to 15 carbon atoms or an aryl group having 6 to 20 carbon atoms, provided that some or all of the hydrogen atoms of the alkyl group or the aryl group are substituted with a substituent, at least one substituent being a group that includes a hydroxyl group or an amino group [0014-0015]. The surfactant may be added to improve the applicability of the resist lower layer film-forming composition, reduce nonuniform application, and improve the developability of the irradiated area. Examples of a preferable surfactant include nonionic surfactants, fluorine-based surfactants, and silicone surfactants. Examples of the nonionic surfactants include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, and polyoxyethylene oleyl ether; polyoxyethylene aryl ethers such as polyoxyethylene octyl phenyl ether and polyoxyethylene nonyl phenyl ether; polyethylene glycol dialkyl esters such as polyethylene glycol dilaurate and polyethylene glycol distearate; (meth)acrylic acid copolymers; and the like. Examples of the (meth)acrylic acid copolymers include Polyflow No. 57, Polyflow No. 95 (manufactured by Kyoeisha Chemical Co., Ltd.), and the like Examples of the fluorine-based surfactants include fluoroethers such as 1,1,2,2-tetrafluorooctyl (1,1,2,2-tetrafluoropropyl)ether, 1,1,2,2-tetrafluorooctyl hexyl ether, octaethylene glycol di(1,1,2,2-tetrafluorobutyl)ether, hexaethylene glycol (1,1,2,2,3,3-hexafluoropentyl)ether, octapropylene glycol di(1,1,2,2-tetrafluorobutyl)ether, and hexapropylene glycol di(1,1,2,2,3,3-hexafluoropentyl)ether; sodium perfluorododecylsulfonate; fluoroalkanes such as 1,1,2,2,8,8,9,9,10,10-decafluorododecane and 1,1,2,2,3,3-hexafluorodecane; sodium fluoroalkylbenzenesulfonates; fluoroalkyloxyethylene ethers; fluoroalkyl ammonium iodides; fluoroalkyl polyoxyethylene ethers; perfluoroalkylpolyoxyethanols; perfluoroalkyl alkoxylates; fluorine-containing alkyl esters; and the like. Examples of commercially available products of the fluorine-based surfactants include EFTOP EF301, EFTOP EF303, EFTOP EF352 (manufactured by JEMCO, Inc.), Megafac F171, Megafac F172, Megafac F173 (manufactured by DIC Corporation), Fluorad FC430, Fluorad FC431 (manufactured by Sumitomo 3M Ltd.), Asahi Guard AG710, Surflon S-382, Surflon SC-101, Surflon SC-102, Surflon SC-103, Surflon SC-104, Surflon SC-105, Surflon SC-106 (manufactured by Asahi Glass Co., Ltd.), FTX-218 (manufactured by NEOS Co., Ltd.), and the like. Examples of the silicone surfactants include SH200-100cs, SH28PA, SH30PA, ST89PA, SH190 (manufactured by Dow Corning Toray Silicone Co., Ltd.), KP341 (organosiloxane polymer) (manufactured by Shin-Etsu Chemical Co., Ltd.), and the like. The surfactant (E) is preferably used in an amount of 0.001 to 10 parts by mass, and more preferably 0.005 to 5 parts by mass, based on 100 parts by mass of the polymer (A). If the surfactant (E) is used in an amount of 0.001 to 10 parts by mass, the applicability of the resist lower layer film-forming composition can be optimized [0097-0102]. The resist lower layer film-forming composition normally includes the solvent (D). The solvent (D) is not particularly limited as long as the solvent (D) can dissolve at least the polymer (A), the crosslinking agent (B), and an additional optional component. Examples of the solvent (D) include alcohol solvents, ether solvents, ketone solvents, amide solvents, ester solvents, hydrocarbon solvents, a mixed solvent thereof, and the like. Examples of the alcohol solvents include monohydric alcohol solvents such as methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, sec-butanol, tert-butanol, n-pentanol, i-pentanol, 2-methylbutanol, sec-pentanol, tert-pentanol, 3-methoxybutanol, n-hexanol, 2-methylpentanol, sec-hexanol, 2-ethylbutanol, sec-heptanol, 3-heptanol, n-octanol, 2-ethylhexanol, sec-octanol, n-nonyl alcohol, 2,6-dimethyl-4-heptanol, n-decanol, sec-undecyl alcohol, trimethylnonyl alcohol, sec-tetradecyl alcohol, sec-heptadecyl alcohol, furfuryl alcohol, phenol, cyclohexanol, methylcyclohexanol, 3,3,5-trimethylcyclohexanol, benzyl alcohol, and diacetone alcohol; polyhydric alcohol solvents such as ethylene glycol, 1,2-propylene glycol, 1,3-butylene glycol, 2,4-pentanediol, 2-methyl-2,4-pentanediol, 2,5-hexanediol, 2,4-heptanediol, 2-ethyl-1,3-hexanediol, diethylene glycol, dipropylene glycol, triethylene glycol, and tripropylene glycol; polyhydric alcohol partial ether solvents such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, ethylene glycol monophenyl ether, ethylene glycol mono-2-ethyl butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monohexyl ether, propylene glycol methyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropyleneglycol monomethylether, dipropylene glycol monoethyl ether, and dipropylene glycol monopropyl ether; and the like. Examples of the ether solvents include diethyl ether, dipropyl ether, dibutyl ether, diphenyl ether, and the like Examples of the ketone solvents include acetone, methyl ethyl ketone, methyl n-propyl ketone, methyl n-butyl ketone, diethyl ketone, methyl i-butyl ketone, methyl n-pentyl ketone, ethyl n-butyl ketone, methyl n-hexyl ketone, di-i-butyl ketone, trimethylenonane, cyclopentanone, cyclohexanone, cycloheptanone, cyclooctanone, methylcyclohexanone, 2,4-pentanedione, acetonylacetone, acetophenone, and the like. Examples of the amide solvents include N,N'-dimethylimidazolidinone, N-methylformamide, N,N-dimethylformamide, N,N-dimethylformamide, acetamide, N-methylacetamide, N,N-dimethylacetamide, N-methylpropioneamide, N-methylpyrrolidone, and the like. Examples of the ester solvents include diethyl carbonate, propylene carbonate, methyl acetate, ethyl acetate, .gamma.-butyrolactone, .gamma.-valerolactone, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, sec-butyl acetate, n-pentyl acetate, sec-pentyl acetate, 3-methoxybutyl acetate, methylpentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, benzyl acetate, cyclohexyl acetate, methylcyclohexyl acetate, n-nonyl acetate, methyl acetoacetate, ethyl acetoacetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol mono-n-butyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, glycol diacetate, methoxy triglycol acetate, ethyl propionate, n-butyl propionate, i-amyl propionate, diethyl oxalate, di-n-butyl oxalate, methyl lactate, ethyl lactate, n-butyl lactate, n-amyl lactate, diethyl malonate, dimethyl phthalate, diethyl phthalate, and the like. Examples of the hydrocarbon solvents include aliphatic hydrocarbon solvents such as n-pentane, i-pentane, n-hexane, i-hexane, n-heptane, i-heptane, 2,2,4-trimethylpentane, n-octane, i-octane, cyclohexane, and methylcyclohexane; aromatic hydrocarbon solvents such as benzene, toluene, xylene, mesitylene, ethylbenzene, trimethylbenzene, methylethylbenzene, n-propylbenzene, i-propylbenzene, diethylbenzene, i-butylbenzene, triethylbenzene, diisopropylbenzene, and n-amylnaphthalene; and the like. ] Among these, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, and cyclohexanone are preferable. These organic solvents may be used either individually or in combination [0089-0096]. Examples of the crosslinking catalyst (C) include amine compounds, phenol resins, amino resins, mercaptan compounds, hydrazides, polyphenol, polybasic acids, photoacid generators, thermal acid generators, and the like. Among these, it is preferable to use a photoacid generator or a thermal acid generator since a decrease in productivity or a deterioration in optical properties due to the remaining catalyst occurs to only a small extent [0087]. The crosslinking agent (B) that may be used for the resist lower layer film-forming composition according to one embodiment of the invention is a compound that forms a bond with another component (e.g., resin) or another crosslinkable molecule due to heat or an acid. Examples of the crosslinking agent (B) include polyfunctional (meth)acrylate compounds, epoxy compounds, hydroxymethyl group-substituted phenol compounds, alkoxyalkylated amino group-containing compounds, and the like. Examples of the polyfunctional (meth)acrylate compounds include trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, glycerol tri(meth)acrylate, tris(2-hydroxyethyl)isocyanurate tri(meth)acrylate, ethylene glycol di(meth)acrylate, 1,3-butanediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, bis(2-hydroxyethyl)isocyanurate di(meth)acrylate, and the like. Examples of the epoxy compounds include novolac-type epoxy resins, bisphenol-type epoxy resins, alicyclic epoxy resins, aliphatic epoxy resins, and the like. Examples of the hydroxymethyl group-substituted phenol compounds include 2-hydroxymethyl-4,6-dimethylphenol, 1,3,5-trihydroxymethylbenzene, 3,5-dihydroxymethyl-4-methoxytoluene[2,6-bis(hydroxymethyl)-p-cresol], and the like. Examples of the alkoxyalkylated amino group-containing compounds include nitrogen-containing compounds that include a plurality of active methylol groups in one molecule (e.g., (poly)methylol melamine, (poly)methylol glycoluril, (poly)methylol benzoquanamine, and (poly)methylol urea) wherein at least one of the hydrogen atoms of the hydroxyl groups of the methylol groups is substituted with an alkyl group (e.g., methyl group or butyl group), and the like. Note that the alkoxyalkylated amino group-containing compounds may be a mixture of a plurality of substituted compounds, and may include a self-condensed oligomer component. Such alkoxyalkylated amino group-containing compounds may also be used. Among these, alkoxyalkylated amino group-containing compounds are preferable. It is more preferable to use methylol melamine or methylol glycoluril. The crosslinking agent (B) is more preferably a compound that includes at least two crosslinkable functional groups. The term "crosslinkable functional group" used herein refers to a functional group that exhibits crosslinking reactivity with the polymer (A). Examples of the crosslinkable functional group include a glycidyl ether group, a glycidyl ester group, a glycidyl amino group, a methoxymethyl group, an ethoxymethyl group, a benzyloxymethyl group, an acetoxymethyl group, a benzoyloxymethyl group, a formyl group, an acetyl group, a vinyl group, an isopropenyl group, a dimethylaminomethyl group, a diethylolaminomethyl group, a dimethylolaminomethyl group, a diethylolaminomethyl group, a morpholinomethyl group, and the like. The compound that includes a crosslinkable functional group is preferably methoxymethyl glycoluril or methoxymethylmelamine, and particularly preferably hexamethoxymethylmelamine or tetramethoxymethyl glycoluril. These crosslinking agents (B) may be used either individually or in combination [0077-0083]. The resist lower layer film-forming composition may be applied by spin coating, roll coating, dip coating, or the like. The film is normally heated at 50 to 450.degree. C [0109].
Nakahara et al. 20120077124 does not exemplify the process where the underlayer compositions include a polymer with thiol/mercaptan (SH), azide (N3), -S(=O)-, alkyne, imine, ahdehyde, acetic acid, cyanide/cyano, allene, amine, phosphine, phosphite, aniline, pyridine or pyrrole group, the underlayer polymers are combined with a combination of acid generators, where the underlayer polymers are combined with a surfactant, where the underlayer compositions are baked at temperature other than 205 degrees C, where the underlayer polymers are combined with solvents other than PGME or where the resist is exposed using KrF or EUV
With respect to claims 1,3-4 and 7, it would have been obvious to modify the process of using composition of polymers A5 or A6 by replacing at least a portion of the hydroxy functional groups on the hydroxycontaining groups with amines based upon the disclosed equivalence at [0014-0015] with a reasonable expectation of forming a useful resist pattern, noting the equivalence disclosed. The carbonate -O-C(=O)-O and any remaining hydroxy moieties are considered to meet the polar group limitations.
With respect to claims 8 and 10-11 and 13, it would have been obvious to modify the process of using composition of polymers A5 or A6 by replacing at least a portion of the hydroxy functional groups on the hydroxycontaining groups with amines based upon the disclosed equivalence at [0014-0015] with a reasonable expectation of forming a useful resist pattern, noting the equivalence disclosed. The carbonate -O-C(=O)-O and any remaining hydroxy moieties are considered to meet the affinity group limitations.
With respect to claims 1,3,4,7,8,10-11,13,21,23-24 and 26-27, it would have been obvious to modify the process of using composition of polymers A5 or A6 by replacing at least a portion of the hydroxy functional groups on the hydroxycontaining groups with amines based upon the disclosed equivalence at [0014-0015] and replacing at least a portion of the solvent with alcohol solvents, ether solvents, ketone solvents, amide solvents, ester solvents, hydrocarbon solvents, a mixed solvent thereof, and the like. Examples of the alcohol solvents include monohydric alcohol solvents such as methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, sec-butanol, tert-butanol, n-pentanol, i-pentanol, 2-methylbutanol, sec-pentanol, tert-pentanol, 3-methoxybutanol, n-hexanol, 2-methylpentanol, sec-hexanol, 2-ethylbutanol, sec-heptanol, 3-heptanol, n-octanol, 2-ethylhexanol, sec-octanol, n-nonyl alcohol, 2,6-dimethyl-4-heptanol, n-decanol, sec-undecyl alcohol, trimethylnonyl alcohol, sec-tetradecyl alcohol, sec-heptadecyl alcohol, furfuryl alcohol, phenol, cyclohexanol, methylcyclohexanol, 3,3,5-trimethylcyclohexanol, benzyl alcohol, and diacetone alcohol; polyhydric alcohol solvents such as ethylene glycol, 1,2-propylene glycol, 1,3-butylene glycol, 2,4-pentanediol, 2-methyl-2,4-pentanediol, 2,5-hexanediol, 2,4-heptanediol, 2-ethyl-1,3-hexanediol, diethylene glycol, dipropylene glycol, triethylene glycol, and tripropylene glycol; polyhydric alcohol partial ether solvents such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, ethylene glycol monophenyl ether, ethylene glycol mono-2-ethyl butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monohexyl ether, propylene glycol methyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropyleneglycol monomethylether, dipropylene glycol monoethyl ether, and dipropylene glycol monopropyl ether; and the like. Examples of the ether solvents include diethyl ether, dipropyl ether, dibutyl ether, diphenyl ether, and the like Examples of the ketone solvents include acetone, methyl ethyl ketone, methyl n-propyl ketone, methyl n-butyl ketone, diethyl ketone, methyl i-butyl ketone, methyl n-pentyl ketone, ethyl n-butyl ketone, methyl n-hexyl ketone, di-i-butyl ketone, trimethylenonane, cyclopentanone, cyclohexanone, cycloheptanone, cyclooctanone, methylcyclohexanone, 2,4-pentanedione, acetonylacetone, acetophenone, and the like. Examples of the amide solvents include N,N'-dimethylimidazolidinone, N-methylformamide, N,N-dimethylformamide, N,N-dimethylformamide, acetamide, N-methylacetamide, N,N-dimethylacetamide, N-methylpropioneamide, N-methylpyrrolidone, and the like. Examples of the ester solvents include diethyl carbonate, propylene carbonate, methyl acetate, ethyl acetate, .gamma.-butyrolactone, .gamma.-valerolactone, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, sec-butyl acetate, n-pentyl acetate, sec-pentyl acetate, 3-methoxybutyl acetate, methylpentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, benzyl acetate, cyclohexyl acetate, methylcyclohexyl acetate, n-nonyl acetate, methyl acetoacetate, ethyl acetoacetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol mono-n-butyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, glycol diacetate, methoxy triglycol acetate, ethyl propionate, n-butyl propionate, i-amyl propionate, diethyl oxalate, di-n-butyl oxalate, methyl lactate, ethyl lactate, n-butyl lactate, n-amyl lactate, diethyl malonate, dimethyl phthalate, diethyl phthalate, and the like. Examples of the hydrocarbon solvents include aliphatic hydrocarbon solvents such as n-pentane, i-pentane, n-hexane, i-hexane, n-heptane, i-heptane, 2,2,4-trimethylpentane, n-octane, i-octane, cyclohexane, and methylcyclohexane; aromatic hydrocarbon solvents such as benzene, toluene, xylene, mesitylene, ethylbenzene, trimethylbenzene, methylethylbenzene, n-propylbenzene, i-propylbenzene, diethylbenzene, i-butylbenzene, triethylbenzene, diisopropylbenzene, and n-amylnaphthalene; and the like disclosed at [0089-0096] with a reasonable expectation of forming a useful resist pattern based upon the disclosure that these organic solvents may be used either individually or in combination with a reasonable expectation [0096]
With respect to claims 1,3,4,7,8,10-11,13,21,23-24 and 26-27, it would have been obvious to modify the process of using composition of polymers A5 or A6 by replacing at least a portion of the hydroxy functional groups on the hydroxy containing groups with amines based upon the disclosed equivalence at [0014-0015] and exposing the resist with KrF or EUV as taught at [0120] with a reasonable expectation of forming a useful resist pattern based upon the disclosure of these as useful exposure wavelengths.
With respect to claims 1,3,4,7,8,10-11,13,21,23-24 and 26-27, it would have been obvious to modify the process of using composition of polymers A5 or A6 by replacing at least a portion of the hydroxy functional groups on the hydroxy containing groups with amines based upon the disclosed equivalence at [0014-0015] and heating the underlayer at any temperature between 160-250 degrees C , which is within the 50 to 450.degree. C taught at [0109] with a reasonable expectation of successfully forming a useful resist pattern based upon this being within the disclosed useful temperature range.
With respect to claims 1,3,4,7-8,10-11,13,21,23-24 and 26-27, it would have been obvious to modify the process of using composition of polymers A5 or A6 by replacing at least a portion of the hydroxy functional groups on the hydroxy containing groups with amines based upon the disclosed equivalence at [0014-0015] and adding a surfactant such as nonionic surfactants, fluorine-based surfactants, and silicone surfactants. Examples of the nonionic surfactants include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, and polyoxyethylene oleyl ether; polyoxyethylene aryl ethers such as polyoxyethylene octyl phenyl ether and polyoxyethylene nonyl phenyl ether; polyethylene glycol dialkyl esters such as polyethylene glycol dilaurate and polyethylene glycol distearate; (meth)acrylic acid copolymers; and the like. Examples of the (meth)acrylic acid copolymers include Polyflow No. 57, Polyflow No. 95 (manufactured by Kyoeisha Chemical Co., Ltd.), and the like Examples of the fluorine-based surfactants include fluoroethers such as 1,1,2,2-tetrafluorooctyl (1,1,2,2-tetrafluoropropyl)ether, 1,1,2,2-tetrafluorooctyl hexyl ether, octaethylene glycol di(1,1,2,2-tetrafluorobutyl)ether, hexaethylene glycol (1,1,2,2,3,3-hexafluoropentyl)ether, octapropylene glycol di(1,1,2,2-tetrafluorobutyl)ether, and hexapropylene glycol di(1,1,2,2,3,3-hexafluoropentyl)ether; sodium perfluorododecylsulfonate; fluoroalkanes such as 1,1,2,2,8,8,9,9,10,10-decafluorododecane and 1,1,2,2,3,3-hexafluorodecane; sodium fluoroalkylbenzenesulfonates; fluoroalkyloxyethylene ethers; fluoroalkyl ammonium iodides; fluoroalkyl polyoxyethylene ethers; perfluoroalkylpolyoxyethanols; perfluoroalkyl alkoxylates; fluorine-containing alkyl esters; and the like. Examples of commercially available products of the fluorine-based surfactants include EFTOP EF301, EFTOP EF303, EFTOP EF352 (manufactured by JEMCO, Inc.), Megafac F171, Megafac F172, Megafac F173 (manufactured by DIC Corporation), Fluorad FC430, Fluorad FC431 (manufactured by Sumitomo 3M Ltd.), Asahi Guard AG710, Surflon S-382, Surflon SC-101, Surflon SC-102, Surflon SC-103, Surflon SC-104, Surflon SC-105, Surflon SC-106 (manufactured by Asahi Glass Co., Ltd.), FTX-218 (manufactured by NEOS Co., Ltd.), and the like. Examples of the silicone surfactants include SH200-100cs, SH28PA, SH30PA, ST89PA, SH190 (manufactured by Dow Corning Toray Silicone Co., Ltd.), KP341 (organosiloxane polymer) (manufactured by Shin-Etsu Chemical Co., Ltd.), and the like taught at [0097-0102] with a reasonable expectation of improving the coating of the underlayer.
With respect to claims 1,3,4,7,8,10-11,13,21,23-24 and 26-27, it would have been obvious to modify the process of using composition of polymers A5 or A6 by replacing at least a portion of the hydroxy functional groups on the hydroxy containing groups with amines based upon the disclosed equivalence at [0014-0015] and adding a further acid generator, such as thermal acid generator disclosed at [0087] with a reasonable expectation of forming a useful resist pattern.
In the arguments of 2/126/2026, the applicant argues that the references do not teach the recited photoresist affinity groups (claim 1 and dependent claims) or the recited polar groups (claims 8, 21 and those dependent upon them) As indicated in the interview summary, Nakahara et al. 20120077124 teaches amine groups ([0020]) as an alternative to hydroxy groups, both of which are polar and adhesive to inorganic materials. The rejection as modified stands.
Claims 1-13 and 21-27 are rejected under 35 U.S.C. 103 as being unpatentable over Nakahara et al. 20120077124, in view of Kamimura et al. 20190258168.
Nakahara et al. 20120077124 does not teach the use of resists including the metals recited in claims 12 or 24.
It would have been obvious to modify the embodiments exemplified or rendered obvious by the teachings of Nakahara et al. 20120077124 by adding which is a complex of chromium, iron, cobalt, nickel, tin or zirconium taught by Kamimura et al. 20190258168 to improve the sensitivity of the resist to ArF as taught at [0302].
Claims 1-13 and 21-27 are rejected under 35 U.S.C. 103 as being unpatentable over Nakahara et al. 20120077124, in view of Kamimura et al. 20190258168, further in view of Cardineau et al. 20210011383.
With respect to claims 1-13 and 21-27, it would have been obvious to modify the process of using compositions rendered obvious by the combination of Nakahara et al. 20120077124 and Kamimura et al. 20190258168 by adding (or replacing at least a portion of the hydroxy groups with) an amine group repeating unit as taught in Nakahara et al. 20120077124 and one of an amine, imine, thiol (SH or sulfinic acid [-S(=O)-OH] moiety taught at adhesion promoting moieties in Cardineau et al. 20210011383 at [0048,0058] with a reasonable expectation of forming a useful resist pattern based upon the disclosed equivalence with hydroxy/alcohol moieties to improve adhesion between the underlayer and the organometallic resist and the underlayer and the substrate in Cardineau et al. 20210011383 at [0028,0047-0048,0058] and Hatakeyama et al. 20080220381 at [0063].
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.
Claims 1,3,4,7,8,11,12,21 and 24-27 are rejected on the ground of nonstatutory double patenting as being unpatentable over claims 1-20 of U.S. Patent No.11782345.
Claim 1 recites:
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Other independent claims are similar.
Claims 5 and 6 recite
Although the claims at issue are not identical, they are not patentably distinct from each other because the claims of the patent recite a fluorine containing group as part of the polarity switching group and the photoresist affinity group includes —I, —Br, —Cl, —NH.sub.2, —SH, —N.sub.3, —S(═O)—, imine, aldehyde, amide, and sulfone and the claims rejected under this heading do not require that the polar and affinity groups be different and it would have been obvious to use composition within the scope of the claims where the affinity and polar groups are NH2 (amine), SH, (thiol), N3 (azide) , —S(═O)—, imine or aldehyde with a reasonable expectation of forming a useful resist pattern. Further it would have been obvious to one skilled in the art to perform the processes where the limitations of claims 5 and 6 are included. Photoacid generators are inherently able to thermally generate acid.
Applicant's amendment necessitated the new ground(s) of rejection presented in this Office action. Accordingly, THIS ACTION IS MADE FINAL. See MPEP § 706.07(a). Applicant is reminded of the extension of time policy as set forth in 37 CFR 1.136(a).
A shortened statutory period for reply to this final action is set to expire THREE MONTHS from the mailing date of this action. In the event a first reply is filed within TWO MONTHS of the mailing date of this final action and the advisory action is not mailed until after the end of the THREE-MONTH shortened statutory period, then the shortened statutory period will expire on the date the advisory action is mailed, and any nonprovisional extension fee (37 CFR 1.17(a)) pursuant to 37 CFR 1.136(a) will be calculated from the mailing date of the advisory action. In no event, however, will the statutory period for reply expire later than SIX MONTHS from the mailing date of this final action.
Any inquiry concerning this communication or earlier communications from the examiner should be directed to Martin J Angebranndt whose telephone number is (571)272-1378. The examiner can normally be reached 7-3:30 pm EST.
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MARTIN J. ANGEBRANNDT
Primary Examiner
Art Unit 1737
/MARTIN J ANGEBRANNDT/Primary Examiner, Art Unit 1737 March 20, 2026