Detailed Action
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 .
Response to Amendment
Applicant’s Amendment filed 12/23/2025 has been entered and is being considered. Claims 1, 3, 4, 5, 6, 10, 11, 14, 15, 16, 17, and 18 are amended.
Response to Arguments
Applicant’s Amendment and arguments based thereon regarding claim 4, 14, and 15 have changed the scope of the claim to as to overcome the prior art. As such, the rejection over 35 USC 103 for claims 4, 14, and 15 as set forth are withdrawn.
Applicant’s Amendment and arguments based thereon regarding claims 1, 3, 5, 6, 10, 11, 16, 17, and 18 are considered but are not persuasive as for the reasons below:
As a matter of claim interpretation: The instant claim 1 and all dependents except for claim 4 and 14 use “comprising” and as such any unrecited components may be present, including organic components – the scope of the claimed composition does not exclude organometallic embodiments comprising organic photoacid generators, polymers, and other components not explicitly recited in the claims (except for Claim 4 and 14, which do explicitly exclude polymeric materials and photoacid generators).
Regarding Claims 1, 17, and 18, the Examiner disagrees with the characterization that Talapin fails to teach metal nitrate hydrates and that Talapin and Telecky only disclose oxo-clusters, organometallic frameworks, and ligand-stabilized nanocrystals. Talapin explicitly discloses, as was stated in the prior office action, that an embodiment may comprise patterning a film composed of inorganic particles in a sol-gel as described in [0040], wherein the film comprises inorganic molecular precursors that are exposed to a solution including PAG cations and anions, wherein the photogenerated protons accelerate hydrolysis and cause polymerization of precursors in the portions of the film that are irradiated to form particles. The unexposed regions can be washed away (therefore, there is a solubility switch). The resultant inorganic particles can be nanocrystals such as aluminum oxide, zirconium oxide, silicon oxide, and InGaZnO (IGZO) materials – molecular precursors for these compounds comprise a mixture of aluminum tris-sec-butoxide, zirconium acetyl acetonate, zinc acetate, tetraethoxysilane, and/or a mixture of indium nitrate, gallium nitrate, and zinc acetate respectively. The unexposed portions of the film remain unreacted and can be removed. In the Materials and Methods section ([0053]) recites that indium nitrate hydrate (99.99% Aesar) is used.
In [0064], IGZO sol-gel precursor solutions were prepared using a modified recipe from Y. S. Rim et al., Boost Up Mobility of Solution-Processed Metal Oxide Thin-Film Transistors via Confining Structure on Electron Pathways. Adv. Mater. 26, 4273-4278 (2014). Indium nitrate hydrate, gallium nitrate hydrate, and zinc acetate hydrate were dissolved in 2-methoxyethanol and stirred at 70 degrees Celsius for an hour, then filtered, and stored in darkness for future use. These precursor solutions are mask-wise exposed to radiation as described in [0081] and [0084]-[0085], where IGZO sol-gel precursors were mixed with a substituted triphenylsulfonium triflate solution, then spin-coated onto substrates. An optical patterning process was performed with a UV-light source equipped with a mercury vapor 254nm lamp or a dual 254nm/365nm wavelength lamp and a mask. An alternative embodiment is described in Example 3, wherein an e-beam lithography process is carried out.
The reference Telecky is relevant to the reference and the application by way of its focus on metal-containing resist compositions and lithographic exposure. In response to applicant's argument that the examiner's conclusion of obviousness is based upon improper hindsight reasoning, it must be recognized that any judgment on obviousness is in a sense necessarily a reconstruction based upon hindsight reasoning. But so long as it takes into account only knowledge which was within the level of ordinary skill at the time the claimed invention was made, and does not include knowledge gleaned only from the applicant's disclosure, such a reconstruction is proper. See In re McLaughlin, 443 F.2d 1392, 170 USPQ 209 (CCPA 1971).
Concerning the limitation of claim 1 “wherein the chemical changes comprise radiation-induced decomposition of nitrate groups resulting in a solubility switch of the film” this limitation is met inherently by the nature of exposure and the chemical precursors present. Talapin and Telecky together explicitly teach the indium nitrate hydrate composition(s) and an EUV exposure – this chemical transformation is a property of the reaction, and the reaction must occur when the corresponding components (the indium nitrate hydrate and the incoming radiation) are present. The components required are present, and as such the corresponding reaction must be present – and the examiner points out that applicant’s independent claim has not excluded additional components.
Concerning the limitation of claims 10 and 17 where the chemical changes comprise radiation-induced conversion of the metal nitrate hydrate to a metal oxide, this is also inherently met by the references – the precursor solutions are converted to IGZO sol-gels upon exposure, where IGZO stands for “Indium Gallium Zirconium Oxide”, which is a metal oxide species.
Concerning claim 5, the limitation of the claim “sufficient to induce chemical decomposition of nitrate groups without bulk thermal conversion” is considered inherent when the limitation “an electron beam with an energy of less than 1 kilo electron volt (keV)” is met as was set forth in the prior office action – Kocsis teaches an electron beam disclosure ranging from 5 eV to 200keV as recited at [0038] and was mentioned in the previous office action. This range completely encompasses the claimed range of “less than 1keV” – the reference teaches embodiments meeting the limitations of the claim and its silence on bulk thermal conversion is interpreted as an affirmation that bulk thermal conversion does not happen during exposure.
Concerning claim 7, the art does teach a mask exposure, and such was stated in the prior office action.
After further search and consideration, the examiner makes a new grounds over claim 15 over the same references as set forth in the prior office action, necessitated by amendment.
Concerning claim 15, Telecky discloses a post-application bake ranging from 45 degrees to 250 degrees Celsius at a time from 45 seconds to 10 minutes to remove solvent – applicant’s own disclosure in Figure 7A recites temperatures of up to 100 degrees in a post-application bake that do not undergo thermal conversion. A person having ordinary skill in the art would consider the entire range of the disclosure and as such the reference covers embodiments that would not thermally convert the precursors of Talapin.
After further search and consideration, the examiner makes a new grounds of rejection over claims 1-4, 6, 7, 9-10, and 15-18 in view of Shiratani et al (US 20190227434 A1), and further rejections over claims 11 and 14 in view of Shiratani and secondary references. Applicant’s amendment to the claims necessitated the new grounds of rejection.
Claim Rejections - 35 USC § 103
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.
The factual inquiries for establishing a background for determining obviousness under 35 U.S.C. 103 are summarized as follows:
1. Determining the scope and contents of the prior art.
2. Ascertaining the differences between the prior art and the claims at issue.
3. Resolving the level of ordinary skill in the pertinent art.
4. Considering objective evidence present in the application indicating obviousness or nonobviousness.
Claim(s) 1 – 3, 6 -10, 14-16, and 17-18 is/are rejected under 35 U.S.C. 103 as being unpatentable over Talapin et al (US 20200249570 A1) and Telecky et al (US 20210271170 A1).
Regarding claims 1- 4, 6-10, 14-16, and 17-18, Talapin discusses ligand-capped inorganic particles, films derived therefrom, and methods of patterning the films. Additional disclosure discusses devices incorporating said films. Ligands bound to the inorganic particles include cation-anion pairs, where at least one of the cation or anion is photosensitive.
Ligand-capped nanocrystals covered by the discloses include Group II through Group VI nanocrystals, such as InAs, InSb, InP, and others ([0021]-[0026].
Photosensitive cations can be associated with a variety of inorganic anions, such as metal anions, metal halide anions, and others such as nitrate. Stripping agents can be used to introduce these anions into the solution by removing organic anions bound to inorganic nanoparticle s- exemplary stripping agents include indium nitrate.
Photosensitive cations covered by the disclosure include sulfonium cations such as in [0027]-[0029]. Other cations may be photobase generators as discussed in [0031].
Photosensitive anions are discussed from [0033]-[0034], such as dithiocarbamates.
Films are generated from these compositions by coating a substrate with a dispersion of these particles and then allowing the coating to dry. The resultant films are then patterned by exposing a portion of the film to radiation while a second portion is protected from radiation using a mask. The film is then treated so as to remove either the first or second portion with a developing agent ([0035]-[0037]. Films formed by these compositions may range from 5nm-200nm (claim 6) in thickness for use in thin-film lithography.
Alternative/additional methods of patterning a film composed of inorganic particles in a sol-gel are described in [0040], wherein the film comprises inorganic molecular precursors that are exposed to a solution including PAG cations and anions, wherein the photogenerated protons accelerate hydrolysis and cause polymerization of precursors in the portions of the film that are irradiated (claim 10) to form particles. The unexposed regions can be washed away (claim 14). The resultant inorganic particles can be nanocrystals such as aluminum oxide, zirconium oxide, silicon oxide, and InGaZnO (IGZO) materials – molecular precursors for these compounds comprise a mixture of aluminum tris-sec-butoxide, zirconium acetyl acetonate, zinc acetate, tetraethoxysilane, and/or a mixture of indium nitrate, gallium nitrate, and zinc acetate respectively. The unexposed portions of the film remain unreacted and can be removed. In the Materials and Methods section ([0053]) recites that indium nitrate hydrate (99.99% Aesar) is used.
In [0064], IGZO sol-gel precursor solutions were prepared using a modified recipe from Y. S. Rim et al., Boost Up Mobility of Solution-Processed Metal Oxide Thin-Film Transistors via Confining Structure on Electron Pathways. Adv. Mater. 26, 4273-4278 (2014). Indium nitrate hydrate, gallium nitrate hydrate, and zinc acetate hydrate were dissolved in 2-methoxyethanol and stirred at 70 degrees Celsius for an hour, then filtered, and stored in darkness for future use (claims 2, 3).
In [0081] and [0084]-[0085], IGZO sol-gel precursors were mixed with a substituted triphenylsulfonium triflate solution, then spin-coated onto substrate (claim 18). An optical patterning process was performed with a UV-light source equipped with a mercury vapor 254nm lamp or a dual 254nm/365nm wavelength lamp and a mask. An alternative embodiment is described in Example 3, wherein an e-beam lithography process is carried out.
Various experimental embodiments disclose glass, SiO2, and silicon substrates of various sizes. These wafers are described as ranging from 1cm x 1cm and 1.5cm x 1.5cm (claim 8).
Talapin does not disclose a specific EUV or low-energy electron exposure – it teaches a generic electron beam exposure.
This limitation is met by Telecky.
Telecky discloses a method of processing organometallic coatings, wherein a coated wafer is subjected to process delays and heating steps so as to improve the development of the pattern.
Telecky’s disclosure arrives at metal oxide-bearing compositions through the use of a tin-based precursor solution, which arrives at a metal-oxide and metal-oxide-hydroxide embodiment upon exposure to radiation. The compositions of Telecky are coated onto a wafer and then dried using a post-application bake (PAB – [0032], claim 15) ranging from 45 degrees to 250 degrees Celsius at a time from 45 seconds to 10 minutes to remove solvent (the Examiner points out that as per applicant’s own specification as per Fig 7A, a post-application bake may take place at a temperature ranging up to 100 degrees Celsius without thermal conversion, with longer bake times at lower temperatures also not showing thermal conversion).
A post-coating delay time may be enforced prior to exposure – exposure is performed using an electron beam or a light source over a wide range of wavelengths such as extreme ultraviolet at 13.5 nm ( [0033]-[0036], claim 9), where exposure may be performed with a mask or with a direct-write radiation beam exposure (claim 7 – [0034]). After exposure, a post-exposure bake (PEB – claim 16, [0037]-[0043] and other post-exposure processing is performed. A developer is then used to remove unwanted portions of the coating – for negative development, methanol is a preferred developer.
A person of ordinary skill in the art would have found it obvious to incorporate the EUV exposure and baking steps of Telecky into the method of Talapin with the expectation that such steps would result in a patterned resist having high resolution imparted by the manipulations thereof, such as the in the developing and exposure steps.
Claim(s) 5 and 11 is/are rejected under 35 U.S.C. 103 as being unpatentable over Talapin et al (US 20200249570 A1) and Telecky et al (US 20210271170 A1) as applied to claim 1 above, and further in view of Kocsis et al (US 20200124970 A1).
Regarding Claim 5 and claim 11, Talapin and Telecky disclose the limitations of the claim as discussed above regarding claim 1.
Neither Talapin nor Telecky disclose a specific energy for an electron beam – Telecky does teach electron beams but does not specify the energy thereof.
This limitation is met by Kocsis.
Kocsis discloses a patterned organometallic photoresist composition and methods of arriving at such, as well as rinse processes for post-irradiation processing.
The patterned photoresists of Kocsis may be generic organometallic resist compositions, or as an exemplified embodiment they may be alkyl tin oxide hydroxide compositions. The coating of the organometallic resist composition is performed so as to deposit the composition onto a substrate. A pre-exposure bake may be performed ([0033]), after which the material is exposed to radiation. The radiation may be an electron beam, where suitable energies will range from 5eV to 200keV, encompassing the claimed range. After exposure, a baking step may be performed and then a developer is used to process the exposed resist. The structure (wafer plus assembly atop) may be dipped or immersed in the developer. Development may be performed from 5 seconds to 30 minutes.
A person of ordinary skill in the art would have found it obvious to arrive at the claimed invention from the general disclosure of the reference, which teaches e-beam patterning to desirable for patterning metal-containing resists to achieve high resolution patterns.
Claim(s) 12 and 13 are rejected under 35 U.S.C. 103 as being unpatentable over Talapin et al (US 20200249570 A1), Telecky et al (US 20210271170 A1), and Kocsis et al (US 20200124970 A1) as applied to claim 1 above, and further in view of Liu et al (US 20210364924 A1).
Regarding Claims 12 and 13, Talapin, Telecky, and Kocsis disclose the limitations of the claim as required by claim 11 as discussed above.
These references fail to disclose a specific ratio of developer solvents in a developer composition used for developing a processed resist pattern. Kocsis does teach a range of development times that read upon the claim limitations of claim 13, but does not meet the claim limitations of claim 12.
These limitations are met by Liu.
Liu teaches a method of manufacturing a semiconductor device comprising the provision of a photoresist layer over a substrate and the exposure and development thereof to form a pattern (abstract).
The resist layer is described in [0046]-[0055], where the resist comprises metallic compounds of tin, indium , bismuth, and other transition metals. After deposition, the resist is then exposed to radiation and a post-exposure bake may be performed.
Development is performed using a mixture of solvents, wherein a first solvent comprises 60 to 99wt% of a first solvent such as butyl acetate or hexane. A second solvent is present in 0.1wt% to 40wt% by weight of a second solvent or mix thereof, such as methanol and/or acetic acid. When combined the sum of the amounts of acetic acid and methanol must comprise 0.1 to 40wt%. The developer may also include water in a concentration of 0.001wt% to about 30wt% (See [0069]-[0081]). For example, the developer composition of the reference may comprise, butyl acetate in 79 wt%, methanol in 15wt%, water in 5wt%, and acetic acid in 1wt% as these amounts and solvents are all enclosed within the disclosure. The reference asserts that varying from the disclosed developer solvents and concentrations thereof would have deleterious effects on performance – implying that the solvents and concentrations disclosed demonstrate superior performance with regards to parameters such as line edge roughness and line width roughness. Further, the development of a resist composition may take place for 10 seconds to 10 minutes.
A person of ordinary skill in the art would have found it obvious to arrive at the claimed invention from the general disclosure of Liu, which ascribes improved patterning performance to the developers and concentrations taught therein, and to incorporate such developer compositions and times into the method of Talapin, Telecky, and Kocsis in order to arrive at an improved method and resultant product.
Claim(s) 1-4, 6, 7, 9-10, and 15-18 is/are rejected under 35 U.S.C. 103 as being unpatentable over Shiratani et al (US 20190227432 A1) as evidenced by a disclosure from Indium Corp
Regarding Claims 1-4, 6, 7, 9-10, and 15-18 , Shiratani is directed to a radiation-sensitive composition comprising particles that include a metal oxide, a cation that includes a metal, and an anion, wherein the anion is the conjugate base of an acid that has a pKa of no more than 3.
The composition comprises particles (A) as described from [0012]-[0103]
The cation (B) includes a metal, as described from [0104]-[0134], where that cation is preferably a copper, zinc, barium, lanthanum, cerium, yttrium, silver, or indium, where these cations may be present in Mn+ form or be in the form of a metal complex. Preferred ligands present in a metal complex include acetylacetone (acetylacetonate ligand) as per [0118].
The anion (C) is discussed from [0135]-[0197] is preferably a conjugated base of an acid (I) having a pKa of no more than 3, such as sulfonic acid or nitric acid. The conjugated base of nitric acid is the nitrate anion.
Cation (B) and anion (C) constituted the metal salt (X) described from [0198]-[0204]. More than one salt (X) may be present as per [0197], where the cation may be another metal and the anion may be nitrate, for example - zinc nitrate (claim 3). The salt functions by generating an acid through the action of the
Additional components include a carboxylic acid (D), which is used to prevent the aggregation of particles, and a solvent (E ) as described from [0205]-[0247].
Optional components – which are not required components - are discussed from [0248]-[0269]. Optional components are not required in the sum total of the embodiments covered by the disclosure of Shiratani and as such the disclosure covers embodiments that do not feature these components. As such, these embodiments composition are free of polymeric materials and photoacid generators – the disclosure contemplates a composition comprising indium nitrate salt in solution with metal particles, a carboxylic acid, and solvent (claim 4).
As per [0011], the composition, upon exposure to incident radiation, generates a secondary electron from the metal cation (B) which generates the acid from the anion (C), which acts upon the particles (A) and the cation (B), and leads to a change of solubility.
The components of the composition are mixed and filtered to produce solutions for use in patterning as per [0270], wherein the composition is developable with alkali or with organic solvents as per [0271]. The composition is applied such as by (spin-coating) to a substrate, then prebaked as needed to remove solvent to arrive at a predetermined thickness, where the temperature of the prebake ranges from 60 degree Celsius to 140 degrees Celsius for between 5 seconds and 10 minutes (the Examiner points out that as per applicant’s own specification as per Fig 7A, a post-application bake may take place at a temperature ranging up to 100 degrees Celsius without thermal conversion, with longer bake times at lower temperatures also not showing thermal conversion – claim 15). After, the composition is exposed through a mask to radiation such as a 13.5 nm EUV ray (claim 6, claim 7, and claim 9). After exposure, an optional post-exposure bake may be performed (claim 16), and then a developer is used - organic developer solutions are used to obtain negative tone patterns (See [0272]-[0286]) by removing the unexposed regions.
The reference does not explicitly disclose a metal nitrate hydrate salt as the salt (X). However, indium nitrate is a hygroscopic salt that readily takes in water from the environment – meaning that hydrated indium nitrate may be introduced even when ostensibly “anhydrous” indium nitrate is used, and indium nitrate hydrate is readily available for purchase as evidenced by the disclosure from Indium Corp (see attached document). Further, indium nitrate and indium nitrate hydrate are substantially structurally similar – the only difference being the associated water molecules to the salt. A person having ordinary skill in the art would consider the hydrated salt a likely source of indium cations and nitrate anions akin to the anhydrous salt and expect them to behave similarly once incorporated into the composition.
Claim(s) 11 and 14 is/are rejected under 35 U.S.C. 103 as being unpatentable over Shiratani et al (US 20190227432 A1) as evidenced by a disclosure from Indium Corp
claim 1 above, and further in view of Kocsis et al (US 20200124970 A1).
Regarding claim 11 and 14, Shiratani teaches the limitations of the claim as discussed above regarding claim 1.
Shiratani does not disclose the explicit submerging of an exposed resist film in developer, rather teaching that development may be performed but not specific as to development methods
This limitation is met by Kocsis.
Kocsis discloses a patterned organometallic photoresist composition and methods of arriving at such, as well as rinse processes for post-irradiation processing.
The patterned photoresists of Kocsis may be generic organometallic resist compositions, or as an exemplified embodiment they may be alkyl tin oxide hydroxide compositions. The coating of the organometallic resist composition is performed so as to deposit the composition onto a substrate. A pre-exposure bake may be performed ([0033]), after which the material is exposed to radiation. The radiation may be an electron beam. After exposure, a baking step may be performed and then a developer is used to process the exposed resist. The structure (wafer plus assembly atop) may be dipped or immersed in the developer. Development may be performed from 5 seconds to 30 minutes.
Kocsis and Shiratani are both directed to lithographic patterning methods including the application of metal-containing compositions to wafers, exposure of these compositions to radiation, and development of the exposed wafers. A person having ordinary skill in the art would consider the disclosure of Kocsis relevant to both Shiratani and the claimed invention in view of this commonality of method steps.
A person of ordinary skill in the art would have found it obvious to arrive at the claimed invention by incorporating the submerging/immersion of the exposed wafer of Shiratani into a developer as contemplated by Kocsis to arrive at a developed wafer having a pattern disposed thereon.
Conclusion
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 ANDREW PRESTON TRAYWICK whose telephone number is (571)272-2982. The examiner can normally be reached Monday - Friday 8-5.
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If attempts to reach the examiner by telephone are unsuccessful, the examiner’s supervisor, Sally Merkling can be reached at (571) 272-6297. The fax phone number for the organization where this application or proceeding is assigned is 571-273-8300.
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/A.P.T./Examiner, Art Unit 1737
/SALLY A MERKLING/SPE, Art Unit 1738
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