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 .
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 – 4, 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 ligan-capped organic polymers, 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 nanoparticles- exemplary stripping agents include indium nitrate.
Photosensitive cations covered by the disclosure include sulfonium cations such as in [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)
Alternative methods of patterning a film composed of inorganic particles in a sol-gel is described in [0040], wherein the film comprises inorganic molecular precursors, 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). The unexposed regions can be washed away (claim 14). The 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. 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 (claim 2, 3, and 4), .
In [0084], 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) to remove solvent. 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.
Conclusion
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/A.P.T./Examiner, Art Unit 1737
/JONATHAN JOHNSON/Supervisory Patent Examiner, Art Unit 1734
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