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 .
Priority
Receipt is acknowledged of certified copies of papers required by 37 CFR 1.55.
Information Disclosure Statement
The information disclosure statement (IDS) submitted on 11/02/2023, 05/05/026, are being considered by the examiner.
Claim Rejections - 35 USC § 102
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.
Claim(s) 1-4, 9-11, and 13-16 is/are rejected under 35 U.S.C. 102(a)(1) and (a)(2) as being anticipated by Shibayama et al (US 20170153549 A1).
Regarding Claims 1, 4, 9-11, and 13-16, Shibayama disclsoses a resist underlayer film forming composition for lithography comprising an aliphatic polycyclic structure including a hydrolysable silane, a hydrolysis product thereof, a condensation-hydrolysis product thereof, or a combination thereof (Abstract).
The silane is discussed from [0011]- [0058] and conforms to general formula (I) presented at [0011].
PNG
media_image1.png
26
334
media_image1.png
Greyscale
Where:
R1 is an organic group having an aliphatic polycyclic structure and is bonded to the Si atom through a silicon-carbon bond
Subscript a is 1
R2 is an alkyl or haloalkyl group, or an aryl or haloaryl group, or an alkoxyaryl group, or an alkenyl group, or an organic group that has an epoxy, acryloyl, methacryloyl, mercapto, amino, or cyano group – where R2 is bonded to the silicon atom by a silicon-carbon bond
Subscript b is 0-2
The sum of a and b is an integer of 1-3
R3 is an ethoxy group
Examples of the hydrolysable silane are depicted at [0049]- [0051], where T is an ethyl group.
An additional hydrolysable silane is added to the composition, where this saline may be one or both of a silane conforming to Formulas (2) and/or (3), presented at [0014] and further discussed at [0052]- [0058].
Specific examples of the polysiloxane product made from the hydrolysis-condensation of the silanes discussed by the reference are depicted in Formulas (2-1) through (2-22) at [0059].
In the experimental examples, Example 10 (See Table 2) comprises:
The Si polymer of Synthesis Example 4 (2 parts by mass)
Maleic acid (MA) (0.02 parts)
monotriphenylsulfonium maleate (curing catalyst – TPSMA) (0.06 parts) (claim 9)
triphenylsulfonium camphorsulfonate (Additive – TPSCS) (0.1 part) (claim 11, where the reference describes this additive to be an acidity adjuster at [0120]- [0122])
propylene glycol methyl ether (PGME) (15 parts)
propylene glycol ethyl ether (PGEE) (65 parts)
propylene glycol monomethyl ether acetate (PGMEA) (5 parts)
water (15 parts) (claim 10)
The Si polymer of Synthesis example 4 is the polymer of formula (2-3) (see [0156]).
PNG
media_image2.png
182
344
media_image2.png
Greyscale
Where the composition used to make the polymer comprises 70mol% tetraethoxysilane, 20mol% methyltriethoxysilane, and 10mol% t-butyl-5-(triethoxysilyl)bicyclo[2.2.1]
heptane-2-carboxylate (see [0156] – claim 4, where the range of ester-bearing subunits is 0.1 to 10mol% of all siloxane subunits is anticipated by the 10mol% of the reference),
The composition, Example 10, of Shibayama meets the limitations of claim 1 for where it comprises:
a solvent (PGME, PGEE, PGMEA, and Water)
a polysiloxane containing a siloxane unit structure having an ester
As per the experimental procedure at [0196]- [0198], an organic underlayer film A was formed onto a silicon wafer (a substrate) and baked. After, each of the experimental compositions (such as Example 10) were applied to the organic underlayer film A and then baked to form a silicon-containing resist underlayer film B (claim 14 and 15). After, a commercial photoresist solution was spin-coated onto the film(s) B to form a photoresist film C (claim 16). Exposure was performed using an ArF exposure apparatus at 193nm using a photomask with a line-and-space pattern, after which a post-bake was performed and then the post-baked assembly was developed using an aqueous tetramethylammonium hydroxide developer.
At [0205]- [0206], Example 10 was applied to an organic underlayer film A, baked to form a silicon-containing underlayer film B, and an EUV photoresist film was deposited atop the film B. An EUV exposure was performed, a post-exposure bake was performed after exposure, and an alkaline development and subsequent rinse treatment were used to form the resist pattern (claim 13 – the composition of Example 10 is used in an EUV lithographic process as a resist underlayer film).
Regarding Claims 2 and 3, claim 2 appears to be written as a product-by-process claim, where the structure of the product (the siloxane unit structure having an ester structure contained in the polysiloxane [A]) is made by the process (formed by a reaction between a hydroxy group and/or an epoxy group and a compound selected from the group consisting of a carboxylic acid, dicarboxylic acid, and a dicarboxylic acid anhydride). See MPEP 2123 - the patentability of the claim is based on the product, not the method of production.
The Example 10 of the composition bears the siloxane (2-3) having the following structure as mentioned above:
PNG
media_image2.png
182
344
media_image2.png
Greyscale
The third subunit structure comprises an ester and as such meets the product limitations of the claims. Further, the structure meets the limitations of the claim 3 where the carboxylic acid-derived fragment of the ester bears an alicyclic ring (norbornane ring).
Claim(s) 1-4, 6-7, 10, and 14-15 is/are rejected under 35 U.S.C. 102(a)(1) and (a)(2) as being anticipated by Shibayama et al (WO 2019/124514 A1, published 06/27/2019- US 20210054231 A1 used in lieu of translation, hereafter Shibayama-2).
Regarding Claims 1, 4, 10, and 14-15, Shibayama-2 disclsoses a resist underlayer film forming composition for lithography comprising an aliphatic polycyclic structure including a hydrolysable silane, a hydrolysis product thereof, a condensation-hydrolysis product thereof, or a combination thereof (Abstract).
The silane is discussed from [0020]- [0091] and conforms to general formula (I) presented at [0020] and [0056].
PNG
media_image1.png
26
334
media_image1.png
Greyscale
Where:
R1 is an organic group having a multiple bond structure between a carbona tom and a carbon/oxygen/nitrogen/epoxide-containing group/sulfur-containing group/amide-containing group/primary to tertiary ammonium group/ or other group described in [0058], and is bonded to the Si atom through a silicon-carbon bond
Subscript a is 1
R2 is an alkyl– where R2 is bonded to the silicon atom by a silicon-carbon bond
Subscript b is 0-2
The sum of a and b is an integer of 1-3
R3 is an alkoxy group or acyloxy group or halogen group.
Examples of the hydrolysable silane are depicted at [0085], where T is a group corresponding to R3.
An additional hydrolysable silane is added to the composition, where this saline may be one or both of a silane conforming to Formulas (2) and/or (3), presented at [0060] and further discussed at [0061]- [0067].
Specific examples of the polysiloxane product made from the hydrolysis-condensation of the silanes discussed by the reference are depicted in Formulas (A-1) through (A-19) at [0092].
Experimental examples are tabulated at tables 1-3 - The examiner notes that while the Example 1 appears to use “Synthesis example 12” – all of the synthetic examples recited in tables 1-3 appear to have an extra “2” digit – where the numbers start at 12 and continue as 22, 32,42,52,62. As there are no synthetic examples recited higher than 23 ([0211]), it is apparent that the tables contain a typographical error, where the additional “2” is referring to the parts by mass of the polymer. Example 1 comprises Synthesis Example 1 in 2 parts by mass and is not Synthesis example 12, Example 12 comprises Synthesis Example 12 in 2 parts by mass and is not Synthesis Example 122, and so forth.
In the experimental examples, Example 23 (See Table 1) comprises:
The Si polymer of Synthesis Example 1 (2 parts by mass)
Maleic acid (MA) (0.06 parts)
Triphenylsulfonium nitrate (TPSNO3) (0.6 parts)
propylene glycol methyl ether (PGME) (38 parts)
propylene glycol ethyl ether (PGEE) (40parts)
propylene glycol monomethyl ether acetate (PGMEA) (10 parts)
water (12 parts) (claim 10)
The Si polymer of Synthesis example 1 is the polymer of formula (A-1) (see [0092]).
PNG
media_image3.png
200
362
media_image3.png
Greyscale
PNG
media_image4.png
68
96
media_image4.png
Greyscale
Where the composition used to make the polymer comprises 70mol% tetraethoxysilane, 5mol% phenyltrimethoxysilane, 15mol% methyltriethoxysilane, and 10mol% acryloyloxypropyl trimethoxysilane (see [0156] – claim 4 and 7, where the range of ester-bearing subunits is 0.1 to 10mol% of all siloxane subunits is anticipated by the 10mol% of the reference),
The composition, Example 11, of Shibayama meets the limitations of claim 1 for where it comprises:
a solvent (PGME, PGEE, PGMEA, and Water)
a polysiloxane containing a siloxane unit structure having an ester
the acryloyl ester-bearing subunit’s precursor meets the further limitations of dependent claim 6 for where:
subscript a is 1
R1 is R1-1
R101 is an n-propylenediyl group
R102 is a C2 alkenyl group
subscript b is 0
R2 is not present
R3 is a methoxy group bonded to the silicon atom
As per the experimental procedure at [0217], an organic underlayer film was formed onto a silicon wafer (a substrate) and baked. After, each of the experimental compositions (such as Example 23) were applied to the organic underlayer film and then baked to form a silicon-containing resist underlayer film. Exposure (photocuring) was performed using an exposure apparatus at 172 nm using a photomask with a line-and-space pattern, after which the exposed wafers were immersed in solvent and then dried (claim 14 and 15).
Regarding Claims 2 and 3, claim 2 appears to be written as a product-by-process claim, where the structure of the product (the siloxane unit structure having an ester structure contained in the polysiloxane [A]) is made by the process (formed by a reaction between a hydroxy group and/or an epoxy group and a compound selected from the group consisting of a carboxylic acid, dicarboxylic acid, and a dicarboxylic acid anhydride). See MPEP 2123 - the patentability of the claim is based on the product, not the method of production.
The Example 1 of the composition bears the siloxane (A-1) having the following structure as mentioned above:
PNG
media_image3.png
200
362
media_image3.png
Greyscale
The third subunit structure comprises an ester and as such meets the product limitations of the claims. Further, the structure meets the limitations of the claim 3 where the carboxylic acid-derived fragment of the ester bears an alkenyl group.
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) 18 is rejected under 35 U.S.C. 103 as being unpatentable over Shibayama et al (US 20170153549 A1).
Regarding Claim 18, Shibayama discloses the limitations of the claim as discussed above regarding claim 1.
Shibayama does not explicitly disclose a pattern formation method having all of the steps of the instant claim in an experimental procedure.
These limitations are met by the general disclosure of the reference, where at [0020] a pattern formation method for manufacturing a semiconductor device is described, wherein the method comprises:
Forming an organic underlayer film on a semiconductor substrate
Applying the resist underlayer film-forming composition (the silicon-containing composition discussed above regarding claim 1) onto the organic underlayer film
Baking the composition so as to form a resist underlayer film
Applying a resist composition onto the resist underlayer film to form a resist film
Exposing the resist film to light and then developing the resist film after exposure to obtain a resist pattern
Etching the resist underlayer film (the silicon-containing film discussed above regarding claim 1) using the resist pattern as a mask
Etching the organic underlayer film using the patterned resist underlayer film as a mask
Further, processing the semiconductor substrate using the patterned organic underlayer film.
Shibayama describes that patterning using the underlayer film using a norbornane skeleton, such as that of the example 10 described above regarding claim 1, can exhibit ultrafine patterning performance and good adhesion at each of ArF, EB, and EUV exposures.
A person having ordinary skill in the art would have found it obvious to arrive at the claimed invention prior to the effective filing date by incorporating the composition of Shibayama into the taught patterning method to arrive at an improved pattern due to improved ultrafine patterning performance imparted by the composition and method.
Claim(s) 5 and 8 are rejected under 35 U.S.C. 103 as being unpatentable over Shibayama et al (WO 2019/124514 A1, published 06/27/2019- US 20210054231 A1 used in lieu of translation, hereafter Shibayama-2).
Regarding Claims 5 and 8, Shibayama-2 disclsoses the limitations of the claims as discussed above regarding claims 1 and 6.
Shibayama-2, however, does not explicitly disclose an experimental embodiment that meets the limitations of the instant claims 5 and 8.
These limitations are met by the general disclosure of the reference.
Shibayama disclsoses monomeric and polymeric embodiments that include subunits comprising an ammonium nitrate functionality, such as in Formula (A-13):
PNG
media_image5.png
200
346
media_image5.png
Greyscale
Where the quaternary ammonium nitrate salt subunit meets the limitations of claim 5 for where it is a quaternary ammonium nitrate.
The hydrolysis-condensation reaction for synthesis of the siloxane polymer is discussed from [0095] to [0108], where nitric acid is an inorganic acid used – the Synthetic examples also use nitric acid at Synthesis examples 4, 5, 6, and 14.
The quaternary ammonium structure further meets the limitations of formula (2) in claim 8 for where the corresponding precursor compound bears:
Claimed subscript c is 1
R4 is an organic group containing an amino group (that has been modified with nitric acid to give the ammonium nitrate salt during hydrolysis)
Claimed subscript d is 0
Claimed R6 is an alkoxy group so as to be labile during the hydrolysis (see synthetic examples 4,5,6,14, where ethoxy and methoxy groups are removed during hydrolysis).
A person having ordinary skill in the art would have found it obvious to incorporate the claimed quaternary ammonium-bearing subunit into the polymer of Shibayama-2 from the reaction conditions and components described in the disclosure and enable the synthesis of such a subunit in tandem with other siloxane subunits to make a polysiloxane hydrolysis-condensate. Further, Shibayama-2 presents both the polymers of A-1 and A-13 as suitable for underlayer film-forming compositions - it therefore stands obvious for a person having ordinary skill in the art to select monomers from these polymers to combine and use in forming a third polymeric embodiment with the expectation that it too would be suitable for an underlayer film-forming composition (See MPEP 2144.06.1, in re Kerkhoven).
A person having ordinary skill in the art would have found it obvious to arrive at the claimed invention prior to the effective filing date in view of the disclosure of Shibayama-2 by combining the subunits of polymeric embodiments explicitly taught by the reference so as to arrive at a polymeric embodiment to be used in an underlayer film-forming composition.
Claim 12 is/are rejected under 35 U.S.C. 103 as being unpatentable over Shibayama et al (US 20170153549 A1) as applied to claim 1 above, and further in view of Nakajima et al (US 20160251546 A1)
Regarding Claim 12, Shibayama disclsoses the limitations of the claim as discussed above regarding claim 1.
Shibayama does not disclose or teach a metal oxide component as part of the composition.
This limitation is met by Nakajima.
Nakajima discloses a resist underlayer film-forming composition comprising a polysiloxane, polyhafnium oxide, or polyzirconium oxide or a combination thereof, and an isopoly or heteropoly acid compound or salt thereof or combination thereof (Abstract).
The composition of Nakajima may comprise a polysiloxane such as those conforming to formulas (5-1) through (5-8) at [0067], where the polysiloxane is a hydrolysis-condensation product of a hydrolysable silane.
Examples of the polyacid include those discussed at [0037]- [0039], such as metatungstic acid, ammonium metamolybdate, and phosphovanadic acid.
Polyzirconium and/or polyhafnium oxides are discussed from [0014]- [0015] and [0064]- [0066]. These compounds are metal oxides.
Nakajima ascribes an improved dry etching rate in this underlayer film-forming composition relative to the top-layer when an oxygen-containing etch gas is used, as it is resistant to this type of etch chemistry and therefore will not be substantially removed during the process of removing top-layer resists ([0031]- [0032]). Further, Nakajima and Shibayama are both directed to compositions comprising polysiloxanes and resist underlayer film-forming compositions for photolithography – the combination of compositions or compositional elements from one composition to another to be used for the same purpose is prima facie obvious (See MPEP 2144.06, in re Kerkhoven).
A person having ordinary skill in the art would have found it obvious to arrive at the claimed invention prior to the effective filing date by adding the poly zirconium or hafnium oxide(s) of Nakajima to the composition of Shibayama to improve the composition’s resistance to an oxygen-containing etch gas.
Claim 17 is/are rejected under 35 U.S.C. 103 as being unpatentable over Shibayama et al (US 20170153549 A1) as applied to claim 1 and 16 above, and further in view of Tokunaga et al (US 20190354018 A1).
Regarding claim 17, Shibayama disclsoses the limitations of the claim as discussed above regarding claims 1 and 16.
Shibayama, however, does not disclose filtration through a nylon filter. Shibayama disclsoses filtration through a fluororesin filter at [0180].
This limitation is met by Tokunaga.
Tokunaga disclsoses a resist underlayer film-forming composition and method for forming a resist pattern and manufacturing a semiconductor device (Abstract).
The resist underlayer composition of Tokunaga is generally discussed from [0032]- [0265], where the resist underlayer composition comprises a polymer, a solvent, and an amide compound additive.
The compositions of Tokunaga are mixed in solvent and filtered to remove any solid particular matter. Filters used may be fluororesins, polysulfone, or nylon ([0265]).
Tokunaga and Shibayama both disclose similar filters and disclose compositions directed to the formation of underlayer films for photolithography. The substitution of a functional element for a structurally similar functional element – a filter for another filter to be used in filtration – would be obvious for a person of ordinary skill in view of the reference’s respective teachings that filtration with a filter is used.
A person having ordinary skill in the art would have found it obvious to arrive at the claimed invention prior to the effective filing date by substituting the fluororesin filter of Shibayama for the nylon filter of Tokunaga with the expectation that the filtration would still function as intended and arrive at a resist composition that is substantially free of solid particulate matter.
Conclusion
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.
Examiner interviews are available via telephone, in-person, and video conferencing using a USPTO supplied web-based collaboration tool. To schedule an interview, applicant is encouraged to use the USPTO Automated Interview Request (AIR) at http://www.uspto.gov/interviewpractice.
If attempts to reach the examiner by telephone are unsuccessful, the examiner’s supervisor, 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.
Information regarding the status of published or unpublished applications may be obtained from Patent Center. Unpublished application information in Patent Center is available to registered users. To file and manage patent submissions in Patent Center, visit: https://patentcenter.uspto.gov. Visit https://www.uspto.gov/patents/apply/patent-center for more information about Patent Center and https://www.uspto.gov/patents/docx for information about filing in DOCX format. For additional questions, contact the Electronic Business Center (EBC) at 866-217-9197 (toll-free). If you would like assistance from a USPTO Customer Service Representative, call 800-786-9199 (IN USA OR CANADA) or 571-272-1000.
/A.P.T./Examiner, Art Unit 1737
/SALLY A MERKLING/SPE, Art Unit 1738
Prosecution Insights