DETAILED ACTION
Notice of Pre-AIA or AIA Status
1. The present application, filed on or after March 16, 2013, is being examined under the first inventor to file provisions of the AIA .
Election/Restrictions
2. Applicant’s election without traverse of Specie B (claims 1-13, 15-21) in the reply filed on 11/13/2025 is acknowledged. Claim 14 is cancelled by applicants.
Claim Rejections - 35 USC § 102
3. 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.
4. 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.
5. Claims 8-9, 11-13, 15, 17-21 are rejected under 35 U.S.C. 102(a)(2) as being anticipated by Lo et al. (US 2024,0047208 A1).
The applied reference has a common assignee with the instant application. Based upon the earlier effectively filed date of the reference, it constitutes prior art under 35 U.S.C. 102(a)(2). This rejection under 35 U.S.C. 102(a)(2) might be overcome by: (1) a showing under 37 CFR 1.130(a) that the subject matter disclosed in the reference was obtained directly or indirectly from the inventor or a joint inventor of this application and is thus not prior art in accordance with 35 U.S.C. 102(b)(2)(A); (2) a showing under 37 CFR 1.130(b) of a prior public disclosure under 35 U.S.C. 102(b)(2)(B) if the same invention is not being claimed; or (3) a statement pursuant to 35 U.S.C. 102(b)(2)(C) establishing that, not later than the effective filing date of the claimed invention, the subject matter disclosed in the reference and the claimed invention were either owned by the same person or subject to an obligation of assignment to the same person or subject to a joint research agreement.
As to claim 8, Lo discloses a method of manufacturing a semiconductor device, comprising:
forming a photoresist layer (46) over a target layer(44) (Fig 3, paragraph 0043-0044);
exposing the photoresist layer to form an exposed photoresist layer comprising a plurality of pores (48) (paragraph 0047-0048; Fig 5);
filling a photoresist-strengthening material (52) into the plurality of pores (paragraph 0049-0054 Fig 6-7);
after filling the photoresist-strengthening material into the plurality of pores, developing the exposed photoresist layer to form a patterned photoresist (paragraph 057; Fig 8) and
etching the target layer by using the patterned photoresist as an etching mask (paragraph 0058, Fig 9).
As to claim 9, Lo discloses wherein the photoresist-strengthening material comprises a silane having a formula of RaSiXb, a sum of a and b is equal to 4, R is a branched, unbranched, or cyclic alkyl, alkenyl, or alkynyl, or a branched, unbranched, or cyclic alkyl, alkenyl, or alkynyl substituted with one or more functional groups comprising a hydroxyl group, an amine group, an epoxy group, an amide group, an ester group, a carboxyl group, a sulfate group, a sulfonyl group, an ether group, a halogen group, a carbonyl group, an aryl group, or an organometallic complex, and X is a halogen group, an alkoxy group, or a fluoroalkoxy group (paragraph 0053).
As to claim 11, Lo discloses wherein the photoresist-strengthening material comprises a metal oxide comprising RaSnbOcR'dXe, RaTibOcR'dXe, RaZrbOcR'dXe, RaHfbOcR'dXe, RaZnbOcR'dXe, RaAIbOcR'dXe, or RaCubOcR'dXe, R is a mono-dentate organic ligand or a multi-dentate organic ligand comprising an amide, a carboxyl group, an aryl group, a branched, unbranched, or cyclic alkyl, alkenyl, or alkynyl, a branched, unbranched, or cyclic alkyl, alkenyl, or alkynyl substituted with a carbonyl group, or a derivative thereof substituted with a halogen group, R' is H or an organic ligand comprising an amide, a carboxyl group, an aryl group, a branched, unbranched, or cyclic alkyl, alkenyl, or alkynyl, a branched, unbranched, or cyclic alkyl, alkenyl, or alkynyl substituted with a carbonyl group, or a derivative thereof substituted with a halogen group, X is a halide anion or a carboxylic anion, and a sum of a, c, d and e equals to a multiplied value obtained by multiplying b and an oxidation number of a metal of the metal oxide (paragraph 0054).
As to claim 12, Lo discloses wherein filling the photoresist-strengthening material into the plurality of pores is performed by using a solution-coating method or a sol-gel process (paragraph 0051).
As to claim 13, Lo discloses after filling the photoresist-strengthening material into the plurality of pores or when filling the photoresist-strengthening material into the plurality of pores, irradiating the photoresist layer with light having a wavelength between 1 nm and 100 nm, including example of 13.5 nm (See paragraph 0016, 0023, 0057).
As to claim 15, Lo discloses filling the photoresist- strengthening material into the plurality of pores comprises applying a solution comprising an organic solvent and the photoresist-strengthening material or water and the photoresist-strengthening material on the photoresist layer (paragraph 0051).
As to claim 17, Lo discloses a method of manufacturing a semiconductor device, comprising:
forming a photoresist layer (46) over a target layer (paragraph 0043-0046);
exposing the photoresist layer to form an exposed photoresist layer having at least one exposed portion (paragraph 0048, Fig 5);
forming a coating layer (52) on the at least one exposed portion (paragraph 0049-0054);
after forming the coating layer on the at least one exposed portion, developing the exposed photoresist layer to form a patterned photoresist (paragraph 0057); and
etching the target layer by using the patterned photoresist as an etching mask (paragraph 0058-0060).
As to claim 18, Lo discloses the coating layer comprises a silane, a metal oxide or a combination thereof (paragraph 0053-0055).
As to claim 19, Lo discloses the metal oxide comprises Sn, Ti, Zr, Hf, Zn, Al, or Cu (paragraph 0054).
As to claim 20, Lo discloses wherein forming the coating on the at last one exposed portion comprises applying a solution comprises silane or the metal oxide and an organic solvent or water (paragraph 0051, -0053-0055).
As to claim 21, Lo discloses after filling the photoresist-strengthening material into the plurality of pores or when filling the photoresist-strengthening material into the plurality of pores, irradiating the photoresist layer with light having a wavelength between 1 nm and 100 nm, including example of 13.5 nm (See paragraph 0016, 0023, 0057).
6. Claims 17-21 are rejected under 35 U.S.C. 102(a)(1) and/or 102(a)(2) as being anticipated by de Schepper et al. (US 2021/0349390 A1).
As to claim 17, de Schepper discloses a method of manufacturing a semiconductor device, comprising:
forming a photoresist layer over a target layer (Fig 2A, step 14, paragraph 0100)
exposing the photoresist layer to form an exposed photoresist layer having at least one exposed portion (Fig 2A, step 16; paragraph 0100)
forming a coating layer on the at least one exposed portion (Fig 2A step 22, paragraph 0101);
after forming the coating layer on the at least one exposed portion, developing the exposed photoresist layer to form a patterned photoresist (Fig 2A, step 26; paragraph 0101); and
etching the target layer by using the patterned photoresist as an etching mask (paragraph 0104).
As to claim 18, de Schepper discloses the coating layer comprises a metal oxide (paragraph 00063-0065).
As to claim 19, de Schepper discloses the metal oxide comprises Sn (paragraph 0064-0065).
As to claim 20, de Schepper discloses wherein forming the coating on the at least one exposed portion comprises applying a solution comprises the metal oxide and an organic solvent (paragraph 0064-0065, 00758).
As to claim 21, de Schepper discloses after filling the photoresist-strengthen material, or when filling the photoresist-strengthen material, irradiating the photoresist layer with light having a wavelength between 10 nm to less than 121 nm or greater than 122 nm to less than 200 nm (paragraph 0085, within applicant’s range between 13 nm and 700 nm); or thermally baking the photoresist layer at a temperature between 50 °C and 200 °C (See paragraph 0082, within applicant’s range of “a temperature between 50 °C and 800 °C”).
Claim Rejections - 35 USC § 103
7. 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.
This application currently names joint inventors. In considering patentability of the claims the examiner presumes that the subject matter of the various claims was commonly owned as of the effective filing date of the claimed invention(s) absent any evidence to the contrary. Applicant is advised of the obligation under 37 CFR 1.56 to point out the inventor and effective filing dates of each claim that was not commonly owned as of the effective filing date of the later invention in order for the examiner to consider the applicability of 35 U.S.C. 102(b)(2)(C) for any potential 35 U.S.C. 102(a)(2) prior art against the later invention.
8. Claims 1-4, 7 are rejected under 35 U.S.C. 103 as being unpatentable over Weidman (US 2022/0299877 A1) in view of de Schepper (US 20210349390 A1).
Note:
As to claim 1, Weidman discloses a method of manufacturing a semiconductor device, comprising:
forming a metal oxide photoresist layer (211) over a target layer, wherein the metal oxide photoresist layer comprises a metal oxide core with organic ligands, a metal oxide framework with organic ligands, or a combination thereof (paragraph 0074, 0111-0159;
exposing the metal oxide photoresist layer to an extreme ultraviolet (EUV) radiation (paragraph 0075, 0186-0192Fig 2, );
treating the metal oxide photoresist layer with a ligand leaving promoter (paragraph 0157);
developing the metal oxide photoresist layer to form a patterned photoresist (paragraph 0193-0202); and
As to claim 1, Weidman fails to disclose etching the target layer by using the patterned photoresist as an etching mask. De Schepper discloses etching the target layer by using the patterned photoresist as an etching mask (paragraph 0071-0072, 0104, 0108). It would have been obvious to one of ordinary skill in the art, before the effective filing date of the claimed invention, to modify Weidman in view of de Schepper by etching the target layer by using the patterned photoresist as an etching mask because it helps to create a desired pattern on the target layer.
As to claim 2, Weidman discloses the ligand leaving promoter comprises a peroxide (paragraph 0157).
As to claim 3, Weidman discloses the peroxide comprise oxygen, ozone (O3) (paragraph 0157).
As to claim 4, Weidman discloses the peroxide comprise hydrogen peroxide (aka H2O2) which has a formula structure of H-O-O-H (See paragraph 0157).
As to claim 7, Weidman discloses after treating the metal oxide photoresist layer with the ligand promoter, thermally baking the metal oxide photoresist layer at a temperature between 100 °C to 250 °C, or 190 °C to 350 °C (paragraph 0080, within applicant’s range).
9. Claims 5-6 are rejected under 35 U.S.C. 103 as being unpatentable over Weidman (US 2022/0299877 A1) in view of de Schepper et al. (US 2021/0349390 A1) as applied to claims 1-4, 7 above, and further in view of Chen et al. (US 2021/0271164 A1).
As to claim 5, Weidman fails to disclose the ligand leaving promoter comprises a radical generator, wherein the radical generators comprises an aromatic ring, a ketone, an alkoxyamine, a dialkyl hydroxylamine, an azo compound, or combinations thereof, the aromatic ring and the ketone are respectively substituted with one or more functional groups comprising an aryl group, a branched, unbranched, or cyclic alkyl, alkenyl, or alkynyl, or a branched, unbranched, or cyclic alkyl, alkenyl, or alkynyl substituted with one or more functional groups comprising a hydroxyl group, an amine group, an epoxy group, an amide group, an ester group, a carboxyl group, a sulfate group, a sulfonyl group,
PNG
media_image1.png
94
140
media_image1.png
Greyscale
an ether group, a halogen group, a carbonyl group, an aryl group, or combinations thereof.
However, Weidman clearly teaches the ligand leaving promoter comprises a peroxide. Chen teaches to treat the metal oxide photoresist with photoacid generator compound (PACs) such as radical generators comprises an aromatic ring, a ketone, a azo compound, wherein the aromatic ring and the ketone are respectively substituted with one or more functional groups comprising an aryl group, a branched, unbranched, or cyclic alkyl, alkenyl, or alkynyl, or a branched, unbranched, or cyclic alkyl, alkenyl, or alkynyl substituted with one or more functional groups comprising a hydroxyl group, an amine group, an epoxy group, an amide group, an ester group (paragraph 0059-0061). It would have been obvious to one of ordinary skill in the art, before the effective filing date of the claimed invention, to modify Weidman and de Schepper in view of Chen by using radical generators comprises an aromatic ring, a ketone, a azo compound, wherein the aromatic ring and the ketone are respectively substituted with one or more functional groups comprising an aryl group, a branched, unbranched, or cyclic alkyl, alkenyl, or alkynyl, or a branched, unbranched, or cyclic alkyl, alkenyl, or alkynyl substituted with one or more functional groups comprising a hydroxyl group, an amine group, an epoxy group, an amide group, an ester group because equivalent and substitution of one for the other would produce an expected result (See MPEP 2143(I)(B)).
As to claim 6, Weidman and de Schepper fail to disclose the radical generator comprises
PNG
media_image2.png
123
230
media_image2.png
Greyscale
And Ra, and Rb are independently H or a branched, unbranched, or cyclic alkyl, alkenyl, or alkynyl.
Chen discloses the radical generator comprises benzophenone, N,N′-tetramethyl-4,4′-diaminobenzophenone, N,N′-tetraethyl-4,4′-diaminobenzophenone, 4-methoxy-4′-dimethylaminobenzo-phenone, 3,3′-dimethyl-4-methoxybenzophenone, p,p′-bis(dimethylamino)benzo-phenone, p,p′-bis(diethylamino)-benzophenone; anthraquinone, 2-ethylanthraquinone; naphthaquinone; and phenanthraquinone (See paragraph 0061). It is well known in the art that benzophenone has the following structure as shown below:
PNG
media_image3.png
209
330
media_image3.png
Greyscale
(See evidence reference National Library of Medicine, PubChem “Benzophenone” via https://pubchem.ncbi.nlm.nih.gov/compound/Benzophenone
Therefore, Chen teaches the radical generator comprises
PNG
media_image2.png
123
230
media_image2.png
Greyscale
Wherein Ra and Rb are independently H.
It would have been obvious to one of ordinary skill in the art, before the effective filing date of the claimed invention, to modify Weidman and de Schepper in view of Chen by using radical generator comprises benzophenone because equivalent and substitution of one for the other would produce an expected result (See MPEP 2143(I)(B)).
10. Claims 8-9, 11-13, 15-16 are rejected under 35 U.S.C. 103 as being unpatentable over de Schepper et al. (US 2021/0349390 A1) in view of Huang et al. (US 2023/0095970 A1).
As to claim 8, de Schepper discloses a method of manufacturing a semiconductor device, comprising:
forming a photoresist layer over a target layer (Fig 2A, step 14, paragraph 0100)
exposing the photoresist layer to form an exposed photoresist layer comprising
filling a photoresist-strengthening material
after filling the photoresist-strengthening material into the plurality of pores, developing the exposed photoresist layer to form a patterned photoresist; (Fig 2A, step 26, paragraph 0101); and
etching the target layer by using the patterned photoresist as an etching mask (paragraph 0104).
As to claim 8, de Schepper fails to disclose the photoresist comprising a plurality of pores and filling a photoresist strengthening material into the plurality of pores. However, de Schepper clearly teaches filling/depositing a photo-resist strengthen material on the photoresist layer. Huang discloses the photoresist comprising a plurality of pores and filling a photoresist strengthening material into the plurality of pores (paragraph 0008-0010, 0018, 0032-0033, 0037-0038). It would have been obvious to one of ordinary skill in the art, before the effective filing date of the claimed invention, to modify de Schepper in view of Huang by having the photoresist comprising a plurality of pores and filling a photoresist strengthening material into the plurality of pores because it helps to create denser and hard patterned photoresist material (See abstract).
As to claim 9, de Schepper fails to disclose wherein the photoresist-strengthening material comprises a silane having a formula of RaSiXb, a sum of a and b is equal to 4, R is a branched, unbranched, or cyclic alkyl, alkenyl, or alkynyl, or a branched, unbranched, or cyclic alkyl, alkenyl, or alkynyl substituted with one or more functional groups comprising a hydroxyl group, an amine group, an epoxy group, an amide group, an ester group, a carboxyl group, a sulfate group, a sulfonyl group,
PNG
media_image1.png
94
140
media_image1.png
Greyscale
an ether group, a halogen group, a carbonyl group, an aryl group, or an organometallic complex, and X is a halogen group, an alkoxy group, or a fluoroalkoxy group.
However, de Schepper clearly discloses depositing the photoresist-strengthen material . Huang discloses to use photoresist-strengthen material comprises aminoalkyl alkoxy silane having a formula (RO)4-nSi(OH)n or (R”O)4-nSi(R’NH2)n where R’ is independently methylene, ethylene, propylene, or butylene and R” is independently methylene, ethylene, propylene, or butylene, including example of (3-aminopropyl)trimethoxysilane, (3-aminopropyl)triethoxysilane (APTES), (3-aminopropyl)triproxysilane (See paragraph 0025). It is noted that Huang formula (R”O)4-nSi(R’NH2)n such as (3-aminopropyl)trimethoxysilane, (3-aminopropyl)triethoxysilane (APTES), (3-aminopropyl)triproxysilane read on applicants formula RaSiXb, a sum of a and b is equal to 4 (Note: 4-n + n = 4); wherein R is a branched or unbranded alkyl, alkenyl substituted with one or more functional group comprising an amine, and X is a alkoxy group. It would have been obvious to one of ordinary skill in the art, before the effective filing date of the claimed invention, to modify de Schepper in view of Huang by using the photoresist-strengthen material comprising RaSiXb, a sum of a and b is equal to 4, wherein R is a branched or unbranded alkyl, alkenyl substituted with one or more functional group comprising an amine, and X is a alkoxy group because equivalent and substitution of one for the other would produce an expected result (See MPEP 2143(I)(B)).
As to claim 11, de Schepper discloses the photoresist-strengthen material comprises metal oxide comprising RaSnbOcR'dXe, R is a mono-dentate organic ligand or a multi-dentate organic ligand comprising an amide, a carboxyl group, an aryl group, a branched, unbranched, or cyclic alkyl, alkenyl, or alkynyl, a branched, unbranched, or cyclic alkyl, alkenyl, or alkynyl substituted with a carbonyl group, or a derivative thereof substituted with a halogen group, R' is H or an organic ligand comprising an amide, a carboxyl group, an aryl group, a branched, unbranched, or cyclic alkyl, alkenyl, or alkynyl, a branched, unbranched, or cyclic alkyl, alkenyl, or alkynyl substituted with a carbonyl group, or a derivative thereof substituted with a halogen group, X is a halide anion or a carboxylic anion, and a sum of a, c, d and e equals to a multiplied value obtained by multiplying b and an oxidation number of a metal of the metal oxide (See paragraph 0064-0066).
As to claim 12, de Schepper discloses the filing the photoresist-strengthen material is performed by using a solution coating method (paragraph 0075).
As to claim 13, de Schepper discloses after filling the photoresist-strengthen material, or when filling the photoresist-strengthen material, irradiating the photoresist layer with light having a wavelength between 10 nm to less than 121 nm or greater than 122 nm to less than 200 nm (paragraph 0085, within applicant’s range between 13 nm and 700 nm); or thermally baking the photoresist layer at a temperature between 50 °C and 200 °C (See paragraph 0082, within applicant’s range of “a temperature between 50 °C and 800 °C”).
As to claim 15, de Schepper discloses filling the photoresist-strengthen material comprises applying a solution comprising an organic solvent and the photoresist strengthen material (paragraph 0075).
As to claim 16, de Schepper discloses the organic solvent comprises an aromatic ring, a cyclic ketone (e.g. cyclohexanone), a cyclic alkane (See paragraph 0075, 00090).
11. Claim 10 is rejected under 35 U.S.C. 103 as being unpatentable over de Schepper et al. (US 2021/0349390 A1) in view of Huang et al. (US 2023/0095970 A1) as applied to claims 8-9, 11-13, 15-16 above, and further in view of Chen (US 2021/0271164 A1).
As to claim 10, de Schepper and Huang fail to disclose the photoresist-strengthening material further comprises a photobase generator, a photoacid generator, a thermal base generator, a thermal acid generator, or combinations thereof. However, de Schepper clearly teaches depositing photoresist strengthen material comprises depositing photoresist material using precursors. Chen teaches depositing photoresist material using precursor includes one or more photoactive compounds (PACs), wherein the photoactive compounds includes photoacid generator, photobase generator or combination thereof (paragraph 0059). It would have been obvious to one of ordinary skill in the art, before the effective filing date of the claimed invention, to modify de Schepper and Huang in view of Chen by having the photoresist-strengthening material comprises a photobase generator, a photoacid generator, or combination thereof because equivalent and substitution of one for the other would produce an expected result (See MPEP 2143(I)(B)).
Conclusion
12. Any inquiry concerning this communication or earlier communications from the examiner should be directed to BINH X TRAN whose telephone number is (571)272-1469. The examiner can normally be reached Monday-Friday.
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, Joshua Allen can be reached at 571-270-3176. 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.
BINH X. TRAN
Examiner
Art Unit 1713
/BINH X TRAN/ Primary Examiner, Art Unit 1713