US-12628623-B2 - Selective deposition for sub 20 nm pitch EUV patterning

Abstract

Methods of selectively depositing a carbon-containing layer are described. Exemplary processing methods may include treating a substrate comprising a carbon-containing surface and a silicon-containing surface with one or more of ozone or hydrogen peroxide to passivate the silicon-containing surface. In one or more embodiments, a carbon-containing layer is then selectively deposited on the carbon-containing surface and not on the silicon-containing surface by flowing a first precursor over the substrate to form a first portion of an initial carbon-containing film on the carbon-containing surface and not on the silicon-containing surface. The methods may include removing a first precursor effluent from the substrate. A second precursor may then be flowed over the substrate to react with the first portion of the initial carbon-containing layer. The methods may include removing a second precursor effluent from the substrate.

Inventors

• Zeqing Shen
• Xinke WANG
• Susmit Singha Roy
• Abhijit Basu Mallick
• Bhaskar Jyoti Bhuyan
• John Sudijono

Assignees

• APPLIED MATERIALS, INC.

Dates

Publication Date

20260512

Application Date

20220804

Claims (20)

1. 1 . A method of selectively depositing a film, the method comprising: treating a carbon-containing surface and a silicon-containing surface with one or more of ozone or hydrogen peroxide to form hydroxide groups on the silicon-containing surface, wherein the carbon-containing surface is a chemical amplified resist (CAR) layer and the silicon-containing surface is a spin-on-glass layer, the spin-on-glass layer on a hardmask layer on a target layer, and wherein the carbon-containing surface has at least one feature formed therein, the at least one feature having a bottom surface that is the silicon-containing surface; exposing the silicon-containing surface and hydroxide groups to an alkylating precursor to form a passivated silicon-containing surface; flowing a first precursor over a substrate comprising the carbon-containing surface and the passivated silicon-containing surface to form a first portion of a carbon-containing layer on the carbon-containing surface, the first precursor comprising a first reactive group; removing a first precursor effluent comprising the first precursor from the substrate; flowing a second precursor comprising a second reactive group over the substrate to react with the first reactive group to form the carbon-containing layer on the carbon-containing surface of the substrate and not on the silicon-containing surface; and removing a second precursor effluent comprising the second precursor from the substrate.
2. 2 . The method of claim 1 , wherein the alkylating precursor has a general formula (A) wherein R 3 and R 4 independently comprise one or more of hydrogen, an alkyl group, a halide, an alkenyl group, an aryl or aromatic group, a cycloalkyl group, and a trimethylsilyl group (Si(CH 3 ) 3 ), and wherein q is an integer in a range of from 0 to 5.
3. 3 . The method of claim 2 , wherein the alkylating precursor is selected from one or more of hexamethyldisiliazane, N,N-dimethyltrimethylsilylamine, tris(trimethylsilyl)amine, chlorotrimethylsilane, 1-(Trimethylsilyl)pyrrolidine, and iodo trimethylsilane.
4. 4 . The method of claim 1 , wherein the first precursor has a general formula R 1 —(X) n wherein R 1 comprises one or more of an alkyl group, an alkenyl group, an aryl or aromatic group, and a cycloalkyl group, X n comprises one or more of a hydroxide group, an aldehyde group, a ketone group, an acid group, an amino group, an isocyanate group, a thiocyanate group, and an acyl chloride group, and n is an integer in a range of from 1 to 6.
5. 5 . The method of claim 1 , wherein the second precursor has a general formula R 2 —(Y) n wherein R 2 comprises one or more of an alkyl group, an alkenyl group, an aryl or aromatic group, and a cycloalkyl group, Yn comprises one or more of a hydroxide group, an aldehyde group, a ketone group, an acid group, an amino group, an isocyanate group, a thiocyanate group, and an acyl chloride group, and n is an integer in a range of from 1 to 6.
6. 6 . The method of claim 1 , wherein the first precursor and the second precursor are independently selected from one or more of terephthaldehyde, phenylenediamine, ethylenediamine, hexamethylenediamine, terephthaloyl chloride, 1,3,5-benzenetricarbonyl trichloride, pyromellitic dianhydride, benzene-1,3,5-tricarboxaldehyde, 1,4-phenylene diisocyanate, 4,4′-oxydianiline, and tris(2-aminoethyl)amine.
7. 7 . The method of claim 6 , wherein the first precursor comprises terephthaldehyde and the second precursor comprises phenylenediamine.
8. 8 . The method of claim 1 , further comprising depositing at least one additional carbon-containing layer on the carbon-containing layer, wherein the carbon-containing layer and the at least one additional carbon-containing layer form the carbon-containing layer on the carbon-containing surface of the substrate.
9. 9 . The method of claim 1 , wherein removing the first precursor comprises: flowing a purge gas over the substrate; and removing a mixture of the first precursor effluent and the purge gas from the substrate.
10. 10 . The method of claim 9 , wherein the purge gas is selected from argon (Ar), helium (He), and nitrogen (N 2 ).
11. 11 . The method of claim 1 , further comprising patterning the substrate to expose the hardmask layer.
12. 12 . A method of selectively depositing a film, the method comprising: treating a substrate comprising a carbon-containing surface and a silicon-containing surface with one or more of ozone or hydrogen peroxide to form hydroxide groups on the silicon-containing surface, wherein the carbon-containing surface is a chemical amplified resist (CAR) layer and the silicon-containing surface is a spin-on-glass layer, the spin-on-glass layer on a hardmask layer on a target layer, and wherein the carbon-containing surface has at least one feature formed therein, the at least one feature having a bottom surface that is the silicon-containing surface; exposing the silicon-containing surface and the hydroxide groups to an alkylating precursor to form a passivated surface, wherein the alkylating precursor has a general formula (A) wherein R 3 and R 4 independently comprise one or more of hydrogen, an alkyl group, a halide, an alkenyl group, an aryl or aromatic group, a cycloalkyl group, and a trimethylsilyl group (Si(CH 3 ) 3 ), and wherein q is an integer in a range of from 0 to 5; flowing a first precursor over the substrate, the first precursor having a general formula R 1 —(X)n wherein R 1 comprises one or more of an alkyl group, an alkenyl group, an aryl or aromatic group, and a cycloalkyl group, X n comprises one or more of a hydroxide group, an aldehyde group, a ketone group, an acid group, an amino group, an isocyanate group, a thiocyanate group, and an acyl chloride group, and n is an integer in a range of from 1 to 6, wherein the first precursor reacts with a reactive group on the carbon-containing surface to form a first portion of a carbon-containing layer on the carbon-containing surface; removing a first precursor effluent comprising the first precursor from the substrate; flowing a second precursor over the substrate to form a carbon-containing layer on the carbon-containing surface and not on the passivated surface, the second precursor having a general formula R 2 —(Y) n wherein R 2 comprises one or more of an alkyl group, an alkenyl group, an aryl or an aromatic group, and a cycloalkyl group, Yn comprises one or more of a hydroxide group, an aldehyde group, a ketone group, an acid group, an amino group, an isocyanate group, a thiocyanate group, and an acyl chloride group, and n is an integer in a range of from 1 to 6, wherein the second precursor reacts with the first portion to form the carbon-containing layer; and removing a second precursor effluent comprising the second precursor from the substrate.
13. 13 . The method of claim 12 , wherein the first precursor and the second precursor are independently selected from one or more of terephthaldehyde, phenylenediamine, ethylenediamine, hexamethylenediamine, terephthaloyl chloride, 1,3,5-benzenetricarbonyl trichloride, pyromellitic dianhydride, benzene-1,3,5-tricarboxaldehyde, 1,4-phenylene diisocyanate, 4,4′-oxydianiline, and tris(2-aminoethyl) amine.
14. 14 . The method of claim 12 , further comprising depositing at least one additional carbon-containing layer on the carbon-containing layer, wherein the carbon-containing layer and the at least one additional carbon-containing layer form the carbon-containing layer on the carbon-containing surface of the substrate.
15. 15 . The method of claim 12 , wherein removing the first precursor comprises: flowing a purge gas over the substrate, wherein the purge gas is selected from argon (Ar), helium (He), and nitrogen (N 2 ); and removing a mixture of the first precursor effluent and the purge gas from the substrate.
16. 16 . The method of claim 12 , further comprising patterning the substrate to expose a hardmask layer.
17. 17 . The method of claim 1 , wherein the carbon-containing layer has a selectivity ratio of the carbon-containing surface to the silicon-containing surface of at least 100:1.
18. 18 . The method of claim 1 , wherein the carbon-containing layer has a thickness of about 50 nm to about 300 nm.
19. 19 . The method of claim 12 , wherein the carbon-containing layer has a selectivity ratio of the carbon-containing surface to the silicon-containing surface of at least 100:1.
20. 20 . The method of claim 12 , wherein the carbon-containing layer has a thickness of about 50 nm to about 300 nm.

Description

TECHNICAL FIELD Embodiments of the disclosure relate to methods for selectively depositing a carbon-based film. In particular, embodiments of the disclosure are directed to methods of depositing carbon-based layers selectively on carbon-containing surfaces over silicon-containing surfaces, such as silicon and silicon oxide (SiOx) surfaces. BACKGROUND Photolithography employs photoresists, which are photosensitive films, for transfer of negative or positive images onto a substrate, e.g., a semiconductor wafer. Subsequent to coating a substrate with a photoresist, the coated substrate is exposed to a source of activating radiation, which causes a chemical transformation in the exposed areas of the surface. The photoresist coated substrate is then treated with a developer solution to dissolve or otherwise remove either the radiation-exposed or unexposed areas of the coated substrate, depending on the type of photoresist employed. Current EUV patterning processes suffer from inefficient underlayer opening. The tapered shape of chemically amplified resists (CAR) and the limited height of the CAR versus the underlayer may lead to inefficient underlayer etch-through in small pitch EUV patterning. Current approaches to solving these issues involve increasing CAR thickness before EUV exposure and development, and increasing CAR etch selectivity versus underlayer by metal doping. These approaches, however, can lead to bridging defects or left over hard-to-remove CAR residue. There is an ongoing need in the art, therefore, for methods to improve deposition selectivity and to avoid the problems encountered during EUV patterning. SUMMARY One or more embodiments of the disclosure are directed to a method of selectively depositing a film. A method of selectively depositing a film comprises: flowing a first precursor over a substrate comprising a carbon-containing surface and a silicon-containing surface to form a first portion of a carbon-containing layer on the carbon-containing surface, the first precursor comprising a first reactive group; removing a first precursor effluent comprising the first precursor from the substrate; flowing a second precursor comprising a second reactive group over the substrate to react with the first reactive group to form the carbon-containing layer on the carbon-containing surface of the substrate and not on the silicon-containing surface; and removing a second precursor effluent comprising the second precursor from the substrate. Another embodiment of the disclosure is directed to a method of selectively depositing a film. In one or more embodiments, a method of selectively depositing a film comprises treating a substrate comprising a carbon-containing surface and a silicon-containing surface with one or more of ozone or hydrogen peroxide to form hydroxide groups on the silicon-containing surface; exposing the silicon-containing surface and the hydroxide groups to an alkylating precursor to form a passivated surface, wherein the alkylating precursor has a general formula (A) wherein R3 and R4 independently comprise one or more of hydrogen, an alkyl group, a halide, an alkenyl group, an aryl or aromatic group, a cycloalkyl group, and a trimethylsilyl group (Si(CH3)3), and wherein q is an integer in a range of from 0 to 5; flowing a first precursor over the substrate, the first precursor having a general formula R1—(X)n wherein R1 comprises one or more of an alkyl group, an alkenyl group, an aryl or aromatic group, and a cycloalkyl group, Xn comprises one or more of a hydroxide group, an aldehyde group, a ketone group, an acid group, an amino group, an isocyanate group, a thiocyanate group, and an acyl chloride group, and n is an integer in a range of from 1 to 6, wherein the first precursor reacts with a reactive group on the carbon-containing surface to form a first portion of a carbon-containing layer on the carbon-containing surface; removing a first precursor effluent comprising the first precursor from the substrate; flowing a second precursor over the substrate to form a carbon-containing layer on the carbon-containing surface and not on the passivated surface, the second precursor having a general formula R2—(Y)n wherein R2 comprises one or more of an alkyl group, an alkenyl group, an aryl or an aromatic group, and a cycloalkyl group, Yn comprises one or more of a hydroxide group, an aldehyde group, a ketone group, an acid group, an amino group, an isocyanate group, a thiocyanate group, and an acyl chloride group, and n is an integer in a range of from 1 to 6, wherein the second precursor reacts with the first portion to form the carbon-containing layer; and removing a second precursor effluent comprising the second precursor from the substrate. BRIEF DESCRIPTION OF THE DRAWING So that the manner in which the above recited features of the present disclosure can be understood in detail, a more particular description of the disclosure, briefly summarized above, may be had by reference