Formation of SiOCN thin films
Methods for depositing silicon oxycarbonitride (SiOCN) thin films on a substrate in a reaction space are provided. The methods can include at least one plasma enhanced atomic layer deposition (PEALD) cycle including alternately and sequentially contacting the substrate with a silicon precursor and a second reactant that does not include oxygen. In some embodiments the methods allow for the deposition of SiOCN films having improved acid-based wet etch resistance.
1. A method of forming a silicon oxycarbonitride (SiOCN) thin film on a substrate in a reaction space by a plasma enhanced atomic layer deposition (PEALD) process, wherein the PEALD process comprises at least one deposition cycle comprising:
contacting a surface of the substrate with a vapor phase silicon precursor to thereby adsorb a silicon species on the surface of the substrate;
contacting the adsorbed silicon species with at least one reactive species generated by plasma formed from gas that does not comprise oxygen, wherein the adsorbed silicon species is not contacted with oxygen-containing reactive species formed from gas; and
optionally repeating the contacting steps until a SiOCN film of a desired thickness has been formed;
wherein the silicon precursor is selected from the group consisting of the following general formulas:
(R I O) 4-x Si(R II —NH 2 ) x (1)
wherein x is an integer from 1 to 4;
R I is independently selected from the group consisting of alkyl groups; and
R II is an independently selected from the group consisting of hydrocarbon groups;
(R I O) 3 Si—R II —NH 2 (2)
wherein R I is independently selected from the group consisting of alkyl groups; and
R II is independently selected from the group consisting of hydrocarbon groups; and
(R I O) 4-x Si(—[CH 2 ] n —NH 2 ) x (3)
wherein x is an integer from 1 to 4;
n is an integer from 1-5; and
R I is independently selected from the group consisting of alkyl groups.
2. The method of claim 1 , wherein a ratio of a wet etch rate the SiOCN thin film to a wet etch rate of thermal silicon oxide is less than about 5.
3. The method of claim 1 , wherein a ratio of a wet etch rate the SiOCN thin film to a wet etch rate of thermal silicon oxide is less than about 0.3.
4. The method of claim 1 , wherein a ratio of a wet etch rate the SiOCN thin film to a wet etch rate of thermal silicon oxide is less than about 0.1.
5. The method of claim 1 , wherein the SiOCN thin film is deposited on a three-dimensional structure on the substrate.
6. The method of claim 5 , wherein a wet etch rate ratio of a wet etch rate of SiOCN formed on a top surface of the three-dimensional structure to a wet etch rate of the SiOCN formed on a sidewall surface of the three-dimensional structure is about 1:1 in dilute HF.
7. The method of claim 1 , wherein the vapor phase silicon precursor does not comprise a halogen.
8. The method of claim 1 , wherein the silicon precursor comprises (3-aminopropyl)trimethoxysilane (APTMS).
9. The method of claim 1 , wherein the reactive species comprises hydrogen plasma, hydrogen atoms, hydrogen radicals, or hydrogen ions.
10. The method of claim 1 , wherein the reactive species is generated from a second reactant comprising a noble gas.
11. The method of claim 9 , wherein the reactive species further comprises nitrogen plasma, nitrogen atoms, nitrogen radicals, or nitrogen ions.
12. The method of claim 1 , wherein the reactive species is generated by plasma from a second reactant comprising hydrogen.
13. The method of claim 12 , wherein the second reactant comprises H 2 .
14. The method of claim 1 , wherein the SiOCN thin film comprises at least 20 at % oxygen.
15. The method of claim 1 , wherein the SiOCN thin film comprises at least 5 at % carbon.
16. The method of claim 1 , wherein the SiOCN thin film comprises at least 5 at % nitrogen.
17. A method of forming a silicon oxycarbonitride (SiOCN) thin film on a substrate in a reaction space comprising a plurality of deposition cycles, wherein at least one deposition cycle comprises:
alternately and sequentially contacting a surface of the substrate with a silicon precursor and a second reactant comprising at least one reactive species generated by plasma from gas that does not comprise oxygen, wherein the surface of the substrate is not contacted with oxygen-containing reactive species generated from gas;
wherein the deposition cycle is repeated two or more times to form the SiOCN thin film; and
wherein the silicon precursor has a general formula:
L n Si(OR I ) 4-x-y-z-n (R II NR III R IV ) x H y (OH) z
wherein n is an integer from 0 to 3, x is an integer from 1 to 4, y is an integer from 0 to 3, z is an integer from 0 to 3; and 4-x-y-z-n is from 0 to 3;
R I is independently selected from the group consisting of alkyl groups;
R II is independently selected from the group consisting of hydrocarbon groups;
R III and R IV are independently selected from the group consisting of alkyl groups and hydrogen; and
L is independently selected from the group consisting of alkyl groups and halogens.
18. The method of claim 17 , wherein the silicon precursor has a general formula:
L n Si(OR I ) 4-x-n (R II NR III R IV ) x
wherein n is an integer from 0 to 3, x is an integer from 1 to 3;
L is independently selected from the group consisting of alkyl groups and halogens;
R I is independently selected from the group consisting of alkyl groups;
R II is independently selected from the group consisting of hydrocarbon groups; and
R III and R IV are independently selected from the group consisting of alkyl groups and hydrogen.
19. The method of claim 17 , wherein the silicon precursor has a general formula:
Si(OR I ) 4-x-y-z (R II NR III R IV ) x H y (OH) z
wherein x is an integer from 1 to 4, y is an integer from 0 to 3, z is an integer from 0 to 3;
R I is independently selected from the group consisting of alkyl groups;
R II is independently selected from the group consisting of hydrocarbon groups; and
R III and R IV are independently selected from the group consisting of alkyl and hydrogen.
20. The method of claim 17 , wherein the silicon precursor has a general formula:
Si(OR I ) 4-x (R II NR III R IV ) x
wherein x is an integer from 1 to 4;
R I is independently selected from the group consisting of alkyl groups;
R II is independently selected from the group consisting of hydrocarbon groups; and
R III and R IV are independently selected from the group consisting of alkyl groups and hydrogen.
21. The method of claim 17 , wherein the silicon precursor comprises APTMS.
22. The method of claim 17 , wherein at least one deposition cycle is a PEALD cycle.
23. The method of claim 17 , wherein a reactive species is generated by applying RF power of 100 Watts (W) to about 1000 W to the second reactant.
24. The method of claim 17 , wherein the deposition cycle is carried out at a process temperature of about 300° C. to about 400° C.
25. The method of claim 17 , wherein the deposition cycle is carried out at a process temperature of less than about 100° C.
26. The method of claim 17 , wherein the substrate comprises an organic material.
27. A method for depositing a silicon oxycarbonitride (SiOCN) thin film on a substrate in a reaction space comprising:
contacting a surface of the substrate with a silicon precursor comprising;
at least one ligand bonded through carbon to a silicon atom and containing an NH 2 -group attached to a carbon chain; and
at least one ligand bonded to the silicon atom through an oxygen atom and in which an alkyl group is bonded to the oxygen atom;
exposing the substrate to a purge gas and/or vacuum to remove excess silicon precursor and reaction byproducts, if any;
contacting a surface of the substrate with a second reactant comprising hydrogen, wherein the second reactant comprises at least one reactive species generated by plasma and wherein surface of the substrate is not contacted with oxygen-containing reactive species generated from gas;
exposing the substrate to a purge gas and/or vacuum to remove excess second reactant and reaction byproducts, if any;
repeating the contacting steps until a SiOCN thin film of desired thickness has been formed.