Functionalized Cyclosilazanes as Precursors For High Growth Rate Silicon-Containing Films

• US 20180342390A1
• Filed: 05/22/2018
• Published: 11/29/2018
• Est. Priority Date: 05/24/2017
• Status: Active Grant

• Current Assignee: Versum Materials US Inc.
• Original Assignee: Versum Materials US Inc.
• Inventors: Xiao, Manchao, MacDonald, Matthew R.
• Granted Patent: US 11,177,127 B2
• Time in Patent Office: Days
• CPC Class Codes: C07F 7/10 containing nitrogen having a Si-N linkage
• CPC Class Codes: C23C 16/345 Silicon nitride
• CPC Class Codes: C23C 16/402 Silicon dioxide
• CPC Class Codes: C23C 16/45553 characterized by the use of precursors specially adapted for ALD
• CPC Class Codes: C23C 16/56 After-treatment
• CPC Class Codes: H01L 21/02126 the material containing Si, O, and at least one of H, N, C, F, or other non-metal elements, e.g. SiOC, SiOC:H or SiONC
• CPC Class Codes: H01L 21/02164 the material being a silicon oxide, e.g. SiO2
• CPC Class Codes: H01L 21/0217 the material being a silicon nitride not containing oxygen, e.g. SixNy or SixByNz H01L21/02126 and H01L21/0214 take precedence
• CPC Class Codes: H01L 21/02216 the compound being a molecule comprising at least one silicon-oxygen bond and the compound having hydrogen or an organic group attached to the silicon or oxygen, e.g. a siloxane
• CPC Class Codes: H01L 21/02222 the compound being a silazane
• CPC Class Codes: H01L 21/02274 in the presence of a plasma [PECVD]
• CPC Class Codes: H01L 21/02277 the reactions being activated by other means than plasma or thermal, e.g. photo-CVD
• CPC Class Codes: H01L 21/0228 deposition by cyclic CVD, e.g. ALD, ALE, pulsed CVD
• CPC Class Codes: H01L 21/0234 treatment by exposure to a plasma

Abstract

Described herein are functionalized cyclosilazane precursor compounds and compositions and methods comprising same to deposit a silicon-containing film such as, without limitation, silicon oxide, silicon nitride, silicon oxynitride, silicon carbonitride, silicon oxycarbonitride, or carbon-doped silicon oxide via a thermal atomic layer deposition (ALD) or plasma enhanced atomic layer deposition (PEALD) process, or a combination thereof.

Claims

1. A silicon precursor compound according to one of Formulae A, B, C, D, or E:

2. The composition of claim 1 further comprising at least one purge gas.

3. A composition of claim 1, wherein the at least one silicon precursor compound selected from one of Formulae A to E comprises at least one selected from the group consisting of 1-silyl-2,2,4,4,6,6-hexamethylcyclotrisilazane, 1-(iso-propylaminosilyl)-2,2,4,4,6,6-hexamethylcyclotrisilazane, 1-(dimethylaminosilyl)-2,2,4,4,6,6-hexamethylcyclotrisilazane, 1-(iso-propylaminosilyl)-2,2,4,4,6,6-hexamethylcyclotrisilazane, 1-(methylaminosilyl)-2,2,4,4,6,6-hexamethylcyclotrisilazane, 1-(dimethylaminomethylsilyl)-2,2,4,4,6,6-hexamethylcyclotrisilazane, 2-dimethylamino-1,2,3,4,5,6-hexamethylcyclotrisilazane, 1-(dimethylamino-methylsilyl)-2,4,6-trimethylcyclotrisilazane, 1,2,3-trisilyl-2,2,4,4,6,6-hexamethylcyclotrisilazane, 1,2,3-trisilyl-2,4,6-trimethylcyclotrisilazane, 2,2,4,4,5,6,6-heptamethyl-1,3-dioxa-5-aza-2,4,6-trisilacyclohexane, 5-ethyl-2,2,4,4,6,6-hexamethyl-1,3-dioxa-5-aza-2,4,6-trisilacyclohexane, 5-n-propyl-2,2,4,4,6,6-hexamethyl-1,3-dioxa-5-aza-2,4,6-trisilacyclohexane, 5-iso-propyl-2,2,4,4,6,6-hexamethyl-1,3-dioxa-5-aza-2,4,6-trisilacyclohexane, 5-silyl-2,2,4,4,6,6-hexamethyl-1,3-dioxa-5-aza-2,4,6-trisilacyclohexane, 5-methylsilyl-2,2,4,4,6,6-hexamethyl-1,3-dioxa-5-aza-2,4,6-trisilacyclohexane, 5-(dimethylaminosilyl)-2,2,4,4,6,6-hexamethyl-1,3-dioxa-5-aza-2,4,6-trisilacyclohexane, 5-(dimethylaminomethylsilyl)-2,2,4,4,6,6-hexamethyl-1,3-dioxa-5-aza-2,4,6-trisilacyclohexane.

5. A method of depositing a silicon-containing film onto a substrate, the method comprising the steps of:

a) providing a substrate in a reactor;

b) introducing into the reactor at least one silicon precursor compound of claim 1;

c) purging the reactor with purge gas;

d) introducing an oxygen-containing or nitrogen-containing source (or combination thereof) into the reactor; and

e) purging the reactor with purge gas,

wherein steps b through e are repeated until a desired thickness of film is deposited, and

wherein the method is conducted at one or more temperatures ranging from about 25°

C. to 600°

C.

6. The method of claim 5, wherein the at least one silicon precursor compound is selected from the group consisting of 2,2,4,4,6,6-hexamethylcyclotrisilazane, 1-silyl-2,2,4,4,6,6-hexamethylcyclotrisilazane, 1-(iso-propylaminosilyl)-2,2,4,4,6,6-hexamethylcyclotrisilazane, 1-(dimethylaminosilyl)-2,2,4,4,6,6-hexamethylcyclotrisilazane, 1-(iso-propylaminosilyl)-2,2,4,4,6,6-hexamethylcyclotrisilazane, 1-(methylaminosilyl)-2,2,4,4,6,6-hexamethylcyclotrisilazane, 1-(dimethylaminomethylsilyl)-2,2,4,4,6,6-hexamethylcyclotrisilazane, 1,2,3,4,5,6-hexamethylcyclotrisilazane, 2-dimethylamino-1,2,3,4,5,6-hexamethylcyclotrisilazane, 1-(dimethylamino-methylsilyl)-2,4,6-trimethylcyclotrisilazane, 1,2,3-trisilyl-2,2,4,4,6,6-hexamethylcyclotrisilazane, 1,2,3-trisilyl-2,4,6-trimethylcyclotrisilazane, 2,2,4,4,6,6-hexamethyl-1,3-dioxa-5-aza-2,4,6-trisilacyclohexane, 2,2,4,4,5,6,6-heptamethyl-1,3-dioxa-5-aza-2,4,6-trisilacyclohexane, 5-ethyl-2,2,4,4,6,6-hexamethyl-1,3-dioxa-5-aza-2,4,6-trisilacyclohexane, 5-n-propyl-2,2,4,4,6,6-hexamethyl-1,3-dioxa-5-aza-2,4,6-trisilacyclohexane, 5-iso-propyl-2,2,4,4,6,6-hexamethyl-1,3-dioxa-5-aza-2,4,6-trisilacyclohexane, 5-silyl-2,2,4,4,6,6-hexamethyl-1,3-dioxa-5-aza-2,4,6-trisilacyclohexane, 5-methylsilyl-2,2,4,4,6,6-hexamethyl-1,3-dioxa-5-aza-2,4,6-trisilacyclohexane, 5-(dimethylaminosilyl)-2,2,4,4,6,6-hexamethyl-1,3-dioxa-5-aza-2,4,6-trisilacyclohexane, 5-(dimethylaminomethylsilyl)-2,2,4,4,6,6-hexamethyl-1,3-dioxa-5-aza-2,4,6-trisilacyclohexane

7. The method of claim 5, wherein the oxygen-containing source is selected from the group consisting of an ozone, an oxygen plasma, a plasma comprising oxygen and argon, a plasma comprising oxygen and helium, an ozone plasma, a water plasma, a nitrous oxide plasma, a carbon dioxide plasma, and combinations thereof.

8. The method of claim 5, wherein the nitrogen-containing source is selected from the group consisting of ammonia, hydrazine, monoalkylhydrazine, dialkylhydrazine, nitrogen, nitrogen/hydrogen, nitrogen/argon plasma, nitrogen/helium plasma, ammonia plasma, nitrogen plasma, nitrogen/hydrogen plasma, organic amines such as tert-butylamine, dimethylamine, diethylamine, isopropylamine, diethylamine plasma, dimethylamine plasma, trimethyl plasma, trimethylamine plasma, ethylenediamine plasma, and an alkoxyamine such as ethanolamine plasma and mixtures thereof.

9. The method of claim 5 wherein the oxygen-containing source and/or the nitrogen-containing source comprises plasma.

10. The method of claim 9 wherein the plasma is generated in situ.

11. The method of claim 9 wherein the plasma is generated remotely.

12. The method of claim 5 wherein a density of the film is about 2.1 g/cc or greater.

13. The method of claim 5 wherein the film further comprises carbon.

14. The method of claim 5 wherein a density of the film is about 1.8 g/cc or greater.

15. The method of claim 5 wherein a carbon content of the film is 0.5 atomic weight percent (at. %) as measured by X-Ray photospectroscopy or greater.

16. A film formed by the method of claim 5.

17. A film formed by the method of claim 9.

4. A composition comprising at least one silicon precursor compound selected from one of Formulae B, C, or E: