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

Patent metadata

Field	Value
Publication number	US-2018342390-A1
Application number	US-201815986030-A
Country	US
Kind code	A1
Filing date	May 22, 2018
Priority date	May 24, 2017
Publication date	Nov 29, 2018
Grant date	—

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.

First claim

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

wherein
R 1-3 are each independently selected from the group consisting of hydrogen, methyl, and an organoamino group (NR′R″), wherein R′ and R″ are each independently selected from the group consisting of hydrogen, a C 1-10 linear alkyl group, a C 3-10 branched alkyl group, a C 3-10 cyclic alkyl group, a C 2-10 alkenyl group, a C 4-10 aryl group, and a C 4-10 heterocyclic group, with the proviso that R′ and R″ cannot both be hydrogen;
R 4 and R 5 are each independently selected from the group consisting of hydrogen, a C 1-10 linear alkyl group, a C 3-10 branched alkyl group, a C 3-10 cyclic alkyl group, a C 2-10 alkenyl group, a C 4-10 aryl group, and a C 4-10 heterocyclic group;
R 6-8 are each independently selected from the group consisting of hydrogen, methyl, an organoamino group (NR′R″) as defined above, a C 3-10 branched alkyl group, a C 3-10 cyclic alkyl group, a C 2-10 alkenyl group, a C 4-10 aryl group, and a C 4-10 heterocyclic group, with the proviso that R′ and R″ cannot both be hydrogen,
wherein two or more of substituents R 1-8 , R′, and R″ may be linked to form a substituted or unsubstituted, saturated or unsaturated, cyclic group, and
wherein at least one of R 6-8 must be hydrogen, and at least two of R 6-8 must not be methyl.

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.

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

wherein
R 1-3 are each independently selected from the group consisting of hydrogen, methyl, and an organoamino group (NR′R″), wherein R′ and R″ are each independently selected from the group consisting of hydrogen, a C 1-10 linear alkyl group, a C 3-10 branched alkyl group, a C 3-10 cyclic alkyl group, a C 2-10 alkenyl group, a C 4-10 aryl group, and a C 4-10 heterocyclic group, with the proviso that R′ and R″ cannot both be hydrogen;
R 4 and R 5 are each independently selected from the group consisting of hydrogen, a C 1-10 linear alkyl group, a C 3-10 branched alkyl group, a C 3-10 cyclic alkyl group, a C 2-10 alkenyl group, a C 4-10 aryl group, and a C 4-10 heterocyclic group;
R 6-8 are each independently selected from the group consisting of hydrogen, methyl, an organoamino group (NR′R″) as defined above, a C 3-10 branched alkyl group, a C 3-10 cyclic alkyl group, a C 2-10 alkenyl group, a C 4-10 aryl group, and a C 4-10 heterocyclic group, with the proviso that R′ and R″ cannot both be hydrogen,
wherein two or more of substituents R 1-8 , R′, and R″ may be linked to form a substituted or unsubstituted, saturated or unsaturated, cyclic group, and
wherein at least one of R 6-8 must be hydrogen, and at least two of R 6-8 must not be methyl.

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 . Th

Assignees

• Versum Mat Us Llc

Inventors

• Xiao Manchao
• Macdonald Matthew R

Classifications

• H10P14/69433

  the material being a silicon nitride not containing oxygen, e.g. SixNy or SixByNz · CPC title

• H10P14/69215

  the material being a silicon oxide, e.g. SiO2 · CPC title

• H10P14/6922 Primary

  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 title

• H10P14/6686

  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 title

• H10P14/6532

  by exposure to a plasma · CPC title