Methods to prepare silicon-containing films
View Patent ↗Described herein are methods of forming dielectric films such as non-porous dielectric films, comprising silicon, oxide, and optionally nitrogen, carbon, hydrogen, and boron. Also disclosed herein are the methods to form dielectric films or coatings on an object to be processed, such as, for example, a semiconductor wafer. Specifically the methods include silanes that have bulky alkoxy groups as well as SiH groups. Examples of such silanes used in the methods including di-tert-pentoxysilane, di-tert-butoxysilane and silanes having the formula (H) 2 Si(OR)(OR 1 ) wherein R is tert-butyl and R 1 is selected from the group consisting of methyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, pentyl, isopentyl, tert-pentyl and hexyl.
1. A silicon precursor for depositing a film and having the following Formula II:
wherein both R and R 1 are tert-pentyl; or wherein R is tert-butyl and R 1 is selected from the group consisting of methyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, pentyl, isopentyl, tert-pentyl, and hexyl.
2. The silicon precursor of claim 1 wherein both R and R 1 are tert-pentyl.
3. The silicon precursor of claim 1 wherein R is tert-butyl and R 1 is selected from the group consisting of methyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, pentyl, isopentyl, tert-pentyl, and hexyl.
4. A method of forming a film comprising silicon, oxygen, and nitrogen, the method comprising the steps of:
a. placing a substrate into an ALD reactor;
b. introducing into the reactor a silicon precursor comprising at least one selected from the group of precursors having the following Formula II:
wherein both R and R 1 are tert-pentyl; or wherein R is tert-butyl and R 1 is selected from the group consisting of methyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, pentyl, isopentyl, tert-pentyl, and hexyl; and optionally an oxygen source;
c. purging the reactor with a purge gas;
d. introducing a nitrogen source into the reactor;
e. purging the reactor with a purge gas;
f. introducing an oxygen source into the ALD reactor; and
g. purging the ALD reactor with a purge gas, wherein steps b to g are repeated until a desired thickness of the film is obtained.
5. The method of claim 4 wherein the nitrogen source is at least one selected from the group consisting of NH 3 , N 2 O, organic amines such as methylamine (NH 2 (CH 3 )), ethylamine, diethylamine, iso-butylamine, tert-butylamine, nitrogen plasma, a plasma comprising nitrogen and argon, a plasma comprising nitrogen and helium, a plasma comprising nitrogen and hydrogen, a plasma comprising ammonia, and combinations thereof.
6. A method of forming a film comprising silicon, oxygen, and nitrogen, the method comprising the steps of:
a. placing a substrate into an ALD reactor;
b. introducing into the reactor a silicon precursor comprising at least one selected from the group of precursors having the following Formula II:
wherein both R and R 1 are tert-pentyl; or wherein R is tert-butyl and R 1 is selected from the group consisting of methyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, pentyl, isopentyl, tert-pentyl, and hexyl; and optionally an oxygen source;
c. purging the reactor with a purge gas;
d. introducing a nitrogen source into the reactor; and
e. purging the ALD reactor with a purge gas wherein steps b to e are repeated until a desired thickness of the film is obtained.
7. The method of claim 6 wherein the nitrogen source is at least one selected from the group consisting of NH 3 , N 2 O, an organic amines, nitrogen plasma, a plasma comprising nitrogen and argon, a plasma comprising nitrogen and helium, a plasma comprising nitrogen and hydrogen, a plasma comprising ammonia, and combinations thereof.
8. A method for forming a film on at least one surface of a substrate, the method comprising:
providing the at least one surface of the substrate in a reaction chamber; and
introducing into the reaction chamber a silicon precursor to form the film comprising at least one precursor selected from the group of precursors having the following Formula II:
wherein both R and R 1 are tert-pentyl; or wherein R is tert-butyl and R 1 is selected from the group consisting of methyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, pentyl, isopentyl, tert-pentyl, and hexyl; and
introducing into the reaction chamber at least one source comprising an oxygen source wherein the at least one precursor and the at least one source react to form the film on the at least one surface of the substrate.
9. The method of claim 8 wherein at least one source further comprises a nitrogen source.
10. The method of claim 8 wherein the forming is at least one selected from cyclic chemical vapor deposition, plasma enhanced chemical vapor deposition, or atomic layer deposition.
11. The method of claim 8 wherein the silicon precursor further comprises di-tert-butoxysilane.
12. The method of claim 8 wherein the silicon precursor comprises di-tert-pentoxysilane.
13. The method of claim 9 wherein the oxygen source comprises oxygen.
14. The method of claim 9 wherein the oxygen source comprises ozone.
15. The method of claim 10 wherein the at least one source further comprises a nitrogen source.
16. The method of claim 9 wherein the nitrogen source is one selected from the group consisting of NH 3 , N 2 O, NH 2 (CH 3 ), nitrogen plasma, a plasma comprising nitrogen and argon, a plasma comprising nitrogen and helium, a plasma comprising nitrogen and hydrogen, a plasma comprising ammonia, and combinations thereof.
17. A method of forming a non-porous dielectric film comprising silicon and oxygen via an atomic layer deposition process, the method comprising the steps of:
a. placing a substrate into an ALD reactor;
b. introducing into the ALD reactor a silicon precursor comprising at least one selected from the group of precursors having the following Formula II:
wherein both R and R 1 are tert-pentyl; or wherein R is tert-butyl and R 1 is selected from the group consisting of methyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, pentyl, isopentyl, tert-pentyl, and hexyl;
c. purging the ALD reactor with a gas;
d. introducing an oxygen source into the ALD reactor;
e. purging the ALD reactor with the gas; and
f. repeating the steps b through e until a desired thickness of the non-porous dielectric film is obtained wherein the dielectric film comprises from up to about 30 atomic weight % nitrogen as measured by XPS.
18. The method of claim 17 wherein a nitrogen source thereof is introduced into the ALD reactor.
19. The method of claim 17 using a thermal CVD process, wherein the dielectric film comprises up to about 30 atomic weight % nitrogen as measured by XPS.
20. An electropolished stainless steel vessel with an inlet and an outlet having high purity low deadspace valves, comprising at least one silicon precursor having a formula II:
wherein both R and R 1 are tert-pentyl; or wherein R is tert-butyl and R 1 is selected from the group consisting of methyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, pentyl, isopentyl, tert-pentyl, and hexyl.