Methods for depositing silicon nitride films

Patent metadata

Field	Value
Publication number	US-9905415-B2
Application number	US-201414498044-A
Country	US
Kind code	B2
Filing date	Sep 26, 2014
Priority date	Oct 3, 2013
Publication date	Feb 27, 2018
Grant date	Feb 27, 2018

Abstract

Methods for forming silicon nitride films are disclosed that comprise the steps of: providing a substrate in a reactor; introducing into the reactor an at least one organoaminosilane having a least one SiH 3 group described herein wherein the at least one organoaminosilane reacts on at least a portion of the surface of the substrate to provide a chemisorbed layer; purging the reactor with a purge gas; introducing a plasma comprising nitrogen and an inert gas into the reactor to react with at least a portion of the chemisorbed layer and provide at least one reactive site wherein the plasma is generated at a power density ranging from about 0.01 to about 1.5 W/cm 2 .

First claim

The invention claimed is:

1. A plasma enhanced atomic layer deposition method of forming a silicon nitride film onto at least a surface of a substrate, the method comprising
a. providing a substrate in a reactor;
b. introducing into the reactor an at least one organoaminosilane represented by the following Formulas I, II and III below:

wherein R 1 is selected from a linear or branched C 3 to C 10 alkyl group, a linear or branched C 3 to C 10 alkenyl group, a linear or branched C 3 to C 10 alkynyl group, a C 1 to C 6 dialkylamino group, an electron withdrawing group, and a C 6 to C 10 aryl group; R 2 is selected from hydrogen, a linear or branched C 1 to C 10 alkyl group, a linear or branched C 3 to C 6 alkenyl group, a linear or branched C 3 to C 6 alkynyl group, a C 1 to C 6 dialkylamino group, a C 6 to C 10 aryl group, an electron withdrawing group, and a C 4 to C 10 aryl group; optionally wherein R 1 and R 2 are linked together to form a ring selected from a substituted or unsubstituted aromatic ring or a substituted or unsubstituted aliphatic ring, and in Formula III n=1 or 2, wherein the at least one organoaminosilane reacts on at least a portion of the surface of the substrate to provide a chemisorbed layer;
c. purging the reactor with a purge gas;
d. introducing a plasma consisting essentially of nitrogen and noble gas into the reactor to react with at least a portion of the chemisorbed layer and provide at least one reactive site; and
e. purge the reactor with an inert gas; and wherein the steps b through e are repeated until a desired thickness of the silicon nitride film is obtained; wherein the silicon nitride film has a density of at least 2.7 g/cc.

2. The method of claim 1 wherein the at least one organoaminosilane precursor is selected from the group consisting of di-iso-propylaminosilane, di-sec-butylaminosilane, phenylmethylaminosilane, 2,6-dimethylpiperidinosilane, N-methylcyclohexylaminosilane, N-ethylcyclohexylaminosilane, N-isopropylcyclohexylaminosilane, 2-methylpiperidinosilane, N-silyldecahydroquinoline, 2,2,6,6-tetramethylpiperidinosilane, 2-(N-silylmethylamino)pyridine, N-t-butyldisilazane, N-t-pentyldisilazane, N-(3-methyl-2-pyridyl)disilazane, N-(2-methylphenyl)disilazane, N-(2-ethylphenyl)disilazane, N-(2,4,6-trimethylphenyl)disilazane, N-(2,6-di-iso-pripylphenyl)disilazane, di-iso-propylaminodisilane, di-iso-butylaminodisilane, di-sec-butylaminodisilane, 2,6-dimethylpiperidinosilane, N-methylcyclohexylaminodisilane, N-ethylcyclohexylaminodisilane, phenylmethylaminodisilane, 2-(N-disilylmethylamino)pyridine, N-phenylethyldisilane, N-isopropylcyclohexylaminodisilane, 1,1-(N,N′-di-tert-butylethylenediamino)disilane.

3. The method of claim 1 wherein the plasma comprises a noble gas selected from the group consisting of neon (Ne), argon (Ar), Xenon (Xe), krypton (Kr) and mixtures thereof.

4. The method of claim 1 wherein the method is conducted at one or more temperatures of about 400° C. or less.

5. The method of claim 1 wherein the method is conducted at one or more temperatures of about 300° C. or less.

6. A plasma enhanced atomic layer deposition method of forming a silicon nitride film onto at least a surface of a substrate, the method comprising the steps of:
a. providing a substrate in a reactor;
b. introducing into the reactor at least one organoaminosilane precursor is selected from the group consisting of di-iso-propylaminosilane, di-sec-butylaminosilane, phenylmethylaminosilane, 2,6-dimethylpiperidinosilane, N-methylcyclohexylaminosilane, N-ethylcyclohexylaminosilane, N-isopropylcyclohexylaminosilane, 2-methylpiperidinosilane, N-silyldecahydroquinoline, 2,2,6,6-tetramethylpiperidinosilane, 2-(N-silylmethylamino)pyridine, N-t-butyldisilazane, N-t-pentyldisilazane, N-(3-methyl-2-pyridyl)disilazane, N-(2-methylphenyl)disilazane, N-(2-ethylphenyl)disilazane, N-(2,4,6-trimethylphenyl)disilazane, N-(2,6-di-iso-pripylphenyl)disilazane, di-iso-propylaminodisilane, di-iso-butylaminodisilane, di-sec-butylaminodisilane, 2,6-dimethylpiperidinosilane, N-methylcyclohexylaminodisilane, N-ethylcyclohexylaminodisilane, phenylmethylaminodisilane, 2-(N-disilylmethylamino)pyridine, N-phenylethyldisilane, N-isopropylcyclohexylaminodisilane, 1,1-(N,N′-di-tert-butylethylenediamino)disilane wherein said introducing is for a period of 0.2 to 5 seconds and the at least one organoaminosilane reacts on at least a portion of the surface of the substrate;
c. purging the reactor with a purge gas comprising at least one selected from nitrogen, a noble gas, and combinations thereof;
d. introducing a nitrogen-noble gas containing plasma into the reactor; and
e. purge the reactor with an inert gas; and wherein the steps b through e are repeated until a desired thickness of the silicon nitride film is obtained wherein the nitride film has a refractive index of greater than 1.9 and a density of greater than 2.7 g/cc.

7. The method of claim 6 wherein the method is conducted at a temperature of 400° C. or less.

8. The method of claim 6 wherein the method is conducted at a temperature of 300° C. or less.

9. The method of claim 6 where the nitrogen-noble gas containing plasma consists essentially of a member selected from the group consisting of an argon/nitrogen plasma, a neon/nitrogen plasma, a krypton/nitrogen plasma, a xenon/nitrogen plasma, and combinations thereof.

10. A plasma enhanced atomic layer deposition method of forming a silicon nitride film onto at least a surface of a substrate, the method comprising the steps of:
a. providing a substrate in a reactor;
b. introducing into the reactor at least one organoaminosilane precursor is selected from the group consisting of di-iso-propylaminosilane, di-sec-butylaminosilane, phenylmethylaminosilane, 2,6-dimethylpiperidinosilane, N-methylcyclohexylaminosilane, N-ethylcyclohexylaminosilane, N-isopropylcyclohexylaminosilane, 2-methylpiperidinosilane, N-silyldecahydroquinoline, 2,2,6,6-tetramethylpiperidinosilane, 2-(N-silylmethylamino)pyridine, N-t-butyldisilazane, N-t-pentyldisilazane, N-(3-methyl-2-pyridyl)disilazane, N-(2-methylphenyl)disilazane, N-(2-ethylphenyl)disilazane, N-(2,4,6-trimethylphenyl)disilazane, N-(2,6-di-iso-pripylphenyl)disilazane, di-iso-propylaminodisilane, di-iso-butylaminodisilane, di-sec-butylaminodisilane, 2,6-dimethylpiperidinosilane, N-methylcyclohexylaminodisilane, N-ethylcyclohexylaminodisilane, phenylmethylaminodisilane, 2-(N-disilylmethylamino)pyridine, N-phenylethyldisilane, N-isopropylcyclohexylaminodisilane, 1,1-(N,N′-di-tert-butylethylenediamino)disilane wherein the at least one organoaminosilane reacts on at least a portion of the surface of the substrate to provide a chemisorbed layer;
c. purging the reactor with a purge gas comprising at least one selected from nitrogen, a noble gas, and combinations thereof;
d. introducing a plasma comprising a noble gas into the reactor to react with at least a portion of the chemisorbed layer and provide an at least one reactive site wherein the plasma is generated at a power density ranging from about 0.01 to about 1.5 W/cm 2 ; and
e. purge the reactor with an inert gas; and wherein the steps b through e are repeated until a desired thickness of the silicon nitride film is obtained; wherein the silicon nitride film has a density of at least 2.7 g/cc.

11. The method of claim 10 wherein the method is conducted at a temperature of 400° C. or less.

12. The method of claim 10 wherein the noble gas plasma comprises a noble gas selected from the group consisting of neon (Ne), argon (Ar), Xenon (Xe), krypton (Kr) and

Assignees

• Air Prod & Chem
• Versum Mat Us Llc

Inventors

• Chandra Haripin
• Mallikarjunan Anupama
• Lei Xinjian
• Kim Moo Sung
• Cuthill Kirk Scott
• Oneill Mark Leonard

Classifications

• H10P14/6689

  the compound being a silazane · CPC title

• H10P14/6682

  the compound being a silane, e.g. disilane, methylsilane or chlorosilane · CPC title

• H10P14/6339

  deposition by cyclic CVD, e.g. ALD, ALE or pulsed CVD · CPC title

• H10P14/6336

  in the presence of a plasma [PECVD] · CPC title

• H10P14/69433 Primary

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