High temperature atomic layer deposition of silicon oxide thin films

Patent metadata

Field	Value
Publication number	US-10242864-B2
Application number	US-201615248214-A
Country	US
Kind code	B2
Filing date	Aug 26, 2016
Priority date	Apr 12, 2012
Publication date	Mar 26, 2019
Grant date	Mar 26, 2019

Abstract

Atomic layer deposition (ALD) process formation of silicon oxide with temperature >500° C. is disclosed. Silicon precursors used have a formula of:

R 1 R 2 m Si(NR 3 R 4 ) n X p   I.

wherein R 1 , R 2 , and R 3 are each independently selected from hydrogen, a linear or branched C 1 to C 10 alkyl group, and a C 6 to C 10 aryl group; R 4 is selected from, a linear or branched C 1 to C 10 alkyl group, and a C 6 to C 10 aryl group, a C 3 to C 10 alkylsilyl group; wherein R 3 and R 4 are linked to form a cyclic ring structure or R 3 and R 4 are not linked to form a cyclic ring structure; X is a halide selected from the group consisting of Cl, Br and I; m is 0 to 3; n is 0, 1 or 2; and p is 0, 1 or 2 and m+n+p=3; and

R 1 R 2 m Si(OR 3 ) n (OR 4 ) q X p   II.

wherein R 1 and R 2 are each independently selected from hydrogen, a linear or branched C 1 to C 10 alkyl group, and a C 6 to C 10 aryl group; R 3 and R 4 are each independently selected from a linear or branched C 1 to C 10 alkyl group, and a C 6 to C 10 aryl group; wherein R 3 and R 4 are linked to form a cyclic ring structure or R 3 and R 4 are not linked to form a cyclic ring structure; X is a halide atom selected from the group consisting of Cl, Br and I; m is 0 to 3; n is 0 to 2; q is 0 to 2; p is 0 to 2; and m+n+q+p=3.

First claim

The invention claimed is:

1. A process to deposit silicon oxide comprising the steps of:
a. providing a substrate in a reactor;
b. introducing into the reactor at least one silicon precursor;
c. purging reactor with purge gas;
d. introducing an oxygen source into the reactor; and
e. purging reactor with purge gas; and
wherein steps b through e are repeated until a desired thickness of silicon oxide is deposited;
wherein the process is conducted at one or more temperatures ranging from over 600 to 800° C. and one or more pressures ranging from 50 miliTorr (mT) to 760 Torr; and
wherein the at least one silicon precursor has a formula:
R 1 R 2 m Si(NR 3 R 4 ) n X p   I.

wherein R 1 is methyl; R 2 is methyl; R 3 is selected from hydrogen, a linear or branched C 1 to C 10 alkyl group, and a C 6 to C 10 aryl group; and R 4 is selected from, a linear or branched C 1 to C 10 alkyl group, a C 6 to C 10 aryl group, and a C 3 to C 10 alkylsilyl group, wherein R 3 and R 4 are linked to form a cyclic ring structure or R 3 and R 4 are not linked to form a cyclic ring structure X is a halide selected from the group consisting of Cl, Br and I, m is 2, n is 0 or 1, p is 0 or 1, and m+n+p=3.

2. The process of claim 1 , wherein the at least one silicon precursor is selected from the group consisting of diethylaminotrimethylsilane, dimethylaminotrimethylsilane, ethylmethylaminotrimethylsilane, t-butylaminotrimethylsilane, iso-propylaminotrimethylsilane, di-isopropylaminotrimethylsilane, pyrrolidinotrimethylsilane, 2,6-dimethylpiperidinotrimethylsilane, and mixtures thereof.

3. The process of claim 1 , wherein the at least one silicon precursor is selected from the group consisting of iso-propylaminotrimethylsilane, tert-butylaminotrimethylsilane, iso-butylaminotrimethylsilane, Cyclohexaminotrimethylsilane, pyrrolidinotrimethylsilane, 2-methylpyrrolidinotrimethylsilane, 2,5-dimethylpyrrolidinotrimethylsilane, piperidinotrimethylsilane, 2,6-dimethylpiperidinotrimethylsilane, 1-methylpiperazinotrimethylsilane, pyrrolyltrimethylsilane, 2,5-dimethylpyrrolyltrimethylsilane, imidazolyltrimethylsilane, 1,1,1,3,3,3-hexamethyldisilazane, and chlorotrimethylsilane.

4. The process of claim 1 , wherein the pressure ranges from 50 miliTorr (mT) to 100 Torr.

5. The process of claim 1 , wherein the purge gas is selected from the group consisting of nitrogen, helium and argon.

6. The process of claim 1 , wherein the oxygen source is selected from the group consisting of oxygen, peroxide, oxygen plasma, water vapor, water vapor plasma, hydrogen peroxide, nitrous oxide and ozone source.

7. The process of claim 1 , further comprising, after step e, the steps of:
f. introducing water vapor or hydroxyl source into the reactor; and
g. purging reactor with purge gas;
wherein steps b through g are repeated until a desired thickness of silicon oxide is deposited.

8. The process of claim 2 , further comprising, after step e, the steps of:
f. introducing water vapor or hydroxyl source into the reactor; and
g. purging reactor with purge gas;
wherein steps b through g are repeated until a desired thickness of silicon oxide is deposited.

Assignees

• Air Prod & Chem
• Versum Mat Us Llc

Inventors

• Chandra Haripin
• Wang Meiliang
• Xiao Manchao
• Lei Xinjian
• Pearlstein Ronald Martin
• O'Neill Mark Leonard
• Han Bing

Classifications

• 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

• H10P14/69215 Primary

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

• C23C16/45553

  characterized by the use of precursors specially adapted for ALD · CPC title

• C23C16/52

  Controlling or regulating the coating process {(C23C16/45557, C23C16/279 take precedence)} · CPC title