Methods for depositing silicon dioxide or silicon oxide films using aminovinylsilanes
View Patent ↗Described herein are methods to form silicon dioxide films that have extremely low wet etch rate in HF solution using a thermal CVD process, ALD process or cyclic CVD process in which the silicon precursor is selected from one of: R 1 n R 2 m Si(NR 3 R 4 ) 4-n-m ; and, a cyclic silazane of (R 1 R 2 SiNR 3 ) p , where R 1 is an alkenyl or an aromatic, such as vinyl, allyl, and phenyl; R 2 , R 3 , and R 4 are selected from H, alkyl with C 1 -C 10 , linear, branched, or cyclic, an alkenyl with C 2 -C 10 linear, branched, or cyclic, and aromatic; n=1-3, m=0-2; p=3-4.
1. A low pressure, thermal chemical vapor deposition method of forming a silicon dioxide film that has extremely low wet etch rate in HF solution, comprising:
a. delivering a first precursor that provides a source for silicon to a low pressure, thermal chemical vapor deposition reactor in which the first precursor is selected from the group consisting of: R 1 n R 2 m Si(NR 3 R 4 ) 4-n-m , and a cyclic silazane of (R 1 R 2 SiNR 3 ) p ; where R 1 is a C 2 -C 10 alkenyl or aromatic; R 2 , R 3 , and R 4 are selected from H, alkyl with C 1 -C 10 , linear, branched, or cyclic, an alkenyl with C 2 -C 10 linear, branched, or cyclic, and aromatic; and n=1-3, m=0-2, p=3-4;
b. delivering a second precursor that provide a source for oxygen to the reactor;
c. reacting the first and second precursors at temperature between 400° C. to 700° C. under a pressure of 100 mT to 1 T.
2. The method of claim 1 in which R 1 is selected from the group consisting of vinyl, allyl, and phenyl.
3. The method of claim 1 in which the first precursor is Bis(isopropylamino)vinylmethylsilane.
4. The method of claim 1 in which the oxygen precursor is selected from the group consisting of oxygen, ozone and mixtures thereof.
5. An atomic layer deposition method of forming a film selected from a silicon oxide or silicon diaxide film, wherein the film has a wet etch rate in HF solutiion that is lower than an etch rate of a thermal silicon dioxide film, comprising:
a. delivering a first precursor that provides a source for silicon to an atomic layer deposition reactor in which the first precursor is selected from the group consisting of: R 1 n R 2 m Si(NR 3 R 4 ) 4-n-m , and a cyclic silazane of (R 1 R 2 SiNR 3 ) p ; where R 1 is a C 2 -C 10 alkenyl or an aromatic; R 2 , R 3 , and R 4 are selected from H, alkyl with C 1 -C 10 , linear, branched, or cyclic, an alkenyl with C 2 -C 10 linear, branched, or cyclic, and aromatic; and n=1-3, m=0-2, p=3-4;
b. purging the reactor with an inert gas;
c. delivering a second precursor that provide a source for oxygen to the reactor;
d. purging the reactor with an inert gas;
e. repeating the steps between (a) and (d) until a desired thickness of the films is achieved.
6. The method of claim 5 in which R 1 is selected from the group consisting of vinyl, allyl, and phenyl.
7. The method of claim 5 in which the first precursor is Bis(isopropylamino)vinylmethylsilane.
8. The method of claim 5 in which the oxygen precursor is selected from the group consisting of oxygen, ozone and mixtures thereof.
9. A cyclic chemical vapor deposition method of forming a film selected from a silicon oxide or silicon dioxide film wherein the film has a wet etch rate in HF solution that is lower than an etch rate of a thermal silicon dioxide film, comprising:
a. delivering a first precursor that provides a source for silicon to a cyclic chemical vapor deposition reactor in which the first precursor is selected from the group consisting of: R1nR2mSi(NR3R4)4-n-m, and a cyclic silazane of (R1R2SiNR3)p; where R1 is a C2-C10 alkenyl or an aromatic; R2, R3, and R4 are selected from H, alkyl with C1-C10, linear, branched, or cyclic, an alkenyl with C2-C10 linear, branched, or cyclic, and aromatic; and n=1-3, m=0-2, p=3-4;
b. purging the reactor with an inert gas for 0.1 to 1 seconds;
c. delivering a second precursor that provides a source of oxygen to the reactor;
d. purging the reactor with an inert gas for 0.1-1 seconds;
e. repeating the steps between (a) and (d) until a desired thickness of the films is achieved.
10. The method of claim 9 in which R 1 is selected from the group consisting of vinyl, allyl, and phenyl.
11. The method of claim 9 in which the first precursor is Bis(isopropylamino)vinylmethylsilane.
12. The method of claim 9 in which the oxygen precursor is selected from the group consisting of oxygen, ozone and mixtures thereof.
13. An atomic layer deposition method of forming a film selected from a silicon dioxide or a silicon oxide film, comprising:
a. delivering a first precursor that provides a source for silicon to an atomic layer deposition reactor in which the first precursor comprises a compound having the following formula: R 1 n R 2 m Si(NR 3 R 4 ) 4-n-m where R 1 is a C 2 -C 10 alkenyl or an aromatic; R 2 , R 3 , and R 4 are selected from H, alkyl with C 1 -C 10 , linear, branched, or cyclic, an alkenyl with C 2 -C 10 linear, branched, or cyclic, and aromatic; and n=1-3 and m=0-2;
b. purging the reactor with an inert gas;
c. delivering a second precursor that provide a source for oxygen to the reactor;
d. purging the reactor with an inert gas;
e. repeating the steps between (a) and (d) until a desired thickness of the films is achieved.
14. The method of claim 13 wherein the first precursors is at least one selected from the group consisting of: Bis(isopropylamino)vinylmethylsilane (BIPAVNS), Bis(isopropylamino)divinylsilane (BIPADVS), Bis(isopropylamino)vinylsilane, Bis(isopropylamino)allylmethylsilane, Bis(isopropylamino)diallylsilane, Bis(isopropylamino)allylsilane, Bis(t-butylamino)vinylmethylsilane, Bis(t-butylaminoamino)divinylsilane, Bis(t-butylaminoamino)vinylsilane, Bis(t-butylaminoamino)allylmethylsilane, Bis(t-butylaminoamino)diallylsilane, Bis(t-butylaminoamino)allylsilane, Bis(diethylamino)vinylmethylsilane, Bis(diethylamino)divinylsilane, Bis(diethylamino)vinylsilane, Bis(diethylamino)allylmethylsilane, Bis(diethylamino)diallylsilane, Bis(diethylamino)allylsilane, Bis(dimethylamino)vinylmethylsilane, Bis(dimethylamino)divinylsilane, Bis(dimethylamino)vinylsilane, Bis(dimethylamino)allylmethylsilane, Bis(dimethylamino)diallylsilane, Bis(dimethylamino)allylsilane, Bis(methylethylamino)vinylmethylsilane, Bis(methyethylamino)divinylsilane, Bis(methyethylamino)vinylsilane, Bis(methyethylamino)allylmethylsilane, Bis(methyethylamino)diallylsilane, Bis(methyethylamino)allylsilane, Dipiperidinovinylmethylsilane, Dipiperidinodivinylsilane, Dipiperidinovinylsilane, Dipiperidinoallylmethylsilane, Dipiperidinodiallylsilane, Dipiperidinoallylsilane, Dipyrrolidinovinylmethylsilane, Dipyrrolidinodivinylsilane, Dipyrrolidinovinylsilane, Dipyrrolidinoallylmethylsilane, Dipyrrolidinodiallylsilane, Dipyrrolidinoallylsilane, Tris(isopropylamino)vinylsilane, Tris(isopropylamino)allylsilane, Tris(t-butylamino)vinylsilane, Tris(t-butylamino)allylsilane, Tris(diethylamino)vinylsilane, Tris(diethylamino)allylsilane, Tris(dimethylamino)vinylsilane, Tris(dimethylamino)allylsilane, Tris(methylethylamino)vinylsilane, Tris(methylethylamino)allylsilane, Tripiperidinovinylsilane, Tripiperidinoallylsilane, Tripyrrolidinovinylsilane, and Tripyrrolidinoallylsilane.
15. A cyclic chemical vapor deposition method of forming a film selected from a silicon dioxide or a silicon oxide film, comprising:
a. delivering a first precursor that provides a source for silicon to a cyclic chemical vapor deposition reactor in which the first precursor comprises a compound having the following formula: R 1 n R 2 m Si(NR 3 R 4 ) 4-n-m ; where R 1 is a C 2 -C 10 alkenyl or an aromatic; R 2 , R 3 , and R 4 are selected from H, alkyl with C 1 -C 10 , linear, branched, or cyclic, an alkenyl with C 2 -C 10 linear, branched, or cyclic, and aromatic; and n=1-3 and m=0-2;
b. purging the reactor with an inert gas;
c. delivering a second precursor that provides a source of oxygen to the reactor;
d. purging the reactor with an inert gas;
e. repeating the steps between (a) and (d) until a desired thickness of the films is achieved.
16. The method of claim 15 wherein the first precursors is at least one selected from the group consisting of: Bis(isopropylamino)vinylmethylsilane (BIPAVNS), Bis(isopropylamino)divinylsilane (BIPADVS), Bis(isopropylamino)vinylsilane, Bis(isopropylamino)allylmethylsilane, Bis(isopropylamino)diallylsilane, Bis(isopropylamino)allylsilane, Bis(t-butylamino)vinylmethylsilane, Bis(t-butylaminoamino)divinylsilane, Bis(t-butylaminoamino)vinylsilane, Bis(t-butylaminoamino)allylmethylsilane, Bis(t-butylaminoamino)diallylsilane, Bis(t-butylaminoamino)allylsilane, Bis(diethylamino)vinylmethylsilane, Bis(diethylamino)divinylsilane, Bis(diethylamino)vinylsilane, Bis(diethylamino)allylmethylsilane, Bis(diethylamino)diallylsilane, Bis(diethylamino)allylsilane, Bis(dimethylamino)vinylmethylsilane, Bis(dimethylamino)divinylsilane, Bis(dimethylamino)vinylsilane, Bis(dimethylamino)allylmethylsilane, Bis(dimethylamino)diallylsilane, Bis(dimethylamino)allylsilane, Bis(methylethylamino)vinylmethylsilane, Bis(methyethylamino)divinylsilane, Bis(methyethylamino)vinylsilane, Bis(methyethylamino)allylmethylsilane, Bis(methyethylamino)diallylsilane, Bis(methyethylamino)allylsilane, Dipiperidinovinylmethylsilane, Dipiperidinodivinylsilane, Dipiperidinovinylsilane, Dipiperidinoallylmethylsilane, Dipiperidinodiallylsilane, Dipiperidinoallylsilane, Dipyrrolidinovinylmethylsilane, Dipyrrolidinodivinylsilane, Dipyrrolidinovinylsilane, Dipyrrolidinoallylmethylsilane, Dipyrrolidinodiallylsilane, Dipyrrolidinoallylsilane, Tris(isopropylamino)vinylsilane, Tris(isopropylamino)allylsilane, Tris(t-butylamino)vinylsilane, Tris(t-butylamino)allylsilane, Tris(diethylamino)vinylsilane, Tris(diethylamino)allylsilane, Tris(dimethylamino)vinylsilane, Tris(dimethylamino)allylsilane, Tris(methylethylamino)vinylsilane, Tris(methylethylamino)allylsilane, Tripiperidinovinylsilane, Tripiperidinoallylsilane, Tripyrrolidinovinylsilane, and Tripyrrolidinoallylsilane.