Silicon-based films and methods of forming the same
Disclosed herein are containing silicon-based films and compositions and methods for forming the same. The silicon-based films contain <50 atomic % of silicon. In one aspect, the silicon-based films have a composition Si x C y N z wherein x is about 0 to about 55, y is about 35 to about 100, and z is about 0 to about 50 atomic weight (wt.) percent (%) as measured by XPS. In another aspect, the silicon-based films were deposited using at least one organosilicon precursor comprising two silicon atoms, at least one Si-Me group, and an ethylene or propylene linkage between the silicon atoms such as 1,4-disilapentane.
1. A method for forming a silicon-based film on at least a portion of the surface of a substrate, the method comprising:
providing at least one surface of the substrate in a reactor;
introducing at least one organosilicon precursor compound having the following Formulae A through D into the reactor:
wherein X 1 and X 2 are each independently selected from the group consisting of a hydrogen atom, and an organoamino group having the formula NR 1 R 2 wherein R 1 is selected from the group consisting of a linear C 1 to C 10 alkyl group, a branched C 3 to C 10 alkyl group, a cyclic 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, wherein X 1 and X 2 cannot both be hydrogen; R 2 is selected from the group consisting of a hydrogen atom, a linear C 1 to C 10 alkyl group, a branched C 3 to C 10 alkyl group, a cyclic C 3 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, a linear C 1 to C 6 fluorinated alkyl group, a branched C 3 to C 6 fluorinated alkyl group, an electron withdrawing group, and a C 4 to C 10 aryl group and 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; R 3 , R 4 , and R 5 are each independently selected from the group consisting of a hydrogen atom and a methyl (CH 3 ) group; and R 6 is selected from the group consisting of a hydrogen atom, a linear C 1 to C 10 alkyl group, a branched C 3 to C 10 alkyl group, a cyclic 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; and
forming the silicon-based film on the at least one surface by a deposition process selected from the group consisting of chemical vapor deposition (CVD), low pressure chemical vapor deposition (LPCVD), plasma enhanced chemical vapor deposition (PECVD), cyclic chemical vapor deposition (CCVD), plasma enhanced cyclic chemical vapor deposition (PECCVD, atomic layer deposition (ALD), and plasma enhanced atomic layer deposition (PEALD), wherein the silicon-based film comprises from about 0 to about 50 atomic weight percent silicon as measured by X-ray photoelectron spectroscopy (XPS).
2. The method of claim 1 wherein the forming step is conducted at one or more temperatures ranging from about 100° C. to 650° C.
3. The method of claim 1 wherein the silicon-based film is selected from the group consisting of a silicon carbide film, a silicon nitride film, and a silicon carbonitride film.
4. The method of claim 1 wherein the deposition process is LPCVD.
5. The method of claim 1 wherein the deposition process comprises PECVD.
6. The method of claim 1 further comprising: providing a nitrogen-containing precursor and wherein a ratio of the amount of the nitrogen-containing precursor to the amount of at least one organosilicon precursor ranges from 0.25 to 1.
7. A method for forming a silicon-based film on at least one surface of a substrate, the method comprising:
providing at least one surface of the substrate in a reaction chamber;
introducing at least one organosilicon precursor compound having the following Formulae A through D into the reactor:
wherein X 1 and X 2 are each independently selected from the group consisting of a hydrogen atom, and an organoamino group having the formula NR 1 R 2 wherein R 1 is selected from the group consisting of a linear C 1 to C 10 alkyl group, a branched C 3 to C 10 alkyl group, a cyclic 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, wherein X 1 and X 2 cannot both be hydrogen; R 2 is selected from the group consisting of a hydrogen atom, a linear C 1 to C 10 alkyl group, a branched C 3 to C 10 alkyl group, a cyclic C 3 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, a linear C 1 to C 6 fluorinated alkyl group, a branched C 3 to C 6 fluorinated alkyl group, an electron withdrawing group, and a C 4 to C 10 aryl group, and 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; R 3 , R 4 , and R 5 are each independently selected from the group consisting of a hydrogen atom and a methyl (CH 3 ) group; and R 6 is selected from the group consisting of a hydrogen atom, a linear C 1 to C 10 alkyl group, a branched C 3 to C 10 alkyl group, a cyclic 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;
optionally providing a nitrogen-containing precursor selected from the group consisting of ammonia, hydrazine, monoalkylhydrazine, dialkylhydrazine, primary amine, secondary amine, tertiary amine, and mixture thereof in the reaction chamber; and
forming the silicon-based film on the at least one surface by a deposition process comprising plasma enhanced chemical vapor deposition (PECVD), wherein the silicon-based film comprise from about 0 to about 50 atomic weight percent silicon as measured by XPS.
8. The method of claim 7 wherein the forming step is conducted at one or more temperatures ranging from 100° C. to 650° C.
9. The method of claim 1 wherein the method is an atomic layer deposition method.
10. The method of claim 1 wherein the method is a plasma enhanced atomic layer deposition method.
11. The method of claim 1 wherein the deposition process is PEALD.
12. The method of claim 11 wherein the at least one organosilicon precursor comprises at least one selected from the group consisting of dimethylamino-1,4-disilapentane, 1-diethylamino-1,4-disilapentane, 1-methylethylamino-1,4-disilapentane, 1-di-n-propylamino-1,4-disilapentane, 1-di-iso-propylamino-1,4-disilapentane, 1-iso-propylamino-1,4-disilapentane, 1-sec-butylamino-1,4-disilapentane, 1-tert-butylamino-1,4-disilapentane, 1-(2,6-dimethylpiperidino)-1,4-disilapentane, 1-piperidino-1,4-disilapentane, 1-(cyclohexyl-iso-propylamino)-1,4-disilapentane, and 1-(n-propyl-iso-propylamino)-1,4-disilapentane.