Thio(di)silanes

1. A method of forming a silicon-containing film on a substrate, the method comprising: heating a thiodisilane according to formula (I)

(R 1a R 1b R 1c CS) S (R 2 2 N) n (Si-Si)X X H h   (I),

wherein: subscript s is an integer from 1 to 6; subscript n is an integer from 0 to 5; subscript x is an integer from 0 to 5; subscript h is an integer from 0 to 5; with the proviso that sum s+n+x+h=6;

each H, when present in formula (I), is independently bonded to the same or different one of the silicon atoms in formula (I);

each X is a monovalent halogen atom F, Cl, I, or Br and, when present in formula (I), is independently bonded to the same or different one of the silicon atoms in formula (I);

wherein R 1a , R 1b , and R 1c are defined by limitation (a), (b), or (c):

(a) at least one R 1a independently is (C 1 -C 20 )alkyl or phenyl and each of any remaining R 1a , R 1b , and R 1c independently is H or (C 1 -C 20 )hydrocarbyl; or

(b) there is at least one group R 1a R 1b R 1c C that independently is a substituted or unsubstituted (C 6 -C 20 )aryl, and each of any remaining R 1a , R 1b , and R 1c independently is H or (C 1 -C 20 )hydrocarbyl; or

(c) any two of R 1a , R 1b , and R 1c (collectively R 1 groups), in the same or different R 1a R 1b R 1c C group, are bonded together to form a divalent group, —R 11 —, wherein —R 11 — is a CH 2 or a (C 3 -C 20 )hydrocarbylene and each of any remaining R 1a , R 1b , and R 1c independently is H or (C 1 -C 20 )hydrocarbyl;

each R 2 group independently is H or a (C 1 -C 20 )hydrocarbyl; or any two R 2 groups may be bonded together to form a divalent group, —R 22 —, wherein —R 22 — is a (C 2 -C 20 )hydrocarbylene and each of any remaining R 2 groups independently is H or a (C 1 -C 20 )hydrocarbyl;

each hydrocarbyl and hydrocarbylene independently is unsubstituted or substituted with from 1 to 5 substituents SUB; and

each SUB independently is unsubstituted (C 1 -C 6 )alkyl, unsubstituted (C 3 -C 6 )cycloalkyl, unsubstituted (C 2 -C 6 )alkenyl, unsubstituted (C 2 -C 6 )alkynyl, unsubstituted (C 6 -C 7 )aryl, fluoro, chloro, or bromo,

in a chemical vapor deposition (CVD) or atomic layer deposition (ALD) process under thermal or plasma conditions to give the silicon-containing film disposed on the substrate.

2. The method of claim 1 :

wherein subscript s is an integer from 1 to 4; subscript n is an integer from 0 to 2; subscript x is an integer from 0 to 2; subscript h is an integer from 0 to 2; with the proviso that sum s+n+x+h=6; and wherein X, R 1a , R 1b , R 1c , and R 2 are as defined above for formula (I); or

wherein subscript s is an integer from 1 to 4; each of subscripts n and x is 0; subscript h is 2 to 5; with the proviso that sum s+h=6; and wherein R 1a , R 1b , and R 1c are as defined above for formula (I); or

wherein subscript s is an integer from 1 to 4; each of subscripts n and h independently is from 1 to 5; subscript x is 0; with the proviso that sum s+n+h=6; and wherein R 1a , R 1b , R 1c , and R 2 are as defined above for formula (I).

3. The method of claim 1 , wherein subscript s is 1 or 2, wherein:

each X is Cl and each (C 1 -C 20 )hydrocarbyl independently is a (C 1 -C 12 )hydrocarbyl, a (C 1 -C 8 )hydrocarbyl, or a (C 3 -C 8 )hydrocarbyl; wherein each hydrocarbyl is an unsubstituted alkyl, a substituted alkyl, an unsubstituted aryl, or an alkyl-substituted aryl, or

subscript s is 1 or 2 and each X is Cl and each (C 1 -C 20 )hydrocarbyl independently is a (C 1 -C 12 )hydrocarbyl, a (C 1 -C 8 )hydrocarbyl, or a (C 3 -C 8 )hydrocarbyl; wherein each hydrocarbyl is an unsubstituted alkyl, a substituted alkyl, an unsubstituted aryl, or an alkyl-substituted aryl.

4. The method of claim 1 , wherein the thiodisilane is according to formula (I-a):

(R 1a R 1b R 1c CS) s (Si-Si)H h   (I-a),

wherein: subscript s is an integer from 1 to 6; subscript h is an integer from 0 to 5; with the proviso that sum s+h=6; and wherein R 1a , R 1b , and R 1c are as defined above in claim 1 .

5. The method of claim 4 , wherein subscript s is an integer from 1 to 3; subscript h is an integer from 3 to 5; and each (C 1 -C 20 )hydrocarbyl independently is an unsubstituted (C 1 -C 6 )alkyl, substituted (C 1 -C 6 )alkyl, unsubstituted aryl, or a (C 1 -C 3 )alkyl-substituted (C 6 )aryl, or wherein the thiodisilane is selected from: (1,1-dimethylethylthio)disilane; bis(1,1-dimethylethylthio)disilane; (phenylthio)disilane; bis(phenylthio)disilane; (t-pentylthio)disilane; bis(t-pentylthio)disilane; (benzylthio)disilane; bis(benzylthio)disilane; (2-methylphenylthio)disilane; bis(2-methylphenylthio)disilane; (2,6-dimethylphenylthio)disilane; bis(2,6-dimethylphenylthio)disilane; 1, 1-diphenylthiodisilane; (1,2-dimethylpropylthio)disilane; and bis(1,2-dimethylpropylthio)disilane.

6. A method of forming a film on a substrate, the method comprising: heating a thiosilane according to formula (A)

(R 1a R 1b R 1c CS) S (si)x X H h   (A),

wherein:

subscript s is an integer from 1 to 4;

subscript x is an integer from 0 to 3;

subscript h is an integer from 0 to 3;

with the proviso that sum s+x+h=4;

each X is a monovalent halogen atom F, Cl, or Br;

wherein R 1a , R 1b , and R 1c are defined by limitation (a), (b), or (c): (a) R 1a is (C 1 -C 6 )alkyl, R 1b is (C 2 -C 6 )alkyl or H, and R 1c is H; or (b) each of R 1a , R 1b , and R 1c independently is (C 1 -C 6 )alkyl; or (c) R 1a R 1b R 1c C together represents a substituted or unsubstitued phenyl group, wherein the substitute groups on the phenyl are one or more methyl groups;

each alkyl independently is unsubstituted or substituted with from 1 to 5 substituents SUB; and

each SUB independently is unsubstituted (C 1 -C 6 )alkyl, unsubstituted (C 3 -C 6 )cycloalkyl, unsubstituted (C 2 -C 6 )alkenyl, unsubstituted (C 2 -C 6 )alkynyl, unsubstituted (C 6 -C 7 )aryl, fluoro, chloro, or bromo,

in a chemical vapor deposition (CVD) or atomic layer deposition (ALD) process under thermal or plasma conditions to give a silicon-containing film disposed on the substrate.

7. The method of claim 6 , wherein s is 2, x is 2, and h is 0, wherein R 1a is (C 1 -C 6 )alkyl, R 1b is (C 3 -C 6 )alkyl, and R 1c is H; or wherein R 1a is (C 1 -C 2 )alkyl, R 1b is (C 3 -C 4 )alkyl, and R 1c is H; or wherein each of R 1a , R 1b , and R 1c independently is (C 1 -C 6 )alkyl; or wherein each of R 1a , R 1b , and R 1c independently is (C 1 -C 2 )alkyl.

8. The method of claim 6 , wherein the thiosilane is bis(1,1-dimethylethylthio)silane; bis(1,2-dimethylpropylthio)silane; dichloro-bis(1,2-dimethylpropylthio)silane; t-pentylthiosilane; bis(phenylthio)silane; phenylthiosilane; (benzylthio)silane; (2-methylphenylthio)silane; bis(2-methylphenylthio)silane; (2,6-dimethylphenylthio)silane; bis(2,6-dimethylphenylthio)silane; or bis(2-methyl-phenylthio)silane.

9. The method of claim 1 , further comprising: heating a co-reactant in the CVD or ALD process.

10. A method of depositing a silicon-containing film on a substrate, the method comprising: heating a co-reactant and a thio(di)silane in a chemical vapor deposition (CVD) or atomic layer deposition (ALD) process under thermal or plasma conditions to give a silicon-containing film disposed on the substrate; wherein the thio(di)silane is a thiodisilane selected from the group consisting of: methylthio-disilane; 1,2-Bis(phenylthio)-disilane; 1,4-Dithia-2,3-disilacyclohexane; 2,2,3,3,-Tetramethyl-1,4-dithia-2,3-disilacyclohexane; 2,3-Dihydro-2,2,3,3,-tetramethyl-1,4,2,3-benzodithiadisilane; 1,1,2,2-Tetramethyl-1,2-bis(methylthio)-disilane; 1,1,2,2-Tetramethyl-1,2-bis(ethylthio)-disilane; 1,1,2,2-Tetramethyl-1,2-bis(propylthio)-disilane; 1,1,2,2-Tetramethyl-1,2-bis(butylthio)-disilane; 1-Chloro-,1,2,2-trimethyl-1,2-bis(butylthio)-disilane; 1,2-Bis(butylthio)-1,2-dichloro-1,2-dimethyl-disilane; 1,2-Bis [(1,1-dimethylethyl)thio]-1,1,2,2-tetramethyl-disilane; 1,2-Dichloro-1,2-bis [(1,1-dimethylethyl)thio]-1,2-dimethyl-disilane; Dihydro-2,2,4,6,6,8-hexamethyl-[1,4,2,3]dithiadisilolo[2,3-b][1,4,2,3]dithiadisilole, and combinations thereof.

11. A method of depositing a silicon-containing film on a substrate, the method comprising: heating a co-reactant and a thiosilane in a chemical vapor deposition (CVD) or atomic layer deposition (ALD) process under thermal or plasma conditions to give a silicon-containing film disposed on the substrate; wherein the thiosilane is selected from the group consisting of: Tri(methylthio)silane; Tri(ethylthio)silane; Tri(propylthio)silane; Tri(1-methylethylthio)silane; Trichloro-(ethylthio)silane; Trichloro-(butylthio)silane; Trichloro-(1,1-dimethylethylthio)silane; Dichloro-di(ethylthio)silane; Dichloro-di(butylthio)silane; Dichloro-di(1,1-dimethylethylthio)silane; Chloro-tri(methylthio)silane; Chloro-tri(ethylthio)silane; Chloro-tri(propylthio)silane; Chloro-tri(1-methylethylthio)silane; Tetra(methylthio)silane; Tetra(ethylthio)silane; Tetra(propylthio)silane; Tetra(1-methylethylthio)silane, and combinations thereof.

12. The method of claim 9 , wherein the co-reactant comprises hydrogen sulfide or hydrogen disulfide and the film comprises a silicon sulfide; wherein the co-reactant comprises ammonia, molecular nitrogen, or hydrazine and the film comprises a silicon nitride; wherein the co-reactant comprises an organohydrazine, an amine, or an imine and the film comprises a silicon carbonitride; wherein the co-reactant comprises molecular oxygen, ozone, water, or hydrogen peroxide and the film comprises a silicon oxide; wherein the co-reactant comprises nitric oxide or nitrogen dioxide and the film comprises a silicon oxynitride; or wherein the co-reactant comprises an alcohol and the film comprises a silicon oxycarbonitride.

13. The method of claim 6 , further comprising: heating a co-reactant in the CVD or ALD process.

14. The method of claim 10 , wherein the co-reactant comprises hydrogen sulfide or hydrogen disulfide and the film comprises a silicon sulfide; wherein the co-reactant comprises ammonia, molecular nitrogen, or hydrazine and the film comprises a silicon nitride; wherein the co-reactant comprises an organohydrazine, an amine, or an imine and the film comprises a silicon carbonitride; wherein the co-reactant comprises molecular oxygen, ozone, water, or hydrogen peroxide and the film comprises a silicon oxide; wherein the co-reactant comprises nitric oxide or nitrogen dioxide and the film comprises a silicon oxynitride; or wherein the co-reactant comprises an alcohol and the film comprises a silicon oxycarbonitride.

15. The method of claim 11 , wherein the co-reactant comprises hydrogen sulfide or hydrogen disulfide and the film comprises a silicon sulfide; wherein the co-reactant comprises ammonia, molecular nitrogen, or hydrazine and the film comprises a silicon nitride; wherein the co-reactant comprises an organohydrazine, an amine, or an imine and the film comprises a silicon carbonitride; wherein the co-reactant comprises molecular oxygen, ozone, water, or hydrogen peroxide and the film comprises a silicon oxide; wherein the co-reactant comprises nitric oxide or nitrogen dioxide and the film comprises a silicon oxynitride; or wherein the co-reactant comprises an alcohol and the film comprises a silicon oxycarbonitride.

16. The method of claim 6 , wherein the co-reactant comprises hydrogen sulfide or hydrogen disulfide and the film comprises a silicon sulfide; wherein the co-reactant comprises ammonia, molecular nitrogen, or hydrazine and the film comprises a silicon nitride; wherein the co-reactant comprises an organohydrazine, an amine, or an imine and the film comprises a silicon carbonitride; wherein the co-reactant comprises molecular oxygen, ozone, water, or hydrogen peroxide and the film comprises a silicon oxide; wherein the co-reactant comprises nitric oxide or nitrogen dioxide and the film comprises a silicon oxynitride; or wherein the co-reactant comprises an alcohol and the film comprises a silicon oxycarbonitride.