1. A method of depositing a film comprising silicon and oxygen onto a substrate, comprising the steps of:

a) providing a substrate in a reactor;

b) introducing at least one silicon precursor compound into the reactor, wherein the at least one silicon precursor compound is selected from the group consisting of formulas A and B:

wherein the content of the first and second substances,

R¹independently selected from straight chain C₁To C₁₀Alkyl, branched C₃To C₁₀Alkyl radical, C₃To C₁₀Cycloalkyl radical, C₃To C₁₀Heterocyclic group, C₃To C₁₀Alkenyl radical, C₃To C₁₀Alkynyl and C₄To C₁₀An aryl group;

R²selected from hydrogen, straight chain C₁To C₁₀Alkyl, branched C₃To C₁₀Alkyl radical, C₃To C₁₀Cycloalkyl radical, C₃To C₁₀Heterocyclic group, C₃To C₁₀Alkenyl radical, C₃To C₁₀Alkynyl and C₄To C₁₀Aryl, wherein R in formula A or B¹And R²Linked to form a cyclic ring structure or not linked to form a cyclic ring structure;

R³-R⁸each independently selected from hydrogen, straight chain C₁To C₁₀Alkyl, branched C₃To C₁₀Alkyl radical, C₃To C₁₀Cycloalkyl radical, C₂To C₁₀Alkenyl radical, C₂To C₁₀Alkynyl and C₄To C₁₀An aryl group;

x is selected from hydrogen and straight chain C₁To C₁₀Alkyl, branched C₃To C₁₀Alkyl radical, C₃To C₁₀Cycloalkyl radical, C₂To C₁₀Alkenyl radical, C₂To C₁₀Alkynyl, C₄To C₁₀Aryl, halogen and NR⁹R¹⁰Wherein R is⁹And R¹⁰Each independently selected from hydrogen, straight chain C₁To C₆Alkyl, branched C₃To C₆Alkyl radical, C₃To C₁₀Cycloalkyl radical, C₃To C₁₀Alkenyl radical, C₃To C₁₀Alkynyl and C₄To C₁₀Aryl, wherein R⁹And R¹⁰Linked to form a cyclic ring structure or not linked to form a cyclic ring structure, and wherein R¹And R⁹Connected to form a cyclic ring or not connected to form a cyclic ring;

c) purging the reactor with a purge gas;

d) introducing an oxygen-containing source into the reactor; and

e) purging the reactor with a purge gas,

wherein steps b to e are repeated until a desired thickness of the film is deposited, and

wherein the process is carried out at one or more temperatures of about 25 ℃ to 600 ℃.

2. The method of claim 1, wherein the at least one silicon precursor compound is at least one selected from the group consisting of: 1-dimethylaminodisiloxane, 1-diethylaminodisiloxane, 1-diisopropylaminodisiloxane, 1-di-sec-butylaminodisiloxane, 1-phenylmethylaminodisiloxane, 1-phenylethylaminodisiloxane, 1-cyclohexylmethylaminodisiloxane, 1-cyclohexylethylaminodisiloxane, 1-piperidinodisiloxane, 1- (2, 6-dimethylpiperidino) disiloxane, 1-dimethylamino-1, 3-dimethyldisiloxane, 1-diethylamino-1, 3-dimethyldisiloxane, 1-diisopropylamino-1, 3-dimethyldisiloxane, 1-di-sec-butylamino-1, 3-dimethyldisiloxane, 1-diisopropylaminodisiloxane, 1-di-sec-butylamino-1, 3-dimethyldisiloxane, 1-cyclohexylaminodisiloxane, 1-piperidinodisiloxane, 1-dimethylaminodioxane, 1-cyclohexylsiloxane, 1-piperidinodisiloxane, 1-dimethylaminodioxane, 1-dimethylaminodisiloxane, 1-1, 3-dimethyldisiloxane, 1-aminodisiloxane, 1-cyclohexylsiloxane, 1-piperidinodisiloxane, 1-piperidino-dimethylsiloxane, 1-piperidino-1, 3-dimethylsiloxane, 1, 6-piperidino-dimethylsiloxane, 1, 6-dimethylaminobilisiloxane, 6-piperazino-1, 3, 1, and a, 1-Phenylmethylamino-1, 3-dimethyldisiloxane, 1-phenylethylamino-1, 3-dimethyldisiloxane, 1-cyclohexylmethylamino-1, 3-dimethyldisiloxane, 1-cyclohexylethylamino-1, 3-dimethyldisiloxane, 1-dimethylamino-1, 1,3, 3-tetramethyldisiloxane, 1-diethylamino-1, 1,3, 3-tetramethyldisiloxane, 1-diisopropylamino-1, 1,3, 3-tetramethyldisiloxane, 1-di-sec-butylamino-1, 1,3, 3-tetramethyldisiloxane, 1-phenylmethylamino-1, 1,3, 3-tetramethyldisiloxane, 1-phenylethylamino-1, 1,3, 3-tetramethyldisiloxane, 1-phenylethylamino-1, 1,3, 3-tetramethyldisiloxane, 1-dimethylamino-1, 1,3,3, 3-pentamethyldisiloxane, 1-diethylamino-1, 1,3,3, 3-pentamethyldisiloxane, 1-diisopropylamino-1, 1,3,3, 3-pentamethyldisiloxane, 1-di-sec-butylamino-1, 1,3,3, 3-pentamethyldisiloxane, 1-pyrrolyl-1, 1,3,3, 3-pentamethyldisiloxane, 1-pyrrolidinyl-1, 1,3,3, 3-pentamethyldisiloxane, 1-piperidino-1, 1,3,3, 3-pentamethyldisiloxane, 1- (2, 6-dimethylpiperidino) -3,3, 3-pentamethyldisiloxane, 1-isopropylamino-3, 3, 3-trimethyldisiloxane, 1-tert-butylamino-3, 3, 3-trimethyldisiloxane, 1-dimethylamino-3, 3, 3-trimethyldisiloxane, 1-diethylamino-3, 3, 3-trimethyldisiloxane, 1-diisopropylamino-3, 3, 3-trimethyldisiloxane, 1-di-sec-butylamino-3, 3, 3-trimethyldisiloxane, 1-cyclohexylmethylamino-3, 3, 3-trimethyldisiloxane, 1-cyclohexylethylamino-3, 3, 3-trimethyldisiloxane, 1-isopropylamino-3, 3, 3-trimethyldisiloxane, 1-piperidino-3, 3, 3-trimethyldisiloxane, 1- (2, 6-dimethylpiperidino) -3,3, 3-trimethyldisiloxane, 1-dimethylamino-3, 3-dimethyldisiloxane, 1-diethylamino-3, 3-dimethyldisiloxane, 1-diisopropylamino-3, 3-dimethyldisiloxane, 1-di-sec-butylamino-3, 3-dimethyldisiloxane, 1-cyclohexylmethylamino-3, 3-dimethyldisiloxane, 1-cyclohexylethylamino-3, 3-dimethyldisiloxane, 1-piperidino-3, 3-dimethyldisiloxane, 1- (2, 6-dimethylpiperidino) -3, 3-dimethyldisiloxane, 1, 3-bis (dimethylamino) disiloxane, 1, 3-bis (diethylamino) disiloxane, 1, 3-bis (diisopropylamino) disiloxane, 1, 3-bis (di-sec-butylamino) disiloxane, 1, 3-bis (dimethylamino) -1, 3-dimethyldisiloxane, 1, 3-bis (diethylamino) -1, 3-dimethyldisiloxane, 1, 3-bis (diisopropylamino) -1, 3-dimethyldisiloxane, 1, 3-bis (di-sec-butylamino) -1, 3-dimethyldisiloxane, 1, 3-bis (dimethylamino) -1,1,3, 3-tetramethyldisiloxane, 1, 3-bis (diethylamino) -1,1,3, 3-tetramethyldisiloxane, 1-dimethylamino-1, 1,3, 3-tetramethyl-3-chlorodisiloxane, 1-diethylamino-1, 1,3, 3-tetramethyl-3-chlorodisiloxane, 1-diisopropylamino-1, 1,3, 3-tetramethyl-3-chlorodisiloxane, 1-di-sec-butylamino-1, 1,3, 3-tetramethyl-3-chlorodisiloxane, 1-dimethylamino-1, 1,3, 3-tetramethyl-3-bromodisiloxane, 1-diethylamino-1, 1,3, 3-tetramethyl-3-bromodisiloxane, 1-diisopropylamino-1, 1,3, 3-tetramethyl-3-bromodisiloxane, 1-di-sec-butylamino-1, 1,3, 3-tetramethyl-3-bromodisiloxane, 1-tert-butylaminodisiloxane, 1-isopropylaminodisiloxane, 1-tert-butylamino-1, 1,3, 3-tetramethyldisiloxane, 1-isopropyl-1, 1,3, 3-tetramethyldisiloxane, 1-dimethylaminotriesiloxane, 1-diethylaminotrisiloxane, 1-isopropylaminotrisiloxane, 1-di-sec-butylaminotrisiloxane, 1-phenylmethylaminotrisiloxane, 1-phenylethylaminotrisiloxane, 1-cyclohexylmethylaminotrisiloxane, 1-butylaminotrisiloxane, 1-phenylaminotrisiloxane, 1-butylaminotrisiloxane, 1,3, 3-butylaminotrisiloxane, 1,3, 3-butylaminotrisiloxane, 1,3, 1,3, 1,3, one, 1-cyclohexylethylaminotrisiloxane, 1-piperidinotrisiloxane, 1- (2, 6-dimethylpiperidino) trisiloxane, 1-dimethylamino-1, 1,3,3,5, 5-hexamethyltrisiloxane, 1-diethylamino-1, 1,3,3,5, 5-hexamethyltrisiloxane, 1-diisopropylamino-1, 1,3,3,5, 5-hexamethyltrisiloxane, 1-sec-butylamino-1, 1,3,3,5, 5-hexamethyltrisiloxane, 1-phenylmethylamino-1, 1,3,3,5, 5-hexamethyltrisiloxane, 1-phenylethylamino-1, 1,3,3,5, 5-hexamethyltrisiloxane, 1, 5-bis (dimethylamino) -1,1,3,3,5, 5-hexamethyltrisiloxane, 1, 5-bis (diethylamino) -1,1,3,3,5, 5-hexamethyltrisiloxane, 1, 5-bis (diisopropylamino) -1,1,3,3,5, 5-hexamethyltrisiloxane, 1, 5-bis (sec-butylamino) -1,1,3,3,5, 5-hexamethyltrisiloxane, 1, 5-bis (phenylmethylamino) -1,1,3,3,5, 5-hexamethyltrisiloxane, 1, 5-bis (phenylethylamino) -1,1,3,3,5, 5-hexamethyltrisiloxane, 1-diisopropylamino-3, 3,5, 5-pentamethyltrisiloxane, 1-sec-butylamino-3, 3,5,5, 5-pentamethyltrisiloxane, 1-cyclohexylmethylamino-3, 3,5,5, 5-pentamethyltrisiloxane, 1-cyclohexylethylamino-3, 3,5,5, 5-pentamethyltrisiloxane, 1-piperidino-3, 3,5,5, 5-pentamethyltrisiloxane, 1- (2, 6-dimethylpiperidino) -3,3,5,5, 5-pentamethyltrisiloxane, 1-dimethylamino-1, 1,3,3,5,5, 5-heptamethyltrisiloxane, 1-diethylamino-1, 1,3,3,5, 5-heptamethyltrisiloxane, 1-diethylamino-1, 3,3,5, 5-heptamethyltrisiloxane, 1-bis (methyl-ethyl-methyl-siloxane), 1-diisopropylamino-1, 1,3,3,5,5, 5-heptamethyltrisiloxane, 1-sec-butylamino-1, 1,3,3,5,5, 5-heptamethyltrisiloxane, 1-cyclohexylmethylamino-1, 1,3,3,5,5, 5-heptamethyltrisiloxane, 1-cyclohexylethylamino-1, 1,3,3,5,5, 5-heptamethyltrisiloxane, 1-piperidino-1, 1,3,3,5,5, 5-heptamethyltrisiloxane, 1- (2, 6-dimethylpiperidino) -1,1,3,3,5,5, 5-heptamethyltrisiloxane, 1-pyrrolyl-1, 1,3,3,5,5, 5-heptamethyltrisiloxane and 1-pyrrolidinyl-1, 1,3,3,5,5, 5-heptamethyltrisiloxane.

3. The method of claim 1, wherein the oxygen-containing source is selected from the group consisting of ozone, oxygen plasma, oxygen and argon containing plasma, oxygen and helium containing plasma, ozone plasma, water plasma, nitrous oxide plasma, carbon dioxide plasma, carbon monoxide plasma, and combinations thereof.

4. The method of claim 1, wherein the oxygen-containing source comprises a plasma.

5. The method of claim 4, wherein the plasma is generated in-situ.

6. The method of claim 4, wherein the plasma is generated remotely.

7. The method of claim 4, wherein the film has a density of about 2.1g/cc or greater.

8. The method of claim 1, wherein the film further comprises carbon.

9. The method of claim 8, wherein the film has a density of about 1.8g/cc or greater.

10. The method of claim 8, wherein the carbon content of the film is 0.5 atomic weight percent (at.%) or greater as measured by X-ray photoelectron spectroscopy.

11. A composition for depositing a film selected from a silicon oxide or carbon doped silicon oxide film using a vapor deposition process, the composition comprising: at least one silicon precursor compound selected from the group consisting of formulas A and B:

wherein the content of the first and second substances,

R¹independently selected from straight chain C₁To C₁₀Alkyl, branched C₃To C₁₀Alkyl radical, C₃To C₁₀Cycloalkyl radical, C₃To C₁₀Heterocyclic group, C₃To C₁₀Alkenyl radical, C₃To C₁₀Alkynyl and C₄To C₁₀An aryl group;

R²selected from hydrogen, straight chain C₁To C₁₀Alkyl, branched C₃To C₁₀Alkyl radical, C₃To C₁₀Cycloalkyl radical, C₃To C₁₀Heterocyclic group, C₃To C₁₀Alkenyl radical, C₃To C₁₀Alkynyl and C₄To C₁₀Aryl, wherein R in formula A or B¹And R²Linked to form a cyclic ring structure or not linked to form a cyclic ring structure;

R³-R⁸each independently selected from hydrogen, straight chain C₁To C₁₀Alkyl, branched C₃To C₁₀Alkyl radical, C₃To C₁₀Cycloalkyl radical, C₂To C₁₀Alkenyl radical, C₂To C₁₀Alkynyl and C₄To C₁₀An aryl group;

x is selected from hydrogen and straight chain C₁To C₁₀Alkyl, branched C₃To C₁₀Alkyl radical, C₃To C₁₀Cycloalkyl radical, C₂To C₁₀Alkenyl radical, C₂To C₁₀Alkynyl, C₄To C₁₀Aryl, halogen (Cl, Br, I) and NR⁹R¹⁰Wherein R is⁹And R¹⁰Each independently selected from hydrogen, straight chain C₁To C₆Alkyl, branched C₃To C₆Alkyl radical, C₃To C₁₀Cycloalkyl radical, C₃To C₁₀Alkenyl radical, C₃To C₁₀Alkynyl and C₄To C₁₀Aryl, wherein R⁹And R¹⁰Linked to form a cyclic ring structure or not linked to form a cyclic ring structure, and wherein R¹And R⁹Linked to form a cyclic ring or not linked to form a cyclic ring, and wherein the composition is substantially free of halogens selected fromOne or more impurities of a compound, water, metal ions, and combinations thereof.

12. The composition of claim 11, wherein the at least one silicon precursor compound is at least one selected from the group consisting of:

1-dimethylaminodisiloxane, 1-diethylaminodisiloxane, 1-diisopropylaminodisiloxane, 1-di-sec-butylaminodisiloxane, 1-phenylmethylaminodisiloxane, 1-phenylethylaminodisiloxane, 1-cyclohexylmethylaminodisiloxane, 1-cyclohexylethylaminodisiloxane, 1-piperidinodisiloxane, 1- (2, 6-dimethylpiperidino) disiloxane, 1-dimethylamino-1, 3-dimethyldisiloxane, 1-diethylamino-1, 3-dimethyldisiloxane, 1-diisopropylamino-1, 3-dimethyldisiloxane, 1-di-sec-butylamino-1, 3-dimethyldisiloxane, 1-diisopropylaminodisiloxane, 1-di-sec-butylamino-1, 3-dimethyldisiloxane, 1-cyclohexylaminodisiloxane, 1-piperidinodisiloxane, 1-dimethylaminodioxane, 1-cyclohexylsiloxane, 1-piperidinodisiloxane, 1-dimethylaminodioxane, 1-dimethylaminodisiloxane, 1-1, 3-dimethyldisiloxane, 1-aminodisiloxane, 1-cyclohexylsiloxane, 1-piperidinodisiloxane, 1-piperidino-dimethylsiloxane, 1-piperidino-1, 3-dimethylsiloxane, 1, 6-piperidino-dimethylsiloxane, 1, 6-dimethylaminobilisiloxane, 6-piperazino-1, 3, 1, and a, 1-Phenylmethylamino-1, 3-dimethyldisiloxane, 1-phenylethylamino-1, 3-dimethyldisiloxane, 1-cyclohexylmethylamino-1, 3-dimethyldisiloxane, 1-cyclohexylethylamino-1, 3-dimethyldisiloxane, 1-dimethylamino-1, 1,3, 3-tetramethyldisiloxane, 1-diethylamino-1, 1,3, 3-tetramethyldisiloxane, 1-diisopropylamino-1, 1,3, 3-tetramethyldisiloxane, 1-di-sec-butylamino-1, 1,3, 3-tetramethyldisiloxane, 1-phenylmethylamino-1, 1,3, 3-tetramethyldisiloxane, 1-phenylethylamino-1, 1,3, 3-tetramethyldisiloxane, 1-phenylethylamino-1, 1,3, 3-tetramethyldisiloxane, 1-dimethylamino-1, 1,3,3, 3-pentamethyldisiloxane, 1-diethylamino-1, 1,3,3, 3-pentamethyldisiloxane, 1-diisopropylamino-1, 1,3,3, 3-pentamethyldisiloxane, 1-di-sec-butylamino-1, 1,3,3, 3-pentamethyldisiloxane, 1-pyrrolyl-1, 1,3,3, 3-pentamethyldisiloxane, 1-pyrrolidinyl-1, 1,3,3, 3-pentamethyldisiloxane, 1-piperidino-1, 1,3,3, 3-pentamethyldisiloxane, 1- (2, 6-dimethylpiperidino) -3,3, 3-pentamethyldisiloxane, 1-isopropylamino-3, 3, 3-trimethyldisiloxane, 1-tert-butylamino-3, 3, 3-trimethyldisiloxane, 1-dimethylamino-3, 3, 3-trimethyldisiloxane, 1-diethylamino-3, 3, 3-trimethyldisiloxane, 1-diisopropylamino-3, 3, 3-trimethyldisiloxane, 1-di-sec-butylamino-3, 3, 3-trimethyldisiloxane, 1-cyclohexylmethylamino-3, 3, 3-trimethyldisiloxane, 1-cyclohexylethylamino-3, 3, 3-trimethyldisiloxane, 1-isopropylamino-3, 3, 3-trimethyldisiloxane, 1-piperidino-3, 3, 3-trimethyldisiloxane, 1- (2, 6-dimethylpiperidino) -3,3, 3-trimethyldisiloxane, 1-dimethylamino-3, 3-dimethyldisiloxane, 1-diethylamino-3, 3-dimethyldisiloxane, 1-diisopropylamino-3, 3-dimethyldisiloxane, 1-di-sec-butylamino-3, 3-dimethyldisiloxane, 1-cyclohexylmethylamino-3, 3-dimethyldisiloxane, 1-cyclohexylethylamino-3, 3-dimethyldisiloxane, 1-piperidino-3, 3-dimethyldisiloxane, 1- (2, 6-dimethylpiperidino) -3, 3-dimethyldisiloxane, 1, 3-bis (dimethylamino) disiloxane, 1, 3-bis (diethylamino) disiloxane, 1, 3-bis (diisopropylamino) disiloxane, 1, 3-bis (di-sec-butylamino) disiloxane, 1, 3-bis (dimethylamino) -1, 3-dimethyldisiloxane, 1, 3-bis (diethylamino) -1, 3-dimethyldisiloxane, 1, 3-bis (diisopropylamino) -1, 3-dimethyldisiloxane, 1, 3-bis (di-sec-butylamino) -1, 3-dimethyldisiloxane, 1, 3-bis (dimethylamino) -1,1,3, 3-tetramethyldisiloxane, 1, 3-bis (diethylamino) -1,1,3, 3-tetramethyldisiloxane, 1-dimethylamino-1, 1,3, 3-tetramethyl-3-chlorodisiloxane, 1-diethylamino-1, 1,3, 3-tetramethyl-3-chlorodisiloxane, 1-diisopropylamino-1, 1,3, 3-tetramethyl-3-chlorodisiloxane, 1-di-sec-butylamino-1, 1,3, 3-tetramethyl-3-chlorodisiloxane, 1-dimethylamino-1, 1,3, 3-tetramethyl-3-bromodisiloxane, 1-diethylamino-1, 1,3, 3-tetramethyl-3-bromodisiloxane, 1-diisopropylamino-1, 1,3, 3-tetramethyl-3-bromodisiloxane, 1-di-sec-butylamino-1, 1,3, 3-tetramethyl-3-bromodisiloxane, 1-tert-butylaminodisiloxane, 1-isopropylaminodisiloxane, 1-tert-butylamino-1, 1,3, 3-tetramethyldisiloxane, 1-isopropyl-1, 1,3, 3-tetramethyldisiloxane, 1-dimethylaminotriesiloxane, 1-diethylaminotrisiloxane, 1-isopropylaminotrisiloxane, 1-di-sec-butylaminotrisiloxane, 1-phenylmethylaminotrisiloxane, 1-phenylethylaminotrisiloxane, 1-cyclohexylmethylaminotrisiloxane, 1-butylaminotrisiloxane, 1-phenylaminotrisiloxane, 1-butylaminotrisiloxane, 1,3, 3-butylaminotrisiloxane, 1,3, 3-butylaminotrisiloxane, 1,3, 1,3, 1,3, one, 1-cyclohexylethylaminotrisiloxane, 1-piperidinotrisiloxane, 1- (2, 6-dimethylpiperidino) trisiloxane, 1-dimethylamino-1, 1,3,3,5, 5-hexamethyltrisiloxane, 1-diethylamino-1, 1,3,3,5, 5-hexamethyltrisiloxane, 1-diisopropylamino-1, 1,3,3,5, 5-hexamethyltrisiloxane, 1-sec-butylamino-1, 1,3,3,5, 5-hexamethyltrisiloxane, 1-phenylmethylamino-1, 1,3,3,5, 5-hexamethyltrisiloxane, 1-phenylethylamino-1, 1,3,3,5, 5-hexamethyltrisiloxane, 1, 5-bis (dimethylamino) -1,1,3,3,5, 5-hexamethyltrisiloxane, 1, 5-bis (diethylamino) -1,1,3,3,5, 5-hexamethyltrisiloxane, 1, 5-bis (diisopropylamino) -1,1,3,3,5, 5-hexamethyltrisiloxane, 1, 5-bis (sec-butylamino) -1,1,3,3,5, 5-hexamethyltrisiloxane, 1, 5-bis (phenylmethylamino) -1,1,3,3,5, 5-hexamethyltrisiloxane, 1, 5-bis (phenylethylamino) -1,1,3,3,5, 5-hexamethyltrisiloxane, 1-diisopropylamino-3, 3,5, 5-pentamethyltrisiloxane, 1-sec-butylamino-3, 3,5,5, 5-pentamethyltrisiloxane, 1-cyclohexylmethylamino-3, 3,5,5, 5-pentamethyltrisiloxane, 1-cyclohexylethylamino-3, 3,5,5, 5-pentamethyltrisiloxane, 1-piperidino-3, 3,5,5, 5-pentamethyltrisiloxane, 1- (2, 6-dimethylpiperidino) -3,3,5,5, 5-pentamethyltrisiloxane, 1-dimethylamino-1, 1,3,3,5,5, 5-heptamethyltrisiloxane, 1-diethylamino-1, 1,3,3,5, 5-heptamethyltrisiloxane, 1-diethylamino-1, 3,3,5, 5-heptamethyltrisiloxane, 1-bis (methyl-ethyl-methyl-siloxane), 1-diisopropylamino-1, 1,3,3,5,5, 5-heptamethyltrisiloxane, 1-sec-butylamino-1, 1,3,3,5,5, 5-heptamethyltrisiloxane, 1-cyclohexylmethylamino-1, 1,3,3,5,5, 5-heptamethyltrisiloxane, 1-cyclohexylethylamino-1, 1,3,3,5,5, 5-heptamethyltrisiloxane, 1-piperidino-1, 1,3,3,5,5, 5-heptamethyltrisiloxane, 1- (2, 6-dimethylpiperidino) -1,1,3,3,5,5, 5-heptamethyltrisiloxane, 1-pyrrolyl-1, 1,3,3,5,5, 5-heptamethyltrisiloxane and 1-pyrrolidinyl-1, 1,3,3,5,5, 5-heptamethyltrisiloxane, and combinations thereof.

13. The composition of claim 11, wherein the halide comprises chloride.

14. The composition of claim 13, wherein the concentration of chloride ions is less than 50 ppm.

15. The composition of claim 13, wherein the concentration of chloride ions is less than 10 ppm.

16. The composition of claim 13, wherein the concentration of chloride ions is less than 5 ppm.

17. A film obtained by the method of claim 1.

18. A film comprising at least one of the following features: a density of at least about 2.1 g/cc; wet etch rates measured in a 1:100 HF to water acid solution (0.5 wt.% dHF) are less than aboutUntil the electric leakage under 6MV/cm is less than about 1e-8A/cm²(ii) a And a hydrogen impurity of less than about 5e20at/cc as measured by SIMS.

19. A method of depositing a film comprising silicon and an oxide onto a substrate, comprising the steps of:

a) providing a substrate in a reactor;

b) introducing at least one silicon precursor compound into the reactor, wherein the at least one silicon precursor compound is selected from the group consisting of formulas A and B:

wherein the content of the first and second substances,

R¹independently selected from straight chain C₁To C₁₀Alkyl, branched C₃To C₁₀Alkyl radical, C₃To C₁₀Cycloalkyl radical, C₃To C₁₀Heterocyclic group, C₃To C₁₀Alkenyl radical, C₃To C₁₀Alkynyl and C₄To C₁₀An aryl group;

R²selected from hydrogen, straight chain C₁To C₁₀Alkyl, branched C₃To C₁₀Alkyl radical, C₃To C₁₀Cycloalkyl radical, C₃To C₁₀Heterocyclic group, C₃To C₁₀Alkenyl radical, C₃To C₁₀Alkynyl and C₄To C₁₀Aryl, wherein R in formula A or B¹And R²Linked to form a cyclic ring structure or not linked to form a cyclic ring structure; and

R³-R⁸and X is methyl;

c) purging the reactor with a purge gas;

d) introducing an oxygen-containing source into the reactor; and

e) purging the reactor with a purge gas,

wherein steps b to e are repeated until a film of a desired thickness is deposited, and

wherein the process is carried out at one or more temperatures of about 600 ℃ to 800 ℃.

20. The method of claim 19, wherein the at least one silicon precursor compound is at least one selected from the group consisting of: 1-dimethylamino-1, 1,3,3, 3-pentamethyldisiloxane, 1-diethylamino-1, 1,3,3, 3-pentamethyldisiloxane, 1-diisopropylamino-1, 1,3,3, 3-pentamethyldisiloxane, 1-di-sec-butylamino-1, 1,3,3, 3-pentamethyldisiloxane, 1-pyrrolyl-1, 1,3,3, 3-pentamethyldisiloxane, 1-pyrrolidinyl-1, 1,3,3, 3-pentamethyldisiloxane, 1-piperidino-1, 1,3,3, 3-pentamethyldisiloxane, 1- (2, 6-dimethylpiperidino) -3,3, 3-pentamethyldisiloxane, 1-diethylamino-1, 1,3, 3-pentamethyldisiloxane, 1-diethylamino-1, 3, 3-pentamethyldisiloxane, 1-pyrrolidino-1, 3, 3-pentamethyldisiloxane, 1- (2, 6-dimethylpiperidino) -3,3, 3-pentamethyldisiloxane, 1-dimethylamino-1, 1,3,3,5,5, 5-heptamethyltrisiloxane, 1-diethylamino-1, 1,3,3,5,5, 5-heptamethyltrisiloxane, 1-diisopropylamino-1, 1,3,3,5,5, 5-heptamethyltrisiloxane, 1-sec-butylamino-1, 1,3,3,5,5, 5-heptamethyltrisiloxane, 1-cyclohexylmethylamino-1, 1,3,3,5,5, 5-heptamethyltrisiloxane, 1-cyclohexylethylamino-1, 1,3,3,5,5, 5-heptamethyltrisiloxane, 1-piperidino-1, 1,3,3,5,5, 5-heptamethyltrisiloxane, 1- (2), 6-dimethylpiperidino) -1,1,3,3,5,5, 5-heptamethyltrisiloxane, 1-pyrrolyl-1, 1,3,3,5,5, 5-heptamethyltrisiloxane, 1-pyrrolidinyl-1, 1,3,3,5,5, 5-heptamethyltrisiloxane.

21. A film obtained by the method of claim 19.

22. A film formed by claim 19, comprising at least one of the following features: a density of at least about 2.1 g/cc; wet etch rates measured in a 1:100 HF to water acid solution (0.5 wt.% dHF) are less than aboutUntil the electric leakage under 6MV/cm is less than about 1e-8A/cm²(ii) a And a hydrogen impurity of less than about 5e20at/cc as measured by SIMS.

Background

Compositions and methods for forming films containing silicon and oxides are described herein. More specifically, described herein are compositions and methods for forming stoichiometric or non-stoichiometric silicon oxide films or materials at one or more deposition temperatures of about 300 ℃ or less, or more specifically, at one or more deposition temperatures in the range of about 25 ℃ to about 300 ℃.

Atomic Layer Deposition (ALD) and Plasma Enhanced Atomic Layer Deposition (PEALD) are processes for depositing conformal silicon oxide films at low temperatures (<500 ℃). In both ALD and PEALD processes, the precursor and the reactive gas (e.g., oxygen or ozone) are pulsed separately for a number of cycles to form a single layer of silicon oxide in each cycle. However, silicon oxides deposited at low temperatures using these processes may contain impurity levels such as, but not limited to, nitrogen (N), which may be detrimental in certain semiconductor applications. To address this problem, one possible solution is to increase the deposition temperature to 500 ℃ or higher. However, at these higher temperatures, the conventional precursors employed by the semiconductor industry tend to self-react, thermally decompose, and deposit in a Chemical Vapor Deposition (CVD) mode rather than an ALD mode. CVD mode deposition has reduced conformality compared to ALD deposition, especially for high aspect ratio structures required in many semiconductor applications. Furthermore, CVD mode deposition has lower control of film or material thickness than ALD mode deposition.

References entitled "Some New Alkylaminosilicans", Abel, E.W. et al, J.chem.Soc., (1964), Vol.26, pp.1528-1530 describe the reaction product from trimethylchlorosilane (Me)₃SiCl) with appropriate amines to prepare various aminosilane compounds, e.g., Me₃SiNHBu-iso、Me₃SiNHBu-sec、Me₃SiN(Pr-iso)₂And Me₃SiN(Bu-sec)₂Wherein Me is methyl, Bu-sec is sec-butyl and Pr-iso is isopropyl.

Titled as "SiO₂Reference to The Atomic Layer Deposition Using Tris (dimethyl) silane and Hydrogen Peroxide synthesized by in Situ Transmission FTIR Spectroscopy ", Burton, B.B. et al, The Journal of Physical Chemistry (2009), Vol.113, pp.8249-57 describes The results of The methods described in H₂O₂Silicon dioxide (SiO) of various silicon precursors is used as the oxidizing agent₂) Atomic Layer Deposition (ALD). The silicon precursor is (N, N-dimethylamino) trimethylsilane) (CH₃)₃SiN(CH₃)₂Vinyl trimethoxy silane CH₂CHSi(OCH₃)₃Trivinylmethoxysilane (CH)₂CH)₃SiOCH₃Tetra (dimethylamino) silane Si (N (CH)₃)₂)₄And tris (dimethylamino) silane (TDMAS) SiH (N (CH)₃)₂)₃. TDMAS was identified as the most effective of these precursors. However, additional studies determined that SiH surface species from TDMAS are difficult to use using only H₂And removing the O. Subsequent toInvestigation of the use of TDMAS and H as an oxidizing agent₂O₂And explores SiO in the temperature range of 150-₂ALD. TDMAS and H₂O₂The exposure required for the surface reaction to reach completion was monitored using in situ FTIR spectroscopy. FTIR spectra after TDMAS exposure show a loss in absorbance of O-H stretching vibrations and an increase in absorbance of C-Hx and Si-H stretching vibrations. H₂O₂FTIR vibration spectra after exposure showed a loss in absorbance of C-Hx and Si-H stretching vibrations and an increase in absorbance of O-H stretching vibrations. Surface material of SiH>Complete removal takes place at a temperature of 450 ℃. SiO 2₂The body vibration mode is in the range of 1000-1250cm^-1Observed in (1) and following TDMAS and H₂O₂The number of reaction cycles increases gradually. Transmission Electron Microscopy (TEM) at 50 TDMAS and H₂O₂After the reaction cycle at ZrO₂The nano-particles are carried out at a temperature of 150-550 ℃. The film thickness determined by TEM at each temperature was used to obtain SiO₂ALD growth rate. Growth per cycle from 150 deg.CCycle Change to 550 deg.CCirculation, and associated with removal of SiH surface species. Using TDMAS and H₂O₂SiO of (2)₂ALD for temperature>SiO at 450 DEG C₂ALD should be valuable.

JP2010275602 and JP2010225663 disclose the use of raw materials to form Si-containing thin films such as silicon oxide by a Chemical Vapor Deposition (CVD) process at a temperature range of 300-. The starting material is an organosilicon compound represented by the formula: (a) HSi (CH)₃)(R¹)(NR²R³) Wherein R is¹Represents NR⁴R⁵Or 1C-5C alkyl; r²And R⁴Each represents a 1C-5C alkyl group or a hydrogen atom; and R is³And R⁵Each represents a 1C-5C alkyl group; or (b) HSiCl (NR)¹R²)(NR³R⁴) WhereinR¹And R³Independently represents an alkyl group having 1 to 4 carbon atoms or a hydrogen atom; and R is²And R⁴Independently represents an alkyl group having 1 to 4 carbon atoms. The organosilicon compound contains H-Si bonds.

U.S. patent No. 5,424,095 describes a method of reducing the rate of coke formation during commercial pyrolysis of hydrocarbons, the reactor interior surfaces being coated with a uniform layer of ceramic material deposited by thermal decomposition of a non-alkoxylated organosilicon precursor in vapor phase in a vapor-containing gas atmosphere to form an oxide ceramic.

U.S. publication No. 2012/0291321 describes a PECVD process for forming a high quality silicon carbonitride barrier dielectric film between the dielectric film and the metal interconnects of an integrated circuit substrate comprising the steps of: providing an integrated circuit substrate having dielectric films or metal interconnects; a substrate and a substrate containing R_xR_y(NRR')_zSi, wherein R, R ', R, and R' are each independently selected from H, linear or branched saturated or unsaturated alkyl, or aromatic groups; wherein x + y + z is 4; z is 1 to 3; however, R, R' may not all be H; and when z is 1 or 2, then x and y are each at least 1; forming a C/Si ratio on an integrated circuit substrate>0.8 and N/Si ratio>0.2 of a silicon carbonitride barrier dielectric film.

U.S. publication No. 2013/0295779a describes an Atomic Layer Deposition (ALD) process for forming a silicon oxide film at a deposition temperature >500 ℃ using a silicon precursor having the formula:

I.R¹R² _mSi(NR³R⁴)_nX_p

wherein R is¹、R²And R³Each independently selected from hydrogen, straight or branched C₁-C₁₀Alkyl and C₆-C₁₀An aryl group; r⁴Selected from straight or branched C₁-C₁₀Alkyl and C₆-C₁₀Aryl radical, C₃-C₁₀An alkylsilyl group; wherein R is³And R⁴Linked to form a cyclic ring structure or R³And R⁴Are not linked to form a cyclic ring structure; x is selected from Cl, Br and IHalogen; m is 0 to 3; n is 0 to 2; and p is 0 to 2, and m + n + p is 3; and

II.R¹R² _mSi(OR³)_n(OR⁴)_qX_p

wherein R and R²Each independently selected from hydrogen, straight or branched C₁-C₁₀Alkyl and C₆-C₁₀An aryl group; r³And R⁴Each independently selected from straight or branched chain C₁-C₁₀Alkyl and C₆-C₁₀An aryl group; wherein R is³And R⁴Linked to form a cyclic ring structure or R³And R⁴Are not linked to form a cyclic ring structure; x is a halogen atom selected from Cl, Br and I; m is 0 to 3; n is 0 to 2; q is 0 to 2, and p is 0 to 2, and m + n + q + p is 3.

U.S. patent No. 7,084,076 discloses halogenated siloxanes, such as Hexachlorodisiloxane (HCDSO), which are used in conjunction with pyridine as a catalyst for ALD deposition at temperatures below 500 ℃ to form silicon dioxide.

U.S. patent No. 6,992,019 discloses a catalyst assisted Atomic Layer Deposition (ALD) process for forming a silicon dioxide layer on a semiconductor substrate with superior performance by using a first reactant component composed of a silicon compound having at least two silicon atoms, or using an aliphatic tertiary amine as a catalyst component, or a combination of both, and related purging processes and sequencing. The precursor used was hexachlorodisilane. The deposition temperature is between 25 and 150 ℃.

The disclosures of the foregoing identified patents, patent applications, and other publications are incorporated herein by reference.

However, the above-described prior art still suffers from certain drawbacks, as there is still a need to develop a method for forming a silicon oxide film having at least one or more of the following properties: a density of about 2.1g/cc or greater; the growth rate during deposition isCycle or higher; low chemical impurities; and/or deposition on thermal atomic layers, plasma enhancementHigh conformality in Atomic Layer Deposition (ALD) processes or plasma-enhanced ALD-like processes that use cheaper, reactive and more stable silicon precursor compounds. In addition, there is a need to develop precursors that can provide tunable films (e.g., from silicon oxide to carbon-doped silicon oxide).

Disclosure of Invention

Described herein are methods of depositing stoichiometric or non-stoichiometric silicon oxide materials or films (such as, but not limited to, silicon oxide, carbon-doped silicon oxide, silicon oxynitride films, or carbon-doped silicon oxynitride films) at relatively low temperatures, such as at one or more temperatures of 300 ℃ or less, or in other embodiments, at relatively high temperatures, such as at one or more temperatures of 600 ℃ or more, in plasma-enhanced ALD, plasma-enhanced cyclic chemical vapor deposition (PECCVD), plasma-enhanced ALD-like processes, or ALD processes employing oxygen-containing reactant sources.

In one aspect, there is provided a method of depositing a film comprising silicon and an oxide onto a substrate, the method comprising the steps of:

a) providing a substrate in a reactor;

b) introducing at least one silicon precursor compound into the reactor, wherein the at least one silicon precursor compound has at least one Si-O-Si bond and is selected from the group consisting of formulas a and B:

wherein R is¹Independently selected from straight chain C₁To C₁₀Alkyl, branched C₃To C₁₀Alkyl radical, C₃To C₁₀Cycloalkyl radical, C₃To C₁₀Heterocyclic group, C₃To C₁₀Alkenyl radical, C₃To C₁₀Alkynyl and C₄To C₁₀An aryl group; r²Selected from hydrogen, straight chain C₁To C₁₀Alkyl, branched C₃To C₁₀Alkyl radical, C₃To C₁₀Cycloalkyl radical, C₃To C₁₀Heterocyclic group, C₃To C₁₀Alkenyl radical, C₃To C₁₀Alkynyl and C₄To C₁₀Aryl, wherein R in formula A or B¹And R²Linked to form a cyclic ring structure or not linked to form a cyclic ring structure; r³-R⁸Each independently selected from hydrogen, straight chain C₁To C₁₀Alkyl, branched C₃To C₁₀Alkyl radical, C₃To C₁₀Cycloalkyl radical, C₂To C₁₀Alkenyl radical, C₂To C₁₀Alkynyl and C₄To C₁₀An aryl group; x is selected from hydrogen and straight chain C₁To C₁₀Alkyl, branched C₃To C₁₀Alkyl radical, C₃To C₁₀Cycloalkyl radical, C₂To C₁₀Alkenyl radical, C₂To C₁₀Alkynyl, C₄To C₁₀Aryl, halogen (Cl, Br, I) and NR⁹R¹⁰Wherein R is⁹And R¹⁰Each independently selected from hydrogen, straight chain C₁To C₆Alkyl, branched C₃To C₆Alkyl radical, C₃To C₁₀Cycloalkyl radical, C₃To C₁₀Alkenyl radical, C₃To C₁₀Alkynyl and C₄To C₁₀Aryl, wherein R⁹And R¹⁰Linked to form a cyclic ring structure or not linked to form a cyclic ring structure, and wherein R¹And R⁹Connected to form a cyclic ring or not connected to form a cyclic ring;

c) purging the reactor with a purge gas;

d) introducing an oxygen-containing source into the reactor; and

e) purging the reactor with a purge gas,

wherein steps b to e are repeated until a film of a desired thickness is deposited; and wherein the process is carried out at one or more temperatures of about 25 ℃ to 600 ℃.

In this or other embodiments, the oxygen-containing source is selected from the group consisting of oxygen plasma, ozone, water vapor plasma, nitrogen oxides with or without inert gases (e.g., N₂O、NO、NO₂) Plasma, carbon oxides (e.g. CO)₂CO), plasma, and combinations thereof. In certain embodiments, the oxygen-containing source further comprises an inert gas. In these embodiments, the inert gas is selected from the group consisting of argon, helium, nitrogen, hydrogen, and combinations thereof. In an alternative embodiment, the oxygenate source does not comprise an inert gas. In another embodiment, the oxygen-containing source comprises nitrogen that reacts with a reagent under plasma conditions to provide a silicon oxynitride film.

In one or more of the above embodiments, the oxygen-containing plasma source is selected from the group consisting of oxygen plasma with or without inert gas, water vapor plasma with or without inert gas, nitrogen oxide (N) with or without inert gas₂O、NO、NO₂) Plasma, Carbon Oxides (CO) with or without inert gas₂CO), plasma, and combinations thereof. In certain embodiments, the oxygen-containing plasma source further comprises an inert gas. In these embodiments, the inert gas is selected from argon, helium, nitrogen, hydrogen, or combinations thereof. In an alternative embodiment, the oxygen-containing plasma source does not contain an inert gas.

One embodiment of the invention relates to a composition for depositing a film selected from a silicon oxide or carbon doped silicon oxide film using a vapor deposition process, the composition comprising: at least one silicon precursor comprising a compound selected from formulas a and B:

wherein R is¹Independently selected from straight chain C₁To C₁₀Alkyl, branched C₃To C₁₀Alkyl radical, C₃To C₁₀Cycloalkyl radical, C₃To C₁₀Heterocyclic group, C₃To C₁₀Alkenyl radical, C₃To C₁₀Alkynyl and C₄To C₁₀An aryl group; r²Selected from hydrogen, straight chain C₁To C₁₀Alkyl, branched C₃To C₁₀Alkyl radical, C₃To C₁₀Cycloalkyl radical, C₃To C₁₀Heterocyclic group, C₃To C₁₀Alkenyl radical, C₃To C₁₀Alkynyl and C₄To C₁₀Aryl, wherein R in formula A or B¹And R²Linked to form a cyclic ring structure or not linked to form a cyclic ring structure; r³-R⁸Each independently selected from hydrogen, straight chain C₁To C₁₀Alkyl, branched C₃To C₁₀Alkyl radical, C₃To C₁₀Cycloalkyl radical, C₂To C₁₀Alkenyl radical, C₂To C₁₀Alkynyl and C₄To C₁₀An aryl group; x is selected from hydrogen and straight chain C₁To C₁₀Alkyl, branched C₃To C₁₀Alkyl radical, C₃To C₁₀Cycloalkyl radical, C₂To C₁₀Alkenyl radical, C₂To C₁₀Alkynyl, C₄To C₁₀Aryl, halogen (Cl, Br, I) and NR⁹R¹⁰Wherein R is⁹And R¹⁰Each independently selected from hydrogen and C₁To C₆Straight chain alkyl, branched C₃To C₆Alkyl radical, C₃To C₁₀Cycloalkyl radical, C₃To C₁₀Alkenyl radical, C₃To C₁₀Alkynyl and C₄To C₁₀Aryl, wherein R⁹And R¹⁰Linked to form a cyclic ring structure or not linked to form a cyclic ring structure, and wherein R¹And R⁹Either linked to form a cyclic ring or not linked to form a ring.

Another embodiment of the invention relates to a silicon oxide film comprising at least one of the following features: a density of at least about 2.1 g/cc; wet etch rates measured in a 1:100 HF to water acid solution (0.5 wt.% dHF) are less than aboutUntil the electric leakage under 6MV/cm is less than about 1e-8A/cm²(ii) a And hydrogen impurity as measured by SIMS is less than about 5e20 at/cc.

Embodiments of the present invention may be used alone or in combination with one another.

Detailed Description

Described herein relate to the use of about 300 ℃ or less orCompositions and methods of forming stoichiometric or non-stoichiometric films or materials comprising silicon and oxide (such as, but not limited to, silicon oxide, carbon doped silicon oxide film, silicon oxynitride or carbon doped silicon oxynitride film, or combinations thereof) at one or more temperatures of about 25 ℃ to about 300 ℃, or about 250 ℃ to about 600 ℃, or about 600 ℃ to about 800 ℃. The films described herein are deposited in a deposition process, such as Atomic Layer Deposition (ALD) or an ALD-like process, such as, but not limited to, plasma-enhanced ALD or a plasma-enhanced cyclic chemical vapor deposition process (CCVD). The low temperature deposition (e.g., one or more deposition temperatures ranging from about ambient temperature to about 300 ℃) methods described herein provide films or materials that exhibit at least one or more of the following advantages: a density of about 2.1g/cc or greater,a growth rate of/cycles or higher, low chemical impurities, high conformality in a thermal atomic layer deposition, plasma enhanced Atomic Layer Deposition (ALD) process, or plasma enhanced ALD-like process, the ability to adjust the carbon content in the resulting film; and/or the film has 5 angstroms per second when measured in 0.5 wt.% dilute HFOr a lower etch rate. For carbon doped silicon oxide films, greater than 1% carbon is desirable to adjust the etch rate in 0.5 wt.% dilute HF to less than the etch rate in, among other features (e.g., without limitation, about 1.8g/cc or higher or a density of 2.0g/cc or higher)The value of (c).

The present invention may be practiced using equipment known in the art. For example, the process of the present invention may employ reactors conventional in the semiconductor manufacturing art.

In one aspect, a composition is provided that includes at least one silicon precursor compound having at least one Si-O-Si bond and at least one organoamino functional group. Such silicon precursor compounds have a structure represented by formula a and/or B:

wherein R is¹Independently selected from straight chain C₁To C₁₀Alkyl, branched C₃To C₁₀Alkyl radical, C₃To C₁₀Cycloalkyl radical, C₃To C₁₀Heterocyclic group, C₃To C₁₀Alkenyl radical, C₃To C₁₀Alkynyl and C₄To C₁₀An aryl group; r²Selected from hydrogen, straight chain C₁To C₁₀Alkyl, branched C₃To C₁₀Alkyl radical, C₃To C₁₀Cycloalkyl radical, C₃To C₁₀Heterocyclic group, C₃To C₁₀Alkenyl radical, C₃To C₁₀Alkynyl and C₄To C₁₀Aryl, wherein R in formula A or B¹And R²Linked to form a cyclic ring structure or not linked to form a cyclic ring structure; r³-R⁸Each independently selected from hydrogen, straight chain C₁To C₁₀Alkyl, branched C₃To C₁₀Alkyl radical, C₃To C₁₀Cycloalkyl radical, C₂To C₁₀Alkenyl radical, C₂To C₁₀Alkynyl and C₄To C₁₀An aryl group; x is selected from hydrogen and straight chain C₁To C₁₀Alkyl, branched C₃To C₁₀Alkyl radical, C₃To C₁₀Cycloalkyl radical, C₂To C₁₀Alkenyl radical, C₂To C₁₀Alkynyl, C₄To C₁₀Aryl, halogen (Cl, Br, I) and NR⁹R¹⁰Wherein R is⁹And R¹⁰Each independently selected from hydrogen, straight chain C₁To C₆Alkyl, branched C₃To C₆Alkyl radical, C₃To C₁₀Cycloalkyl radical, C₃To C₁₀Alkenyl radical, C₃To C₁₀Alkynyl and C₄To C₁₀Aryl, wherein R⁹And R¹⁰Linked to form a cyclic ring structure or not linked to form a cyclic ring structure, and wherein R¹And R⁹Either linked to form a cyclic ring or not linked to form a cyclic ring.

In another aspect, there is provided a composition comprising: (a) at least one silicon precursor compound having at least one Si-O-Si bond and at least one organic amino functional group. Such silicon precursor compounds have a structure represented by formula a or B:

wherein R is¹Independently selected from straight chain C₁To C₁₀Alkyl, branched C₃To C₁₀Alkyl radical, C₃To C₁₀Cycloalkyl radical, C₃To C₁₀Heterocyclic group, C₃To C₁₀Alkenyl radical, C₃To C₁₀Alkynyl and C₄To C₁₀An aryl group; r²Selected from hydrogen, straight chain C₁To C₁₀Alkyl, branched C₃To C₁₀Alkyl radical, C₃To C₁₀Cycloalkyl radical, C₃To C₁₀Heterocyclic group, C₃To C₁₀Alkenyl radical, C₃To C₁₀Alkynyl and C₄To C₁₀Aryl, wherein R in formula A or B¹And R²Linked to form a cyclic ring structure or not linked to form a cyclic ring structure; r³-R⁸Each independently selected from hydrogen, straight chain C₁To C₁₀Alkyl, branched C₃To C₁₀Alkyl radical, C₃To C₁₀Cycloalkyl radical, C₂To C₁₀Alkenyl radical, C₂To C₁₀Alkynyl and C₄To C₁₀An aryl group; x is selected from hydrogen and straight chain C₁To C₁₀Alkyl, branched C₃To C₁₀Alkyl radical, C₃To C₁₀Cycloalkyl radical, C₂To C₁₀Alkenyl radical, C₂To C₁₀Alkynyl, C₄To C₁₀Aryl, halogen (Cl, Br, I) and NR⁹R¹⁰Wherein R is⁹And R¹⁰Each independently selected from hydrogen, straight chain C₁To C₆Alkyl, branched C₃To C₆Alkyl radical, C₃To C₁₀Cycloalkyl radical, C₃To C₁₀Alkenyl radical, C₃To C₁₀Alkynyl and C₄To C₁₀Aryl, wherein R⁹And R¹⁰Linked to form a cyclic ring structure or not linked to form a cyclic ring structure, and wherein R¹And R⁹Connected to form a cyclic ring or not connected to form a cyclic ring; and (b) a solvent. In certain embodiments of the compositions described herein, exemplary solvents may include, but are not limited to, ethers, tertiary amines, alkyl hydrocarbons, aromatic hydrocarbons, tertiary amino ethers, and combinations thereof. In certain embodiments, the difference between the boiling point of the silicon precursor and the boiling point of the solvent is 40 ℃ or less.

In one embodiment of the methods described herein, the methods are performed by an ALD process using an oxygen-containing source comprising ozone or a plasma, wherein the plasma may further comprise an inert gas, such as one or more of the following: oxygen plasma with or without inert gas, water vapor plasma with or without inert gas, nitrogen oxide (e.g., N) with or without inert gas₂O、NO、NO₂) Plasma, carbon oxides with or without inert gases (e.g. CO)₂CO), plasma, and combinations thereof. In this embodiment, a method for depositing a silicon oxide film on at least one surface of a substrate comprises the steps of:

a) providing a substrate in a reactor;

b) introducing into the reactor at least one silicon precursor selected from the group consisting of formulas a and B described herein;

c) purging the reactor with a purge gas;

d) introducing an oxygen-containing source comprising a plasma into the reactor; and

e) purging the reactor with a purge gas.

In the above method, steps b to e are repeated until a film of a desired thickness is deposited on the substrate. The oxygen containing plasma source may be generated in situ or, alternatively, remotely. In a particular embodiment, the oxygen-containing source comprises oxygen and is flowed with or introduced during method steps b to d with other reagents, such as, but not limited to, at least one silicon precursor and optionally an inert gas.

In another aspect, a method of depositing a silicon-containing film is provided, the method comprising:

placing a substrate comprising surface features into a reactor, wherein the substrate is maintained at one or more temperatures of about-20 ℃ to about 400 ℃ and the pressure of the reactor is maintained at 100 torr or less;

introducing at least one silicon precursor having formula a or B as described herein;

providing an oxygen-containing source into the reactor to react with the at least one compound to form a film and cover at least a portion of the surface feature;

annealing the film at one or more temperatures of about 100 ℃ to 1000 ℃ to coat at least a portion of the surface features; and

treating the substrate with an oxygen-containing source at one or more temperatures from about 20 ℃ to about 1000 ℃ to form a silicon-containing film on at least a portion of the surface features. In certain embodiments, the oxygen-containing source is selected from the group consisting of water vapor, water plasma, ozone, oxygen plasma, oxygen/helium plasma, oxygen/argon plasma, nitrogen oxide plasma, carbon dioxide plasma, hydrogen peroxide, organic peroxides, and mixtures thereof. In this or other embodiments, the method steps are repeated until the surface features are filled with the silicon-containing film. In embodiments using water vapor as the oxygen-containing source, the substrate temperature is from about-20 ℃ to about 40 ℃ or from about-10 ℃ to about 25 ℃.

In another embodiment of the methods described herein, the methods are performed by an ALD process using an oxygen-containing source comprising ozone or a plasma, wherein the plasma may further comprise an inert gas, such as one or more of the following:oxygen plasma with or without inert gas, water vapor plasma with or without inert gas, nitrogen oxide (e.g., N) with or without inert gas₂O、NO、NO₂) Plasma, carbon oxides with or without inert gases (e.g. CO)₂CO), plasma, and combinations thereof. In this embodiment, a method of depositing a silicon oxide film on at least one surface of a substrate at a temperature of less than 300 ℃, preferably less than 150 ℃, comprises the steps of:

a) providing a substrate in a reactor;

b) introducing at least one silicon precursor selected from the group consisting of formulas A and B into a reactor, wherein R³And R⁴Are all hydrogen;

c) purging the reactor with a purge gas;

d) introducing an oxygen-containing source comprising a plasma into the reactor; and

e) purging the reactor with a purge gas.

In the above method, steps b to e are repeated until a film of a desired thickness is deposited on the substrate. The oxygen containing plasma source may be generated in situ or, alternatively, remotely. In a particular embodiment, the oxygen-containing source comprises oxygen and is flowed with or introduced during method steps b to d with other reagents, such as, but not limited to, at least one silicon precursor and optionally an inert gas.

However, in another embodiment of the methods described herein, the methods are performed by an ALD process that uses an oxygen-containing source comprising ozone or a plasma, wherein the plasma may further comprise an inert gas, such as one or more of the following: oxygen plasma with or without inert gas, water vapor plasma with or without inert gas, nitrogen oxide (e.g., N) with or without inert gas₂O、NO、NO₂) Plasma, carbon oxides with or without inert gases (e.g. CO)₂CO), plasma, and combinations thereof. In this embodiment, a method of depositing a silicon oxide film on at least one surface of a substrate at a temperature greater than 600 ℃ comprises the steps of:

a) providing a substrate in a reactor;

b) introducing at least one silicon precursor selected from the group consisting of formulas A and B into a reactor, wherein R³-R⁸And X are both methyl;

c) purging the reactor with a purge gas;

d) introducing an oxygen-containing source comprising a plasma into the reactor; and

e) purging the reactor with a purge gas.

In the above method, steps b to e are repeated until a film of a desired thickness is deposited on the substrate. The oxygen containing plasma source may be generated in situ or, alternatively, remotely. In a particular embodiment, the oxygen-containing source comprises oxygen and is flowed with or introduced during method steps b to d with other reagents, such as, but not limited to, at least one silicon precursor and optionally an inert gas.

In one or more embodiments, the at least one silicon precursor comprises an organoaminodisiloxane compound having formula a described above. In a particular embodiment, R in the formula³-R⁶Containing hydrogen or C₁Alkyl or methyl. Further exemplary precursors are listed in table 1.

TABLE 1 organic aminodisiloxane compounds having one Si-O-Si bond in formula A.

In one or more embodiments, the at least one silicon precursor comprises an organoaminotrisiloxane compound having formula B described herein. In a particular embodiment, R in the formula³-R⁸Containing hydrogen or C₁Alkyl or methyl. Further exemplary precursors are listed in table 2.

TABLE 2 Organoaminotrisiloxane compounds having two Si-O-Si bonds in formula B

In the above formula and throughout the specification, the term "alkyl" denotes a straight or branched chain functional group having 1 to 10 carbon atoms. Exemplary straight chain alkyl groups include, but are not limited to, methyl, ethyl, propyl, butyl, pentyl, and hexyl. Exemplary branched alkyl groups include, but are not limited to, isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, tert-pentyl, isohexyl, and neohexyl. In certain embodiments, the alkyl group may have one or more functional groups attached thereto, such as, but not limited to, alkoxy groups, dialkylamino groups, or combinations thereof attached thereto. In other embodiments, the alkyl group does not have one or more functional groups attached thereto. The alkyl group may be saturated or unsaturated.

In the above formula and throughout the specification, the term "cycloalkyl" denotes a cyclic functional group having 3 to 10 carbon atoms. Exemplary cycloalkyl groups include, but are not limited to, cyclobutyl, cyclopentyl, cyclohexyl, and cyclooctyl.

In the above formula and throughout the specification, the term "alkenyl" denotes a group having one or more carbon-carbon double bonds and having 2 to 10 or 2 to 6 carbon atoms.

In the above formula and throughout the specification, the term "alkynyl" denotes a group having one or more carbon-carbon triple bonds and having 3 to 10 or 2 to 6 carbon atoms.

In the above formula and throughout the specification, the term "aryl" denotes an aromatic cyclic functional group having 4 to 10 carbon atoms, 5 to 10 carbon atoms, or 6 to 10 carbon atoms. Exemplary aryl groups include, but are not limited to, phenyl, benzyl, chlorobenzyl, tolyl, o-xylyl, 1,2, 3-triazolyl, pyrrolyl, and furanyl.

In the above formula and throughout the specification, the term "amino" denotes an organic amino group having 1 to 10 carbon atoms, derived from a compound having the formula HNR¹R²The organic amine of (1). Exemplary amino groups include, but are not limited to, secondary amino groups derived from secondary amines, such as dimethylamino (Me)₂N-), diethylamino (Et)₂N-, diisopropylamino group(s) ((s))ⁱPr₂N-); primary amino groups derived from primary amines, e.g. methylamino (MeNH-) ethylamino (EtNH-) isopropylamino ()ⁱPrNH-) sec-butylamino (^sBuNH-) and tert-butylamino(s), (B)^tBuNH-)。

The compounds of the invention having formula a or B may be prepared, for example, by one or more of the reactions shown in the following reaction equations (1) to (10):

the reactions in reaction equations (1) to (12) may be carried out with (e.g., in the presence of) or without (e.g., in the absence of) an organic solvent. In embodiments where an organic solvent is used, examples of suitable organic solvents include, but are not limited to, hydrocarbons such as hexane, octane, toluene, and ethers such as diethyl ether and Tetrahydrofuran (THF). In these or other embodiments, the reaction temperature is in the range of about-70 ℃ to the boiling point of the solvent used (if a solvent is used) or to the boiling point of the most volatile component of the reaction. In other embodiments, if a high pressure reactor is used, the reaction temperature may be above the normal boiling point of the most volatile component. The resulting silicon precursor compound may be purified, for example by vacuum distillation, after removal of all by-products and any solvent, if present.

Reaction equations (1) and (2) are one synthetic route for preparing silicon precursor compounds having formula a or B involving the reaction between a halodisiloxane or a halotrisiloxane and an organic amine. Reaction equations (3) and (4) are a synthetic route to the preparation of silicon precursor compounds having formula a or B involving a dehydrocoupling reaction between a hydridosiloxane or hydridosiloxane and an organic amine in the presence of a catalyst. Alternatively, in reaction equations (1) to (4), these reactions may replace the free organic amine (HNR) with a metal amide in the presence or absence of a catalyst¹R²) Metal amides such as, but not limited to, lithium amide (LiNR)¹R²) Sodium amide (NaNR)¹R²) Or potassium amide (KNR)¹R²). The hydrido disiloxane or hydrido trisiloxane starting materials in equations (3) and (4) can be synthesized, for example, by the synthetic routes shown in equations (5) through (8), which involve the metallated form of silanol, disiloxanol, or both (e.g., potassium trimethylsilanolate, potassium pentamethyldisiloxanolate) with an organoaminosilane or with a compound containing at least one of the foregoingReaction between halosilanes of one Si-H bond. Reaction equations (9) and (10) are another synthetic route for preparing silicon precursor compounds having formula a or B involving the reaction of a silanol, disiloxanol, or a metallated form of both with an organoaminohalosilane. Reaction equations (11) and (12) are another synthetic route for preparing silicon precursor compounds having formula a or B involving the reaction of a silanol, disiloxanol, or a metallated form of both with a bis (organo-amino) silane. Other synthetic routes may also be used to prepare these silicon precursor compounds of formula a or B, as disclosed in the prior art, for example with metal hydrides such as LiH, LiAlH, in the presence or absence of a catalyst₄Reduction of an organic amino chlorodisiloxane or an organic amino chlorotrisiloxane or reaction of a hydridosiloxane or hydridosiloxane with an imine (hydrosilylation of an imine).

The silicon precursor compound according to the invention having the formula a or B and the composition comprising the silicon precursor compound according to the invention having the formula a or B are preferably substantially free of halide ions. As used herein, the term "substantially free" when it relates to halide ions (or halides), such as chloride, fluoride, bromide and iodide, means less than 5ppm (by weight), preferably less than 3ppm, more preferably less than 1ppm, most preferably 0 ppm. Chlorides are known to act as decomposition catalysts for silicon precursor compounds having formula a or B. Significant levels of chloride in the final product can lead to degradation of the silicon precursor compounds. The gradual degradation of silicon precursor compounds can directly affect the film deposition process, making it difficult for semiconductor manufacturers to meet film specifications. The silicon precursor compound having formula A or B is preferably substantially free of metal ions, such as Al³⁺Ions, Fe²⁺、Fe³⁺、Ni²⁺、Cr³⁺. As used herein, the term "substantially free" as it relates to Al³⁺Ions, Fe²⁺、Fe³⁺、Ni²⁺、Cr³⁺By weight, it is meant less than 5ppm (by weight), preferably less than 3ppm, more preferably less than 1ppm, most preferably 0.1 ppm. In some embodiments, the silicon precursor compound having formula a or B is free of metal ions, such as Al³⁺Ions, Fe²⁺、Fe³⁺、Ni²⁺、Cr³⁺. As used herein, the term "free" as it relates to Al³⁺Ions, Fe²⁺、Fe³⁺、Ni²⁺、Cr³⁺By 0ppm (by weight) is meant, and in addition, shelf life or stability is negatively affected by the higher degradation rate of the silicon precursor compound, thereby making it difficult to guarantee a shelf life of 1-2 years. Furthermore, silicon precursor compounds are known to form flammable and/or pyrophoric gases upon decomposition, such as hydrogen and disiloxanes or trisiloxanes. Thus, the accelerated decomposition of silicon precursor compounds presents safety and performance issues related to the formation of these flammable and/or pyrophoric gaseous byproducts.

For those embodiments in which a silicon precursor having formula a or B is used in a composition comprising a solvent and a silicon precursor compound having formula a or B described herein, the selected solvent or mixture thereof does not react with the silicon precursor. The amount of solvent in the composition is 0.5 to 99.5 or 10 to 75 wt% in wt%. In this or other embodiments, the boiling point (b.p.) of the solvent is similar to, or the difference between, the b.p. of the solvent and the b.p. of the silicon precursor of formula a or B is 40 ℃ or less, 30 ℃ or less, or 20 ℃ or less, or 10 ℃. Alternatively, the difference between the boiling points is within the range of any one or more of the following endpoints: 0. 10, 20, 30 or 40 ℃. Examples of suitable ranges for the b.p. difference include, but are not limited to, 0 to 40 ℃, 20 to 30 ℃, or 10 to 30 ℃. Examples of suitable solvents in the composition include, but are not limited to, ethers (e.g., 1, 4-dioxane, dibutyl ether), tertiary amines (e.g., pyridine, 1-methylpiperidine, 1-ethylpiperidine, N '-dimethylpiperazine, N' -tetramethylethylenediamine), nitriles (e.g., benzonitrile), alkyl hydrocarbons (e.g., octane, nonane, dodecane, ethylcyclohexane), aromatic hydrocarbons (e.g., toluene, mesitylene), tertiary amino ethers (e.g., bis (2-dimethylaminoethyl) ether), or mixtures thereof.

Throughout the specification, the term "ALD or ALD-like" refers to processes including, but not limited to, the following processes: a) sequentially introducing respective reactants including a silicon precursor and a reactive gas into a reactor, such as a single wafer ALD reactor, a semi-batch ALD reactor, or a batch furnace ALD reactor; b) each reactant comprising a silicon precursor and a reactive gas is exposed to the substrate by moving or rotating the substrate to a different section of the reactor, and each section is separated by a curtain of inert gas, i.e. a spatial ALD reactor or a roll-to-roll ALD reactor.

Throughout the specification, the term "alkyl hydrocarbon" refers to a straight or branched chain C₁To C₂₀Hydrocarbons, cyclic C₆To C₂₀A hydrocarbon. Exemplary hydrocarbons include, but are not limited to, heptane, octane, nonane, decane, dodecane, cyclooctane, cyclononane, cyclodecane. Throughout the specification, the term "aromatic hydrocarbon" means C₆To C₂₀An aromatic hydrocarbon. Exemplary aromatic hydrocarbons include, but are not limited to, toluene, mesitylene.

In certain embodiments, the substituent R in formulas A and B¹And R²May be joined together to form a ring structure. As the skilled person will appreciate, at R¹And R²In the case where R is linked together to form a ring¹Comprising a base for connecting to R²And vice versa. In these embodiments, the ring structure may be unsaturated, such as a cycloalkyl ring, or saturated, such as an aromatic ring. Furthermore, in these embodiments, the ring structure may also be substituted with one or more atoms or groups or unsubstituted. Exemplary cyclic ring groups include, but are not limited to, pyrrolyl, pyrrolidinyl, piperidino, and 2, 6-dimethylpiperidino. However, in other embodiments, the substituent R¹And R²Are not connected to form a ring structure.

In certain embodiments, the silicon oxide or carbon-doped silicon oxide film deposited using the methods described herein comprises ozone, water (H)₂O) (e.g., deionized, purified, and/or distilled water), oxygen (O)₂) Oxygen plasma, NO, N₂O、NO₂Carbon monoxide (CO) and carbon dioxide (CO)₂) And combinations thereof in the presence of an oxygen-containing source. Passing an oxygen-containing source through, for example, an in situ or remote plasma generator to provide an oxygen-containing plasma source comprising oxygen, such as an oxygen plasma, oxygen-containing and oxygen-containingArgon plasma, oxygen and helium containing plasma, ozone plasma, water plasma, nitrous oxide plasma, or carbon dioxide plasma. In certain embodiments, the oxygen containing plasma source comprises an oxygen containing source gas introduced into the reactor at a flow rate of about 1 to about 2000 standard cubic centimeters (sccm) or about 1 to about 1000 sccm. The oxygen-containing plasma source may be introduced for a time of about 0.1 to about 100 seconds. In a particular embodiment, the oxygen-containing plasma source comprises water at a temperature of 10 ℃ or greater. In embodiments where the film is deposited by a PEALD or plasma enhanced cyclic CVD process, the precursor pulse may have a pulse duration of greater than 0.01 seconds (e.g., about 0.01 to about 0.1 seconds, about 0.1 to about 0.5 seconds, about 0.5 seconds to about 10 seconds, about 0.5 seconds to about 20 seconds, about 1 second to about 100 seconds), depending on the volume of the ALD reactor, and the oxygen-containing plasma source may have a pulse duration of less than 0.01 seconds (e.g., about 0.001 to about 0.01 seconds).

The deposition methods disclosed herein may involve one or more purge gases. The purge gas used to purge unconsumed reactants and/or reaction byproducts is an inert gas that does not react with the precursor. Exemplary purge gases include, but are not limited to, argon (Ar), nitrogen (N)₂) Helium (He), neon, hydrogen (H)₂) And mixtures thereof. In certain embodiments, a purge gas, such as Ar, is supplied to the reactor at a flow rate of about 10 to about 2000sccm for about 0.1 to 1000 seconds, thereby purging unreacted material and any byproducts that may remain in the reactor.

The respective steps of supplying the precursors, oxygen-containing sources, and/or other precursors, source gases, and/or reagents may be performed by varying the time they are supplied to alter the stoichiometric composition of the resulting dielectric film.

Energy is applied to at least one of the silicon precursor, the oxygen-containing source, or a combination thereof to initiate the reaction and form a dielectric film or coating on the substrate. Such energy may be provided by, but is not limited to, thermal, plasma, pulsed plasma, helicon plasma, high density plasma, inductively coupled plasma, X-ray, electron beam, photon, remote plasma methods, and combinations thereof. In some embodiments, a secondary RF source may be used to alter the plasma properties at the substrate surface. In embodiments where the deposition involves a plasma, the plasma generation process may comprise a direct plasma generation process (where the plasma is generated directly in the reactor) or a remote plasma generation process (where the plasma is generated outside the reactor and supplied into the reactor).

The at least one silicon precursor may be delivered to the reaction chamber in various ways, such as a plasma enhanced cyclic CVD or PEALD reactor or a batch furnace type reactor. In one embodiment, a liquid delivery system may be used. In an alternative embodiment, a combined liquid delivery and flash processing unit, such as a turbo evaporator manufactured by MSP Corporation, shorevew, MN, may be used to enable the low volatility material to be delivered quantitatively (volumetrically), which results in repeatable delivery and deposition without thermal decomposition of the precursor. In a liquid delivery configuration, the precursors described herein may be delivered in a pure liquid form, or may be used in a solvent formulation or composition comprising the same. Thus, in certain embodiments, the precursor formulation may comprise a solvent component having suitable characteristics (as may be desired and advantageous in a given end-use application) to form a film on a substrate.

For those embodiments in which at least one silicon precursor described herein is used in a composition comprising a solvent and at least one silicon precursor described herein, the selected solvent or mixture thereof does not react with the silicon precursor. The amount of solvent in the composition in weight percent ranges from 0.5 wt% to 99.5 wt% or from 10 wt% to 75 wt%. In this or other embodiments, the boiling point (b.p.) of the solvent is similar to the b.p. of the at least one silicon precursor, or the difference between the b.p. of the solvent and the b.p. of the at least one silicon precursor is 40 ℃ or less, 30 ℃ or less, or 20 ℃ or less, or 10 ℃ or less. Alternatively, the difference in boiling points is within the range constituted by any one or more of the following endpoints: 0. 10, 20, 30 or 40 ℃. Examples of suitable ranges for the b.p. difference include, but are not limited to, 0 to 40 ℃, 20 to 30 ℃, or 10 to 30 ℃. Examples of suitable solvents in the composition include, but are not limited to, ethers (e.g., 1, 4-dioxane, dibutyl ether), tertiary amines (e.g., pyridine, 1-methylpiperidine, 1-ethylpiperidine, N '-dimethylpiperazine, N' -tetramethylethylenediamine), nitriles (e.g., benzonitrile), alkanes (e.g., octane, nonane, dodecane, ethylcyclohexane), aromatic hydrocarbons (e.g., toluene, mesitylene), tertiary amino ethers (e.g., bis (2-dimethylaminoethyl) ether), or mixtures thereof.

As previously mentioned, the purity level of the at least one silicon precursor is sufficiently high to be acceptable for reliable semiconductor fabrication. In certain embodiments, at least one silicon precursor described herein comprises less than 2 wt%, or less than 1 wt%, or less than 0.5 wt%, or less than 0.1 wt%, or less than 0.01 wt% (100ppm), or 0.001 wt% (10ppm), or 0.0001 wt% (1ppm) of one or more of the following impurities: free amines, free halides or halides such as chloride (Cl), bromide (Br), and higher molecular weight species. The impurity level of the halide (Cl or Br) in the silicon precursor should be less than 100ppm, 50ppm, 20ppm, 10ppm, 5ppm or 1 ppm. Higher purity levels of the silicon precursors described herein may be obtained by one or more of the following processes: purification, adsorption and/or distillation.

In one embodiment of the methods described herein, a plasma enhanced cyclic deposition process, such as PEALD-like or PEALD, may be used, wherein the deposition is performed using at least one silicon precursor and an oxygen-containing source. A PEALD-like process is defined as a plasma-enhanced cyclic CVD process, but still provides a highly conformal silicon oxide film.

In certain embodiments, the gas lines connected from the precursor tanks to the reaction chamber are heated to one or more temperatures according to process requirements, and the container of the at least one silicon precursor is maintained at the one or more temperatures used for sparging. In other embodiments, a solution comprising at least one silicon precursor is injected into a vaporizer maintained at one or more temperatures for direct liquid injection.

A flow of argon and/or other gases may be used as a carrier gas to assist in the delivery of the vapor of the at least one silicon precursor to the reaction chamber during the precursor pulse. In some embodiments, the reaction chamber process pressure is about 50 mtorr to 10 torr. In other embodiments, the reaction chamber process pressure may be up to 760 torr (e.g., about 50 mtorr to about 100 torr).

In a typical PEALD or PEALD-like process (e.g., a PECCVD process), a substrate, such as a silicon oxide substrate, is heated on a heater stage in a reaction chamber that is initially exposed to a silicon precursor to allow the compound to be chemisorbed onto the substrate surface.

A purge gas, such as argon, purges the process chamber of unadsorbed excess complex. After sufficient purging, an oxygen-containing source may be introduced into the reaction chamber to react with the adsorption surface, followed by another gas purge to remove reaction by-products from the reaction chamber. The process cycle may be repeated to achieve the desired film thickness. In some cases, pumping may replace the purging of the inert gas, or both may be used to remove unreacted silicon precursor.

In this or other embodiments, it is understood that the steps of the methods described herein can be performed in various orders, can be performed sequentially, can be performed simultaneously (e.g., during at least a portion of another step), and any combination thereof. The respective steps of supplying the precursor and the oxygen-containing source gas may be performed by varying the duration of supplying them to vary the stoichiometric composition of the resulting dielectric film. In addition, the purge time after the precursor or oxidant step can be minimized to <0.1s, such that throughput is improved.

One particular embodiment of the method described herein for depositing a high quality silicon oxide film on a substrate at a temperature below 300 ℃ comprises the steps of:

a. providing a substrate in a reactor;

b. introducing into the reactor at least one silicon precursor selected from the group consisting of formula A and B, having one SiH₂The silicon precursor of the group is linked to an organoamino functional group as described herein;

c. purging the reactor with a purge gas to remove at least a portion of the unabsorbed precursor;

d. introducing an oxygen-containing plasma source into the reactor;

e. purging the reactor with a purge gas to remove at least a portion of the unreacted oxygenate source,

wherein steps b through e are repeated until a desired thickness of silicon oxide film is deposited. Is believed to have one SiH₂The silicon precursor of the group is anchored on the surface with hydroxyl groups by liberating an organic amine and reacts with SiHMe or SiMe with functional groups linked to organic amino groups₂Small SiH as compared to the silicon precursor₂The radicals allow more silicon segments to be anchored, thereby achieving a higher thanGrowth rate per cycle.

Another particular embodiment of the method for depositing a high quality silicon oxide film on a substrate at a temperature greater than 600 ℃ described herein comprises the steps of:

a. providing a substrate in a reactor;

b. introducing into a reactor at least one silicon precursor selected from the group consisting of formulas A and B as described herein, wherein R³-R⁸And X are both methyl;

c. purging the reactor with a purge gas to remove at least a portion of the unabsorbed precursor;

d. introducing an oxygen-containing plasma source into the reactor;

e. purging the reactor with a purge gas to remove at least a portion of the unreacted oxygenate source,

wherein steps b through e are repeated until a desired thickness of silicon oxide film is deposited. It is believed that the Si-methyl groups are stable at temperatures above 600 ℃, preventing any chemical vapor deposition due to thermal decomposition of silicon precursors (such as those with Si-H groups) and enabling high temperature deposition of high quality silicon oxide.

Yet another method disclosed herein forms a carbon-doped silicon oxide film using an organoaminodisiloxane compound or an organoaminotrisiloxane compound and an oxygen-containing source.

A further exemplary method is described below:

a. providing a substrate in a reactor

b. Contacting a vapor generated from an organoaminodisiloxane compound or an organoaminotrisiloxane compound selected from formulas a and B described herein, with or without a co-current of an oxygen-containing source, to chemisorb a precursor to a heated substrate;

c. purging any unabsorbed precursor;

d. introducing an oxygen-containing source onto the heated substrate to react with the adsorbed precursor; and the combination of (a) and (b),

e. purging away any unreacted oxygen-containing source,

wherein steps b to e are repeated until the desired thickness is reached.

Solid silicon oxide or carbon doped silicon oxide can be deposited using various commercial ALD reactors such as single wafer, semi-batch, or roll-to-roll reactors.

In one embodiment, the process temperature of the methods described herein uses as endpoints one or more of the following temperatures: 0. 25, 50, 75, 100, 125, 150, 175, 200, 225, 250, 275, and 300 ℃. Exemplary temperature ranges include, but are not limited to, the following: from about 0 ℃ to about 300 ℃; or from about 25 ℃ to about 300 ℃; or from about 50 ℃ to about 290 ℃; or from about 25 ℃ to about 250 ℃, or from about 25 ℃ to about 200 ℃. In other embodiments, the process temperatures of the methods described herein use one or more of the following temperatures as endpoints: 300. 325, 350, 375, 400, 425, 450, 475, 500, 525, 550, 575, and 600 ℃. However, in other embodiments, the process temperatures of the methods described herein use one or more of the following temperatures as endpoints: 600. 625, 650, 675, 700, 725, 750, 775 and 800 ℃. Depending on the structure of the silicon precursor, some suitable deposition temperatures are below 600 ℃, while others may be more suitable at temperatures above 600 ℃. For example, a silicon precursor having the formula A or B (wherein R is³And R⁴Both hydrogen) are suitable for depositing high quality silicon oxide at temperatures below 600 c, on the other hand, silicon precursors having the formula a or B (wherein R is³-R⁸And X is both methyl) can be used to deposit high quality silica at temperatures from room temperature to 800 ℃, especially above 600 ℃, because the Si-Me groups are more reactive than the Si-H groupsThe clusters are more resistant to oxidation. It is believed that the Si-methyl groups are stable at temperatures above 600 ℃, preventing any chemical vapor deposition due to thermal decomposition of silicon precursors (such as those with Si-H groups) and enabling high temperature deposition of high quality silicon oxide.

In yet another embodiment of the method described herein, the film or the film so deposited is subjected to a treatment step. The treating step can be performed during at least a portion of the depositing step, after the depositing step, and combinations thereof. Exemplary processing steps include, but are not limited to, high temperature thermal annealing processes; plasma processing; ultraviolet (UV) light treatment; laser; e-beam processing, and combinations thereof, to affect one or more properties of the film. The films deposited with the silicon precursors of formulas a or B described herein have improved properties such as, but not limited to, a wet etch rate that is lower than the wet etch rate of the film prior to the processing step, or a density that is higher than the density prior to the processing step, as compared to films deposited with the previously disclosed silicon precursors under the same conditions. In a particular embodiment, the film thus deposited is treated intermittently during the deposition process. These intermittent or in-deposition processes may be performed, for example, after each ALD cycle, after each number of ALD cycles (e.g., without limitation, one (1) ALD cycle, two (2) ALD cycles, five (5) ALD cycles, or after every ten (10) or more ALD cycles).

In embodiments where the film is treated with a high temperature annealing step, the annealing temperature is at least 100 ℃ or higher than the deposition temperature. In this or other embodiments, the annealing temperature is in the range of about 400 ℃ to about 1000 ℃. In this or other embodiments, the annealing process may be performed under vacuum (C:)<760 torr), inert environment, or oxygen containing environment (e.g., H)₂O、N₂O、NO₂Or O₂) Is carried out in (1).

In embodiments where the film is UV treated, the film is exposed to broadband UV, or a UV source having a wavelength in the range of about 150 nanometers (nm) to about 400 nm. In a particular embodiment, after the desired film thickness is reached, the film so deposited is exposed to UV in a chamber different from the deposition chamber.

In embodiments where the film is plasma treated, a passivation layer (e.g., SiO) is deposited₂Or carbon doped SiO₂) To prevent chlorine and nitrogen contamination from penetrating into the film during subsequent plasma processing. The passivation layer may be deposited using atomic layer deposition or cyclic chemical vapor deposition.

In embodiments where the film is treated with a plasma, the plasma source is selected from the group consisting of a hydrogen plasma, a plasma comprising hydrogen and helium, a plasma comprising hydrogen and argon. The hydrogen plasma reduces the dielectric constant of the film and enhances the damage resistance to subsequent plasma ashing processes while still keeping the bulk carbon content nearly unchanged.

It is believed that the silicon precursor having formula a or B may be anchored on the substrate surface to provide Si-O-Si or Si-O-Si fragments to increase the growth rate of silicon oxide or carbon doped silicon oxide compared to conventional silicon precursors, such as bis (tert-butylamino) silane or bis (diethylamino) silane having only one silicon atom. Importantly, the so deposited Si-O-Si or Si-O-Si fragments in a given pulse of the silicon precursor may provide better protection for the substrate, possibly avoiding or reducing substrate oxidation in subsequent pulses of the oxygen-containing source during the ALD process, since conventional silicon precursors such as bis (tert-butylamino) silane or bis (diethylamino) silane may only provide a single layer of silicon fragments.

In certain embodiments, silicon precursors having formula a or B as described herein may also be used as dopants for metal-containing films (such as, but not limited to, metal oxide films or metal nitride films). In these embodiments, the metal-containing film is deposited using an ALD or CVD process (such as those described herein) using a metal alkoxide, metal amide, or volatile organometallic precursor. Examples of suitable metal alkoxide precursors that may be used with the methods disclosed herein include, but are not limited to: group 3 to 6 metal alkoxides, group 3 to 6 metal complexes with both alkoxy and alkyl substituted cyclopentadienyl ligands, group 3 to 6 metal complexes with both alkoxy and alkyl substituted pyrrolyl ligands, group 3 to 6 metal complexes with both alkoxy and diketonate (diketonate) ligands; group 3-6 metal complexes with both alkoxy and ketoester ligands. Examples of suitable metal amide precursors that may be used with the methods disclosed herein include, but are not limited to, tetrakis (dimethylamino) zirconium (TDMAZ), tetrakis (diethylamino) zirconium (TDEAZ), tetrakis (ethylmethylamino) zirconium (TEMAZ), tetrakis (dimethylamino) hafnium (TDMAH), tetrakis (diethylamino) hafnium (TDEAH), and tetrakis (ethylmethylamino) hafnium (TEMAH), tetrakis (dimethylamino) titanium (TDMAT), tetrakis (diethylamino) titanium (TDEAT), tetrakis (ethylmethylamino) titanium (TEMAT), t-butyliminotris (diethylamino) tantalum (TBTDET), t-butyliminotris (dimethylamino) tantalum (tdtbmt), t-butyliminotris (ethylmethylamino) tantalum (TBTEMT), ethyliminotris (diethylaminotantalum (eitdetet), ethyliminotris (dimethylamino) tantalum (eit), ethyliminotris (ethylmethylamino) tantalum (temt), tetr (ethyliminotris (ethylmethylamino) tantalum (temt), etc, T-amyliminotris (dimethylamino) tantalum (taimit), t-amyliminotris (diethylamino) tantalum, pentakis (dimethylamino) tantalum, t-amyliminotris (ethylmethylamino) tantalum, bis (t-butylimino) bis (dimethylamino) tungsten (BTBMW), bis (t-butylimino) bis (diethylamino) tungsten, bis (t-butylimino) bis (ethylmethylamino) tungsten, and combinations thereof. Examples of suitable organometallic precursors that can be used with the methods disclosed herein include, but are not limited to, group 3 metal cyclopentadienyls or alkyl cyclopentadienyls. Exemplary group 3 to 6 metals herein include, but are not limited to, Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Er, Yb, Lu, Ti, Hf, Zr, V, Nb, Ta, Cr, Mo, and W.

In certain embodiments, the resulting silicon-containing film or coating can be exposed to post-deposition treatments such as, but not limited to, plasma treatments, chemical treatments, ultraviolet light exposure, electron beam exposure, and/or other treatments that affect one or more properties of the film.

In certain embodiments, the silicon-containing films described herein have a dielectric constant of 6 or less, 5 or less, 4 or less, and 3 or less. In these or other embodiments, the film may have a dielectric constant of about 5 or less, or about 4 or less, or about 3.5 or less. However, it is contemplated that the shape may be varied depending on the desired end use of the filmInto films having other dielectric constants (e.g., higher or lower). An example of a silicon-containing film formed using the silicon precursor having the precursor of formula a or B and the methods described herein has the formula Si_xO_yC_zN_vH_wWherein Si ranges from about 10% to about 40%; o is in the range of about 0% to about 65%; c ranges from about 0% to about 75% or from about 0% to about 50%; n ranges from about 0% to about 75% or about 0% to 50%; and H ranges from about 0% to about 50% (atomic weight percent), where x + y + z + v + w is 100 atomic weight percent, as determined, for example, by XPS or other methods. Another example of a silicon-containing film formed using the organoaminodisiloxane and organoaminotrisiloxane precursors and methods described herein having formula a or B is silicon carbonitride, wherein the carbon content is 1 atomic% to 80 atomic% as measured by XPS. Yet another example of a silicon-containing film formed using the organoaminodisiloxane and organoaminotrisiloxane precursors and methods described herein having formula a or B is amorphous silicon, where the sum of the nitrogen and carbon contents is measured by XPS<10 atom%, preferably<5 atomic%, most preferably<1 atom%.

As previously described, the methods described herein can be used to deposit a silicon-containing film on at least a portion of a substrate. Examples of suitable substrates include, but are not limited to, silicon, SiO₂、Si₃N₄OSG, FSG, silicon carbide, hydrogenated silicon carbide, silicon nitride, hydrogenated silicon nitride, silicon carbonitride, hydrogenated silicon carbonitride, boron nitride, anti-reflective coatings, photoresists, germanium-containing, boron-containing, Ga/As, flexible substrates, organic polymers, porous organic and inorganic materials, metals such As copper and aluminum, and diffusion barriers such As, but not limited to, TiN, Ti (C) N, TaN, Ta (C) N, Ta, W, or WN. The film is compatible with various subsequent processing steps, such as Chemical Mechanical Planarization (CMP) and anisotropic etch processes.

The deposited films have a variety of applications including, but not limited to, computer chips, optical devices, magnetic information storage devices, coatings on supporting materials or substrates, micro-electro-mechanical systems (MEMS), nano-electro-mechanical systems, Thin Film Transistors (TFTs), Light Emitting Diodes (LEDs), Organic Light Emitting Diodes (OLEDs), IGZO, and Liquid Crystal Displays (LCDs). Potential uses of the resulting solid silicon oxide or carbon doped silicon oxide include, but are not limited to, shallow trench isolation, interlayer dielectric layers, passivation layers, etch stop layers, portions of dual spacers, and sacrificial layers for patterning.

The methods described herein provide high quality silicon oxide or carbon doped silicon oxide films. The term "high quality" refers to a film that exhibits one or more of the following characteristics: a density of about 2.1g/cc or greater, 2.2g/cc or greater, 2.25g/cc or greater; as measured in a solution of HF: water 1:100 in dilute HF acid (0.5 wt.% dHF)Or even lower, in the case of,or even lower, in the case of,or even lower, in the case of,or even lower, in the case of,or even lower, in the case of,or even lower, in the case of,or even lower, in the case of,or a lower wet etch rate; up to about 1e-8A/cm at 6MV/cm²Or less leakage current; and a hydrogen impurity of about 5e20at/cc or less as measured by SIMS; and combinations thereof. With respect to the etching rate, the thermally grown silicon oxide film had a chemical composition in 0.5 wt.% HFEtching ofThe rate.

In certain embodiments, one or more silicon precursors having formula a or B described herein can be used to form a silicon oxide film that is solid and non-porous or substantially non-porous.

Thus, the present invention provides at least the following:

1. a method of depositing a film comprising silicon and oxygen onto a substrate, comprising the steps of:

a) providing a substrate in a reactor;

b) introducing at least one silicon precursor compound into the reactor, wherein the at least one silicon precursor compound is selected from the group consisting of formulas A and B:

wherein the content of the first and second substances,

R¹independently selected from straight chain C₁To C₁₀Alkyl, branched C₃To C₁₀Alkyl radical, C₃To C₁₀Cycloalkyl radical, C₃To C₁₀Heterocyclic group, C₃To C₁₀Alkenyl radical, C₃To C₁₀Alkynyl and C₄To C₁₀An aryl group;

R²selected from hydrogen, straight chain C₁To C₁₀Alkyl, branched C₃To C₁₀Alkyl radical, C₃To C₁₀Cycloalkyl radical, C₃To C₁₀Heterocyclic group, C₃To C₁₀Alkenyl radical, C₃To C₁₀Alkynyl and C₄To C₁₀Aryl, wherein R in formula A or B¹And R²Linked to form a cyclic ring structure or not linked to form a cyclic ring structure;

R³-R⁸each independently selected from hydrogen, straight chain C₁To C₁₀Alkyl, branched C₃To C₁₀Alkyl radical, C₃To C₁₀Cycloalkyl radical, C₂To C₁₀Alkenyl radical, C₂To C₁₀Alkynyl and C₄To C₁₀An aryl group;

x is selected from hydrogen and straight chain C₁To C₁₀Alkyl, branched C₃To C₁₀Alkyl radical, C₃To C₁₀Cycloalkyl radical, C₂To C₁₀Alkenyl radical, C₂To C₁₀Alkynyl, C₄To C₁₀Aryl, halogen and NR⁹R¹⁰Wherein R is⁹And R¹⁰Each independently selected from hydrogen, straight chain C₁To C₆Alkyl, branched C₃To C₆Alkyl radical, C₃To C₁₀Cycloalkyl radical, C₃To C₁₀Alkenyl radical, C₃To C₁₀Alkynyl and C₄To C₁₀Aryl, wherein R⁹And R¹⁰Linked to form a cyclic ring structure or not linked to form a cyclic ring structure, and wherein R¹And R⁹Connected to form a cyclic ring or not connected to form a cyclic ring;

c) purging the reactor with a purge gas;

d) introducing an oxygen-containing source into the reactor; and

e) purging the reactor with a purge gas,

wherein steps b to e are repeated until a desired thickness of the film is deposited, and

wherein the process is carried out at one or more temperatures of about 25 ℃ to 600 ℃.

2. The method of item 1, wherein the at least one silicon precursor compound is at least one selected from the group consisting of: 1-dimethylaminodisiloxane, 1-diethylaminodisiloxane, 1-diisopropylaminodisiloxane, 1-di-sec-butylaminodisiloxane, 1-phenylmethylaminodisiloxane, 1-phenylethylaminodisiloxane, 1-cyclohexylmethylaminodisiloxane, 1-cyclohexylethylaminodisiloxane, 1-piperidinodisiloxane, 1- (2, 6-dimethylpiperidino) disiloxane, 1-dimethylamino-1, 3-dimethyldisiloxane, 1-diethylamino-1, 3-dimethyldisiloxane, 1-diisopropylamino-1, 3-dimethyldisiloxane, 1-di-sec-butylamino-1, 3-dimethyldisiloxane, 1-diisopropylaminodisiloxane, 1-di-sec-butylamino-1, 3-dimethyldisiloxane, 1-cyclohexylaminodisiloxane, 1-piperidinodisiloxane, 1-dimethylaminodioxane, 1-cyclohexylsiloxane, 1-piperidinodisiloxane, 1-dimethylaminodioxane, 1-dimethylaminodisiloxane, 1-1, 3-dimethyldisiloxane, 1-aminodisiloxane, 1-cyclohexylsiloxane, 1-piperidinodisiloxane, 1-piperidino-dimethylsiloxane, 1-piperidino-1, 3-dimethylsiloxane, 1, 6-piperidino-dimethylsiloxane, 1, 6-dimethylaminobilisiloxane, 6-piperazino-1, 3, 1, and a, 1-Phenylmethylamino-1, 3-dimethyldisiloxane, 1-phenylethylamino-1, 3-dimethyldisiloxane, 1-cyclohexylmethylamino-1, 3-dimethyldisiloxane, 1-cyclohexylethylamino-1, 3-dimethyldisiloxane, 1-dimethylamino-1, 1,3, 3-tetramethyldisiloxane, 1-diethylamino-1, 1,3, 3-tetramethyldisiloxane, 1-diisopropylamino-1, 1,3, 3-tetramethyldisiloxane, 1-di-sec-butylamino-1, 1,3, 3-tetramethyldisiloxane, 1-phenylmethylamino-1, 1,3, 3-tetramethyldisiloxane, 1-phenylethylamino-1, 1,3, 3-tetramethyldisiloxane, 1-phenylethylamino-1, 1,3, 3-tetramethyldisiloxane, 1-dimethylamino-1, 1,3,3, 3-pentamethyldisiloxane, 1-diethylamino-1, 1,3,3, 3-pentamethyldisiloxane, 1-diisopropylamino-1, 1,3,3, 3-pentamethyldisiloxane, 1-di-sec-butylamino-1, 1,3,3, 3-pentamethyldisiloxane, 1-pyrrolyl-1, 1,3,3, 3-pentamethyldisiloxane, 1-pyrrolidinyl-1, 1,3,3, 3-pentamethyldisiloxane, 1-piperidino-1, 1,3,3, 3-pentamethyldisiloxane, 1- (2, 6-dimethylpiperidino) -3,3, 3-pentamethyldisiloxane, 1-isopropylamino-3, 3, 3-trimethyldisiloxane, 1-tert-butylamino-3, 3, 3-trimethyldisiloxane, 1-dimethylamino-3, 3, 3-trimethyldisiloxane, 1-diethylamino-3, 3, 3-trimethyldisiloxane, 1-diisopropylamino-3, 3, 3-trimethyldisiloxane, 1-di-sec-butylamino-3, 3, 3-trimethyldisiloxane, 1-cyclohexylmethylamino-3, 3, 3-trimethyldisiloxane, 1-cyclohexylethylamino-3, 3, 3-trimethyldisiloxane, 1-isopropylamino-3, 3, 3-trimethyldisiloxane, 1-piperidino-3, 3, 3-trimethyldisiloxane, 1- (2, 6-dimethylpiperidino) -3,3, 3-trimethyldisiloxane, 1-dimethylamino-3, 3-dimethyldisiloxane, 1-diethylamino-3, 3-dimethyldisiloxane, 1-diisopropylamino-3, 3-dimethyldisiloxane, 1-di-sec-butylamino-3, 3-dimethyldisiloxane, 1-cyclohexylmethylamino-3, 3-dimethyldisiloxane, 1-cyclohexylethylamino-3, 3-dimethyldisiloxane, 1-piperidino-3, 3-dimethyldisiloxane, 1- (2, 6-dimethylpiperidino) -3, 3-dimethyldisiloxane, 1, 3-bis (dimethylamino) disiloxane, 1, 3-bis (diethylamino) disiloxane, 1, 3-bis (diisopropylamino) disiloxane, 1, 3-bis (di-sec-butylamino) disiloxane, 1, 3-bis (dimethylamino) -1, 3-dimethyldisiloxane, 1, 3-bis (diethylamino) -1, 3-dimethyldisiloxane, 1, 3-bis (diisopropylamino) -1, 3-dimethyldisiloxane, 1, 3-bis (di-sec-butylamino) -1, 3-dimethyldisiloxane, 1, 3-bis (dimethylamino) -1,1,3, 3-tetramethyldisiloxane, 1, 3-bis (diethylamino) -1,1,3, 3-tetramethyldisiloxane, 1-dimethylamino-1, 1,3, 3-tetramethyl-3-chlorodisiloxane, 1-diethylamino-1, 1,3, 3-tetramethyl-3-chlorodisiloxane, 1-diisopropylamino-1, 1,3, 3-tetramethyl-3-chlorodisiloxane, 1-di-sec-butylamino-1, 1,3, 3-tetramethyl-3-chlorodisiloxane, 1-dimethylamino-1, 1,3, 3-tetramethyl-3-bromodisiloxane, 1-diethylamino-1, 1,3, 3-tetramethyl-3-bromodisiloxane, 1-diisopropylamino-1, 1,3, 3-tetramethyl-3-bromodisiloxane, 1-di-sec-butylamino-1, 1,3, 3-tetramethyl-3-bromodisiloxane, 1-tert-butylaminodisiloxane, 1-isopropylaminodisiloxane, 1-tert-butylamino-1, 1,3, 3-tetramethyldisiloxane, 1-isopropyl-1, 1,3, 3-tetramethyldisiloxane, 1-dimethylaminotriesiloxane, 1-diethylaminotrisiloxane, 1-isopropylaminotrisiloxane, 1-di-sec-butylaminotrisiloxane, 1-phenylmethylaminotrisiloxane, 1-phenylethylaminotrisiloxane, 1-cyclohexylmethylaminotrisiloxane, 1-butylaminotrisiloxane, 1-phenylaminotrisiloxane, 1-butylaminotrisiloxane, 1,3, 3-butylaminotrisiloxane, 1,3, 3-butylaminotrisiloxane, 1,3, 1,3, 1,3, one, 1-cyclohexylethylaminotrisiloxane, 1-piperidinotrisiloxane, 1- (2, 6-dimethylpiperidino) trisiloxane, 1-dimethylamino-1, 1,3,3,5, 5-hexamethyltrisiloxane, 1-diethylamino-1, 1,3,3,5, 5-hexamethyltrisiloxane, 1-diisopropylamino-1, 1,3,3,5, 5-hexamethyltrisiloxane, 1-sec-butylamino-1, 1,3,3,5, 5-hexamethyltrisiloxane, 1-phenylmethylamino-1, 1,3,3,5, 5-hexamethyltrisiloxane, 1-phenylethylamino-1, 1,3,3,5, 5-hexamethyltrisiloxane, 1, 5-bis (dimethylamino) -1,1,3,3,5, 5-hexamethyltrisiloxane, 1, 5-bis (diethylamino) -1,1,3,3,5, 5-hexamethyltrisiloxane, 1, 5-bis (diisopropylamino) -1,1,3,3,5, 5-hexamethyltrisiloxane, 1, 5-bis (sec-butylamino) -1,1,3,3,5, 5-hexamethyltrisiloxane, 1, 5-bis (phenylmethylamino) -1,1,3,3,5, 5-hexamethyltrisiloxane, 1, 5-bis (phenylethylamino) -1,1,3,3,5, 5-hexamethyltrisiloxane, 1-diisopropylamino-3, 3,5, 5-pentamethyltrisiloxane, 1-sec-butylamino-3, 3,5,5, 5-pentamethyltrisiloxane, 1-cyclohexylmethylamino-3, 3,5,5, 5-pentamethyltrisiloxane, 1-cyclohexylethylamino-3, 3,5,5, 5-pentamethyltrisiloxane, 1-piperidino-3, 3,5,5, 5-pentamethyltrisiloxane, 1- (2, 6-dimethylpiperidino) -3,3,5,5, 5-pentamethyltrisiloxane, 1-dimethylamino-1, 1,3,3,5,5, 5-heptamethyltrisiloxane, 1-diethylamino-1, 1,3,3,5, 5-heptamethyltrisiloxane, 1-diethylamino-1, 3,3,5, 5-heptamethyltrisiloxane, 1-bis (methyl-ethyl-methyl-siloxane), 1-diisopropylamino-1, 1,3,3,5,5, 5-heptamethyltrisiloxane, 1-sec-butylamino-1, 1,3,3,5,5, 5-heptamethyltrisiloxane, 1-cyclohexylmethylamino-1, 1,3,3,5,5, 5-heptamethyltrisiloxane, 1-cyclohexylethylamino-1, 1,3,3,5,5, 5-heptamethyltrisiloxane, 1-piperidino-1, 1,3,3,5,5, 5-heptamethyltrisiloxane, 1- (2, 6-dimethylpiperidino) -1,1,3,3,5,5, 5-heptamethyltrisiloxane, 1-pyrrolyl-1, 1,3,3,5,5, 5-heptamethyltrisiloxane and 1-pyrrolidinyl-1, 1,3,3,5,5, 5-heptamethyltrisiloxane.

3. The method of item 1, wherein the oxygen-containing source is selected from the group consisting of ozone, oxygen plasma, oxygen and argon containing plasma, oxygen and helium containing plasma, ozone plasma, water plasma, nitrous oxide plasma, carbon dioxide plasma, carbon monoxide plasma, and combinations thereof.

4. The method of item 1, wherein the oxygen-containing source comprises a plasma.

5. The method of clause 4, wherein the plasma is generated in situ.

6. The method of clause 4, wherein the plasma is generated remotely.

7. The method of clause 4, wherein the film has a density of about 2.1g/cc or more.

8. The method of item 1, wherein the film further comprises carbon.

9. The method of clause 8, wherein the film has a density of about 1.8g/cc or more.

10. The method of item 8, wherein the carbon content of the film is 0.5 atomic weight percent (at.%) or greater as measured by X-ray photoelectron spectroscopy.

11. A composition for depositing a film selected from a silicon oxide or carbon doped silicon oxide film using a vapor deposition process, the composition comprising: at least one silicon precursor compound selected from the group consisting of formulas A and B:

wherein the content of the first and second substances,

R¹independently selected from straight chain C₁To C₁₀Alkyl, branched C₃To C₁₀Alkyl radical, C₃To C₁₀Cycloalkyl radical, C₃To C₁₀Heterocyclic group, C₃To C₁₀Alkenyl radical, C₃To C₁₀Alkynyl and C₄To C₁₀An aryl group;

R²selected from hydrogen, straight chain C₁To C₁₀Alkyl, branched C₃To C₁₀Alkyl radical, C₃To C₁₀Cycloalkyl radical, C₃To C₁₀Heterocyclic group, C₃To C₁₀Alkenyl radical, C₃To C₁₀Alkynyl and C₄To C₁₀Aryl, wherein R in formula A or B¹And R²Linked to form a cyclic ring structure or not linked to form a cyclic ring structure;

R³-R⁸each independently selected from hydrogen, straight chain C₁To C₁₀Alkyl, branched C₃To C₁₀Alkyl radical, C₃To C₁₀Cycloalkyl radical, C₂To C₁₀Alkenyl radical, C₂To C₁₀Alkynyl and C₄To C₁₀An aryl group;

x is selected from hydrogen and straight chain C₁To C₁₀Alkyl, branched C₃To C₁₀Alkyl radical, C₃To C₁₀Cycloalkyl radical, C₂To C₁₀Alkenyl radical, C₂To C₁₀Alkynyl, C₄To C₁₀Aryl, halogen (Cl, Br, I) and NR⁹R¹⁰Wherein R is⁹And R¹⁰Each independently selected from hydrogen, straight chain C₁To C₆Alkyl, branched C₃To C₆Alkyl radical, C₃To C₁₀Cycloalkyl radical, C₃To C₁₀Alkenyl radical, C₃To C₁₀Alkynyl and C₄To C₁₀Aryl, wherein R⁹And R¹⁰Linked to form a cyclic ring structure or not linked to form a cyclic ring structure, and wherein R¹And R⁹Linked to form a cyclic ring or not linked to form a cyclic ring, and wherein the composition is substantially free of one or more impurities selected from the group consisting of halides, water, metal ions, and combinations thereof.

12. The composition of item 11, wherein the at least one silicon precursor compound is at least one selected from the group consisting of:

1-dimethylaminodisiloxane, 1-diethylaminodisiloxane, 1-diisopropylaminodisiloxane, 1-di-sec-butylaminodisiloxane, 1-phenylmethylaminodisiloxane, 1-phenylethylaminodisiloxane, 1-cyclohexylmethylaminodisiloxane, 1-cyclohexylethylaminodisiloxane, 1-piperidinodisiloxane, 1- (2, 6-dimethylpiperidino) disiloxane, 1-dimethylamino-1, 3-dimethyldisiloxane, 1-diethylamino-1, 3-dimethyldisiloxane, 1-diisopropylamino-1, 3-dimethyldisiloxane, 1-di-sec-butylamino-1, 3-dimethyldisiloxane, 1-diisopropylaminodisiloxane, 1-di-sec-butylamino-1, 3-dimethyldisiloxane, 1-cyclohexylaminodisiloxane, 1-piperidinodisiloxane, 1-dimethylaminodioxane, 1-cyclohexylsiloxane, 1-piperidinodisiloxane, 1-dimethylaminodioxane, 1-dimethylaminodisiloxane, 1-1, 3-dimethyldisiloxane, 1-aminodisiloxane, 1-cyclohexylsiloxane, 1-piperidinodisiloxane, 1-piperidino-dimethylsiloxane, 1-piperidino-1, 3-dimethylsiloxane, 1, 6-piperidino-dimethylsiloxane, 1, 6-dimethylaminobilisiloxane, 6-piperazino-1, 3, 1, and a, 1-Phenylmethylamino-1, 3-dimethyldisiloxane, 1-phenylethylamino-1, 3-dimethyldisiloxane, 1-cyclohexylmethylamino-1, 3-dimethyldisiloxane, 1-cyclohexylethylamino-1, 3-dimethyldisiloxane, 1-dimethylamino-1, 1,3, 3-tetramethyldisiloxane, 1-diethylamino-1, 1,3, 3-tetramethyldisiloxane, 1-diisopropylamino-1, 1,3, 3-tetramethyldisiloxane, 1-di-sec-butylamino-1, 1,3, 3-tetramethyldisiloxane, 1-phenylmethylamino-1, 1,3, 3-tetramethyldisiloxane, 1-phenylethylamino-1, 1,3, 3-tetramethyldisiloxane, 1-phenylethylamino-1, 1,3, 3-tetramethyldisiloxane, 1-dimethylamino-1, 1,3,3, 3-pentamethyldisiloxane, 1-diethylamino-1, 1,3,3, 3-pentamethyldisiloxane, 1-diisopropylamino-1, 1,3,3, 3-pentamethyldisiloxane, 1-di-sec-butylamino-1, 1,3,3, 3-pentamethyldisiloxane, 1-pyrrolyl-1, 1,3,3, 3-pentamethyldisiloxane, 1-pyrrolidinyl-1, 1,3,3, 3-pentamethyldisiloxane, 1-piperidino-1, 1,3,3, 3-pentamethyldisiloxane, 1- (2, 6-dimethylpiperidino) -3,3, 3-pentamethyldisiloxane, 1-isopropylamino-3, 3, 3-trimethyldisiloxane, 1-tert-butylamino-3, 3, 3-trimethyldisiloxane, 1-dimethylamino-3, 3, 3-trimethyldisiloxane, 1-diethylamino-3, 3, 3-trimethyldisiloxane, 1-diisopropylamino-3, 3, 3-trimethyldisiloxane, 1-di-sec-butylamino-3, 3, 3-trimethyldisiloxane, 1-cyclohexylmethylamino-3, 3, 3-trimethyldisiloxane, 1-cyclohexylethylamino-3, 3, 3-trimethyldisiloxane, 1-isopropylamino-3, 3, 3-trimethyldisiloxane, 1-piperidino-3, 3, 3-trimethyldisiloxane, 1- (2, 6-dimethylpiperidino) -3,3, 3-trimethyldisiloxane, 1-dimethylamino-3, 3-dimethyldisiloxane, 1-diethylamino-3, 3-dimethyldisiloxane, 1-diisopropylamino-3, 3-dimethyldisiloxane, 1-di-sec-butylamino-3, 3-dimethyldisiloxane, 1-cyclohexylmethylamino-3, 3-dimethyldisiloxane, 1-cyclohexylethylamino-3, 3-dimethyldisiloxane, 1-piperidino-3, 3-dimethyldisiloxane, 1- (2, 6-dimethylpiperidino) -3, 3-dimethyldisiloxane, 1, 3-bis (dimethylamino) disiloxane, 1, 3-bis (diethylamino) disiloxane, 1, 3-bis (diisopropylamino) disiloxane, 1, 3-bis (di-sec-butylamino) disiloxane, 1, 3-bis (dimethylamino) -1, 3-dimethyldisiloxane, 1, 3-bis (diethylamino) -1, 3-dimethyldisiloxane, 1, 3-bis (diisopropylamino) -1, 3-dimethyldisiloxane, 1, 3-bis (di-sec-butylamino) -1, 3-dimethyldisiloxane, 1, 3-bis (dimethylamino) -1,1,3, 3-tetramethyldisiloxane, 1, 3-bis (diethylamino) -1,1,3, 3-tetramethyldisiloxane, 1-dimethylamino-1, 1,3, 3-tetramethyl-3-chlorodisiloxane, 1-diethylamino-1, 1,3, 3-tetramethyl-3-chlorodisiloxane, 1-diisopropylamino-1, 1,3, 3-tetramethyl-3-chlorodisiloxane, 1-di-sec-butylamino-1, 1,3, 3-tetramethyl-3-chlorodisiloxane, 1-dimethylamino-1, 1,3, 3-tetramethyl-3-bromodisiloxane, 1-diethylamino-1, 1,3, 3-tetramethyl-3-bromodisiloxane, 1-diisopropylamino-1, 1,3, 3-tetramethyl-3-bromodisiloxane, 1-di-sec-butylamino-1, 1,3, 3-tetramethyl-3-bromodisiloxane, 1-tert-butylaminodisiloxane, 1-isopropylaminodisiloxane, 1-tert-butylamino-1, 1,3, 3-tetramethyldisiloxane, 1-isopropyl-1, 1,3, 3-tetramethyldisiloxane, 1-dimethylaminotriesiloxane, 1-diethylaminotrisiloxane, 1-isopropylaminotrisiloxane, 1-di-sec-butylaminotrisiloxane, 1-phenylmethylaminotrisiloxane, 1-phenylethylaminotrisiloxane, 1-cyclohexylmethylaminotrisiloxane, 1-butylaminotrisiloxane, 1-phenylaminotrisiloxane, 1-butylaminotrisiloxane, 1,3, 3-butylaminotrisiloxane, 1,3, 3-butylaminotrisiloxane, 1,3, 1,3, 1,3, one, 1-cyclohexylethylaminotrisiloxane, 1-piperidinotrisiloxane, 1- (2, 6-dimethylpiperidino) trisiloxane, 1-dimethylamino-1, 1,3,3,5, 5-hexamethyltrisiloxane, 1-diethylamino-1, 1,3,3,5, 5-hexamethyltrisiloxane, 1-diisopropylamino-1, 1,3,3,5, 5-hexamethyltrisiloxane, 1-sec-butylamino-1, 1,3,3,5, 5-hexamethyltrisiloxane, 1-phenylmethylamino-1, 1,3,3,5, 5-hexamethyltrisiloxane, 1-phenylethylamino-1, 1,3,3,5, 5-hexamethyltrisiloxane, 1, 5-bis (dimethylamino) -1,1,3,3,5, 5-hexamethyltrisiloxane, 1, 5-bis (diethylamino) -1,1,3,3,5, 5-hexamethyltrisiloxane, 1, 5-bis (diisopropylamino) -1,1,3,3,5, 5-hexamethyltrisiloxane, 1, 5-bis (sec-butylamino) -1,1,3,3,5, 5-hexamethyltrisiloxane, 1, 5-bis (phenylmethylamino) -1,1,3,3,5, 5-hexamethyltrisiloxane, 1, 5-bis (phenylethylamino) -1,1,3,3,5, 5-hexamethyltrisiloxane, 1-diisopropylamino-3, 3,5, 5-pentamethyltrisiloxane, 1-sec-butylamino-3, 3,5,5, 5-pentamethyltrisiloxane, 1-cyclohexylmethylamino-3, 3,5,5, 5-pentamethyltrisiloxane, 1-cyclohexylethylamino-3, 3,5,5, 5-pentamethyltrisiloxane, 1-piperidino-3, 3,5,5, 5-pentamethyltrisiloxane, 1- (2, 6-dimethylpiperidino) -3,3,5,5, 5-pentamethyltrisiloxane, 1-dimethylamino-1, 1,3,3,5,5, 5-heptamethyltrisiloxane, 1-diethylamino-1, 1,3,3,5, 5-heptamethyltrisiloxane, 1-diethylamino-1, 3,3,5, 5-heptamethyltrisiloxane, 1-bis (methyl-ethyl-methyl-siloxane), 1-diisopropylamino-1, 1,3,3,5,5, 5-heptamethyltrisiloxane, 1-sec-butylamino-1, 1,3,3,5,5, 5-heptamethyltrisiloxane, 1-cyclohexylmethylamino-1, 1,3,3,5,5, 5-heptamethyltrisiloxane, 1-cyclohexylethylamino-1, 1,3,3,5,5, 5-heptamethyltrisiloxane, 1-piperidino-1, 1,3,3,5,5, 5-heptamethyltrisiloxane, 1- (2, 6-dimethylpiperidino) -1,1,3,3,5,5, 5-heptamethyltrisiloxane, 1-pyrrolyl-1, 1,3,3,5,5, 5-heptamethyltrisiloxane and 1-pyrrolidinyl-1, 1,3,3,5,5, 5-heptamethyltrisiloxane, and combinations thereof.

13. The composition of item 11, wherein the halide comprises chloride.

14. The composition of item 13, wherein the concentration of chloride ions is less than 50 ppm.

15. The composition of item 13, wherein the concentration of chloride ions is less than 10 ppm.

16. The composition of item 13, wherein the concentration of chloride ions is less than 5 ppm.

17. A film obtained by the method of item 1.

18. A film comprising at least one of the following features: a density of at least about 2.1 g/cc; wet etch rates measured in a 1:100 HF to water acid solution (0.5 wt.% dHF) are less than aboutUntil the electric leakage under 6MV/cm is less than about 1e-8A/cm²(ii) a And hydrogen impurity as measured by SIMS is less than about 5e20 at/cc.

19. A method of depositing a film comprising silicon and an oxide onto a substrate, comprising the steps of:

a) providing a substrate in a reactor;

b) introducing at least one silicon precursor compound into the reactor, wherein the at least one silicon precursor compound is selected from the group consisting of formulas A and B:

wherein the content of the first and second substances,

R¹independently selected from straight chain C₁To C₁₀Alkyl, branched C₃To C₁₀Alkyl radical, C₃To C₁₀Cycloalkyl radical, C₃To C₁₀Heterocyclic group, C₃To C₁₀Alkenyl radical, C₃To C₁₀Alkynyl and C₄To C₁₀An aryl group;

R²selected from hydrogen, straight chain C₁To C₁₀Alkyl, branched C₃To C₁₀Alkyl radical, C₃To C₁₀Cycloalkyl radical, C₃To C₁₀Heterocyclic group, C₃To C₁₀Alkenyl radical, C₃To C₁₀Alkynyl and C₄To C₁₀Aryl, wherein R in formula A or B¹And R²Linked to form a cyclic ring structure or not linked to form a cyclic ring structure; and

R³-R⁸and X is methyl;

c) purging the reactor with a purge gas;

d) introducing an oxygen-containing source into the reactor; and

e) purging the reactor with a purge gas,

wherein steps b to e are repeated until a film of a desired thickness is deposited, and

wherein the process is carried out at one or more temperatures of about 600 ℃ to 800 ℃.

20. The method of item 19, wherein the at least one silicon precursor compound is at least one selected from the group consisting of: 1-dimethylamino-1, 1,3,3, 3-pentamethyldisiloxane, 1-diethylamino-1, 1,3,3, 3-pentamethyldisiloxane, 1-diisopropylamino-1, 1,3,3, 3-pentamethyldisiloxane, 1-di-sec-butylamino-1, 1,3,3, 3-pentamethyldisiloxane, 1-pyrrolyl-1, 1,3,3, 3-pentamethyldisiloxane, 1-pyrrolidinyl-1, 1,3,3, 3-pentamethyldisiloxane, 1-piperidino-1, 1,3,3, 3-pentamethyldisiloxane, 1- (2, 6-dimethylpiperidino) -3,3, 3-pentamethyldisiloxane, 1-diethylamino-1, 1,3, 3-pentamethyldisiloxane, 1-diethylamino-1, 3, 3-pentamethyldisiloxane, 1-pyrrolidino-1, 3, 3-pentamethyldisiloxane, 1- (2, 6-dimethylpiperidino) -3,3, 3-pentamethyldisiloxane, 1-dimethylamino-1, 1,3,3,5,5, 5-heptamethyltrisiloxane, 1-diethylamino-1, 1,3,3,5,5, 5-heptamethyltrisiloxane, 1-diisopropylamino-1, 1,3,3,5,5, 5-heptamethyltrisiloxane, 1-sec-butylamino-1, 1,3,3,5,5, 5-heptamethyltrisiloxane, 1-cyclohexylmethylamino-1, 1,3,3,5,5, 5-heptamethyltrisiloxane, 1-cyclohexylethylamino-1, 1,3,3,5,5, 5-heptamethyltrisiloxane, 1-piperidino-1, 1,3,3,5,5, 5-heptamethyltrisiloxane, 1- (2), 6-dimethylpiperidino) -1,1,3,3,5,5, 5-heptamethyltrisiloxane, 1-pyrrolyl-1, 1,3,3,5,5, 5-heptamethyltrisiloxane, 1-pyrrolidinyl-1, 1,3,3,5,5, 5-heptamethyltrisiloxane.

21. A film obtained by the method of item 19.

22. Formed by item 19A film comprising at least one of the following features: a density of at least about 2.1 g/cc; wet etch rates measured in a 1:100 HF to water acid solution (0.5 wt.% dHF) are less than aboutUntil the electric leakage under 6MV/cm is less than about 1e-8A/cm²(ii) a And hydrogen impurity as measured by SIMS is less than about 5e20 at/cc.

The following examples illustrate the methods described herein for depositing silicon oxide films, but are not intended to be limiting in any way.

Examples

Thermal atomic layer deposition of silicon oxide films was performed on a laboratory scale ALD processing apparatus. The silicon precursor is delivered to the chamber by vapor pumping. All gases (e.g., purge and reactant gases or precursor and oxygenate sources) are preheated to 100 ℃ prior to entering the deposition zone. The ALD diaphragm valve with high speed actuation controls the flow rate of the gas and precursor. The substrate used in the deposition was a 12 inch long strip of silicon. A thermocouple was attached to the sample holder to confirm the substrate temperature. The deposition is performed using ozone as the oxygen source gas. The normal deposition process and parameters are shown in table 4. The thickness and refractive index of the film were measured using a FilmTek 2000SE ellipsometer by fitting the reflection data from the film to a pre-set physical model (e.g., lorentz dipole model).

All Plasma Enhanced Ald (PEALD) was performed on a commercial type side flow reactor (300 mm PEALD equipment manufactured by ASM) equipped with 27.1MHz direct plasma capability with a fixed spacing of 3.5mm between electrodes. This design utilizes an outer chamber and an inner chamber with independent pressure settings. The inner chamber is a deposition reactor where all reactant gases (e.g., precursors, Ar) are mixed in a manifold and delivered to a process reactor. The reactor pressure in the outer chamber was maintained using Ar gas. All precursors were liquids maintained at room temperature in a stainless steel bubbler and delivered to the chamber with an Ar carrier gas (typically set at 200 seem flow). All depositions reported in this study were done on 8-12Ohm-cm native oxide-containing Si substrates. Film thickness and Refractive Index (RI) were measured using Rudolph FOCUS ellipsometer FE-IVD (rotary compensator ellipsometer).

Example 1: synthesis of 1-diisopropylamino-3, 3, 3-trimethyldisiloxane.

A solution of potassium trimethylsilanolate in diethyl ether and THF was added dropwise to a stirred solution of 1 equivalent of diisopropylaminochlorosilane in THF. After 20 minutes, the solid precipitate was removed by filtration and the filtrate was concentrated under reduced pressure. The resulting liquid contained 1-diisopropylamino-3, 3, 3-trimethyldisiloxane and other products as determined by GC-MS. GC-MS showed the following mass peaks: 219(M +), 204(M-15), 188, 174, 162, 146, 132, 119, 105, 89, 73, 59.

Example 2: synthesis of 1, 3-bis (dimethylamino) -1,1,3, 3-tetramethyldisiloxane

The solution of trimethylamine and dimethylamine in THF and hexane was cooled to below 0 ℃.1, 3-dichlorotetramethyldisiloxane was slowly added dropwise to the solution while stirring. The solids were removed by filtration and the filtrate was purified by vacuum distillation to provide 1, 3-bis (dimethylamino) -1,1,3, 3-tetramethyldisiloxane (56 ℃/5 torr). GC-MS showed the following mass peaks: 220(M +), 205(M-15), 196, 175, 162, 146, 133, 119, 102.

Examples 3 to 10: synthesis of additional organoaminodisiloxanes or organoaminotrisiloxanes.

Additional organoaminodisiloxanes or organoaminotrisiloxanes were synthesized in a similar manner to that described in examples 1 and 2 and characterized by GC-MS. The Molecular Weight (MW), structure and corresponding major MS fragment peaks for each compound are provided in table 3 to confirm their identity.

TABLE 3 Organoaminodisiloxane and Organoaminotrisiloxane

Comparative example 11 a: thermal atomic layer deposition of silicon oxide film using Dimethylaminotrimethylsilane (DMATMS).

Atomic layer deposition of silicon oxide films was performed using the following precursors: DMATMS. The deposition was performed on a laboratory scale ALD processing apparatus. The silicon precursor is delivered to the chamber by vapor pumping. The deposition process and parameters are provided in table 4. Steps 1 to 6 are repeated until the desired thickness is reached. At 500 deg.C, DMATMS precursor feed time was 8 seconds, ozone flow was 4 seconds, and the film growth rate was measured per cycle asPer cycle, and the film refractive index was 1.43.

Example 11: atomic layer deposition of silicon oxide films using 1, 3-bis (dimethylamino) -1,1,3, 3-tetramethyldisiloxane.

Atomic layer deposition of silicon oxide films was performed using the following precursors: 1, 3-bis (dimethylamino) -1,1,3, 3-tetramethyldisiloxane. The deposition was performed on a laboratory scale ALD processing apparatus. The silicon precursor is delivered to the chamber by vapor pumping. The deposition process and parameters are provided in table 4. Steps 1 to 6 are repeated until the desired thickness is reached.

TABLE 4: a process for atomic layer deposition of a silicon oxide film with an oxygen source using DMATMS.

The process parameters, deposition rate and refractive index for the deposition are provided in table 5.

TABLE 5: summary of the Process parameters and results for 1, 3-bis (dimethylamino) -1,1,3, 3-tetramethyldisiloxane

It can be seen that the precursor 1, 3-bis (dimethylamino) -1,1,3, 3-tetramethyldisiloxane with Si-O-Si bonds provides a higher growth rate per cycle compared to the precursor DMATMS without Si-O-Si bonds.

The composition of the films deposited at 650 ℃ and 700 ℃ was analyzed by SIMS. The membrane WER was performed in a 1:99 dilute HF solution, with a thermal oxide wafer used as a reference. SIMS analysis data and relative WER are shown in table 6. The film showed low C, H, N impurity and low WER, indicating that a high quality film was obtained.

Table 6: SIMS analysis and relative WER relative to thermal oxide of 1, 3-bis (dimethylamino) -1,1,3, 3-tetramethyldisiloxane deposited at 650 ℃ and 700 ℃.

Comparative example 10 a: PEALD silica using Dimethylaminotrimethylsilane (DMATMS).

DMATMS was used as the Si precursor and O under the conditions given in Table 7₂The plasma is used for deposition. DMATMS as Si precursor was delivered by steam pumping at ambient temperature (25 ℃). The vessel was equipped with a 0.005 "diameter orifice to restrict precursor flow.

TABLE 7: PEALD parameters for silica Using DMATMS

Steps b to e were repeated 500 times to obtain the desired thickness of silicon oxide for measurement. At a 4 second Si precursor pulse, the measured film growth rate was about 0.8 per cycle for different precursor pulse times.

Example 12: PEALD silica Using 1, 3-bis (dimethylamino) -1,1,3, 3-tetramethyldisiloxane

1, 3-bis (dimethylamino) -1,1,3, 3-tetramethyldisiloxane as Si precursor and O under the conditions given in Table 8₂The plasma is used for deposition. 1, 3-bis (dimethylamino) -1,1,3, 3-tetramethyldisiloxane as the Si precursor was transported by a carrier gas at ambient temperature (25 ℃).

TABLE 8: PEALD parameters for silica Using 1, 3-bis (dimethylamino) -1,1,3, 3-tetramethyldisiloxane

Steps b to e were repeated 200 times to obtain the desired thickness of silicon oxide for measurement. The film growth rate and refractive index are shown in table 9.

Table 9: summary of PEALD Process parameters and results for 1, 3-bis (dimethylamino) -1,1,3, 3-tetramethyldisiloxane

It can be seen that 1, 3-bis (dimethylamino) -1,1,3, 3-tetramethyldisiloxane with Si-O-Si bonds gives a higher growth rate per cycle compared to the precursor dimethylaminotrimethylsilane without Si-O-Si bonds.

Example 13: atomic layer deposition of silicon oxide films using 1-dimethylamino-1, 1,3,3, 3-pentamethyldisiloxane

Atomic layer deposition of silicon oxide films was performed using the following precursors: 1-dimethylamino-1, 1,3,3, 3-pentamethyldisiloxane. The deposition was performed on a laboratory scale ALD processing apparatus. The silicon precursor is delivered to the chamber by vapor pumping. The deposition process and parameters are provided in table 4. Steps 1 to 6 are repeated until the desired thickness is reached. The process parameters, deposition rate and refractive index for the deposition are provided in table 10.

Table 10: summary of process parameters and results for 1-dimethylamino-1, 1,3,3, 3-pentamethyldisiloxane.

The compositional analysis of the high temperature deposited (. gtoreq.650 ℃) films is shown in Table 11.

TABLE 11: SIMS compositional analysis of films deposited from 1-dimethylamino-1, 1,3,3, 3-pentamethyldisiloxane

It can be seen that the precursor 1-dimethylamino-1, 1,3,3, 3-pentamethyldisiloxane with Si-O-Si bonds gives a higher growth rate per cycle than the precursor DMATMS without Si-O-Si bonds. Films deposited at high temperatures have low C, N, H impurities and low WER relative to thermal oxides, indicating that high quality films are obtained.

The conformality of films deposited at 650 ℃ was investigated by TEM. The samples were imaged with a FEI Tecnai TF-20FEG/TEM operating at 200kV in a Bright Field (BF) TEM mode, a High Resolution (HR) TEM mode, and a High Angle Annular Dark Field (HAADF) STEM mode. STEM probe size is 1-2nm nominal diameter. The film surface coverage was 102% on the center side and 97% on the bottom, confirming excellent step coverage of the structured features.

Example 14: PEALD silica using 1, 5-bis (dimethylamino) -1,1,3,3,5, 5-hexamethyltrisiloxane.

1, 5-bis (dimethylamino) -1,1,3,3,5, 5-hexamethyltrisiloxane as Si precursor and O under the conditions given in Table 12₂The plasma is used for deposition. 1, 5-bis (dimethylamino) -1,1,3,3,5, 5-hexamethyltrisiloxane as a Si precursor was delivered at 70 ℃ by a carrier gas.

Table 12: PEALD parameters for silica using 1, 5-bis (dimethylamino) -1,1,3,3,5, 5-hexamethyltrisiloxane.

Steps b to e were repeated 200 times to obtain the desired thickness of silicon oxide for measurement. The film growth rate and refractive index are shown in table 13.

Table 13: summary of PEALD process parameters and results for 1, 5-bis (dimethylamino) -1,1,3,3,5, 5-hexamethyltrisiloxane.

It can be seen that 1, 5-bis (dimethylamino) -1,1,3,3,5, 5-hexamethyltrisiloxane with Si-O-Si bonds gives a higher growth rate per cycle compared to the precursor dimethylaminotrimethylsilane without Si-O-Si bonds.

While certain principles of the invention have been described above in connection with various aspects or embodiments, it is to be clearly understood that this description is made only by way of example and not as a limitation on the scope of the invention.