Organoamino-alkoxy-carbosilanes and methods for depositing silicon-containing films using same

Abstract

Atomic layer deposition (ALD) process formation of silicon-containing film at temperature of about 700°C or lower is disclosed, wherein at least one organoamino- alkoxy-carbosilane precursor compound having two Si-C-Si linkages and selected from the group consisting of Formula IA, IB, IC, and ID: wherein R is selected from a linear or branched Ci to C10 alkyl group; R1 and R2 are each independently selected from hydrogen, a linear or branched Ci to C10 alkyl group, a linear or branched C2 to C10 alkenyl, and a C6 to C10 aryl group with a proviso that R1 and R2 cannot both be hydrogen, and with the proviso that for IC and ID, every R and every R1 and R2 cannot all be methyl; R1 and R2 are either linked to form a cyclic ring structure or R1 and R2 are not linked to form a cyclic ring structure.

Description

P25-105-SEC-W001TITLE OF THE INVENTIONORGANOAMINO-ALKOXY-CARBOSILANES AND METHODS FOR DEPOSITING SILICON-CONTAINING FILMS USING SAMECROSS-REFERNCE TO RELATED APPLICATION

[0001] This application claims the benefit of U.S. Provisional Application No.63 / 883,507, filed September 17, 2025, and U.S. Provisional Application No.63 / 761,410, filed February 21, 2025, the entire disclosures of which are hereby incorporated in its entirety.BACKGROUND OF THE INVENTION

[0002] Described herein are a composition and a method for the formation of a silicon-containing film. More specifically, described herein is a composition and a method for formation of a silicon-containing film at one or more deposition temperatures of about 700°C or lower and using an atomic layer deposition (ALD) process.

[0003] Thermal oxidation is a process commonly used when depositing high purity and highly conformal silicon oxide films such as silicon dioxide (SiOg) in semiconductor applications. However, the thermal oxidation process has a very low deposition rate, e.g., less than 0.03 A / s at 700°C, which makes it impractical for high volume manufacturing processes (see, for example, Wolf, S., “Silicon Processing for the VLSI Era Vol. 1 - Process Technology”, Lattice Press, GA, 1986).

[0004] Atomic Layer Deposition (ALD) and Plasma Enhanced Atomic Layer Deposition (PEALD) are processes used to deposit silicon dioxide (SiOg) conformal films at low temperatures (<500°C). In both ALD and PEALD processes, the precursor and reactive gas (such as oxygen or ozone) are separately pulsed in a certain number of cycles to form a monolayer of silicon dioxide (SiOg) at each cycle. However, silicon dioxide (SiOs) deposited at low temperatures using these processes may contain levels of impurities such as carbon (C), nitrogen (N), or both, which in some cases may be detrimental to semiconductor applications. To remedy this, one possible solution would be to increase deposition temperatures above 500°C.However, at these higher temperatures, conventional precursors employed by semiconductor industries tend to self-react, thermally decompose, and deposit in chemicalP25-105-SEC-W001vapor deposition (CVD) mode rather than ALD mode. The CVD mode deposition typically has reduced conformality compared to ALD deposition, especially in high aspect ratio structures in semiconductor applications. In addition, when depositing thin films in CVD mode it is less easy to control the film or material thickness compared to ALD mode deposition.

[0005] JP2010275602 and JP2010225663 disclose the use of a raw material to form a Si containing thin film such as silicon oxide by a chemical vapor deposition (CVD) process at a temperature range of from 300-500°C. The raw material is an organic silicon compound, represented by formula: (a) HSi(CH3)(R1)(NR2R3), wherein R1represents NR4R5or a 1C-5C alkyl group; R2and R4each represent a 1C-5C alkyl group or hydrogen atom; and R3and R5each represent a 1C-5C alkyl group; or formula (b) HSiCI(NR1R2)(NR3R4), wherein R1and R3independently represent an alkyl group having 1 to 4 carbon atoms, or a hydrogen atom; and R2and R4independently represent an alkyl group having 1 to 4 carbon atoms. The organic silicon compounds contained H-Si bonds.

[0006] US Pat. No. 7,084,076 discloses a halogenated siloxane such as hexachlorodisiloxane (HCDSO) that is used in conjunction with pyridine as a catalyst for ALD deposition below 500°C to form silicon dioxide.

[0007] US Pat. No. 6,992,019 discloses a method for catalyst-assisted atomic layer deposition (ALD) to form a silicon dioxide layer having superior properties on a semiconductor substrate by using a first reactant component consisting of a silicon compound having at least two silicon atoms, or using a tertiary aliphatic amine, as the catalyst component, or both in combination, together with related purging methods and sequencing. The precursor used is hexachlorodisilane. The deposition temperature is between 25 -150°C.

[0008] US Pat. No. 11 ,186,909 discloses methods for atomic layer deposition (ALD) of plasma enhanced atomic layer deposition (PEALD) of IOW-K films.

[0009] There is a need for a process for forming a high quality, low impurity, high conformal silicon-containing film using an atomic layer deposition (ALD) process or an ALD-like process such as, without limitation, acyclic CVD process, to replace thermal-based deposition processes. Further, it is desirable to develop a low temperature deposition method (e.g., deposition at one or more temperatures of 700 °C or lower) to improve one or more film properties, such as purity and / or density, in an ALD or ALD-like process.P25-105-SEC-W001BRIEF SUMMARY OF THE INVENTION

[0010] Described herein is a process for the deposition of a silicon-containing material or film at high temperatures, e.g., at one or more temperatures of 700 °C, or lower, in an atomic layer deposition (ALD) or an ALD-like process.

[0011] This invention is related to organoamino-alkoxy-carbosilane precursor compounds having two Si-C-Si linkages and selected from the group consisting of Formulae IA, IB, IC, and ID:wherein R is selected from a linear or branched Ci to C10 alkyl group; R1and R2are each independently selected from hydrogen, a linear or branched Ci to C10 alkyl group, a linear or branched C2 to C10 alkenyl, and a Ceto C10 aryl group with a proviso that R1and R2cannot both be hydrogen, and with the proviso that for IB if every R is ethyl, every R1and every R2cannot be methyl, and with the proviso that for IC and ID, every R and every R1and R2cannot all be methyl; R1and R2are either linked to form a cyclic ring structure or R1and R2are not linked to form a cyclic ring structure.

[0012] This invention is also related to use of organoamino-alkoxy-carbosilane precursor compounds having two Si-C-Si linkages and selected from the group consisting of Formulae IA, IB, IC, and ID in vapor deposition processes:P25-105-SEC-W001wherein R is selected from a linear or branched Ci to C10 alkyl group; R1and R2are each independently selected from hydrogen, a linear or branched Ci to C10 alkyl group, a linear or branched C2 to C10 alkenyl, and a Ce to C10 aryl group with a proviso that R1and R2cannot both be hydrogen, and and with the proviso that for IC and ID, every R and every R1and R2cannot all be methyl; R1and R2are either linked to form a cyclic ring structure or R1and R2are not linked to form a cyclic ring structure.

[0013] One embodiment provides a process to deposit a silicon-containing film, which comprises the steps of:a. providing a substrate in a reactor;b. introducing into the reactor at least one organoamino-alkoxy-carbosilane precursor compound having two Si-C-Si linkages according to Formula IA or IB or IC or ID as defined herein;c. purging the reactor with purge gas;d. introducing an oxygen source into the reactor; ande. purging the reactor with purge gas;wherein steps b through e are repeated until a desired thickness of silicon oxide is deposited; and wherein the process is conducted at one or more temperatures ranging from 20 °C to 700 °C and at one or more pressures ranging from 50 miliTorr (mT) to 760 Torr. In one or more embodiments the purge gas is selected from the group consisting of nitrogen, helium, argon and combinations thereof.

[0014] Another embodiment provides a process to deposit a silicon-containing film, which comprises the steps of:a. providing a substrate in a reactor;b. introducing into the reactor at least one organoamino-alkoxy-carbosilane precursor compound having two Si-C-Si linkages according to Formula IA or IB or IC or ID as defined herein;c. purging the reactor with purge gas;d. introducing an oxygen source into the reactor;e. purging the reactor with purge gas;P25-105-SEC-W001f. introducing water vapor or a hydroxyl source into the reactor; and g. purging the reactor with purge gas;wherein steps b through g are repeated until a desired thickness of silicon and oxygen containing film is deposited; and wherein the process is conducted at one or more temperatures ranging from 20 °C to 700 °C and at one or more pressures ranging from 50 miliTorr (mT) to 760 Torr.

[0015] Another embodiment provides a process to deposit a silicon-containing film, which comprises the steps of:a. providing a substrate in a reactor;b. introducing into the reactor at least one organoamino-alkoxy-carbosilane precursor compound having two Si-C-Si linkages according to Formula IA or IB or IC or ID as defined herein;c. purging the reactor with purge gas;d. introducing an oxygen source and a nitrogen source simultaneously into the reactore. purging the reactor with purge gas;wherein steps b through e are repeated until a desired thickness of silicon and oxygen containing film is deposited; and wherein the process is conducted at one or more temperatures ranging from 20 °C to 700 °C and at one or more pressures ranging from 50 miliTorr (mT) to 760 Torr.

[0016] In one or more embodiments described above, the oxygen source may include, for example, water (H2O) (e.g., deionized water, purifier water, and / or distilled water), hydrogen peroxide, oxygen (O2), oxygen plasma, ozone (O3), N2O, N2O plasma, NO2plasma, carbon monoxide (CO) plasma, carbon dioxide (CO2) plasma, and combinations thereof.

[0017] The nitrogen source can be selected from the group consisting of ammonia, hydrazine, monoalkylhydrazine, symmetrical or unsymmetrical dialkylhydrazine, methylamine, ethylamine, ethylenediamine, ethanolamine, piperazine, N,N’-dimethylethylenediamine, imidazolidine, cyclotrimethylenetriamine, pyridine, piperazine, and other organic amines.DETAILED DESCRIPTION OF THE INVENTION

[0018] Described herein are compositions and processes related to the formation of a silicon-containing film, such as a silicon oxynitride film, a stoichiometric or non-P25-105-SEC-W001stoichiometric silicon oxide film, a carbon doped silicon oxide film or combinations thereof with one or more process temperatures of 700 °C or lower, in an atomic layer deposition (ALD) or in an ALD-like process, such as, without limitation, a cyclic chemical vapor deposition process (CCVD).

[0019] In one embodiment, a composition for depositing a silicon-containing film using a vapor deposition process comprises at least one organoamino-alkoxy-carbosilane having two Si-C-Si linkages and selected from the group consisting of Formulae IA, IB, IC and ID:wherein R is selected from a linear or branched Ci to C10 alkyl group; R1and R2are each independently selected from hydrogen, a linear or branched Ci to C10 alkyl group, a linear or branched C2 to C10 alkenyl, and a Ce to C10 aryl group with a proviso that R1and R2cannot both be hydrogen, and with the proviso that for IB if every R is ethyl, every R1and every R2cannot be methyl, and with the proviso that for IC and ID, every R and every R1and R2cannot all be methyl; R1and R2are either linked to form a cyclic ring structure or R1and R2are not linked to form a cyclic ring structure. In some embodiments, the two RO groups are trans to each other for IB while in other embodiments, the two RO groups are cis to each other. The composition may consist of or consist essentially of the at least one organoamino-alkoxy-carbosilane having two Si-C-Si linkages and selected from the group consisting of Formulae IA, IB, IC and ID. According to other embodiments the composition may further comprise other components such as a carrier or a solvent.

[0020] Tables 1 , 2 and 3 provide exemplary organoamino-alkoxy-carbosilanes.P25-105-SEC-W001

[0021] Table 1. Organoamino-alkoxy-carbosilanes with Si-C-Si linkages having Formula IA which are suitable for vapor deposition.P25-105-SEC-W001

[0022] Table 2. Organoamino-alkoxy-carbosilanes with Si-C-Si linkages having Formulae IB and IC which are suitable for vapor deposition.P25-105-SEC-W001>P25-105-SEC-W001>P25-105-SEC-W001

[0023] Table 3. Organoamino-alkoxy-carbosilanes with Si-C-Si linkages having Formula ID which are suitable for vapor deposition."

[0024] In another embodiment, this invention is related to use of organoamino-alkoxy-carbosilane precursor compounds having two Si-C-Si linkages and selected from the group consisting of Formulae I A, IB, IC, and ID in vapor deposition processes:wherein R is selected from a linear or branched Ci to Cw alkyl group; R1and R2are each independently selected from hydrogen, a linear or branched Ci to Cw alkyl group, a linear or branched C2to Cw alkenyl, and a C6to Cw aryl group with a proviso that R1and R2cannot both be hydrogen, and with the proviso that for IC and ID, every R and every R1and R2cannot all be methyl; wherein R1and R2are eitherP25-105-SEC-W001linked to form a cyclic ring structure or R1and R2are not linked to form a cyclic ring structure.

[0025] One embodiment of the invention provides a process to deposit a silicon-containing film comprising steps of:a. providing a substrate in a reactor;b. introducing into the reactor at least one organoamino-alkoxy-carbosilane precursor compound having two Si-C-Si linkages according to Formula IA or IB or IC or ID as defined herein;c. purging the reactor with purge gas;d. introducing an oxygen source into the reactor; ande. purging the reactor with purge gas,wherein steps b through e are repeated until a desired thickness of film is deposited.

[0026] The oxygen source is selected from water (H2O) (e.g., deionized water, purifier water, and / or distilled water), hydrogen peroxide, oxygen (O2), oxygen plasma, ozone (O3), N2O, N2O plasma, NO2plasma, carbon monoxide (CO) plasma, carbon dioxide (CO2) plasma and combinations thereof. Not being bound by theory, for ALD or ALD-like deposition process at one or more temperatures less than 700 °C, the organoamino-alkoxy-carbosilane precursor compound having two Si-C-Si linkages should have at least one anchoring functionality, which reacts with certain reactive sites on the substrate surface to anchor a monolayer of silicon species. The anchoring functionality of a smaller organoamino group such as dimethylamino, ethylmethylamino or diethylamino allow the organoamino-alkoxy-carbosilane to have a relatively low boiling point and a relatively high reactivity. The organoamino-alkoxy-carbosilane precursor compound having two Si-C-Si linkages should also have a passive functionality in that it is chemically stable to prevent further surface reaction, leading to a self-limiting process. The passivating functionality is selected from different alkyl groups such as hydrogen or a methyl group. The remaining groups on the surface can then be oxidized to form a Si-O-Si linkage as well as hydroxyl groups. In addition, hydroxyl sources such as H2O or water plasma can also be introduced into the reactor to form more hydroxyl groups as reactive sites for the next ALD cycle.

[0027] Another embodiment provides a process to a deposit silicon-containing film, which comprises the steps of:P25-105-SEC-W001a. providing a substrate in a reactor;b. introducing into the reactor at least one organoamino-alkoxy-carbosilane precursor compound having two Si-C-Si linkages according to Formula IA or IB or IC or ID as defined herein;c. purging the reactor with purge gas;d. introducing an oxygen source and a nitrogen source simultaneously into the reactore. purging the reactor with purge gaswherein steps b through e are repeated until a desired thickness of silicon and oxygen containing film is deposited; and wherein the process is conducted at one or more temperatures ranging from 20 °C to 700 °C and at one or more pressures ranging from 50 miliTorr (mT) to 760 Torr.

[0028] Another embodiment of the method described herein introduces a hydroxyl or OH source such as H2O vapor after the oxidizing step to repopulate the anchoring functionality or reactive sites for organoamino-alkoxy-carbosilane having two Si-C-Si linkages to anchor on the surface to form the monolayer. The deposition method comprises the following steps:a. providing a substrate in a reactor;b. introducing into the reactor at least one organoamino-alkoxy-carbosilane precursor compound having two Si-C-Si linkages according to Formula IA or IB or IC or ID as defined herein;c. purging the reactor with purge gas;d. introducing an oxygen source and optionally a nitrogen source into the reactor;e. purging the reactor with purge gas;f. introducing water vapor or hydroxyl source into the reactor; and g. purging the reactor with purge gas,wherein steps b through g are repeated until a film of desired thickness is deposited. In one particular embodiment, the organoamino-alkoxy-carbosilane precursor compound is selected from the group consisting of 1 ,3-bis(dimethylamino)-1 ,3-dimethoxy-1 ,3-disilacyclobutane, 1 ,3-bis(dimethylamino)-1 ,3-diethoxy-1 ,3-disilacyclobutane, 1 ,3-bis(ethylmethylamino)-1 ,3-dimethoxy-1 ,3-disilacyclobutane, 1.3-bis(ethylmethylamino)-1 ,3-diethoxy-1 ,3-disilacyclobutane, 1 ,3-bis(diethylamino)- 1.3-diethoxy-1 ,3-disilacyclobutane.P25-105-SEC-W001

[0029] Another embodiment of the method described herein is provided to deposit carbon doped silicon oxide film. The deposition steps are as follows:a. providing a substrate in a reactor;b. introducing into the reactor at least one organoamino-alkoxy-carbosilane precursor compound having two Si-C-Si linkages according to Formula IA or IB or IC or ID as defined herein;c. purging the reactor with purge gas;d. introducing a mild oxidant into the reactor;e. purging the reactor with purge gas; andf. optionally treating the film with a plasma comprising hydrogenwherein steps b through e or f are repeated until a film of desired thickness is deposited. Step f is optionally performed on deposited films to improve the film properties. The mild oxidant is used in order to keep some of the carbon in the film. The mild oxidant can be selected from sources other than oxygen plasma, including water (H2O) (e.g., deionized water, purifier water, and / or distilled water), hydrogen peroxide, N2O plasma, NO2plasma, carbon monoxide (CO) plasma, carbon dioxide (CO2) plasma and combinations thereof.

[0030] According to yet another embodiment, a method of depositing a carbon doped silicon oxide film comprises steps as below:a. providing a substrate in a reactor;b. introducing into the reactor at least one organoamino-alkoxy-carbosilane precursor compound having two Si-C-Si linkages according to Formula IA or IB or IC or ID as defined herein;c. purging the reactor with purge gas;d. introducing an oxygen source into the reactor;e. purging the reactor with purge gas;f. exposing the resulting film to a plasma comprising hydrogen;g. purging the reactor with purge gaswherein steps b to g are repeated to achieve a desired film thickness. In some embodiments, steps b to e are repeated to provide a desired thickness of carbonP25-105-SEC-W001doped silicon oxide film before steps f to g are conducted. In other embodiments, steps f to g are conducted before steps d to e are performed.

[0031] According to yet another embodiment, a method of depositing a carbon doped silicon oxide film comprises steps as below:a. providing a substrate in a reactor;b. introducing into the reactor at least one organoamino-alkoxy-carbosilane precursor compound having two Si-C-Si linkages according to Formula IA or IB or IC or ID as defined herein.c. purging the reactor with purge gas;d. introducing a nitrogen source into the reactor;e. purging the reactor with purge gas;f. exposing the resulting film to a plasma comprising hydrogen;g. purging the reactor with purge gas;wherein steps b to g are repeated to achieve a desired film thickness. In some embodiments, steps b to e are repeated to provide a desired thickness of carbon doped silicon oxide film before steps f to g are conducted. In other embodiments, steps f to g are conducted before steps d to e are performed.

[0032] According to yet another embodiment, a method of depositing a carbon doped silicon oxide film comprises steps as below:a. providing a substrate in a reactor;b. introducing into the reactor at least one organoamino-alkoxy-carbosilane precursor compound having two Si-C-Si linkages according to Formula IA or IB or IC or ID as defined herein;c. purging the reactor with purge gas;d. introducing nitrogen source into the reactor;e. purging the reactor with purge gas;f. introducing oxygen source into the reactorg. purging the reactor with purge gash. optionally exposing the resulting film to a plasma comprising hydrogen;P25-105-SEC-W001i. purging the reactor with purge gas;wherein steps b to i are repeated to achieve a desired film thickness. In one particular embodiment, the organoamino-alkxy-carbosilane precursor compound is selected from the group consisting of 1 ,3-bis(dimethylamino)-1 ,3-dimethoxy-1 ,3-disilacyclobutane, 1 ,3-bis(dimethylamino)-1 ,3-diethoxy-1 ,3-disilacyclobutane, 1 ,3-bis(ethylmethylamino)-1 ,3-dimethoxy-1 ,3-disilacyclobutane, 1 ,3-bis(ethylmethylamino)-1 ,3-diethoxy-1 ,3-disilacyclobutane, 1 ,3-bis(diethylamino)-1 ,3-diethoxy-1 ,3-disilacyclobutane.

[0033] According to yet another embodiment, a method of depositing a carbon doped silicon oxide film comprises steps as below:a. providing a substrate in a reactor;b. introducing into the reactor at least one organoamino-alkoxy-carbosilane precursor compound having two Si-C-Si linkages according to Formula IA or IB or IC or ID as defined herein;c. purging the reactor with purge gas;d. introducing nitrogen source into the reactor;e. purging the reactor with purge gas;f. optionally introducing oxygen source;g. purging the reactor with purge gas;h. optionally purging the reactor with purge gas;i. optionally exposing the substrate to a hydrogen containing plasma. wherein steps b to g or i are repeated to achieve a desired film thickness. Steps f and g could be performed on the same reactor or on a different reactor. In one particular embodiment, the organoamino-alkxy-carbosilane precursor compound is selected from the group consisting of 1 ,3-bis(dimethylamino)-1 ,3-dimethoxy-1 ,3-disilacyclobutane, 1 ,3-bis(dimethylamino)-1 ,3-diethoxy-1 ,3-disilacyclobutane, 1 ,3-bis(ethylmethylamino)-1 ,3-dimethoxy-1 ,3-disilacyclobutane, 1 ,3-bis(ethylmethylamino)-1 ,3-diethoxy-1 ,3-disilacyclobutane, 1 ,3-bis(diethylamino)-1 ,3-diethoxy-1 ,3-disilacyclobutane.

[0034] In the Formulae above and throughout the description, the term “alkyl” denotes a linear or branched functional group having from 1 to 10, 3 to 10, or 1 to 6 carbon atoms. Exemplary linear alkyl groups include, but are not limited to, methyl,P25-105-SEC-W001ethyl, n-propyl (n-Pr ornPr), n-butyl, n-pentyl, and n-hexyl groups. Exemplary branched alkyl groups include, but are not limited to, isopropyl (i-Pr or Pr), isobutyl (i-Bu or'Bu), sec-butyl (s-Bu orsBu, tert-butyl (t-Bu or’Bu, iso-pentyl, tert-pentyl, isohexyl, and neohexyl. In certain embodiments, the alkyl group may have one or more functional groups such as, but not limited to, an alkoxy group, a dialkylamino group 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.

[0035] In the Formulae above and throughout the description, the term “aryl” denotes an aromatic cyclic functional group having from 3 to 10 carbon atoms, from 5 to 10 carbon atoms, or from 6 to 10 carbon atoms. Exemplary aryl groups include, but are not limited to, phenyl, benzyl, chlorobenzyl, tolyl, and o-xylyl.

[0036] Throughout the description, the term “silicon-containing film” denotes a film comprising silicon and oxygen atoms. Examples of such films include, but not limited to, silicon oxide, carbon doped silicon oxide, carbon doped silicon oxynitride.

[0037] Throughout the description, the term “purge gas” refers to an inert gas which is not reactive and can be selected from the group consisting of argon (Ar), nitrogen (N2), helium (He), neon (Ne), hydrogen (H2), and mixtures thereof. In certain embodiments, a purge gas such as N2is supplied into the reactor at a flow rate ranging from about 10 to about 5000 seem for about 0.1 to 1000 seconds, thereby purging the unreacted material and any byproduct that may remain in the reactor.

[0038] Throughout the description, the term “an oxygen or hydrogen source” refers to a reactant comprising oxygen or hydrogen. The oxygen source can be selected from the group consisting of water (H2O) (e.g., deionized water, purified water, distilled water, water vapor, water vapor plasma, oxygenated water, air, a composition comprising water and other organic liquid), oxygen (O2), oxygen plasma, ozone (O3), nitric oxide (NO), nitrogen dioxide (NO2), carbon monoxide (CO), a plasma comprising water, a plasma comprising water and argon, hydrogen peroxide ,a composition comprising hydrogen, a composition comprising hydrogen and oxygen, carbon dioxide (CO2), air, and combinations thereof. The hydrogen source can be selected from the group consisting of hydrogen plasma, plasma comprising hydrogen and helium, plasma comprising hydrogen and argon, hydrogen and oxygen, and combination thereof. The plasma can be in situ or remote plasma.P25-105-SEC-W001

[0039] Throughout the description, the term “nitrogen source” refers a reactant comprising nitrogen. The nitrogen source can be selected from the group consisting of ammonia, hydrazine, monoalkylhydrazine, symmetrical or unsymmetrical dialkylhydrazine, methylamine, ethylamine, ethylenediamine, ethanolamine, piperazine, N,N’-dimethylethylenediamine, imidazolidine, cyclotrimethylenetriamine, pyridine, piperazine, ammonia, or other organic amines.

[0040] In certain embodiments, substituents R1and R2in Formula IA or IB can be linked together to form a ring structure. As the skilled person will understand, when R3and R4are linked together to form a ring R3will include a bond for linking to R4and vice versa. In these embodiments, the ring structure can be unsaturated such as, for example, acyclic alkyl ring, or saturated, for example, an aryl ring. Further, in these embodiments, the ring structure can also be substituted or substituted. Exemplary cyclic ring groups include, but are not limited to, pyrrolidine, 2-methylpyrrolidino, 2,5-dimethylpyrrolidino, pyrrolyl, piperidine, and 2,6-dimethylpiperidino groups. In other embodiments, however, substituents R1and R2are not linked.

[0041] In certain embodiments, the silicon-containing films deposited using the methods described herein are formed in the presence of oxygen using an oxygen source, reagent or precursor comprising oxygen. An oxygen source may be introduced into the reactor in the form of at least one oxygen source and / or may be present incidentally in the other precursors used in the deposition process. Suitable oxygen source gases may include, for example, water (H2O) (e.g., deionized water, purifier water, and / or distilled water), hydrogen peroxide, oxygen (O2), hydrogen peroxide, oxygen plasma, ozone (O3), N2O, N2O plasma, NO2plasma, carbon monoxide (CO) plasma, carbon dioxide (CO2) plasma and combinations thereof. In certain embodiments, the oxygen source comprises an oxygen source gas that is introduced into the reactor at a flow rate ranging from about 1 to about 2000 standard cubic centimeters (seem) or from about 1 to about 1000 seem. The oxygen source can be introduced for a time that ranges from about 0.1 to about 100 seconds. In one particular embodiment, the oxygen source comprises water having a temperature of 10 °C or lower. In embodiments wherein the film is deposited by an ALD or a cyclic CVD process, the precursor pulse can have a pulse duration that is greater than 0.01 seconds, and the oxygen source can have a pulse duration that is less than 0.01 seconds, while the water pulse duration can have a pulse duration that is less than 0.01 seconds. In yet another embodiment, the purge duration between the pulses that can be as low as 0 seconds or is continuously pulsed without a purgeP25-105-SEC-W001in-between. The oxygen source or reagent is provided in a molecular amount less than a 1 :1 ratio to the organoamino-alkoxy-carbosilane precursor, so that at least some carbon is retained in the as deposited dielectric film.

[0042] In certain embodiments, the silicon oxide films further comprise nitrogen. In these embodiments, the films are deposited using the methods described herein and formed in the presence of a nitrogen-containing source. A nitrogen-containing source may be introduced into the reactor in the form of at least one nitrogen source and / or may be present incidentally in the other precursors used in the deposition process. Suitable nitrogen-containing source gases may include, for example, ammonia, hydrazine, monoalkylhydrazine, dialkylhydrazine, nitrogen, nitrogen / hydrogen, ammonia plasma, nitrogen plasma, nitrogen / hydrogen plasma, and mixture thereof. In certain embodiments, the nitrogen-containing source comprises an ammonia plasma or hydrogen / nitrogen plasma source gas that is introduced into the reactor at a flow rate ranging from about 1 to about 2000 square cubic centimeters (seem) or from about 1 to about 1000 seem. The nitrogencontaining source can be introduced for a time that ranges from about 0.1 to about 100 seconds. In embodiments wherein the film is deposited by an ALD or a cyclic CVD process, the precursor pulse can have a pulse duration that is greater than 0.01 seconds, and the nitrogen-containing source can have a pulse duration that is less than 0.01 seconds, while the water pulse duration can have a pulse duration that is less than 0.01 seconds. In yet another embodiment, the purge duration between the pulses that can be as low as 0 seconds or is continuously pulsed without a purge inbetween.

[0043] The respective step of supplying the precursors, oxygen source, the nitrogen-containing source, and / or other precursors, source gases, and / or reagents may be performed by changing the time for supplying them to change the stoichiometric composition of the resulting dielectric film.

[0044] Energy is applied to the at least one of the organoamino-alkoxy-carbosilane precursor, oxygen containing source, or combination thereof to induce reaction and to form the dielectric film or coating on the substrate. Such energy can be provided by, but not limited to, thermal, plasma, pulsed plasma, helicon plasma, high density plasma, inductively coupled plasma, X-ray, e-beam, photon, remote plasma methods, and combinations thereof. In certain embodiments, a secondary RF frequency source can be used to modify the plasma characteristics at the substrate surface. In embodiments wherein the deposition involves plasma, the plasma-P25-105-SEC-W001generated process may comprise a direct plasma-generated process in which plasma is directly generated in the reactor, or alternatively a remote plasmagenerated process in which plasma is generated outside of the reactor and supplied into the reactor.

[0045] The at least one organoamino-alkoxy-carbosilane precursors may be delivered to the reaction chamber such as a cyclic CVD or ALD reactor in a variety of ways. In one embodiment, a liquid delivery system may be utilized. In an alternative embodiment, a combined liquid delivery and flash vaporization process unit may be employed, such as, for example, the turbo vaporizer manufactured by MSP Corporation of Shoreview, MN, to enable low volatility materials to be volumetrically delivered, which leads to reproducible transport and deposition without thermal decomposition of the precursor. In liquid delivery formulations, the precursors described herein may be delivered in neat liquid form, or alternatively, may be employed in solvent formulations or compositions comprising same. Thus, in certain embodiments the precursor formulations may include solvent component(s) of suitable character as may be desirable and advantageous in a given end use application to form a film on a substrate.

[0046] For those embodiments wherein the at least one precursor having two Si-C-Si linkages precursor(s) having Formula IA or IB or IC or ID is used in a composition comprising a solvent and an at least one organoamino-alkoxy-carbosilane precursor, the solvent or mixture thereof selected does not react with the organoamino-alkoxy-carbosilane precursor. The amount of solvent by weight percentage in the composition ranges from 0.5% by weight to 99.5% or from 10% by weight to 75%. In this or other embodiments, the solvent has a boiling point (b.p.) similar to the b.p. of the at least one organoamino-alkoxy-carbosilane precursor having two Si-C-Si linkages of Formula IA or IB or IC or ID, where the difference between the b.p. of the solvent and the b.p. of the at least one organoamino-alkoxy-carbosilane having two Si-C-Si linkages precursor of Formula IA or IB or IC or ID is 40 °C or less, 30 °C or less, 20 °C or less, or 10 °C or less. Alternatively, the difference between the boiling points ranges from any one or more of the following end-points: 0 °C, 10°C, 20 °C, 30 °C, or 40 °C. Examples of suitable ranges of b.p. difference include without limitation, 0 °C to 40 °C, 20 °C to 30 °C, or 10 °C to 30 °C. Examples of suitable solvents in the compositions include, but are not limited to, an ether (such as 1 ,4-dioxane, dibutyl ether), a tertiary amine (such as pyridine, 1 -methylpiperidine, 1-ethylpiperidine, N,N'-dimethylpiperazine, N,N,N',N'-tetramethylethylenediamine), aP25-105-SEC-W001nitrile (such as benzonitrile), an alkane (such as hexane, heptane, octane, nonane, dodecane, ethylcyclohexane), an aromatic hydrocarbon (such as toluene, mesitylene, xylene), a tertiary aminoether (such as bis(2-dimethylaminoethyl) ether), or mixtures thereof.

[0047] As previously mentioned, the purity level of the at least one organoamino-alkoxy-carbosilane precursor having two Si-C-Si linkages of Formula IA or IB or IC or ID is sufficiently high to be acceptable for reliable semiconductor manufacturing. In certain embodiments, the at least one organoamino-alkoxy-carbosilane precursor having two Si-C-Si linkages of Formulae I A or IB or IC or ID described herein comprise less than 2% by weight, or less than 1% by weight, or less than 0.5% by weight of one or more of the following impurities: free amines, free halides or halogen ions, and higher molecular weight species. Higher purity levels of the organoamino-alkoxy-carbosilane precursor having two Si-C-Si linkages described herein can be obtained through one or more of the following processes: purification, adsorption, recrystallization, and / or distillation.

[0048] In one embodiment of the method described herein, a cyclic deposition process such as ALD-like, ALD, or PEALD may be used wherein the deposition is conducted using the at least one organoamino-alkoxy-carbosilane precursor having two Si-C-Si linkages of Formula IA or IB or IC or ID and an oxygen or hydrogen source. The ALD-like process is defined as a cyclic CVD process but still provides high conformal silicon oxide films.

[0049] In certain embodiments, the gas lines connecting from the precursor canisters to the reaction chamber are heated to one or more temperatures depending upon the process requirements and the container of the at least one organoamino-alkoxy-carbosilane precursor having two Si-C-Si linkages of Formula I A or IB or IC or ID is kept at one or more temperatures for bubbling. In other embodiments, a solution comprising the at least one organoamino-alkoxy-carbosilane precursor having two Si-C-Si linkages of Formula IA or IB or IC or ID is injected into a vaporizer kept at one or more temperatures for direct liquid injection.

[0050] A flow of argon and / or other gas may be employed as a carrier gas to help deliver the vapor of the at least one organoamino-alkoxy-carbosilane precursor having two Si-C-Si linkages of Formulae IA or IB or IC or ID to the reaction chamber during the precursor pulsing. In certain embodiments, the reaction chamber process pressure is about 1 Torr.P25-105-SEC-W001

[0051] In atypical ALD or an ALD-like process such as a CCVD process, the substrate such as a silicon oxide substrate is heated on a heater stage in a reaction chamber that is exposed to the organoamino-alkoxy-carbosilane having two Si-C-Si linkages initially to allow the complex to chemically adsorb onto the surface of the substrate.

[0052] A purge gas such as argon purges away unabsorbed excess complex from the process chamber. After sufficient purging, an oxygen source may be introduced into reaction chamber to react with the absorbed surface followed by another gas purge to remove reaction by-products from the chamber. The process cycle can be repeated to achieve the desired film thickness. In some cases, pumping can replace a purge with inert gas or both can be employed to remove unreacted organoamino-alkoxy-carbosilane precursors.

[0053] In this or other embodiments, it is understood that the steps of the methods described herein may be performed in a variety of orders, may be performed sequentially, may be performed concurrently (e.g., during at least a portion of another step), and any combination thereof. The respective step of supplying the precursors and the oxygen source gases may be performed by varying the duration of the time for supplying them to change the stoichiometric composition of the resulting dielectric film.

[0054] A PEALD process for this or other embodiments may include a hydrogen and inert gas combination in plasma. The inert gas may be selected from argon, neon, helium, and combinations thereof.

[0055] Process temperature for the method described herein are one or more temperatures ranging from 20 °C to 600 °C; or 50 °C to 500 °C; or 100 °C to 500 °C; or 100 °C to 600 °C; or 100 °C to 700 °C;

[0056] Deposition pressure ranges are one or more pressures ranging from 50 miliTorr (mT) to 760 Torr, or from 500 mT - 100 Torr. Purge gases can be selected from inert gases such as nitrogen, helium or argon as well as other non-reactive gases. An oxygen source may be selected from oxygen, a composition comprising oxygen and hydrogen, hydrogen peroxide, ozone or molecular oxygen from plasma process.

[0057] The organoamino-alkoxy-carbosilane having two Si-C-Si linkages compounds having Formula I A or IB or IC or ID can be synthesized, for example as described in reaction equations (1) to (4):P25-105-SEC-W001Other synthetic routes can be also applied to make the organoamino-alkoxy-carbosilane having two Si-C-Si linkages compounds, for example Uhlig, W. disclosed a method to synthesize 1 ,3-dimethylamino-1 ,3-diethoxy-1 ,3-disilacyclobutane in Z. Naturforsch., B Chem. Sci. 52(5): 577-586 (1997).

[0058] The organoamino-alkoxy-carbosilane compounds having two Si-C-Si linkages in Formula IA or IB or IC or ID according to the present invention and compositions comprising the organoamino-alkoxy-carbosilane precursor compounds having Formula I A or IB or IC or ID according to the present invention are preferably substantially free of halide ions. As used herein, the term “substantially free” as it relates to halide ions (or halides) such as, for example, chlorides (i.e. chloride-containing species such as HCI or silicon compounds having at least one Si-CI bond) and fluorides, bromides, and iodides, means less than 5 ppm (by weight) measured by ion chromatography ( IC), preferably less than 3 ppm measured by IC, and more preferably less than 1 ppm measured by IC, and most preferably 0 ppm measured by IC. Chlorides are known to act as decomposition catalysts for the organoamino-alkoxy-carbosilane compounds having two Si-C-Si linkages in Formula IA or IB or IC or ID. Significant levels of chloride in the final product can cause the organoamino-alkoxy-carbosilane precursor compounds to degrade. The gradual degradation of the organoamino-alkoxy-carbosilane compounds having two Si-C-Si linkages mayP25-105-SEC-WG01directly impact the film deposition process making it difficult for the semiconductor manufacturer to meet film specifications. In addition, the shelf-life or stability is negatively impacted by the higher degradation rate of the organoamino-alkoxy-carbosilane compounds having two Si-C-Si linkages in Formula IA or IB or IC or ID thereby making it difficult to guarantee a 1-2 year shelf-life. Therefore, the accelerated decomposition of the organoamino-alkoxy-carbosilane compounds having two Si-C-Si linkages in Formula IA or IB or ID or ID performance concerns. The organoamino-alkoxy-carbosilane compounds having two Si-C-Si linkages in Formula I A or IB or ID or ID are preferably substantially free of metal ions such as, Li+, Na+, K+, Mg2+, Ca2+, Al3+, Fe2+, Fe2+, Fe3+, Ni2+, Cr3+. As used herein, the term “substantially free” as it relates to Li, Na, K, Mg, Ca, Al, Fe, Ni, Cr means less than 5 ppm (by weight), preferably less than 3 ppm, and more preferably less than 1 ppm, and most preferably 0.1 ppm as measured by ICP-MS. In some embodiments, the organoamino-alkoxy-carbosilane compounds having two Si-C-Si linkages in Formula IA or IB or IC or ID are free of metal ions such as, Li+, Na+, K+, Mg2+, Ca2+, Al3+, Fe2+, Fe2+, Fe3+, Ni2+, Cr3+. As used herein, the term “free of” metal impurities as it relates to Li, Na, K, Mg, Ca, Al, Fe, Ni, Cr, noble metal such as volatile Ru or Pt complexes from ruthenium or platinum catalysts used in the synthesis, means less than 1 ppm, preferably 0.1 ppm (by weight) as measured by ICP-MS or other analytical method for measuring metals. The organoamino-alkoxy-carbosilane compounds having two Si-C-Si linkages in Formula IA or IB or IC or ID according to the present invention and compositions comprising the organoamino-alkoxy-carbosilane precursor compounds having Formula IA or IB or IC or ID according to the present invention are having purity of 98% or higher, preferably 99% or higher, most preferably 99.5% or higher based on Gas Chromatography (GC) analysis.EXAMPLES

[0059] Example 1 : Synthesis of 1 ,3-bis(dimethylamino)-1 ,3-dimethoxy-1 ,3-disilacyclobutane

[0060] 1 ,3-dichloro- 1 ,3-bis(dimethylamino)-1 ,3-disilacyclobutane (0.61 g, 2.5 mmol) was added as 30wt% solution in THF to a 50 mL round bottom flask equipped with a magnetic stir bar and was diluted with 3 mL of hexanes. Next, lithium methoxide (0.19 g, 5 mmol) was added to the flask directly and left to stir for the extent of 30 minutes. GC-MS analysis of the resulting reaction solution showed conversion to the desired 1 ,3-bis(dimethylamino)-1 ,3-dimethoxy-1 ,3-disilacyclobutane. GC-MS showedP25-105-SEC-W001the following peaks: m / z = 234 (M+), 219 (M-15), 189, 176, 162, 149, 133, 117, 103, 89, 72, 59, 45.

[0061] Example 2: Synthesis of 1 ,3-bis(diethylamino)-1 ,3-dimethoxy-1 ,3-disilacyclobutane

[0062] In the glovebox, 0.50g of 1 ,3-dichloro-1 ,3-bis(diethylamino)-1 ,3-disilacyclobutane was weighed out into a 20mL vial equipped with a small magnetic stir bar. Next, roughly ~5mL of hexanes was added to the vial using a pipette. Using a small weigh boat, 0.18g of lithium methoxide (made in house) was weighed out and then added to the vial containing the 1 ,3-dichloro-1 ,3-bis(diethylamino)-1 ,3-disilacyclobutane and hexanes. The reaction was placed on a stir plate and left to stir overnight. A sample was run by GC-MS and showed the following peaks: m / z = 290 (M+), 275 (M-15), 261, 247, 232, 218, 204, 190, 176, 162, 149, 130, 117, 103, 89, 72, 59, 42.

[0063] Example 3: Synthesis of 1 ,3-bis(diethylamino)-1 ,3-diethoxy-1 ,3-disilacyclobutane

[0064] In the glovebox, 0.94g of 1 ,3-dichloro-1 ,3-bis(diethylamino)-1 ,3-disilacyclobutane was weighed out into a 20mL vial equipped with a small magnetic stir bar. Next, roughly ~5mL of hexanes was added to the vial using a pipette. Using a small weigh boat, 0.24g of lithium ethoxide (made in house) was weighed out and then added to the vial containing the 1 ,3-dichloro-1 ,3-bis(diethylamino)-1 ,3-disilacyclobutane and hexanes. The reaction was placed on a stir plate and left to stir overnight. A sample was run by GC-MS and showed the following peaks: m / z = 318 (M+), 303 (M-15), 289, 275, 261, 246, 232, 218, 204, 190, 177, 160, 144, 131, 119, 103, 89, 72, 58, 45.

[0065] Example 4: Synthesis of 1 ,3-bis(dimethylamino)-1 ,3-diisopropoxy-1 ,3-disilacyclobutane

[0066] In the glovebox, 4.61 g of 1 ,3-dich loro- 1 ,3-bis(dimethylamino)-1 ,3-disilacyclobutane was loaded into a three-neck 250ml_ round bottom flask equipped with a magnetic stir bar. Next, roughly ~50mL of hexanes was added to the flask. A suspension of 2.5g of lithium isopropoxide in hexanes (made in house) was loaded into an addition funnel then added drop-wise to the flask containing the 1 ,3-dichloro-1 ,3-bis(dimethylamino)-1 ,3-disilacyclobutane and hexanes at room temperature. The reaction was left to stir overnight. A sample was run by GC-MS and showed theP25-105-SEC-W001following peaks: m / z = 290 (M+), 275 (M-15), 247, 231 , 204, 189, 175, 162, 146, 132, 119, 103, 89, 75, 58, 44.

[0067] Example 5: Synthesis of 1 ,3-bis(diethylamino)-1 ,3-diisopropoxy-1 ,3-disilacyclobutane

[0068] In the glovebox, 0.86g of 1 ,3-bis(diethylamino)-1 ,3-dichloro-1 ,3-disilacyclobutane was weighed out into a 20mL vial with a small magnetic stir bar. Next, roughly ~5mL of hexanes was added using a plastic pipette. The vial was set on the stir plate and stirring was turned on. 0.38g of lithium isopropoxide (made in house, suspension in hexanes) was measured out and transferred via pipette into the 20mL vial containing our 1 ,3-bis(diethylamino)-1 ,3-dichloro- 1 ,3-disilacyclobutane (in hexanes). The reaction was left capped inside the glovebox to stir overnight. The following morning, a sample was taken into a GC vial. GC-MS confirmed the product peak at 346amu. GC-MS data showed the following peaks: m / z = 346 (M+), 331 (M-15), 303, 279, 250, 236, 208, 192, 180, 166, 152, 137, 119, 103, 86, 72, 58, 43.

[0069] Example 6: Synthesis of 1 ,3-bis(dimethylamino)-1 ,3-di-sec-butoxy-1 ,3-disilacyclobutane

[0070] In the glovebox, 0.76g of 1 ,3-bis(dimethylamino)-1 ,3-dichloro-1 ,3-disilacyclobutane was weighed out into a 20mL vial with a small magnetic stir bar. Next, roughly ~5mL of hexanes was added using a plastic pipette. The vial was set on the stir plate and stirring was turned on. 0.50g of lithium sec-butoxide (made in house, suspension in hexanes) was measured out and transferred via pipette into the 20mL vial containing our 1 ,3-bis(dimethylamino)-1 ,3-dichloro- 1 ,3-disilacyclobutane (in hexanes). The reaction was left capped inside the glovebox to stir overnight. The following morning, a sample was taken into a GC vial. GC-MS confirmed the product peak at 318amu. GC-MS data showed the following: m / z = 318 (M+), 303 (M-15), 289, 261 , 245, 218, 189, 162, 146, 119, 103, 152, 137, 119, 103, 75, 44.

[0071] Example 7: Deposition of silicon-containing films using 1 ,3-bis(dimethylamino)-1,3-dimethoxy-1,3-disilacyclobutane and NH3Film depositions were performed in a screening reactor using 1,3-bis(dimethylamino)-1 ,3-dimethoxy-1 ,3-disilacyclobutane as silicon precursor, and ammonia as nitrogen source. The Si precursor container was heated to 75 °C. The ALD cycle steps, and process conditions are provided in Table 1.P25-105-SEC-W001

[0072] Table 1 : ALD Cycle Steps and Process Conditions<<< <During the deposition, steps 3 to 10 were repeated for a number of cycles to get a desired thickness of the silicon-containing films.

[0073] Refractive index and thickness were measured directly after deposition using an ellipsometer at 632.8 nm. XPS was used to determine the bulk film composition, CV / IV to measure the dielectric constant and leakage at 1 MV / cm andP25-105-SEC-W001WER under dilute hydrofluoric acid (dHF) with concentration of 1 :99 ratio of 49% HF to DI water were performed on the films and WER is reported as relative to the etch rate of thermal oxide. The thermal silicon oxide etch rate was 0.5 A / s

[0074] The deposition growth per cycle (GPC) was 0.2 A / cycle. Film has composition of 21.7 at % C, 7.9 at % N, 32.7 at % O and 37.6 at % Si. The etch rate of the film in 1 :99 dilute HF was less than 0.01 relative to that of thermal silicon oxide.

[0075] Example 8: Deposition of silicon-containing films using 1 ,3-bis(dimethylamino)-1,3-bis(dimethylamino)-1,3-disilacyclobutane and NHs and H2O

[0076] Film depositions were performed in a screening reactor using 1 ,3-bis(dimethylamino)-1,3-dimethoxy-1,3-disilacyclobutane as silicon precursor, ammonia as nitrogen source, and water as oxygen source. The Si precursor container was heated to 75 °C while the H2O container was heated to 40 °C. The ALD cycle steps, and process conditions are provided in Table 2.

[0077] Table 2: ALD Cycle Steps and Process Conditions<<P25-105-SEC-W001<<

[0078] During the deposition, steps 3 to 10 were repeated for a number of cycles to get a desired thickness of the silicon-containing films.

[0079] The deposition growth per cycle (GPC) was 0.3 A / cycle. Film has composition of 19.6 at. % C, 4.5 at. % N, 34.4 at. % O and 41.4 at. % Si. The etch rate of the film in 1 :99 dilute HF was less than 0.01 relative to that of thermal silicon oxide. The film k-value was 3.7 while leakage at 1 MV / cm was 5E-8 A / cm2.

[0080] Other processes used the O2flow step in ALD process under 7 Torr after H2O step. The deposition growth per cycle (GPC) was 0.5 A / cycle. Film has composition of 5.6 at. % C, 0.7 at. % N, 40.5 at. % O and 53.0 at. % Si. The etch rate of the film in 1 :99 dilute HF was less than 0.05 relative to that of thermal silicon oxide. The film k-value was 4.9 while leakage at 1 MV / cm was 6E-7 A / cm2. Residual -OH content in the film is likely to cause high k.

[0081] In other example, additional ALD water cycle was added after co-flow of water and NH3. The deposition growth per cycle (GPC) was 0.5 A / cycle. Film has composition of 16.3 at. % C, 1.3 at. % N, 45.2 at. % O and 37.1 at. % Si. The etch rate of the film in 1 :99 dilute HF was less than 0.05 relative to that of thermal silicon oxide. The film k-value was 5.0 while leakage at 1 MV / cm was 5E-7 A / cm2. Residual -OH content in the film is likely to cause high k.

[0082] H2plasma treatment under 200W for 3 min was performed on films with H2O / NH3, H2O / NH3 + H2O, and H2O + O2processes. The H2plasma treatment successfully removed the -OH in the films and the k values were reduced to 3.5 for all processes. Leakage showed more than two orders of magnitude reduction to mid-E-9 A / cm2at 1 MV / cm.

Claims

P25-105-SEC-W001CLAIMS1 . A process to deposit a silicon-containing film onto a substrate comprises steps of:a. providing a substrate in a reactor;b. introducing into the reactor at least one organoamino-alkoxy-carbosilane precursor compound having two Si-C-Si linkages and selected from the group consisting of Formula IA, IB, IC, and ID:wherein R is selected from a linear or branched Ci to Cw alkyl group; R1and R2are each independently selected from hydrogen, a linear or branched Ci to C10 alkyl group, a linear or branched C2 to C10 alkenyl, and a C6to Cw aryl group with a proviso that R1and R2cannot both be hydrogen, and with the proviso that for IC and ID, every R and every R1and R2cannot all be methyl; R1and R2are either linked to form a cyclic ring structure or R1and R2are not linked to form a cyclic ring structure; c. purging the reactor with purge gas;d. introducing at least one of an oxygen source, a hydrogen source, and a nitrogen source into the reactor; ande. purging the reactor with purge gas;wherein steps b through e are repeated until a desired thickness of silicon-containing film is deposited, wherein the process in conducted at one or more temperatures ranging from 20 to 700°C and one or more pressures ranging from 50 miliTorr (mT) to 760 Torr.

2. The process of claim 1 , wherein the at least one organoamino-alkoxy-carbosilane precursor compound according to Formula IA is selected from the groupP25-105-SEC-W001consisting of 1 -diisopropylamino-1 , 3, 3-trimethoxy-1 ,3-disilacyclobutane, 1-dimethylamino-1 ,3 ,3-triethoxy-1 ,3-disilacyclobutane, 1 -ethylmethylamino-1 ,3,3-trimethoxy-1 ,3-disilacyclobutane, 1 -ethylmethylamino-1 ,3,3-triethoxy- 1 ,3-disilacyclobutane, 1-diethylamino-1 ,3,3-trimethoxy-1 ,3-disilacyclobutane, 1-dimethylamino-1 ,3,3-triethoxy-1 ,3-disilacyclobutane, 3-pyrrolidino- 1 ,3,3-trimethoxy- 1 .3-disilacyclobutane, 1 -piperidino- 1 ,3,3-trimethoxy-1 ,3-disilacyclobutane, 1 -dimethylamino-1 ,3,3-triisopropoxy-1 ,3-disilacyclobutane, 1 -ethylmethylamno-1 ,3,3-triisopropoxy -1 ,3-disilacyclobutane, 1 -diethylamino-1 ,3,3-triisopropoxy- 1 ,3-disilacyclobutane, 1 -pyrrolidino-1 ,3,3-triisopropoxy-1 ,3-disilacyclobutane, and combinations thereof.

3. The process of claim 1 , wherein the at least one organoamino-alkoxy-carbosilane precursor compound having two Si-C-Si linkages according to Formula IB or IC is selected from the group consisting of 1 ,3-bis(dimethylamino)-1 ,3-dimethoxy-1 ,3-disilacyclobutane, 1 ,3-bis(dimethylamino)-1 ,3-diethoxy-1 ,3-disilacyclobutane, 1 ,3-bis(ethylmethylamino)-1 ,3-dimethoxy-1 ,3-disilacyclobutane, 1 .3-bis(ethylmethylamino)-1 ,3-diethoxy-1 ,3-disilacyclobutane, 1 ,3-bis(diethylamino)- 1 .3-diethoxy-1 ,3-disilacyclobutane, 1 ,3-bis(diisopropylamino)-1 ,3-dimethoxy-1 ,3-disilacyclobutane, 1 ,3-bis(diisopropylamino)-1 ,3-diethoxy-1 ,3-disilacyclobutane, 1 ,3-bis(dimethylamino)-1 ,3-diisopropoxy-1 ,3-disilacyclobutane, 1 ,3-bis(ethylmethylamino)-1 ,3-diisopropoxy-1 ,3-disilacyclobutane, 1 ,3-bis(diethylamino)- 1 .3-diisopropoxy-1 ,3-disilacyclobutane, 1 ,3-bis(dimethylamino)-1,3-di-sec-butoxy-1 ,3-disilacyclobutane, 1 ,3-bis(ethylmethylamino)-1 ,3-di-sec-butoxy-1 ,3-disilacyclobutane, 1 .3-bis(diethylamino)-1 ,3-di-sec-butoxy-1 ,3-disilacyclobutane, 1 ,3-bis(dimethylamino)-1 ,3-di-tert-butoxy-1 ,3-disilacyclobutane, 1 ,3-dipyrrolidino-1 ,3-diisopropoxy-1 ,3-disilacyclobutane, 1 ,3-dipyrrolidino- 1 ,3-methoxy-1 ,3-disilacyclobutane, 1 ,3-dipyrrolidino-1 ,3-diethoxy-1,3-disilacyclobutane, 1 ,3-dimethoxy-1 ,3-bis(piperidinyl)-1 ,3-disilacyclobutane, 1 ,3-dimethoxy-1 ,3-bis(piperidinyl)- 1 ,3-disilacyclobutane, 1 ,3-dipyrrolyl-1 ,3-methoxy-1 ,3-disilacyclobutane, 1 ,3-dipyrrolyl-1 ,3-diethoxy-1 ,3-disilacyclobutane, 1 , 1 -dipyrrolidino- 3.3-dimethoxy-1 ,3-disilacyclobutane, 1 ,1-bis(ethylmethylamino)-3,3-dimethoxy-1 ,3-disilacyclobutane, 1 ,1-bis(dimethylamino)-3,3-diethoxy-1 ,3-disilacyclobutane, 1 ,1-bis(ethylmethylamino)-3,3-diethoxy-1 ,3-disilacyclobutane, 1 ,1-bis(dimethylamino)- 3.3-di-n-propoxy-1 ,3-disilacyclobutane, 1 ,1-bis(dimethylamino)-3,3-diisopropoxy-1 ,3-disilacyclobutane, and combinations thereof.P25-105-SEC-W0014. The process of claim 1 , wherein the at least one organoamino-alkoxy-carbosilane precursor compound having two Si-C-Si linkages according to Formula ID is selected from the group consisting of 1 ,1,3-tris(dimethylamino)-3-methoxy-1 ,3-disilacyclobutane, 1 ,1 ,3-tris(dimethylamino)-3-ethoxy-1 ,3-disilacyclobutane, 1,1,3-tris(dimethylamino)-3-isopropoxy-1 ,3-disilacyclobutane, 1 ,1 ,3-tris(dimethylamino)-3-n-propoxy-1 ,3-disilacyclobutane, and combinations thereof.

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

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

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

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

9. The process of claim 1 , wherein the nitrogen source is selected from the group consisting of ammonia, hydrazine, monoalkylhydrazine, symmetrical or unsymmetrical dialkyl hydrazine, methylamine, ethylamine, ethylenediamine, ethanolamine, piperazine, N,N’-dimethylethylenediamine, imidazolidine, cyclotrimethylenetriamine, pyridine, piperazine, ammonia, or other organic amines.

10. The process of claim 1 , wherein the step of introducing at least one of an oxygen source, a hydrogen source, and a nitrogen source into the reactor comprises introducing the oxygen source and the nitrogen source together.

11. The process of claim 10, wherein the oxygen source is water vapor and the nitrogen source is ammonia.P25-105-SEC-W00112. The process of claim 1 , further comprising the steps off. introducing at least one of an oxygen source, a hydrogen source, and a nitrogen source different from step d into the reactor; andg. purging the reactor with purge gas,wherein steps f and g are repeated along with steps b through e until a desired thickness of the silicon-containing film is deposited.

13. A composition for depositing a silicon-containing film using a vapor deposition process, wherein the composition comprises: at least one organoamino-alkoxy-carbosilane precursor having two Si-C-Si linkages and selected from the group consisting of Formula IA, IB, IC and ID:wherein R is selected from a linear or branched Ci to Cw alkyl group; R1and R2are each independently selected from hydrogen, a linear or branched Ci to Cw alkyl group, a linear or branched C2to Cw alkenyl, and a C6to Cw aryl group with a proviso that R1and R2cannot both be hydrogen, and with the proviso that for IB if every R is ethyl, every R1and every R2cannot be methyl, and with the proviso that for IC and ID, every R and every R1and R2cannot all be methyl; R1and R2are either linked to form a cyclic ring structure or R1and R2are not linked to form a cyclic ring structure.

14. The composition of claim 13, wherein the at least one organoamino-alkoxy-carbosilane precursor with Formula IA is selected from the group consisting of 1 -diisopropylamino-1 ,3,3-trimethoxy-1 ,3-disilacyclobutane, 1 -dimethylamino-1 ,3,3-P25-105-SEC-W001triethoxy-1 ,3-disilacyclobutane, 1 -ethylmethylamino-1 ,3,3-trimethoxy-1 ,3-disilacyclobutane, 1 -ethylmethylamino-1 ,3,3-triethoxy- 1 ,3-disilacyclobutane, 1 -diethylamino-1 ,3,3-trimethoxy-1 ,3-disilacyclobutane, 1 -dimethylamino-1 , 3 , 3-triethoxy- 1.3-disilacyclobutane, 3-pyrrolidino-1 ,3,3-trimethoxy-1 ,3-disilacyclobutane, 1-piperidino-1 ,3,3-trimethoxy-1 ,3-disilacyclobutane, 1 -dimethylamino-1 ,3,3-triisopropoxy-1 ,3-disilacyclobutane, 1 -ethylmethylamno-1 ,3,3-triisopropoxy -1 ,3-disilacyclobutane, 1 -diethylamino-1 ,3,3-triisopropoxy-1 ,3-disilacyclobutane, 1-pyrrolidino-1 ,3,3-triisopropoxy-1 ,3-disilacyclobutane, and combinations thereof.

15. The composition of claim 13, wherein the at least one organoamino-alkoxy-carbosilane precursor with Formula IB and IC is selected from the group consisting of 1 .3-bis(dimethylamino)-1 ,3-dimethoxy-1 ,3-disilacyclobutane, 1 ,3-bis(ethylmethylamino)-1 ,3-dimethoxy-1 ,3-disilacyclobutane, 1 ,3-bis(ethylmethylamino)-1 ,3-diethoxy-1 ,3-disilacyclobutane, 1 ,3-bis(diethylamino)-1 ,3-diethoxy-1 ,3-disilacyclobutane, 1 ,3-bis(diisopropylamino)-1 ,3-dimethoxy-1 ,3-disilacyclobutane, 1 ,3-bis(diisopropylamino)-1 ,3-diethoxy-1 ,3-disilacyclobutane, 1 ,3-bis(dimethylamino)-1 ,3-diisopropoxy-1 ,3-disilacyclobutane, 1 ,3-bis(ethylmethylamino)-1 ,3-diisopropoxy-1 ,3-disilacyclobutane, 1 ,3-bis(diethylamino)- 1.3-diisopropoxy-1 ,3-disilacyclobutane, 1 ,3-bis(dimethylamino)-1 ,3-di-sec-butoxy-1 ,3-disilacyclobutane, 1 ,3-bis(ethylmethylamino)-1 ,3-di-sec-butoxy-1 ,3-disilacyclobutane, 1 ,3-bis(diethylamino)-1 ,3-di-sec-butoxy-1 ,3-disilacyclobutane, 1 ,3-bis(dimethylamino)-1 ,3-di-tert-butoxy- 1 ,3-disilacyclobutane, 1 ,3-dipyrrolidino-1 ,3-diisopropoxy-1 ,3-disilacyclobutane, 1 ,3-dipyrrolidino- 1 ,3-methoxy-1 ,3-disilacyclobutane, 1 ,3-dipyrrolidino-1 ,3-diethoxy-1,3-disilacyclobutane, 1 ,3-dimethoxy-1 ,3-bis(piperidinyl)-1 ,3-disilacyclobutane, 1 ,3-dimethoxy-1 ,3-bis(piperidinyl)- 1 ,3-disilacyclobutane, 1 ,3-dipyrrolyl-1 ,3-methoxy-1 ,3-disilacyclobutane, 1 ,3-dipyrrolyl-1 ,3-diethoxy-1 ,3-disilacyclobutane, 1 , 1 -dipyrrolidino- 3.3-dimethoxy-1 ,3-disilacyclobutane, 1 ,1-bis(ethylmethylamino)-3,3-dimethoxy-1 ,3-disilacyclobutane, 1 ,1-bis(dimethylamino)-3,3-diethoxy-1 ,3-disilacyclobutane, 1,1-bis(ethylmethylamino)-3,3-diethoxy-1 ,3-disilacyclobutane, 1 ,1-bis(dimethylamino)- 3.3-di-n-propoxy-1 ,3-disilacyclobutane, 1 ,1-bis(dimethylamino)-3,3-diisopropoxy-1 ,3-disilacyclobutane, and combinations thereof.

16. The composition of claim 13, wherein the at least one organoamino-alkoxy-carbosilane precursor with Formula ID is selected from the group consisting of 1 ,1,3-P25-105-SEC-W001tris(dimethylamino)-3-methoxy-1 ,3-disilacyclobutane, 1 ,1 ,3-tris(dimethylamino)-3-ethoxy-1 ,3-disilacyclobutane, 1 ,1 ,3-tris(dimethylamino)-3-isopropoxy-1 ,3-disilacyclobutane, 1 ,1 ,3-tris(dimethylamino)-3-n-propoxy-1 ,3-disilacyclobutane, and combinations thereof17. The composition of claim 13 wherein the composition is substantially free of one or more impurities selected from the group consisting of halide compounds, metal ions, metal, and combinations thereof.

18. The composition of claim 17, wherein the halide compounds comprise chloride-containing species and wherein the chloride concentration is less than 5 ppm measured by IC.

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

20. The film of claim 19 comprising at least one of the following characteristics: a density of at least about 2.0 g / cm3; a wet etch rate that is less than about 2.5 A / s as measured in a solution of 1 :100 of HF to water (0.5 wt. % dHF) acid; an electrical leakage of less than about 1 x 108A / cm2 up to 6 MV / cm; and a hydrogen impurity of less than about 4 x 1021at / cc as measured by SIMS.

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