WO2019118019A1

WO2019118019A1 - Method of depositing a silicon-containing film on a substrate using organo(halo) siloxane precursors

Info

Publication number: WO2019118019A1
Application number: PCT/US2018/049314
Authority: WO
Inventors: Noel Mower CHANG; Byung K. Hwang; Brian D. Rekken; Vasgen Shamamian; Travis SUNDERLAND; Michael D. Telgenhoff; Xiaobing Zhou
Original assignee: Dow Silicones Corporation
Priority date: 2017-12-12
Filing date: 2018-09-04
Publication date: 2019-06-20
Also published as: TW201928101A

Abstract

A method of depositing a silicon-containing film on a substrate, the method comprising: A) contacting an organo(halo)siloxane precursor, wherein the organo(halo)siloxane precursor comprises a siloxane bond, a silicon-bonded halogen atom, and a silicon-bonded unsaturated hydrocarbyl group having from 1-10 carbon atoms with a substrate in a reactor at conditions sufficient to deposit the silicon-containing film on the substrate.

Description

METHOD OF DEPOSITING A SILICON-CONTAINING FILM ON A SUBSTRATE USING ORGANO(HALO)SILOXANE PRECURSORS

CROSS-REFERENCE TO RELATED APPLICATIONS

None

FIELD OF THE INVENTION

The present invention pertains to methods for depositing a film on a substrate comprising contacting a silicon precursor with a substrate in a reactor at conditions sufficient to deposit the film on the substrate. The film may contain silicon, oxygen, nitrogen, and carbon.

BACKGROUND OF THE INVENTION

Elemental silicon and silicon compounds with one or more of oxygen, carbon, or nitrogen have a variety of uses. For example, a film composed of elemental silicon, silicon oxide, silicon carbide, silicon nitride, silicon carbonitride, silicon oxycarbide, or silicon oxycarbonitride may be used as a semiconductor, an insulating layer or a sacrificial layer in the manufacture of electronic circuitry for electronic or photovoltaic devices.

Known methods of preparing the silicon material may use one or more silicon-yielding precursor materials using processes such as chemical vapor deposition or atomic layer deposition processes. Use of these precursors is not limited to making silicon for electronic or photovoltaic applications.

Carbon-doped silicon-containing film, such as silicon oxide and silicon oxynitride films, have been used in semiconductor fabrication as dielectric layers for benefits such as low dielectric constant (k) and low wet etch rate. These films have been typically produced by chemical vapor deposition or solution deposition processes.

As research progresses, semiconductor features are quickly shrinking in size to the point where atomic layer deposition (ALD) processes are required to provide the precise film thicknesses now required. However, the production of carbon-doped silicon-containing films by ALD having adequate carbon amounts, growth rates, and wet etch rates has proven difficult with existing silicon precursors.

We see a need in the electronics and photovoltaic industries for methods of forming silicon-containing films using improved silicon-yielding precursors. In particular, we see a need for processes and precursors that can be used in ALD processes to produce carbon-doped silicon-containing films with finer features and that have adequate carbon content, acceptable growth rates, and sufficient wet etch rates. In addition, the new precursors may also enable lower of deposition temperatures.

BRIEF SUMMARY OF THE INVENTION

The present invention is directed to A method of depositing a silicon-containing film on a substrate, the method comprising: A) contacting an organo(halo)siloxane precursor, wherein the organo(halo)siloxane precursor comprises a silicon-bonded halogen atom and a silicon- bonded unsaturated hydrocarbyl group having from 1 -10 carbon atoms with a substrate in a reactor at conditions sufficient to deposit the silicon-containing film on the substrate.

The present invention is further directed to a silicon-containing film produced by the method of the invention.

The method of the invention deposits fine carbon-doped silicon-containing films that have good wet etch rates, acceptable growth rates, and good carbon content.

DETAILED DESCRIPTION OF THE INVENTION

Aspects of the invention are described herein using various common conventions. For example, all states of matter are determined at 25° C. and 101 .3 kPa unless indicated otherwise. All % are by weight unless otherwise noted or indicated. All % values are, unless otherwise noted, based on total amount of all ingredients used to synthesize or make the composition, which adds up to 100 %. Any Markush group comprising a genus and subgenus therein includes the subgenus in the genus, e.g., in“R is hydrocarbyl or alkenyl,” R may be alkenyl, alternatively R may be hydrocarbyl, which includes, among other subgenuses, alkenyl. For U.S. practice, all U.S. patent application publications and patents referenced herein, or a portion thereof if only the portion is referenced, are hereby incorporated herein by reference to the extent that incorporated subject matter does not conflict with the present description, which would control in any such conflict.

Aspects of the invention are described herein using various patent terms. For example, “alternatively” indicates a different and distinct embodiment.“Comparative example” means a non-invention experiment.“Comprises” and its variants (comprising, comprised of) are open ended.“Consists of” and its variants (consisting of) is closed ended.“Contacting” means bringing into physical contact.“May” confers a choice, not an imperative.“Optionally” means is absent, alternatively is present.

Aspects of the invention are described herein using various chemical terms. The meanings of said terms correspond to their definitions promulgated by IUPAC unless otherwise defined herein. For convenience, certain chemical terms are defined. The term “deposition” is a process of generating, on a specific place, condensed matter. The condensed matter may or may not be restricted in dimension. Examples of deposition are film-forming, rod-forming, and particle-forming depositions.

The term“film” means a material that is restricted in one dimension. The restricted dimension may be characterized as“thickness” and as the dimension that, all other things being equal, increases with increasing length of time of a process of depositing said material to form the film.

The term“IUPAC” refers to the International Union of Pure and Applied Chemistry.

The term“precursor” means a substance or molecule containing atoms of the indicated element and being useful as a source of that element in a film formed by a deposition method.

The term“separate” means to cause to physically move apart, and thus as a result is no longer in direct touching.

The term“substrate” means a physical support having at least one surface upon which another material may be hosted.

A method of depositing a silicon-containing film on a substrate, the method comprising:

A) contacting an organo(halo)siloxane precursor, wherein the organo(halo)siloxane precursor comprises a silicon-bonded halogen atom and a silicon-bonded unsaturated hydrocarbyl group having from 1 -10 carbon atoms with a substrate in a reactor at conditions sufficient to deposit the silicon-containing film on the substrate.

The organo(halo)siloxane precursor comprises a silicon-bonded halogen atom, and a silicon-bonded unsaturated hydrocarbyl group having from 1 -10 carbon atoms.

The siloxane portion of the organo(halo)siloxane has at least one group comprising a silicon bonded to an oxygen bonded to a silicon: Si-O-Si. The organo(halo)siloxane has 0 or more, alternatively 0 to 10, alternatively 0 to 3, alternatively 0, siloxane repeat units (i.e., (- S1R2O-], where R is H, halogen or hydrocarbyl). One skilled in the art would know what a siloxane repeat unit is. As used herein,“siloxane” is intended to include siloxane oligomers and polysiloxanes.

The silicon-bonded halogen atom is any halogen, alternatively chlorine, bromine, or iodine, alternatively chlorine or bromine, alternatively chlorine.

The silicon-bonded unsaturated hydrocarbyl group typically has from 2 to 10, alternatively 2-6, alternatively 2 or 3 carbon atoms. Acyclic unsaturated hydrocarbyl groups having at least 3 carbon atoms can have a branched or unbranched structure. The unsaturated hydrocarbyl group includes, but is not limited to, alkenyl, alkynyl, aryl, arylalkenyl, alkaryl, and aralkyl, alternatively alkenyl or alkynyl, alternatively alkenyl. Examples of alkenyl, alkynyl, aryl, arylalkenyl, alkaryl, and aralkyl groups include, but are not limited to, alkenyl, such as vinyl, allyl, and propenyl, butenyl, hexenyl, octenyl; alkynyl, such as ethynyl and propynyl; aryl, such as phenyl and naphthyl; arylalkenyl, such as styryl and cinnamyl; alkaryl, such as tolyl and xylyl; and aralkyl, such as benzyl and phenylethyl.

In one embodiment, the organo(halo)siloxane precursor is according to formula (I)

R¹ R²R³Si0[SiR⁴R³0]_nSiR¹ R²R³ (I) wherein n is 0 to 10, alternatively 0 to 3, alternatively 0 to 2, alternatively 0, each R¹ , R² and R³ is independently halo, H, hydrocarbyl having from 1 to 10 carbon atoms, at least one of R¹ , R², and R³ is halo, at least one of R¹ , R² and R³ is alkenyl or alkynyl, and each R⁴ and R³ is independently halo, H, or hydrocarbyl having from 1 to 10 carbon atoms, alternatively H, alkyl, alkenyl or alkynyl, alternatively H, alkyl, or alkenyl.

Halo groups represented by R^{1 3} are as described above for the organo(halo)siloxane.

Hydrocarbyl groups represented by R^{1 3} typically have from 1 to 10 carbon atoms, alternatively 1 to 6, alternatively 2 to 4 carbon atoms. Acyclic hydrocarbyl groups containing at least 2 carbon atoms can have a branched or unbranched structure. Examples of alkyl groups represented by R¹ include, but are not limited to, methyl, ethyl, propyl, 1 -methylethyl, butyl, pentyl, hexyl, octyl, nonyl, and decyl, and their isomers; cycloalkyl, such as cyclopentyl, cyclohexyl, methylcyclohexyl. Examples of alkenyl, alkynyl, aryl, arylalkenyl, alkaryl, and aralkyl groups represented by R^{1 3} include, but are not limited to, those described above for the organo(halo)siloxane precursor.

Examples of the organo(halo)siloxane precursor include, but are not limited to, 1 ,3- dichloro-1 ,3-diethenyl-1 ,3-dimethyldisiloxane and 1 ,1 ,3,3-tetrachloro-1 ,3- diethyenyldisiloxane.

The organo(halo)siloxane precursor may be provided in any manner. For example, the organo(halo)siloxane precursor may by synthesized or otherwise obtained for use in the method. Many organo(halo)siloxanes according to the invention are available commercially. For example, 1 ,3-dichloro-1 ,3-diethenyl-1 ,3-dimethyldisiloxane may be purchased commercially. One method of making 1 ,3-Dichloro-1 ,3-diethenyl-1 ,3-dimethyldisiloxane is taught in, Harris, G.I.,“Inter- and Intra-Molecular Association of Poly(diorganosiloxane) - aw- Diols”, Journal of the Chemical Society B 1970, 488 - 492, which is hereby incorporated by reference, where water (2.25 moles) in dioxane (40.5 ml) was added to dichloromethylvinylsilane (3.0 moles) in diethyl ether (400 ml) to give a mixture of aw- dichlorosiloxanes from which 1 ,3-dichloro-1 ,3-dimethyl-1 ,3-divinyldisiloxane (30 g, 8.8%), b.p.

61 -63 °C/0.9 mmHg (Found: Si, 24.9; Cl, 30.5. CeH-^C^OS^ requires Si, 24.7; Cl, 31 .2%), was isolated.

In one embodiment, the organo(halo)siloxane precursor may be contacted with the substrate as part of a composition comprising the organo(halo)siloxane precursor and at least one additional material. The additional material is at least one of an inert gas, molecular hydrogen, a carbon precursor, a nitrogen precursor, and an oxygen precursor, where the inert gas, molecular hydrogen, a carbon precursor, a nitrogen precursor, and an oxygen precursor are known in the art such as argon, helium, nitrogen, hydrazine, ammonia, an amine or organohydrazine comprising 0 to 10 carbon atoms such as methylhydrazine or methylamine, oxygen, water, nitrous oxide and ozone. In one embodiment, the organo(halo)siloxane precursor is contacted as part of a composition consisting essentially of the organo(halo)siloxane precursor, alternatively consisting of the organo(halo)siloxane precursor.

The substrate utilized in the method is not limited. In certain embodiments, the substrate is limited only by the need for thermal and chemical stability at the temperature and in the environment of the deposition chamber. Thus, the substrate can be, for example, glass, metal, plastic, ceramic, silicon (e.g. monocrystalline silicon, polycrystalline silicon, amorphous silicon, etc). In one embodiment, the substrate is composed of a semiconductor material. Alternatively, the semiconductor material is a silicon-based semiconductor material. Alternatively, the semiconductor material is an elemental silicon. One skilled in the art would know how to provide the substrate.

The method of forming a film uses a deposition apparatus. The deposition apparatus utilized in the method is generally selected based upon the desired method of forming the film. In one embodiment, the reactor may be a chemical vapor deposition (CVD) or atomic layer deposition (ALD) reactor, alternatively and ALD reactor. One skilled in the art would know CVD and ALD reactors.

The method of depositing the silicon-containing film on a substrate comprises contacting the organo(halo)siloxane precursor with the substrate. The contacting may be conducted by heating the organo(halo)siloxane precursor with the substrate in a CVD or ALD reactor, alternatively an ALD reactor, under thermal or plasma conditions to give a silicon- containing film disposed on the substrate. The method may use a CVD or ALD process, alternatively an ALD process to deposit the film from the organo(halo)siloxane precursor.

The CVD process comprises a plasma-enhanced chemical vapor deposition (PECVD) process, a low-pressure chemical vapor deposition (LPCVD) process, a cyclic chemical vapor deposition (cyclic CVD) process, an atmospheric-pressure chemical vapor deposition (APCVD) process, a metal-organic chemical vapor deposition (MOCVD) process, a flowable chemical vapor deposition (FCVD) process, a high density-plasma chemical vapor deposition (HDPCVD) process, or a hot-filament chemical vapor deposition (HFCVD) process; and wherein the ALD process comprises a plasma-enhanced atomic layer deposition (PEALD) process or a spatial atomic layer deposition (spatial ALD) process. Alternatively, the method comprises the CVD process, wherein the CVD process is the PECVD process, alternatively the LPCVD process, alternatively the cyclic CVD process, alternatively the APCVD process, alternatively the MOCVD process, alternatively the FCVD process, alternatively the HDPCVD process, alternatively the HFCVD process. Alternatively, the method comprises the ALD process, wherein the ALD process comprises the PEALD process, alternatively the spatial ALD process.

In thermal CVD or ALD, the film is deposited by passing a stream of a vaporized form of the Silicon Precursor Compound over a heated substrate. When the vaporized form of the Silicon Precursor Compound contacts the heated substrate, the Silicon Precursor Compound generally reacts and/or decomposes to form the film.

The silicon-containing film is deposited on the substrate at conditions sufficient to deposit the silicon-containing film from the organo(halo)siloxane precursor. Deposition can be done at a deposition temperature of 50 degrees Celsius (°C) to 800°C, alternatively from 200 to 800 °C. At the same time, deposition can be done at a deposition pressure of 0.01 Torr or higher, 0.05 Torr or higher and even one Torr or higher while at the same time at a pressure of 760 Torr or less, preferably 100 Torr or less and can be 80 Torr or less Deposition is done for sufficient time to deposit the silicon-containing film, which is typically in a range from 0.1 second to 5 minutes. The conditions described are for the deposition chamber of the reactor.

The deposition process of the invention may also require manipulation of gas flow rates, plasma powers and locations when a plasma is applied, gas dosage times and gas and co-reactant concentrations within the abilities of those with skill in the art. The method of depositing the silicon-containing film on a substrate may further comprise heating a co-reactant with the organo(halo)siloxane precursor, wherein the co reactant may be any co-reactant typically used in ALD processes .

The method of the invention may further comprise B) contacting the substrate with an activating gas or a plasma of the activating gas, wherein the activating gas comprises oxygen, nitrogen, or carbon atoms or a combination thereof.

The substrate is as defined above.

The activating gas comprises oxygen, nitrogen, or carbon atoms, alternatively, the activating gas is oxygen, ozone, H2O, hydrogen peroxide, nitrogen precursor, a saturated hydrocarbon having 1 to 20 carbon atoms, an unsaturated hydrocarbon having 2 to 20 carbon atoms, or a combination of one or more of oxygen, ozone, H2O, hydrogen peroxide, ammonia, the amine, the saturated hydrocarbon, and the unsaturated hydrocarbon.

The nitrogen precursor may be used with the organo(halo)siloxane precursor in the composition for forming a film comprising silicon, nitrogen, carbon, and oxygen atoms according to an embodiment of the method. The nitrogen precursor is different than the organo(halo)siloxane precursor. The film comprising silicon, nitrogen, carbon, and oxygen atoms may comprise silicon oxycarbonitride. The nitrogen precursor may comprise N atoms and optionally H atoms, alternatively the nitrogen precursor may consist essentially of N atoms and optionally H atoms, alternatively the nitrogen precursor may consist of N and optionally H atoms. The nitrogen precursor that comprises N and optionally H atoms may further comprise C or O atoms or may further comprise C and O atoms. The nitrogen precursor that consists essentially of N atoms and optionally H atoms lacks C and O atoms, but optionally may have one or more halogen atoms (e.g., Cl). An example of the nitrogen precursor consisting of N atoms is molecular nitrogen. Examples of the nitrogen precursor consisting of N and H atoms are ammonia and hydrazine. An example of the nitrogen precursor consisting of O and N atoms is nitrous oxide (N2O) and nitrogen dioxide (NO2)·

In one embodiment, the activating gas comprises a nitrogen precursor comprising an organoamine, alternatively a primary, secondary, or tertiary organoamine. The amine may be substituted with one or more hydrocarbyl groups having from 1 to 10 carbon atoms.

Hydrocarbyl groups substituted on the amine precursor typically have from 1 to 10 carbon atom alternatively 1 to 6 carbon atoms, alternatively 1 to 3 carbon atoms. Examples of hydrocarbyl groups of the amine include, but are not limited to, those described above for the organo(halo)siloxane precursor. Amine groups substituted on the amine precursor include groups such as

where each R6 is H or hydrocarbyl having from 1 to 10, alternatively 1 to 6, alternatively 1 to 3 carbon atoms. Hydrocarbyl groups represented by R^ are as described above for R¹ to R^. In some embodiments, the hydrocarbyl groups may further be substituted with alcohol groups.

Examples of amines include, but are not limited to, methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, isopropylamine, diisopropylamine, triisopropylamine, and 2-amino-2-methyl-1 -propanol.

The saturated hydrocarbon activating gas has from 1 to 20, alternatively 5 to 18 carbon atoms. Acyclic saturated hydrocarbons having 4 or more carbon atoms can be branched or non-branched. Examples of the saturated hydrocarbon included, but are not limited to, alkanes, such as methane, ethane, propane, butane, n-butane, isobutene, pentane, n- pentane, isopentane, hexane, cyclohexane, heptane, octane, cyclooctane, nonane, decane, dodecane, and heptadecane.

The unsaturated hydrocarbon activating gas has from 2 to 20, alternatively 5 to 18 carbon atoms. Acyclic unsaturated hydrocarbons having 4 or more carbon atoms can be branched or non-branched. Examples of unsaturated hydrocarbons include, but are not limited to, alkenes, such as ethylene, propene, butene, hexene, cyclohexene, and dodecene; alkynes such as ethyne, propyne, butyne, pentyne; and aromatics such as benzene and toluene, and naphthalene.

In one embodiment, the substrate is contacted with a plasma of the activating gas, where the activating gas is as described above. One skilled in the art would know how to make a plasma of the activating gas. For example, the plasma of the activating gas may be formed by applying an electrical current across the gas.

The contacting of the activating gas or the plasma of the activating gas with the substrate may be conducted in the same manner that the organo(halo)siloxane precursor may be contacted with the substrate as described above. In one embodiment, the activating gas or plasma of the activating gas are introduced into a CVD or ALD reactor containing the substrate.

The conditions that the activating gas is contacted with the substrate are as described above for the contacting of the organo(halo)siloxane precursor with the substrate.

In atomic layer deposition, gases for forming the film are typically introduced and reacted in a deposition chamber in a series of cycles, where a cycle comprises filling the reaction chamber with the organo(halo)siloxane precursor (half reaction), purging the reactor with an inert gas, filling the reaction chamber with another reactive gas (second half reaction) and/or activating gas, and then purging the reactor with an inert gas. A series of cycles of the two half reactions (first and second) form the proper film elements or molecules on the substrate surface. Atomic layer deposition generally requires the addition of energy to the system, such as heating of the deposition chamber and substrate.

Alternatively, in atomic layer deposition, gases for forming the film are introduced and reacted in a deposition chamber in a series of cycles, where a cycle comprises filling the reaction chamber with the organo(halo)siloxane precursor, purging the reactor with an inert gas, filling the reaction chamber with a first activating gas purging the reactor with an inert gas, filling the reaction chamber with a second activating gas, where the second activating gas is the same or different than the first activating gas, and the purging the reactor with an inert gas, where the activating gas is as described above. A series of cycles of the three reactions (first, second and third) form the proper film elements or molecules on the substrate surface.

In one embodiment, the contacting the substrate with an activating gas or a plasma of the activating gas B) is conducted prior to the contacting of the organo(halo)siloxane precursor with the substrate A), alternatively B) is conducted prior to A) and the contacting of B) then A) are alternated repeatedly until a silicon-containing film of desired thickness has been deposited on the substrate. In one embodiment, each contacting A) results in a film depositing on the substrate of approximately one atomic layer in thickness, alternatively one silicon atomic layer in thickness.

The method of the invention may further comprise C) purging the reactor with an inert gas before the contacting in A), the contacting in B), or the contacting in A) and B). The inert gas may be any inert gas typically used to purge CVD or ALD reactors prior to introducing an activating or reactive gas into the reactor with the substrate, alternatively, the inert gas is argon or helium, alternatively argon.

A film produced by the method of the invention.

The film produced by a method of depositing a silicon-containing film on a substrate, the method comprising:

A) contacting an organo(halo)siloxane precursor, wherein the organo(halo)siloxane precursor comprises a silicon-bonded halogen atom and a silicon-bonded unsaturated hydrocarbyl group having from 1 -10 carbon atoms with a substrate in a reactor at conditions sufficient to deposit the silicon-containing film on the substrate. The contacting, organo(halo)siloxane precursor, substrate, reactor, reactor conditions, and other method parameters are as described for the method above.

A film produced by the method described above further comprising B) contacting the substrate with an activating gas or a plasma of the activating gas, wherein the activating gas comprises oxygen, nitrogen, or carbon, where the contacting, substrate, activating gas, reactor, conditions, and other parameters for B) are as described for the method above.

A film produced by the method described above further comprising C) purging the reactor with an inert gas before the contacting A), the contacting B), or the contacting A) and B), wherein the purging and inert gas are as described for the method above.

Because the organo(halo)siloxane precursor contains silicon, oxygen, and carbon, the organo(halo)siloxane precursor may be utilized to form silicon-containing films containing carbon without use of a carbon precursor, although a nitrogen precursor may be also used if desired to produce films comprising nitrogen in addition to silicon, oxygen, and carbon. That is, the addition of a nitrogen precursor (e.g., second vapor) may be necessary to form a film comprising silicon, carbon, oxygen, and nitrogen atoms. In one embodiment, the film produced by the method of the invention comprises silicon, carbon and oxygen, or silicon, carbon, oxygen, and nitrogen. In one embodiment, the film is a carbon-doped silicon oxide, silicon oxycarbonitride, or silicon oxynitride film.

The film produced according the method of the invention comprises at least 1 , alternatively at least 3, alternatively at least 10, alternatively from 0.1 to 5 atomic% of carbon.

In one embodiment, the film formed by the method is restricted in one dimension, which may be referred to as thickness of the material. The film produced according the method of the invention has a thickness of from 0.1 nm to 100 nm, alternatively from 0.1 to 25 nm.

The composition and structure of the film is a function of not only the deposition apparatus and its parameters, but also the organo(halo)siloxane precursor utilized and the presence or absence of any reactive environment during the method.

The silicon-containing film may be used as a semiconductor, an insulating layer or a sacrificial layer in the manufacture of electronic circuitry for electronic or photovoltaic devices.

An electronic device comprising the silicon-containing film produced by the method of the invention. Electronic devices include, but are not limited to, solar cells and computer chips. EXAMPLES

The following examples are included to demonstrate preferred embodiments of the invention. It should be appreciated by those of skill in the art that the techniques disclosed in the examples which follow represent techniques discovered by the inventor to function well in the practice of the invention, and thus can be considered to constitute preferred modes for its practice. However, those of skill in the art should, in light of the present disclosure, appreciate that many changes can be made in the specific embodiments which are disclosed and still obtain a like or similar result without departing from the spirit and scope of the invention. Unless otherwise noted, all percentages are in wt. %; pressure is at 1 atm; and temperature is 20 °C.

Table 1 . List of abbreviations used in the examples.

EXAMPLE 1 . Synthesis of 1 ,3-Dichloro-1 ,3-Dimethyl-1 ,3-Divinyldisiloxane (CMVDSO). To a 250 ml round-bottom flask was loaded 60.0 g (0.425 mol) of dichloromethylvinylsilane, CLSiMeVinyl. While the starting material was refluxed in the flask, a solution of 1 .92 g (0.106 mol) of water in 30.0 ml of TEGDME was added dropwise in 35 minutes. The reaction temperature varied between 87 and 96 °C. The HCI by-product was vented through a 1 .0 M NaOH scrubber. After the addition, the reaction mixture was maintained at 90 °C for 60 minutes. Than it was distilled under vacuum at up to 90 °C pot temperature and down to 1 torr pressure. The distillate condensed at 0 °C contained 9.8 g of CMVDSO, which accounted for 41% isolated yield. Out of this crude product was fractionally distilled 99.6% pure CMVDSO. EXAMPLE 2. Synthesis of 1 ,1 ,3,3-Tetrachloro-1 ,3-Divinyldisiloxane (CVDSO). To a 250 ml round-bottom flask was loaded 120.0 g (0.743 mol) of trichlorovinylsilane, ChSiVinyl. While the starting material was refluxed in the flask, a solution of 3.34 g (0.186 mol) of water in 52.8 ml of TEGDME was added dropwise in 20 minutes. The reaction temperature varied between 83 and 95 °C. The HCI by-product was vented through a 1 .0 M NaOH scrubber. After the addition, the reaction mixture was maintained at 90 °C for 60 minutes. Than it was distilled under vacuum at up to 90 °C pot temperature and down to 1 torr pressure. The distillate condensed at 0 °C contained 1 1 .0 g of CVDSO, which accounted for 22% isolated yield. Out of this crude product was fractionally distilled 99.6% pure CVDSO.

EXAMPLE 3. Atomic Layer Deposition of Silicon Oxycarbonitride (SiOCN) Films. A SiOCN film is formed using CMVDSO with ammonia. An ALD reactor and a canister containing CMVDSO in fluid communication with the ALD reactor are used. The canister containing CMVDSO is maintained at 50 °C to increase the vapor pressure. The ALD reactor is purged with argon, wherein the ALD reactor contains a plurality of horizontally oriented and spaced apart silicon wafers heated to a temperature from 500 to 800 °C. Then the vapor of CMVDSO is flowed into the ALD reactor. The ALD reactor is then purged again with argon to remove any residual vapor of CMVDSO. Next, ammonia is flowed into the ALD reactor. The ALD reactor is then purged again with argon to remove any residual ammonia. The foregoing sequence of steps is then repeated until a silicon oxycarbonitride film with a desired thickness is formed on the wafers. One cycle in the table is equal to one sequence of a precursor dose, followed by an argon purge, followed by an ammonia dose, and followed by a second argon purge. The examples in the table, the duration of argon purge was 10 second and varied precursor dose time and ammonia dose time.

The thickness and refractive index (at the wavelength of 632 nm) of SiOCN film were characterized using spectroscopic ellipsometry (M-2000DI, J.A. Woollam). Ellipsometry data were collected from the wavelength range from 375 nm to 1690 nm and analyzed using Tauc- Lorentz oscillator model with a software provided by J.A. Woollam. Growth per cycle (GPC, nm/cycle) is determined by dividing average film thickness by the number of cycles. Wet etch rate tests of the thin films grown by ALD processes were performed using 100:1 HF solution diluted in D.l. water at room temperature. The wet etch rate was calculated by dividing the difference in thickness measured before and after etching with HF solution by the etching time. Film composition of ALD SiOCN film was measured using X-ray photoelectron spectroscopy (XPS).

In order to characterize the film composition of ALD SiOCN film, ex-situ XPS was performed on the sample (C5) deposited at 800°C and shown in the table below. The XPS analysis was done on ALD SiOCN film after 1 min argon sputtering in the XPS chamber to remove the surface oxidation layer.

PROPHETIC EXAMPLE 4. Atomic Layer Deposition of Silicon Oxycarbonitride (SiOCN) Films with Higher Oxygen Content. A SiOCN film with higher oxygen content is formed using CMVDSO with ammonia and oxygen. An ALD reactor and a canister (“bubbler”) containing CMVDSO in fluid communication with the ALD reactor are used. The bubbler containing CMVDSO is maintained at 70 °C to increase the vapor pressure. The ALD reactor is purged with nitrogen, wherein the ALD reactor contains a plurality of horizontally oriented and spaced apart silicon wafers heated to a temperature from 200 to 800 °C. Then the vapor of CMVDSO is flowed into the ALD reactor. The ALD reactor is then purged again with nitrogen to remove any residual vapor of CMVDSO. Next, ammonia is flowed into the ALD reactor. The ALD reactor is then purged again with nitrogen to remove any residual ammonia. Then next, oxygen is flowed into the ALD reactor. The ALD reactor is then purged again with nitrogen to remove any residual oxygen. The foregoing sequence of steps is then repeated until a conformal silicon oxycarbonitride film with a desired thickness was formed on the wafers. PROPHETIC EXAMPLE 5. Plasma Enhanced Atomic Layer Deposition of Silicon Oxycarbonitride (SiOCN) Films. A SiOCN film is formed using CMVDSO with ammonia plasma. A PEALD reactor and a canister (“bubbler”) containing CMVDSO in fluid communication with the PEALD reactor are used. The bubbler containing CMVDSO is maintained at 70 °C to increase the vapor pressure. The PEALD reactor is purged with nitrogen, wherein the ALD reactor contains a plurality of horizontally oriented and spaced apart silicon wafers heated to a temperature from 200 to 500 °C. Then the vapor of CMVDSO is flowed into the ALD reactor. The ALD reactor is purged again with nitrogen to remove any residual vapor of CMVDSO. Next, ammonia is flowed into the ALD reactor with plasma power being turned on. The ALD reactor is purged again with nitrogen to remove any residual ammonia plasma. The foregoing sequence of steps is then repeated until a conformal silicon oxycarbonitride film with a desired thickness is formed on the wafers.

PROPHETIC EXAMPLE 6. Plasma Enhanced Atomic Layer Deposition of Silicon Oxycarbonitride (SiOCN) Films with higher oxygen content. A SiOCN film with higher oxygen content is formed using CMVDSO with ammonia plasma and oxygen plasma. A PEALD reactor and a canister (“bubbler”) containing CMVDSO in fluid communication with the PEALD reactor are used. The bubbler containing CMVDSO is maintained at 70 °C to increase the vapor pressure. The PEALD reactor is purged with nitrogen, wherein the ALD reactor contains a plurality of horizontally oriented and spaced apart silicon wafers heated to a temperature from 200 to 500 °C. Then the vapor of CMVDSO is flowed into the ALD reactor. The ALD reactor is then purged again with nitrogen to remove any residual vapor of CMVDSO. Next, ammonia is flowed into the ALD reactor with plasma power being turned on. The ALD reactor is then purged again with nitrogen to remove any residual ammonia plasma. Then next, oxygen is flowed into the ALD reactor with plasma power being turned on. The ALD reactor is then purged again with nitrogen to remove any residual oxygen plasma. The foregoing sequence of steps is then repeated until a conformal silicon oxycarbonitride film with a desired thickness is formed on the wafers.

Claims

CLAIMS:

1 . A method of depositing a silicon-containing film on a substrate, the method comprising:

2. A method according to claim 1 , wherein the organo(halo)siloxane precursor is according to formula (I)

R³R²R¹ Si0[SiR¹ R²0]_nSiR¹ R²R³ (l)

wherein n is 0-3, each R ! , R² and R³ is independently halo, H, alkyl, alkenyl or alkynyl, and at least one of R¹ , R² and R³ is halo and at least one of R¹ , R² and R³ is alkenyl or alkynyl.

3. A method according to claim 2, wherein n = 0, R^ is Cl, R² is methyl, and R³ is alkenyl or alkynyl.

4. A method according to any one of the preceding claims, wherein the method further comprises B) contacting the substrate with an activating gas or a plasma of the activating gas, wherein the activating gas comprises oxygen, nitrogen, or carbon.

5. A method according to claim 4, wherein the activating gas is oxygen, ozone, H2O, hydrogen peroxide, ammonia, an amine, hydrazine, organohydrazine, a saturated hydrocarbon having 1 to 20 carbon atoms, an unsaturated hydrocarbon having 2 to 20 carbon atoms, or a combination of one or more of oxygen, ozone, H2O, hydrogen peroxide, ammonia, the amine, hydrazine, the organohydrazine, the saturated hydrocarbon, and the unsaturated hydrocarbon.

6. A method according to claim 4 or 5, wherein the contacting B) is conducted before the contacting A).

7. A method according to any one of claims 4 to 6, wherein the contacting B) and the contacting A) are repeated at least once, and wherein the activating gas in the repeat contacting B) may be the same or different as in the previous activating gas contacting.

8. A method according to claim 4, 5, 6, or 7, further comprising C) purging the reactor with an inert gas before the contacting A), the contacting B), or the contacting A) and B).

9. A method according to any one of the preceding claims, wherein each contacting A) forms a single atomic layer on the substrate.

10. A method according to any one of the preceding claims wherein the deposition is at a temperature from 200 to 800 °C and a pressure from 0.01 T orr to 100 T orr.

1 1 . A method according to any one of the preceding claims wherein the deposition is thermal atomic layer deposition or plasma enhanced atomic layer deposition.

12. A method according to any one of the preceding claims, wherein the orano(halo)siloxane precursor is 1 ,3-dichloro-1 ,3-dimethyl-1 ,3-divinyldisiloxane or 1 ,1 ,3,3-tetrachloro-1 ,3- divinyldisiloxane

13. A film produced by any one of the preceding claims.

14. A film according to claim 13, wherein the film further comprised one or both of limitations a) and b):

a) the film comprises at least 10 atomic% of carbon, the film; and

b) the film has a thickness of from 0.1 nm to 100 nm.

15. An electronic device comprising the film produced by any one of claims 1 to 12.