Functionalized cyclosilazanes as precursors for high growth rate silicon-containing films

Abstract

To provide a process for forming uniform and conformal silicon-containing films such as silicon oxide having at least one or more of the following attributes: a density of about 2.1 g / cc or more, a growth rate of 2.0 Å / cycle or more, low chemical impurity and / or high conformality, using cheaper, more reactive and more stable silicon precursor compounds.SOLUTION: Described herein are functionalized cyclosilazane precursor compounds and compositions and methods comprising the same for depositing a silicon-containing film such as, without limitation, silicon oxide, silicon nitride, silicon oxynitride, silicon carbonitride, silicon oxycarbonitride, or carbon-doped silicon oxide, via a thermal atomic layer deposition (ALD) or plasma enhanced atomic layer deposition (PEALD) process or a combination thereof.SELECTED DRAWING: None

Description

[Technical field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims priority under 35 U.S.C. §119(e) to U.S. Provisional Patent Application No. 62 / 510,506, filed May 24, 2017, the entirety of which is incorporated herein by reference. [Background technology]

[0002] Described herein are functionalized cyclosilazane precursor compounds, and compositions and methods including same, for depositing silicon-containing films, such as, but not limited to, silicon oxide, silicon nitride, silicon oxynitride, silicon carbonitride, silicon oxycarbonitride, or carbon-doped silicon oxide, by thermal atomic layer deposition (ALD) or plasma-enhanced atomic layer deposition (PEALD) processes, or combinations thereof. More particularly, described herein are compositions and methods for forming stoichiometric or non-stoichiometric silicon-containing films or materials at one or more deposition temperatures up to about 600° C., such as from about 25° C. to about 300° C.

[0003] Atomic layer deposition (ALD) and plasma enhanced atomic layer deposition (PEALD) are processes used to deposit, for example, silicon oxide conformal films at low temperatures (<500°C). In both ALD and PEALD processes, precursors and reactive gases (such as oxygen and ozone) are pulsed separately for a specific number of cycles to form a monolayer of silicon oxide with each cycle. However, silicon oxide deposited at low temperatures using these processes can contain levels of impurities, such as, but not limited to, nitrogen (N), that can be harmful in certain semiconductor applications. One solution to remedy this is to increase the deposition temperature to 500°C or higher. However, at these high temperatures, traditional precursors used in the semiconductor industry tend to self-react, pyrolyze, and deposit in chemical vapor deposition (CVD) mode rather than ALD mode. CVD mode deposition has reduced conformality compared to ALD deposition, especially for the high aspect ratio structures required in many semiconductor applications. Furthermore, CVD mode deposition provides less control over the thickness of the film or material than ALD mode deposition.

[0004] An article entitled "Some New Alkylaminosilanes" (Abel, EW et al., J. Chem. Soc., (1961), Vol. 26, p. 1528-1530) describes the preparation of various aminosilane compounds such as Me3SiNHBu-iso, Me3SiNHBu-sec, Me3SiN(Pr-iso)2, and Me3SiN(Bu-sec)2 from the direct interaction of trimethylchlorosilane (Me3SiCl) with appropriate amines, where Me=methyl, Bu-sec=sec-butyl, and Pr-iso=isopropyl.

[0005] The article entitled “SiO2 Atomic Layer Deposition Using Tris(dimethylamino)silane and Hydrogen Peroxide Studied by in Situ Transmission FTIR Spectroscopy” (Burton, BB et al., The Journal of Physical Chemistry (2009), Vol. 113, p.8249-57) describes the atomic layer deposition (ALD) of silicon dioxide (SiO2) using a variety of silicon precursors, including H2O2 as the oxidant. The silicon precursors were (N,N-dimethylamino)trimethylsilane)(CH3)3SiN(CH3)2, vinyltrimethoxysilaneCH2CHSi(OCH3)3, trivinylmethoxysilane(CH2CH)3SiOCH3, tetrakis(dimethylamino)silaneSi(N(CH3)2)4, and tris(dimethylamino)silane (TDMAS)SiH(N(CH3)2)3. TDMAS was determined to be the most effective of these precursors. However, further investigations have revealed that SiH * The surface species were determined to be difficult to remove using H2O alone. Subsequent studies tested SiO2ALD using TDMAS and H2O2 as the oxidant at temperatures ranging from 150 to 550 °C. The exposure required for the surface reaction between TDMAS and H2O2 to reach completion was monitored using in situ FTIR spectroscopy. FTIR vibrational spectra after TDMAS exposure showed a disappearance of absorbance for the OH stretching vibration and an increase in absorbance for the C-Hx and Si-H stretching vibrations. FTIR vibrational spectra after H2O2 exposure showed a disappearance of absorbance for the C-Hx and Si-H stretching vibrations and an increase in absorbance for the OH stretching vibration. SiH * Surface species were completely removed only at temperatures above 450 °C. The bulk vibrational modes of SiO2 range from 1000 to 1250 cm -1The growth rate of the SiO2 ALD nanoparticles was observed between 150 and 550 °C, and gradually grew with the number of TDMAS and H2O2 reaction cycles. Transmission electron microscopy (TEM) examination was performed after 50 TDMAS and H2O2 reaction cycles on the ZrO2 nanoparticles at temperatures from 150 to 550 °C. The film thickness measured by TEM at each temperature was used to obtain the SiO2 ALD growth rate. The growth per cycle varied from 0.8 Å / cycle at 150 °C to 1.8 Å / cycle at 550 °C, and the growth rate of the SiH * Correlated with the removal of surface species. SiO2ALD using TDMAS and H2O2 should be beneficial for SiO2ALD at temperatures above 450 °C.

[0006] Japanese Patent Application Nos. 2010-275602 and 2010-225663 disclose the use of a source material for forming a Si-containing thin film, such as silicon oxide, by a chemical vapor deposition (CVD) process in the temperature range of 300-500° C. The source material is a compound represented by the formula (a) HSi(CH3)(R 1 )(NR 2 R 3 ) [where R 1 is NR 4 R 5 or a C1-C5 alkyl group, R 2 and R 4 each represents a C1-C5 alkyl group or a hydrogen atom, and R 3 and R 5 each represents a C1-C5 alkyl group; or (b) HSiCl(NR 1 R 2 )(NR 3 R 4 ) [where R 1 and R 3 each independently represents an alkyl group having 1 to 4 carbon atoms or a hydrogen atom; R 2 and R 4 each independently represents an alkyl group having 1 to 4 carbon atoms. This organosilicon compound contained an H-Si bond.

[0007] U.S. Pat. No. 5,424,095 describes a method for reducing the rate of coke formation during industrial pyrolysis of hydrocarbons, in which the inner surface of a reactor is coated with a uniform layer of ceramic material, which is deposited by pyrolysis of a gas phase non-alkoxylated organosilicon precursor in a water vapor-containing gas atmosphere to form an oxide ceramic.

[0008] US Patent Publication No. 2012 / 0291321 describes a PECVD process for forming a high quality Si carbonitride barrier dielectric film between a dielectric film and a metal wiring of an integrated circuit substrate, the process comprising the steps of providing an integrated circuit substrate having a dielectric film or a metal wiring; x R y (NRR') z wherein R, R', R and R' are each independently selected from H, a straight or branched chain saturated or unsaturated alkyl, or an aromatic group, and x+y+z=4, and z=1-3; however, R and R' cannot both be H, and when z=1 or 2, then x and y are each at least 1; and forming a Si carbonitride barrier dielectric film on the integrated circuit substrate, the Si carbonitride barrier dielectric film having a C / Si ratio>0.8 and a N / Si ratio>0.2.

[0009] US 2013 / 0295779 describes an atomic layer deposition (ALD) process for forming silicon oxide films at deposition temperatures above 500° C. using a silicon precursor having the following formula: I.R. 1 R 2 m Si(NR 3 R 4 ) n X p In the formula, R 1 , R 2 , and R 3 are each independently hydrogen, a straight or branched chain C1-C 10 Alkyl groups and C6-C 10 aryl groups; R 4is a straight or branched chain C1-C 10 Alkyl groups, C6-C 10 Aryl groups, C3-C 10 alkylsilyl groups; In the formula, R 3 and R 4 may be linked together to form a ring structure, or R 3 and R 4 do not join together to form a ring structure; X is a halide selected from the group consisting of Cl, Br, and I; m is 0 to 3; n is 0 to 2; p is 0 to 2, and m+n+p=3; and II. R 1 R 2 m Si(OR 3 ) n (OR 4 ) q X p In the formula, R 1 and R 2 are each independently hydrogen, a straight or branched chain C1-C 10 Alkyl groups and C6-C 10 aryl groups; R 3 and R 4 are each independently a linear or branched chain C1 to C 10 Alkyl groups and C6-C 10 aryl groups; In the formula, R 3 and R 4 may be linked together to form a ring structure, or R 3 and R 4 do not combine together to form a ring structure; X is a halogen atom selected from the group consisting of Cl, Br, and I; m is 0 to 3; n is 0 to 2; q is 0 to 2; p is 0 to 2, and m+n+q+p=3.

[0010] U.S. Pat. No. 7,084,076 discloses halogenated siloxanes such as hexachlorodisiloxane (HCDSO) used with pyridine as a catalyst for ALD deposition below 500° C. to form silicon dioxide.

[0011] US Patent No. 6,992,019 discloses a catalyst-assisted atomic layer deposition (ALD) method for forming silicon dioxide layers with excellent properties on semiconductor substrates by using a first reaction component consisting of a silicon compound having at least two silicon atoms, or by using a tertiary aliphatic amine as a catalyst component, or by using a combination of both with associated purging methods and sequencing. The precursor used is hexachlorodisilane. The deposition temperature is 25-150°C.

[0012] WO 2015 / 0105337 discloses novel trisilylamine derivatives and methods for forming silicon-containing thin films, where the trisilylamine derivatives have thermal stability, high volatility, and high reactivity, exist in a liquid state at room temperature and under manageable pressures, and can form high-purity silicon-containing thin films with excellent physical and electrical properties by various deposition methods.

[0013] WO 2015 / 0190749 describes novel aminosilylamine compounds (MeNSiR 3 R 4 )N(SiHR 1 R 2 )2[R 1 ~R 4 =C 1-3 Alkyl, C 2-3 Alkenyl, C 2-3 Alkynyl, C 3-7 Cycloalkyl, C 6-12 The aminosilylamine compounds of the present invention, which are thermally stable and highly volatile compounds, can be processed at room temperature and used as liquid compounds at room temperature and pressure, and therefore the present invention provides a method for producing high purity dielectric films containing Si-N bonds even at low temperatures and plasma conditions by using atomic layer deposition (PEALD).

[0014] In the specification of U.S. Patent No. 9,245,740, a novel aminosilylamine compound, a preparation method thereof, and a silicon-containing thin film using the same are provided, in which the aminosilylamine compound has thermal stability and high volatility, and is maintained in a liquid state at room temperature and under pressure that is easy to handle, so that a silicon-containing thin film having high purity and excellent physical and electrical properties can be formed by various deposition methods.

[0015] US 2015 / 0376211 discloses a Si-containing film-forming composition of a mono-substituted TSA precursor having the formula (SiH3)2N-SiH2-X, where X is a halogen atom, an isocyanato group, an amino group, an N-containing C4-C 10 The mono-substituted TSA precursor is selected from a saturated or unsaturated heterocycle, or an alkoxy group. Methods of forming Si-containing films using the disclosed mono-substituted TSA precursors are also disclosed.

[0016] US Pat. No. 3,444,127 describes the synthesis of polymeric arene-linked silicones by reacting functionalized 1,3-dioxa-5-aza-trisilacyclohexanes with arene-linked silanols and heating the mixture to 180°C.

[0017] U.S. Pat. Nos. 5,413,813 and 5,424,095 describe the use of different hexamethylcyclotrisilazane and other silazanes to coat metal or metal oxide surfaces in reactor chambers with ceramic materials at high temperatures to prevent coking in subsequent reactor processes involving the thermal cracking of hydrocarbons.

[0018] US Patent Application Publication No. 2015 / 126045 describes the deposition of a silicon nitride layer on a substrate by using a remote plasma and hexamenthylcyclotrisilazane or other aminosilanes in a plasma-enhanced CVD process at temperatures below 300° C.

[0019] US Patent Application Publication No. 2016 / 379819 describes the use of UV-assisted photochemical vapor containing different silazanes, including hexamethylcyclotrisilazane, to pore seal porous low dielectric constant films.

[0020] US Patent Application Publication No. 2013 / 0330482 describes the deposition of carbon-doped silicon nitride films by a plasma-enhanced CVD process using vinyl-substituted cyclotrisilazane or other silazanes as precursors.

[0021] US 2016 / 0032452 describes an ALD process in which at least one metal-organic precursor molecule reacts with hydrogen radicals and another source gas to produce a metal-containing film.

[0022] The above identified patents, patent applications, and publications are hereby incorporated by reference. Summary of the Invention [Problem to be solved by the invention]

[0023] There is a need in the art for a process for forming uniform, conformal silicon-containing films, such as silicon oxide, using cheaper, more reactive, and more stable silicon precursor compounds by thermal atomic layer deposition, plasma-enhanced atomic layer deposition (ALD) processes, or plasma-enhanced ALD-like processes, having at least one or more of the following attributes: density of about 2.1 g / cc or greater, growth rate of 2.0 Å / cycle or greater, low chemical impurities, and / or high conformality. [Means for solving the problem]

[0024] The present invention solves a need in the art by providing compositions and processes for depositing stoichiometric or non-stoichiometric silicon-containing materials or films, such as, but not limited to, silicon oxide, carbon-doped silicon oxide, silicon oxynitride films, silicon nitride, carbon-doped silicon nitride, or carbon-doped silicon oxynitride films, at relatively low temperatures, e.g., one or more temperatures below 600° C., by plasma-enhanced ALD, plasma-enhanced cyclic chemical vapor deposition (PECCVD), flowable chemical vapor deposition (FCVD), plasma-enhanced flowable chemical vapor deposition (PEFCVD), plasma-enhanced ALD-like processes, or ALD processes using oxygen-containing reactant sources, nitrogen-containing reactant sources, or combinations thereof.

[0025] In one embodiment, a silicon precursor compound of one of formulas A, B, C, D, or E is provided: [ka] During the ceremony, R 1-3 are each independently selected from the group consisting of hydrogen, methyl, and an organic amino group (NR′R″), where R′ and R″ are each independently selected from the group consisting of hydrogen, C 1-10 Straight chain alkyl group, C 3-10 Branched alkyl group, C 3-10 Cyclic alkyl groups, C 2-10 Alkenyl group, C 4-10 Aryl groups, and C 4-10 heterocyclic groups, with the proviso that R′ and R″ cannot both be hydrogen; R 4 and R 5 are each independently hydrogen, C 1-10 Straight chain alkyl group, C 3-10 Branched alkyl group, C 3-10 Cyclic alkyl groups, C 2-10 Alkenyl group, C 4-10 Aryl groups, and C 4-10 R is selected from the group consisting of heterocyclic groups; 6-8 are each independently hydrogen, methyl, an organic amino group (NR′R″) as defined above, C 3-10 Branched alkyl group, C 3-10Cyclic alkyl groups, C 2-10 Alkenyl group, C 4-10 Aryl groups, and C 4-10 heterocyclic groups, with the proviso that R′ and R″ cannot both be hydrogen, where the substituents R 1-8 two or more of R, R', and R'' may combine to form a substituted or unsubstituted, saturated or unsaturated cyclic group; and 6-8 must be hydrogen, and R 6-8 At least two of the groups may not be methyl.

[0026] In addition to conventional methods of synthesizing silazane molecules, such as reaction of chlorosilanes with amines or metal amides to form Si-N bonds, compounds having formulas A-E can be synthesized, for example, by catalytic dehydrocoupling between at least one N-H bond of an organic amine, linear silazane, or cyclosilazane moiety and a hydridosilane bearing at least one Si-H group (e.g., formulas 1-5). [ka]

[0027] Exemplary dehydrocoupling catalysts include, but are not limited to, tris(pentafluorophenyl)borane, BR3 (wherein R is a linear, branched, or cyclic C1-C 10 Alkyl groups, C5-C 10 Aryl group or C1-C 10 alkoxy groups), 1,3-diisopropyl-4,5-dimethylimidazol-2-ylidene, 2,2'-bipyridyl, phenanthroline, Mg[N(SiMe3)2]2, [tris(4,4-dimethyl-2-oxazolinyl)phenylborate]MgMe, [tris(4,4-dimethyl-2-oxazolinyl)phenylborate]MgH, trimethylaluminum, triethylaluminum, aluminum chloride, Ca[N(SiMe3)2]2, dibenzylcalcium, {CH-[CMeNC6H3-2,6- iPr2]2}CaH, triruthenium dodecacarbonyl, {CH-[CMeNC6H3-2,6- i Pr2]2}Ca[N(SiMe3)2], bis(cyclopentadienyl)dialkyltitanium(IV), bis(cyclopentadienyl)titanium(IV) difluoride, bis(cyclopentadienyl)titanium(IV) dichloride, bis(cyclopentadienyl)titanium(IV) dihydride, TiMe2(dmpe)2 [dmpe = 1,2-bis(dimethylphosphino)ethane], (C5H5)2Ti(OAr)2 [Ar = (2,6-(iPr)2C6H3)], (C5H5)2Ti(SiHRR')PMe3 [wherein R , R' is independently selected from a hydrogen atom, (H), a methyl group (Me), and a phenyl group (Ph)], bis(benzene)chromium(0), chromium hexacarbonyl, dimanganese decacarbonyl, [Mn(CO)4Br]2, iron pentacarbonyl, (C5H5)Fe(CO)2Me, dicobalt octacarbonyl, nickel(II) acetate, nickel(II) chloride, [(dippe)Ni(μ-H)]2 [dippe=1,2-bis(diisopropylphosphino)ethane], (R-indenyl)Ni(PR'3)M e [wherein R is selected from 1-i-Pr, 1-SiMe3, and 1,3-(SiMe3)2; where R' is selected from methyl (Me) and phenyl (Ph) groups], [{Ni(η-CH2:CHSiMe2)2O}2{μ-(η-CH2:CHSiMe2)2O}], nickel(II) acetylacetonate, ni(cyclooctadiene)2, copper(II) fluoride, copper(I) chloride, copper(II) chloride, copper(I) bromide, copper(II) bromide, copper(I) iodide, copper(I) acetate, Cu(PPh3)3Cl, zinc chloride, [tris (4,4-Dimethyl-2-oxazolinyl)phenylborate]ZnH, Sr[N(SiMe3)2]2, bis(cyclopentadienyl)dialkylzirconium(IV), bis(cyclopentadienyl)zirconium(IV) difluoride, bis(cyclopentadienyl)zirconium(IV) dichloride, bis(cyclopentadienyl)zirconium(IV) dihydride, [(Et3P)Ru(2,6-dimesitylthiophenolate)][B[3,5-(CF3)2C6H3]4], (C5Me5)Ru(R3P) x(NCMe) 3-x ] + (In the formula, R is a linear, branched, or cyclic C1-C 10 Alkyl groups and C5-C 10 aryl group, x=0, 1, 2, 3), tris(triphenylphosphine)rhodium(I) carbonyl hydride, di-μ-chloro-tetracarbonyldirhodium(I), tris(triphenylphosphine)rhodium(I) chloride (Wilkinson's catalyst), hexarhodium hexadecacarbonyl, tris(triphenylphosphine)rhodium(I) carbonyl hydride, bis(triphenylphosphine)rhodium(I) carbonyl chloride, [RhCl(cyclooctadiene)]2, tris(dibenzylideneacetone)dipalladium(0), tetrakis(triphenylphosphine)palladium(I), tungsten hexacarbonyl, dirhenium decacarbonyl, triosmium dodecacarbonyl, tetrairidium dodecacarbonyl, (acetylacetonato)dicarbonyliridium(I), (POCOP)IrHCl [(POCOP)=2,6-(R2PO)2C6H3, (R is isopropyl ( i Pr), normal butyl ( n (Bu), and methyl (Me), Ir(Me)2(C5Me5)L, where L is selected from PMe3 and PPh3, [Ir(cyclooctadiene)OMe]2, platinum(0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane (Karstedt's catalyst), HPtCl6·nH2O (chloroplatinic acid), bis(tri-tert-butylphosphine)platinum(0), PtO2, and Pt(cyclooctadiene)2.

[0028] The catalyst may also be present fixed on a support. A support is a solid with a high surface area. Typical support materials include, but are not limited to, alumina, MgO, zeolite, carbon, monolith cordierite, diatomaceous earth, silica gel, silica / alumina, ZrO, and TiO2. Preferred supports are carbon (e.g., platinum on carbon, palladium on carbon, rhodium on carbon, ruthenium on carbon), alumina, silica, and MgO. The metal loading of the catalyst ranges from about 0.01% to about 50% by weight. A preferred range is from about 0.5% to about 20% by weight. A more preferred range is from about 0.5% to about 10% by weight. Catalysts that require activation can be activated by a number of known methods. Heating the catalyst under vacuum is a preferred method. The catalyst can be activated before being added to the reaction vessel or in the reaction vessel before adding the reactants. The catalyst may include a promoter. A promoter is a substance that is not itself a catalyst, but when mixed in small amounts with an active catalyst, improves its efficiency (activity and / or selectivity). Promoters are usually metals such as Mn, Ce, Mo, Li, Re, Ga, Cu, Ru, Pd, Rh, Ir, Fe, Ni, Pt, Cr, Cu, and Au, and / or their oxides. They can be added separately to the reaction vessel, or they can be part of the catalyst itself. For example, Ru / Mn / C (manganese promoted ruthenium on carbon) or Pt / CeO2 / Ir / SiO2 (ceria and iridium promoted platinum on silica). Some promoters can act as catalysts themselves, but when used in combination with the main catalyst, they can improve the activity of the main catalyst. Catalysts may act as promoters for other catalysts. In this context, the catalysts can be called bimetallic (or polymetallic) catalysts. For example, Ru / Rh / C can refer to a ruthenium and rhodium supported bimetallic catalyst, or ruthenium supported on carbon promoted by rhodium. An active catalyst is a material that acts as a catalyst in a particular chemical reaction.

[0029] In another embodiment, a method of depositing a silicon-containing film on a substrate is provided, the method comprising the steps of: providing a substrate in a reactor; Introducing at least one silicon precursor compound comprising at least one silicon precursor compound of one of formulas A, B, C, D, or E into a reactor: [ka] During the ceremony, R 1-3 are each independently selected from the group consisting of hydrogen, methyl, and an organic amino group (NR′R″), where R′ and R″ are each independently selected from the group consisting of hydrogen, C 1-10 Straight chain alkyl group, C 3-10 Branched alkyl group, C 3-10 Cyclic alkyl groups, C 2-10 Alkenyl group, C 4-10 Aryl groups, and C 4-10 heterocyclic groups, with the proviso that R′ and R″ cannot both be hydrogen; R 4 and R 5 are each independently hydrogen, C 1-10 Straight chain alkyl group, C 3-10 Branched alkyl group, C 3-10 Cyclic alkyl groups, C 2-10 Alkenyl group, C 4-10 Aryl groups, and C 4-10 R is selected from the group consisting of heterocyclic groups; 6-8 are each independently hydrogen, methyl, an organic amino group (NR′R″) as defined above, C 3-10 Branched alkyl group, C 3-10 Cyclic alkyl groups, C 2-10 Alkenyl group, C 4-10 Aryl groups, and C 4-10 heterocyclic groups, with the proviso that R′ and R″ cannot both be hydrogen, where the substituents R 1-8 two or more of R, R', and R'' may combine to form a substituted or unsubstituted, saturated or unsaturated cyclic group; and 6-8 must be hydrogen, and R 6-8 At least two of the groups must not be methyl; purging the reactor with a purge gas; introducing an oxygen-containing source or a nitrogen-containing source (or a combination thereof) into the reactor; and purging the reactor with said purge gas; The above steps are repeated until a film of the desired thickness is deposited, and The method is carried out at one or more temperatures ranging from about 25°C to 600°C.

[0030] In some embodiments, the oxygen-containing source used in this method is a source selected from the group consisting of oxygen plasma, ozone, water vapor, water vapor plasma, nitrogen oxide (e.g., N2O, NO, NO2) plasma with or without inert gas, carbon oxide (e.g., CO2, CO) plasma, and combinations thereof.In certain embodiments, the oxygen source further comprises an inert gas.In these embodiments, the inert gas is selected from the group consisting of argon, helium, nitrogen, hydrogen, and combinations thereof.In another embodiment, the oxygen source does not comprise an inert gas.In yet another embodiment, the oxygen-containing source comprises nitrogen, which reacts with the reagent under plasma conditions to provide a silicon oxynitride film.

[0031] In some embodiments, the nitrogen-containing source may be introduced into the reactor in the form of at least one nitrogen-containing source and / or may be present concomitantly with other precursors used in the deposition process.Suitable nitrogen source gases include, for example, ammonia, hydrazine, monoalkylhydrazine, dialkylhydrazine, nitrogen, nitrogen / hydrogen, nitrogen / argon plasma, nitrogen / helium plasma, ammonia plasma, nitrogen plasma, nitrogen / hydrogen plasma, organic amines such as tert-butylamine, dimethylamine, diethylamine, isopropylamine, diethylamine plasma, dimethylamine plasma, trimethylamine plasma, trimethylamine plasma, ethylenediamine plasma, and alkoxyamines such as ethanolamine plasma, and mixtures thereof.In certain embodiments, the nitrogen-containing source includes ammonia plasma, plasma comprising nitrogen and argon, plasma comprising nitrogen and helium, or plasma comprising hydrogen and nitrogen source gas.

[0032] In the above-mentioned embodiments and throughout the present invention, the inert gas is selected from the group consisting of argon, helium, nitrogen, hydrogen, or combinations thereof. In another embodiment, the oxygen-containing plasma source does not include an inert gas.

[0033] One embodiment of the present invention relates to uniform, conformal silicon-containing films, such as silicon oxide, formed by thermal atomic layer deposition, plasma-enhanced atomic layer deposition (ALD) processes, or plasma-enhanced ALD-like processes using cheaper, more reactive, and more stable silicon precursor compounds, and having at least one or more of the following attributes: density of about 2.1 g / cc or greater, growth rate of 2.0 Å / cycle or greater, low chemical impurities, and / or high conformality.

[0034] The embodiments of the present invention may be used alone or in combination with each other. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0035] All references cited in this specification, including publications, patent applications, and patents, are herein incorporated by reference to the same extent as if each reference was individually and specifically indicated to be incorporated by reference and was set forth in its entirety herein.

[0036] In the context of describing the present invention (particularly in the context of the claims below), the use of the terms "a" and "an" and "the" and similar referents should be construed to include both the singular and the plural unless specifically stated otherwise or clearly contradicted by context. Unless specifically stated otherwise, the terms "comprising," "having," "including," and "containing" should be construed as open ended (i.e., meaning "including, but not limited to") unless otherwise indicated. The recitation of ranges of values ​​herein is intended only to serve as a shorthand method of individually referring to each individual value falling within the range, unless specifically stated otherwise, and each individual value is incorporated into the specification as if it were individually set forth herein. All methods described herein can be performed in any suitable order unless specifically indicated otherwise herein or clearly contradicted by context. The use of all examples or exemplary language (e.g., "etc.") provided herein is intended only to better illustrate the invention and does not limit the scope of the invention unless specifically claimed. No language in the specification should be construed as indicating any non-claimed element as essential to the practice of the invention.

[0037] The preferred embodiments of the invention described herein are illustrative and not limiting of the scope of the invention. Variations of these preferred embodiments will become apparent to those skilled in the art upon reading the foregoing description. The inventors contemplate that such variations may be used by those skilled in the art as appropriate, and intend the invention to be practiced otherwise than as specifically described herein. Thus, the present invention includes all modifications and equivalents of the subject matter recited in the claims appended hereto as permitted by applicable law. Moreover, any combination of the above-described elements in all possible variations thereof is encompassed by the invention unless otherwise expressly indicated or clearly contradicted by context.

[0038] Described herein are methods for forming stoichiometric or non-stoichiometric films or materials comprising silicon, such as, but not limited to, silicon oxide, carbon-doped silicon oxide films, silicon oxynitride, silicon nitride, carbon-doped silicon nitride, carbon-doped silicon oxynitride films, or combinations thereof, at one or more temperatures below about 600° C., or from about 25° C. to about 600° C., and in some embodiments from 25° C. to about 300° C. The films described herein are deposited by atomic layer deposition (ALD) or ALD-like processes, such as, but not limited to, plasma enhanced ALD (PEALD), or deposition processes such as plasma enhanced cyclic chemical vapor deposition (PECCVD), flowable chemical vapor deposition (FCVD), or plasma enhanced flowable chemical vapor deposition (PEFCVD). The low temperature (e.g., one or more deposition temperatures ranging from about ambient to 600° C.) deposition methods described herein provide films or materials that exhibit at least one or more of the following advantages: a density of about 2.1 g / cc or greater, low chemical impurities, high conformality in thermal atomic layer deposition, plasma-enhanced atomic layer deposition (ALD) processes, or plasma-enhanced ALD-like processes; the ability to tailor the carbon content of the resulting film; and / or an etch rate of 5 angstroms per second (Å / sec) or less, as measured in 0.5% by weight dilute HF. In the case of carbon-doped silicon oxide films, for example, greater than 1% carbon is desirable to tailor the etch rate to values ​​less than 2 Å / sec in 0.5% by weight dilute HF, in addition to other properties such as, but not limited to, a density of about 1.8 g / cc or greater or about 2.0 g / cc or greater.

[0039] The present invention can be practiced using equipment known in the art, for example, the method of the present invention can use reactors commonly used in the semiconductor manufacturing industry.

[0040] In one embodiment, the silicon precursor composition described herein comprises at least one functionalized cyclosilazane having the following formula A, B, C, D, or E: [ka] During the ceremony, R 1-3 are each independently selected from the group consisting of hydrogen, methyl, and an organic amino group (NR′R″), where R′ and R″ are each independently selected from the group consisting of hydrogen, C 1-10 Straight chain alkyl group, C 3-10 Branched alkyl group, C 3-10 Cyclic alkyl groups, C 2-10 Alkenyl group, C 4-10 Aryl groups, and C 4-10 heterocyclic groups, with the proviso that R′ and R″ cannot both be hydrogen; R 4 and R 5 are each independently hydrogen, C 1-10 Straight chain alkyl group, C 3-10 Branched alkyl group, C 3-10 Cyclic alkyl groups, C 2-10 Alkenyl group, C 4-10 Aryl groups, and C 4-10 R is selected from the group consisting of heterocyclic groups; 6-8 are each independently hydrogen, methyl, an organic amino group (NR′R″) as defined above, C 3-10 Branched alkyl group, C 3-10 Cyclic alkyl groups, C 2-10 Alkenyl group, C 4-10 Aryl groups, and C 4-10 heterocyclic groups, with the proviso that R′ and R″ cannot both be hydrogen, and the substituent R 1-8 Two or more of R, R', and R'' may combine to form a substituted or unsubstituted, saturated or unsaturated cyclic group; R 6-8 At least one of must be hydrogen, and R 6-8 At least two of the groups may not be methyl.

[0041] In certain embodiments, the composition described herein further comprises solvent.Exemplary solvents include, but are not limited to, ether, tertiary amine, alkyl hydrocarbon, aromatic hydrocarbon, tertiary amino ether, and combinations thereof.In certain embodiments, the difference between the boiling point of silicon precursor and the boiling point of solvent is 40 ℃ or less.

[0042] In the above formula and throughout the description, the term "alkyl" refers to a straight or branched chain functional group having 1 to 10 carbon atoms. Exemplary straight chain alkyl groups include, but are not limited to, methyl, ethyl, propyl, butyl, pentyl, and hexyl groups. Exemplary branched alkyl groups include, but are not limited to, isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, tert-pentyl, isohexyl, and neohexyl. In certain embodiments, the alkyl group can have one or more functional groups attached thereto, such as, but not limited to, an alkoxy group, a dialkylamino group, or a combination thereof. In other embodiments, the alkyl group does not have one or more functional groups attached thereto. The alkyl group can be saturated or unsaturated.

[0043] In the above formula and throughout the description, the term "cyclic alkyl" refers to a cyclic functional group having 3 to 10 carbon atoms. Exemplary cyclic alkyl groups include, but are not limited to, cyclobutyl, cyclopentyl, cyclohexyl, and cyclooctyl groups.

[0044] In the above formula and throughout the description, the term "alkenyl group" means a group having one or more carbon-carbon double bonds and having 2 to 10 or 2 to 6 carbon atoms.

[0045] Throughout the above formulas and descriptions, the term "dialkylamino or alkylamino" refers to a group having two alkyl groups attached to the nitrogen atom or one alkyl group attached to the nitrogen atom and having 1-10, 2-6, or 2-4 carbon atoms. Examples include, but are not limited to, HNMe, HNBu. t , NMe2, NMeEt, NEt2, NPr i 2 is an example.

[0046] In the above formula and throughout the description, the term "aryl" refers to an aromatic cyclic functional group having 4 to 10 carbon atoms, 5 to 10 carbon atoms, or 6 to 10 carbon atoms. Exemplary aryl groups include, but are not limited to, phenyl, benzyl, chlorobenzyl, tolyl, o-xylyl, 1,2,3-triazolyl, pyrrolyl, and furanyl.

[0047] In the above formula and throughout the description, the term "heterocyclic" refers to a non-aromatic saturated monocyclic or polycyclic ring system of about 3 to about 10 ring atoms, preferably about 5 to about 10 ring atoms, where one or more atoms of the ring system is an element other than carbon, such as nitrogen, oxygen, or sulfur. Preferred heterocycles contain about 5 to about 6 ring atoms. The prefix aza, oxa, or thia before a heterocycle means that at least a nitrogen, oxygen, or sulfur atom, respectively, is present as a ring atom. Heterocyclic groups are optionally substituted.

[0048] Exemplary functionalized cyclosilazane precursors are listed in Table 1: [Table 1-1] [Table 1-2]

[0049] In another embodiment of the present invention, a method for depositing a silicon-containing film on at least one surface of a substrate is described, the method comprising the steps of: a. providing a substrate in a reactor; b. introducing into a reactor at least one silicon precursor having formulae A to E as defined above; c. purging the reactor with a purge gas; d. introducing an oxygen-containing source containing a plasma into the reactor; and e. purging the reactor with a purge gas.

[0050] In this method, steps b through e are repeated until a film of the desired thickness is deposited on the substrate.

[0051] The methods of the invention are carried out via an ALD process using an oxygen-containing source including ozone or a plasma, where the plasma can further include an inert gas and can be one or more of the following: oxygen plasma with or without an inert gas, water vapor plasma with or without an inert gas, nitrogen oxide (e.g., NO, NO) plasma with or without an inert gas, carbon oxide (e.g., CO, CO) plasma with or without an inert gas, and combinations thereof.

[0052] The oxygen-containing plasma source can be generated in situ or remotely. In one particular embodiment, the oxygen-containing source contains oxygen and is flowable or is introduced during steps b-d of the method together with other reagents, such as, but not limited to, at least one silicon precursor and optionally an inert gas.

[0053] In certain embodiments, the silicon precursor compounds having formulae A-E according to the present invention and compositions comprising the silicon precursor compounds having formulae A-E according to the present invention are preferably substantially free of halide ions. The term "substantially free" as used herein means less than 5 ppm (by mass), preferably less than 3 ppm, more preferably less than 1 ppm, and most preferably 0 ppm, as measured by ICP-MS, for halide ions (or halides), such as chloride, fluoride, bromide, and iodide. Impurities including chloride are known to act as decomposition catalysts for silicon precursor compounds having formulae A-E. In some cases, significant levels of chloride in the final product may cause the decomposition of the silicon precursor compounds. The gradual degradation of silicon precursor compounds can directly affect the film deposition process, making it difficult for semiconductor manufacturers to meet film specifications. Furthermore, shelf life or stability is adversely affected by the higher decomposition rate of silicon precursor compounds, making it difficult to guarantee a shelf life of 1 to 2 years. Accelerated decomposition of silicon precursor compounds therefore presents safety and performance issues associated with the formation of these flammable and / or pyrophoric gas by-products.

[0054] In embodiments in which at least one silicon precursor having formulas A-E is used in a composition containing a solvent, the selected solvent or mixture thereof does not react with the silicon precursor. The amount (wt%) of the solvent in the composition ranges from 0.5 wt% to 99.5 wt%, or from 10 wt% to 75 wt%. In this or other embodiments, the solvent has a boiling point (bp) similar to that of the silicon precursor of formulas A-E, or the difference between the boiling point of the solvent and the boiling point of the silicon precursor of formulas A-E is 40°C or less, 30°C or less, or 20°C or less, or 10°C. Alternatively, the difference between the boiling points ranges from any one or more of the following endpoints: 0, 10, 20, 30, or 40°C. Examples of suitable ranges of boiling point difference include, but are not limited to, 0°C to 40°C, 20°C to 30°C, or 10°C to 30°C. Examples of suitable solvents in the composition include, but are not limited to, ethers (e.g., 1,4-dioxane, dibutyl ether), tertiary amines (e.g., pyridine, 1-methylpiperidine, 1-ethylpiperidine, N,N'-dimethylpiperazine, N,N,N',N'-tetramethylethylenediamine), nitriles (e.g., benzonitrile), alkyl hydrocarbons (e.g., octane, nonane, dodecane, ethylcyclohexane), aromatic hydrocarbons (e.g., toluene, mesitylene), tertiary amino ethers (e.g., bis(2-dimethylaminoethyl) ether), or mixtures thereof.

[0055] Throughout this description, the term "ALD or ALD-like" refers to a process that includes, but is not limited to, the following steps: a) a process in which reactants including a silicon precursor and a reactive gas are introduced sequentially into a reactor, such as a single-wafer ALD reactor, a semi-batch ALD reactor, or a batch furnace ALD reactor; b) a process in which reactants including a silicon precursor and a reactive gas are exposed to the substrate by moving or rotating the substrate into different compartments of the reactor, each compartment being separated by an inert gas curtain, i.e., a spatial ALD reactor or a roll-to-roll ALD reactor.

[0056] In certain embodiments, the silicon oxide film or carbon-doped silicon oxide film deposited using the methods described herein is formed in the presence of an oxygen-containing source including ozone, water (H2O) (e.g., deionized water, purified water, and / or distilled water), oxygen (O2), oxygen plasma, NO, NO2O, NO2, carbon monoxide (CO), carbon dioxide (CO2), and combinations thereof. The oxygen-containing source may be, for example, an in-situ or remote plasma generator that provides an oxygen-containing plasma source, such as oxygen plasma, plasma containing oxygen and argon, plasma containing oxygen and helium, ozone plasma, water plasma, nitrous oxide plasma, or carbon dioxide plasma. In certain embodiments, the oxygen-containing plasma source includes an oxygen source gas that is introduced into the reactor at a flow rate ranging from about 1 to about 2000 standard cubic centimeters (sccm) or from about 1 to about 1000 sccm. The oxygen-containing plasma source may be introduced for a time period ranging from about 0.1 to about 100 seconds. In one specific embodiment, the oxygen-containing plasma source comprises water having a temperature of 10° C. or greater. In embodiments in which the film is deposited by a PEALD or plasma-enhanced cyclic CVD process, the precursor pulse can have a pulse duration of greater than 0.01 seconds (e.g., from about 0.01 to about 0.1 seconds, from about 0.1 to about 0.5 seconds, from about 0.5 to about 10 seconds, from about 0.5 to about 20 seconds, from about 1 to about 100 seconds), depending on the volume of the ALD reactor, and the oxygen-containing plasma source can have a pulse duration of less than 0.01 seconds (e.g., from about 0.001 to about 0.1 seconds).

[0057] The deposition methods disclosed herein may include one or more purge gases. Purge gases used to purge away unconsumed reactants and / or reaction by-products are inert gases that do not react with the precursors, thereby forming compositions containing the foregoing. Exemplary purge gases include, but are not limited to, argon (Ar), nitrogen (N2), helium (He), neon, hydrogen (H2), and mixtures thereof. In certain embodiments, a purge gas, such as Ar, is supplied to the reactor at a flow rate ranging from about 10 to about 2000 sccm for about 0.1 to 1000 seconds, thereby purging away unreacted materials and by-products that may remain in the reactor.

[0058] Each step of supplying the precursor, oxygen source, and / or other precursors, source gases, and / or reagents can be performed by varying the time for which they are supplied to vary the stoichiometric composition of the resulting dielectric film.

[0059] Energy is added to at least one of the silicon precursors of formulas A-E, an oxygen-containing source, or a combination thereof to induce a reaction and form a dielectric film or coating on the substrate. Such energy can be provided by, but is not limited to, heat, plasma, pulsed plasma, helicon plasma, high density plasma, inductively coupled plasma, X-ray, electron 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 where deposition involves plasma, the plasma generation process can include a direct plasma generation process in which the plasma is generated directly in the reactor, or alternatively, a remote plasma generation process in which the plasma is generated outside the reactor and fed into the reactor.

[0060] At least one silicon precursor can be delivered to a reaction chamber, such as a plasma-enhanced cyclic CVD or PEALD reactor or a batch furnace type reactor, in various ways. In one embodiment, a liquid delivery system can be utilized. In another embodiment, a process unit combining liquid delivery and flash vaporization, such as a turbo vaporizer manufactured by MSP Corporation of Shoreview, Minnesota, can be used to provide low volatility material in a volumetric manner, which can result in reproducible transport and deposition without precursor thermal decomposition. In liquid delivery formulations, the precursors described herein can be delivered in pure liquid form or used in solvent formulations or compositions containing the same. Thus, in certain embodiments, precursor formulations can include solvent components with suitable properties that may be desirable and advantageous in a given end use application for forming a film on a substrate.

[0061] As mentioned above, the purity level of at least one silicon precursor is high enough to be acceptable for reliable semiconductor manufacturing.In certain embodiments, at least one silicon precursor described herein contains 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 amine, free halide or halide ion, and high molecular weight species.Higher purity levels of the silicon precursor described herein can be obtained through one or more processes of purification, adsorption, and / or distillation.

[0062] In one embodiment of the method described herein, a plasma-enhanced cyclic deposition process such as PEALD-like or PEALD can be used, in which deposition is performed using at least one silicon precursor and an oxygen plasma source. PEALD-like processes, defined as plasma-enhanced cyclic CVD processes, provide highly conformal silicon and oxygen-containing films.

[0063] In certain embodiments, the gas line connecting precursor canister to reaction chamber is heated to one or more temperatures according to process requirements, and the container of at least one silicon precursor is maintained at one or more temperatures for bubbling.In other embodiments, the solution containing at least one silicon precursor is injected into a vaporizer that is maintained at one or more temperatures for direct liquid injection.

[0064] A flow of argon and / or other gases can be used as carrier gas to help supply at least one silicon precursor vapor to reaction chamber during precursor pulse.In certain embodiments, the process pressure of reaction chamber is about 50 mTorr to 10 Torr.In other embodiments, the process pressure of reaction chamber can be up to 760 Torr (for example, about 50 mTorr to about 100 Torr).

[0065] In a typical PEALD or PEALD-like process, such as a PECCVD process, a substrate, such as a silicon oxide substrate, is first heated on a heater pedestal within a reaction chamber where it is exposed to a silicon precursor, allowing complexes to chemisorb onto the surface of the substrate.

[0066] A purge gas such as argon purges the excess unabsorbed complex from the process chamber. After sufficient purging, an oxygen source can be introduced into the reaction chamber to react with the absorbed surface, followed by another gas purge to remove reaction by-products from the chamber. This process cycle can be repeated to achieve a desired film thickness. In some cases, a pump can be used instead of purging with an inert gas, or both, to remove unreacted silicon precursor.

[0067] In this or other embodiments, the steps of the methods described herein can be performed in various orders, either sequentially or simultaneously (e.g., during at least a portion of another step), or any combination thereof. Each step of supplying a precursor and an oxygen source gas can be performed to modify the stoichiometric composition of the resulting dielectric film, for example, by varying the length of time for which they are supplied. Also, purge times after a precursor or oxidizer step can be minimized to less than 0.1 seconds, thereby improving throughput.

[0068] In one specific embodiment, the method described herein deposits a high quality silicon-containing film, e.g., a silicon and oxygen-containing film, on a substrate. The method comprises the steps of: a. providing a substrate in a reactor; b. introducing at least one silicon precursor having the above formulae A-E into a reactor; c. purging the reactor with a purge gas to remove at least a portion of the unabsorbed precursor; d. introducing an oxygen-containing plasma source into the reactor; e. purging the reactor with a purge gas to remove at least a portion of the unreacted oxygen source; Now, steps b through e are repeated until a silicon-containing film of the desired thickness is deposited.

[0069] Another method disclosed herein uses silicon precursor compounds having chemical structures represented by Formulas A-E defined above and an oxygen source to form carbon-doped silicon oxide films.

[0070] Another exemplary process is described as follows: a. providing a substrate in a reactor; b. contacting vapor generated from at least one silicon precursor compound having a structure represented by Formulae A-E as defined above, with or without co-flow of an oxygen source, onto a heated substrate to chemically adsorb the precursor; c. purging away any unabsorbed precursor; d. introducing an oxygen source to the heated substrate to react with the absorbed precursor; e. purging away unreacted oxygen source; Now steps b through e are repeated until the desired thickness is achieved.

[0071] In another particular embodiment, the method described herein deposits a high quality silicon-containing film, such as, for example, a silicon nitride film, on a substrate. The method comprises the steps of: a. providing a substrate in a reactor; b. introducing at least one silicon precursor having the above formulae A-E into a reactor; c. purging the reactor with a purge gas to remove at least a portion of the unabsorbed precursor; d. introducing a nitrogen-containing plasma source into the reactor; e. purging the reactor with a purge gas to remove at least a portion of the unreacted nitrogen source; Now, steps b through e are repeated until a silicon-containing film of the desired thickness is deposited.

[0072] Another exemplary process is described as follows. a. providing a substrate in a reactor; b. contacting a vapor generated from at least one silicon precursor compound having a structure represented by Formulas A-E as defined above, with or without co-flow of a nitrogen source, with a heated substrate so as to chemically adsorb the precursor; c. purging to remove unabsorbed precursor; d. introducing a nitrogen-containing plasma source to the heated substrate to react with the absorbed precursor; e. purging away unreacted nitrogen source; Now steps b through e are repeated until the desired thickness is deposited.

[0073] A variety of commercial ALD reactors, such as single wafer, semi-batch, batch furnace, or roll-to-roll reactors, can be used to deposit solid silicon oxide, silicon nitride, silicon oxynitride, carbon-doped silicon nitride, carbon-doped silicon oxynitride, or carbon-doped silicon oxide.

[0074] The process temperatures of the methods described herein may use one or more of the following temperatures as endpoints: 0, 25, 50, 75, 100, 125, 150, 175, 200, 225, 250, 275, 300°C, 325°C, 350°C, 375°C, 400°C, 425°C, 450°C, 500°C, 525°C, 550°C. Exemplary temperature ranges include, but are not limited to, about 0°C to about 300°C, or about 25°C to about 300°C, or about 50°C to about 290°C, or about 25°C to about 250°C, or about 25°C to about 200°C.

[0075] In another aspect, a method for depositing a silicon-containing film by flowable chemical vapor deposition (FCVD) is provided, the method comprising: placing a substrate having surface features in a reactor, the substrate being maintained at one or more temperatures ranging from about −20° C. to about 400° C. and the reactor pressure being maintained at or below 100 Torr; introducing at least one compound selected from the group consisting of formulae A to E; providing an oxygen source to the reactor to react with the at least one compound to form a film and cover at least a portion of the surface features; annealing the film at one or more temperatures in the range of about 100° C. to 1000° C. to coat at least a portion of the surface features; treating the substrate with an oxygen source at one or more temperatures in a range from about 20° C. to about 1000° C. to form a silicon-containing film on at least a portion of the surface features.

[0076] In another aspect, a method for depositing a silicon-containing film by flowable chemical vapor deposition (FCVD) is provided, the method comprising: placing a substrate having surface features in a reactor, the substrate being maintained at one or more temperatures ranging from about −20° C. to about 400° C. and the reactor pressure being maintained at or below 100 Torr; introducing at least one compound selected from the group consisting of formulae A to E; providing a nitrogen source to the reactor to react with the at least one compound to form a film and cover at least a portion of the surface features; annealing the film at one or more temperatures in the range of about 100° C. to 1000° C. to coat at least a portion of the surface features; treating the substrate with an oxygen source at one or more temperatures in a range from about 20° C. to about 1000° C. to form a silicon-containing film on at least a portion of the surface features.

[0077] In certain embodiments, the oxygen source is selected from the group consisting of water vapor, water plasma, ozone, oxygen, oxygen plasma, oxygen / helium plasma, oxygen / argon plasma, nitrogen oxide plasma, carbon dioxide plasma, hydrogen peroxide, organic peroxide, and mixtures thereof.In other embodiments, the nitrogen source is selected from the group consisting of, for example, ammonia, hydrazine, monoalkylhydrazine, dialkylhydrazine, nitrogen, nitrogen / hydrogen, nitrogen / argon plasma, nitrogen / helium plasma, ammonia plasma, nitrogen plasma, nitrogen / hydrogen plasma, organic amines such as tert-butylamine, dimethylamine, diethylamine, isopropylamine, diethylamine plasma, dimethylamine plasma, trimethylamine plasma, trimethylamine plasma, ethylenediamine plasma, and alkoxyamines such as ethanolamine plasma, and mixtures thereof.In yet other embodiments, the nitrogen-containing source comprises ammonia plasma, plasma comprising nitrogen and argon, plasma comprising nitrogen and helium, or plasma comprising hydrogen and nitrogen source gas.In this or other embodiments, the steps of the method are repeated until the surface features are filled with silicon-containing film. In embodiments in which water vapor is used as the oxygen source, the substrate temperature ranges from about -20°C to about 40°C, or from about -10°C to about 25°C.

[0078] In yet another embodiment of the method described herein, the film deposited or as-deposited from ALD, ALD-like, PEALD, PEALD-like, or FCVD is subjected to a treatment step (post-deposition). The treatment step can be performed during at least a portion of the deposition step, after the deposition step, and combinations thereof. Exemplary treatment steps include, but are not limited to, treatment with high temperature thermal annealing, plasma treatment, ultraviolet (UV) treatment, laser, electron beam treatment, and combinations thereof to affect one or more properties of the film.

[0079] Films deposited with silicon precursors having formulas A-E described herein have improved properties, such as, but not limited to, a wet etch rate lower than the wet etch rate of the film before the treatment step, or a density higher than the density before the treatment step, when compared to films deposited with silicon precursors previously disclosed under the same conditions. In one specific embodiment, the as-deposited film is treated intermittently during the deposition process. These intermittent or inter-deposition treatments can be performed, for example, after each ALD cycle, after a certain number of ALD cycles, such as, but not limited to, after 1 ALD cycle, 2 ALD cycles, 5 ALD cycles, or 10 or more ALD cycles.

[0080] Precursors of formulas A-E exhibit growth rates of 1.0 Å / cycle or greater, preferably 1.5 Å / cycle or greater, and most preferably 2.0 Å / cycle or greater.

[0081] In embodiments in which the film is subjected to a high temperature annealing step, the annealing temperature is at least 100° C. higher than the deposition temperature. In this or other embodiments, the annealing temperature ranges from about 400° C. to about 1000° C. In this or other embodiments, the annealing process can be performed in a vacuum (<760 Torr), in an inert environment, or in an oxygen-containing environment (such as HO, NO, NO, or O, etc.).

[0082] In embodiments in which the film is UV treated, the film is exposed to broadband UV, or alternatively to a UV source having a wavelength in the range of about 150 nanometers (nm) to about 400 nm. In one specific embodiment, after the desired film thickness is reached, the as-deposited film is exposed to UV in a chamber separate from the deposition chamber.

[0083] In embodiments in which the film is treated with plasma, a passivation layer, such as SiO2 or carbon-doped SiO2, is deposited to prevent chlorine and nitrogen contamination from penetrating the film during subsequent plasma treatment. The passivation layer can be deposited using atomic layer deposition or cyclic chemical vapor deposition.

[0084] In embodiments in which the film is treated with a plasma, the plasma source is selected from the group consisting of a hydrogen plasma, a hydrogen and helium-containing plasma, and a hydrogen and argon-containing plasma. The hydrogen plasma lowers the dielectric constant of the film and increases its damage resistance to a subsequent plasma ashing process, while keeping the carbon content in the bulk essentially unchanged.

[0085] Without intending to be bound by any particular theory, it is believed that silicon precursor compounds having the chemical structures shown in formulas A-E defined above can anchor by breaking Si-N bonds, organoaminosilyl groups, or silazane groups with hydroxyls on the substrate surface to provide Si-O-Si' fragments, where the Si' fragments are bonded to nitrogen atoms that are part of a six-membered ring containing at least two additional silicon atoms, thus increasing the growth rate of silicon oxide or carbon-doped silicon oxide compared to conventional silicon precursors having only one silicon atom, such as bis(tert-butylamino)silane or bis(diethylamino)silane. Using functionalized cyclosilazanes having formulas A-E, as many as 3-6 silicon atoms per molecule can be anchored to the substrate during the silicon precursor pulsing step.

[0086] In certain embodiments, silicon precursors having formulas A-E as defined above can also be used as dopants for metal-containing films, such as, but not limited to, metal oxide or metal nitride films. In these embodiments, the metal-containing films are deposited using ALD or CVD processes, such as those described herein, using metal alkoxides, metal amides, or volatile organometallic precursors. Examples of suitable metal alkoxide precursors that can be used in the methods disclosed herein include, but are not limited to, Group 3-6 metal alkoxides, Group 3-6 metal complexes having both alkoxy and alkyl-substituted cyclopentadienyl ligands, Group 3-6 metal complexes having both alkoxy and alkyl-substituted pyrrolyl ligands, Group 3-6 metal complexes having both alkoxy and diketonate ligands, and Group 3-6 metal complexes having both alkoxy and ketoester ligands.

[0087] Examples of suitable metal amide precursors that may be used in the methods disclosed herein include, but are not limited to, tetrakis(dimethylamino)zirconium (TDMAZ), tetrakis(diethylamino)zirconium (TDEAZ), tetrakis(ethylmethylamino)zirconium (TEMAZ), tetrakis(dimethylamino)hafnium (TDMAH), tetrakis(diethylamino)hafnium (TDEAH), tetrakis(ethylmethylamino)hafnium (TEMAH), tetrakis(dimethylamino)titanium (TDMAT), tetrakis(diethylamino)titanium (TDEAT), tetrakis(ethylmethylamino)titanium (TEMAT), tert-butyliminotri(diethylamino)tantalum (TBTDET), tert-butyliminotri(dimethylamino)tantalum (TBTDMT ), tert-butylimino tri(ethylmethylamino)tantalum (TBTEMT), ethylimino tri(diethylamino)tantalum (EITDET), ethylimino tri(dimethylamino)tantalum (EITDMT), ethylimino tri(ethylmethylamino)tantalum (EITEMT), tert-amylimino tri(dimethylamino)tantalum (TAIMAT), tert-amylimino tri(diethylamino)tantalum, pentakis(dimethylamino)tantalum, tert-amylimino tri(ethylmethylamino)tantalum, bis(tert-butylimino)bis(dimethylamino)tungsten (BTBMW), bis(tert-butylimino)bis(diethylamino)tungsten, bis(tert-butylimino)bis(ethylmethylamino)tungsten, and combinations thereof. Examples of suitable organometallic precursors that may be used in the methods disclosed herein include, but are not limited to, Group 3 metal cyclopentadienyls or alkylcyclopentadienyls. Exemplary Group 3-6 metals herein include, but are not limited to, Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Er, Yb, Lu, Ti, Hf, Zr, V, Nb, Ta, Cr, Mo, and W.

[0088] In certain embodiments, the silicon-containing films described herein have a dielectric constant of 6 or less, 5 or less, 4 or less, and 3 or less. In these or other embodiments, the films can have a dielectric constant of about 5 or less, or about 4 or less, or about 3.5 or less. However, it is contemplated that films having other dielectric constants (e.g., higher or lower) may be formed depending on the desired end use of the film. Examples of silicon-containing films formed using the silicon precursors and processes having precursors of formulas A-E described herein include those having the formulas Si x O y C z N v H w where Si ranges from about 10% to about 40%, O ranges from about 0% to about 65%, C ranges from about 0% to about 75% or about 0% to about 50%, N ranges from about 0% to about 75% or about 0% to about 50%, and H ranges from about 0% to about 50% atomic percent by weight, where x+y+z+v+w=100 atomic weight percent. Another example of a silicon-containing film formed using the silicon precursors and processes of formulas A-E described herein is silicon carbonitride having a carbon content of 1 at% to 80 at% as measured by XPS. Yet another example of a silicon-containing film formed using the silicon precursors and processes of formulas A-E described herein is amorphous silicon having a combined nitrogen and carbon content of <10 at%, preferably <5 at%, and most preferably <1 at%, as measured by XPS.

[0089] As mentioned above, the method described herein can be used to deposit a silicon-containing film on at least a portion of a substrate. Examples of suitable substrates include, but are not limited to, silicon, SiO2, Si3N4, OSG, FSG, silicon carbide, hydrogenated silicon carbide, silicon nitride, hydrogenated silicon nitride, silicon carbonitride, hydrogenated silicon carbonitride, boron nitride, anti-reflective coatings, photoresists, germanium, germanium-containing, boron-containing, Ga / As, flexible substrates, organic polymers, porous organic and inorganic materials, metals such as copper and aluminum, and diffusion barrier layers such as, but not limited to, TiN, Ti(C)N, TaN, Ta(C)N, Ta, W, or WN. These films are compatible with various subsequent processing steps, such as chemical mechanical planarization (CMP) and anisotropic etching processes.

[0090] The deposited films have applications including, but not limited to, computer chips, optical devices, magnetic information storage, coatings on supporting materials or substrates, microelectromechanical systems (MEMS), nanoelectromechanical systems, thin film transistors (TFTs), light emitting diodes (LEDs), organic light emitting diodes (OLEDs), IGZO, and liquid crystal displays (LCDs). Potential applications of the resulting solid silicon oxide or carbon doped silicon oxide include, but are not limited to, shallow trench insulation, interlayer dielectrics, passivation layers, etch stop layers, part of a dual spacer, and sacrificial layers for patterning.

[0091] The methods described herein provide high quality silicon oxide, silicon nitride, silicon oxynitride, carbon-doped silicon nitride, carbon-doped silicon oxynitride, or carbon-doped silicon oxide films. The term "high quality" refers to films that exhibit one or more of the following characteristics: a density of about 2.1 g / cc or greater, 2.2 g / cc or greater, 2.25 g / cc or greater; a wet etch rate of 2.5 Å / s or less, 2.0 Å / s or less, 1.5 Å / s or less, 1.0 Å / s or less, 0.5 Å / s or less, 0.1 Å / s or less, 0.05 Å / s or less, 0.01 Å / s or less, when measured in a solution of dilute HF (0.5 wt. % dHF) acid in 1:100 HF:water; -8 A / cm 2 or less; hydrogen impurities of about 5 × 10 20 at / cc or less; and combinations thereof. With regard to etch rate, thermally grown silicon oxide films have an etch rate of 0.5 Å / s in 0.5 wt % Hf.

[0092] In certain embodiments, one or more silicon precursors having formulas A-E described herein can be used to form solid, non-porous or substantially pore-free silicon and oxygen-containing films.

[0093] The following examples illustrate methods of depositing silicon oxide films described herein and are not intended to limit the scope of the appended claims. EXAMPLES

[0094] Thermal atomic layer deposition of silicon oxide films was carried out in a laboratory-scale ALD processing tool. Silicon precursors were delivered to the chamber by drawing vapor. All gases (e.g., purge and reactant gases or precursors and oxygen source) were preheated to 100 °C before entering the deposition zone. Gas and precursor flow rates were controlled by fast-acting ALD diaphragm valves. The substrates used for deposition were 12-inch long silicon strips. Thermocouples were attached to the sample holder to check the substrate temperature. Deposition was performed using ozone as the oxygen source gas. The typical deposition process and parameters are shown in Table 2. [Table 2]

[0095] Plasma-enhanced ALD (PEALD) was performed in a commercial lateral flow reactor (a 300 mm PEALD unit manufactured by ASM) equipped with 27.1 MHz direct plasma capability with a fixed spacing of 3.5 mm between the electrodes. The laminar flow chamber design uses an outer and inner chamber with independent pressure settings. The inner chamber is the deposition reactor, where all reactant gases (precursors, argon, etc.) are mixed in a manifold and delivered to the process reactor. Argon gas was used to maintain the reactor pressure in the outer chamber. The precursors were liquids maintained in stainless steel bubblers and delivered to the chamber with Ar carrier gas (typically set at a flow rate of 200 sccm). All depositions reported in this study were performed on Si substrates containing native oxide, with a resistivity of 8–12 ohm-cm. Film thickness and refractive index were measured using a FilmTek 2000SE ellipsometer. Growth rate per cycle (GPC) is calculated by dividing the measured thickness of the resulting silicon oxide film by the total number of ALD / PEALD cycles.

[0096] Example 1: Synthesis of 1-(dimethylaminomethylsilyl)-2,2,4,4,6,6-hexamethylcyclotrisilazane (hypothetical example) In a round-bottom flask, 1-methylsilyl-2,2,4,4,6,6-hexamethylcyclotrisilazane is mixed with dimethylamine in THF solvent. With stirring, 1 mol% of Ru3(CO) 12 A catalyst is added. The reaction mixture is stirred at room temperature for 1 day while venting the H2 gas by-product. The reaction mixture is purified by vacuum distillation to give 1-(dimethylaminomethylsilyl)-2,2,4,4,6,6-hexamethylcyclotrisilazane.

[0097] Example 2: Synthesis of 2-dimethylamino-1,2,3,4,5,6-hexamethylcyclotrisilazane 1,2,3,4,5,6-Hexamethylcyclotrisilazane (200 g, 0.91 mmol) and Ru(CO) were stirred in a 1 L round-bottom flask. 12 To a mixture of catalyst (1.45 g, 0.00227 mol) was added dimethylamine (230 mL of a 2.0 M solution in THF, 0.46 mol) in three portions over 6 h. The reaction mixture was stirred at room temperature for 1 day while venting H2 gas by-product. Volatiles were vacuum transferred in a flask-to-flask apparatus with a receiver flask cooled to -78 °C. Condensed volatiles were purified by vacuum distillation to give 2-dimethylamino-1,2,3,4,5,6-hexamethylcyclotrisilazane. GC-MS showed the following peaks: 262 (M+), 247 (M-15), 231, 218, 202, 189, 175, 159, 145, 131, 118, 102, 88, 72.

[0098] Example 3: Synthesis of 1,2,3-trisilyl-2,2,4,4,6,6-hexamethylcyclotrisilazane (hypothetical example) 2,2,4,4,6,6-Hexamethylcyclotrisilazane is mixed with 3 equivalents of triethylamine in hexane solvent and cooled to -50°C. Then 3 equivalents of monochlorosilane are slowly condensed into the reaction vessel with stirring at -50°C. The resulting slurry is slowly warmed to room temperature with stirring. The solids are removed by filtration and the solvent and other low boilers are removed under reduced pressure. The crude product is purified by vacuum distillation to give 1,2,3-trisilyl-2,2,4,4,6,6-hexamethylcyclotrisilazane.

[0099] Example 4: Synthesis of 2,2,4,4,5,6,6-heptamethyl-1,3-dioxa-5-aza-2,4,6-trisilacyclohexane (hypothetical example) 1,1,1,2,3,3,3-heptamethyldisilazane is mixed with one equivalent of 1,5-dichloro-1,1,3,3,5,5-hexamethyltrisiloxane in the presence of a catalytic amount of pyridine. After the reaction is judged complete by GC analysis, the crude reaction mixture is purified by vacuum distillation to yield 2,2,4,4,5,6,6-heptamethyl-1,3-dioxa-5-aza-2,4,6-trisilacyclohexane.

[0100] Example 5: Synthesis of 5-(dimethylaminosilyl)-2,2,4,4,6,6-hexamethyl-1,3-dioxa-5-aza-2,4,6-trisilacyclohexane (hypothetical example) Dimethylamine was dissolved in 5-silyl-2,2,4,4,6,6-hexamethyl-1,3-dioxa-5-aza-2,4,6-trisilacyclohexane and 0.1 mol% of Ru(CO) as a 2.0 M solution in THF. 12 Add to the stirred mixture of catalyst. Stir the mixture at room temperature for 1 day and vent the H2 gas by-product. Purify the reaction mixture by vacuum distillation to obtain 5-(dimethylaminosilyl)-2,2,4,4,6,6-hexamethyl-1,3-dioxa-5-aza-2,4,6-trisilacyclohexane.

[0101] Example 6: Synthesis of 5-isopropyl-2,2,4,4,6,6-hexamethyl-1,3-dioxa-5-aza-2,4,6-trisilacyclohexane A solution of 1,5-dichloro-1,1,3,3,5,5-hexamethyltrisiloxane (0.5 g, 0.0018 mol) in pentane (5 mL) was added dropwise to a stirred solution of isopropylamine (0.40 g, 0.0068 mol) in pentane (4 mL). The resulting white slurry was stirred overnight. The solids were removed by filtration and the resulting filtrate was determined by GC-MS analysis to contain 5-isopropyl-2,2,4,4,6,6-hexamethyl-1,3-dioxa-5-aza-2,4,6-trisilacyclohexane as one of the products. GC-MS showed the following peaks: 262 (M+), 248, 234, 218, 207, 193, 177, 160, 147, 133, 119, 110, 96, 88, 73.

[0102] Example 7: Synthesis of 5-n-propyl-2,2,4,4,6,6-hexamethyl-1,3-dioxa-5-aza-2,4,6-trisilacyclohexane A solution of n-propylamine (0.30 g, 0.0051 mol) in hexane (4 mL) was added dropwise to a stirred mixture of 5-dichloro-1,1,3,3,5,5-hexamethyltrisiloxane (0.5 g, 0.0018 mol) and triethylamine (0.40 g, 0.0020 mol) in hexane (4 mL). The resulting slurry was stirred overnight. The solids were removed by filtration and the resulting filtrate was determined by GC-MS to contain 5-n-propyl-2,2,4,4,6,6-hexamethyl-1,3-dioxa-5-aza-2,4,6-trisilacyclohexane as one of the products. GC-MS showed the following peaks: 262 (M+), 248, 234, 218, 207, 193, 177, 160, 147, 133, 119, 110, 96, 88, 73.

[0103] Example 8: Synthesis of 1-(diisopropylaminosilyl)-2,2,4,4,6,6-hexamethylcyclotrisilazane Under the protection of nitrogen atmosphere, 116 mL of butyllithium solution (2.5 M in hexane, 0.29 mol) was added dropwise to a stirred solution of 2,2,4,4,6,6-hexamethylcyclotrisilazane (66 g, 0.30 mol) in hexane (140 mL) at −30° C. After the addition was complete, the reaction was allowed to warm to room temperature and stirred for 2 hours. The resulting reaction mixture was then cooled to −30° C. To this mixture, (diisopropylamino)chlorosilane (48 g, 0.29 mol) was added dropwise through a dropping funnel at −30° C. The reaction mixture was allowed to warm to room temperature with stirring. The white solid was removed by filtration and the solvent was removed under reduced pressure. The crude product was purified by vacuum distillation to give the desired product, 1-(diisopropylaminosilyl)-2,2,4,4,6,6-hexamethylcyclotrisilazane. GC-MS showed the following peaks: 349 (M+), 334 (M-15), 318, 306, 292, 276, 248, 234, 218, 203, 188, 175, 159, 142, 130, 116, 100, 86, 73.

[0104] Examples 9-11: Synthesis of further functionalized cyclosilazane precursor compounds Additional functionalized cyclosilazane precursor compounds were prepared in a similar manner to Example 8 and characterized by GC-MS. The molecular weight (MW), structure, and corresponding major MS fragmentation peaks of each compound are shown in Table 3 to support their identification. [Table 3]

[0105] Comparative Example 12a: Thermal atomic layer deposition of silicon oxide films using hexamethyldisilazane (HMDSZ) Atomic layer deposition of silicon oxide films was performed using HMDSZ as the silicon precursor. The deposition was carried out in a laboratory-scale ALD processing system. The silicon precursor was delivered to the chamber by drawing vapor. The deposition process and parameters are shown in Table 2. Steps 1-6 were repeated in cycles multiple times until the desired thickness was reached. The deposition process parameters and results are shown in Table 4. [Table 4]

[0106] Comparative Example 12b: PEALD silicon oxide using hexamethyldisilazane (HMDSZ) in a laminar flow reactor with a 27.1 MHz plasma Deposition was carried out using HMDSZ as the silicon precursor and O2 plasma under the conditions shown in Table 5. HMDSZ was delivered to the chamber with 100 sccm of Ar carrier gas. Steps b-e were repeated multiple times to obtain the desired thickness of silicon oxide for metrology. Film deposition parameters and GPC of deposition and wafer uniformity are shown in Table 6. The deposition wafer shows poor uniformity and very low GPC. [Table 5] [Table 6]

[0107] Example 13: Thermal atomic layer deposition of silicon oxide films using 2,2,4,4,6,6-hexamethylcyclotrisilazane Atomic layer deposition of silicon oxide films was carried out using 2,2,4,4,6,6-hexamethylcyclotrisilazane as the silicon precursor. The deposition was carried out in a laboratory-scale ALD processing equipment. The silicon precursor was delivered to the chamber by drawing vapor. The deposition process and parameters are shown in Table 2. Steps 1-6 were repeated in cycles multiple times until the desired thickness was reached. The deposition process parameters and results are shown in Table 7. [Table 7]

[0108] Example 14: PEALD Silicon Oxide using 2,2,4,4,6,6-Hexamethylcyclotrisilazane in a Laminar Flow Reactor with a 27.1 MHz Plasma Deposition was carried out using 2,2,4,4,6,6-hexamethylcyclotrisilazane as the silicon precursor and O2 plasma under the conditions shown in Table 8. The precursor was delivered to the chamber with a carrier gas Ar flow of 200 sccm. Steps b-e were repeated multiple times to obtain the desired thickness of silicon oxide for measurement. The deposition parameters of the film and the GPC of the deposition are shown in Table 9. It can be seen that the GPC shows saturation for precursor pulses longer than 8 seconds. [Table 8] [Table 9]

[0109] Example 15: PEALD Silicon Oxide Using 1,2,3,4,5,6-Hexamethylcyclotrisilazane in a Laminar Flow Reactor with a 27.1 MHz Plasma Deposition was carried out using 1,2,3,4,5,6-hexamethylcyclotrisilazane as the silicon precursor and O2 plasma under the conditions shown in Table 8. The precursor was delivered to the chamber with a carrier gas Ar flow of 200 sccm. Steps b-e were repeated multiple times to obtain the desired thickness of silicon oxide for measurement. The deposition parameters and GPC of the film are shown in Table 10. [Table 10]

[0110] Example 16: PEALD Silicon Oxide using 1-Dimethylamino-1,2,3,4,5,6-Hexamethylcyclotrisilazane in a Laminar Flow Reactor with a 27.1 MHz Plasma Deposition was carried out using 1-dimethylamino-1,2,3,4,5,6-hexamethylcyclotrisilazane as the silicon precursor and O2 plasma under the conditions shown in Table 8. The precursor was delivered to the chamber with a carrier gas Ar flow of 200 sccm. Steps b-e were repeated multiple times to obtain the desired thickness of silicon oxide for measurement. The deposition parameters and GPC of the film are shown in Table 11. [Table 11]

[0111] Example 17: PEALD Silicon Nitride using 1-Dimethylamino-1,2,3,4,5,6-hexamethylcyclotrisilazane and Ar / N2 Plasma Silicon-containing films were deposited using 1-dimethylamino-1,2,3,4,5,6-hexamethylcyclotrisilazane as the silicon precursor and Ar / N2 plasma. The silicon precursor was delivered from a vessel maintained at 55 °C using 100 sccm of Ar carrier gas. The susceptor temperature was set at 300 °C, and the reactor was equipped with parallel plate in-situ electrodes. The plasma frequency and power were 13.56 MHz and 200 W, respectively. The deposition process steps were carried out as described in Table 12, and steps b to e were repeated multiple times to obtain the desired thickness of silicon oxide for measurement. [Table 12] The resulting deposited film had a GPC of 0.24 A / cycle and a refractive index of 1.97.

[0112] The foregoing description is primarily for purposes of illustration, and while the invention has been shown and described with respect to illustrative embodiments thereof, it will be understood by those skilled in the art that the foregoing and various other changes, omissions, and additions in form and detail of the invention may be made therein without departing from the spirit and scope of the invention.

Claims

1. A silicon precursor compound of formula D: 【Chemistry 1】 During the ceremony, R １－３ are each independently selected from the group consisting of hydrogen, methyl, and an organic amino group (NR′R″), where R′ and R″ are each independently selected from the group consisting of hydrogen, C １－１０ Straight chain alkyl group, C ３－１０ Branched alkyl group, C ３－１０ Cyclic alkyl group, C ２－１０ Alkenyl group, C ４－１０ Aryl groups, and C ４－１０ heterocyclic groups, with the proviso that R′ and R″ cannot both be hydrogen; R ５ are independently hydrogen, C １－１０ Straight chain alkyl group, C ３－１０ Branched alkyl group, C ３－１０ Cyclic alkyl group, C ２－１０ Alkenyl group, C ４－１０ Aryl groups, and C ４－１０ heterocyclic groups; Here, the substituent R 1-3，5 two or more of R, R', and R'' may combine to form a substituted or unsubstituted, saturated or unsaturated cyclic group; Silicon precursor compounds.

2. A composition comprising the silicon precursor compound of claim 1 and at least one purge gas.

3. The silicon precursor compound of formula D is 2,2,4,4,6,6-hexamethyl-1,3-dioxa-5-aza-2,4,6-trisilacyclohexane, 2,2,4,4,5,6,6-heptamethyl-1,3-dioxa-5-aza-2,4,6-trisilacyclohexane, 5-ethyl-2,2,4,4,6,6-hexamethyl-1,3-dioxa-5-aza-2,4,6-trisilylcyclohexane, 2. The silicon precursor compound of claim 1, comprising at least one selected from the group consisting of 5-n-propyl-2,2,4,4,6,6-hexamethyl-1,3-dioxa-5-aza-2,4,6-trisilacyclohexane, 5-n-propyl-2,2,4,4,6,6-hexamethyl-1,3-dioxa-5-aza-2,4,6-trisilacyclohexane, and 5-isopropyl-2,2,4,4,6,6-hexamethyl-1,3-dioxa-5-aza-2,4,6-trisilacyclohexane.

4. 1. A method for depositing a silicon-containing film on a substrate, comprising: a) providing a substrate in a reactor; b) introducing at least one silicon precursor compound according to claim 1 into a reactor; c) purging the reactor with a purge gas; d) introducing an oxygen-containing source or a nitrogen-containing source (or a combination thereof) into the reactor; e) purging the reactor with a purge gas; where steps b through e are repeated until a film of the desired thickness is deposited, and The method is carried out at one or more temperatures ranging from about 25° C. to 600° C. method.

5. 5. The method of claim 4, wherein the silicon precursor compound is selected from the group consisting of 2,2,4,4,6,6-hexamethyl-1,3-dioxa-5-aza-2,4,6-trisilacyclohexane, 2,2,4,4,5,6,6-heptamethyl-1,3-dioxa-5-aza-2,4,6-trisilacyclohexane, 5-ethyl-2,2,4,4,6,6-hexamethyl-1,3-dioxa-5-aza-2,4,6-trisilacyclohexane, 5-n-propyl-2,2,4,4,6,6-hexamethyl-1,3-dioxa-5-aza-2,4,6-trisilacyclohexane, and 5-isopropyl-2,2,4,4,6,6-hexamethyl-1,3-dioxa-5-aza-2,4,6-trisilacyclohexane.

6. 5. The method of claim 4, wherein the oxygen-containing source is selected from the group consisting of ozone, oxygen plasma, plasma comprising oxygen and argon, plasma comprising oxygen and helium, ozone plasma, water plasma, nitrous oxide plasma, carbon dioxide plasma, and combinations thereof.

7. 5. The method of claim 4, wherein the nitrogen-containing source is selected from the group consisting of ammonia, hydrazine, monoalkylhydrazine, dialkylhydrazine, nitrogen, nitrogen / hydrogen, nitrogen / argon plasma, nitrogen / helium plasma, ammonia plasma, nitrogen plasma, nitrogen / hydrogen plasma, organic amines such as tert-butylamine, dimethylamine, diethylamine, isopropylamine, diethylamine plasma, dimethylamine plasma, trimethylamine plasma, trimethylamine plasma, ethylenediamine plasma, and alkoxyamines such as ethanolamine plasma, and mixtures thereof.

8. The method of claim 4 , wherein the oxygen-containing source and / or the nitrogen-containing source comprises a plasma.

9. The method of claim 8 , wherein the plasma is generated in situ.

10. The method of claim 8 , wherein the plasma is generated remotely.

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

12. The method of claim 4 , wherein the film further comprises carbon.

13. The method of claim 4 , wherein the film has a density of about 1.8 g / cc or greater.

14. 5. The method of claim 4, wherein the carbon content of the film is greater than or equal to 0.5 atomic weight percent (at. %) as measured by x-ray photospectroscopy.

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