Halide-functionalized cyclotrisilazanes as precursors for the deposition of silicon-containing films

Abstract

Halide-functionalized cyclotrisilazane precursor compounds according to formulas A and B and methods of using same to deposit silicon-containing films, such as silicon oxide, silicon nitride, silicon oxynitride, silicon carbonitride, silicon oxycarbonitride, or carbon-doped silicon oxide, via thermal atomic layer deposition (ALD) or plasma-enhanced atomic layer deposition (PEALD) processes, and combinations thereof. JPEG2025504911000016.jpg47128

Description

[Technical field]

[0001] Described herein are halide-functionalized cyclotrisilazane precursor compounds, compositions comprising same, and methods for depositing silicon-containing films, such as, but not limited to, silicon oxide, silicon nitride, silicon oxynitride, silicon carbonitride, silicon oxycarbonitride, and carbon-doped silicon oxide, via thermal atomic layer deposition (thermal ALD) or plasma-enhanced atomic layer deposition (PEALD) processes, or combinations thereof. The silicon-containing films may be stoichiometric or non-stoichiometric silicon-containing films or materials, and may be deposited at one or more deposition temperatures up to about 600°C, including, for example, temperatures ranging from about 25°C to about 300°C. [Background technology]

[0002] ALD and PEALD are processes used to deposit silicon oxide conformal films at low temperatures (<600° C.), for example. In both ALD and PEALD processes, precursors and reactive gases (such as oxygen or 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 may contain some levels of impurities, such as, but not limited to, nitrogen (N), which may be harmful in certain semiconductor applications. To remedy this, one possible solution is to increase the deposition temperature to 600° C. or higher. However, at these higher temperatures, traditional precursors used by the semiconductor industry tend to self-react, pyrolyze, and / or deposit in chemical vapor deposition (CVD) mode rather than ALD mode. The CVD mode of deposition has reduced conformality compared to ALD deposition, especially for high aspect ratio structures required in many semiconductor applications. Additionally, the CVD mode of deposition provides less control over the thickness of the film or material than the ALD mode deposition.

[0003] Nos. 5,413,813 and 5,424,095 describe the use of various hexamethylcyclotrisilazane and other silazanes to coat metal or metal oxide surfaces in reaction chambers with ceramic materials at high temperatures to prevent coking in subsequent reaction processes involving the pyrolysis of hydrocarbons.

[0004] US Patent No. 10,023,958 discloses and discusses the atomic layer deposition of films containing silicon, carbon and nitrogen using halogenated silicon precursors.A particular method includes exposing a substrate surface to a silicon precursor, where the silicon precursor is halogenated with Cl, Br or I, and the silicon precursor includes a halogenated silane, a halogenated carbosilane, a halogenated aminosilane or a halogenated carbosilylamine.Then, the substrate surface can be exposed to a nitrogen-containing plasma or a nitrogen precursor and a densified plasma.

[0005] U.S. Pat. No. 8,460,753 discloses a method for forming a silicon dioxide film having an extremely low wet etch rate in an HF solution using a thermal CVD process, an ALD process, or a cyclic CVD process, in which the silicon precursor is R 1 n R 2 m Si(NR 3 R 4 ) 4-n-m , and (R 1 R 2 SiNR 3 ) p wherein R 1 is alkenyl or aromatic, e.g., vinyl, allyl, and phenyl; R 2 , R 3 , and R 4 H, C1~C 10 Linear, branched or cyclic alkyl having C2-C 10 and aromatic; n=1-3, m=0-2; and p=3-4.

[0006] US Pat. No. 9,583,333 describes the deposition of a silicon nitride layer on a substrate by using a remote plasma and hexamethylcyclotrisilazane or other aminosilanes in a plasma-enhanced CVD process at temperatures below 300° C.

[0007] US Pat. No. 9,793,108 describes the use of UV-assisted photochemical vapors containing different silazanes, including hexamethylcyclotrisilazane, for the purpose of pore sealing of porous low dielectric constant films.

[0008] 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.

[0009] There is a need in the art for a process for forming uniform and conformal silicon-containing films, such as silicon oxide or silicon nitride, 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 high conformality in thermal ALD, PEALD processes, or PEALD-like processes that use cheaper, more reactive, and more stable silicon precursor compounds. Summary of the Invention

[0010] The present invention overcomes the above needs, as well as other needs 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, and carbon-doped silicon oxynitride films, at relatively low temperatures, e.g., at or below 600° C., in one or more of the following deposition processes: PEALD, plasma-enhanced cyclic CVD (PECCVD), PEALD-like processes, or ALD processes employing an oxygen-containing reactant source, a nitrogen-containing reactant source, or a combination thereof.

[0011] In one aspect, there is provided at least one silicon precursor compound selected from the group consisting of formulas A and B: [ka] In the formula, R 1~6 are each independently selected from the group consisting of hydrogen, methyl, and halides including Cl, Br, and I; R 7 and R 8 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 heterocyclic groups; R 9~11 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 group, C 4~10 and the substituent R is selected from the group consisting of heterocyclic groups and halides including Cl, Br and I. 1~11 may combine to form a substituted or unsubstituted, saturated or unsaturated cyclic group, and the substituents R of formula A 1~6 At least one of R in formula A is a halide. 7 and R8 cannot both be hydrogen, and the substituent R 9~11 at least one of which is a halide. The compounds of formulas A and B are halide-functionalized cyclotrisilazanes having at least three silicon atoms and a Si3N3 six-membered ring.

[0012] In another embodiment, a method of depositing a silicon-containing film on a substrate comprises the steps of: a) providing a substrate in a reactor; and b) introducing at least one silicon precursor compound selected from the group consisting of Formulas A and B into the reactor, [ka] In the formula, R 1~6 are each independently selected from the group consisting of hydrogen, methyl, and halides including Cl, Br, and I; R 7 and R 8 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 heterocyclic groups; R 9~11 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 group, C 4~10 and the substituent R is selected from the group consisting of heterocyclic groups and halides including Cl, Br and I. 1~11 may combine to form a substituted or unsubstituted, saturated or unsaturated cyclic group, and the substituents R of formula A 1~6 At least one of R in formula A is a halide containing Cl, Br, or I. 7 and R 8 cannot both be hydrogen, and the substituent R 9~11where at least one of is a halide comprising Cl, Br, or I; 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; and e) purging the reactor with a purge gas, wherein steps b-e are repeated until a film of a desired thickness is deposited, and the method is performed at one or more temperatures in the range of about 25° C. to 600° C.

[0013] In some embodiments, the oxygen-containing source used in the method is a source selected from the group consisting of oxygen, oxygen plasma, ozone, water vapor, water vapor plasma, nitrogen oxide (e.g., NO, NO) plasma with or without an inert gas, carbon oxide (e.g., CO, CO) plasma, and combinations thereof. In certain embodiments, the oxygen-containing source further comprises an inert gas. In these embodiments, the inert gas is selected from the group consisting of argon, helium, nitrogen, hydrogen, and combinations thereof. In another embodiment, the oxygen-containing source does not comprise an inert gas. In yet another embodiment, the oxygen-containing source comprises nitrogen, which reacts with a reagent under plasma conditions to provide a silicon oxynitride film.

[0014] In some embodiments, a nitrogen-containing source is introduced into the reactor. Suitable nitrogen-containing source gases can 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, ethylenediamine plasma, alkoxyamines such as ethanolamine plasma, and mixtures thereof. In certain embodiments, the nitrogen-containing source includes ammonia plasma, plasma containing nitrogen and argon, plasma containing nitrogen and helium, or plasma containing hydrogen and nitrogen.

[0015] In the above embodiment and throughout the present invention, the inert gas is selected from the group consisting of argon, helium, nitrogen, hydrogen, or combinations thereof. In alternative embodiments, the oxygen-containing or nitrogen-containing plasma source does not include an inert gas.

[0016] One embodiment of the present invention relates to uniform and conformal silicon-containing films, such as silicon oxide or silicon nitride, 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 in thermal ALD, PEALD processes, or PEALD-like processes using cheaper, more reactive, and more stable silicon precursor compounds.

[0017] The embodiments of the present invention may be used alone or in combination with each other. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0018] All references cited in this specification, including publications, patent applications, and patents, are hereby 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.

[0019] 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 references should be construed to cover both the singular and the plural, unless otherwise indicated herein or clearly contradicted by context. The terms "comprising," "having," "including," and "containing" should be construed as open-ended terms (i.e., meaning "including, but not limited to"), unless otherwise indicated. The recitation of ranges of values ​​herein is merely intended to serve as a shorthand method of referring individually to each individual value falling within the range, unless otherwise indicated herein, and each individual value is incorporated herein as if it were individually recited herein. All methods described herein can be performed in any suitable order, unless otherwise indicated herein or clearly contradicted by context. The use of any and all examples or exemplary language (e.g., "such as") provided herein is intended merely to better elucidate the invention and does not impose a limitation on the scope of the invention unless otherwise claimed. No language in the specification should be construed as indicating any non-claimed element essential to the practice of the invention.

[0020] The preferred embodiments of the invention described herein are illustrative and not limiting of the scope of the invention. Variations of these preferred embodiments may become apparent to those skilled in the art upon reading the foregoing description. The inventors anticipate that those skilled in the art will use such variations as necessary, and the inventors intend for the invention to be practiced otherwise than as specifically described herein. Accordingly, this 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 indicated herein or clearly contradicted by context.

[0021] Described herein are methods for forming stoichiometric or non-stoichiometric films or materials that include 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 temperatures up to about 600° C., or one or more of about 25° C. to about 600° C., in some embodiments, from 25° C. to about 300° C. The films described herein are deposited by deposition processes such as atomic layer deposition (ALD) or ALD-like processes, such as, but not limited to, plasma-enhanced ALD (PEALD) or plasma-enhanced cyclic chemical vapor deposition (PECCVD). The low temperature deposition (e.g., one or more deposition temperatures ranging from about ambient to 600° C.) methods described herein provide films or materials that exhibit at least one or more of the following advantages: density of about 2.1 g / cc or more, low chemical impurities, high conformality in thermal ALD, PEALD or PEALD-like processes, ability to tailor carbon content in the resulting film; and / or the film has an etch rate of 5 angstroms / second (Å / sec) or less as measured in 0.5 wt.% dilute HF. For carbon-doped silicon oxide and carbon-doped silicon nitride films, greater than 1% carbon is desirable to tailor the etch rate to values ​​less than 2 Å / sec in 0.5 wt.% dilute HF, in addition to other properties such as, but not limited to, density of about 1.8 g / cc or more or about 2.0 g / cc or more.

[0022] The present invention can be practiced using equipment known in the art, for example, the method of the present invention can use reactors conventional in the semiconductor manufacturing art.

[0023] In one embodiment, the silicon precursor composition described herein comprises at least one silicon precursor compound selected from the group consisting of Formulas A and B, [ka] In the formula, R 1~6 are each independently selected from the group consisting of hydrogen, methyl, and halides including Cl, Br, and I; R7 and R 8 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 heterocyclic groups; R 9~11 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 group, C 4~10 and the substituent R is selected from the group consisting of heterocyclic groups and halides including Cl, Br and I. 1~11 may combine to form a substituted or unsubstituted, saturated or unsaturated cyclic group, and the substituents R of formula A 1~6 At least one of R in formula A is a halide containing Cl, Br, or I. 7 and R 8 cannot both be hydrogen, and the substituent R 9~11 at least one of which is a halide containing Cl, Br, or I. The compounds of formulas A and B are halide-functionalized cyclotrisilazanes having at least three silicon atoms and a Si3N3 six-membered ring.

[0024] In certain embodiments, R 1-6 The halide for R is selected from the group consisting of Cl, Br, and I. In other embodiments, R 9~11 The halide for R is selected from the group consisting of Cl, Br, and I. In yet another embodiment, R 1~6 and R 9~11 The halide for is selected from the group consisting of Cl, Br, and I.

[0025] In certain embodiments, R 1~6 The halide for at least one of R is Cl. In certain embodiments, R 9~11In yet another embodiment, the halide for at least one of R 1~6 At least one of and R 9~11 The halide for at least one of is Cl.

[0026] In one embodiment, R 1-6 Each of is Cl. In some embodiments, R 1 , R 3 and R 5 Each of R is hydrogen. 9-11 Each of is Cl. In some embodiments, R 1-6 and R 9-11 Each of is hydrogen.

[0027] In certain embodiments, the composition described herein further comprises a 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° C. or less.

[0028] 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, iso-propyl, iso-butyl, sec-butyl, tert-butyl, iso-pentyl, tert-pentyl, iso-hexyl, and neo-hexyl. In certain embodiments, the alkyl group may have one or more functional groups attached thereto, such as, but not limited to, an alkoxy group, a dialkylamino group, or a combination thereof attached thereto. In other embodiments, the alkyl group does not have one or more functional groups attached thereto.

[0029] In the formula above 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.

[0030] In the above formula and throughout the description, the term "alkenyl group" denotes a group having one or more carbon-carbon double bonds and having 2 to 10 or 2 to 6 carbon atoms.

[0031] In the formula above 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.

[0032] In the formula above and throughout the description, the term "halide," when the term refers to a substituent, means that the substituent is selected from the halogen group on the periodic table of the elements, which includes fluorine, bromine, chlorine, and iodine.

[0033] 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, in which one or more of the atoms in 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 may be optionally substituted.

[0034] Exemplary halide-functionalized cyclotrisilazane precursors are listed in Table 1. [Table 1-1] [Table 1-2] [Table 1-3]

[0035] The silicon precursor composition described herein, which comprises at least one silicon precursor compound selected from the group consisting of formulas A and B according to the present invention, is preferably Li + , Na + , K + , Mg 2+ , Ca 2+ , Al 3+ , Fe 2+ , Fe 3+ , Ni 2+ , Cr 3+ Substantially free of metal ions such as. As used herein, the term "substantially free" means that when referring to such metal ions, the metal ions are less than 5 ppm (by weight), preferably less than 3 ppm, more preferably less than 1 ppm, more preferably less than 0.1 ppm, and most preferably less than 0.05 ppm, as measured by ICP-MS or other analytical methods for measuring metals.In addition, the silicon precursor composition having formula A and / or B has a purity of 98% by weight or more, more preferably 99% by weight or more, as measured by GC, when used as precursor for depositing silicon-containing film.

[0036] Without wishing to be bound by theory, it is believed that the advantage of these precursors over unfunctionalized or amino-functionalized cyclotrisilazanes is that they contain at least one Si-halide anchoring unit. This Si-X (X = Cl, Br, or I) bond reacts much more readily with NH-terminated surfaces to form Si x N yThe rings should conformally anchor to the surface, and thus silicon- and nitrogen-containing films, such as silicon nitride or carbon-doped silicon nitride, should be able to grow after repeated [precursor->purge->nitridation->purge] cycles at temperatures much lower than previously disclosed cyclotrisilazane. It is also believed that the multiple Si-N bond networks pre-established in the Si3N3 rings of these precursors allow more robust and therefore higher quality silicon- and nitrogen-containing films, such as stoichiometric silicon nitride with a formula of Si3N4, to be deposited with higher growth per cycle compared to conventional chlorosilane precursors under the same deposition conditions. It is also believed that these halide-functionalized cyclotrisilazane precursors may be suitable for high growth rate deposition of conformal silicon- and oxygen-containing films, such as silicon oxide, carbon-doped silicon oxide, silicon oxynitride, and carbon-doped silicon oxynitride, when an oxygen-containing reactant source is used in conjunction with, in addition to, or instead of a nitrogen-containing reactant source. This dual functionality makes these precursors useful in applications where, for example, multiple alternating layers of silicon nitride and silicon oxide are deposited into nanolaminate multilayer structures without altering the silicon-containing precursor.

[0037] In addition to conventional methods of synthesizing cyclotrisilazane molecules, such as the reaction of chlorosilanes with amines or metal amides to form Si-N bonds, compounds having formula A or B can be synthesized according to the reactions exemplified by Schemes 1 and 2. [ka]

[0038] It will be apparent to one skilled in the art that the use of other carbonyl chloride, carbonyl bromide, or carbonyl iodide reagents in Scheme 1, as well as a variety of other amino-functionalized cyclotrisilazane starting materials, will enable the synthesis of numerous combinations of halide-functionalized cyclotrisilazanes having formula A. It will also be apparent to one skilled in the art that the use of other deprotonating agents, such as alkali or alkaline earth metals, metal hydrides, or metal alkyls, in the first step of Scheme 2, as well as other simple halide silane reagents, such as SiCl4, Cl3SiH, Cl2SiMeH, Cl3SiMe, Br2SiH2, or I2SiH2, in the second step of Scheme 2, will provide a variety of other halide-functionalized cyclotrisilazanes having formula B.

[0039] Another synthetic method for producing halide-functionalized cyclotrisilazane having formula B involves the direct reaction of simple halide silanes, such as those described above, with the NH-functionalized cyclotrisilazane starting material, optionally in the presence of a Lewis base, as illustrated in Scheme 3. [ka]

[0040] Another alternative method for synthesizing halide-functionalized cyclotrisilazanes having formula A or B involves the direct conversion of at least one Si-H bond on a hydride-functionalized cyclotrisilazane to a Si-X bond (X=Cl, Br, I), as illustrated in Reaction Schemes 4 and 5. Many halogenation reagents known in the literature for effecting this conversion that can be used in such halogenation reactions include, but are not limited to, Cl2, Br2, I2, HCl, HBr, HI, acetyl halides, alkyl halides, aryl halides, trityl halides, tin halides, antimony halides, mercury halides, iron halides, nickel halides, palladium halides, phosphorus halides, boron halides, N-succinimide halides, other organic halides, other main group element halides, or transition metal halides. Some of these Si-H to Si-X halogenation reactions may require a catalyst. [ka]

[0041] 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 herein, the method comprising: a. providing a substrate in a reactor; b. introducing into a reactor at least one silicon precursor compound having a structure selected from the group consisting of formulas A and B defined above; c. purging the reactor with a purge gas; d. introducing an oxygen-containing source containing a plasma into the reactor; e. purging the reactor with a purge gas.

[0042] In this method, steps b through e are repeated until a film of the desired thickness is deposited on the substrate.

[0043] The methods of the invention are carried out via an ALD process using an oxygen-containing source, including ozone or a plasma, which may further include an inert gas, such as one or more of an oxygen plasma with or without an inert gas, a water vapor plasma with or without an inert gas, a nitrogen oxide (e.g., NO, NO) plasma with or without an inert gas, a carbon oxide (e.g., CO, CO) plasma with or without an inert gas, and combinations thereof.

[0044] The oxygen-containing plasma source may be generated in situ or remotely. In one particular embodiment, the oxygen-containing source comprises oxygen and is co-flowed or introduced with at least one silicon precursor compound and optionally other reagents, such as, but not limited to, an inert gas, during method steps b-e.

[0045] In an embodiment in which at least one silicon precursor compound having a structure selected from the group consisting of formulas A and B is used in a composition containing a solvent, the selected solvent or mixture thereof does not react with the silicon precursor. The amount of solvent by weight percentage in the composition ranges from 0.5 wt% to 99.5 wt% or 10 wt% to 75 wt%. In this or other embodiments, the solvent has a boiling point (bp) similar to that of the silicon precursor compound of formula A or B, or the difference between the bp of the solvent and the bp of the silicon precursor of formula A or B 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 bp 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 (such as 1,4-dioxane, dibutyl ether, etc.), tertiary amines (such as trimethylamine, pyridine, 1-methylpiperidine, 1-ethylpiperidine, N,N'-dimethylpiperazine, N,N,N',N'-tetramethylethylenediamine, etc.), nitriles (such as acetonitrile or benzonitrile), alkyl hydrocarbons (such as octane, nonane, dodecane, ethylcyclohexane, etc.), aromatic hydrocarbons (such as toluene, xylene, mesitylene, etc.), tertiary amino ethers (such as bis(2-dimethylaminoethyl) ether), or mixtures thereof.

[0046] Throughout the description, the term "ALD or ALD-like" refers to processes including, but not limited to, the following processes: a) reactants, including silicon precursor and 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) reactants, including silicon precursor and reactive gas, are exposed to the substrate by moving or rotating the substrate into different sections of the reactor, each section separated by an inert gas curtain, i.e., a spatial ALD reactor or a roll-to-roll ALD reactor.

[0047] In certain embodiments, the silicon oxide or carbon-doped silicon oxide films deposited using the methods described herein are formed in the presence of an oxygen-containing source including ozone, water (HO) (e.g., deionized water, purified water, and / or distilled water), hydrogen peroxide (HO), oxygen (O), oxygen plasma, NO, NO, NO, carbon monoxide (CO), carbon dioxide (CO), and combinations thereof. The oxygen-containing source may, for example, be passed through either an in-situ or remote plasma generator to provide an oxygen-containing plasma source including oxygen, such as an oxygen plasma, a plasma comprising oxygen and argon, a plasma comprising oxygen and helium, an ozone plasma, a water plasma, a nitrous oxide plasma, or a carbon dioxide plasma. In certain embodiments, the oxygen-containing plasma source includes an oxygen source gas 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 ranging from about 0.1 to about 100 seconds. In one particular 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 0.01 seconds).

[0048] The deposition methods disclosed herein may involve one or more purge gases. Purge gases used to purge 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 argon (Ar), nitrogen (N2), helium (He), neon, hydrogen (H2), and mixtures thereof. In certain embodiments, a purge gas, such as Ar, is fed into the reactor at a flow rate ranging from about 10 to about 2000 sccm for about 0.1 to 1000 seconds, thereby purging unreacted materials and any by-products that may remain in the reactor.

[0049] Each step of supplying the precursor, oxygen source, and / or other precursors, source gases, and / or reagents may be performed by varying the time for which they are supplied to vary the stoichiometric composition of the resulting dielectric film.

[0050] Energy is applied to at least one silicon precursor compound having a structure selected from the group consisting of formulas A and B, 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 method, 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 a remote plasma generation process in which the plasma is generated outside the reactor and delivered into the reactor.

[0051] At least one silicon precursor compound can be delivered to a reaction chamber, such as a plasma-enhanced cyclic CVD or PEALD reactor or a batch furnace type reactor, in a variety of ways. In one embodiment, a liquid delivery system can be utilized. In an alternative embodiment, a combined liquid delivery and flash evaporation process unit, such as a turbo vaporizer manufactured by MSP Corporation of Shoreview, MN, can be used to enable volumetric delivery of low volatility materials, which results in reproducible transport and deposition without thermal decomposition of the precursor compound. In a liquid delivery formulation, the precursor compound described herein can be delivered in pure liquid form or can be used in a solvent formulation or composition that includes it. Thus, in certain embodiments, the precursor formulation can include a solvent component(s) of suitable properties that may be desirable and advantageous in a given end use application for forming a film on a substrate.

[0052] As mentioned above, the purity level of at least one silicon precursor compound is high enough to be acceptable for reliable semiconductor manufacturing.In certain embodiments, at least one silicon precursor compound described herein contains less than 2 wt%, or less than 1 wt%, or less than 0.5 wt% of one or more of the following impurities: free amine, free halide or halide ion, and higher molecular weight species.Higher purity levels of the silicon precursor compounds described herein can be obtained by one or more of the following processes: purification, adsorption, crystallization, and / or distillation.

[0053] In one embodiment of the method described herein, a plasma-enhanced cyclic deposition process such as PEALD-like or PEALD may be used, in which deposition is carried out using at least one silicon precursor compound and an oxygen plasma source. A PEALD-like process is defined as a plasma-enhanced cyclic CVD process, but still provides highly conformal silicon-containing films.

[0054] In certain embodiments, the gas lines connecting the precursor canister to the reaction chamber are heated to one or more temperatures depending on the process requirements, and the container of at least one silicon precursor compound is maintained at one or more temperatures for bubbling. In other embodiments, a solution containing at least one silicon precursor compound is injected into a vaporizer maintained at one or more temperatures for direct liquid injection.

[0055] A flow of argon and / or other gases can be used as a carrier gas to help deliver vapor of at least one silicon precursor compound to the reaction chamber during precursor pulsing. In certain embodiments, the reaction chamber process pressure is between about 50 mTorr and 10 Torr. In other embodiments, the reaction chamber process pressure can be up to 760 Torr (e.g., between about 50 mTorr and about 100 Torr).

[0056] 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 stage within a reaction chamber where it is exposed to a silicon precursor compound, allowing the complexes to chemisorb onto the surface of the substrate.

[0057] A purge gas such as argon purges excess unabsorbed complex from the process chamber. After sufficient purging, an oxygen-containing source can be introduced into the reaction chamber to react with the absorbing surface, followed by another gas purge to remove reaction by-products from the chamber. The process cycle can be repeated to achieve a desired film thickness. In some cases, the purge can be replaced by an inert gas by pumping to remove unreacted silicon precursor compound, or both can be used.

[0058] It is understood that in this or other embodiments, the steps of the methods described herein may be performed in various orders, sequentially, simultaneously (e.g., during at least a portion of another step), or any combination thereof. Each step of supplying a precursor compound and an oxygen-containing source may be performed by varying the duration of time for which they are supplied, for example, to vary the stoichiometric composition of the resulting dielectric film. Also, purge times after a precursor or oxidant step may be minimized to <0.1 seconds to improve throughput.

[0059] In one particular embodiment, the method described herein deposits a high quality silicon-containing film, such as, for example, a silicon and oxygen-containing film, on a substrate. The method includes the following steps: a. providing a substrate in a reactor; b. introducing into a reactor at least one silicon precursor compound having a structure selected from the group consisting of Formulas A and B described herein; c. purging the reactor with a purge gas to remove at least a portion of the unabsorbed precursor compound; 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-containing source; Steps b through e are repeated until a silicon-containing film of the desired thickness is deposited.

[0060] Another method disclosed herein uses at least one silicon precursor compound having a structure selected from the group consisting of Formulas A and B defined above, plus an oxygen source, to form a carbon-doped silicon oxide film.

[0061] 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 selected from the group consisting of formulas A and B defined above with or without a co-flowing oxygen source to chemically absorb the precursor compound onto a heated substrate; c. purging away unabsorbed precursor compound; d. introducing an oxygen source onto the heated substrate to react with the absorbed precursor; and e. purging away any unreacted oxygen sources; Here, steps b to e are repeated until the desired thickness is achieved.

[0062] 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 includes the following steps: a. providing a substrate in a reactor; b. introducing into a reactor at least one silicon precursor compound having a structure selected from the group consisting of Formulas A and B described herein; c. purging the reactor with a purge gas to remove at least a portion of the unabsorbed precursor compound; 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-containing source; Steps b through e are repeated until a silicon-containing film of a desired thickness is deposited.

[0063] 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 selected from the group consisting of formulas A and B defined above with or without a co-flowing nitrogen source to chemically absorb the precursor compound onto the heated substrate; c. purging to remove unabsorbed precursor compound; d. introducing a nitrogen-containing source onto the heated substrate to react with the absorbed precursor; and e. purging away any unreacted nitrogen source; Here, steps b to e are repeated until the desired thickness is achieved.

[0064] In some embodiments, the methods described herein also employ a volatile amine catalyst, such as triethylamine, trimethylamine, dimethylamine, methylamine, 4-dimethylaminopyridine, N,N-dimethylethylenediamine, ethylenediamine, or pyridine, co-flowed during either the silicon precursor pulse step or the oxygen and / or nitrogen containing source pulse step, or during both chemical source pulse steps, to facilitate the reaction of the precursor with the substrate surface and / or the reaction of the immobilized precursor compound with a co-reactant gas.

[0065] An exemplary method using a volatile amine catalyst includes the following steps: a. providing a substrate in a reactor; b. introducing at least one silicon precursor compound having a structure selected from the group consisting of Formulas A and B described herein into a reactor, while also introducing a volatile amine catalyst, such as pyridine, into the reactor; c. purging the reactor with a purge gas to remove at least a portion of the unabsorbed precursor compound; d. introducing a nitrogen and / or oxygen containing source into the reactor; e. purging the reactor with a purge gas to remove at least a portion of the unreacted nitrogen-containing source and / or oxygen-containing source; Steps b through e are repeated until a silicon-containing film of a desired thickness is deposited. Further exemplary methods may include introducing a volatile amine catalyst into the reactor during both steps b and d, or only during step d.

[0066] A variety of commercially available ALD reactors, such as single wafer, semi-batch, or batch furnace 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.

[0067] Process temperatures for the methods described herein use one or more of the following temperatures as endpoints: 0°C, 25°C, 50°C, 75°C, 100°C, 125°C, 150°C, 175°C, 200°C, 225°C, 250°C, 275°C, 300°C, 325°C, 350°C, 375°C, 400°C, 425°C, 450°C, 475°C, 500°C, 525°C, 550°C, 575°C, 600°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.

[0068] In certain embodiments, the oxygen-containing source is selected from the group consisting of water vapor, ozone, oxygen, hydrogen peroxide, organic peroxides, and mixtures thereof. In other embodiments, the oxygen-containing source is an oxygen-containing plasma source selected from the group consisting of water plasma, oxygen plasma, oxygen / helium plasma, oxygen / argon plasma, nitrogen oxide plasma, carbon dioxide plasma, carbon monoxide plasma, 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 is a nitrogen-containing plasma source selected from the group consisting of an ammonia plasma, a plasma comprising nitrogen and argon, a plasma comprising nitrogen and helium, or a plasma comprising hydrogen and a nitrogen source gas, and combinations thereof. In this or other embodiments, the method steps are repeated until the surface features are filled with the silicon-containing film. In embodiments where 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.

[0069] In still further embodiments of the methods described herein, the film deposited from ALD, ALD-like, PEALD, or PEALD-like or as-deposited film is subjected to a treatment step (post-deposition). The treatment step can occur 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) light treatment; laser; electron beam treatment, and combinations thereof, to affect one or more properties of the film.

[0070] Films deposited using silicon precursor compounds having formula A or B described herein have improved properties, such as, but not limited to, a relatively low wet etch rate of the film before a treatment step or a relatively high density before a treatment step, when compared with films deposited using silicon precursor compounds previously disclosed under the same conditions. In a particular embodiment, the as-deposited film is intermittently treated during the deposition process. These intermittent or intermediate deposition treatments can be performed, for example, after each ALD cycle, such as, but not limited to, after every specific number of ALD cycles, such as every 1 ALD cycle, every 2 ALD cycles, every 5 ALD cycles, or every 10 or more ALD cycles.

[0071] The precursor compounds of formulas A and B can exhibit film growth rates of 2.0 Å / cycle or greater.

[0072] 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 is performed in a vacuum (<760 Torr), an inert environment, an oxygen-containing environment (such as H2O, N2O, NO2, or O2), or a nitrogen-containing environment (such as H2 / N2, hydrazine, triethylamine, pyridine, or ammonia).

[0073] In embodiments in which the film is subjected to UV treatment, the film is exposed to broadband UV, or a UV source having a wavelength in the range of about 150 nanometers (nm) to about 400 nm. In one particular embodiment, the as-deposited film is exposed to UV in a chamber separate from the deposition chamber after the desired film thickness is reached.

[0074] In embodiments where 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.

[0075] In embodiments where 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 while keeping the carbon content in the bulk nearly unchanged, making it more resistant to damage from subsequent plasma ashing processes.

[0076] Without being bound to any particular theory, it is believed that silicon precursor compounds having the chemical structure represented by formula A or B defined above can be immobilized by reacting halide groups such as chloro with NH or hydroxyl groups on the substrate surface to provide Si-N-Si or Si-O-Si fragments, thus increasing the growth rate of silicon nitride, silicon carbonitride, silicon oxide or carbon-doped silicon oxide compared to conventional silicon precursors such as bis(tert-butylamino)silane or bis(diethylamino)silane, which have only one silicon atom. With halide-functionalized cyclotrisilazane having formula A or B, as many as 3-4 silicon atoms per molecule can be immobilized on the substrate during the silicon precursor pulse step.

[0077] In certain embodiments, silicon precursor compounds having formula A or B 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 with 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.

[0078] Examples of suitable metal amide precursors that may be used with the methods disclosed herein include tetrakis(dimethylamino)zirconium (TDMAZ), tetrakis(diethylamino)zirconium (TDEAZ), tetrakis(ethylmethylamino)zirconium (TEMAZ), tetrakis(dimethylamino)hafnium (TDMAH), tetrakis(diethylamino)hafnium (TDEAH), and tetrakis(ethylmethylamino)hafnium (TEMAH), tetrakis(dimethylamino)titanium (TDMAT), tetrakis(diethylamino)titanium (TDEAT), tetrakis(ethylmethylamino)titanium (TEMAT), tert-butylminotri(diethylamino)tantalum (TBTDET), tert-butylminotri(dimethylamino)tantalum (TBTDMT ... Examples of suitable organometallic precursors include, but are not limited to, tri(ethylmethylamino)tantalum (TBTEMT), ethyliminotri(diethylamino)tantalum (EITDET), ethyliminotri(dimethylamino)tantalum (EITDMT), ethyliminotri(ethylmethylamino)tantalum (EITEMT), tert-amyliminotri(dimethylamino)tantalum (TAIMAT), tert-amyliminotri(diethylamino)tantalum, pentakis(dimethylamino)tantalum, tert-amyliminotri(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 with 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.

[0079] 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 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) can be formed depending on the desired end use of the film. One example of a silicon-containing film formed using silicon precursor compounds having formula A and / or B and the processes described herein is represented by the formula Si x O y C z N v H w where Si ranges from about 10 atomic % to about 40 atomic %, O ranges from about 0 atomic % to about 65 atomic %, C ranges from about 0 atomic % to about 75 atomic %, or from about 0 atomic % to about 50 atomic %, N ranges from about 0 atomic % to about 75 atomic %, or from about 0 atomic % to about 50 atomic %, and H ranges from about 0 atomic % to about 50 atomic %, and x+y+z+v+w=100 atomic weight percent, as determined by XPS or other means. Another example of a silicon-containing film formed using silicon precursor compounds of formula A and / or B and processes described herein is silicon carbonitride, having a carbon content of 1 atomic % to 80 atomic %, as measured by XPS. Further, another example of a silicon-containing film formed using the silicon precursor compounds of formula A and / or B and the processes described herein is amorphous silicon having a combined nitrogen and carbon content of <10 atomic %, preferably <5 atomic %, and most preferably <1 atomic %, as measured by XPS. The nitrogen to silicon ratio is in the range of 1.20 to 1.40, preferably 1.25 to 1.35, and most preferably 1.27 to 1.34.

[0080] 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. The film is compatible with various subsequent processing steps, such as, for example, chemical mechanical planarization (CMP) and anisotropic etching processes.

[0081] The deposited films have applications including, but not limited to, computer chips, optical devices, magnetic information storage devices, 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 isolation, interlayer dielectrics, passivation layers, etch stop layers, part of dual spacers, and sacrificial layers for patterning.

[0082] 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 having the following properties: density of about 2.1 g / cc or greater, 2.2 g / cc or greater, 2.25 g / cc or greater; current density of about 1e-8 A / cm in a solution of 0.5:100 HF to water diluted HF (0.5 wt % dHF) acid; 2By etch rate is meant films that exhibit one or more of the following: a wet etch rate of 2.5 Å / sec or less, 2.0 Å / sec or less, 1.5 Å / sec or less, 1.0 Å / sec or less, 0.5 Å / sec or less, 0.1 Å / sec or less, 0.05 Å / sec or less, 0.01 Å / sec or less, as measured at a leakage current of up to 6 MV / cm; hydrogen impurities of about 5e20 atoms / cc or less, as measured by SIMS; and combinations thereof. With respect to etch rate, the thermally grown silicon oxide film has an etch rate of 0.5 Å / sec in 0.5 wt % Hf.

[0083] In certain embodiments, one or more silicon precursor compounds having formula A and / or B described herein can be used to form silicon and oxygen-containing and silicon and nitrogen-containing films that are solid and non-porous or substantially pore-free.

[0084] The following examples are illustrative of methods for depositing silicon oxide films described herein and are not intended to limit the scope of the appended claims. EXAMPLES

[0085] Example 1. Synthesis of 1-chloro-1,2,3,4,5,6-hexamethylcyclotrisilazane

[0086] Under the protection of nitrogen, acetyl chloride (31.4 g, 0.400 mol) was added dropwise to 1-dimethylamino-1,2,3,4,5,6-hexamethylcyclotrisilazane (100 g, 0.381 mol) over 1 h with stirring at 5 °C. The reaction solution was slowly warmed to room temperature. This reaction was repeated twice and the two reaction solutions were combined. The N,N-dimethylacetamide by-product was removed under reduced pressure (1-2 torr, 20-35 °C) and the crude product was purified by vacuum distillation (1.0 Torr, 60-62 °C) to obtain 159 g of 1-chloro-1,2,3,4,5,6-hexamethylcyclotrisilazane with a purity of +98%. The normal boiling point was determined to be 230 °C by differential scanning calorimetry (DSC). Analysis by GC-MS showed the following mass peaks: m / z=253 (M+), 239, 219, 209, 195, 179, 165, 152, 145, 138, 131, 119, 102, 93, 86, 79, 72, 59, 45.

[0087] Example 2. Synthesis of 1,3-dichloro-1,2,3,4,5,6-hexamethylcyclotrisilazane

[0088] Under the protection of nitrogen, acetyl chloride (30.6 g, 0.390 mol) was added dropwise to 1,3-bis(dimethylamino)-1,2,3,4,5,6-hexamethylcyclotrisilazane (56.7 g, 0.186 mol) over 1 h with stirring at 5 °C. The reaction solution was allowed to warm slowly to room temperature. The N,N-dimethylacetamide by-product was removed under dynamic vacuum at room temperature, and the crude product was purified by vacuum distillation (0.4 Torr, 52-54 °C) to give 39.6 g of 1,3-dichloro-1,2,3,4,5,6-hexamethylcyclotrisilazane. The normal boiling point was determined to be 256 °C by differential scanning calorimetry (DSC). Analysis by GC-MS showed the following mass peaks: m / z=287 (M+), 273, 252, 244, 230, 210, 199, 179, 166, 152, 145, 138, 131, 122, 106, 93, 86, 79, 72, 59, 45.

[0089] Example 3. Synthesis of 1,3,5-trichloro-1,3,5-trimethylcyclotrisilazane

[0090] A mixture of hexamethyldisilazane (5.0 g, 0.031 g), trichloromethylsilane (23.2 g, 0.155 mol), and FeCl3 (0.05 g, 0.0003 mol) was stirred at room temperature for 3 days in a 40 mL scintillation vial. The resulting reaction mixture was filtered to remove solids, and the filtrate was determined by GC-MS analysis to contain unreacted trichloromethylsilane as well as the following products: chlorotrimethylsilane (major), 1,1-dichloro-1333-tetramethyldisilazane (major), 1133-tetrachloro-1,3-dimethyldisilazane (major), and 135-trichloro-135-trimethylcyclotrisilazane (trace). Analysis by GC-MS showed the following mass peaks for 1,3,5-trichloro-1,3,5-trimethylcyclotrisilazane: m / z=281 (M+), 266 (M-15), 246, 228, 214, 200, 192, 180, 171, 162, 151, 142, 137, 125, 115, 107, 101, 93, 86, 70, 63, 44.

[0091] Example 4. Synthesis of 1-bromo-1,2,3,4,5,6-hexamethylcyclotrisilazane

[0092] Under the protection of nitrogen, acetyl bromide (0.48 g, 0.0039 mol) was added dropwise to 1-dimethylamino-1,2,3,4,5,6-hexamethylcyclotrisilazane (1.00 g, 0.00381 mol) at room temperature with stirring. After stirring for an additional 30 min, the reaction solution was analyzed by GC-MS and found to contain 1-bromo-1,2,3,4,5,6-hexamethylcyclotrisilazane as the major product. GC-MS showed the following mass peaks: m / z=297 (M+), 285, 268, 255, 239, 219, 212, 196, 182, 175, 160, 145, 132, 118, 102, 86, 72, 59, 45.

[0093] Example 5. Synthesis of 1,3-dibromo-1,2,3,4,5,6-hexamethylcyclotrisilazane

[0094] Under the protection of nitrogen, acetyl bromide (0.84 g, 0.0068 mol) was added dropwise to 1,3-bis(dimethylamino)-1,2,3,4,5,6-hexamethylcyclotrisilazane (1.00 g, 0.00327 mol) with stirring at room temperature. After stirring for an additional hour, the reaction solution was analyzed by GC-MS and found to contain 1,3-dibromo-1,2,3,4,5,6-hexamethylcyclotrisilazane among several other products. GC-MS showed the following mass peaks: m / z=377 (M+), 371, 357, 341, 329, 313, 299, 285, 270, 256, 242, 235, 219, 206, 192, 178, 165, 146, 132, 118, 104, 86, 72, 55, 41.

[0095] Example 6. Synthesis of 1-iodo-1,2,3,4,5,6-hexamethylcyclotrisilazane

[0096] Under the protection of nitrogen, a 50 wt% solution of acetyl iodide (0.65 g, 0.0038 mol) in Et2O was added dropwise at room temperature to a stirred solution of 1-dimethylamino-1,2,3,4,5,6-hexamethylcyclotrisilazane (1.00 g, 0.00381 mol) in Et2O (1 mL). After stirring for 30 min, the reaction solution was analyzed by GC-MS and found to contain 1-iodo-1,2,3,4,5,6-hexamethylcyclotrisilazane. GC-MS showed the following mass peaks: m / z=345 (M+), 331, 316, 301, 287, 271, 257, 244, 230, 219, 203, 189, 175, 159, 159, 145, 131, 118, 102, 86, 72, 59, 45.

[0097] Example 7. Synthesis of 1-chlorosilyl-2,2,4,4,6,6-hexamethylcyclotrisilazane

[0098] Under the protection of nitrogen, a solution of n-butyllithium (2.5 M in hexane, 140 mL, 0.35 mol) was added dropwise via an addition funnel to a stirred solution of 2,2,4,4,6,6-hexamethylcyclotrisilazane (100 g, 0.456 mol) in hexane (100 mL) at 0° C. over 90 min. The reaction mixture was allowed to warm to room temperature with stirring. Approximately 50 mL of Et2O was then added and the resulting solution was added dropwise via an addition funnel to a stirred solution of dichlorosilane (25 wt % in heptane, 184 g, 0.455 mol) at −30° C. over 2 h. The resulting white slurry was stirred while slowly warming to room temperature. The white solid was removed by filtration and the volatiles were removed under reduced pressure (5 Torr). The resulting crude concentrate was analyzed by GC-MS and found to contain 1-chlorosilyl-2,2,4,4,6,6-hexamethylcyclotrisilazane. GC-MS showed the following mass peaks: m / z=282 (M-1), 268, 252, 232, 223, 216, 208, 194, 188, 174, 160, 150, 143, 136, 130, 116, 100, 93, 86, 79, 73, 59, 45.

[0099] Example 8. Synthesis of 1-chloromethylsilyl-2,2,4,4,6,6-hexamethylcyclotrisilazane

[0100] Under the protection of nitrogen, a 50 wt% solution of dichloromethylsilane (0.35 g, 0.0030 mol) in hexane was added dropwise to a stirred solution of 2,2,4,4,6,6-hexamethylcyclotrisilazane (2.00 g, 0.00911 mol) and triethylamine (0.62 g, 0.0061 mol) in hexane (7 mL). After stirring for 3 h, the white slurry was filtered to remove solids and the resulting solution was analyzed by GC-MS and found to contain the desired product, 1-chloromethylsilyl-2,2,4,4,6,6-hexamethylcyclotrisilazane. GC-MS showed the following mass peaks: m / z=297 (M+), 283, 267, 247, 231, 208, 194, 189, 174, 158, 151, 141, 131, 116, 100, 93, 86, 79, 73, 59, 45.

[0101] Example 9. Synthesis of 1-chlorodimethylsilyl-2,2,4,4,6,6-hexamethylcyclotrisilazane

[0102] Under the protection of nitrogen, a solution of lithium-2,2,4,4,6,6-hexamethylcyclotrisilazane (0.60 g, 0.0027 mol) in toluene (3 mL) and THF (0.1 mL) was added dropwise to a stirred solution of dichlorodimethylsilane (0.39 g, 0.0030 mol) in hexane (5 mL) at room temperature. After stirring for an additional hour, the mixture was filtered to remove a white solid. The filtrate was analyzed by GC-MS and found to contain the desired product, 1-chlorodimethylsilyl-2,2,4,4,6,6-hexamethylcyclotrisilazane. GC-MS showed the following mass peaks: m / z=311 (M+), 297, 281, 261, 245, 228, 224, 209, 189, 172, 157, 150, 141, 131, 115, 100, 93, 86, 73, 59, 45.

[0103] Example 10. Synthesis of 1-dichloromethylsilyl-2,2,4,4,6,6-hexamethylcyclotrisilazane

[0104] Under the protection of nitrogen, a 50 wt% solution of trichloromethylsilane (0.45 g, 0.0030 mol) in hexane was added dropwise to a stirred solution of 2,2,4,4,6,6-hexamethylcyclotrisilazane (2.00 g, 0.00911 mol) and triethylamine (0.62 g, 0.0061 mol) in hexane (7 mL). After stirring overnight at room temperature, the reaction mixture was heated at 60-80 °C for 3 h and then continued to stir overnight. The resulting white slurry was filtered to remove solids. The filtrate was analyzed by GC-MS and found to contain the desired product, 1-dichloromethylsilyl-2,2,4,4,6,6-hexamethylcyclotrisilazane. GC-MS showed the following mass peaks: m / z=332 (M+), 317, 301, 281, 265, 245, 229, 209, 188, 172, 151, 131, 120, 115, 100, 93, 86, 73, 63, 45.

[0105] Example 11. Synthesis of 1-dichlorosilyl-2,2,4,4,6,6-hexamethylcyclotrisilazane

[0106] Under the protection of nitrogen, a 50 wt% solution of trichlorosilane (0.41 g, 0.0030 mol) in hexane was added dropwise to a stirred solution of 2,2,4,4,6,6-hexamethylcyclotrisilazane (2.00 g, 0.00911 mol) and triethylamine (0.62 g, 0.0061 mol) in hexane (7 mL). After stirring overnight at room temperature, the resulting white slurry was filtered to remove solids. The filtrate was analyzed by GC-MS and found to contain the desired product, 1-dichlorosilyl-2,2,4,4,6,6-hexamethylcyclotrisilazane. GC-MS showed the following mass peaks: m / z=317 (M+), 305, 287, 267, 251, 244, 229, 224, 214, 209, 194, 188, 179, 173, 158, 150, 144, 131, 120, 115, 100, 93, 86, 73, 59, 43.

[0107] Example 12. Synthesis of 1-trichlorosilyl-2,2,4,4,6,6-hexamethylcyclotrisilazane

[0108] Under the protection of nitrogen, a 50 wt% solution of silicon tetrachloride (0.52 g, 0.0031 mol) in hexane was added dropwise to a stirred solution of 2,2,4,4,6,6-hexamethylcyclotrisilazane (2.00 g, 0.00911 mol) and triethylamine (0.62 g, 0.0061 mol) in hexane (7 mL). After stirring at room temperature for 3 days, the resulting white slurry was filtered to remove solids. The filtrate was analyzed by GC-MS and found to contain the desired product, 1-trichlorosilyl-2,2,4,4,6,6-hexamethylcyclotrisilazane. GC-MS showed the following mass peaks: m / z=352 (M+), 339, 322, 301, 287, 265, 248, 228, 209, 193, 172, 162, 150, 143, 131, 122, 113, 100, 93, 86, 73, 63, 45.

[0109] Unless otherwise indicated for the following examples, PEALD was carried out on a commercial lateral flow reactor (300 mm PEALD tool manufactured by ASM) equipped with 13.56 MHz direct plasma capability. Argon gas was used to maintain the reactor pressure. Thermal ALD processes were carried out on a commercial screening tool manufactured by Picosun. In both cases, the precursors were liquids maintained in stainless steel bubblers and delivered to the chamber with Ar carrier gas. Unless otherwise indicated for the following examples, thermal ALD processes were carried out on a commercial screening tool manufactured by Picosun. The silicon precursor was delivered to the chamber by Ar carrier gas at a flow rate of 200 sccm. All gases (e.g., purge and reactant gases and precursors) were preheated to 100° C. before entering the deposition zone. Gas and precursor flow rates were controlled with fast-acting ALD diaphragm valves.

[0110] All depositions reported in the examples were carried out on native oxide-containing Si substrates. Film thickness and refractive index were measured using a FilmTek 3000 SE ellipsometer. Growth rate per cycle (GPC) was calculated by dividing the measured thickness of the resulting silicon- and nitrogen-containing film by the total number of ALD / PEALD cycles.

[0111] Example 13. Deposition of silicon and nitrogen containing films using 1-chloro-1,2,3,4,5,6-hexamethylcyclotrisilazane

[0112] Silicon and nitrogen containing films are deposited under process conditions in a PEALD 300 mm reactor using 1-chloro-1,2,3,4,5,6-hexamethylcyclotrisilazane as the silicon precursor and NH3 plasma. The silicon precursor is delivered from a stainless steel vessel at 100°C. Argon was used as the carrier gas and was set at 200 sccm. The susceptor temperature was set at 300°C. [Table 2]

[0113] Steps 3-6 were repeated multiple times to obtain silicon and nitrogen containing films of desired thickness. The film growth per cycle (GPC) was 0.16 Å / cycle. It has a refractive index of 1.85. The composition of the resulting film was analyzed by X-ray photoelectron spectroscopy (XPS). The bulk film contains 40.8 at.% Si, 52.3 at.% N, 5 at.% O, and 1.3 at.% C with a nitrogen to silicon ratio of 1.28, which is very close to the ratio of 1.33 for stoichiometric silicon nitride with a formula of Si3N4, demonstrating that halide functionalized cyclotrisilazane with at least three silicon atoms and a Si3N3 six-membered ring is suitable to yield stoichiometric silicon nitride. The deposited film has a fluence of 5E-9 A / cm at 1 MV / cm. 2 For comparison, silicon and nitrogen containing films were deposited using SiCl4 and NH3 plasmas using the process parameters listed in Table 2. The as-deposited films have a leakage density of 5E-5 A / cm at 1 MV / cm. 2 , suggesting a much lower film quality than that from 1-chloro-1,2,3,4,5,6-hexamethylcyclotrisilazane.

[0114] Example 14. Thermal ALD deposition of silicon- and nitrogen-containing films using 1,3-dichloro-1,2,3,4,5,6-hexamethylcyclotrisilazane and ammonia.

[0115] Silicon and nitrogen containing films were thermally deposited using 1,3-dichloro-1,2,3,4,5,6-hexamethylcyclotrisilazane and NH3 in a Picosun ALD screening tool. The precursors were delivered from a stainless steel vessel at 100°C. The substrate temperature was set at 600°C. The ALD process is described in Table 3. [Table 3]

[0116] Steps 4-7 were repeated multiple times to obtain the desired film thickness. The resulting silicon- and nitrogen-containing films were deposited with GPC at 0.12 Å / cycle.

[0117] Example 15. Deposition of silicon and nitrogen containing films using 1,3,5-trichloro-1,2,3,4,5,6-hexamethylcyclotrisilazane

[0118] Silicon and nitrogen containing films are deposited under process conditions in a PEALD 300 mm reactor using 1,3,5-trichloro-1,2,3,4,5,6-hexamethylcyclotrisilazane as the silicon precursor and NH3 plasma. The silicon precursor is delivered from a stainless steel vessel at 100°C. Argon is used as the carrier gas with a flow rate of 200 sccm. The susceptor temperature is set to 300°C. The deposition is performed according to the ALD steps and parameters listed in Table 2. Steps 3-6 are repeated multiple times to obtain the desired thickness of the silicon and nitrogen containing film.

[0119] Example 16. Thermal ALD deposition of Si-containing films using 1,3,5-trichloro-1,2,3,4,5,6-hexamethylcyclotrisilazane and ammonia.

[0120] Silicon and nitrogen containing films are deposited using 1,3,5-trichloro-1,2,3,4,5,6-hexamethylcyclotrisilazane and ammonia using a Picosun ALD screening tool. The precursors are delivered from a stainless steel vessel at 100° C. The process parameters are set at 600° C. The deposition is performed according to the ALD steps and parameters listed in Table 3.

[0121] Steps 4 to 7 are repeated multiple times to obtain the desired film thickness.

[0122] The foregoing description has been primarily for purposes of illustration, and while the present invention has been shown and described with respect to exemplary embodiments thereof, it should be understood by those skilled in the art that the foregoing and various other changes, omissions, and additions in form and detail thereof may be made without departing from the spirit and scope of the invention.

Claims

1. A silicon precursor compound selected from the group consisting of formulas A and B, 【Chemistry 1】 In the formula, R １～６ are each independently selected from the group consisting of hydrogen, methyl, and halide; R ７ and R ８ each independently represents 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; R ９～１１ each independently represents 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 group, C ４～１０ The substituent R is selected from the group consisting of heterocyclic groups and halides. １～１１ may or may not combine to form a substituted or unsubstituted saturated or unsaturated cyclic group, and the substituents R １～６ At least one of R in formula A is a halide. ７ and R ８ cannot both be hydrogen, and the substituents R ９～１１ at least one of the silicon precursor compounds is a halide.

2. The at least one silicon precursor compound is selected from the group consisting of 1-chlorosilyl-2,2,4,4,6,6-hexamethylcyclotrisilazane, 1-bromosilyl-2,2,4,4,6,6-hexamethylcyclotrisilazane, 1-iodosilyl-2,2,4,4,6,6-hexamethylcyclotrisilazane, 1-dichlorosilyl-2,2,4,4,6,6-hexamethylcyclotrisilazane, 1-trichlorosilyl-2,2,4,4,6,6-hexamethylcyclotrisilazane, and 1-chloromethylsilyl-2,2,4,4,6,6-hexamethylcyclotrisilazane. , 1-chlorodimethylsilyl-2,2,4,4,6,6-hexamethylcyclotrisilazane, 1-dichloromethylsilyl-2,2,4,4,6,6-hexamethylcyclotrisilazane, 1-chloro-1,2,3,4,5,6-hexamethylcyclotrisilazane, 1,2-dichloro-1,2,3,4,5,6-hexamethylcyclotrisilazane, 1,3,5-trichloro-1,2,3,4,5,6-hexamethylcyclotrisilazane, 1,3,5-trichloro-2,4,6-trimethylcyclotrisilazane, 1,1,3,3,5,5-hexachloro-2,4 ,6-trimethylcyclotrisilazane, 1-chloro-2,4,6-triethylcyclotrisilazane, 1,3-dichloro-2,4,6-triethylcyclotrisilazane, 1,3,5-trichloro-2,4,6-triethylcyclotrisilazane, 1,1,3,3,5,5-hexachloro-2,4,6-triethylcyclotrisilazane, 1-chloro-2,4,6-tri-iso-propylcyclotrisilazane, 1,3-dichloro-2,4,6-tri-iso-propylcyclotrisilazane, 1,3,5-trichloro-2,4,6-tri-iso-propylcyclotrisilazane Silazane, 1,1,3,3,5,5-hexachloro-2,4,6-tri-iso-propylcyclotrisilazane, 1-bromo-1,2,3,4,5,6-hexamethylcyclotrisilazane, 1.3-dibromo-1,2,3,4,5,6-hexamethylcyclotrisilazane, 1,3,5-tribromo-1,2,3,4,5,6-hexamethylcyclotrisilazane, 1,3,5-tribromo-2,4,6-trimethylcyclotrisilazane, 1-iodo-1,2,3,4,5,6-hexamethylcyclotrisilazane, and 1.3-diiodo-1,2,3,4,5,The compound according to claim 1, comprising at least one selected from the group consisting of 6-hexamethylcyclotrisilazane.

3. A composition comprising at least one silicon precursor compound selected from the group consisting of formulas A and B, 【Chemistry 2】 In the formula, R １～６ are each independently selected from the group consisting of hydrogen, methyl, and halide; R ７ and R ８ each independently represents 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; R ９～１１ each independently represents 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 group, C ４～１０ The substituent R is selected from the group consisting of heterocyclic groups and halides. １～１１ may combine to form a substituted or unsubstituted, saturated or unsaturated cyclic group, and the substituents R １～６ At least one of R in formula A is a halide. ７ and R ８ cannot both be hydrogen, and the substituents R ９～１１ at least one of is a halide.

4. The composition of claim 3 further comprising at least one purge gas.

5. The composition of claim 3 further comprising a solvent.

6. At least one silicon precursor compound selected from the formulas A and B is 1-chlorosilyl-2,2,4,4,6,6-hexamethylcyclotrisilazane, 1-bromosilyl-2,2,4,4,6,6-hexamethylcyclotrisilazane, 1-iodosilyl-2,2,4,4,6,6-hexamethylcyclotrisilazane, 1-dichlorosilyl-2,2,4,4,6,6-hexamethylcyclotrisilazane, 1-trichlorosilyl-2,2,4,4,6,6-hexamethylcyclotrisilazane, 1-chloromethylsilyl-2,2,4,4,6,6-hexamethylcyclotrisilazane, 1-chlorodimethylsilyl-2,2,4,4,6,6-hexamethylcyclotrisilazane, 1-dichloromethylsilyl-2,2,4,4,6,6-hexamethylcyclotrisilazane, 1-chloro-1,2,3,4,5,6-hexamethylcyclotrisilazane, 1,2-dichloro-1,2,3,4,5,6-hexamethylcyclotrisilazane, 1,3,5-trichloro-1,2,3,4,5,6-hexamethylcyclotrisilazane, 1,3,5-trichloro-2,4,6-trimethylcyclotrisilazane, 1,1,3,3,5,5-hexamethylcyclotrisilazane 1,3-dichloro-2,4,6-triethylcyclotrisilazane, 1,3,5-trichloro-2,4,6-triethylcyclotrisilazane, 1,1,3,3,5,5-hexachloro-2,4,6-triethylcyclotrisilazane, 1-chloro-2,4,6-trimethylcyclotrisilazane, 1,3-dichloro-2,4,6-triethylcyclotrisilazane, 1,3,5-trichloro-2,4,6-triethylcyclotrisilazane, 1,1,3,3,5,5-hexachloro-2,4,6-triethylcyclotrisilazane, 1-chloro-2,4,6-tri-iso-propylcyclotrisilazane, 1,3-dichloro-2,4,6-tri-iso-propylcyclotrisilazane, 1,3,5-trichloro-2,4,6-tri-iso-propyl Pylcyclotrisilazane, 1,1,3,3,5,5-hexachloro-2,4,6-tri-iso-propylcyclotrisilazane, 1-bromo-1,2,3,4,5,6-hexamethylcyclotrisilazane, 1.3-dibromo-1,2,3,4,5,6-hexamethylcyclotrisilazane, 1,3,5-tribromo-1,2,3,4,5,6-hexamethylcyclotrisilazane, 1,3,5-tribromo-2,4,6-trimethylcyclotrisilazane, 1-iodo-1,2,3,4,5,6-hexamethylcyclotrisilazane, and 1.3-diiodo-1,2,The composition according to claim 3, comprising at least one selected from the group consisting of 3,4,5,6-hexamethylcyclotrisilazane.

7. 1. A method for depositing a silicon-containing film on a substrate, the method comprising: a) providing a substrate in a reactor; b) introducing at least one silicon precursor compound according to claim 1 into said 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 said reactor; e) purging the reactor with a purge gas; Including, Steps b through e are repeated until a film of desired thickness is deposited; The process is carried out with the reactor at one or more temperatures ranging from about 25° C. to 600° C. method.

8. The at least one silicon precursor compound is selected from the group consisting of 1-chlorosilyl-2,2,4,4,6,6-hexamethylcyclotrisilazane, 1-bromosilyl-2,2,4,4,6,6-hexamethylcyclotrisilazane, 1-iodosilyl-2,2,4,4,6,6-hexamethylcyclotrisilazane, 1-dichlorosilyl-2,2,4,4,6,6-hexamethylcyclotrisilazane, 1-trichlorosilyl-2,2,4,4,6,6-hexamethylcyclotrisilazane, and 1-chloromethylsilyl-2,2,4,4,6,6-hexamethylcyclotrisilazane. , 1-chlorodimethylsilyl-2,2,4,4,6,6-hexamethylcyclotrisilazane, 1-dichloromethylsilyl-2,2,4,4,6,6-hexamethylcyclotrisilazane, 1-chloro-1,2,3,4,5,6-hexamethylcyclotrisilazane, 1,2-dichloro-1,2,3,4,5,6-hexamethylcyclotrisilazane, 1,3,5-trichloro-1,2,3,4,5,6-hexamethylcyclotrisilazane, 1,3,5-trichloro-2,4,6-trimethylcyclotrisilazane, 1,1,3,3,5,5-hexachloro-2,4 ,6-trimethylcyclotrisilazane, 1-chloro-2,4,6-triethylcyclotrisilazane, 1,3-dichloro-2,4,6-triethylcyclotrisilazane, 1,3,5-trichloro-2,4,6-triethylcyclotrisilazane, 1,1,3,3,5,5-hexachloro-2,4,6-triethylcyclotrisilazane, 1-chloro-2,4,6-tri-iso-propylcyclotrisilazane, 1,3-dichloro-2,4,6-tri-iso-propylcyclotrisilazane, 1,3,5-trichloro-2,4,6-tri-iso-propylcyclotrisilazane Silazane, 1,1,3,3,5,5-hexachloro-2,4,6-tri-iso-propylcyclotrisilazane, 1-bromo-1,2,3,4,5,6-hexamethylcyclotrisilazane, 1.3-dibromo-1,2,3,4,5,6-hexamethylcyclotrisilazane, 1,3,5-tribromo-1,2,3,4,5,6-hexamethylcyclotrisilazane, 1,3,5-tribromo-2,4,6-trimethylcyclotrisilazane, 1-iodo-1,2,3,4,5,6-hexamethylcyclotrisilazane, and 1.3-diiodo-1,2,3,4,5,The method according to claim 7, wherein the silyl group is selected from the group consisting of 6-hexamethylcyclotrisilazane.

9. 8. The method of claim 7, 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.

10. 8. The method of claim 7, 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.

11. The method of claim 7 , wherein the oxygen-containing source and / or the nitrogen-containing source comprises a plasma.

12. The method of claim 11 , wherein the plasma is generated in situ.

13. The method of claim 11 , wherein the plasma is generated remotely.

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

15. The method of claim 7 , wherein the film further comprises carbon.

16. The method of claim 7, wherein the film has a density of about 1.8 g / cc or greater.

17. 8. The method of claim 7, wherein the carbon content of the film is greater than or equal to 0.5 atomic weight percent (at.%) as measured by X-ray photoelectron spectroscopy.

18. The membrane has a resistance of 5E-9 A / cm at 1 MV / cm ２ 8. The method of claim 7 having a leakage current density of:

19. 8. A silicon-containing film formed by the method of claim 7.

20. 12. A silicon-containing film formed by the method of claim 11.

21. A silicon precursor composition for the deposition of a silicon-containing film selected from the group consisting of formulas A and B, 【Chemistry 3】 In the formula, R １～６ are each independently selected from the group consisting of hydrogen, methyl, and halide; R ７ and R ８ each independently represents 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; R ９～１１ each independently represents 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 group, C ４～１０ The substituent R is selected from the group consisting of heterocyclic groups and halides. １～１１ may or may not combine to form a substituted or unsubstituted saturated or unsaturated cyclic group, and the substituents R １～６ At least one of R in formula A is a halide. ７ and R ８ cannot both be hydrogen, and the substituents R ９～１１ at least one of the following is a halide:

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