Deposition of carbon-doped silicon oxide

Abstract

To provide a method for deposition of a carbon doped silicon oxide film.SOLUTION: A method for depositing on a substrate a film comprising silicon and oxygen includes: (a) providing a substrate into a reactor; (b) introducing into the reactor at least one silicon precursor compound selected from the group consisting of formulas A, B and C described herein; (c) purging the reactor with a purge gas; (d) introducing at least one of an oxygen-containing source and a nitrogen-containing source into the reactor; (e) purging the reactor with the purge gas, where the steps (b) through (e) are repeated until a desired thickness of a resulting silicon-containing film is deposited; and (f) treating the resulting silicon-containing film with R3xSi(NR1R2)4-x, where R1-3 are the same as described in the specification, and are preferably methyl or ethyl; and x=1, 2, or 3. The method is practiced at one or more temperatures ranging from about 20°C to 300°C.SELECTED DRAWING: None

Description

[Technical Field]

[0001] Cross-reference of related applications This application claims priority to U.S. Provisional Application 62 / 801248, filed on 5 February 2019, the entire contents of which are incorporated herein by reference for all possible purposes.

[0002] The present invention relates to organosilicon compounds that can be used to deposit silicon and oxygen-containing films, including carbon-doped silicon oxide films; to methods for using the compounds to deposit silicon oxide-containing films; and to films obtained from the compounds and methods. [Background technology]

[0003] Atomic layer deposition (ALD) and plasma-enhanced atomic layer deposition (PEALD) are processes used, for example, to deposit silicon oxide conformal films at low temperatures (<500°C). In both ALD and PEALD processes, the precursor and reactive gas (e.g., oxygen or ozone) are separated and pulsed for a specific number of cycles, repeatedly forming a silicon oxide monolayer in each cycle.

[0004] Organic aminosilane and chlorosilane precursors are known in the art and can be used to deposit silicon-containing films at relatively low temperatures (<300°C) and relatively high growth rates per cycle (GPC (growth per cycle) > 1.0 Å / cycle) by atomic layer deposition (ALD) and plasma-enhanced atomic layer deposition (PEALD) processes. In the art, there is a demand for compositions and methods for using such compositions to deposit silicon-containing films with high carbon content (e.g., carbon content of about 10 at% or more as measured by X-ray photoelectron spectroscopy (XPS)) for specific applications in the electronics industry. Some important characteristics of carbon-doped silicon-containing films are wet etching resistance and hydrophobicity. Generally speaking, the introduction of carbon into silicon-containing films helps to reduce the wet etching rate and increase hydrophobicity. Further advantages of adding carbon to silicon-containing films include reducing the dielectric constant and / or providing improvements to other electrical or physical properties of the film.

[0005] Examples of known precursors and methods are disclosed in the following publications, patents, and patent applications.

[0006] U.S. Patent Application Publication No. 2015 / 087139 describes the use of amino-functionalized carbosilane for depositing silicon-containing films by a thermal ALD process or a PEALD process.

[0007] U.S. Patent No. 9,337,018 describes the use of organic aminodisilanes for depositing silicon-containing films by thermal ALD or PEALD processes.

[0008] U.S. Patents 8,940,648, 9,005,719, and 8,912,353 describe the use of organic aminosilanes for depositing silicon-containing films by thermal ALD or PEALD processes.

[0009] U.S. Patent Application Publication No. 2015 / 275355 describes the use of mono and bis(organicamino)alkylsilanes for depositing silicon-containing films by a thermal ALD process or a PEALD process.

[0010] U.S. Patent Application Publication No. 2015 / 376211 describes the use of mono(organic amino)-substituted, halide-substituted, and pseudo-halide-substituted trisilylamines for depositing silicon-containing films by thermal ALD or PEALD processes.

[0011] International Publication No. 15 / 105350 describes the use of a four-membered ring cyclodisilazane having at least one Si-H bond for depositing silicon-containing films by thermal ALD or PEALD processes.

[0012] U.S. Patent No. 8575033 describes a method for depositing silicon carbide films onto a substrate surface. The method involves the use of a gas-phase carbosilane precursor and may utilize a plasma-enhanced atomic layer deposition process.

[0013] U.S. Patent Application Publication No. 2013 / 0224964 teaches a method for forming a dielectric film having Si-C bonds on a semiconductor substrate by atomic layer deposition (ALD), comprising the steps of (i) adsorbing a precursor onto the surface of the substrate; (ii) reacting the adsorbed precursor with a reactant gas on the substrate; and (iii) repeating steps (i) and (ii) to form a dielectric film having at least Si-C bonds on the substrate.

[0014] U.S. Patent Application Publication No. 2014 / 302688 describes a method for forming a dielectric layer on a patterned substrate, which may include bonding a silicon- and carbon-containing precursor with a radical oxygen precursor in a plasma-free substrate processing region of a chemical vapor deposition chamber. The silicon- and carbon-containing precursor and the radical oxygen precursor react to deposit a flowable silicon-carbon-oxygen layer on the patterned surface.

[0015] U.S. Patent Application Publication No. 2014 / 302690 describes a method for forming a low dielectric constant (low-k) dielectric material on a substrate. The method may include generating a radical precursor by flowing an unexcited precursor into a remote plasma region, and reacting the radical precursor with a vapor-phase silicon precursor to deposit a flowable film on the substrate. The vapor-phase silicon precursor may include a compound containing at least one silicon and oxygen, and may include at least one silicon and a carbon linker. The flowable film may be cured to form a low dielectric constant dielectric material.

[0016] U.S. Patent Application Publication No. 2014 / 051264 describes a method for depositing an initially flowable dielectric film on a substrate. The method includes introducing a silicon-containing precursor into a deposition chamber containing the substrate. The method further includes using a remote plasma system located outside the deposition chamber to generate at least one excited precursor, such as a radical nitrogen or oxygen precursor. The excited precursor is also introduced into the deposition chamber, where it reacts with the silicon-containing precursor in a reaction region to deposit an initially flowable film on the substrate. The flowable film may be treated, for example, in a vapor environment, to form a silicon oxide film.

[0017] International Publication No. 14 / 134476 describes a method for depositing films containing SiCN and SiCON. A particular method includes exposing a substrate surface to a first precursor and a second precursor, where the first precursor has the formula (X y H 3-y Si) z CH 4-z , (X y H 3-y Si)(CH2)(SiX p H 2-p )(CH2)(SiX y H 3-y ), or (X y H 3-y Si)(CH2) n (SiX y H3-y The formula has a value of 1 to 3, where X is a halogen, y has a value of 1 to 3, z has a value of 1 to 3, p has a value of 0 to 2, and n has a value of 2 to 5, and the second precursor contains a reducing amine. The particular method further includes the step of exposing the surface of a substrate to an oxygen source in order to provide a film containing SiCON.

[0018] The reference, titled "Highly Stable Ultrathin Carbosiloxane Films by Molecular Layer Deposition," by Han, Z. et al., Journal of Physical Chemistry C, 2013, 117, 19967, teaches the growth of carbosiloxane films using 1,2-bis[(dimethylamino)dimethylsilyl]ethane and ozone. Thermal stability is shown to be stable below 40°C, with almost no thickness loss at 60°C. [Overview of the Initiative] [Problems that the invention aims to solve]

[0019] There is a demand for low dielectric constant silicon-containing films produced by thermal atomic layer deposition (ALD) or plasma-enhanced atomic layer deposition (PEALD) processes, such as, but not limited to, silicon oxide, silicon oxynitride, silicon oxycarbonitride, or carbon-doped silicon oxide. As-deposited silicon-containing films produced by thermal atomic layer deposition (ALD) or plasma-enhanced atomic layer deposition (PEALD) processes, such as, but not limited to, silicon oxide, silicon oxynitride, silicon oxycarbonitride, or carbon-doped silicon oxide, may have high k-values ​​due to high moisture absorption, residual Si-OH groups contained in the film, or low ashing resistance due to low film density. Methods for reducing the relative dielectric constant (k-value) of silicon-containing films are also required. [Means for solving the problem]

[0020] This development solves problems related to conventional precursors and processes by providing a silicon and carbon-containing precursor, which has at least one organic amino group that acts to fix the precursor unit to the surface of a substrate as part of a process for depositing a silicon and oxygen-containing film.

[0021] Processes for deposition in plasma-enhanced ALD (PEALD), plasma-enhanced cyclic chemical vapor deposition (PECCVD), plasma-enhanced ALD-like processes, or ALD processes for materials or films containing stoichiometric or non-stoichiometric silicon and oxygen, such as, but not limited to, silicon oxide films, carbon-doped silicon oxide films, silicon oxynitride films, or carbon-doped silicon oxynitride films, at relatively low temperatures, for example, one or more temperatures below 600°C, using an oxygen-containing reactant source, a nitrogen-containing reactant source, or a combination thereof.

[0022] In one embodiment, a method for depositing a film containing silicon and oxygen onto a substrate is described herein, the method comprising: (a) providing the substrate into a reactor; and (b) formulas A, B and C: [ka] Selected from the group consisting of, in the formula, R 1 However, linear C1~C 10 Alkyl groups, branched chains C3-C 10 Alkyl alkyl groups, C3-C 10 Cyclic alkyl groups, C3-C 10 Heterocyclic group, C3~C 10 Alkenyl group, C3~C 10 Alkynyl group and C4~C 10 Selected from aryl groups; R 2 However, hydrogen, C1~C 10 Linear alkyl groups, branched C3-C 10 Alkyl alkyl groups, C3-C 10 Cyclic alkyl groups, C3-C 10 Heterocyclic group, C2~C 10 Alkenyl group, C2~C10 Alkynyl group and C4~C 10 Selected from the group consisting of aryl groups, R in formula A, B, or C 1 and R 2 The two are either connected in such a way as to form an annular ring structure, or not connected in such a way as to form an annular ring structure; R 3-9 However, hydrogen, straight chain C1~C 10 Alkyl groups, branched chains C3-C 10 Alkyl alkyl groups, C3-C 10 Cyclic alkyl groups, C2-C 10 Alkenyl group, C2~C 10 Alkynyl group and C4~C 10 Each is independently selected from the aryl groups; R 10 However, linear C1~C 10 Alkyl alkyl groups, C2-C 10 Alkenyl group and C2-C 10 (c) introducing at least one silicon precursor compound selected from alkynyl groups into the reactor; (d) purging the reactor with a purge gas; (e) introducing at least one of an oxygen source and a nitrogen source into the reactor; (f) purging the reactor with a purge gas (steps b-e are repeated until a silicon-containing film of the desired thickness is deposited); (f) R 3 x Si(NR 1 R 2 ) 4-x A step of treating the resulting silicon-containing film using, in the formula, R 1-3 However, the method includes the same steps as described above, preferably methyl or ethyl, where x = 1, 2, or 3, and is carried out at one or more temperatures in the range of about 20°C to 300°C.

[0023] Methods for producing the above compounds are also disclosed herein.

[0024] Furthermore, methods for treating the deposited film as is, or for capping the film deposits, are disclosed herein by chemical treatment.

[0025] The embodiments of the present invention can be used individually or in combination with each other. [Modes for carrying out the invention]

[0026] In the context of describing the invention (particularly in the context of the claims below), the use of the terms “a,” “an,” and “the,” and similar demonstrative pronouns, shall be construed to cover both singular and plural unless otherwise indicated herein or unless clearly contradicted by the context. The terms “comprising,” “having,” “including,” and “containing,” shall be construed as open-ended terms (i.e., “including, but not limited to,”) unless otherwise indicated herein. Details of ranges of values ​​herein are merely intended to function as abbreviations for each individual value within that range, unless otherwise indicated herein, and each individual value is incorporated herein as it is individually detailed herein. All methods described herein may be performed in any suitable order unless otherwise supported herein or unless clearly contradicted by the context. Any and all examples or illustrative terms provided herein (e.g., "such as") are intended, unless otherwise asserted, merely to better illustrate the invention and not to limit its scope. No term herein should be construed as indicating that any unasserted element is essential to the practice of the invention.

[0027] Compositions and methods relating to the formation of films or materials containing stoichiometric or non-stoichiometric silicon and oxygen at temperatures below approximately 300°C or between approximately 25°C and approximately 300°C, or in some embodiments, at one or more temperatures between 25°C and approximately 300°C, for example, but not limited to, silicon oxide films, carbon-doped silicon oxide films, silicon oxynitride films, carbon-doped silicon oxynitride films, or combinations thereof, are described herein. The films described herein are deposited in a deposition process such as atomic layer deposition (ALD), or in an ALD-like process such as plasma-enhanced ALD (PEALD) or plasma-enhanced cyclic chemical vapor deposition (PECCVD), but not limited to, below. The low-temperature (e.g., one or more deposition temperatures in the range of approximately ambient temperature ~600°C) deposition methods described herein provide films or materials exhibiting at least one or more of the following advantages: low chemical impurities, thermal atomic layer deposition, high conformability in plasma-enhanced atomic layer deposition (ALD) processes or processes similar to plasma-enhanced ALD, the ability to control the carbon content in the resulting film; and / or the film having an etching rate of 5 angstroms / second (Å / sec) or less when measured at a 0.5 wt% diluted HF. For carbon-doped silicon oxide films, in addition to the other features, for example, but not limited to, densities of approximately 1.4 g / cc or more, approximately 1.8 g / cc or more, or approximately 2.0 g / cc or more, more than 1% carbon is desired to adjust the etching rate to less than 2 Å / sec at a 0.5 wt% diluted HF.

[0028] The methods disclosed herein can be carried out using equipment known in the art. For example, the methods can be carried out using reactors that are conventional in the field of semiconductor manufacturing.

[0029] While we do not wish to be bound by any theory or explanation, it is believed that the effectiveness of the precursor compositions disclosed herein can be varied depending on the number of silicon atoms and, in particular, the number of silicon-oxygen bonds. Typically, the precursors disclosed herein have 3 to 5 silicon atoms and 5 to 8 silicon-oxygen bonds.

[0030] The precursors disclosed herein have a structure different from those known in the art, perform better than conventional silicon-containing precursors, can provide relatively large GPCs, result in higher quality films, have a more favorable wet etching rate, or have less elemental contamination.

[0031] A method for depositing a carbon-doped silicon oxide film using a vapor deposition process, wherein the composition is of formula A, B, or C: [ka] It has, in the formula, R 1 However, linear C1~C 10 Alkyl groups, branched chains C3-C 10 Alkyl alkyl groups, C3-C 10 Cyclic alkyl groups, C3-C 10 Heterocyclic group, C3~C 10 Alkenyl group, C3~C 10 Alkynyl group and C4~C 10 Selected from aryl groups; R 2 However, hydrogen, C1~C 10 Linear alkyl groups, branched C3-C 10 Alkyl alkyl groups, C3-C 10 Cyclic alkyl groups, C3-C 10 Heterocyclic group, C2~C 10 Alkenyl group, C2~C 10 Alkynyl group and C4~C 10 Selected from the group consisting of aryl groups, R in formula A or B 1 and R 2 However, they are either connected in such a way as to form a ring-like structure, or they are not connected in such a way as to form a ring-like structure; R 3-9However, hydrogen, straight chain C1~C 10 Alkyl groups, branched chains C3-C 10 Alkyl alkyl groups, C3-C 10 Cyclic alkyl groups, C2-C 10 Alkenyl group, C2~C 10 Alkynyl group and C4~C 10 Each is independently selected from the aryl groups; R 10 However, linear C1~C 10 Alkyl alkyl groups, C2-C 10 Alkenyl group and C2-C 10 A method comprising a compound selected from alkynyl groups is disclosed herein.

[0032] In a preferred embodiment, according to the above conditions, for formulas A and B, the preferred embodiment is R 1-9 Each of these compounds is either hydrogen or methyl, and a preferred embodiment for formula C is R 1-2 Each of them is a C3-C4 alkyl, and R 10 It contains compounds in which the molecule is methyl.

[0033] In the above formula and throughout this specification, the term “oligosiloxane” means a compound containing at least three repeating -Si-O-siloxane units in its cyclic structure.

[0034] In the formulas above and throughout this specification, the term “alkyl” means a linear or branched functional group having 1 to 10 carbon atoms. Exemplary linear 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, an alkyl group may have one or more functional groups bonded to it, for example, an alkoxy group, a dialkylamino group, or a combination thereof, but not limited to the following. In other embodiments, an alkyl group may not have one or more functional groups bonded to it. An alkyl group may be saturated or, instead, unsaturated.

[0035] In the formulas above and throughout this specification, the term “cyclic alkyl” means 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.

[0036] In the above formula and throughout this specification, 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.

[0037] In the formulas described herein and throughout this specification, the terms “dialkylamino” group, “alkylamino” group, or “organoamino” group mean a group having two alkyl groups bonded to a nitrogen atom or one alkyl group bonded to a nitrogen atom, and having 1 to 10, 2 to 6, or 2 to 4 carbon atoms. Examples include HNMe and HNBu. t , NMe2, NMeEt, NET2 and NPr i This includes, but is not limited to, 2.

[0038] In the formulas above and throughout this specification, the term “aryl” means 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.

[0039] Throughout this specification, the term "alkyl hydrocarbon" refers to a linear or branched C1-C1 hydrocarbon. 20 Hydrocarbons, cyclic C6-C 20 This refers to hydrocarbons. Exemplary hydrocarbons include, but are not limited to, heptane, octane, nonane, decane, dodecane, cyclooctane, cyclononane, and cyclodecane.

[0040] Throughout this specification, the term "alkoxy" refers to C1-C1 10 -OR 1 It refers to the base, R 1 The above definition is used. Exemplary alkoxy groups include, but are not limited to, methoxy, ethoxy, isopropoxy, n-propoxy, n-butoxy, sec-butoxy, tert-butoxy, and phenoxide.

[0041] Throughout this specification, the term "ashing" refers to the process of removing a photoresist or carbon hard mask in a semiconductor manufacturing process using a plasma containing an oxygen source, such as an O2 / inert gas plasma, O2 plasma, CO2 plasma, CO plasma, H2 / O2 plasma, or a combination thereof.

[0042] In the formulas above and throughout this specification, the term “heterocyclic” means a non-aromatic saturated monocyclic or polycyclic ring system having about 3 to about 10 ring atoms, preferably about 5 to about 10 ring atoms, in which one or more of the atoms are elements other than carbon, such as nitrogen, oxygen, or sulfur. A preferred heterocyclic ring contains about 5 to about 6 ring atoms. The prefixes aza, oxo, or thio preceding heterocyclic rings mean, respectively, that at least one nitrogen, oxygen, or sulfur atom is present as a ring atom. Heterocyclic groups are optionally substituted.

[0043] Exemplary silicon compounds having formulas A to C are listed in Tables 1a and 1b. Table 1a. Exemplary silicon compounds having formula A or B [Table 1-1] [Table 1-2] [Table 1-3] [Table 1-4] [Table 1-5] [Table 1-6] Table 1b. Exemplary silicon compounds having formula C [Table 2] Preferably, the silicon precursor compound having formula A, B or C according to the present invention, and the composition comprising the silicon precursor compound having formula A or B according to the present invention are substantially free of halide ions. As used herein, the term "substantially free of" means, with respect to halide ions (or halides), such as chloride (i.e., chloride-containing species, such as HCl, or a silicon compound having at least one Si-Cl bond), fluoride, bromide and iodide, less than 5 ppm (by weight) when measured by ICP-MS, preferably less than 3 ppm when measured by ICP-MS, more preferably less than 1 ppm when measured by ICP-MS, and most preferably 0 ppm when measured by ICP-MS. Chloride is known to act as a decomposition catalyst for silicon precursor compounds having formula A - C. A significant level of chloride in the final product can decompose the silicon precursor compound. The slow decomposition of the silicon precursor compound can directly affect the film deposition process, making it difficult for semiconductor manufacturers to meet the film specifications. In addition, the shelf life or stability is negatively affected by a greater decomposition rate of the silicon precursor compound, thereby making it difficult to guarantee a shelf life of 1 - 2 years. Thus, the accelerated decomposition of the silicon precursor compound raises safety and performance concerns related to the formation of these flammable and / or pyrophoric gaseous by-products. Preferably, the silicon precursor compound having formula A or B is free of metal ions, such as Li + , Mg 2+ , Al 3+ , Fe 2+ , Fe 2+ , Fe 3+ , Ni 2+ , Cr 3+Substantially free of Li, Al, Fe, Ni, and Cr, as measured by ICP-MS, the term "substantially free" means less than 5 ppm (by weight), preferably less than 3 ppm, more preferably less than 1 ppm, and most preferably less than 0.1 ppm. In some embodiments, the silicon precursor compound having formula A is free of metal ions, such as Li + Mg 2+ , Al 3+ Fe 2+ Fe 3+ Ni 2+ , Cr 3+ It does not contain. When used herein, the term "does not contain" means less than 1 ppm (by weight), preferably less than 0.1 ppm, when measured by ICP-MS or other analytical methods for measuring metals, in the case of Li, Mg, Al, Fe, Ni, Cr, noble metals, such as ruthenium or platinum catalysts used in synthesis, or volatile Ru or Pt complexes derived from such catalysts.

[0044] One embodiment of the present invention is a method for depositing a carbon-doped silicon and oxygen-containing film on at least one surface of a substrate at a temperature of 20°C to 300°C, a. A step of providing the substrate into the reactor; b. A step of introducing at least one silicon precursor having formulas A to C as described herein into a reactor; c. A step of purging the reactor with a purge gas to remove at least a portion of the unabsorbed precursor; d. The step of introducing an oxygen-containing source into the reactor; e. A step of purging the reactor with a purge gas to remove at least a portion of the unreacted oxygen-containing source; f. A step of repeating steps b to e until a silicon-containing film of the desired thickness is deposited; gR 3 x Si(NR 1 R 2 )4-x The formula has the following, where R 1-3 However, hydrogen, straight chain C1~C 10 Alkyl groups, branched chains C3-C 10 Alkyl alkyl groups, C3-C 10 Cyclic alkyl groups, C3-C 10 Heterocyclic group, C3~C 10 Alkenyl group, C3~C 10 A step of treating the obtained silicon-containing film with a silicon precursor independently selected from an alkynyl group, preferably methyl or ethyl, where x = 1, 2, or 3; h. Purge the reactor using purge gas to remove surface hydroxyls on the silicon-containing film, and R 3 x Si(NR 1 R 2 ) 4-x A step of removing at least a portion of any by-products resulting from the reaction with a silicon precursor having the formula, Methods including the above are described herein.

[0045] In a particular embodiment, during the deposition process, the film as deposited by steps b to f is treated using steps g to h, which are carried out, for example, by one ALD cycle, two ALD cycles, five ALD cycles, or ten or more ALD cycles, until all reactive hydroxyls are consumed, thereby reducing the dielectric constant to 5 or less, preferably 4 or less, most preferably 3 or less. 3 x Si(NR 1 R 2 ) 4-xExemplary silicon precursors having the formula are, but are not limited to, diethylaminotriethylsilane, dimethylaminotriethylsilane, ethylmethylaminotriethylsilane, t-butylaminotriethylsilane, isopropylaminotriethylsilane, di-isopropylaminotriethylsilane, pyrrolidonotriethylsilane, diethylaminotrimethylsilane, dimethylaminotrimethylsilane, ethylmethylaminotrimethylsilane, t-butylaminotrimethylsilane, isopropylaminotrimethylsilane, di-isopropylaminotrimethylsilane, pyrrolidonotrimethylsilane, diethylaminodimethylsilane, dimethylaminodimethylsilane, ethylmethylaminodimethylsilane, t-butylaminodimethylsilane, isopropylaminodimethylsilane, di-isopropylaminodimethylsilane, pyrrolidinodimethylsilane, diethylaminodiethylsilane, dimethylaminodiethylsilane, ethylmethylaminodiethylsilane, t-butylaminodiethylsilane, isopropylaminodiethylsilane, di-isopropylaminodiethylsilane, and pylori. Dinodiethylsilane, bis(diethylamino)dimethylsilane, bis(dimethylamino)dimethylsilane, bis(ethylmethylamino)dimethylsilane, bis(di-isopropylamino)dimethylsilane, bis(isopropylamino)dimethylsilane, bis(tert-butylamino)dimethylsilane, dipyrrolidinodimethylsilane, bis(diethylamino)diethylsilane, bis(dimethylamino)diethylsilane, bis(ethylmethylamino)diethylsilane, bis(diisopropylamino)diethylsilane, bis(isopropylamino) (no)diethylsilane, bis(tert-butylamino)diethylsilane, dipyrrolidinodiethylsilane, bis(diethylamino)methylvinylsilane, bis(dimethylamino)methylvinylsilane, bis(ethylmethylamino)methylvinylsilane, bis(di-isopropylamino)methylvinylsilane, bis(isopropylamino)methylvinylsilane, bis(tert-butylamino)methylvinylsilane, dipyrrolidinomethylvinylsilane, 2,6-dimethylpiperidinomethylsilane, 2,6-dimethylpiperidinodimethylsilane, 2,This includes 6-dimethylpiperidinotrimethylsilane, tris(dimethylamino)phenylsilane, tris(dimethylamino)methylsilane, tris(dimethylamino)ethylsilane, and mixtures thereof. In some embodiments, steps g to h can be performed at a temperature of 300°C to 550°C after steps b to f have been performed for the desired thickness.

[0046] In another specific embodiment, the method described herein involves depositing a silicon and oxygen-containing film, comprising two silicon-containing films, onto a substrate at a temperature of 20°C to 300°C. The method is as follows: a. A step of providing the substrate into the reactor; b. A step of introducing at least one silicon precursor having formulas A to C as described herein into a reactor; c. A step of purging the reactor with a purge gas to remove at least a portion of the unabsorbed precursor; d. The step of introducing an oxygen-containing source into the reactor; e. A step of purging the reactor with a purge gas to remove at least a portion of the unreacted oxygen-containing source; f. A step of repeating steps b to e until a first silicon-containing film of the desired thickness is deposited; g.Formula R 3 x Si(NR 1 R 2 ) 4-x It has, in the formula, R 1-3 However, hydrogen, straight chain C1~C 10 Alkyl groups, branched chains C3-C 10 Alkyl alkyl groups, C3-C 10 Cyclic alkyl groups, C3-C 10 Heterocyclic group, C3~C 10 Alkenyl group and C3-C 10 The process involves introducing at least one silicon precursor into the reactor, each independently selected from an alkynyl group, preferably methyl or ethyl, with x = 1, 2, or 3; h. A step of purging the reactor with a purge gas to remove at least a portion of the unabsorbed precursor; i. The step of introducing an oxygen-containing source into the reactor; j. A step of purging the reactor with a purge gas to remove at least a portion of the unreacted oxygen-containing source: k. A process of repeating steps g to j until a second silicon-containing film of the desired thickness is deposited. Includes.

[0047] In one particular embodiment, during the deposition process, the desired thickness of the first silicon-containing film by steps b-f is 10 Å-500 Å, 10 Å-100 Å, or 10 Å-50 Å. The desired thickness of the second silicon-containing film by steps g-k is 1 Å-50 Å, 2 Å-40 Å, 2 Å-30 Å, 2 Å-20 Å, or 2 Å-10 Å. The second silicon-containing film has a higher density and lower carbon content than the first silicon-containing film, and therefore provides oxygen ashing resistance during the semiconductor manufacturing process, resulting in less damage to the first silicon-containing film. Formula R 3 x Si(NR 1 R 2 ) 4-x (In the formula, R 3 is hydrogen, R 2-3 Exemplary silicon precursors in this embodiment, having hydrogen, linear C1-C5 alkyl groups, and branched C3-C5 alkyl groups (x=1, 2), include, but are not limited to, di-isopropylaminosilane, di-sec-butylaminosilane, bis(diethylamino)silane, bis(tert-butylamino)silane, and mixtures thereof. In some embodiments, steps b-f are carried out at lower temperatures of 20°C-150°C to maximize the carbon content remaining in the carbon-doped silicon oxide, while steps g-k are carried out at higher temperatures of 200°C-300°C to provide a higher density silicon oxide with a lower carbon content, thereby giving the second silicon-containing film better ashing resistance. In certain embodiments, the oxygen source in steps d and i is the same. In alternative embodiments, the oxygen source in steps d and i is different. In some embodiments, steps g to h may be performed at a temperature of 300°C to 550°C after steps b to f have been performed for the desired thickness.

[0048] The methods disclosed herein are characterized by: a density of at least about 1.4 g / cc, about 1.8 g / cc, or about 2.1 g / cc; a wet etching rate of less than about 2.5 Å / s when measured in a 1:100 HF:water diluted HF (0.5 wt% dHF) acid solution; and a rate of about 5 × 10⁻¹⁶ when measured by secondary ion mass spectrometry (SIMS). 20 A carbon-doped silicon oxide film is formed, comprising at least one of the following: hydrogen impurities in a quantity less than at / cc.

[0049] In certain embodiments of the methods and compositions described herein, a layer of silicon-containing dielectric material is deposited on at least a portion of a substrate by, for example, a chemical vapor deposition (CVD) process using a reaction chamber. Suitable substrates include, but are not limited to, semiconductor materials such as gallium arsenide (GaAs), silicon, and silicon-containing compositions such as crystalline silicon, polysilicon, amorphous silicon, epitaxial silicon, silicon dioxide (SiO2), silicon glass, silicon nitride, fused silica, glass, quartz, borosilicate glass, and combinations thereof. Other suitable materials include chromium, molybdenum, and other metals commonly used in semiconductor, integrated circuit, flat panel display, and flexible display applications. The substrate may have further layers made of, for example, silicon, SiO2, organic silicate glass (OSG), fluorinated silicate glass (FSG), boron carbonitride, silicon carbide, silicon hydride carbide, silicon nitride, silicon hydride nitride, silicon carbonitride, silicon hydride carbonitride, boron nitride, organic-inorganic composite materials, photoresists, organic polymers, porous organic and inorganic materials and composites, metal oxides such as aluminum oxide and germanium oxide. The further layers may be germanosilicate, aluminosilicate, copper and aluminum, and diffusion barrier materials such as, for example, TiN, Ti(C)N, TaN, Ta(C)N, Ta, W, or WN, but are not limited to the following.

[0050] The deposition methods disclosed herein may include one or more purge gases. The purge gas used to purge unconsumed reactants and / or reaction by-products is an inert gas that does not react with the precursors. 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, e.g., Ar, is supplied into the reactor at a flow rate of about 10 to about 2000 sccm over a period of about 0.1 to 1000 seconds to purge any unreacted material and any by-products that may remain in the reactor.

[0051] A purge gas, such as argon, purges any unabsorbed excess composite 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 byproducts from the chamber. The process cycle can be repeated to achieve the desired film thickness. In some cases, pumping can be used instead of purging with an inert gas, or both can be used to remove unreacted silicon precursors.

[0052] Throughout this specification, the term “ALD or ALD-like” means, but is not limited to, the following processes: a) a process of successively introducing each reactant, including a silicon precursor and a reactive gas, into a reactor, for example, a single-wafer ALD reactor, a semi-batch ALD reactor, or a batch furnace ALD reactor; b) a process of exposing a substrate to each reactant, including a silicon precursor and a reactive gas, by moving or rotating the substrate into different compartments of the reactor, wherein each compartment is separated by an inert gas curtain, i.e., a spatial ALD reactor or a roll-to-roll ALD reactor.

[0053] The method of the present invention is carried out by an ALD process using an oxygen-containing source, such as ozone, hydrogen peroxide, or plasma, the plasma may further contain an inert gas, for example: an oxygen plasma with or without an inert gas, a water vapor plasma with or without an inert gas, a nitrogen oxide (e.g., N2O, NO, NO2, or a combination thereof) plasma with or without an inert gas, a carbon oxide (e.g., CO2, CO, or a combination thereof) plasma with or without an inert gas, and one or more of the following combinations. In certain embodiments, the oxygen-containing plasma source further contains an inert gas. In these embodiments, the inert gas is selected from the group consisting of argon, helium, nitrogen, hydrogen, or a combination thereof. In alternative embodiments, the oxygen-containing plasma source does not contain an inert gas.

[0054] The oxygen-containing plasma source can be generated in situ or remotely. In one particular embodiment, the oxygen-containing source contains oxygen and is flowed or introduced during steps b to d of the method together with other reagents, for example, at least one silicon precursor and optionally with an inert gas, although this is not limited to the following.

[0055] In certain embodiments, the compositions used in the methods described and disclosed herein further comprise a solvent. Exemplary solvents may include, but are not limited to, ethers, tertiary amines, alkyl hydrocarbons, aromatic hydrocarbons, tertiary amino ethers, and combinations thereof. In certain embodiments, the difference between the boiling point of the silicon precursor and the boiling point of the solvent is 40°C or less. In some embodiments, the compositions can be transported into the reactor chamber for the silicon-containing membrane by direct liquid injection.

[0056] In embodiments of the present invention, in which at least one silicon precursor having formulas A to C 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 in the composition is 0.5 wt% to 99.5 wt% or 10 wt% to 75 wt% by weight. In this embodiment or other embodiments, the solvent has a bp close to the boiling point (bp) of the silicon precursor of formulas A to C, or the difference between the bp of the solvent and the bp of the silicon precursor of formulas A to C is 40°C or less, 30°C or less, 20°C or less, or 10°C. Alternatively, the boiling point difference is a range with any one or more endpoints from the following: 0, 10, 20, 30, or 40°C. Examples of suitable ranges for the bp difference include, but are not limited to, 0°C to 40°C, 20°C to 30°C, or 10°C to 30°C. 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.

[0057] In certain embodiments, silicon oxide films 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 (H2O) (e.g., deionized water, purified water, and / or distilled water), oxygen (O2), oxygen plasma, NO, N2O, NO2, carbon monoxide (CO), carbon dioxide (CO2), and combinations thereof. The oxygen-containing source is provided by passing through, for example, an in-situ or remote plasma generator to provide an oxygen-containing plasma source, such as an oxygen plasma, a plasma containing oxygen and argon, a plasma containing 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 of about 1 to about 2000 standard cubic centimeters (sccm) or about 1 to about 1000 sccm. The oxygen-containing plasma source can be introduced over a period of time ranging from about 0.1 to about 100 seconds. In one particular embodiment, the oxygen-containing plasma source includes water having a temperature of 10°C or higher. In embodiments in which a film is deposited by a PEALD process or a plasma-enhanced cyclic CVD process, depending on the volume of the ALD reactor, the precursor pulse may have a pulse duration longer than 0.01 seconds (e.g., about 0.01 to about 0.1 seconds, about 0.1 to about 0.5 seconds, about 0.5 to about 10 seconds, about 0.5 to about 20 seconds, about 1 to about 100 seconds), and the oxygen-containing plasma source may have a pulse duration shorter than 0.01 seconds (e.g., about 0.001 to about 0.01 seconds).

[0058] Each step of supplying the precursor, oxygen source and / or other precursors, source gas and / or reagent can be varied in terms of the time for supplying them, thereby altering the stoichiometric composition of the resulting dielectric film.

[0059] Energy is applied to at least one of the silicon precursors of formulas A to C, an oxygen-containing source, or a combination thereof to induce a reaction and form a dielectric film or coating on a 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 on the substrate surface. In embodiments in which deposition involves plasma, the plasma generation process may 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 supplied into the reactor.

[0060] At least one silicon precursor can be transported by various means to a reaction chamber, for example, a plasma-enhanced cyclic CVD reactor, a PEALD reactor, or a batch reactor. In one embodiment, a liquid transport system is used. In an alternative embodiment, a device combining a liquid transport process and a flash vaporization process is used, for example, with a turbo vaporizer manufactured by MSP Corporation of Shoreview, MN, to enable the transport of low-volatility materials with volumetric measurement, resulting in reproducible transport and deposition without thermal decomposition of the precursor. In liquid transport formulations, the precursors described herein may be transported in substantially liquid form, or alternatively, in a solvent formulation or composition containing the precursor. Thus, in certain embodiments, the precursor formulation may contain at least one solvent component with suitable characteristics so as to be desirable and advantageous for a given end-use application for forming a film on a substrate.

[0061] As previously stated, the purity level of at least one silicon precursor is sufficiently high to be acceptable for reliable semiconductor manufacturing. In certain embodiments, the at least one silicon precursor described herein contains less than 2 wt%, less than 1 wt%, or less than 0.5 wt%, one or more of the following impurities: one or more of free amines, free halides, or halogen ions, and species of higher molecular weight. Higher purity levels of the silicon precursors described herein can be obtained through one or more of the following processes: purification, adsorption, and / or distillation.

[0062] In one embodiment of the method described herein, the plasma-enhanced cyclic deposition process can be, for example, a PEALD-like process or a PEALD process, and the deposition is carried out using at least one silicon precursor and an oxygen plasma source. The PEALD-like process is defined as a plasma-enhanced cyclic CVD process, but provides a highly conformable silicon and oxygen-containing film.

[0063] The formulas are A to B, and in the formulas, R 3-9 Organic amino-functionalized cyclic oligosiloxane precursors, some of which are methyl groups instead of hydrogen, are considered preferred for this method because these precursors either contain no Si-H groups at all or only a limited number of Si-H groups, and Si-H groups can decompose at temperatures above 600°C, potentially causing undesirable chemical vapor deposition. However, under certain conditions, for example, when using short precursor pulses or low reactor pressure, this method is preferable for a compound having formulas A-B, where R 3-9 This can also be done at temperatures above 600°C without significant undesirable chemical vapor deposition, using organic amino-functionalized cyclic oligosiloxane precursors in which some of the atoms are hydrogen.

[0064] Various commercial ALD reactors, such as single-wafer reactors, semi-batch reactors, batch reactors, or roll-to-roll reactors, can be used to deposit solid silicon oxide, silicon oxynitride, carbon-doped silicon oxynitride, or carbon-doped silicon oxide.

[0065] The 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, and 300°C. Exemplary temperature ranges include, but are not limited to, the following: about 0°C to about 300°C; about 25°C to about 300°C; about 50°C to about 290°C; about 25°C to about 250°C; or about 25°C to about 200°C.

[0066] 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 peroxides, and mixtures thereof.

[0067] In further embodiments of the methods described herein, films deposited from ALD, ALD-like materials, PEALD, or PEALD-like materials, or films left as deposited, undergo a processing step (post-deposition processing). The processing step can be performed during or after the deposition process, or in combination thereof. Exemplary processing steps include, but are not limited to, high-temperature thermal annealing at temperatures in the ranges of 500°C to 1200°C, 600°C to 800°C, 550°C to 750°C, 600°C to 750°C, or 600°C to 700°C; plasma treatment, such as helium plasma or argon plasma; ultraviolet (UV) light treatment; laser treatment; electron beam treatment; and combinations thereof, affecting one or more properties of the film.

[0068] In another embodiment, a vessel or container for depositing a silicon-containing film comprises one or more silicon precursor compounds as described herein. In one particular embodiment, the vessel comprises at least one pressurized vessel (preferably made of stainless steel having a design disclosed, for example, in U.S. Patents 7,334,595; 6,077,356; 5,069,244; and 5,465,766), the disclosures of which are incorporated herein by reference. The vessel may comprise either glass (borosilicate or quartz glass) or 316, 316L, 304, or 304L series stainless steel alloy (S31600, S31603, S30400, S30403 in UNS designations) and comprises suitable valves and fittings enabling transport of one or more precursors to a reactor for a CVD or ALD process. In this embodiment or other embodiments, the silicon precursor is supplied in a pressurized container made of stainless steel, and the purity of the precursor is 98 wt% or higher, or 99.5 wt% or higher, which is suitable for many semiconductor applications. The upper space of the container is filled with an inert gas selected from helium, argon, nitrogen, and combinations thereof.

[0069] In certain embodiments, a gas line connecting a precursor canister to a reaction chamber is heated to one or more temperatures as required by the process, and a container of at least one silicon precursor is kept at one or more temperatures for bubbling. In other embodiments, a solution containing at least one silicon precursor is injected directly into a vaporizer kept at one or more temperatures for liquid injection.

[0070] A stream of argon and / or other gases can be used as a carrier gas to facilitate the transport of vapor of at least one silicon precursor into the reaction chamber during the precursor pulse. In certain embodiments, the process pressure in the reaction chamber is about 50 mTorr to 10 Torr. In other embodiments, the process pressure in the reaction chamber may be 760 Torr or less (e.g., about 50 mTorr to about 100 Torr).

[0071] In a typical PEALD process or a process similar to PEALD, such as the PECCVD process, a substrate, such as a silicon oxide substrate, is heated in a heater stage in a reaction chamber where it is exposed to a silicon precursor, thereby initially causing the complex to chemiadsorb onto the surface of the substrate.

[0072] Films deposited using silicon precursors having formulas A to C described herein exhibit improved properties compared to films deposited under the same conditions using previously disclosed silicon precursors, such as, for example, a wet etching rate lower than that of the film before the processing step, or a density higher than that of the film before the processing step, although these properties are not limited to the following. In one particular embodiment, the as-deposited film is intermittently processed during the deposition process. These intermittent or intermediate processing steps can be performed, for example, after each ALD cycle, after every certain number of ALD cycles, for example, after every one ALD cycle, every two ALD cycles, every five ALD cycles, or every ten or more ALD cycles, although these properties are not limited to the following.

[0073] The precursors of formulas A to C exhibit a growth rate of 1.0 Å / cycle or higher, preferably 1.5 Å / cycle or higher, and most preferably 2.0 Å / cycle or higher.

[0074] In embodiments in which the film is treated by a high-temperature annealing process, the annealing temperature is at least 100°C higher than the deposition temperature. In this embodiment or other embodiments, the annealing temperature is about 400°C to about 1000°C. In this embodiment or other embodiments, the annealing process can be carried out in a vacuum (<760 Torr), in an inert environment, or in an oxygen-containing environment (e.g., H2O, N2O, NO2, or O2).

[0075] In embodiments where the film is treated by UV treatment, the film is exposed to a broadband UV source, or alternatively, a UV source having wavelengths of approximately 150 nanometers (nm) to approximately 400 nm. In one particular embodiment, the as-deposited film is exposed to UV in a chamber different from the deposition chamber after it has reached a desired film thickness.

[0076] 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 contaminants from penetrating the film during subsequent plasma treatment. The passivation layer can be deposited using atomic layer deposition or cyclic chemical vapor deposition.

[0077] In embodiments in which the film is treated with plasma, the plasma source is selected from the group consisting of hydrogen plasma, plasma containing hydrogen and helium, and plasma containing hydrogen and argon. Hydrogen plasma reduces the dielectric constant of the film, increases the damage resistance by the plasma ashing process, while at the same time keeping the carbon content in the bulk virtually unchanged.

[0078] Although not intended to be constrained by any particular theory, silicon precursor compounds having the chemical structures represented by formulas A-C defined above can provide multiple Si-O-Si fragments per precursor molecule by fixing the organic amino group by reacting it with hydroxyl on the substrate surface. Therefore, it is thought that this increases the growth rate of silicon oxide or carbon-doped silicon oxide compared to conventional silicon precursors, such as bis(tert-butylamino)silane or bis(diethylamino)silane having only one silicon atom.

[0079] In certain embodiments, the silicon-containing films described herein have dielectric constants of 6 or less, 5 or less, 4 or less, and 3 or less. In these embodiments or other embodiments, the films may have dielectric constants of about 5 or less, about 4 or less, or about 3.5 or less. However, films having other dielectric constants (e.g., higher or lower dielectric constants) can also be formed depending on the desired end application of the film. An example of a silicon-containing film formed using silicon precursors and processes having formulas A-C described herein is the film of formula Si x O y C z N v H w The formula has the following characteristics, where, as measured by XPS or other means, in atomic percent wt%, Si is about 10% to about 40%; O is about 0% to about 65%; C is about 0% to about 75% or about 0% to about 50%; N is about 0% to about 75% or about 0% to about 50%; and H is about 0% to about 50%, with x+y+z+v+w=100 atoms wt%. Another example of a silicon-containing film formed using the silicon precursors and processes of formulas A to C described herein is silicon carbonate nitride, where the carbon content is 1 at% to 80 at% as measured by XPS. Yet another example of a silicon-containing film formed using the silicon precursors and processes having formulas A to C described herein is amorphous silicon, where the sum of both nitrogen and carbon content is less than 10 at%, preferably less than 5 at%, most preferably less than 1 at% as measured by XPS.

[0080] As described herein, silicon-containing films can be deposited on at least a portion of a substrate using the methods described herein. Examples of suitable substrates include silicon, SiO2, Si3N4, OSG, FSG, silicon carbide, silicon hydride oxycarbide, silicon hydride oxynitride, silicon carbonate, silicon hydride carbonate, 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 are not limited to, TiN, Ti(C)N, TaN, Ta(C)N, Ta, W, or WN. The films are compatible with various subsequent processing steps, such as chemical mechanical planarization (CMP) and anisotropic etching processes.

[0081] The deposited films have applications including, but are not limited to, computer chips, optical devices, magnetic information storage devices, coatings on support materials or substrates, microelectrochemical systems (MEMS), nanoelectrochemical 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 insulators, intermediate dielectrics, passivation layers, etching stop layers, parts of dual spacers, and sacrificial layers for patterning.

[0082] In certain embodiments, one or more silicon precursors having formulas A to C described herein can be used to form a solid, non-porous, or substantially poreless silicon and oxygen-containing film.

[0083] The following embodiments are provided to illustrate specific aspects of the present invention and are not intended to limit the scope of the appended claims. [Examples]

[0084] Thermal atomic layer deposition of silicon oxide films was performed using a laboratory-scale ALD (Advanced Laser Deposition) system. The silicon precursor was transported to the chamber by vapor extraction. All gases (e.g., purge gas and reactant gas or precursor and oxygen source) were preheated to 100°C before being introduced into the deposition area. The gas and precursor flow rates were controlled at high speed using an ALD diaphragm valve. The substrate used for deposition was a 12-inch length silicon strip. A thermocouple was attached to the sample holder to confirm the substrate temperature. Ozone was used as the oxygen source gas during deposition. The typical deposition process and parameters are shown in Table 2.

[0085] Table 2. Process for thermal atomic layer deposition of silicon oxide films using ozone as the oxygen source in laboratory-scale ALD processing tools. [Table 3]

[0086] Following deposition, the sample was subjected to precursor treatment in the same laboratory-scale ALD treatment tool. The silicon precursor was transported to the chamber by vapor extraction. The precursor vapor was preheated to 100°C before being introduced into the deposition area. The gas and precursor flow rates were controlled at high speed using an ALD diaphragm valve.

[0087] Wet etching rate (WER) measurements were performed using a 1:99 diluted hydrofluoric acid (HF) solution. For each experimental set, a thermooxide wafer was used as a standard to verify the etching solution's properties. Before beginning to collect WER from the bulk film, the sample was completely etched in 15 seconds to remove any surface layers. Following this procedure, the typical wet etching rate of a thermooxide wafer for a 1:99 diluted HF aqueous solution was 0.5 Å / s. All density measurements were performed by X-ray reflectivity (XRR). Compositional analysis was performed using secondary ion mass spectrometry (D-SIMS) or X-ray photoelectron spectroscopy (XPS). Dielectric constant (k) measurements were performed using a Materials Development Corporation (MDC) mercury probe (Model 802B) calibrated with a thermooxide standard.

[0088] Example 1: Having formula B, where R 1 =R 2 =R 3 =R 4 =R 6 =R 8 =methyl, R 5 =R 7 =R 9 Chemical treatment in thermal atomic layer deposition of silicon-containing films deposited from hydrogen-containing 2-dimethylamino-2,4,6,8-tetramethylcyclotetrasiloxane

[0089] Atomic layer deposition of silicon and oxygen-containing films was performed using the following precursor: 2-dimethylamino-2,4,6,8-tetramethylcyclotetrasiloxane. Deposition was carried out using a laboratory-scale ALD processing tool. The silicon precursor was transported to the chamber by vapor extraction. The deposition process and parameters are provided in Table 2. Steps 1-6 were repeated until the desired thickness was reached. The temperature, ozone concentration, and GPC of the deposition process are provided in Table 3a, and the film properties are provided in Table 3b. Carbon-doped silicon oxide films were obtained at low temperatures (100°C) and different ozone concentrations.

[0090] Table 3a. Thermal ALD deposition temperature, ozone concentration, and GPC of 2-dimethylamino-2,4,6,8-tetramethylcyclotetrasiloxane in the ozone process. [Table 4]

[0091] Table 3b. Thermal ALD deposition temperature, ozone concentration, and film characteristics of 2-dimethylamino-2,4,6,8-tetramethylcyclotetrasiloxane in the ozone process. [Table 5]

[0092] Films deposited at 100°C (samples A-C) were treated either at 300°C for 5 minutes at a precursor chamber pressure of 0.3 Torr using silicon precursor N,N-dimethyltrimethylsilylamine (DMATMS), or at 450°C for 5 minutes at 0.3 Torr using silicon precursor N,N-diethylaminotrimethylsilylamine (DEATMS). The k-values ​​of the films before and after treatment, and the WER after treatment are shown in Table 4.

[0093] Table 4. k-value and WER of the SiOC film before and after chemical treatment using DMATMS at 300°C or DEATMS at 450°C. [Table 6]

[0094] Example 2: Having formula C, where R 1 and R 2 is ethyl, and R 10 Chemical treatment in thermal atomic layer deposition of carbon-doped silicon oxide films using diethylaminomethylsilane, which is methyl.

[0095] Atomic layer deposition of silicon oxide films was performed using the following precursor: diethylaminomethylsilane. Deposition was carried out using a laboratory-scale ALD processing tool. The silicon precursor was transported to the chamber by vapor extraction. The deposition process and parameters are provided in Table 2. Steps 1-6 were repeated until the desired thickness was reached. The substrate temperature was 100°C. Deposition temperature, ozone concentration, GPC, and film properties are provided in Table 5.

[0096] Table 5. Thermal ALD deposition temperature and GPC of diethylaminomethylsilane in the ozone process. [Table 7]

[0097] Films deposited at 100°C were treated with the silicon precursor N,N-diethylaminotrimethylsilylamine (DEATMS) at 300°C for 5 and 25 minutes, or with the silicon precursor di-isopropylaminosilane (DIPAS) at 300°C for 5 and 10 minutes, or annealed at 300°C without chemical treatment. The k values ​​of the films before and after different treatments are shown in Table 6.

[0098] Table 6. k values ​​of carbon-doped silicon oxide films before and after chemical treatment using DEATMS or DIPAS at 300°C. [Table 8]

[0099] While this disclosure has been described with reference to certain preferred embodiments, it will be understood by those skilled in the art that various modifications can be made and their elements can be replaced with equivalents without departing from the scope of the invention. In addition, many modifications can be made to adapt the teachings of the invention to certain situations or materials without departing from the essential scope of the invention. Accordingly, the invention is not limited to any particular embodiment, and is intended to include all embodiments within the scope of the appended claims. The following embodiments can be cited as examples of the present invention. (Note 1) A method for depositing a carbon-doped silicon oxide film onto a substrate, a) A step of providing the substrate into the reactor; b) Formulas A~C: [ka] Selected from the group consisting of, in the formula, R 1 However, linear C1~C 10 Alkyl groups, branched chains C3-C 10 Alkyl alkyl groups, C3-C 10 Cyclic alkyl groups, C3-C 10 Heterocyclic group, C3~C 10 Alkenyl group, C3~C 10 Alkynyl group and C4~C 10 Selected from aryl groups; R 2 However, hydrogen, C1~C 10 Linear alkyl groups, branched C3-C 10 Alkyl alkyl groups, C3-C 10 Cyclic alkyl groups, C3-C 10 Heterocyclic group, C2~C 10 Alkenyl group, C2~C 10 Alkynyl group and C4~C 10 Selected from the group consisting of aryl groups, R in formula A or B 1 and R 2 The two are either connected in such a way as to form an annular ring structure, or not connected in such a way as to form an annular ring structure; R 3-9 However, hydrogen, straight chain C1~C 10 Alkyl groups, branched chains C3-C 10 Alkyl alkyl groups, C3-C 10 Cyclic alkyl groups, C2-C 10 Alkenyl group, C2~C 10 Alkynyl group and C4~C 10 Each is independently selected from the aryl groups; R 10 However, linear C1~C 10 Alkyl alkyl groups, C2-C 10 Alkenyl group and C2-C 10The steps include: introducing at least one first silicon precursor selected from alkynyl groups into the reactor; c) Purging the reactor using a purge gas to remove at least a portion of any of the at least one first silicon precursor that has not been absorbed by the substrate; d) A step of introducing an oxygen-containing source into the reactor and reacting it with at least one first silicon precursor to form a silicon oxide film; e) Purging the reactor with a purge gas to remove at least a portion of any unreacted oxygen-containing sources; f) A step of repeating steps b) to e) until a silicon oxide film of the desired thickness is deposited; g)R 3 x Si(NR 1 R 2 ) 4-x The formula has the following, where R 1-3 The above is defined, and the process involves treating the silicon oxide film with a second silicon precursor where x=1, 2, or 3 to form a carbon-doped silicon oxide film; h) A step of purging the reactor with a purge gas to remove at least some of any by-products from a treatment step in which the silicon oxide film is treated with a second silicon precursor. A method that includes and is carried out at one or more temperatures in the range of approximately 20°C to 300°C. (Note 2) R 1-2 The method described in Appendix 1, wherein each of the elements is a C1-C4 alkyl group. (Note 3) R 1-3 The method according to Appendix 1, wherein each of the elements is independently selected from the group consisting of methyl and ethyl. (Note 4) At least one first silicon precursor compound is 2-dimethylamino-2,4,4,6,6-pentamethylcyclotrisiloxane, 2-diethylamino-2,4,4,6,6-pentamethylcyclotrisiloxane, 2-ethylmethylamino-2,4,4,6,6-pentamethylcyclotrisiloxane, 2-isopropylamino-2,4,4,6,6-pentamethylcyclotrisiloxane, 2-dimethylamino-2,4,4,6,6,8,8-heptamethylcyclotetrasiloxane, 2-diethylamino-2,4,4,6,6,8,8-heptamethylcyclo Rotetrasiloxane, 2-ethylmethylamino-2,4,4,6,6,8,8-heptamethylcyclotetrasiloxane, 2-isopropylamino-2,4,4,6,6,8,8-heptamethylcyclotetrasiloxane, 2-dimethylamino-2,4,6-trimethylcyclotrisiloxane, 2-diethylamino-2,4,6-trimethylcyclotrisiloxane, 2-ethylmethylamino-2,4,6-trimethylcyclotrisiloxane, 2-isopropylamino-2,4,6-trimethylcyclotrisiloxane, 2-dimethylamino-2,4,6,8- Tetramethylcyclotetrasiloxane, 2-diethylamino-2,4,6,8-tetramethylcyclotetrasiloxane, 2-ethylmethylamino-2,4,6,8-tetramethylcyclotetrasiloxane, 2-isopropylamino-2,4,6,8-tetramethylcyclotetrasiloxane, 2-pyrrolidin-2,4,4,6,6-pentamethylcyclotrisiloxane, 2-pyrrolyl-2,4,4,6,6-pentamethylcyclotrisiloxane, 2-piperidino-2,4,4,6,6-pentamethylcyclotrisiloxane, 2-2,5-dimethylpiperidino -2,4,4,6,6-pentamethylcyclotrisiloxane, 2-cyclohexylmethylamino-2,4,4,6,6-pentamethylcyclotrisiloxane, 2-phenylmethylamino-2,4,4,6,6-pentamethylcyclotrisiloxane, 2-cyclohexylamino-2,4,4,6,6-pentamethylcyclotrisiloxane, 2-cyclopentylamino-2,4,4,6,6-pentamethylcyclotrisiloxane, 2-pyrrolidino-2,4,4,6,6,8,8-heptamethylcyclotetrasiloxane, 2-pyrrolyl-2,4,4,6,6,8,8-Heptamethylcyclotetrasiloxane, 2-Cyclohexylmethylamino-2,4,4,6,6,8,8-Heptamethylcyclotetrasiloxane, 2-Phenylmethylamino-2,4,4,6,6,8,8-Heptamethylcyclotetrasiloxane, 2-Cyclohexylamino-2,4,4,6,6,8,8-Heptamethylcyclotetrasiloxane, 2-Cyclopentylamino-2,4,4,6,6,8,8-Heptamethylcyclotetrasiloxane, 2-Pyrrolidino-2 ,4,6-trimethylcyclotrisiloxane, 2-pyrrolyl-2,4,6-trimethylcyclotrisiloxane, 2-cyclohexylmethylamino-2,4,6-trimethylcyclotrisiloxane, 2-phenylmethylamino-2,4,6-trimethylcyclotrisiloxane, 2-cyclohexylamino-2,4,6-trimethylcyclotrisiloxane, 2-cyclopentylamino-2,4,6-trimethylcyclotrisiloxane, 2-pyrrolidino-2,4,6,8-tetra Methylcyclotetrasiloxane, 2-pyrrolyl-2,4,6,8-tetramethylcyclotetrasiloxane, 2-piperidino-2,4,4,6,6,8,8-heptamethylcyclotetrasiloxane, 2-2,5-dimethylpiperidino-2,4,4,6,6,8,8-heptamethylcyclotetrasiloxane, 2-cyclohexylmethylamino-2,4,6,8-tetramethylcyclotetrasiloxane, 2-phenylmethylamino-2,4,6,8-tetramethylcyclotetrasiloxane The method described in Appendix 1, selected from the group consisting of roxane, 2-cyclohexylamino-2,4,6,8-tetramethylcyclotetrasiloxane, 2-cyclopentylamino-2,4,6,8-tetramethylcyclotetrasiloxane, dimethylaminomethylsilane, diethylaminomethylsilane, di-isopropylaminomethylsilane, di-sec-butylaminomethylsilane, cyclohexylmethylaminomethylsilane, and 2,6-dimethylpiperidinomethylsilane. (Note 5) At least one second silicon precursor compound is diethylaminotriethylsilane, dimethylaminotriethylsilane, ethylmethylaminotriethylsilane, t-butylaminotriethylsilane, isopropylaminotriethylsilane, di-isopropylaminotriethylsilane, pyrrolidinotriethylsilane, diethylaminotrimethylsilane, dimethylaminotrimethylsilane, ethylmethylaminotrimethylsilane, t-butylaminotrimethylsilane, isopropylaminotrimethylsilane, di-isopropylaminotrimethylsilane, pyrrolidinotrimethylsilane, diethylaminodimethylsilane, dimethylaminodimethylsilane, ethylmethylaminodimethylsilane, t-butylaminodimethylsilane, isopropylaminodimethylsilane, di-isopropylaminodimethylsilane, pyrrolidinodimethylsilane, diethylaminodiethylsilane, dimethylaminodiethylsilane, ethylmethylaminodiethylsilane, t-butylaminodiethylsilane, isopropylaminodiethylsilane, di-isopropylaminodiethylsilane, pyrrolidinodiethyl Silane, bis(diethylamino)dimethylsilane, bis(dimethylamino)dimethylsilane, bis(ethylmethylamino)dimethylsilane, bis(di-isopropylamino)dimethylsilane, bis(iso-propylamino)dimethylsilane, bis(tert-butylamino)dimethylsilane, dipyrrolidinodimethylsilane, bis(diethylamino)diethylsilane, bis(dimethylamino)diethylsilane, bis(ethylmethylamino)diethylsilane, bis(diisopropylamino)diethylsilane, bis(isopropylamino)di Ethylsilane, bis(tert-butylamino)diethylsilane, dipyrrolidinodiethylsilane, bis(diethylamino)methylvinylsilane, bis(dimethylamino)methylvinylsilane, bis(ethylmethylamino)methylvinylsilane, bis(di-isopropylamino)methylvinylsilane, bis(isopropylamino)methylvinylsilane, bis(tert-butylamino)methylvinylsilane, dipyrrolidinomethylvinylsilane, 2,6-dimethylpiperidinomethylsilane, 2,6-dimethylpiperidinodimethylsilane, 2,The method described in Appendix 1, selected from the group consisting of 6-dimethylpiperidinotrimethylsilane, tris(dimethylamino)phenylsilane, tris(dimethylamino)methylsilane, and tris(dimethylamino)ethylsilane. (Note 6) When measured in a 1:99 HF:water diluted HF (0.5 wt% dHF) acid solution, the wet etching rate was less than approximately 2.5 Å / s; and when measured by secondary ion mass spectrometry (SIMS), it was approximately 5 × 10⁻⁶. 20 A carbon-doped silicon oxide film deposited by the method described in Appendix 1, having at least one feature selected from the group consisting of hydrogen impurities less than at / cc and a dielectric constant of 5.0 or less. (Note 7) A method for depositing a carbon-doped silicon oxide film onto a substrate, a) A step of providing the substrate into the reactor; b) Formulas A~C: [ka] Selected from the group consisting of, in the formula, R 1 However, linear C1~C 10 Alkyl groups, branched chains C3-C 10 Alkyl alkyl groups, C3-C 10 Cyclic alkyl groups, C3-C 10 Heterocyclic group, C3~C 10 Alkenyl group, C3~C 10 Alkynyl group and C4~C 10 Selected from aryl groups; R 2 However, hydrogen, C1~C 10 Linear alkyl groups, branched C3-C 10 Alkyl alkyl groups, C3-C 10 Cyclic alkyl groups, C3-C 10 Heterocyclic group, C2~C 10 Alkenyl group, C2~C 10 Alkynyl group and C4~C 10 Selected from the group consisting of aryl groups, R in formula A or B 1 and R 2The two are either connected in such a way as to form an annular ring structure, or not connected in such a way as to form an annular ring structure; R 3-9 However, hydrogen, straight chain C1~C 10 Alkyl groups, branched chains C3-C 10 Alkyl alkyl groups, C3-C 10 Cyclic alkyl groups, C2-C 10 Alkenyl group, C2~C 10 Alkynyl group and C4~C 10 Each is independently selected from the aryl groups; R 10 However, linear C1~C 10 Alkyl alkyl groups, C2-C 10 Alkenyl group and C2-C 10 The steps include introducing at least one first organic aminopolysiloxane precursor selected from alkynyl groups into the reactor; c) Purging the reactor with a purge gas to remove at least a portion of any of the at least one first silicon precursor that has not been absorbed by the substrate; d) A step of introducing an oxygen-containing plasma source into the reactor and reacting it with at least one first silicon precursor to form a first silicon-containing film; e) Purging the reactor using a purge gas to remove at least a portion of any unreacted oxygen-containing plasma source; f) a process of repeating steps b) to e) until a first silicon-containing film of the desired thickness is deposited; g)R 3 x Si(NR 1 R 2 ) 4-x The formula has the following, where R 1-3 The process is defined as above, and includes the step of introducing at least one second silicon precursor into the reactor where x = 1, 2, or 3; h) Purging the reactor with a purge gas to remove at least a portion of any of the at least one second silicon precursor that has not been absorbed into the first silicon-containing membrane; i) A step of introducing an oxygen-containing source into the reactor to form a second silicon-containing film; j) A step of purging the reactor with a purge gas to remove at least a portion of any unreacted oxygen-containing sources; k) Repeat steps g) to j) until a second silicon-containing film of the desired thickness is deposited. A method that includes and is carried out at one or more temperatures in the range of approximately 20°C to 300°C. (Note 8) R 1-2 The method described in Appendix 7, wherein each of the elements is a C1-C4 alkyl group. (Note 9) R 1-3 The method according to Appendix 7, wherein each of the elements is independently selected from the group consisting of methyl and ethyl. (Note 10) The first silicon precursor compound is 2-dimethylamino-2,4,4,6,6-pentamethylcyclotrisiloxane, 2-diethylamino-2,4,4,6,6-pentamethylcyclotrisiloxane, 2-ethylmethylamino-2,4,4,6,6-pentamethylcyclotrisiloxane, 2-isopropylamino-2,4,4,6,6-pentamethylcyclotrisiloxane, 2-dimethylamino-2,4,4,6,6,8,8-heptamethylcyclotetrasiloxane, 2-diethylamino-2,4,4,6,6,8,8-heptamethylcyclotetrasiloxane Xane, 2-ethylmethylamino-2,4,4,6,6,8,8-heptamethylcyclotetrasiloxane, 2-isopropylamino-2,4,4,6,6,8,8-heptamethylcyclotetrasiloxane, 2-dimethylamino-2,4,6-trimethylcyclotrisiloxane, 2-diethylamino-2,4,6-trimethylcyclotrisiloxane, 2-ethylmethylamino-2,4,6-trimethylcyclotrisiloxane, 2-isopropylamino-2,4,6-trimethylcyclotrisiloxane, 2-dimethylamino-2,4,6,8-tetramethyl Tylcyclotetrasiloxane, 2-diethylamino-2,4,6,8-tetramethylcyclotetrasiloxane, 2-ethylmethylamino-2,4,6,8-tetramethylcyclotetrasiloxane, 2-isopropylamino-2,4,6,8-tetramethylcyclotetrasiloxane, 2-pyrrolidin-2,4,4,6,6-pentamethylcyclotrisiloxane, 2-pyrrolyl-2,4,4,6,6-pentamethylcyclotrisiloxane, 2-piperidino-2,4,4,6,6-pentamethylcyclotrisiloxane, 2-2,5-dimethylpiperidino-2 ,4,4,6,6-pentamethylcyclotrisiloxane, 2-cyclohexylmethylamino-2,4,4,6,6-pentamethylcyclotrisiloxane, 2-phenylmethylamino-2,4,4,6,6-pentamethylcyclotrisiloxane, 2-cyclohexylamino-2,4,4,6,6-pentamethylcyclotrisiloxane, 2-cyclopentylamino-2,4,4,6,6-pentamethylcyclotrisiloxane, 2-pyrrolidin-2,4,4,6,6,8,8-heptamethylcyclotetrasiloxane, 2-pyrrolyl-2,4,4,6,6,8,8-Heptamethylcyclotetrasiloxane, 2-Cyclohexylmethylamino-2,4,4,6,6,8,8-Heptamethylcyclotetrasiloxane, 2-Phenylmethylamino-2,4,4,6,6,8,8-Heptamethylcyclotetrasiloxane, 2-Cyclohexylamino-2,4,4,6,6,8,8-Heptamethylcyclotetrasiloxane, 2-Cyclopentylamino-2,4,4,6,6,8,8-Heptamethylcyclotetrasiloxane, 2-Pyrrolidino-2 ,4,6-trimethylcyclotrisiloxane, 2-pyrrolyl-2,4,6-trimethylcyclotrisiloxane, 2-cyclohexylmethylamino-2,4,6-trimethylcyclotrisiloxane, 2-phenylmethylamino-2,4,6-trimethylcyclotrisiloxane, 2-cyclohexylamino-2,4,6-trimethylcyclotrisiloxane, 2-cyclopentylamino-2,4,6-trimethylcyclotrisiloxane, 2-pyrrolidino-2,4,6,8-tetra Methylcyclotetrasiloxane, 2-pyrrolyl-2,4,6,8-tetramethylcyclotetrasiloxane, 2-piperidino-2,4,4,6,6,8,8-heptamethylcyclotetrasiloxane, 2-2,5-dimethylpiperidino-2,4,4,6,6,8,8-heptamethylcyclotetrasiloxane, 2-cyclohexylmethylamino-2,4,6,8-tetramethylcyclotetrasiloxane, 2-phenylmethylamino-2,4,6,8-tetramethylcyclotetrasiloxane The method described in Appendix 7, selected from the group consisting of roxane, 2-cyclohexylamino-2,4,6,8-tetramethylcyclotetrasiloxane, 2-cyclopentylamino-2,4,6,8-tetramethylcyclotetrasiloxane, dimethylaminomethylsilane, diethylaminomethylsilane, di-isopropylaminomethylsilane, di-sec-butylaminomethylsilane, cyclohexylmethylaminomethylsilane, and 2,6-dimethylpiperidinomethylsilane. (Note 11) The method according to Appendix 7, wherein at least one second silicon precursor compound is selected from the group consisting of di-isopropylaminosilane, di-sec-butylaminosilane, bis(diethylamino)silane, and bis(tert-butylamino)silane. (Note 12) A density of at least approximately 2.1 g / cc; a wet etching rate less than approximately 2.5 Å / s when measured in a 1:99 HF:water diluted HF (0.5 wt% dHF) acid solution; and approximately 5 × 10⁻¹⁶ when measured by secondary ion mass spectrometry (SIMS). 20 A carbon-doped silicon oxide film deposited by the method described in Appendix 7, having at least one feature selected from the group consisting of hydrogen impurities less than at / cc and a dielectric constant of 5.0 or less.

Claims

1. A method for depositing a carbon-doped silicon oxide film onto a substrate, a) A step of providing the substrate into the reactor; b) Equations A and B: 【Chemistry 1】 Selected from the group consisting of, wherein R 1 is a linear C 1 to C 10 alkyl group, branched C 3 to C 10 alkyl group, C 3 to C 10 cyclic alkyl group, C 3 to C 10 heterocyclic group, C 3 to C 10 alkenyl group, C 3 to C 10 alkynyl group and C 4 to C 10 selected from aryl groups; R 2 is hydrogen, C 1 to C 10 linear alkyl group, branched C 3 to C 10 alkyl group, C 3 to C 10 cyclic alkyl group, C 3 to C 10 heterocyclic group, C 2 to C 10 alkenyl group, C 2 to C 10 alkynyl group and C 4 to C 10 selected from aryl groups, and R in Formula A or B 1 and R 2 are either linked to form a cyclic ring structure or not linked to form a cyclic ring structure; R 3-9 is hydrogen, linear C 1 to C 10 alkyl group, branched C 3 to C 10 alkyl group, C 3 to C 10 cyclic alkyl group, C 2 to C 10 alkenyl group, C 2 to C 10 alkynyl group and C 4 to C 10 introducing at least one first silicon precursor independently selected from aryl groups into a reactor; c) Purging the reactor with a purge gas to remove at least a portion of any of the at least one first silicon precursor that has not been absorbed by the substrate; d) A step of introducing an oxygen-containing plasma source into a reactor and reacting it with at least one first silicon precursor to form a first silicon-containing film; e) Purging the reactor with a purge gas to remove at least a portion of any unreacted oxygen-containing plasma source; f) A step of repeating steps b) to e) until a first silicon-containing film of the desired thickness is deposited; g) R 3 x Si(NR 1 R 2 ) 4-x The formula has the following equation, where R 1-3 The process is defined as above, and includes the step of introducing at least one second silicon precursor into the reactor, wherein x = 1, 2, or 3; h) Purging the reactor with a purge gas to remove at least a portion of any of the at least one second silicon precursor that has not been absorbed into the first silicon-containing membrane; i) A step of introducing an oxygen-containing source into the reactor to form a second silicon-containing film; j) A step of purging the reactor with a purge gas to remove at least a portion of any unreacted oxygen-containing sources; k) A step of repeating steps g) to j) until a second silicon-containing film of the desired thickness is deposited. A method comprising, wherein the method is carried out at one or more temperatures in the range of 20°C to 300°C.

2. R 1-2 Each of them is C 1 ~C 4 The method according to claim 1, wherein the alkyl group is used.

3. R 1-3 The method according to claim 1, wherein each of the elements is independently selected from the group consisting of methyl and ethyl.

4. The first silicon precursor compound is 2-dimethylamino-2,4,4,6,6-pentamethylcyclotrisiloxane, 2-diethylamino-2,4,4,6,6-pentamethylcyclotrisiloxane, 2-ethylmethylamino-2,4,4,6,6-pentamethylcyclotrisiloxane, 2-isopropylamino-2,4,4,6,6-pentamethylcyclotrisiloxane, 2-dimethylamino-2,4,4,6,6,8,8-heptamethylcyclotetrasiloxane, 2-diethylamino-2,4,4,6,6,8,8-heptamethylcyclotetrasiloxane Xane, 2-ethylmethylamino-2,4,4,6,6,8,8-heptamethylcyclotetrasiloxane, 2-isopropylamino-2,4,4,6,6,8,8-heptamethylcyclotetrasiloxane, 2-dimethylamino-2,4,6-trimethylcyclotrisiloxane, 2-diethylamino-2,4,6-trimethylcyclotrisiloxane, 2-ethylmethylamino-2,4,6-trimethylcyclotrisiloxane, 2-isopropylamino-2,4,6-trimethylcyclotrisiloxane, 2-dimethylamino-2,4,6,8-tetramethyl Tylcyclotetrasiloxane, 2-diethylamino-2,4,6,8-tetramethylcyclotetrasiloxane, 2-ethylmethylamino-2,4,6,8-tetramethylcyclotetrasiloxane, 2-isopropylamino-2,4,6,8-tetramethylcyclotetrasiloxane, 2-pyrrolidin-2,4,4,6,6-pentamethylcyclotrisiloxane, 2-pyrrolyl-2,4,4,6,6-pentamethylcyclotrisiloxane, 2-piperidino-2,4,4,6,6-pentamethylcyclotrisiloxane, 2-2,5-dimethylpiperidino-2 ,4,4,6,6-pentamethylcyclotrisiloxane, 2-cyclohexylmethylamino-2,4,4,6,6-pentamethylcyclotrisiloxane, 2-phenylmethylamino-2,4,4,6,6-pentamethylcyclotrisiloxane, 2-cyclohexylamino-2,4,4,6,6-pentamethylcyclotrisiloxane, 2-cyclopentylamino-2,4,4,6,6-pentamethylcyclotrisiloxane, 2-pyrrolidino-2,4,4,6,6,8,8-heptamethylcyclotetrasiloxane, 2-pyrroryl-2,4,4,6,6,8,8-Heptamethylcyclotetrasiloxane, 2-Cyclohexylmethylamino-2,4,4,6,6,8,8-Heptamethylcyclotetrasiloxane, 2-Phenylmethylamino-2,4,4,6,6,8,8-Heptamethylcyclotetrasiloxane, 2-Cyclohexylamino-2,4,4,6,6,8,8-Heptamethylcyclotetrasiloxane, 2-Cyclopentylamino-2,4,4,6,6,8,8- Heptamethylcyclotetrasiloxane, 2-pyrrolidino-2,4,6-trimethylcyclotrisiloxane, 2-pyrrolyl-2,4,6-trimethylcyclotrisiloxane, 2-cyclohexylmethylamino-2,4,6-trimethylcyclotrisiloxane, 2-phenylmethylamino-2,4,6-trimethylcyclotrisiloxane, 2-cyclohexylamino-2,4,6-trimethylcyclotrisiloxane, 2 The method according to claim 1, selected from the group consisting of -cyclopentylamino-2,4,6-trimethylcyclotrisiloxane, 2-pyrrolidino-2,4,6,8-tetramethylcyclotetrasiloxane, 2-pyrrolyl-2,4,6,8-tetramethylcyclotetrasiloxane, 2-piperidino-2,4,4,6,6,8,8-heptamethylcyclotetrasiloxane, 2-2,5-dimethylpiperidino-2,4,4,6,6,8,8-heptamethylcyclotetrasiloxane, 2-cyclohexylmethylamino-2,4,6,8-tetramethylcyclotetrasiloxane, 2-phenylmethylamino-2,4,6,8-tetramethylcyclotetrasiloxane, 2-cyclohexylamino-2,4,6,8-tetramethylcyclotetrasiloxane, and 2-cyclopentylamino-2,4,6,8-tetramethylcyclotetrasiloxane. ,

5. The method according to claim 1, wherein at least one second silicon precursor compound is selected from the group consisting of di-isopropylaminosilane, di-sec-butylaminosilane, bis(diethylamino)silane, and bis(tert-butylamino)silane.

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