Cyclic oligosiloxanes with organic amino functional groups for the deposition of silicon-containing thin films

Abstract

A cyclic oligosiloxane having an amino functional group containing at least three silicon atoms and three oxygen atoms and at least one organic amino group, and a method for producing the oligosiloxane are disclosed. A method for forming a silicon- and oxygen-containing thin film using the cyclic oligosiloxane having an organic amino functional group is also disclosed.

Description

[Technical Field]

[0001] Related technologies This continuation-in-part application claims the interests of U.S. Provisional Patent Application No. 16 / 838,997, filed on 2 April 2020, and U.S. Provisional Patent Application No. 17 / 030,187, filed on 23 September 2020. The disclosures of applications No. 16 / 838,997 and No. 17 / 030,187 are incorporated herein by reference. [Background technology]

[0002] The present invention relates to organosilicon compounds that can be used to deposit silicon and oxygen-containing thin films (for example, silicon oxide, silicon oxycarbonitride, silicon oxycarbide, and carbon-doped silicon oxide, among silicon and oxygen-containing thin films), methods for using the compounds to deposit silicon oxide-containing thin films, and thin films obtained from the compounds and methods.

[0003] This specification describes novel cyclic oligosiloxane precursor compounds having organic amino functional groups, as well as compositions and methods for depositing silicon-containing thin films, such as silicon oxide, silicon oxynitride, silicon oxycarbonitride, or carbon-doped silicon oxide, by thermal atomic layer deposition (ALD) or plasma-accelerated atomic layer deposition (PEALD), or a combination thereof. More specifically, this specification describes compositions and methods for forming stoichiometric or non-stoichiometric silicon-containing thin films or substances at one or more deposition temperatures up to about 600°C, including about 25°C to about 300°C.

[0004] Atomic layer deposition (ALD) and plasma-assisted atomic layer deposition (PEALD) are methods used to deposit conformal thin films, such as silicon oxide, at low temperatures (<500°C). In both ALD and PEALD methods, the precursor and reactive gas (such as oxygen or ozone) are pulsed individually for a specific number of cycles, forming a single layer of silicon oxide in each cycle. However, silicon oxide deposited at low temperatures using these methods may contain certain levels of impurities, such as carbon (C) or hydrogen (H), which can be detrimental in certain semiconductor applications. To improve this, one possible solution is to raise the deposition temperature above 500°C. However, at these high temperatures, conventional precursors used by the semiconductor industry tend to self-react, thermally decompose, and deposit in chemical vapor deposition (CVD) mode rather than ALD mode. CVD mode deposition results in lower conformability compared to ALD deposition, particularly due to the high aspect ratio structures required in many semiconductor applications. In addition, CVD mode deposition does not allow for better control of thin film or material thickness than ALD mode deposition.

[0005] Organic aminosilane and chlorosilane precursors that can be used to deposit silicon-containing thin films by atomic layer deposition (ALD) and plasma-assisted atomic layer deposition (PEALD) at relatively low temperatures (<300°C) and relatively high deposition rates per cycle (GPC > 1.5 Å / cycle) are known in the art.

[0006] Examples of known precursors and methods are disclosed in the following publications, patents, and patent applications.

[0007] U.S. Patent No. 7,084,076(B2) describes the use of halogen-substituted or NCO-substituted disiloxane precursors for depositing silicon oxide thin films used in base-catalyzed ALD methods.

[0008] U.S. Patent Application Publication No. 2015 / 087139(AA) describes the use of amino-functionalized carbosilane for depositing silicon-containing thin films by thermal ALD or PEALD.

[0009] U.S. Patent No. 9,337,018(B2) describes the use of organic aminodisilanes for depositing silicon-containing thin films by thermal ALD or PEALD.

[0010] U.S. Patent No. 8,940,648(B2) and U.S. Patent No. 8,912,353(B2) describe the use of organic aminosilanes for depositing silicon-containing thin films by thermal ALD or PEALD.

[0011] U.S. Patent Application Publication No. 2015 / 275355(AA) describes the use of mono- and bis(organicamino)alkylsilanes for depositing silicon-containing thin films by thermal ALD or PEALD.

[0012] U.S. Patent Application Publication No. 2015 / 376211(A) describes the use of mono(organic amino)-substituted, halogen-substituted, and pseudohalide-substituted trisilylamines for depositing silicon-containing thin films by thermal ALD or PEALD.

[0013] International Publication No. 15 / 105337 and U.S. Patent No. 9,245,740(B2) describe the use of alkylated trisilylamines for depositing silicon-containing thin films by thermal ALD or PEALD.

[0014] International Publication No. 15 / 105350 describes the use of a four-membered ring cyclodisilazane having at least one SH bond for depositing silicon-containing thin films by thermal ALD or PEALD.

[0015] U.S. Patent No. 7,084,076(B2) describes the use of halogen-substituted or NCO-substituted disiloxane precursors for depositing silicon oxide thin films used in base-catalyzed ALD methods.

[0016] U.S. Patent Application Publication No. 2018 / 223047(A) discloses linear and cyclic oligosiloxanes having at least two silicon atoms, two oxygen atoms, and an amino functional group having an organic amino group, for depositing silicon and oxygen-containing thin films.

[0017] The disclosures of the aforementioned patents and patent applications are incorporated herein by reference.

[0018] Despite the developments described above, there is a need in the art for precursors and methods for depositing silicon oxide-containing thin films at high growth per cycle (GPC) to maximize throughput in semiconductor manufacturing facilities. While certain precursors can be deposited at GPC >2.0 Å / cycle, these precursors have drawbacks such as low-quality thin films (elemental impurities, low density, poor electrical properties, high wet etching rates), high process temperatures, the need for catalysts, high costs, and the production of low-conformability thin films. [Overview of the Initiative]

[0019] This development provides a silicon- and oxygen-containing precursor, particularly a cyclic oligosiloxane having an organic amino functional group, which has at least three silicon atoms and three oxygen atoms and has at least one organic amino group that functions to fix a cyclic oligosiloxane compound to a substrate surface as part of a method for depositing a silicon- and oxygen-containing thin film, thereby solving problems related to conventional precursors and methods. The multi-silicon precursors disclosed in the present invention have a novel structure as compared to those described in the background art section, and thus may provide advantages in one or more aspects related to the cost or simplicity of precursor synthesis, thermal stability, reactivity, or volatility of the precursor, the method for depositing a silicon-containing thin film, or the properties of the deposited silicon-containing thin film.

[0020] A composition comprising a cyclic oligosiloxane compound having at least one organic amino functional group, wherein the compound is of formulas A - D:

Chemical formula

[0021] In the above formulas A - D, R 1 is selected from the group consisting of a linear C1 - C 10 alkyl group, a branched C3 - C 10 alkyl group, a C3 - C 10 cyclic alkyl group, a C3 - C 10 heterocyclic group, a C3 - C 10 alkenyl group, a C3 - C 10 alkynyl group, and a C4 - C 10 aryl group; R 2 is hydrogen, a C1 - C 10 linear alkyl group, a branched C3 - C 10 alkyl group, a C3 - C 10 cyclic alkyl group, a C3 - C 10 heterocyclic group, a C3 - C 10 alkenyl group, a C3 - C 10 alkynyl group, and a C4 - C 10Selected from the group consisting of aryl groups, R 1 and R 2 R is either bonded to form a cyclic ring structure or not bonded to form a cyclic ring structure; 3~11 This is 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, C4~C 10 Aryl group, and organic amino group, NR 1 R 2 , R 1 and R 2 Each of the elements is independently selected from the group consisting of the elements defined above; n=1, 2, or 3 and m=2 or 3. Compositions containing compounds are disclosed herein.

[0022] This specification describes methods for depositing stoichiometric or non-stoichiometric silicon and oxygen-containing materials or thin films, such as silicon oxide, carbon-doped silicon oxide, silicon oxynitride thin films, or carbon-doped silicon oxynitride thin films, at relatively low temperatures, for example, one or more temperatures of 600°C or lower, in plasma-accelerated ALD (PEALD), plasma-accelerated cyclic chemical vapor deposition (PECCVD), fluid chemical vapor deposition (FCVD), plasma-accelerated fluid chemical vapor deposition (PEFCVD), plasma-accelerated ALD-like methods, or ALD methods using oxygen-containing reaction materials, nitrogen-containing reaction materials, or combinations thereof.

[0023] In one embodiment, a method for depositing a thin film containing silicon and oxygen onto a substrate, the method comprising: (a) preparing the substrate in a reactor; and (b) in the reactor, formulas A to D: [ka] At least one silicon precursor compound selected from the group consisting of,

[0024] In the above formulas A to D, R1 This is a 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 the group consisting of aryl groups; R 2 is 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, C3~C 10 Alkenyl group, C3~C 10 Alkynyl group, and C4~C 10 Selected from the group consisting of aryl groups, R 1 and R 2 R is either bonded to form a cyclic ring structure or not bonded to form a cyclic ring structure; 3~11 This is 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, C4~C 10 Aryl group, and organic amino group, NR 1 R 2 , R 1 and R 2 Each of the elements is independently selected from the group consisting of the elements defined above; n=1, 2, or 3 and m=2 or 3. A step of introducing a compound; (c) purging the reactor with a purge gas; (d) introducing at least one of an oxygen-containing raw material and a nitrogen-containing raw material into the reactor; and (d) purging the reactor with the purge gas; repeating steps b through e until a desired thickness of the thin film is deposited; and carrying out the method at one or more temperatures in the range of approximately 25°C to 600°C. Methods including the above are disclosed herein.

[0025] Methods for producing the above-mentioned compounds are also disclosed herein. Embodiments of the present invention can be used individually or in combination with each other. [Brief explanation of the drawing]

[0026] [Figure 1] Figure 1 is a graph of the GPC saturation curve against precursor pulse time using bis(dimethylamino)-2,4,6,8-tetramethylcyclotetrasiloxane and 2-dimethylamino-2,4,6,8,10-pentamethylcyclopentasiloxane described in the present invention, as well as conventional BDEAS. [Figure 2] Figure 2 shows the thin-film GPC and WER in response to O2 plasma output using bis(dimethylamino)-2,4,6,8-tetramethylcyclotetrasiloxane in 300°C deposition according to the present invention. [Figure 3] Figure 3 shows the thin-film GPC and WER for O2 plasma output using bis(dimethylamino)-2,4,6,8-tetramethylcyclotetrasiloxane in 100°C deposition according to the present invention. [Figure 4] Figure 4 shows the thin-film GPC and WER as a function of O2 plasma time using bis(dimethylamino)-2,4,6,8-tetramethylcyclotetrasiloxane in 300°C deposition according to the present invention. [Figure 5] Figure 5 shows the thin-film GPC and WER as a function of O2 plasma time using bis(dimethylamino)-2,4,6,8-tetramethylcyclotetrasiloxane in 100°C deposition according to the present invention. [Modes for carrying out the invention]

[0027] In relation to the description of the present invention (particularly in relation to the following claims), the terms “a” and “an,” and “the” and similar reference subjects should be interpreted as encompassing both singular and plural unless otherwise specifically indicated herein or unless it is clearly inconsistent with the context. The terms “comprising,” “having,” “including,” and “containing” should be interpreted as open-ended terms (i.e., meaning “including, but not limited to”) unless otherwise specifically indicated herein. The descriptions of ranges of values ​​herein are merely intended to serve as a convenient way of referring to each individual value within the range, unless otherwise specifically indicated herein, and each individual value is incorporated herein as if it were described individually herein. All methods described herein may be performed in any appropriate order unless otherwise specifically indicated herein or unless it is clearly inconsistent with the context. Any and all examples provided herein, or the use of preferred language (e.g., "such as"), are solely for the purpose of better illustrating the invention and do not attempt to limit the scope of the invention unless otherwise claimed. Nothing in this specification should be construed as indicating that any element not described in the claims is essential to the practice of the invention.

[0028] This specification describes compositions and methods relating to the formation of stoichiometric or non-stoichiometric thin films, or materials containing silicon and oxygen, such as silicon oxide, carbon-doped silicon oxide thin films, silicon oxynitride, or carbon-doped silicon oxynitride thin films or combinations thereof, at temperatures below approximately 600°C, or at one or more temperatures between approximately 25°C and approximately 600°C, and in some embodiments, between 25°C and approximately 300°C, but not limited to these. The thin films described herein are deposited by deposition methods such as plasma-accelerated ALD (PEALD), plasma-accelerated cyclic chemical vapor deposition (PECCVD), fluidized chemical vapor deposition (FCVD), or plasma-accelerated fluidized chemical vapor deposition (PEFCVD), or other atomic layer deposition (ALD) or ALD-like methods, but not limited to these. The low-temperature deposition methods described herein (e.g., one or more deposition temperatures in the range of approximately ambient temperature to 600°C) offer the following advantages: density of approximately 2.1 g / cc or higher, low chemical impurities, high conformability in thermal atomic layer deposition, plasma-accelerated atomic layer deposition (ALD) or plasma-accelerated ALD-like methods, and the ability to adjust the carbon content in the resulting thin film; and / or the thin film has an etching rate of 5 angstroms / second (Å / second) or less when measured in 0.5 mass% diluted HF. For carbon-doped silicon oxide thin films, however, a carbon content greater than 1% is desirable to adjust the etching rate to a value of less than 2 Å / second in 0.5 mass% diluted HF, in addition to other features such as density of approximately 1.8 g / cc or higher or approximately 2.0 g / cc or higher.

[0029] The methods disclosed herein can be carried out using apparatus known in the art. For example, the method can be carried out using a reactor commonly used in the semiconductor manufacturing field.

[0030] While we do not wish to be bound by any theory or explanation, the effectiveness of the precursor compositions disclosed herein may vary as a function of the number of silicon atoms, and in particular, the number of silicon-oxygen bonds. The precursors disclosed herein typically have 3 to 8 silicon atoms and 6 to 16 silicon-oxygen bonds.

[0031] The precursors disclosed herein have different structures from those known in the art and therefore can be implemented better than conventional silicon-containing precursors, provide relatively high GPC, yield higher quality thin films, have a preferred wet etching rate, or contain less elemental contamination.

[0032] A composition for depositing a thin film selected from silicic acid oxide, carbon-doped silicon oxide, or carboxysilicon nitride thin film using vapor phase growth, wherein the composition comprises formulas A to D: [ka] A compound having, In the above formulas A to D, R 1 This is a 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 the group consisting of aryl groups; R 2 is 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, C3~C 10 Alkenyl group, C3~C 10 Alkynyl group, and C4~C 10 Selected from the group consisting of aryl groups, R 1 and R 2 R is either bonded to form a cyclic ring structure or not bonded to form a cyclic ring structure; 3~11 This is 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, C4~C 10 Aryl group, and organic amino group, NR1 R 2 , R 1 and R 2 Each of the elements is independently selected from the group consisting of the elements defined above; n=1, 2, or 3 and m=2 or 3. Compositions comprising compounds are disclosed herein.

[0033] In a preferred embodiment, R 1~9 At least one of them is a C1-C4 alkyl group. A preferred embodiment comprises a compound of formulas A-D, and R 1~9 Each of these is either hydrogen or a C1-C4 alkyl group.

[0034] In the above formula and throughout this specification, the term “oligosiloxane” refers to a compound comprising at least two repeating-Si-O-siloxane units, preferably at least three repeating-Si-O-siloxane units, which may have a cyclic or linear structure, and is preferably a cyclic structure.

[0035] In the above formulas and throughout this specification, the term “alkyl” refers to a linear or branched functional group having 1 to 10 carbon atoms. Preferred linear alkyl groups include, but are not limited to, methyl, ethyl, propyl, butyl, pentyl, and hexyl groups. Preferred 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 bonded to it, such as an alkoxy group, a dialkylamino group, or a combination thereof, but is not limited to these. In other embodiments, the alkyl group may not have one or more functional groups bonded to it. The alkyl group may be saturated or unsaturated.

[0036] In the above formula and throughout this specification, the term "cyclic alkyl" refers to a cyclic functional group having 3 to 10 carbon atoms. Preferred cyclic alkyl groups include, but are not limited to, cyclobutyl, cyclopentyl, cyclohexyl, and cyclooctyl groups.

[0037] In the above formula and throughout this specification, the term "alkenyl group" refers to a group having one or more carbon-carbon double bonds and having 2 to 10 or 2 to 6 carbon atoms.

[0038] In the above formula and throughout this specification, the term "dialkylamino" group, "alkylamino" group, or "organic amino" group refers to an R 1 R 2 N-group, where in the above formula, R 1 is a straight-chain C1 to C 10 alkyl group, a branched-chain C3 to C 10 alkyl group, a C3 to C 10 cyclic alkyl group, a C3 to C 10 heterocyclic group, a C3 to C 10 alkenyl group, a C3 to C 10 alkynyl group, and a C4 to C 10 aryl group selected from the group consisting of; R 2 is hydrogen, a C1 to C 10 straight-chain alkyl group, a branched-chain C3 to C 10 alkyl group, a C3 to C 10 cyclic alkyl group, a C3 to C 10 [[ID=3�]]heterocyclic group, a C3 to C 10 alkenyl group, a C3 to C 10 alkynyl group, and a C4 to C 10 aryl group selected from the group consisting of. In some cases, R 1 and R[[ID=?]] 2 are bonded to form a cyclic ring structure, and in other cases, R 1 and R 2 do not bond to form a cyclic ring structure. R 1 and R 2 are bonded to form a cyclic ring structure. Preferred organic amino groups include R 1 = propyl and R 2 = Me pyrrolidino, R 1 = propyl and R It seems there is an error in the original text where "R " is repeated without proper continuation or completion in some lines. I've translated it as accurately as possible based on the provided text. If you can correct the original text, it would be possible to provide a more accurate translation.2 =Et is 1,2-piperidino, R 1 = isopropyl and R 2 =sec-butyl 2,6-dimethylpiperidino, and R 1 =R 2 Examples include, but are not limited to, 2,5-dimethylpyrrolidino, which is isopropyl.

[0039] In the above formulas and throughout this specification, 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. Preferred aryl groups include, but are not limited to, phenyl, benzyl, chlorobenzyl, tolyl, o-xylyl, 1,2,3-triazolyl, pyrrolyl, and furanyl.

[0040] Throughout this specification, the term "alkyl hydrocarbon" refers to a straight-chain or branched-chain C1-C1 hydrocarbon. 20 Hydrocarbons, cyclic C6-C6 20 This term represents hydrocarbons. Preferred hydrocarbons include, but are not limited to, heptane, octane, nonane, decane, dodecane, cyclooctane, cyclononane, and cyclodecane.

[0041] Throughout this specification, the term "alkoxy" is defined as R in formulas. 1 C1~C as defined above 10 -OR 1 This represents a group. Preferred alkoxy groups include, but are not limited to, methoxy, ethoxy, iso-propoxy, n-propoxy, n-butoxy, sec-butoxy, tert-butoxy, and phenoxide.

[0042] Throughout this specification, the term "carboxylate" refers to the formula R 1 C2~C as defined above 12 -OC(=O)R 1This represents a group. Preferred carboxylate groups include, but are not limited to, acetate (-OC(=O)Me), ethyl carboxylate (-OC(=O)Et), isopropyl carboxylate (-OC(=O)iPr), and benzoate (-OC(=O)Ph).

[0043] Throughout this specification, the term "aromatic hydrocarbon" refers to C6-C6 20 This term represents aromatic hydrocarbons. Preferred aromatic hydrocarbons include, but are not limited to, toluene and mesitylene.

[0044] In the above formulas and throughout this specification, the term “heterocyclic” means a non-aromatic saturated monocyclic or polycyclic ring structure of about 3 to about 10 ring atoms, preferably about 5 to about 10 ring atoms, where one or more atoms in the ring structure are elements other than carbon, such as nitrogen, oxygen, or sulfur. Preferred heterocyclic rings contain about 5 to about 6 ring atoms. The prefixes aza, oxo, or thio preceding heterocyclic rings mean the presence of at least one nitrogen, oxygen, or sulfur atom as a ring atom, respectively. Heterocyclic groups may be substituted.

[0045] Table 1 lists preferred cyclic oligosiloxanes having organic amino functional groups with formulas A to D: [Table 1-1] [Table 1-2] [Table 1-3] [Table 1-4] [Table 1-5] [Table 1-6]

[0046] Compounds having formulas A to D can be synthesized, for example, by catalytic dehydrocoupling a cyclic oligosiloxane having at least one Si-H bond with an organic amine (e.g., formula 1 for cyclotetrasiloxane and formula 2 for larger cyclic oligosiloxanes such as cyclopentasiloxane), or by reacting a chlorinated cyclic oligosiloxane with an organic amine or a metal salt of an organic amine (e.g., formula 2 for cyclotetrasiloxane), or by catalytic hydrosilylation of an imine with a cyclic oligosiloxane, as described in U.S. Patent No. 9,758,534(B2) relating to the synthesis of organic aminosilanes and organic aminodisilanes, thereby using the cyclic oligosiloxane in place of a silane or disilane. [ka]

[0047] Preferably, the molar ratio of the cyclic oligosiloxane to the organic amine in the reaction mixture is about 4-1, 3-1, 2-1, 1.5-1, 1-1.0, 1-1.5, 1-2, 1-3, 1-4, 1-8, or 1-10.

[0048] The catalysts used in the methods of the present invention in Formulas 1 and 3 promote the formation of silicon-nitrogen bonds. Preferred catalysts that can be used with the methods described herein include, but are not limited to, alkaline earth metal catalysts; halide-free main group, transition metal, lanthanide, and actinide catalysts; and halide-containing main group, transition metal, lanthanide, and actinide catalysts.

[0049] Preferred alkaline earth metal catalysts include: Mg[N(SiMe3)2]2, ToMMgMe[ToM=tris(4,4-dimethyl-2-oxazolinyl)phenylborate], ToMMg-H, ToMMg-NR2(R=H, alkyl, aryl)Ca[N(SiMe3)2]2, [(dipp-nacnac)CaX(THF)]2(dipp-nacnac=CH[(CMe)(2,6-iPr2-C6H3N)]2;X=H, alkyl, carbosilyl, organic amino), C a(CH2Ph)2, Ca(C3H5)2, Ca(α-Me3Si-2-(Me2N)-benzyl)2(THF)2, Ca(9-(Me3Si)-fluorenyl)(α-Me3Si-2-(Me2N)-benzyl)(THF), [(Me3TACD)3Ca3(μ3-H)2]+(Me3TACD=Me3

[12] aneN4), Ca(η2-Ph2CNPh)(hmpa)3(hmpa=hexamethylphosphoramide), Sr[N(SiMe3)2]2, dialkylmagnesium and other M 2+ Examples include, but are not limited to, alkaline earth metal-amides, imines, alkyls, halides, and carbosilyl complexes (M=Ca, Mg, Sr, Ba).

[0050] Preferred halide-free, main group, transition metal, lanthanide, and actinide catalysts include: 1,3-di-iso-propyl-4,5-dimethylimidazo-2-ylidene, 2,2'-bipyridyl, phenanthroline, B(C6F5)3, BR3(R=straight-chain, branched-chain, or cyclic C1-C) 10 Alkyl alkyl groups, C5-C 10 Aryl group, or C1-C 10 Alkoxy group), AlR3 (R = straight chain, branched chain, or cyclic C1-C) 10 Alkyl alkyl groups, C5-C 10 Aryl group, or C1-C 10Alkoxy group), (C5H5)2TiR2 (R = alkyl, H, alkoxy, organic amino, carbosilyl), (C5H5)2Ti(OAr)2 [Ar = (2,6-(iPr)2C6H3)], (C5H5)2Ti(SiHRR')PMe3 (wherein R and R' are independently selected from H, Me, and Ph respectively), TiMe2(dmpe)2 (dmpe = 1,2-bis(dimethylphosphinolet)ethane), bis(benzene)chromium(0), Cr(CO)6, Mn2(CO) 12 Fe(CO)5, Fe3(CO) 12 (C5H5)Fe(CO)2Me, Co2(CO)8, Ni(II) acetate, nickel(II) acetylacetonate, Ni(cyclooctadiene)2, [(dippe)Ni(μ-H)]2 (dippe=1,2-bis(di-iso-propylphosphin)ethane), (R-indenyl)Ni(PR'3)Me (R=1-iPr, 1-SiMe3, 1,3-(SiMe3)2; R'=Me,Ph), [{Ni(η-CH2:CHSiMe2)2O}2{μ-(η-CH2:CHSiMe2)2O}], Cu(I) acetate, CuH, [tris(4,4-dimethyl-2-oxazolinyl)phenylborate]ZnH, (C5H5)2ZrR2 (R=alkyl, H, alkoxy, organic amino, carbosilyl), Ru3(CO) 12 [(Et3P)Ru(2,6-Dimethylthiophenolate)][B[3,5-(CF3)2C6H3]4], [(C5Me5)Ru(R3P)x(NCMe)3-x] + (In the formula, R is a straight chain, a branched chain, or a ring C1-C) 10 Alkyl and C5-C 10 Selected from aryl groups; x = 0, 1, 2, 3), Rh6(CO) 16 Tris(triphenylphosphine)rhodium(I)carbonyl hydride, Rh2H2(CO)2(dppm)2(dppm=bis(diphenylphosphinomethane), Rh2(μ-SiRH)2(CO)2(dppm)2(R=Ph,Et,C6H 13), Pd / C, Tris(dibenzylideneacetone)dipalladium(0), Tetrakis(triphenylphosphine)palladium(0), Pd(II) acetate, (C5H5)2SmH, (C5Me5)2SmH, (THF)2Yb[N(SiMe3)2]2, (NHC)Yb(N(SiMe3)2)2[NHC=1,3-bis(2,4,6-trimethylphenyl)imidazole-2-ylidene)], Yb(η2-Ph2CNPh)(hmpa)3(hmpa=hexamethylphosphoramide), W(CO)6, Re2(CO) 10 Os3(CO) 12 Ir4(CO)12, (acetylacetonate)dicarbonyliridium(I), Ir(Me)2(C5Me5)L(L=PMe3,PPh3), [Ir(cyclooctadiene)OMe]2, PtO2 (Adams catalyst), platinum-carbon (Pt / C), ruthenium-carbon (Ru / C), ruthenium-alumina, palladium-carbon, nickel-carbon, osmium-carbon, platinum(0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane (Kersted catalyst), bis(tri-tert-butylphosphine)platinum(0), Pt(cyclooctadiene)2, [(Me3Si)2N]3U][BPh4], [(Et2N)3U][BPh4], and other halide-free M n+Examples of complexes (M=Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Ru, Rh, Pd, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Hf, Ta, W, Re, Os, Ir, Pt, U; n=0, 1, 2, 3, 4, 5, 6) are listed, but are not limited to these. The catalysts listed above, as well as pure noble metals such as ruthenium, platinum, palladium, rhodium, and osmium, can also be immobilized on a support. The support is a solid with a high surface area. Typical support materials include, but are not limited to, alumina, MgO, zeolite, carbon, monolithic cordierite, diatomaceous earth, silica gel, silica / alumina, ZrO, TiO2, metal-organic frameworks (MOFs), and organic polymers such as polystyrene. Preferred supports are carbon (e.g., platinum carbon, palladium carbon, rhodium carbon, ruthenium carbon), alumina, silica, and MgO. The metal load of the catalyst is in the range of about 0.01 mass percent to about 50 mass percent. A preferred range is about 0.5 mass percent to about 20 mass percent. A more preferred range is about 0.5 mass percent to about 10 mass percent. Catalysts requiring activation may be activated by several known methods. Heating the catalyst under vacuum is a preferred method. The catalyst may be activated in the reaction vessel before being added to the reaction vessel or before being added to the reactants. The catalyst may contain a co-catalyst. A co-catalyst is not a catalyst itself, but when mixed in small amounts with the active catalyst, it increases its effectiveness (activity and / or selectivity). Co-catalysts are typically metals and / or oxides thereof, such as Mn, Ce, Mo, Li, Re, Ga, Cu, Ru, Pd, Rh, Ir, Fe, Ni, Pt, Cr, Cu, and Au. Co-catalysts can be added separately to the reaction vessel or they may be part of the catalyst itself. For example, Ru / Mn / C (ruthenium-carbon activated by manganese) or Pt / CeO2 / Ir / SiO2 (platinum activated by cerium oxide and iridium). Some co-catalysts can act as catalysts on their own, but their use in combination with a primary catalyst can enhance the activity of the primary catalyst. Catalysts can also act as co-catalysts for other catalysts.In this context, catalysts can be called binary (or multi-metallic) catalysts. For example, Ru / Rh / C can be referred to as either a ruthenium-rhodium-carbon binary metal catalyst or a rhodium-activated ruthenium-carbon catalyst. An active catalyst is a substance that acts as a catalyst in a particular chemical reaction.

[0051] Preferred halide-containing main group, transition metal, lanthanide, and actinide catalysts include BX3(X=F,Cl,Br,I), BF3·OEt2, AlX3(X=F,Cl,Br,I), (C5H5)2TiX2(X=F,Cl), [Mn(CO)4Br]2, NiCl2, (C5H5)2ZrX2(X=F,Cl), PdCl2, PdI2, CuCl, CuI, CuF2, CuCl2, CuBr2, Cu(PPh3)3Cl, ZnCl2, R uCl3, [(C6H6)RuX2]2 (X=Cl, Br, I), (Ph3P)3RhCl (Wilkinson catalyst), [RhCl(cyclooctadiene)]2, di-μ-chlorotetracarbonyldirhodium(I), bis(triphenylphosphine)rhodium(I)carbonyl chloride, NdI2, SmI2, DyI2, (POCOP)IrHCl (POCOP=2,6-(R2PO)2C6H3; R=iPr, nBu, Me), H2PtCl 6· nH2O (spear catalyst), PtCl2, Pt(PPh3)2Cl2, and other halide-containing M n+ Examples of complexes (M=Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Ru, Rh, Pd, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Hf, Ta, W, Re, Os, Ir, Pt, U; n=0, 1, 2, 3, 4, 5, 6) are listed, but are not limited to these.

[0052] The molar ratio of the catalyst to the cyclic oligosiloxane in the reaction mixture is in the range of 0.1 to 1, 0.05 to 1, 0.01 to 1, 0.005 to 1, 0.001 to 1, 0.0005 to 1, 0.0001 to 1, 0.00005 to 1, or 0.00001 to 1. In one particular embodiment, 0.002 to 0.003 equivalents of the catalyst are used per equivalent of the cyclic oligosiloxane. In another particular embodiment, 0.001 equivalents of the catalyst are used per equivalent of the cyclic oligosiloxane.

[0053] In certain embodiments, the reaction mixture comprising a cyclic oligosiloxane organicamine and a catalyst further comprises an anhydrous solvent. Preferred solvents include, but are not limited to, linear, branched, cyclic, or polyethers (e.g., tetrahydrofuran (THF), diethyl ether, diglyme, and / or tetraglyme); linear, branched, or cyclic alkanes, alkenes, aromatics, and carbon halides (e.g., pentane, hexane, toluene, and dichloromethane). If added, the choice of one or more solvents may be influenced by their compatibility with the reagents contained in the reaction mixture, the solubility of the catalyst, and / or the method of separating the selected intermediate product and / or the final product. In other embodiments, the reaction mixture does not contain a solvent.

[0054] In the method described herein, the reaction of a cyclic oligosiloxane and an organic amine occurs at one or more temperatures in the range of about 0°C to about 200°C, preferably 0°C to about 100°C. Preferred reaction temperatures include a range having one or more of the following endpoints: 0, 10, 20, 30, 40, 50, 60, 70, 80, 90, or 100°C. The appropriate temperature range for this reaction may be determined by the physical properties of the reagents and, optionally, the solvent. Examples of specific reactor temperature ranges include, but are not limited to, 0°C to 80°C or 0°C to 30°C. In some embodiments, it is preferable to maintain a reaction temperature of 20°C to 60°C.

[0055] In certain embodiments of the methods described herein, the reaction pressure is about 1 to about 115 psia (6.89 × 10⁻⁶). 3~7.93×10 5 Pa) or approximately 15 to 45 psia (1.03 × 10⁻¹⁰ 5 ~3.10×10 5 The pressure may be in the range of Pa). In some embodiments where the cyclic oligosiloxane is a liquid under environmental conditions, the reaction is carried out at atmospheric pressure. In some embodiments where the cyclic oligosiloxane is a gas under environmental conditions, the pressure is 15 psia (1.03 × 10⁻⁶ Pa). 5 Perform a pressure reduction reaction at a higher Pa)

[0056] In certain embodiments, one or more reagents may be introduced into the reaction mixture as a liquid or vapor. In embodiments where one or more reagents are added as vapor, an unreactive gas such as nitrogen or an inert gas may be used as a carrier gas to deliver the vapor to the reaction mixture. In embodiments where one or more reagents are added as liquid, the reagents may be added neat or diluted with a solvent. Reagents are supplied to the reaction mixture until the desired conversion to a crude mixture or crude liquid containing the organic aminosilane product is achieved. In certain embodiments, the reaction may be carried out continuously by replenishing the reactants and removing the reaction product and crude liquid from the reactor.

[0057] Crude mixtures containing compounds of formulas A-D, catalysts, and any remaining organic amines, solvents, or undesirable products may require a separation method. Examples of suitable separation methods include, but are not limited to, distillation, evaporation, membrane separation, filtration, centrifugation, crystallization, gas phase transition, extraction, fractional distillation using reverse column, and combinations thereof.

[0058] Formulas 1-3 are preferred representative chemistry and are not intended to limit any method of preparing compounds having formulas A-D.

[0059] The silicon precursor compounds having formulas A to D described in the present invention and compositions comprising the silicon precursor compounds having formulas A to D described in the present invention are preferably substantially free of halide ions. When used herein, 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 0 ppm, when measured by plasma emission-mass spectrometry (ICP-MS), ion chromatography (IC), or any of the many analytical methods. Chlorides are known to act as decomposition catalysts for silicon precursor compounds having formulas A to D. Significant levels of chloride in the final product can decompose the silicon precursor compounds. Slow degradation of silicon precursor compounds can directly affect thin-film deposition methods, making it difficult for semiconductor manufacturers to meet thin-film specifications. In addition, the shelf life or stability is adversely affected by the higher degradation rate of the silicon precursor compound, making it difficult to guarantee a shelf life of 1-2 years. Therefore, the accelerated degradation of the silicon precursor compound raises safety and performance concerns related to the purification of these flammable and / or spontaneously combustible gaseous byproducts. The silicon precursor compound having formulas A-D is preferably Li + kaNa + , K + Mg 2+ Ca 2+ , Al 3+ Fe 2+ Fe 2+ Fe 3+ Ni 2+ , Cr 3+These compounds are substantially free of metal ions such as Li, Na, K, Mg, Ca, Al, Fe, Ni, Cr, and other metal impurities. As used herein, the term “substantially free” in relation to Li, Na, K, Mg, Ca, Al, Fe, Ni, Cr, and other metal impurities means less than 5 ppm (by weight), preferably less than 3 ppm, more preferably less than 1 ppm, and most preferably 0.1 ppm, as measured by ICP-MS. In some embodiments, the silicon precursor compounds having formulas A-D are Li + kaNa + , K + Mg 2+ Ca 2+ , Al 3+ Fe 2+ Fe 2+ Fe 3+ Ni 2+ , Cr 3+ These compounds are substantially free of metal ions such as Li, Na, K, Mg, Ca, Al, Fe, Ni, Cr, and noble metals such as Ru, Rh, Pd, or Pt from catalysts used in their synthesis. When used herein, the term "free of" in relation to Li, Na, K, Mg, Ca, Al, Fe, Ni, Cr, and noble metals such as Ru, Rh, Pd, or Pt from catalysts used in their synthesis means less than 1 ppm, preferably 0.1 ppm (by weight), as measured by ICP-MS or other analytical methods for metal detection.

[0060] In another embodiment, a method for depositing a thin film containing silicon and oxygen on a substrate, wherein the method is a) A step of preparing the substrate in the reactor; b) A step of introducing at least one silicon precursor compound into a reactor, wherein the at least one silicon precursor is a compound of formulas A to D: [ka] A precursor of the above formulas A to D, R 1 This is a linear C1-C 10 Alkyl groups, branched chains C3-C 10 Alkyl alkyl groups, C3-C10 Cyclic alkyl groups, C3-C 10 Heterocyclic group, C3~C 10 Alkenyl group, C3~C 10 Alkynyl group, and C4~C 10 Selected from the group consisting of aryl groups; R 2 is 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, C3~C 10 Alkenyl group, C3~C 10 Alkynyl group, and C4~C 10 Selected from the group consisting of aryl groups, R 1 and R 2 R is either bonded to form a cyclic ring structure or not bonded to form a cyclic ring structure; 3~11 This is 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, C4~C 10 Aryl group, and organic amino group, NR 1 R 2 , R 1 and R 2 Each of the elements is independently selected from the group consisting of the elements defined above; n=1, 2, or 3 and m=2 or 3. A process selected from the group consisting of precursors; c) A step of purging the reactor with a purge gas; d) The process of introducing oxygen-containing raw materials into the reactor; e) A step of purging the reactor with the purge gas; Includes, Steps b through e are repeated until a desired thickness of the thin film is deposited; the method is carried out at one or more temperatures in the range of about 25°C to 600°C. Provide a method.

[0061] The method disclosed herein forms a silicon oxide thin film having at least one of the following properties: density of at least about 2.1 g / cc; wet etching rate of less than about 2.5 Å / sec when measured in a diluted HF (0.5 mass% dHF) acid solution where HF to water is 1:100; and about 1 × 10⁻¹⁶ at 6 MV / cm or less. -8 A / cm 2 Leakage current less than 5 × 10⁻¹⁰; and when measured by secondary ion mass spectrometry (SIMS), approximately 5 × 10⁻¹⁰. 20 A silicon and oxygen-containing thin film containing at least one hydrogen impurity with a concentration of less than one atom / cc.

[0062] 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 chemical vapor deposition (CVD), for example, using a reaction chamber. Suitable substrates include, but are not limited to, gallium arsenide ("GaAs"), silicon, and silicon-containing compositions such as crystalline silicon, polysilicon, amorphous silicon, epitaxial silicon, silicon dioxide ("SiO2"), silicon glass, silicon nitride, quartz glass, glass, crystal, 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 additional layers such as 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 composite materials, metal oxides such as aluminum oxide, and germanium oxide. Further layers may include germanosilicate, aluminosilicate, copper and aluminum, and, although not limited to these, diffusion diaphragm materials such as TiN, Ti(C)N, TaN, Ta(C)N, Ta, W, or WN.

[0063] The deposition methods disclosed herein may include one or more purge gases. The purge gas used to expel unconsumed reactants and / or reaction by-products is an inert gas that does not react with the precursors. Preferred purge gases include, but are not limited to, argon (Ar), nitrogen (N2), helium (He), neon, hydrogen (H2), and combinations thereof. In certain embodiments, a purge gas such as Ar is supplied to the reactor for about 0.1 to 1000 seconds at a flow rate in the range of about 10 to about 2000 sccm (about 0.010 to about 2.000 L / min) to purge any unreacted material and any by-products that may remain in the reactor.

[0064] A purge gas such as argon removes unabsorbed excess complex from the process chamber. After sufficient purging, an oxygen source may be introduced into the reaction chamber to react with the absorption surface, and then further gas purging may be performed to remove reaction byproducts from the chamber. The process cycle can be repeated to obtain the desired thin film thickness. In some cases, pumping may be replaced with an inert gas for purging, or both may be used to remove unreacted silicon precursors.

[0065] Throughout this specification, the term “ALD or ALD-like” refers to a method including, but not limited to, the following: a) continuously introducing each reactant, including the silicon precursor and reaction gas, into a reactor such as a single-wafer ALD reactor, a semi-batch ALD reactor, or a batch furnace ALD reactor; b) exposing a substrate to each reactant, including the silicon precursor and reaction gas, by moving or rotating the substrate between different compartments of the reactor, each compartment separated by an inert gas curtain, i.e., a space ALD reactor or a roll-to-roll ALD reactor.

[0066] The method of the present invention is carried out by an ALD method using an oxygen-containing raw material that includes ozone or plasma which may further contain one or more inert gases such as: oxygen plasma with or without an inert gas; water vapor plasma with or without an inert gas; nitrogen oxide (e.g., N2O, NO, NO2) plasma with or without an inert gas; carbon oxide (e.g., CO2, CO) plasma with or without an inert gas; and combinations thereof.

[0067] Oxygen-containing raw materials can be generated in situ or remotely. In one particular embodiment, the oxygen-containing raw material contains oxygen, is fluid, or is introduced between steps b-d of the method in addition to at least one silicon precursor and optionally other reagents such as an inert gas.

[0068] In certain embodiments, the compositions described herein—and those used in the disclosed methods—further comprise a solvent. Preferred solvents 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 composition can be delivered to the reactor chamber for the silicon-containing thin film by direct liquid injection.

[0069] For these embodiments, which use at least one silicon precursor having formulas A to D in a composition containing a solvent, the selected solvent or a mixture thereof does not react with the silicon precursor. The amount of solvent in the composition by mass % is in the range of 0.5% to 99.5% by mass or 10% to 75% by mass. In this or other embodiments, the solvent has a boiling point (bp) similar to that of the silicon precursors of formulas A to D, and the difference between the boiling point of the solvent and the boiling point of the silicon precursors of formulas A to D is 40°C or less, 30°C or less, 200°C or less, or 100°C. Alternatively, the boiling point difference is in the range of one or more of the following endpoints: 0, 10, 20, 30, or 40°C. Examples of suitable ranges for the bp difference include, but are not limited to, 0 to 40°C, 20 to 30°C, or 10 to 30°C. Examples of suitable solvents in the composition include, but are not limited to, ethers (1,4-dioxane, dibutyl ether, etc.), tertiary amines (pyridine, 1-methylpiperidine, 1-ethylpiperidine, N,N'-dimethylpiperidine, N,N,N',N'-tetramethylethylenediamine, etc.), nitriles (benzonitrile, etc.), alkyl hydrocarbons (octane, nonane, dodecane, ethylcyclohexane, etc.), aromatic hydrocarbons (toluene, mesitylene, etc.), tertiary amino ethers (bis(2-dimethylaminoethyl) ether), or combinations thereof.

[0070] In certain embodiments, silicon oxide or carbon-doped silicon oxide thin films deposited using the methods described herein are formed in the presence of oxygen-containing raw materials including ozone, water (H2O) (e.g., deionized water, pure water, and / or distilled water), hydrogen peroxide (H2O2), oxygen (O2), oxygen plasma, NO, N2O, NO2, carbon monoxide (CO), carbon dioxide (CO2), and combinations thereof. The oxygen-containing raw materials may be passed, for example, through either an in-situ or remote plasma generator to provide an oxygen-containing plasma source such as oxygen plasma, a plasma containing oxygen and argon, a plasma containing oxygen and helium, ozone plasma, water plasma, nitrous oxide plasma, or carbon dioxide plasma. In certain embodiments, the oxygen-containing plasma source comprises an oxygen source gas introduced into the reactor at a flow rate ranging from about 1 to about 2000 standard cubic centimeters per minute (sccm) (about 0.001 to about 2.000 L / min) or about 1 to about 1000 sccm (about 0.001 to about 1.000 L / min). The oxygen-containing plasma source can be introduced over a period of time ranging from about 0.1 to about 100 seconds. In certain embodiments, the oxygen-containing plasma source comprises water having a temperature of 10°C or higher. In embodiments in which thin films are deposited by PEALD or plasma-accelerated cyclic CVD, the precursor pulse can have a pulse duration of more 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) 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., about 0.001 to about 0.01 seconds).

[0071] In one or more embodiments described above, the oxygen-containing plasma source is selected from the group consisting of oxygen plasma with or without an inert gas, water vapor plasma with or without an inert gas, nitrogen oxide (e.g., N2O, NO, NO2) plasma with or without an inert gas, carbon oxide (e.g., CO2, CO) plasma with or without an inert gas, and combinations thereof. In certain embodiments, the oxygen-containing plasma source further includes an inert gas. In these embodiments, the inert gas is selected from the group consisting of argon, helium, nitrogen, hydrogen, or combinations thereof. In alternative embodiments, the oxygen-containing plasma source does not include an inert gas.

[0072] Each step of supplying the precursor, oxygen source, and / or other precursors, source gases, and / or reagents may be carried out by changing the time to alter the stoichiometric composition of the dielectric thin film obtained by supplying these.

[0073] Energy is applied to at least one of the silicon precursors, oxygen-containing raw materials, or combinations thereof according to formulas A to D to induce a reaction and form a dielectric thin film or coating on the substrate. Such energy can be supplied by, but is not limited to, thermal plasma, pulsed plasma, helicon plasma, high-density plasma, inductively coupled plasma, X-rays, E-beams, photons, remote plasma methods, and combinations thereof. In certain embodiments, a secondary RF frequency source can be used to modify the plasma properties 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 within the reactor, or a remote plasma generation process in which the plasma is generated outside the reactor and supplied to the reactor.

[0074] At least one silicon precursor may be delivered to a reaction chamber such as a plasma-accelerated cyclic CVD or PEALD reactor, or to a batch-type reactor by various means. In one embodiment, a liquid delivery system may be utilized. In an alternative embodiment, a combined liquid delivery and flash evaporation process unit, such as a turbo vaporizer manufactured by MSP Corporation in Shoreview, Minnesota, may be used to enable volumetric delivery of low-volatility substances, resulting in reproducible transport and deposition without thermal decomposition of the precursor. In liquid delivery formulations, the precursors described herein may be delivered as neat liquids or used in solvent formulations or compositions containing them. Thus, in particular embodiments, the precursor formulation may contain solvent components of appropriate properties when this is desirable and advantageous in a given end-use application for forming a thin film on a substrate.

[0075] As described above, the purity level of at least one silicon precursor is high enough to be acceptable for reliable semiconductor manufacturing. In certain embodiments, the at least one silicon precursor described herein contains one or more of the following impurities in less than 2% by mass, less than 1% by mass, or less than 0.5% by mass: free amines, free halides or halogen ions, and higher molecular weight species. Higher purity levels of the silicon precursors described herein can be obtained by one or more of the following methods: purification, adsorption, and / or distillation.

[0076] In one embodiment of the method described herein, plasma-accelerated cyclic chemical vapor deposition (CVD) such as PEALD or PEALD may be used to carry out deposition using at least one silicon precursor and an oxygen plasma source. The PEALD-like method is defined as plasma-accelerated cyclic CVD, but further provides highly conformal silicon and oxygen-containing thin films.

[0077] One embodiment of the present invention is described herein for depositing a silicon and oxygen-containing thin film on at least one surface of a substrate, the method being: a. The process of preparing the substrate in the reactor; b. A step of introducing at least one silicon precursor having formulas A to D as defined above into a reactor; c. A step of purging the reactor with purge gas; d. A step of introducing plasma containing oxygen-containing raw materials into the reactor; e. A step of purging the reactor with a purge gas, This method includes repeating steps b to e until a desired thickness of thin film is deposited on the substrate.

[0078] In this or other embodiments, the steps of the method described herein may be performed in various orders, sequentially, simultaneously (e.g., between at least parts of other steps), or in combination thereof. Each step of supplying the precursor and oxygen source may be performed, for example, by changing the length of time for supplying them to alter the stoichiometric composition of the resulting dielectric thin film. Furthermore, the purging time after the precursor or oxidizer step can be minimized to <0.1 seconds to improve throughput.

[0079] In one particular embodiment, the method described herein deposits a high-quality silicon- and oxygen-containing thin film on a substrate. The method consists of the following steps: a. The process of preparing the substrate in the reactor; b. A step of introducing at least one silicon precursor having the above formulas A to D into a reactor; c. A step of purging the reactor with purge gas to remove at least a portion of the unabsorbed precursor; d. The process of introducing an oxygen-containing plasma 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 source, Steps b to e are repeated until a silicon-containing thin film of the desired thickness is deposited.

[0080] In another specific embodiment, the method described herein involves depositing a high-quality silicon- and oxygen-containing thin film on a substrate at a temperature exceeding 600°C. The method consists of the following steps: a. The process of preparing the substrate in the reactor; b. A step of introducing at least one silicon precursor having the above formulas A to D into a reactor; c. A step of purging the reactor with purge gas to remove at least a portion of the unabsorbed precursor; d. The process of introducing an oxygen-containing plasma 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 source, Steps b to e are repeated until a silicon-containing thin film of the desired thickness is deposited.

[0081] Since Si-H groups can decompose at temperatures above 600°C, potentially leading to undesirable chemical vapor deposition, these either contain no Si-H groups at all or have a limited number of Si-H groups, in particular, R 3 ~R 9 Cyclic oligosiloxane precursors having organic amino functional groups of formulas A to D that are not hydrogen are considered preferable for this method. However, under certain conditions such as using short precursor pulses or low reactor pressure, R 3~9 It is also possible to carry out this method at temperatures exceeding 600°C without significantly undesirable chemical vapor deposition, using cyclic oligosiloxane precursors having organic amino functional groups of formulas A to D, where one of the atoms is hydrogen.

[0082] Another method disclosed herein involves forming a carbon-doped silicon oxide thin film using a silicon precursor compound having a chemical structure represented by formulas A to D as defined above, plus an oxygen source.

[0083] Another preferred method is described below: a. Prepare the substrate inside the reactor; b. Chemically absorbing a precursor onto a heated substrate, with or without contact, a vapor generated from at least one silicon precursor compound having a chemical structure represented by formulas A to D of the above definition, in contact with a parallel flow of an oxygen source; c. Displacing any unabsorbed precursor; d. Introducing an oxygen source into a heated substrate and reacting it with the absorbed precursor; e. Remove any unreacted oxygen source. Repeat steps b to e until the desired thickness is achieved.

[0084] In another specific embodiment, the method described herein involves depositing a high-quality silicon oxynitride thin film onto a substrate. The method consists of the following steps: a. The process of preparing the substrate in the reactor; b. A step of introducing at least one silicon precursor having the above formulas A to D into a reactor; c. A step of purging the reactor with purge gas to remove at least a portion of the unabsorbed precursor; d. The process of introducing a nitrogen-containing plasma source into the reactor; e. A step of purging the reactor with purge gas to remove at least a portion of the unreacted nitrogen source. Steps b to e are repeated until a silicon oxynitride-containing thin film of the desired thickness is deposited.

[0085] Another preferred method is described below: a. Prepare the substrate inside the reactor; b. Chemically absorbing a precursor onto a substrate heated with or without contact with a parallel flow of a nitrogen source, using vapor generated from at least one silicon precursor compound having a chemical structure represented by formulas A to D of the above definition; c. Displacing any unabsorbed precursor; d. Introducing a nitrogen source into a heated substrate and reacting it with the absorbed precursor; e. Remove any unreacted nitrogen source. Repeat steps b to e until the desired thickness is achieved.

[0086] Various commercially available ALD reactors, such as single-wafer, semi-batch, or batch furnaces or roll-to-roll reactors, can be used to deposit solid oxysilicon, silicon oxynitride, carbon-doped silicon oxynitride, or carbon-doped silicon oxide.

[0087] For the methods described herein, the process temperature used as the endpoint is one or more of the following temperatures: 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, 625°C, 650°C, 675°C, 700°C, 725°C, 750°C, 775°C, and 800°C. Preferred temperature ranges include, but are not limited to, the following: approximately 0°C to approximately 300°C; or approximately 25°C to approximately 300°C; or approximately 50°C to approximately 290°C; or approximately 25°C to approximately 250°C; or approximately 25°C to approximately 200°C.

[0088] In another embodiment, a method for depositing a silicic acid and oxygen-containing thin film by fluid chemical vapor deposition (FCVD), wherein the method is: The method involves placing a substrate including surface features inside a reactor, maintaining the substrate at a temperature in the range of approximately -20°C to approximately 400°C, and setting the reactor pressure to 100 Torr (1.33 × 10). 5 To keep it below Pa; Introducing at least one compound selected from the group consisting of formulas A to D as defined herein; Providing an oxygen source in the reactor to react with at least one of the compounds to form a thin film, thereby covering at least a portion of the surface feature portion; The thin film is annealed at one or more temperatures between approximately 100°C and 1000°C to cover at least a portion of the surface feature portion; The substrate is treated with an oxygen source at one or more temperatures in the range of approximately 20°C to approximately 1000°C to form a silicon-containing thin film on at least a portion of the surface feature area. This provides a method that includes [something].

[0089] In another embodiment, a method for depositing a silicic acid and oxygen-containing thin film by fluid chemical vapor deposition (FCVD), wherein the method is: The method involves placing a substrate including surface features inside a reactor, maintaining the substrate at a temperature in the range of approximately -20°C to approximately 400°C, and setting the reactor pressure to 100 Torr (1.33 × 10). 5 To keep it below Pa; Introducing at least one compound selected from the group consisting of formulas A to D as defined herein; A nitrogen source and / or an oxygen source are provided in the reactor to react with the at least one compound to form a thin film, thereby covering at least a portion of the surface feature portion; The thin film is annealed at one or more temperatures between approximately 100°C and 1000°C to cover at least a portion of the surface feature portion; The substrate is treated with an oxygen source at one or more temperatures in the range of approximately 20°C to approximately 1000°C to form a silicon-containing thin film on at least a portion of the surface feature area. This provides a method that includes [something].

[0090] 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. 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, trimethyl plasma, trimethylamine plasma, ethylenediamine plasma, and alkoxyamines such as ethanolamine plasma, and mixtures thereof. In yet another embodiment, the nitrogen-containing raw material includes ammonia plasma, a plasma containing nitrogen and argon, a plasma containing nitrogen and helium, or a plasma containing hydrogen and a nitrogen source gas. In this or another embodiment, the steps of the method are repeated until the surface feature is filled with a silicon-containing thin film. In embodiments of fluid chemical vapor deposition where water vapor is used as the oxygen source, the substrate temperature is in the range of approximately -20°C to approximately 40°C or -10°C to approximately 25°C.

[0091] Further embodiments of the methods described herein involve subjecting a thin film deposited by ALD, ALD-like, PEALD, PEALD-like, or FCVD, or an as-deposited thin film, to a post-deposition process. The post-deposition process can be carried out during at least part of the deposition process, after the deposition process, or in combination thereof. Preferred post-deposition processes include, but are not limited to, high-temperature thermal annealing, plasma treatment, ultraviolet (UV) treatment, laser treatment, electron beam treatment, and combinations thereof, which affect one or more properties of the thin film.

[0092] In another embodiment, a tank or vessel for depositing silicon-containing thin films comprising one or more silicon precursor compounds is described herein. In one particular embodiment, the tank comprises at least one pressurized tank (preferably made of stainless steel having a design as disclosed in U.S. Patent No. 7,334,595; U.S. Patent No. 6,077,356; U.S. Patent No. 5,069,244; and U.S. Patent No. 5,465,766 (this disclosure is incorporated herein by reference)). The vessel may be equipped with appropriate valves and may be made of either glass (borosilicate or quartz glass) or a stainless steel alloy of type 316, 316L, 304, or 304L (UNS designations S31600, S31603, S30400, S30403) that allows for the delivery of one or more precursors to a reactor for a CVD or ALD process. In this or other embodiment, the silicon precursor is supplied into a pressurized tank made of stainless steel, the purity of the precursor being 98% by mass or 99.5% by mass or higher, and suitable for most semiconductor applications. The headspace of the tank or container is filled with an inert gas selected from helium, argon, nitrogen, and combinations thereof.

[0093] In certain embodiments, a gas line connecting a precursor vessel to a reaction chamber is heated to one or more temperatures according to process requirements, and a vessel containing at least one silicon precursor is maintained at one or more temperatures for aeration. In other embodiments, a solution containing at least one silicon precursor is injected directly into a vaporizer maintained at one or more temperatures for liquid injection.

[0094] A flow of argon and / or other gases may be used as a carrier gas to assist in the delivery of at least one silicon precursor vapor to the reaction chamber during the precursor pulse. In certain embodiments, the reaction chamber process pressure is about 50 milliliters (66.5 Pa) to 10 milliliters (13.3 Pa). In other embodiments, the reaction chamber process pressure is 760 Torr (1.01 × 10⁻¹⁰). 6 Pa) or less (for example, approximately 50 milliliters (66.5 Pa) to approximately 100 milliliters (1.33 × 10⁻¹⁰ Pa) 5 Pa))

[0095] In typical PEALD methods or PEALD-like methods such as the PECCVD method, a substrate such as a silicon oxide substrate is heated on a heater stage in a reaction chamber where it is first exposed to a silicon precursor, allowing the composite to be chemically adsorbed onto the substrate surface.

[0096] Thin films deposited with silicon precursors having formulas A to D described herein, when compared to thin films deposited with previously disclosed silicon precursors under the same conditions, have improved properties such as a lower wet etching rate than the pre-processing thin film or a higher density than the pre-processing density, but are not limited to these. In one particular embodiment, the as-deposited thin film is intermittently processed during the deposition method. These intermittent or intermediate deposition processes can be performed, for example, after each ALD cycle, but are not limited to, every 1(1) ALD cycle, every 2(2) ALD cycle, every 5(5) ALD cycle, or every 10(10) or more ALD cycles, or after a specific number of ALD cycles.

[0097] The precursors of formulas A to D exhibit a growth rate of 2.0 Å / cycle or higher.

[0098] In embodiments where the thin film is processed by a high-temperature annealing process, the annealing temperature is at least 100°C or higher than the deposition temperature. In this or other embodiments, the annealing temperature is in the range of about 400°C to about 1000°C. In this or other embodiments, the annealing process is carried out under vacuum (<760 Torr(1.01 × 10) 6 This can be carried out in an inert environment or an oxygen-containing environment (such as H2O, N2O, NO2, O2, or ambient air).

[0099] In embodiments of UV treatment of thin films, the thin film is exposed to a broadband UV source or a UV source having wavelengths in the range of approximately 150 nanometers (nm) to approximately 400 nm. In one particular embodiment, the as-deposited thin film is exposed to UV in a chamber different from the deposition chamber after achieving a desired thin film thickness.

[0100] In embodiments where a thin film is treated with plasma, an inactivating layer such as SiO2 or carbon-doped SiO2 is deposited to prevent chlorine and nitrogen from penetrating the thin film during subsequent plasma treatment. The inactivating layer can be deposited using atomic layer deposition or cyclic chemical vapor deposition.

[0101] In embodiments where thin films are 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. The hydrogen plasma reduces the dielectric constant of the thin film and enhances its resistance to damage during subsequent plasma ashing while maintaining little change in the carbon content in the bulk.

[0102] While there is no intention to be bound by any particular theory, silicon precursor compounds having the chemical structures represented by formulas A-D as defined above can be immobilized by reacting at least one organic amino group with a hydroxyl group on the substrate to obtain multiple Si-O-Si fragments per precursor molecule. Therefore, it is thought that this enhances 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, which have only one silicon atom. It is possible that silicon compounds having formulas A-D, which have two or more organic amino groups, can react with two or more adjacent hydroxyl groups on the substrate surface. As the number of silicon atoms increases, it is also conceivable that the cyclic oligosiloxanes having organic amino functional groups disclosed herein will exhibit a higher gross production per cycle (GPC). For example, using 2-dimethylamino-2,4,6,8,10-pentamethylcyclopentasiloxane (5 silicon atoms) as a silicon ALD precursor may yield higher GPC compared to 2-dimethylamino-2,4,6,8-tetramethylcyclotetrasiloxane (4 silicon atoms).

[0103] While not intended to be bound by any particular theory, the functionalization of cyclic oligosiloxane molecules, such as 2,4,6-trimethylcyclotrisiloxane, 2,4,6,8-tetramethylcyclotetrasiloxane, and 2,4,6,8,10-pentamethylcyclopentasiloxane, as well as other cyclic oligosiloxanes having organic amino groups, is thought to increase the thermal stability of cyclic oligosiloxanes, resulting in a longer shelf life and longer maintenance of high purity by inhibiting degradation. In some cases, more organic amino groups can provide the molecule with even greater thermal stability. For specific applications, the improved stability of the silicon precursors described herein having formulas A-D is superior to that of parent cyclic oligosiloxane precursors.

[0104] While not intended to be bound by any particular theory, the functionalization of cyclic oligosiloxane molecules such as 2,4,6-trimethylcyclotrisiloxane, 2,4,6,8-tetramethylcyclotetrasiloxane, and 2,4,6,8,10-pentamethylcyclopentasiloxane, as well as other cyclic oligosiloxanes having organic amino groups, is thought to provide precursors that result in a greater level of networking in the resulting silicon-containing thin films, especially when the oxygen-containing reactants in the deposition method are mild oxidizers such as water or hydrogen peroxide.

[0105] In certain embodiments, silicon precursors having formulas A to D as defined above may also be used as dopants for metal-containing thin films, such as metal oxide thin films or metal oxynitride thin films, but are not limited to these. In these embodiments, the metal-containing thin films are deposited using ALD or CVD methods, such as those described herein using metal alkoxides, metal amides, or volatile organometallic precursors. Examples of suitable metal alkoxide precursors that may be used in the methods disclosed herein include, but are not limited to, group 3-6 metal alkoxides, group 3-6 metal complexes having both alkoxy and alkyl-substituted cyclopentadienyl ligands, group 3-6 metal complexes having both alkoxy and alkyl-substituted pyrrolyl ligands, group 3-6 metal complexes having both alkoxy and diketonate ligands; and group 3-6 metal complexes having both alkoxy and ketoester ligands.

[0106] Examples of suitable metal amide precursors that may be used in 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-butylaminotri(diethylamino)tantalum (TBTDET), tert-butylaminotri(dimethylamino)tantalum (TBTDMT), and tert-butylamino Examples of suitable organometallic precursors that may be used in the methods disclosed herein include, but are not limited to, group 3 metal cyclopentadienyl or alkylcyclopentadienyl. Preferred group 3-6 metals in this specification 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.

[0107] In certain embodiments, the silicon-containing thin films described herein have dielectric constants of 6 or less, 5 or less, 4 or less, and 3 or less. In these or other embodiments, the thin films may have dielectric constants of about 5 or less, about 4 or less, or about 3.5 or less. However, thin films with other dielectric constants (e.g., higher or lower) can be formed depending on the desired end application of the thin film. Examples of silicon precursors having formulas A to D and silicon-containing thin films formed using the methods described herein include those with the composition Si x O y C z N v H w The silicon precursors of formulas A to D and the silicon-containing thin films formed using the methods described herein are silicon oxynitride, which, when measured by XPS, for example, has a carbon content of 1 atom to 80 atoms. Furthermore, another example of a silicon-containing thin film formed using the silicon precursors of formulas A to D and the methods described herein is amorphous silicon, in which the total nitrogen and carbon content is <10 atomic%, preferably <5 atomic%, and most preferably <1 atomic%, as measured by XPS.

[0108] As described above, silicon-containing thin films may be deposited on at least a portion of a substrate using the method described herein. Examples of suitable substrates include silicon, SiO2, Si3N4, OSG, FSG, silicon carbide, silicon hydride oxycarbide, silicon hydride oxynitride, silicon oxycarbonitride, silicon hydride oxycarbonitride, anti-reflective coatings, photoresists, germanium, germanium-containing materials, boron-containing materials, Ga / As, flexible substrates, organic polymers, porous organic and inorganic materials, metals such as copper and aluminum, and, but not limited to, diffusion diaphragm layers such as TiN, Ti(C)N, TaN, Ta(C)N, Ta, W, or WN. The thin films are suitable for various subsequent processing steps, such as chemical mechanical planarization (CMP) and anisotropic etching.

[0109] The deposited thin films have applications including, but are not limited to, computer chips, optical devices, magnetic information storage, coatings on carrier materials or substrates, microelectromechanical systems (MEMS), nanoelectromechanical systems, thin-film transistors (TFTs), light-emitting diodes (LEDs), organic light-emitting diodes (OLEDs), IGZOs, and liquid crystal displays (LCDs). Possible applications of the resulting solid silicon oxide or carbon-doped silicon oxide include, but are not limited to, shallow trench insulators, interlayer dielectrics, deactivation layers, etching stop layers, parts of dual spacers, and patterning sacrificial layers.

[0110] The methods described herein provide high-quality silicon oxide, silicon oxynitride, carbon-doped silicon oxynitride, or carbon-doped silicon oxide thin films. Defending "high quality" means the following characteristics: density of about 2.1 g / cc or more, 2.2 g / cc or more, 2.25 g / cc or more; wet etching rates 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, and 0.01 Å / sec or less when measured in a diluted HF (0.5 mass% dHF) acid solution where HF to water is 1:100; wet etching rates of about 1 × 10⁻¹⁶ 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, and 0.01 Å / sec or less for diluted HF; and about 1 × 10⁻¹⁶ Å / sec or less with an application of 6 MV / cm or less. -8 A / cm 2The following leakage current; when measured by SIMS, approximately 5 × 10⁻⁶ 20 This refers to thin films exhibiting hydrogen impurities of less than or equal to one atom / cc, and one or more combinations thereof. Regarding etching rate, a thermally grown silicon oxide thin film has an etching rate of 0.5 Å / sec in 0.5 mass% HF.

[0111] In certain embodiments, one or more silicon precursors having formulas A to D described herein can be used to form solid, non-porous or substantially pore-free silicon and oxygen-containing thin films.

[0112] The following examples illustrate specific aspects of the present invention, but without limiting the scope of the appended claims. [Examples]

[0113] Example 1a. Synthesis of 2,4-bis(dimethylamino)-2,4,6,8-tetramethylcyclotetrasiloxane and 2,6-bis(dimethylamino)-2,4,6,8-tetramethylcyclotetrasiloxane.

[0114] THF (200 mL), Ru3 (CO2) at room temperature 12 To a stirred solution of (1.12 g, 0.00175 mol, 2.2 mol%) and 2,4,6,8-tetramethylcyclotetrasiloxane (192 g, 0.792 mol), dimethylamine solution in THF (396 mL, 2.0 M solution, 2 equivalents) was added dropwise at room temperature over 4 hours. The reaction solution was stirred overnight at room temperature. The solvent was removed under reduced pressure, and the crude product was fractionally distilled (6 tors (7.98 × 10⁻¹⁴)). 3 Purification by (Pa) / 94℃) yielded a mixture of 2,4-bis(dimethylamino)-2,4,6,8-tetramethylcyclotetrasiloxane and 2,6-bis(dimethylamino)-2,4,6,8-tetramethylcyclotetrasiloxane. GC-MS showed the following peaks for both compounds: 326(M +), 311(M-15), 282, 266, 252, 239, 225, 209, 193, 179, 165, 149, 141, 133, 119, 111, 104, 89, 73, 58, 44.

[0115] Example 1b. Thermal stability of bis(dimethylamino)-2,4,6,8-tetramethylcyclotetrasiloxane.

[0116] Several purified samples of bis(dimethylamino)-2,4,6,8-tetramethylcyclotetrasiloxane (isomer mixture) were heated at 80°C for 7 days. The assay for bis(dimethylamino)-2,4,6,8-tetramethylcyclotetrasiloxane, determined by GC analysis, decreased from 96.47% to an average of 96.37%, indicating that bis(dimethylamino)-2,4,6,8-tetramethylcyclotetrasiloxane has excellent thermal stability and is suitable as a precursor for vapor phase growth.

[0117] Example 2. Synthesis of 2,4-bis(diethylamino)-2,4,6,8-tetramethylcyclotetrasiloxane and 2,6-bis(diethylamino)-2,4,6,8-tetramethylcyclotetrasiloxane.

[0118] A similar procedure was followed according to Example 1, except that diethylamine was used instead of dimethylamine, to obtain a mixture of 2,4-bis(diethylamino)-2,4,6,8-tetramethylcyclotetrasiloxane and 2,6-bis(diethylamino)-2,4,6,8-tetramethylcyclotetrasiloxane. GC-MS showed the following peaks for both compounds: m / z = 382 (M + ), 367(M-15), 353, 340, 326, 310, 296, 280, 266, 252, 239, 225, 207, 193, 179, 165, 147, 133, 119, 111, 104, 86, 72, 59, 42.

[0119] Example 3. Synthesis of 2,4-bis(N-ethylmethylamino)-2,4,6,8-tetramethylcyclotetrasiloxane and 2,6-bis(N-ethylmethylamino)-2,4,6,8-tetramethylcyclotetrasiloxane. A similar procedure was followed according to Example 1, except that N-ethylmethylamine was used instead of dimethylamine, to obtain a mixture of 2,4-bis(N-ethylmethylamino)-2,4,6,8-tetramethylcyclotetrasiloxane and 2,6-bis(N-ethylmethylamino)-2,4,6,8-tetramethylcyclotetrasiloxane. GC-MS showed the following peaks for both compounds: m / z = 355 (M + ), 340(M-15), 324, 312, 297, 283, 267, 253, 240, 226, 194, 179, 163, 141, 133, 119, 111, 103, 89, 73, 58, 44.

[0120] Example 4. Synthesis of 2,4-bis(iso-propylamino)-2,4,6,8-tetramethylcyclotetrasiloxane and 2,6-bis(iso-propylamino)-2,4,6,8-tetramethylcyclotetrasiloxane. A similar procedure was followed according to Example 1, except that iso-propylamine was used instead of dimethylamine, to obtain a mixture of 2,4-bis(iso-propylamino)-2,4,6,8-tetramethylcyclotetrasiloxane and 2,6-bis(N-iso-propylamino)-2,4,6,8-tetramethylcyclotetrasiloxane. GC-MS showed the following peaks for both compounds: m / z = 356 (M + ), 341(M-15), 325, 313, 296, 282, 253, 240, 223, 208, 193, 180, 164, 150, 141, 134, 120, 112, 103, 87, 74, 59, 44.

[0121] Example 5. Synthesis of 2,4-bis(methylamino)-2,4,6,8-tetramethylcyclotetrasiloxane and 2,6-bis(methylamino)-2,4,6,8-tetramethylcyclotetrasiloxane.

[0122] A similar procedure was followed according to Example 1, except that methylamine was used instead of dimethylamine, to obtain a mixture of 2,4-bis(methylamino)-2,4,6,8-tetramethylcyclotetrasiloxane and 2,6-bis(methylamino)-2,4,6,8-tetramethylcyclotetrasiloxane. GC-MS showed the following peaks for both compounds: m / z = 298 (M + ), 283(M-15), 268, 252, 239, 225, 209, 193, 179, 165, 149, 135, 127, 119, 112, 104, 97, 89, 75, 59, 44.

[0123] Example 6a. Synthesis of 2-dimethylamino-2,4,6,8,10-pentamethylcyclopentasiloxane. THF (200 mL), Ru3 (CO2) at room temperature 12 To a stirred solution of (1.12 g, 0.00172 mol) and 2,4,6,8,10-pentamethylcyclopentasiloxane (240 g, 0.798 mol), a dimethylamine solution in THF (176 mL, 2.0 M solution) was added over 4 hours under nitrogen protection. The reaction solution was stirred overnight at room temperature. The solvent was removed under reduced pressure, and the crude product was fractionally distilled (1.5 Torr (2.00 × 10⁻¹⁰). 3 The desired product, 2-dimethylamino-2,4,6,8,10-pentamethylcyclopentasiloxane, was obtained as a colorless liquid by purification using Pa / 60°C. GC-MS showed the following mass peak: m / z = 344 (M + ), 329(M-15), 313, 300, 286, 268, 254, 240, 226, 210, 193, 179, 165, 149, 134, 119, 102, 88, 73, 59, 45.

[0124] Example 6b. Thermal stability of 2-dimethylamino-2,4,6,8,10-pentamethylcyclopentasiloxane. Several purified samples of 2-dimethylamino-2,4,6,8,10-pentamethylcyclopentasiloxane were heated at 80°C for 7 days. The assay for 2-dimethylamino-2,4,6,8,10-pentamethylcyclopentasiloxane, determined by GC analysis, decreased from 97.57% to an average of 97.23%, indicating that 2-dimethylamino-2,4,6,8,10-pentamethylcyclopentasiloxane has excellent thermal stability and is suitable as a precursor for vapor phase growth.

[0125] Example 7: Synthesis of 2-diethylamino-2,4,6,8,10-pentamethylcyclopentasiloxane. THF (1 mL), Ru3 (CO) at room temperature 12 Diethylamine (0.22 g, 0.0030 mol) was added under nitrogen protection to a stirred solution of (0.010 g, 0.000016 mol) and 2,4,6,8,10-pentamethylcyclopentasiloxane (1.0 g, 0.0033 mol). The reaction solution was stirred overnight at room temperature. GC-MS determined that the solution contained 2-diethylamino-2,4,6,8,10-pentamethylcyclopentasiloxane as the main product. GC-MS showed the following mass peak: m / z = 371 (M + ), 357, 341, 327, 311, 300, 286, 268, 254, 240, 226, 210, 193, 179, 165, 149, 133, 116, 102, 86, 73, 59, 45.

[0126] Example 8. Synthesis of 2-(N-ethylmethylamino)-2,4,6,8,10-pentamethylcyclopentasiloxane. THF (1 mL), Ru3 (CO) at room temperature 12N-ethylmethylamine (0.17 g, 0.0029 mol) was added under nitrogen protection to a stirred solution of (0.010 g, 0.000016 mol) and 2,4,6,8,10-pentamethylcyclopentasiloxane (1.0 g, 0.0033 mol). The reaction solution was stirred overnight at room temperature. GC-MS determined that the solution contained 2-(N-ethylmethylamino)-2,4,6,8,10-pentamethylcyclopentasiloxane as the main product. GC-MS showed the following mass peak: m / z = 357 (M + ), 343, 327, 316, 300, 283, 273, 253, 239, 225, 209, 193, 179, 165, 149, 135, 116, 102, 88, 73, 59, 45.

[0127] Example 9. Synthesis of 2,4,6,8-tetrakis(methylamino)-2,4,6,8-tetramethylcyclotetrasiloxane from 2,4,6,8-tetrachloro-2,4,6,8-tetramethylcyclotetrasiloxane and methylamine. A methylamine solution in THF (3.0 mL, 2.0 M solution) was diluted with hexane (3 mL) and stirred. 2,4,6,8-tetrachloro-2,4,6,8-tetramethylcyclotetrasiloxane solid (0.20 g, 0.000529 mol) was slowly added to this solution over 10 minutes, during which time a precipitate formed. After stirring the reaction mixture for 30 minutes, the white solid was removed by filtration, and the filtrate was concentrated under reduced pressure. From the resulting oily residue, a colorless crystalline product, 2,4,6,8-tetrakis(methylamino)-2,4,6,8-tetramethylcyclotetrasiloxane, was obtained by leaving it at room temperature. GC-MS showed the following mass peak: 355 (M + ), 340(M-15), 326, 311, 296, 282, 267, 253, 240, 225, 209, 193, 179, 165, 147, 133, 120, 112, 105, 94, 82, 73, 59, 44.

[0128] Example 10. Synthesis of 2,4,6,8-tetrakis(methylamino)-2,4,6,8-tetramethylcyclotetrasiloxane from 2,4,6,8-tetramethylcyclotetrasiloxane and methylamine (prophetic). Ru3(CO) in THF 12 To a stirred solution of (1.33 g, 0.00208 mol) and methylamine solution (1.04 L, 2.0 M solution), 2,4,6,8-tetramethylcyclotetrasiloxane (100 g, 0.417 mol) is added dropwise at room temperature over 4 hours. The reaction solution is stirred overnight at room temperature. The solvent is removed under reduced pressure, and the crude product is purified by fractional distillation to obtain the desired product, 2,4,6,8-tetrakis(methylamino)-2,4,6,8-tetramethylcyclotetrasiloxane.

[0129] Example 11. Synthesis of 2,4,6,8-tetrakis(dimethylamino)-2,4,6,8-tetramethylcyclotetrasiloxane from 2,4,6,8-tetrachloro-2,4,6,8-tetrachloro-2,4,6,8-tetramethylcyclotetrasiloxane and dimethylamine. A dimethylamine solution in THF (3.0 mL, 2.0 M solution) was diluted with hexane (3 mL) and stirred. 2,4,6,8-tetrachloro-2,4,6,8-tetramethylcyclotetrasiloxane solid (0.20 g, 0.000529 mol) was slowly added to this solution over 10 minutes, during which time a precipitate formed. After stirring the reaction mixture for 30 minutes, the white solid was removed by filtration, and the filtrate was concentrated under reduced pressure. GC-MS determined that the resulting oily residue contained 2,4,6,8-tetrakis(methylamino)-2,4,6,8-tetramethylcyclotetrasiloxane as a single product. GC-MS showed the following mass peak: 413(M + ), 398(M-15), 384, 369, 355, 339, 326, 310, 296, 283, 267, 253, 240, 225, 209, 194, 179, 163, 155, 141, 134, 119, 111, 103, 89, 73, 58, 44.

[0130] Example 12.27. PEALD silicon dioxide using bis(dimethylamino)-2,4,6,8-tetramethylcyclotetrasiloxane (including a mixture of 2,4- and 2,6-isomers) in a laminar flow reactor containing a 1 MHz plasma.

[0131] Plasma-accelerated ALD (PEALD) was performed in a commercially available side-flow reactor (300 mm PEALD tool manufactured by ASM) equipped with a 27.1 MHz direct plasma capability and a fixed 3.5 mm spacing between electrodes. The precursor was a liquid heated to 62°C in a stainless steel bubbler and delivered to the chamber using an Ar carrier gas. The total deposition reported in this test was performed on natural oxides containing Si substrates. The thickness and refractive index of the thin films were measured using a FilmTek 2000SE ellipsometer. Wet etching rate (WER) measurements were performed using a 1:99 (0.5 mass) diluted hydrofluoric acid (HF) solution. Etching solution activity was confirmed using a thermally oxidized wafer as a standard material for each experimental set. All samples were etched for 15 minutes to remove any surface layer before starting the collection of bulk thin film WER. The typical thermally oxidized wafer wet etching rate for a 1:99 (0.5 mass) dHF aqueous solution was 0.5 Å / sec using this procedure.

[0132] As a silicon precursor, bis(dimethylamino)-2,4,6,8-tetramethylcyclotetrasiloxane (including a mixture of 2,4- and 2,6-isomers) was used for deposition using an O2 plasma under the conditions described in Table 2. The silicon precursor was delivered to the chamber by a carrier gas Ar stream of 200 sccm (approximately 0.200 L / min). Steps b to e were repeated many times to obtain the desired silicon oxide thickness for measurement.

[0133] [Table 2]

[0134] Thin film deposition parameters and deposited GPCs are shown in Table 3 for 100°C deposition and in Table 4 for 300°C deposition. Depositions 1-6 and 13-18 show GPCs as a function of precursor pulse time deposition at 100°C and 300°C. Figure 1 shows the saturation curve of bis(dimethylamino)-2,4,6,8-tetramethylcyclotetrasiloxane GPC as a function of precursor pulse number. It can be seen that the GPC increases with the precursor pulse, then saturates, exhibiting the ALD behavior of the precursor. 100°C deposition shows a higher GPC than 300°C deposition. BDEAS (bis(diethylamino)silane) deposition is shown in Figure 1 for comparison. The BDEAS vessel was heated to 28°C and had a similar internal vapor pressure at 62°C as the bis(dimethylamino)-2,4,6,8-tetramethylcyclotetrasiloxane vessel. BDEAS was delivered to the chamber in a carrier gas Ar stream of 200 sccm (0.200 L / min). Bis(dimethylamino)-2,4,6,8-tetramethylcyclotetrasiloxane exhibits a much higher GPC than BDEAS. Depositions 7-12 and 19-24 show the GPC and thin film relative WER at various deposition pressures, oxygen plasma times, or oxygen plasma power levels. Figures 2 and 3 show the thin film GPC and WER against O2 plasma power at deposition temperatures of 300°C and 100°C, respectively, when bis(dimethylamino)-2,4,6,8-tetramethylcyclotetrasiloxane is used as the silicon precursor. The GPC decreased slightly with increasing oxygen plasma power, and the WER also decreased with increasing oxygen plasma power. Thin films deposited at higher temperatures exhibited lower WER. Figures 4 and 5 show the thin film GPC and WER against O2 plasma time at deposition temperatures of 300°C and 100°C, respectively, when bis(dimethylamino)-2,4,6,8-tetramethylcyclotetrasiloxane is used as the silicon precursor. GPC decreased slightly with increasing oxygen plasma time, and WER also decreased with increasing oxygen plasma time. Lower WER in thin films indicates higher thin film quality.

[0135] [Table 3]

[0136] [Table 4]

[0137] Comparative Example 12a. PEALD silicon dioxide using TMCTS (2,4,6,8-tetramethylcyclotetrasiloxane) in a 27.1 MHz plasma laminar flow reactor

[0138] Deposition was carried out using TMCTS and O2 plasma reactants as silicon precursors. TMCTS was delivered to the chamber by vapor inletion, and no carrier gas was used. Steps b to e in Table 2 were repeated many times to obtain the desired silicon oxide thickness for measurement. Thin film deposition parameters, deposited GPC, and wafer uniformity are shown in Table 5. The deposited wafer showed poor uniformity, and the GPC did not show saturation with increasing precursor pulses. This indicates CVD deposition related to TMCTS and is therefore unsuitable as an ALD precursor.

[0139] [Table 5]

[0140] Comparative Example 12b.27.1MHz plasma laminar flow reactor using PEALD silicon dioxide with BDEAS (bis(diethylamino)silane).

[0141] Under the conditions shown in Table 2, deposition was carried out using BDEAS and O2 plasma as silicon precursors. The precursor was delivered to the chamber with a carrier gas Ar flow of 200 sccm (0.200 L / min). Steps b to e were repeated many times to obtain the desired silicon oxide thickness for measurement. Thin film deposition parameters and deposited GPC are shown in Table 6. Figure 1 shows the GPC for different precursor flow times. This shows a much lower GPC than bis(dimethylamino)-2,4,6,8-tetramethylcyclotetrasiloxane.

[0142] [Table 6]

[0143] Example 13.27.1 MHz Plasma Layer Flow Reactor: PEALD Silicon Oxide Using 2-Dimethylamino-2,4,6,8,10-Pentamethylcyclopentasiloxane Under the above conditions in Table 2, deposition was carried out using 2-dimethylamino-2,4,6,8,10-pentamethylcyclopentasiloxane as the silicon precursor and O2 plasma. The precursor was delivered to the chamber with a carrier gas Ar flow of 200 sccm (0.200 L / min). The vessel was heated to 50 °C. Steps b - e were repeated several times to obtain the desired thickness of silicon oxide for measurement. The thin film deposition parameters and deposition GPC, thin film RI, and relative WER with respect to thermal oxide are shown in Tables 7 and 8. Figure 1 shows the saturation curve of 2-dimethylamino-2,4,6,8,10-pentamethylcyclopentasiloxane GPC versus the number of precursor pulses. It can be seen that GPC increases with the precursor pulse and then saturates, indicating the ALD behavior of the precursor. The 100 °C deposition shows a higher GPC than the 300 °C deposition. The BDEAS (bis(diethylamino)silane) deposition is shown in Figure 1 for comparison. When using the 2-dimethylamino-2,4,6,8,10-pentamethylcyclopentasiloxane precursor, the thin film GPC is very high: approximately 3.6 Å / cycle at a deposition temperature of 300 °C and approximately 4.6 Å / cycle at a deposition temperature of 100 °C. A higher O2 plasma time or a longer O2 plasma time reduces the growth rate and the relative WER of the thin film, indicating improved thin film quality.

[0144] [Table 7]

[0145] [Table 8]

[0146] Example 14. Thermal ALD Silicon Oxide (Predictive) Using 2-Dimethylamino-2,4,6,8,10-Pentamethylcyclopentasiloxane and Ozone Thermal atomic layer deposition of silicon oxide thin films is performed using a laboratory-scale ALD (Advanced Laser Deposition) tool. Silicon precursor, 2-dimethylamino-2,4,6,8,10-pentamethylcyclopentasiloxane, and ozone are delivered to the chamber by vapor inhalation. All gases (e.g., purge and reaction gases or precursor and oxygen source) are preheated to 100°C before entering the deposition zone. Gas and precursor flow rates are controlled by a high-speed ALD diaphragm valve. The substrate used for deposition is a 12-inch (30.48 cm) long silicon strip. A thermocouple is coupled to the sample holder to confirm the substrate temperature. Deposition is performed using ozone as the oxygen source gas. A normal deposition method and parameters are shown in Table 9. Steps 1-6 are repeated until the desired thickness is achieved.

[0147] [Table 9] Due to the deposition temperature of 300°C, the deposition rate per cycle (GPC) of the deposited thin film is expected to be greater than 2.5 Å / cycle. When the pure silicon oxide thin film is measured by XPS, it is formed containing <0.1 atomic% carbon and <0.1 atomic% nitrogen impurities. Due to the deposition temperature of 100°C, the thin film is expected to be a carbon-doped silicon oxide thin film with a carbon content of >10 atomic% when measured by XPS, and the thin film WER is expected to be smaller than the thermal oxide film WER using a 1:99 (0.5 mass%) diluted hydrofluoric acid (HF) solution. Using thermal annealing or hydrogen plasma treatment at temperatures of 300°C to 650°C, the thin film is expected to have a k value of <3.5.

[0148] While this disclosure is described with reference to certain preferred embodiments, various modifications may be made without departing the scope of the invention, and those skilled in the art will understand that equivalents can be substituted for those elements. In addition, many modifications may be made to adapt the teachings to certain circumstances or materials without departing the essential scope of the invention. Thus, the invention is not limited to certain embodiments, but it is intended to encompass all embodiments within the scope of the appended claims. The present invention includes the following embodiments. (1) A composition comprising at least one cyclic oligosiloxane compound having an organic amino functional group, wherein the compound is of formula A to D:

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Claims

1. A cyclic oligosiloxane compound having an organic amino functional group, used for depositing silicon and oxygen-containing films by atomic layer deposition (ALD) or plasma-accelerated atomic layer deposition (PEALD), comprising: 2,4-bis(dimethylamino)-2,4,6-trimethylcyclotrisiloxane, 2,4-bis(dimethylamino)-2,4,6,6-tetramethylcyclotrisiloxane, 2,4-bis(dimethylamino)-2,4,6,8-tetramethylcyclotetrasiloxane, and 2,4-bis(dimethylamino)-2,4,6,6,8,8-hexamethyl Clotetrasiloxane, 2,6-bis(dimethylamino)-2,4,6,8-tetramethylcyclotetrasiloxane, 2,6-bis(dimethylamino)-2,4,4,6,8,8-hexamethylcyclotetrasiloxane, 2-dimethylamino-2,4,6,8,10-pentamethylcyclopentasiloxane, 2-dimethylamino-2,4,4,6,6,8,8,10,10-nonamethylcyclopentasiloxane, 2,4-bis(methylamino)-2,4,6-trimethylcyclotrisiloxane, 2,4-bis(methylamino)-2,4,6,6-tetramethyl Lucyclotrisiloxane, 2,4-bis(methylamino)-2,4,6,8-tetramethylcyclotetrasiloxane, 2,4-bis(methylamino)-2,4,6,6,8,8-hexamethylcyclotetrasiloxane, 2,6-bis(methylamino)-2,4,6,8-tetramethylcyclotetrasiloxane, 2,6-bis(methylamino)-2,4,4,6,8,8-hexamethylcyclotetrasiloxane, 2-methylamino-2,4,6,8,10-pentamethylcyclopentasiloxane, 2-methylamino-2,4,4,6,6,8,8,10,1 0-Nonamethylcyclopentasiloxane, 2,4-Bis(iso-propylamino)-2,4,6-trimethylcyclotrisiloxane, 2,4-Bis(iso-propylamino)-2,4,6,6-tetramethylcyclotrisiloxane, 2,4-Bis(iso-propylamino)-2,4,6,8-tetramethylcyclotetrasiloxane, 2,4-Bis(iso-propylamino)-2,4,6,6,8,8-hexamethylcyclotetrasiloxane, 2,6-Bis(iso-propylamino)-2,4,6,8-tetramethylcyclotetrasiloxane, 2,6-bis(iso-propylamino)-2,4,4,6,8,8-hexamethylcyclotetrasiloxane, 2-iso-propylamino-2,4,6,8,10-pentamethylcyclopentasiloxane, 2-iso-propylamino-2,4,4,6,6,8,8,10,10-nonamethylcyclopentasiloxane, 2,4-bis(N-ethylmethylamino)-2,4,6-trimethylcyclotrisiloxane, 2,4-bis(N-ethylmethylamino)-2,4,6,6-tetramethylcyclotrisiloxane, 2,4-bis(N-ethylmethylamino)- 2,4,6,8-tetramethylcyclotetrasiloxane, 2,4-bis(N-ethylmethylamino)-2,4,6,6,8,8-hexamethylcyclotetrasiloxane, 2,6-bis(N-ethylmethylamino)-2,4,6,8-tetramethylcyclotetrasiloxane, 2,6-bis(N-ethylmethylamino)-2,4,4,6,8,8-hexamethylcyclotetrasiloxane, 2-(N-ethylmethylamino)-2,4,6,8,10-pentamethylcyclopentasiloxane, 2-(N-ethylmethylamino)-2,4,4,6,6,8,8,10 ,10-nonamethylcyclopentasiloxane, 2,4-bis(diethylamino)-2,4,6-trimethylcyclotrisiloxane, 2,4-bis(diethylamino)-2,4,6,6-tetramethylcyclotrisiloxane, 2,4-bis(diethylamino)-2,4,6,8-tetramethylcyclotetrasiloxane, 2,4-bis(diethylamino)-2,4,6,6,8,8-hexamethylcyclotetrasiloxane, 2,6-bis(diethylamino)-2,4,6,8-tetramethylcyclotetrasiloxane, 2,6-bis(diethylamino)-2,4 ,4,6,8,8-hexamethylcyclotetrasiloxane, 2-diethylamino-2,4,6,8,10-pentamethylcyclopentasiloxane, 2-diethylamino-2,4,4,6,6,8,8,10,10-nonamethylcyclopentasiloxane, 2,4,6-tris(dimethylamino)-2,4,6-trimethylcyclotrisiloxane, 2,4,6,8-tetrakis(dimethylamino)-2,4,6,8-tetramethylcyclotetrasiloxane, 2,4,6-tris(methylamino)-2,4,6-trimethylcyclotrisiloxane, 2,4,6,A cyclic oligosiloxane compound having an organic amino functional group selected from the group consisting of 8-tetrakis(methylamino)-2,4,6,8-tetramethylcyclotetrasiloxane.

2. A composition comprising the compound described in claim 1, a solvent, and at least one selected from the group consisting of argon, nitrogen, helium, neon, hydrogen, and mixtures thereof as a purge gas.

3. The compound according to claim 1, wherein the compound contains less than 1 ppm of one or more impurities selected from the group consisting of halides, metal ions, metals, and combinations thereof.

4. A method for depositing a thin film containing silicon and oxygen onto a substrate, wherein the method is: a) A step of preparing the substrate in the reactor; b) 2,4-bis(dimethylamino)-2,4,6-trimethylcyclotrisiloxane, 2,4-bis(dimethylamino)-2,4,6,6-tetramethylcyclotrisiloxane, 2,4-bis(dimethylamino)-2,4,6,8-tetramethylcyclotetrasiloxane, 2,4-bis(dimethylamino)-2,4,6,6,8,8-hexamethylcyclotetrasiloxane, 2,6-bis(dimethylamino)-2,4,6,8-tetramethylcyclotetrasiloxane, 2,6-bis(dimethylamino)-2,4,4,6,8,8-hexameth Lucyclotetrasiloxane, 2-dimethylamino-2,4,6,8,10-pentamethylcyclopentasiloxane, 2-dimethylamino-2,4,4,6,6,8,8,10,10-nonamethylcyclopentasiloxane, 2,4-bis(methylamino)-2,4,6-trimethylcyclotrisiloxane, 2,4-bis(methylamino)-2,4,6,6-tetramethylcyclotrisiloxane, 2,4-bis(methylamino)-2,4,6,8-tetramethylcyclotetrasiloxane, 2,4-bis(methylamino)-2,4,6,6,8,8- Hexamethylcyclotetrasiloxane, 2,6-bis(methylamino)-2,4,6,8-tetramethylcyclotetrasiloxane, 2,6-bis(methylamino)-2,4,4,6,8,8-hexamethylcyclotetrasiloxane, 2-methylamino-2,4,6,8,10-pentamethylcyclopentasiloxane, 2-methylamino-2,4,4,6,6,8,8,10,10-nonamethylcyclopentasiloxane, 2,4-bis(iso-propylamino)-2,4,6-trimethylcyclotrisiloxane, 2,4-bis(iso-propylamino) 2,4-bis(iso-propylamino)-2,4,6,6-tetramethylcyclotrisiloxane, 2,4-bis(iso-propylamino)-2,4,6,8-tetramethylcyclotetrasiloxane, 2,4-bis(iso-propylamino)-2,4,6,6,8,8-hexamethylcyclotetrasiloxane, 2,6-bis(iso-propylamino)-2,4,6,8-tetramethylcyclotetrasiloxane, 2,6-bis(iso-propylamino)-2,4,4,6,8,8-hexamethylcyclotetrasiloxane, 2-iso-propylamino-2,4,6,810-Pentamethylcyclopentasiloxane, 2-iso-propylamino-2,4,4,6,6,8,8,10,10-nonamethylcyclopentasiloxane, 2,4-bis(N-ethylmethylamino)-2,4,6-trimethylcyclotrisiloxane, 2,4-bis(N-ethylmethylamino)-2,4,6,6-tetramethylcyclotrisiloxane, 2,4-bis(N-ethylmethylamino)-2,4,6,8-tetramethylcyclotetrasiloxane, 2,4-bis(N-ethylmethylamino)-2,4,6,6,8,8- Hexamethylcyclotetrasiloxane, 2,6-bis(N-ethylmethylamino)-2,4,6,8-tetramethylcyclotetrasiloxane, 2,6-bis(N-ethylmethylamino)-2,4,4,6,8,8-hexamethylcyclotetrasiloxane, 2-(N-ethylmethylamino)-2,4,6,8,10-pentamethylcyclopentasiloxane, 2-(N-ethylmethylamino)-2,4,4,6,6,8,8,8,10,10-nonamethylcyclopentasiloxane, 2,4-bis(diethylamino)-2,4,6-trimethyl Diethylcyclotrisiloxane, 2,4-bis(diethylamino)-2,4,6,6-tetramethylcyclotrisiloxane, 2,4-bis(diethylamino)-2,4,6,8-tetramethylcyclotetrasiloxane, 2,4-bis(diethylamino)-2,4,6,6,8,8-hexamethylcyclotetrasiloxane, 2,6-bis(diethylamino)-2,4,6,8-tetramethylcyclotetrasiloxane, 2,6-bis(diethylamino)-2,4,4,6,8,8-hexamethylcyclotetrasiloxane, 2-diethyl Mino-2,4,6,8,10-pentamethylcyclopentasiloxane, 2-diethylamino-2,4,4,6,6,8,8,10,10-nonamethylcyclopentasiloxane, 2,4,6-tris(dimethylamino)-2,4,6-trimethylcyclotrisiloxane, 2,4,6,8-tetrakis(dimethylamino)-2,4,6,8-tetramethylcyclotetrasiloxane, 2,4,6-tris(methylamino)-2,4,6-trimethylcyclotrisiloxane, 2,4,6,8-tetrakis(methylamino)-2,4,6A step of introducing at least one silicon precursor compound selected from the group consisting of 8-tetramethylcyclotetrasiloxane into the reactor; c) The step of purging the reactor with a purge gas; d) A step of introducing at least one of the oxygen-containing raw material and the nitrogen-containing raw material into the reactor; e) A step of purging the reactor with the purge gas, Includes, Steps b through e are repeated until a desired thickness of the thin film is deposited; the method is carried out at one or more temperatures in the range of 25°C to 600°C. method.

5. A pressurized stainless steel container having a valve inside which the compound according to claim 1 is contained.

6. The pressurizable stainless steel container according to claim 5, wherein the headspace of the pressurizable stainless steel container is filled with an inert gas selected from helium, argon, nitrogen, and combinations thereof.

7. The method according to claim 4, wherein the silicon precursor compound further comprises a solvent and at least one selected from the group consisting of argon, nitrogen, helium, neon, hydrogen, and mixtures thereof.

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