Organoamino-functionalized linear and cyclic oligosiloxanes for the deposition of silicon-containing films

Abstract

It overcomes the challenges associated with conventional precursors and processes for depositing silicon and oxygen-containing films. Amino-functionalized linear and cyclic oligosiloxanes having at least two silicon atoms and two oxygen atoms and an organic amino group, and methods for making the oligosiloxanes are disclosed. Methods for depositing silicon- and oxygen-containing films using the organic amino-functionalized linear and cyclic oligosiloxanes are also disclosed.

Description

[Technical field]

[0001] [CROSS-REFERENCE TO RELATED APPLICATIONS] This application claims the benefit of priority under 35 U.S.C. §119(e) to U.S. Provisional Patent Application No. 62 / 456,297, filed February 8, 2017, and U.S. Provisional Patent Application No. 62 / 574,952, filed October 20, 2017, all of which 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 films (e.g., silicon oxide, silicon oxycarbonitride, silicon oxycarbide, carbon-doped silicon oxide, and other silicon- and oxygen-containing films), methods for using the compounds to deposit silicon oxide-containing films, and films resulting from the compounds and methods.

[0003] Described herein are novel organoamino-functionalized linear and cyclic oligosiloxane precursor compounds, as well as compositions and methods including the same for depositing silicon-containing films, such as, but not limited to, silicon oxide, silicon oxynitride, silicon oxycarbonitride, or carbon-doped silicon oxide, by thermal atomic layer deposition (ALD) or plasma enhanced atomic layer deposition (PEALD) processes, or combinations thereof. More specifically, described herein are compositions and methods for forming stoichiometric or non-stoichiometric silicon-containing films or materials at one or more deposition temperatures of about 600° C. or less, such as from about 25 to about 300° C.

[0004] Atomic layer deposition (ALD) and plasma enhanced atomic layer deposition (PEALD) are processes used to deposit, for example, silicon oxide conformal films at low temperatures (below 500°C). In both ALD and PEALD processes, precursor and reactant gases (e.g., oxygen or ozone) are pulsed separately in multiple cycles, forming a monolayer of silicon oxide in each cycle. However, silicon oxide deposited at low temperatures using these processes may contain certain levels of impurities, such as, but not limited to, carbon (C) or hydrogen (H), which may have adverse effects in some semiconductor applications. To address this, one possible solution is to increase the deposition temperature to 500°C or higher. However, at these higher temperatures, traditional precursors used in the semiconductor industry tend to self-react, thermally decompose, and deposit in chemical vapor deposition (CVD) mode rather than ALD mode. CVD mode deposition has poor conformality compared to ALD deposition, especially for high aspect ratio structures required in many semiconductor applications. Also, CVD mode deposition provides less control over film or material thickness than ALD mode deposition.

[0005] Organoaminosilane and chlorosilane precursors are known in the art that have relatively low temperatures (<300° C.), relatively high growth / cycle (GPC>1.5 Å / cycle), and can be used to deposit silicon-containing films by atomic layer deposition (ALD) and plasma enhanced atomic layer deposition (PEALD) processes.

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

[0007] US Pat. No. 7,084,076 describes the use of halogen- or NCO-substituted disiloxane precursors for depositing silicon oxide films, used in a base-catalyzed ALD process.

[0008] US Patent Application Publication No. 2015 / 087139 describes the use of amino-functionalized carbosilanes to deposit silicon-containing films by thermal ALD or PEALD processes.

[0009] US Pat. No. 9,337,018 describes the use of organoaminodisilanes to deposit silicon-containing films by thermal ALD or PEALD processes.

[0010] U.S. Patent Nos. 8,940,648, 9,005,719, and 8,912,353 describe the use of organoaminosilanes to deposit silicon-containing films by thermal ALD or PEALD processes.

[0011] US Patent Application Publication No. 2015 / 275355 describes the use of mono- and bis(organoamino)alkylsilanes to deposit silicon-containing films by thermal ALD or PEALD processes.

[0012] US 2015 / 376211 describes the use of mono(organoamino)-, halide-, and pseudohalide-substituted trisilylamines to deposit silicon-containing films by thermal ALD or PEALD processes.

[0013] International Application No. 15105337 and US Pat. No. 9,245,740 describe the use of alkylated trisilylamines to deposit silicon-containing films by thermal ALD or PEALD processes.

[0014] WO 15105350 describes the use of four-membered ring cyclodisilazanes having at least one Si—H bond to deposit silicon-containing films by thermal ALD or PEALD processes.

[0015] US Pat. No. 7,084,076 describes the use of halogen- or NCO-substituted disiloxane precursors for depositing silicon oxide films, used in a base-catalyzed ALD process.

[0016] The disclosures of the patents and patent applications identified above are incorporated herein by reference. Summary of the Invention [Problem to be solved by the invention]

[0017] There is a need in the art for precursors and methods for depositing silicon oxide-containing films with high growth / cycle (GPC) to maximize production in semiconductor manufacturing plants. Although some precursors can be deposited with GPC of more than 2.0 Å / cycle, these precursors have drawbacks such as low quality films (elemental contaminants, low density, poor electrical properties, high wet etch rate), high temperature processes require catalysts, are expensive, and result in low conformal films, among other drawbacks. [Means for solving the problem]

[0018] The present invention solves the problems associated with conventional precursors and processes by providing silicon- and oxygen-containing precursors, specifically organoamino-functionalized linear and cyclic oligosiloxanes, having at least two silicon atoms and two oxygen atoms and an organoamino group, which result in anchoring the oligosiloxane units to the surface of a substrate as part of a process for depositing silicon- and oxygen-containing films. The multi-silicon precursors disclosed in the present invention have novel structures relative to those described in the Background section above, and therefore may provide advantages in one or more aspects with respect to either the cost or convenience of precursor synthesis, the physical properties of the precursor, including thermal stability, reactivity or volatility, the process of depositing the silicon-containing film, or the properties of the deposited silicon-containing film.

[0019] Described herein are compounds of formulas A, B, C, D and E: [ka] an organoamino-functionalized oligosiloxane compound selected from the group consisting of:1 However, linear C1-C 10 Alkyl groups, branched C3-C 10 Alkyl groups, C3-C 10 Cyclic alkyl groups, C3-C 10 Heterocyclic groups, C3-C 10 Alkenyl groups, C3-C 10 Alkynyl groups and C4-C 10 aryl groups; R 2 But hydrogen, linear C1-C 10 Alkyl groups, branched C3-C 10 Alkyl groups, C3-C 10 Cyclic alkyl groups, C3-C 10 Heterocyclic groups, C3-C 10 Alkenyl groups, C3-C 10 Alkynyl groups and C4-C 10 aryl groups; R 1 and R 2 are either linked together to form a cyclic ring structure or are not linked together to form a cyclic ring structure; R 3~10 are each independently hydrogen, linear C1-C 10 Alkyl groups, branched C3-C 10 Alkyl groups, C3-C 10 Cyclic alkyl groups, C2-C 10 Alkenyl groups, C2-C 10 Alkynyl groups and C4-C 10 aryl group; X is selected from linear C1-C 10 Alkyl groups, branched C3-C 10 Alkyl groups, C3-C 10 Cyclic alkyl groups, C2-C 10 Alkenyl groups, C2-C 10 Alkynyl groups, C4-C 10 Aryl groups, C1-C 10 Acyl groups, amine groups (NR 1 R 2 ), H, Cl, Br, I, F, C2~C 12 Carboxylate group, C1-C 10 R is selected from the group consisting of linear or branched alkoxy groups, trimethylsiloxy groups, dimethylsiloxy groups, methylsiloxy groups, and siloxy groups; 1and X are either linked together to form a cyclic ring or are not linked together to form a cyclic ring; in formula C, R 1~8 are all methyl groups, X cannot be a trimethylsiloxy group, and R 1~10 are all methyl groups, the composition comprising at least one organoamino-functionalized oligosiloxane compound, where X cannot be a methyl or dimethylamino group.

[0020] Described herein are processes for depositing stoichiometric or non-stoichiometric silicon and oxygen-containing materials or films, such as, but not limited to, silicon oxide, carbon-doped silicon oxide, silicon oxynitride films, carbon-doped silicon oxynitride, using an oxygen-containing reactant source, a nitrogen-containing reactant source, or a combination thereof, in a plasma-enhanced ALD (PEALD), plasma-enhanced cyclic chemical vapor deposition (PECCVD), flowable chemical vapor deposition (FCVD), plasma-enhanced flowable chemical vapor deposition (PEFCVD), plasma-enhanced ALD-type process, or an ALD process at relatively low temperatures, e.g., one or more temperatures below 600° C.

[0021] In one aspect, disclosed herein is a method for depositing a film comprising silicon and oxygen on a substrate, the method comprising: (a) providing the substrate in a reactor; and (b) reacting a silicon-oxygen compound represented by Formulas A, B, C, D, and E: [ka] A silicon precursor compound selected from the group consisting of: 1 However, linear C1-C 10 Alkyl groups, branched C3-C 10 Alkyl groups, C3-C 10 Cyclic alkyl groups, C3-C 10 Heterocyclic groups, C3-C 10 Alkenyl groups, C3-C 10 Alkynyl groups and C4-C 10 aryl groups; R 2 But hydrogen, linear C1-C 10 Alkyl groups, branched C3-C 10 Alkyl groups, C3-C10 Cyclic alkyl groups, C3-C 10 Heterocyclic groups, C3-C 10 Alkenyl groups, C3-C 10 Alkynyl groups and C4-C 10 aryl groups; R 1 and R 2 are either linked together to form a cyclic ring structure or are not linked together to form a cyclic ring structure; R 3~10 are each independently hydrogen, linear C1-C 10 Alkyl groups, branched C3-C 10 Alkyl groups, C3-C 10 Cyclic alkyl groups, C2-C 10 Alkenyl groups, C2-C 10 Alkynyl groups and C4-C 10 aryl group; X is selected from linear C1-C 10 Alkyl groups, branched C3-C 10 Alkyl groups, C3-C 10 Cyclic alkyl groups, C2-C 10 Alkenyl groups, C2-C 10 Alkynyl groups, C4-C 10 Aryl groups, C1-C 10 Acyl groups, amine groups (-NR 1 R 2 ), H, Cl, Br, I, F, C2~C 12 Carboxylate group, C1-C 10 R is selected from the group consisting of a linear or branched alkoxy group, a trimethylsiloxy group, a dimethylsiloxy group, a methylsiloxy group, or a siloxy group; 1 and X are either linked to form a cyclic ring or not linked to form a cyclic ring; (c) purging the reactor with a purge gas; (d) introducing at least one of an oxygen-containing source and a nitrogen-containing source into the reactor; and (e) purging the reactor with a purge gas, wherein steps b-e are repeated until a desired film thickness is deposited, and are conducted at one or more temperatures in the range of about 25-600° C.

[0022] Methods for making the above compounds are also disclosed herein.

[0023] The embodiments of the present invention may be used alone or in combination with each other. [Brief description of the drawings]

[0024] [Figure 1] 13 provides GPC of thermal ALD versus number of precursor pulses of 2-dimethylamino-2,4,6,8-tetramethylcyclotetrasiloxane using an ozone process at 300° C. [Diagram 2] 13 provides GPC of PEALD silicon oxide deposition versus precursor pulse time using 2-dimethylamino-2,4,6,8-tetramethylcyclotetrasiloxane. [Diagram 3] Provided is a GPC of PEALD silicon oxide deposition upon O2 plasma exposure using 2-dimethylamino-2,4,6,8-tetramethylcyclotetrasiloxane. [Figure 4] We provide TEM images of PEALD silicon oxide films deposited with 2-dimethylamino-2,4,6,8-tetramethylcyclotetrasiloxane in a laminar flow reactor, showing excellent step coverage and that 2-dimethylamino-2,4,6,8-tetramethylcyclotetrasiloxane has anchoring groups and therefore can be a good precursor for PEALD silicon oxide. [Diagram 5] 1 provides PEALD silicon oxide deposition GPC versus precursor pulse time using TMCTS in a showerhead chamber, showing that TMCTS is not suitable for atomic layer deposition. [Figure 6] We provide TEM images of silicon oxide films deposited by TMCTS in a showerhead chamber, showing that TMCTS is poorly suited for step coverage, and therefore further demonstrating that TMCTS is not suitable as a precursor for atomic layer deposition. [Figure 7]We provide TEM images of PEALD silicon oxide films deposited with 2-dimethylamino-2,4,6,8-tetramethylcyclotetrasiloxane in a showerhead chamber, showing excellent step coverage and that 2-dimethylamino-2,4,6,8-tetramethylcyclotetrasiloxane has anchoring groups and therefore can be a good precursor for PEALD silicon oxide. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0025] The use of the terms "a", "an" and "the" and similar referents within the scope of the present invention (particularly in the claims that follow) should be construed to encompass both the singular and the plural, unless otherwise indicated herein or clearly contradicted by context. The terms "comprising", "having", "including" and "containing" should be construed as open-ended terms (i.e., meaning "including, but not limited to"), unless otherwise indicated. The recitation of ranges of values ​​herein is intended to merely serve as a shorthand method of referring individually to each individual value falling within the range, unless otherwise indicated herein, and each individual value is incorporated herein as if it were individually recited herein. All methods described herein can be performed in any suitable order, unless otherwise indicated herein or clearly contradicted by context. The use of any and all examples or exemplary language (e.g., "such as") provided herein is intended merely to further clarify the invention and does not pose a limitation on the scope of the invention unless otherwise stated in the claims. No language in the specification should be construed as indicating any non-claimed element as essential to the practice of the invention.

[0026] Described herein are compositions and methods relating to forming stoichiometric or non-stoichiometric silicon and oxygen-containing films or materials, such as, but not limited to, silicon oxide, carbon-doped silicon oxide films, silicon oxynitride, or carbon-doped silicon oxynitride films, or combinations thereof, at one or more temperatures below about 600° C., or from about 25 to about 600° C., in some embodiments, from 25 to about 300° C. The films described herein are deposited by a deposition process, such as, but not limited to, atomic layer deposition (ALD) or ALD-type processes, such as, but not limited to, plasma enhanced ALD (PEALD) or plasma enhanced cyclic chemical vapor deposition (PECCVD), flowable chemical vapor deposition (FCVD), or plasma enhanced flowable chemical vapor deposition (PEFCVD). The low temperature (e.g., deposition temperature or temperatures ranging from about ambient to 600° C.) methods described herein provide films or materials that exhibit at least one or more of the following advantages: high conformality in thermal atomic layer deposition, plasma atomic layer deposition (ALD) processes, or plasma ALD-type processes, low chemical impurities, density of about 2.1 g / cc or more, ability to tailor carbon content in the resulting film, and / or film has an etch rate of 5 angstroms per second (Å / s) when measured in 0.5 wt% dilute HF. For carbon-doped silicon oxide films, more than 1% carbon is desired to tailor the etch rate to a value less than 2Å / s in 0.5 wt% dilute HF, in addition to other characteristics such as, but not limited to, density of about 1.8 g / cc or more or about 2.0 g / cc or more.

[0027] The methods disclosed herein can be carried out using equipment known to those skilled in the art, for example, the methods can use reactors that are conventional in the semiconductor manufacturing art.

[0028] Without wishing to be bound by any theory or explanation, it is believed that the effectiveness of the precursor composition disclosed herein can vary depending on the number of silicon atoms and, in particular, the bonds of the silicon atoms.The precursors disclosed herein typically have 3-5 silicon atoms and 5-8 silicon-oxygen bonds.

[0029] The precursors disclosed herein have a different structure than those known in the art and therefore may perform better than conventional silicon-containing precursors, may provide relatively high GPC, produce higher quality films, have favorable wet etch rates, or have low elemental contaminants.

[0030] Disclosed herein is a composition for depositing a film selected from a silicon oxide, a carbon doped silicon oxide, or a silicon carbonate nitride film using a vapor deposition process, the composition comprising a compound represented by Formula A, Formula B, Formula C, Formula D, or Formula E: [ka] wherein R 1 However, linear C1-C 10 Alkyl groups, branched C3-C 10 Alkyl groups, C3-C 10 Cyclic alkyl groups, C3-C 10 Heterocyclic groups, C3-C 10 Alkenyl groups, C3-C 10 Alkynyl groups and C4-C 10 aryl groups; R 2 But hydrogen, linear C1-C 10 Alkyl groups, branched C3-C 10 Alkyl groups, C3-C 10 Cyclic alkyl groups, C3-C 10 Heterocyclic groups, C3-C 10 Alkenyl groups, C3-C 10 Alkynyl groups and C4-C 10 aryl groups; R 1 and R 2 are either linked together to form a cyclic ring structure or are not linked together to form a cyclic ring structure; R 3~10 are each independently hydrogen, linear C1-C 10 Alkyl groups, branched C3-C 10 Alkyl groups, C3-C 10 Cyclic alkyl groups, C2-C 10 Alkenyl groups, C2-C 10Alkynyl groups and C4-C 10 aryl group; X is selected from linear C1-C 10 Alkyl groups, branched C3-C 10 Alkyl groups, C3-C 10 Cyclic alkyl groups, C2-C 10 Alkenyl groups, C2-C 10 Alkynyl groups, C4-C 10 Aryl groups, C1-C 10 Acyl groups, amine groups (-NR 1 R 2 ), H, Cl, Br, I, F, C2~C 12 Carboxylate group, C1-C 10 R is selected from the group consisting of linear or branched alkoxy groups, trimethylsiloxy groups, dimethylsiloxy groups, methylsiloxy groups, and siloxy groups; 1 and X are either linked together to form a cyclic ring or are not linked together to form a cyclic ring; in formula C, R 1~8 are all methyl groups, X cannot be a trimethylsiloxy group, and R 1~10 When all are methyl groups, this includes compounds where X cannot be a methyl or dimethylamino group.

[0031] In a preferred embodiment, subject to the above proviso, R 1~10 At least one of R is a C1-C4 alkyl group. 1~9 Each of these groups is a C1 to C4 alkyl group.

[0032] In the above formula and throughout the description, the term "oligosiloxane" denotes a compound comprising at least two repeating -Si-O-siloxane units, preferably at least three repeating -Si-O-siloxane units, which can be of cyclic or linear structure, preferably of cyclic structure.

[0033] In the formula above and throughout the description, the term "alkyl" refers to a straight or branched chain functional group having 1 to 10 terminal atoms. Exemplary straight chain alkyl groups include, but are not limited to, methyl, ethyl, propyl, butyl, pentyl, and hexyl groups. Exemplary branched alkyl groups include, but are not limited to, isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, tert-pentyl, isohexyl, and neohexyl. In some embodiments, the alkyl groups can have one or more functional groups attached thereto, such as, but not limited to, an alkoxy group, a dialkylamino group, or combinations thereof attached thereto. In other embodiments, the alkyl groups do not have one or more functional groups attached thereto. The alkyl groups may be substituted or alternatively unsubstituted.

[0034] In the formula above and throughout the description, the term "cyclic alkyl" refers to a cyclic functional group having from 3 to 10 carbon atoms. Exemplary cyclic alkyl groups include, but are not limited to, cyclobutyl, cyclopentyl, cyclohexyl, and cyclooctyl groups.

[0035] In the above formula and throughout the description, the term "alkenyl group" denotes a group having one or more carbon-carbon double bonds and having 2 to 10 or 2 to 6 carbon atoms.

[0036] In the formulas described herein and throughout the description, the terms "dialkylamino", "alkylamino", or "organoamino" refer to groups having two alkyl groups attached to the nitrogen atom or one alkyl attached to the nitrogen atom and having 1-10, 2-6, or 2-4 carbon atoms. Examples include, but are not limited to, HNMe, HNBu. t , NMe2, NMeEt, NEt2, and NPr i 2 is an example.

[0037] In the formula above and throughout the description, the term "aryl" refers to an aromatic cyclic functional group having 4 to 10 carbon atoms, 5 to 10 carbon atoms, or 6 to 10 carbon atoms. Exemplary aryl groups include, but are not limited to, phenyl, benzyl, chlorobenzyl, tolyl, o-xylyl, 1,2,3-triazolyl, pyrrolyl, and furanyl.

[0038] Throughout the description, the term "alkyl hydrocarbon" refers to linear or branched C1-C 20 Hydrocarbons, cyclic C6-C 20 Refers to hydrocarbons. Exemplary hydrocarbons include, but are not limited to, heptane, octane, nonane, decane, dodecane, cyclooctane, cyclononane, and cyclodecane.

[0039] Throughout the description, the term "alkoxy" means C1-C 10 -OR 1 R 1 is defined above. Exemplary alkoxy groups include, but are not limited to, methoxy, ethoxy, isopropoxy, n-propoxy, n-butoxy, sec-butoxy, tert-butoxy, and phenoxy.

[0040] Throughout the description, the term "carboxylate" refers to C2-C 12 -OC(=O)R 1 R 1 is as defined above. Exemplary carboxylate groups include, but are not limited to, acetate (-OC(=O)Me), ethyl carboxylate (-OC(=O)Et), isopropyl carboxylate (-OC(=O) i Pr), and benzoate (-OC(=O)Ph).

[0041] Throughout the description, the term "aromatic hydrocarbons" refers to C6-C 20 Refers to aromatic hydrocarbons. Exemplary aromatic hydrocarbons include, but are not limited to, toluene and mesitylene.

[0042] In the above formula and throughout the description, the term "heterocycle" refers to a non-aromatic saturated monocyclic or multicyclic ring system of about 3 to about 10 ring atoms, preferably about 5 to about 10 ring atoms, where one or more of the atoms in the ring system is an element other than carbon, such as nitrogen, oxygen, or sulfur. Preferred heterocycles contain about 5 to about 6 ring atoms. The prefix aza, oxo, or thio before a heterocycle means that at least a nitrogen, oxygen, or sulfur atom, respectively, is present as a ring atom. Heterocycles are optionally substituted.

[0043] Exemplary organoamino-functionalized linear and cyclic oligosiloxanes having formulas A through E are shown in Table 1.

[0044] [Table 1:R 1~10 Exemplary organoamino-functionalized linear and cyclic oligosiloxanes having formulas A-E, wherein: [Table 1] [Table 2] [Table 3]

[0045] Compounds having formula A or B can be synthesized, for example, by catalytic dehydrogenative coupling of cyclotrisiloxanes or cyclotetrasiloxanes with organic amines (e.g., formula (1) for cyclotrisiloxane; cyclotetrasiloxanes can also be used in the case of formula (3)) or by reaction of chlorinated cyclotrisiloxanes with organic amines or metal salts of organic amines (e.g., formula (2); chlorinated cyclotetrasiloxanes can also be used in the case of formula (4)). [ka]

[0046] Preferably, the molar ratio of cyclotrisiloxane or cyclotetrasiloxane to organic amine in the reaction mixture is about 1-1.0, 1-1.5, 1-2, 1-3, 1-4, or 1-10.

[0047] The catalysts used in the process of the present invention in formulas (1) and (3) are those that promote the formation of silicon-nitrogen bonds. Exemplary catalysts that can be used in the process described herein include, but are not limited to, the following: alkaline earth metal catalysts; non-halide-containing main group, transition metal, lanthanide, and actinide catalysts; and halide-containing main group, transition metal, lanthanide, and actinide catalysts.

[0048] Exemplary alkaline earth metal catalysts include, but are not limited to, the following: Mg[N(SiMe3)2]2, To M MgMe[To M = tris(4,4-dimethyl-2-oxazolinyl)phenylborate], To M Mg-H, To M Mg-NR2 (R = H, alkyl, aryl) Ca[N(SiMe3)2]2, [(dipp-nacnac)CaX(THF)]2 (dipp-nacnac = CH[(CMe)(2,6- i Pr2-C6H3N)]2;X=H, alkyl, carbosilyl, organic amino), Ca(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(μ 3 -H)2] + (Me3TACD=Me3

[12] aneN4), Ca(η 2 -Ph2CNPh)(hmpa)3 (hmpa = hexamethylphosphoramide), Sr[N(SiMe3)2]2, and other M 2+ These include alkaline earth metal-amide, -imine, -alkyl, -hydride, and -carbosiyl complexes (M=Ca, Mg, Sr, Ba).

[0049] Exemplary halide-free, main group, transition metal, lanthanide, and actinide catalysts include, but are not limited to, the following: 1,3-di-iso-propyl-4,5-dimethylimidazol-2-ylidene, 2,2'-bipyridyl, phenanthroline, B(CF), BR (R = linear, branched, or cyclic C-C 10 Alkyl groups, C5-C 10 Aryl group or C1-C 10 Alkoxy group), AlR3 (R = linear, branched, or cyclic C1-C 10 Alkyl groups, C5-C 10 Aryl group or C1-C 10 Alkoxy group), (C5H5)2TiR2 (R = alkyl, H, alkoxy, organic amino, carbosilyl), (C5H5)2Ti(OAr)2[Ar = (2,6-( i (C5H5)2Ti(SiHRR')PMe3 (wherein R and R' are each independently selected from H, Me, and Ph), TiMe2(dmpe)2 (dmpe = 1,2-bis(dimethylphosphino)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-propylphosphino)ethane), (R-indenyl)Ni(PR'3)Me (R=1- i Pr, 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-dimesitylthiophenolate)][B[3,5-(CF3)2C6H3]4], [(C5Me5)Ru(R3P) x (NCMe)3-x ] + (Wherein, R is a linear, branched, or cyclic C1-C 10 Alkyl groups and C5-C 10 aryl group; x=0, 1, 2, 3), Rh(CO) 16 , tris(triphenylphosphine)rhodium(I) carbonyl hydride, Rh2H2(CO)2(dppm)2 (dppm = bis(diphenylphosphino)methane, Rh2(μ-SiRH)2(CO)2(dppm)2 (R = Ph, Et, CH 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)imidazol-2-ylidene)], Yb(η 2 -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 on carbon (Pt / C), ruthenium on carbon (Ru / C), ruthenium on alumina, palladium on carbon, nickel on carbon, osmium on carbon, platinum(0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane (Karstedt's catalyst), bis(tri-tert-butylphosphine)platinum(0), Pt(cyclooctadiene)2, [(Me3Si)2N]3U][BPh4], [(Et2N)3U][BPh4], and other halide-free M n+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). The catalysts listed above, as well as pure precious metals such as ruthenium, platinum, palladium, rhodium, osmium, can also be fixed on a support. A support is a solid with a high surface area. Exemplary support materials include, but are not limited to, alumina, MgO, zeolite, carbon, monolith cordierite, diatomaceous earth, silica gel, silica / alumina, ZrO, and TiO2. Preferred supports are carbon (e.g., platinum on carbon, palladium on carbon, rhodium on carbon, ruthenium on carbon), alumina, silica, and MgO. The metal loading of the catalyst ranges from about 0.01 to about 50 wt%. A preferred range is from about 0.5 to about 20 wt%. A more preferred range is from about 0.5 to about 10 wt%. Catalysts that require activation can be activated by a number of known methods. Heating the catalyst under vacuum is a preferred method. The catalyst can be activated prior to addition to the reaction vessel or activated in the reaction vessel prior to adding the reactants. The catalyst can contain a promoter. A promoter is not itself a catalyst, but increases their performance (activity and / or selectivity) when mixed in small amounts with the active catalyst. Promoters are typically metals, such as Mn, Ce, Mo, Li, Re, Ga, Cu, Ru, Pd, Rh, Ir, Fe, Ni, Pt, Cr, Cu, and Au, and / or their oxides. They can be added separately to the reaction vessel or they can be part of the catalyst itself, for example Ru / Mn / C (ruthenium on carbon promoted with manganese) or Pt / CeO2 / Ir / SiO2 (platinum on silica promoted with ceria and iridium). Some promoters can act as catalysts themselves, but their use in combination with the main catalyst can improve the performance of the main catalyst. Catalysts can act as promoters for other catalysts. In this context, catalysts are sometimes referred to as bimetallic (or multimetallic) catalysts.For example, Ru / Rh / C can be referred to as either a ruthenium-rhodium bimetallic catalyst on carbon, or ruthenium on carbon promoted by rhodium. An active catalyst is a material that acts as a catalyst in a particular chemical reaction.

[0050] Exemplary halide-containing, main group, transition metal, lanthanide, and actinide catalysts include, but are not limited to, the following: BX3 (X=F, Cl, Br, I), BF3·OEt2, AlX3 (X=F, Cl, Br, I), (C5H5)2TiX2 (X=F, CI), [Mn(CO)4Br]2, NiCl2, (C5H5)2ZrX2 (X=F, CI), PdCl2, PdI2, CuCl, CuI, CuF2, CuCl2, CuBr2, Cu (PPh3)3Cl, ZnCl2, [(C6H6)RuX2]2 (X = Cl, Br, I), (P3P)3RhCl (Wilkinson's catalyst), [RhCl(cyclooctadiene)]2, di-μ-chloro-tetracarbonyldirhodium(I), bis(triphenylphosphine)rhodium(I) carbonylchloride, NdI2, SmI2, DyI2, (POCOP)IrHCl (POCOP = 2,6-(R2PO)2C6H3; R = i Pr, n Bu, Me), H2PtCl6·nH2O (Spiel's catalyst), PtCl2, Pt(PPh3)2Cl2, and other halide-containing M n+ 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).

[0051] The molar ratio of catalyst to cyclotrisiloxane or cyclotetrasiloxane in the reaction mixture ranges from 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, 0.05 to 0.07 equivalents of catalyst are used per equivalent of cyclotrisiloxane or cyclotetrasiloxane. In another particular embodiment, 0.00008 equivalents of catalyst are used per equivalent of cyclotrisiloxane or cyclotetrasiloxane.

[0052] In some embodiments, the reaction mixture containing cyclotrisiloxane or cyclotetrasiloxane, organic amine, and one or more catalysts further comprises an anhydrous solvent. Exemplary 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 halohydrocarbons (e.g., pentane, hexane, toluene, and dichloromethane). The choice of one or more solvents, if any, may be influenced by compatibility with the reactants contained in the reaction mixture, solubility of the catalyst, and / or separation processes for intermediate products and / or selected final products. In other embodiments, the reaction mixture does not comprise a solvent.

[0053] In the methods described herein, the reaction between the cyclotrisiloxane or cyclotetrasiloxane and the organic amine occurs at one or more temperatures ranging from about 0 to 200° C., preferably from 0 to about 100° C. Exemplary temperatures for the reaction include ranges having any 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 can be determined by the physical properties of the reactants and optional solvent. Exemplary temperature ranges for a particular reactor include, but are not limited to, 0 to 80° C. or 0 to 30° C.

[0054] In some embodiments of the methods described herein, the pressure of the reaction can range from about 1 to about 115 psia, or from about 15 to about 45 psia. In some embodiments where the cyclotrisiloxane or cyclotetrasiloxane is a liquid under ambient conditions, the reaction proceeds at atmospheric pressure. In some embodiments where the cyclotrisiloxane or cyclotetrasiloxane is a gas under ambient conditions, the reaction proceeds above 15 psia.

[0055] In some embodiments, one or more reactants can be introduced into the reaction mixture as a liquid or vapor. In embodiments where one or more of the reactants are added as a vapor, a non-reactive gas such as nitrogen or an inert gas can be used as a carrier gas to transport the vapor into the reaction mixture. In embodiments where one or more of the reactants are added as a liquid, the reactants can be added neat or alternatively diluted with a solvent. The reactants are fed into the reaction mixture until the desired conversion to a crude mixture or liquid containing the organoaminosilane product is achieved. In some embodiments, the reaction can proceed in a continuous manner by replenishing the reactants and removing the reaction product and crude liquid from the reactor.

[0056] The crude mixture containing the compounds of formulae A-E, one or more catalysts, optionally residual organic amines, one or more solvents, or one or more undesired products may require one or more separation processes. Examples of suitable separation processes include, but are not limited to, distillation, evaporation, thin film separation, filtration, vapor phase transfer, extraction, fractional distillation using an inverted column, and combinations thereof.

[0057] Compounds having formula C, D, or E can be synthesized, for example, by ring opening of cyclotrisiloxane or cyclotetrasiloxane with, for example, acetyl chloride, methyl iodide, trimethylchlorosilane, or other chlorosilane reactants to produce halide-substituted linear trisiloxanes or tetrasiloxanes, which are then reacted with an organic amine (e.g., Formulas 5-7). Alternatively, compounds having formula C, D, or E can be synthesized by the addition of R 1 R 2 Compounds having formula C, D, or E can also be synthesized by ring-opening cyclotrisiloxanes or cyclotetrasiloxanes with organolithium reagents such as methyllithium or lithium amide, followed by reaction with organoaminochlorosilanes or chlorosilanes (e.g., formulas 9-10). These ring-opening reactions exemplified by formulas 5-10 may require the presence of a catalyst. The halogenated oligosiloxane compound or intermediate may be prepared by reacting two equivalents of an organoamine HNR 1 R 2 In the reaction (Eqs. 5-7), alternatively, only one equivalent of an organic amine HNR 1 R 2 It should be noted that can be used in the presence of a tertiary amine such as Et3N, thus creating the tertiary amine hydrochloride as a salt by-product. [ka] [ka] The synthetic methods exemplified in formulas 5-10 may also be used to prepare a compound represented by formula (vi): [ka] This can be done using a cyclotetrasiloxane starting material having the formula:

[0058] Schemes 1-10 are exemplary preparation chemical schemes and are not intended to be limiting in any way with respect to the preparation of compounds having formula A, B, C, D, or E.

[0059] The silicon precursor compounds having formula A, B, C, D or E according to the present invention and compositions comprising the silicon precursor compounds having formula A, B, C, D or E according to the present invention are preferably substantially free of halide ions. As used herein, the term "substantially free" means that the halide ions (or halides), such as chlorides (i.e., chlorine-containing species, such as HCl or silicon compounds having at least one Si-Cl bond), fluorides, bromides, and iodides, are less than 5 ppm (by weight) as measured by ICP-MS, preferably less than 3 ppm as measured by ICP-MS, more preferably less than 1 ppm as measured by ICP-MS, and most preferably less than 0 ppm as measured by ICP-MS. Chlorides are known to act as decomposition catalysts for silicon precursor compounds having formula A. Significant levels of chlorides in the final product may degrade the silicon precursor compounds. The gradual degradation of silicon precursor compounds may directly affect the film deposition process, making it difficult for semiconductor manufacturers to meet film specifications. And the shelf life or stability is adversely affected by the higher degradation rate of the silicon precursor compounds, making it difficult to guarantee a shelf life of 1-2 years.Accordingly, the accelerated decomposition of the silicon precursor compounds raises safety and performance concerns regarding the formation of these flammable and / or pyrophoric gaseous by-products.The silicon precursor compounds having the formula A, B, C, D or E preferably contain a metal ion, such as Li + , Na + , K + , Mg 2+ , Ca 2+ , Al 3+ , Fe 2+ , Fe 2+ , Fe 3+ , Ni 2+ , Cr 3+As used herein, the term "substantially free" means that the metal ions, as measured by ICP-MS, are less than 5 ppm (by weight), preferably less than 3 ppm, more preferably less than 1 ppm, and most preferably less than 0.1 ppm, as related to Li, Na, K, Mg, Ca, Al, Fe, Ni, Cr. In some embodiments, the silicon precursor compound having formula A is free of metal ions, such as Li + , Na + , K + , Mg 2+ , Ca 2+ , Al 3+ , Fe 2+ , Fe 2+ , Fe 3+ , Ni 2+ , Cr 3+ As used herein, the term "free" of metal impurities, as it relates to Li, Na, K, Mg, Ca, Al, Fe, Ni, Cr, precious metals, e.g., volatile Ru or Pt complexes from ruthenium or platinum catalysts used in the synthesis, means less than 1 ppm, preferably less than 0.1 ppm (by weight), as measured by ICP-MS or other analytical methods for measuring metals.

[0060] In another embodiment, a method for depositing a film comprising silicon and oxygen on a substrate comprises the steps of: a) providing a substrate in a reactor; b) introducing at least one silicon precursor compound into the reactor, the at least one silicon precursor compound being represented by Formulae A-E: [ka] wherein R 1 However, independently, linear C1 to C 10 Alkyl groups, branched C3-C 10 Alkyl groups, C3-C 10 Cyclic alkyl groups, C3-C 10 Heterocyclic groups, C3-C 10 Alkenyl groups, C3-C 10 Alkynyl groups and C4-C 10aryl groups; R 2 But hydrogen, linear C1-C 10 Alkyl groups, branched C3-C 10 Alkyl groups, C3-C 10 Cyclic alkyl groups, C3-C 10 Heterocyclic groups, C3-C 10 Alkenyl groups, C3-C 10 Alkynyl groups and C4-C 10 aryl groups; R 1 and R 2 are either linked together to form a cyclic ring structure or are not linked together to form a cyclic ring structure; R 3~10 are each independently hydrogen, linear C1-C 10 Alkyl groups, branched C3-C 10 Alkyl groups, C3-C 10 Cyclic alkyl groups, C2-C 10 Alkenyl groups, C2-C 10 Alkynyl groups and C4-C 10 aryl group; X is selected from linear C1-C 10 Alkyl groups, branched C3-C 10 Alkyl groups, C3-C 10 Cyclic alkyl groups, C2-C 10 Alkenyl groups, C2-C 10 Alkynyl groups, C4-C 10 Aryl groups, C1-C 10 Acyl groups, amine groups (-NR 1 R 2 ), H, Cl, Br, I, F, C2~C 12 Carboxylate group, C1-C 10 R is selected from the group consisting of linear or branched alkoxy groups, trimethylsiloxy groups, dimethylsiloxy groups, methylsiloxy groups, and siloxy groups; 1 and X are either linked to form a cyclic ring or not linked to form a cyclic ring; c) purging the reactor with a purge gas; d) introducing an oxygen-containing source into the reactor; and e) purging the reactor with a purge gas, wherein steps b-e are repeated until a desired film thickness is deposited, and are conducted at one or more temperatures in the range of about 25-600° C.

[0061] The methods disclosed herein provide a method for producing a quartz crystal having the following characteristics: density of about 2.1 g / cc or greater; wet etch rate of less than about 2.5 Å / sec as measured in a solution of dilute HF (0.5 wt % dHF) acid in 1:100 HF:water; and about 1e-8 A / cm at 6 MV / cm or less. 2 and a hydrogen impurity of less than about 5e20 at / cc as measured by secondary ion mass spectrometry (SIMS).

[0062] In some 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, for example, by a chemical vapor deposition (CVD) process using a reaction chamber. Suitable substrates include, but are not limited to, semiconductor materials, such as gallium arsenide ("GaAs"), silicon, and silicon-containing compositions, such as crystalline silicon, polysilicon, amorphous silicon, epitaxial silicon, silicon dioxide ("SiO2"), silicon glass, silicon nitride, fused silica, glass, quartz, borosilicate glass, and combinations thereof. Other suitable materials include chromium, molybdenum, and other metals commonly used in semiconductor, integrated circuit, flat panel display, and flexible display applications. The substrate may have additional layers, such as silicon, SiO2, organosilicate glass (OSG), fluorinated silicate glass (FSG), boron carbonitride, silicon carbide, hydrogenated hydrocarbons, silicon nitride, hydrogenated silicon nitride, silicon carbonitride, hydrogenated silicon carbonitride, boron nitride, organic-inorganic composites, photoresists, organic polymers, porous organic and inorganic materials and composites, metal oxides, such as aluminum oxide and germanium oxide. The additional layers may also be germanosilicates, aluminosilicates, copper and aluminum, and diffusion barrier materials, such as, but not limited to, TiN, Ti(C)N, TaN, Ta(C)N, Ta, W, or WN.

[0063] The deposition methods disclosed herein can involve one or more purge gases. Purge gases used to purge unconsumed reactants and / or reaction by-products are inert gases that do not react with the precursors. Exemplary purge gases include, but are not limited to, argon (Ar), nitrogen (N2), helium (He), neon, hydrogen (H2), and mixtures thereof. In some embodiments, a purge gas, such as Ar, is fed into the reactor at a flow rate ranging from about 10 to about 2000 sccm for about 0.1 to 1000 seconds, thereby purging unreacted materials and any by-products that may remain in the reactor.

[0064] A purge gas such as argon purges the unabsorbed excess complex from the process chamber. After sufficient purging, an oxygen source can be introduced into the reaction chamber to react with the absorbed surface, followed by another gas purge to remove reaction by-products from the chamber. The process cycle can be repeated until the desired film thickness is achieved. In some cases, purging can replace the purge gas with an inert gas, or both can be used to remove unreacted silicon precursor.

[0065] Throughout the description, the term "ALD or ALD-type" refers to, but is not limited to, the following processes: a) sequentially introducing reactants, including a silicon precursor and a reactant gas, into a reactor, e.g., a single-wafer ALD reactor, a semi-batch ALD reactor, or a batch furnace ALD reactor; b) exposing the reactants, including a silicon precursor and a reactant gas, to a substrate by moving or rotating the substrate through various sections of a reactor, i.e., a spatial ALD reactor or a roll-to-roll ALD reactor, where the sections are separated by an inert gas curtain.

[0066] The methods of the invention are carried out by an ALD process using an oxygen-containing source or ozone, including a plasma, where the plasma can further include an inert gas, such as one or more of the following: oxygen plasma with or without an inert gas, water vapor plasma with or without an inert gas, nitrogen oxide (e.g., 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] The oxygen-containing plasma source can be generated in situ or alternatively remotely. In one particular embodiment, the oxygen-containing source comprises oxygen and is co-flowed or introduced with other reactants, such as, but not limited to, at least one silicon precursor and optionally an inert gas, during steps b-d of the method.

[0068] In some embodiments, the composition used in the method described and disclosed herein further comprises a solvent.Exemplary solvents include, but are not limited to, ethers, tertiary amines, alkyl hydrocarbons, aromatic hydrocarbons, tertiary amino ethers, and combinations thereof.In some 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 reaction chamber for silicon-containing film through direct liquid injection.

[0069] In embodiments where at least one silicon precursor having formula A-E is used in a composition containing a solvent, the selected solvent or mixture thereof does not react with the silicon precursor. The amount of solvent in the composition in weight percent ranges from 0.5 to 99.5 wt%, or from 10 to 75 wt%. In this or other embodiments, the solvent has a boiling point (bp) similar to that of the silicon precursor of formula A-E, or the difference between the bp of the solvent and the bp of the silicon precursor of formula A-E is 40°C or less, 30°C or less, or 20°C or less, or 10°C or less. Alternatively, the difference between the boiling points ranges between any one or more of the following endpoints: 0, 10, 20, 30, or 40°C. Examples of suitable ranges of bp difference include, but are not limited to, 0 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 (e.g., 1,4-dioxane, dibutyl ether), tertiary amines (e.g., pyridine, 1-methylpiperidine, 1-ethylpiperidine, N,N'-dimethylpiperazine, N,N,N',N'-tetramethylethylenediamine), nitriles (e.g., benzonitrile), alkyl hydrocarbons (e.g., octane, nonane, dodecane, ethylcyclohexane), aromatic hydrocarbons (e.g., toluene, mesitylene), tertiary amino ethers (e.g., bis(2-dimethylaminoethyl) ether), or mixtures thereof.

[0070] In some embodiments, the silicon oxide or carbon-doped silicon oxide films deposited using the methods described herein are formed in the presence of an oxygen-containing source, including ozone, water (HO) (e.g., deionized water, purified water, and / or distilled water), oxygen (O), oxygen plasma, NO, NO, NO, carbon monoxide (CO), carbon dioxide (CO), and combinations thereof. The oxygen-containing source may, for example, be passed through either an in-situ or remote plasma generator to provide an oxygen-containing plasma source that includes oxygen, such as an oxygen plasma, a plasma that includes oxygen and argon, a plasma that includes oxygen and helium, an ozone plasma, a water plasma, a nitrous oxide plasma, or a carbon dioxide plasma. In some embodiments, the oxygen-containing plasma source includes an oxygen source gas that is introduced into the reactor at a flow rate ranging from about 1 to about 2000 standard cubic centimeters per minute (sccm), or from about 1 to about 1000 sccm. The oxygen-containing plasma source may be introduced for a time period ranging from about 0.1 to about 100 seconds. In one particular embodiment, the oxygen-containing plasma source comprises water having a temperature of 10° C. or greater. In embodiments in which the film is deposited by a PEALD or plasma cyclic CVD process, the precursor pulse can have a pulse width of greater than 0.01 seconds (e.g., from about 0.01 to about 0.1 seconds, from about 0.1 to about 0.5 seconds, from about 0.5 to about 10 seconds, from about 0.5 to about 20 seconds, from about 1 to about 100 seconds), depending on the volume of the ALD reactor, and the oxygen-containing plasma source can have a pulse width of less than 0.01 seconds (e.g., from about 0.001 to about 0.01 seconds).

[0071] In one or more of the 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 (NO, NO, NO) plasma with or without an inert gas, carbon oxide (CO, CO) plasma with or without an inert gas, and combinations thereof. In some embodiments, the oxygen-containing plasma source further comprises 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 comprise an inert gas.

[0072] Each step of supplying the precursor, oxygen source, and / or other precursors, source gases, and / or reactants can be performed by varying the time for which they are supplied in order to change the stoichiometry of the resulting dielectric film.

[0073] Energy is applied to at least one of the silicon precursors of formulas A-E, oxygen-containing sources, or combinations thereof to induce a reaction and form a dielectric film or coating on the substrate. Such energy can be provided by, but is not limited to, thermal, plasma, pulsed plasma, helicon plasma, high density plasma, inductively coupled plasma, x-ray, e-beam, photon, remote plasma methods, and combinations thereof. In some embodiments, a secondary RF frequency source can be used to modify the plasma characteristics at the substrate surface. In embodiments where deposition involves plasma, the plasma generation process can include a direct plasma generation process where the plasma is generated directly in the reactor, or alternatively, a remote plasma generation process where the plasma is generated outside the reactor and fed into the reactor.

[0074] At least one silicon precursor can be delivered to the reaction chamber, for example, a plasma cyclic CVD or PEALD reactor or a batch furnace type reactor, in various ways. In one embodiment, a liquid delivery system can be used. In an alternative embodiment, a combined liquid delivery and flash vaporization process unit, for example, a turbo vaporizer manufactured by MSP Corporation of Shoreview, MN, can be used to volumetrically deliver low volatility materials, resulting in reproducible delivery and deposition without thermal decomposition of the precursor. In the liquid delivery formulation, the precursor described herein can be delivered in neat form, or alternatively, can be used in a solvent formulation or composition containing it. Thus, in some embodiments, the precursor formulation can include one or more solvent components of suitable characteristics to be desirable and advantageous in a given end use application to form a film on a substrate.

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

[0076] In one embodiment of the method described herein, a plasma cyclic deposition process, such as PEALD type or PEALD, can be used, in which the deposition is carried out using at least one silicon precursor and an oxygen plasma source. PEALD type processes, defined as plasma cyclic CVD processes, provide highly conformal silicon and oxygen-containing films.

[0077] In one embodiment of the invention, there is provided a method for depositing a silicon and oxygen containing film on at least one surface of a substrate, comprising the steps of: a. providing a substrate in a reactor; b. introducing at least one silicon precursor having formula A-E as defined above into a reactor; c. purging the reactor with a purge gas; d. introducing an oxygen-containing source containing a plasma into the reactor; e. purging the reactor with a purge gas; Described herein is a method comprising: In this method, steps b through e are repeated until a desired film thickness is deposited on the substrate.

[0078] In this or other embodiments, it is understood that the steps of the methods described herein can be performed in various orders, sequentially, simultaneously (e.g., during at least a portion of another step), and any combination thereof. Each step of supplying a precursor and an oxygen source gas can be performed by varying the time interval between their supply to, for example, change the stoichiometry of the resulting dielectric film. Also, the time of purging after a precursor or oxidizer step can be minimized to less than 0.1 seconds to improve throughput.

[0079] In one particular embodiment, the method described herein deposits high quality silicon and oxygen containing films on a substrate. The method comprises the following steps: a. providing a substrate in a reactor; b. introducing at least one silicon precursor having formula A-E described herein into a reactor; c. purging the reactor with a purge gas to remove at least a portion of the unabsorbed precursor; d. introducing an oxygen-containing plasma source into the reactor; and e. purging the reactor with a purge gas to remove at least a portion of the unreacted oxygen source, and steps b through e are repeated until a desired silicon-containing film thickness is deposited.

[0080] In another specific embodiment, the method described herein deposits high quality silicon and oxygen containing films on a substrate at temperatures above 600° C. The method comprises the following steps: a. providing a substrate in a reactor; b. introducing into a reactor at least one organoaminopolysiloxane precursor having formulas A-E described herein; c. purging the reactor with a purge gas to remove at least a portion of the unabsorbed precursor; d. introducing an oxygen-containing plasma source into the reactor; and e. purging the reactor with a purge gas to remove at least a portion of the unreacted oxygen source, and steps b through e are repeated until a desired silicon-containing film thickness is deposited.

[0081] Formulae A to E, in particular formulae C, D and E, in which R 10 Organoamino-functionalized linear and cyclic oligosiloxane precursors where R is not hydrogen are believed to be preferred for this method because they either do not contain Si-H bonds or have a limited number of Si-H groups, which may decompose at temperatures above 600° C., potentially resulting in undesirable chemical vapor deposition. However, under some conditions, such as using short precursor pulses or low reactor pressures, the method can also be used to prepare compounds having the formulae A-E and R at temperatures above 600° C. without significant undesirable chemical vapor deposition. 3~10 can be carried out using organoamino-functionalized linear and cyclic oligosiloxane precursors, both of which are hydrogen.

[0082] Another method disclosed herein uses silicon precursor compounds having chemical structures represented by Formulas A-E defined above, in addition to an oxygen source, to form carbon-doped silicon oxide films.

[0083] Another example process is as follows: a. providing a substrate in a reactor; b. chemically absorbing the precursor onto a heated substrate with or without contacting vapor generated from at least one silicon precursor compound having a structure represented by Formulas A-E as described above with a co-flowing oxygen source; c. purging any unabsorbed precursor; d. introducing an oxygen source onto the heated substrate to react with the absorbed precursor; and e. purging any unreacted oxygen source, and steps b through e are repeated until the desired thickness is deposited.

[0084] In another particular embodiment, the method described herein deposits a high quality silicon oxynitride film on a substrate. The method comprises the steps of: a. providing a substrate in a reactor; b. introducing at least one silicon precursor having formula A-E described herein into a reactor; c. purging the reactor with a purge gas to remove at least a portion of the unabsorbed precursor; d. introducing a nitrogen-containing plasma source into the reactor; and e. purging the reactor with a purge gas to remove at least a portion of the unreacted nitrogen source, and steps b through e are repeated until a desired thickness of a silicon oxynitride-containing film is deposited.

[0085] Another example process is described as follows: a. providing a substrate in a reactor; b. chemically absorbing the precursor onto a heated substrate with or without contacting vapor generated from at least one silicon precursor compound having a structure represented by formulas A-E as defined above with a co-flowing nitrogen source; c. purging any unabsorbed precursor; d. introducing a nitrogen source onto the heated substrate to react with the absorbed precursor; and e. purging any unreacted nitrogen source, and steps b through e are repeated until the desired thickness is deposited.

[0086] A variety of commercial ALD reactors, such as single-wafer, semi-batch, batch furnace, or roll-to-roll reactors, can be used to deposit solid silicon oxide, silicon oxynitride, carbon-doped silicon oxynitride, or carbon-doped silicon oxide.

[0087] Process temperatures for the methods described herein use one or more of the following temperatures as endpoints: 0°C, 25°C, 50°C, 75°C, 100°C, 125°C, 150°C, 175°C, 200°C, 225°C, 250°C, 275°C, 300°C, 325°C, 350°C, 375°C, 400°C, 425°C, 450°C, 500°C, 525°C, 550°C, 600°C, 650°C, 700°C, 750°C, 760°C, and 800°C. Exemplary temperature ranges include, but are not limited to, the following: from about 0 to about 300°C, or from about 25 to about 300°C, or from about 50 to about 290°C, or from about 25 to about 250°C, or from about 25 to about 200°C.

[0088] In another aspect, a method for depositing a silicon and oxygen containing film by flowable chemical vapor deposition (FCVD) comprising: placing a substrate including surface features in a reactor, the substrate being maintained at one or more temperatures ranging from about -20 to about 400°C, and the reactor pressure being maintained at or below 100 torr; introducing at least one compound selected from the group consisting of formulae A to E; providing an oxygen source into the reactor to react with the at least one compound to form a film and cover at least a portion of the surface features; annealing the film at one or more temperatures between about 100 and 1000° C. to coat at least a portion of the surface features; treating the substrate with an oxygen source at one or more temperatures in the range of about 20 to about 1000° C. to form a silicon-containing film on at least a portion of the surface features; A method is provided that includes:

[0089] In another aspect, a method for depositing a silicon and oxygen containing film by flowable chemical vapor deposition (FCVD) comprising: placing a substrate including surface features in a reactor, the substrate being maintained at one or more temperatures ranging from about -20 to about 400°C, and the reactor pressure being maintained at or below 100 torr; introducing at least one compound selected from the group consisting of formulae A to E; providing a nitrogen source into the reactor to react with the at least one compound to form a film and cover at least a portion of the surface features; annealing the film at one or more temperatures between about 100 and 1000° C. to coat at least a portion of the surface features; treating the substrate with an oxygen source at one or more temperatures in the range of about 20 to about 1000° C. to form a silicon-containing film on at least a portion of the surface features; A method is provided that includes:

[0090] In some embodiments, the oxygen source is selected from the group consisting of water vapor, water plasma, ozone, oxygen, oxygen plasma, oxygen / helium plasma, oxygen / argon plasma, nitrogen oxide plasma, carbon dioxide plasma, hydrogen peroxide, organic peroxide, and mixtures thereof. In another embodiment, the nitrogen source is selected from the group consisting of, for example, ammonia, hydrazine, monoalkylhydrazine, dialkylhydrazine, nitrogen, nitrogen / hydrogen, nitrogen / argon plasma, nitrogen / helium plasma, ammonia plasma, nitrogen plasma, nitrogen / hydrogen plasma, organic amines such as tert-butylamine, dimethylamine, diethylamine, isopropylamine, diethylamine plasma, dimethylamine plasma, trimethylamine plasma, trimethylamine plasma, ethylenediamine plasma, and alkoxyamines such as ethanolamine plasma, and mixtures thereof. In yet another embodiment, the nitrogen-containing source comprises ammonia plasma, plasma comprising nitrogen and argon, plasma comprising nitrogen and helium, or plasma comprising hydrogen and nitrogen source gas. In this or other embodiments, the steps of the method are repeated until the surface features are filled with silicon-containing film. In embodiments in which water vapor is used as the oxygen source in the flowable chemical vapor deposition process, the substrate temperature ranges from about -20 to about 40°C, or from about -10 to about 25°C.

[0091] In yet further embodiments of the methods described herein, the film deposited or deposited film from ALD, ALD-type, PEALD, PEALD-type, or FCVD is subjected to a treatment step (post-deposition). The treatment step can be performed during at least a portion of the deposition step, after the deposition step, and combinations thereof. Exemplary treatment steps include, but are not limited to, treatment with high temperature thermal annealing, plasma treatment, ultraviolet (UV) light treatment, laser, electron beam treatment, and combinations thereof, to affect one or more properties of the film.

[0092] In another embodiment, a container or vessel for depositing silicon-containing film comprising one or more silicon precursor compounds is described herein.In one particular embodiment, the vessel comprises at least one pressurizable vessel (preferably made of stainless steel with a design as disclosed in US Pat. Nos. 7,334,595, 6,077,356, 5,069,244 and 5,465,766, the disclosures of which are incorporated herein by reference).The vessel comprises either glass (borosilicate or quartz glass) or 316, 316L, 304 or 304L series stainless steel alloy (UNS designation S31600, S31603, S30400, S30403), and is equipped with appropriate valves and fittings to allow one or more precursors to be transported to the reactor for CVD or ALD process. In this or other embodiments, the silicon precursor is provided in a pressurizable vessel made of stainless steel, the purity of the precursor being 98 wt% or greater or 99.5 wt% or greater, suitable for most semiconductor applications, and the headspace of the vessel or container is filled with an inert gas selected from helium, argon, nitrogen, and combinations thereof.

[0093] In some embodiments, the gas lines connecting the precursor canister to the reaction chamber are heated to one or more temperatures depending on the process requirements, and the container of at least one silicon precursor is maintained at one or more temperatures for bubbling. In another embodiment, a solution containing at least one silicon precursor is injected into a vaporizer maintained at one or more temperatures for direct liquid injection.

[0094] A flow of argon and / or other gases can be used as a carrier gas to help transport vapor of at least one silicon precursor into the reaction chamber during the precursor pulse. In some embodiments, the process pressure of the reaction chamber is between about 50 mTorr and 10 Torr. In other embodiments, the process pressure of the reaction chamber can be 760 Torr or less (e.g., between about 50 mTorr and about 100 Torr).

[0095] In a typical PEALD or PELAD type process, e.g., a PECCVD process, 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 to allow a complex to chemically adsorb onto the surface of the substrate.

[0096] Films deposited with silicon precursors having formulas A-E described herein have improved properties, such as, but not limited to, a wet etch rate less than the wet etch rate of the film before the treatment step or a density greater than the density before the treatment step, compared to films deposited with silicon precursors previously disclosed under the same conditions. In one particular embodiment, the deposited film is treated intermittently during the deposition process. These intermittent or inter-deposition treatments can be performed, for example, after each ALD cycle, after every number of ALD cycles, such as, but not limited to, after one (1) ALD cycle, two (2) ALD cycles, five (5) ALD cycles, or after ten (10) or more ALD cycles.

[0097] Precursors of formulas A-E exhibit growth rates of 2.0 Å / cycle or greater.

[0098] In embodiments in which the film is subjected to a high temperature annealing step, the annealing temperature is at least 100° C. higher than the deposition temperature. In this or other embodiments, the annealing temperature ranges from about 400° C. to about 1000° C. In this or other embodiments, the annealing process can be performed in a vacuum (<760 Torr), in an inert environment, or in an oxygen-containing environment (e.g., H2O, N2O, NO2, or O2).

[0099] In embodiments in which the film is treated with a UV treatment, the film is exposed to broadband UV, or alternatively, a UV source having a wavelength in the range of about 150 nanometers (nm) to about 400 nm. In one particular embodiment, the deposited film is exposed to UV in a chamber separate from the deposition chamber after the desired film thickness is reached.

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

[0101] In embodiments in which the film is treated with a plasma, the plasma source is selected from the group consisting of a hydrogen plasma, a hydrogen and helium-containing plasma, and a hydrogen and argon-containing plasma. The hydrogen plasma lowers the dielectric constant of the film, promoting damage resistance to a subsequent plasma ashing process, and leaving the carbon content in the bulk nearly unchanged.

[0102] Without intending to be bound by any particular theory, it is believed that the silicon precursor compounds having the chemical structures represented by formulas A-E as defined above can be immobilized on the substrate surface by the organic amino group reacting with the hydroxyl to provide multiple Si-O-Si fragments per precursor molecule, thus promoting 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.

[0103] In some embodiments, silicon precursors having formulas A-E as defined above can also be used as dopants for metal-containing films, such as, but not limited to, metal oxide films or metal oxynitride films. In these embodiments, metal-containing films are deposited using ALD or CVD processes, such as those described herein using metal alkoxides, metal amides, or volatile organometallic precursors. Examples of suitable metal alkoxide precursors that can be used in the methods disclosed herein include, but are not limited to, Group 3-6 metal alkoxides, Group 3-6 metal complexes with both alkoxy and alkyl-substituted cyclopentadienyl ligands, Group 3-6 metal complexes with both alkoxy and alkyl-substituted pyrrolyl ligands, Group 3-6 metal complexes with both alkoxy and diketonate ligands, and Group 3-6 metal complexes with both alkoxy and ketoester ligands.

[0104] Examples of suitable metal amide precursors that can be used in the methods disclosed herein include, but are not limited to, tetrakis(dimethylamino)zirconium (TDMAZ), tetrakis(diethylamino)zirconium (TDEAZ), tetrakis(ethylmethylamino)zirconium (TEMAZ), tetrakis(dimethylamino)hafnium (TDMAH), tetrakis(diethylamino)hafnium (TDEAH), and tetrakis(ethylmethylamino)hafnium (TEMAH), tetrakis(dimethylamino)titanium (TDMAT), tetrakis(diethylamino)titanium (TDEAT), tetrakis(ethylmethylamino)titanium (TEMAT), tert-butyliminotri(diethylamino)tantalum (TBTDET), tert-butyliminotri(dimethylamino)tantalum (TBTDMT), and tert-butyliminotri(dimethylamino)tantalum (TBTDMT). ), tert-butylimino tri(ethylmethylamino)tantalum (TBTEMT), ethylimino tri(diethylamino)tantalum (EITDET), ethylimino tri(dimethylamino)tantalum (EITDMT), ethylimino tri(ethylmethylamino)tantalum (EITEMT), tert-amylimino tri(dimethylamino)tantalum (TAIMAT), tert-amylimino tri(diethylamino)tantalum, pentakis(dimethylamino)tantalum, tert-amylimino tri(ethylmethylamino)tantalum, bis(tert-butylimino)bis(dimethylamino)tungsten (BTBMW), bis(tert-butylimino)bis(diethylamino)tungsten, bis(tert-butylimino)bis(ethylmethylamino)tungsten, and combinations thereof. Examples of suitable organometallic precursors that can be used in the methods disclosed herein include, but are not limited to, Group 3 metal cyclopentadienyls or alkylcyclopentadienyls. Exemplary Group 3-6 metals herein include, but are not limited to, Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Er, Yb, Lu, Ti, Hf, Zr, V, Nb, Ta, Cr, Mo, and W.

[0105] In some embodiments, the silicon-containing films described herein have a dielectric constant of 6 or less, 5 or less, 4 or less, and 3 or less. In these or other embodiments, the films can have a dielectric constant of about 5 or less, or about 4 or less, or about 3.5 or less. However, it is contemplated that films having other dielectric constants (e.g., higher or lower) can be formed depending on the desired end use of the film. Examples of silicon-containing films formed using the processes described herein and silicon precursors having formulas A-E include those having the formulas Si x O y C z N v H w and, for example, as determined by XPS or other means, Si ranges from about 10 to about 40 atomic wt%, O ranges from about 0 to about 65 atomic wt%, C ranges from about 0 to about 75 atomic wt% or about 0 to about 50 atomic wt%, N ranges from about 0 to about 75 atomic wt% or about 0 to about 50 atomic wt%, and H ranges from about 0 to about 50 atomic wt%, with x+y+z+v+w=100 atomic wt%. Another example of a silicon-containing film formed using the processes and silicon precursors of formulas A-E described herein is silicon carbonate nitride, with a carbon content of 1 to 80 atomic % as measured by XPS. Yet another example of a silicon-containing film formed using the processes and silicon precursors of formulas A-E described herein is amorphous silicon, with the sum of both the nitrogen content and the carbon content being less than 10 atomic %, preferably less than 5 atomic %, and most preferably less than 1 atomic %, as measured by XPS.

[0106] As previously mentioned, the method described herein can be used to deposit a silicon-containing film on at least a portion of a substrate. Examples of suitable substrates include, but are not limited to, silicon, SiO2, Si3N4, OSG, FSG, silicon carbide, hydrogenated silicon oxycarbide, hydrogenated silicon oxynitride, silicon carbonate nitride, hydrogenated silicon carbonate nitride, anti-reflective coating, photoresist, germanium, germanium-containing, boron-containing, Ga / As, flexible substrates, organic polymers, porous organic and inorganic materials, metals such as copper and aluminum, and diffusion barrier layers such as, but not limited to, TiN, Ti(C)N, TaN, Ta(C)N, Ta, W, or WN. The film is compatible with various subsequent processing steps, such as chemical mechanical planarization (CMP) and anisotropic etching processes.

[0107] The deposited films have applications including, but not limited to, computer chips, optical devices, magnetic information storage, coatings on supporting materials or substrates, microelectromechanical systems (MEMS), nanoelectromechanical systems, thin film transistors (TFTs), light emitting diodes (LEDs), organic light emitting diodes (OLEDs), IGZO, and liquid crystal displays (LCDs).Potential uses of the resulting solid silicon oxide or carbon doped silicon oxide include, but are not limited to, shallow trench insulators, interlayer dielectrics, passivation layers, etch stop layers, part of a dual spacer, and sacrificial layers for patterning.

[0108] The methods described herein provide high quality silicon oxide, silicon oxynitride, carbon doped silicon oxynitride, and carbon doped silicon oxide films. The term "high quality" refers to films that have the following characteristics: density of about 2.1 g / cc or greater, about 2.2 g / cc or greater, about 2.25 g / cc or greater; wet etch rate of 2.5 Å / sec or less, 2.0 Å / sec or less, 1.5 Å / sec or less, 1.0 Å / sec or less, 0.5 Å / sec or less, 0.1 Å / sec or less, 0.05 Å / sec or less, 0.01 Å / sec or less, when measured in a solution of dilute HF (0.5 wt % dHF) acid in 1:100 HF:water; 2It means a film that exhibits one or more of the following: less than about 5e20 at / cc hydrogen impurity as measured by SIMS; and combinations thereof. With respect to etch rate, the thermally grown silicon oxide film has an etch rate of 0.5 Å / sec in 0.5 wt % HF.

[0109] In some embodiments, one or more silicon precursors having formulas A-E described herein can be used to form silicon and oxygen-containing films, which are solid and non-porous or substantially free of pores.

[0110] The following examples are provided to illustrate certain aspects of the present invention and do not limit the scope of the appended claims. EXAMPLES

[0111] Thermal atomic layer deposition of silicon oxide films was performed in a laboratory-scale ALD processing tool. The silicon precursor was delivered to the chamber by vapor draw. All gases (e.g., purge and reactant gases or precursors and oxygen precursor) were preheated to 100° C. before entering the deposition region. The flow rates of gases and precursors were controlled using ALD diaphragm valves with fast actuation. The substrates used in the deposition were 12-inch long silicon strips. Thermocouples were installed on the sample holder to check the substrate temperature. The deposition was performed using ozone as the oxygen source gas. The standard deposition process and parameters are shown in Table 2.

[0112] [Table 4]

[0113] Plasma-enhanced ALD (PEALD) was performed in a commercial lateral flow reactor (300 mm PEALD tool manufactured by ASM) equipped with 27.1 MHz direct plasma capability with a fixed spacing of 3.5 mm between the electrodes or a showerhead reactor (300 mm PEALD tool manufactured by ASM) equipped with 13.56 MHz direct plasma capability. The laminar flow chamber design utilizes an outer reactor and an inner reactor with independent pressure settings. The inner reactor is the deposition chamber where all reactant gases (e.g., precursors, argon) are mixed in a manifold and transported to the process reactor. Argon gas was used to maintain the reactor pressure in the outer chamber. The showerhead chamber has only one chamber, which is typically operated at 2 Torr. The precursors were liquids kept at room temperature in a stainless bubbler, and the precursors were transported to the chamber using Ar carrier gas (typically set at 200 sccm flow) or a vapor draw. All depositions reported in this work were performed on native oxide-containing Si substrates with a pressure of 8–12 Ω·cm. The thickness and reflectance of the films were measured using a FilmTeK2000SE ellipsometer by fitting the reflectance data from the films to a pre-established physical model (e.g., Lorentzian oscillator model). The growth rate / cycle was calculated by dividing the measured thickness of the resulting silicon oxide film by the number of all ALD / PEALD cycles. Wet etch rate (WER) measurements were performed using a 1:99 diluted hydrofluoric (HF) acid solution. A thermal oxide wafer was used as a standard for each set of experiments to check the activity of the etch solution. Before starting to collect the WER of the bulk film, all samples were etched for 15 seconds to remove any surface layer. A typical thermal oxide wafer wet etch rate for a 1:99 dHF aqueous solution was 0.5 Å / sec by this procedure. All density measurements were measured by x-ray reflectance (XRR) technique. Compositional analysis was performed using secondary ion mass spectrometry (D-SIMS) or X-ray photoelectron spectroscopy (XPS).

[0114] Example 1a. Synthesis of 2-dimethylamino-2,4,6,8-tetramethylcyclotetrasiloxane A solution containing 2.4 mmol of 2-chloro-2,4,6,8-tetramethylcyclotetrasiloxane in Et2O (5 mL), prepared from the reaction of phosphorus pentachloride with excess 2,4,6,8-tetramethylcyclotetrasiloxane, was added dropwise to one equivalent of dimethylamine and triethylamine in hexane. The resulting white slurry was stirred for 1 h. The reaction mixture was filtered to remove solids and the low boiling solvents were removed under reduced pressure. The crude liquid product was analyzed by GC-MS and determined to be 2-dimethylamino-2,4,6,8-tetramethylcyclotetrasiloxane. GC-MS showed the following peaks: 283 (M+), 268 (M-15), 239, 225, 209, 193, 179, 165, 149, 133, 119, 105, 89, 75, 59, 44.

[0115] Example 1b. Synthesis of 2-dimethylamino-2,4,6,8-tetramethylcyclotetrasiloxane At room temperature, THF (200 mL), Ru(CO) 12 To a stirred solution of dimethylamine (1.12 g, 0.00172 mol) and 2,4,6,8-tetramethylcyclotetrasiloxane (192 g, 0.792 mol) was added a solution of dimethylamine in THF (176 mL, 2.0 M solution) in four portions spaced 1 hour apart. The reaction solution was allowed to stir overnight at room temperature. The solvent was removed under reduced pressure and the crude product was purified by fractional distillation to give 56 g of 2-dimethylamino-2,4,6,8-tetramethylcyclotetrasiloxane with a purity of 98% by GC analysis.

[0116] Example 1c. Thermal stability of 2-dimethylamino-2,4,6,8-tetramethylcyclotetrasiloxane 2-Dimethylamino-2,4,6,8-tetramethylcyclotetrasiloxane was heated at 80° C. for 7 days. Analysis of 2-dimethylamino-2,4,6,8-tetramethylcyclotetrasiloxane dropped from 96.41% to an average value of 96.02%, indicating that 2-dimethylamino-2,4,6,8-tetramethylcyclotetrasiloxane has excellent thermal stability and is suitable as a precursor for vapor deposition processes.

[0117] Example 2. Synthesis of 2-diethylamino-2,4,6,8-tetramethylcyclotetrasiloxane 2,4,6,8-tetramethylcyclotetrasiloxane (308 g, 1.28 mol), diethylamine (34.3 g, 0.469 mol), and Ru(CO) 12 The catalyst solids (1.36 g, 0.00213 mol) were combined in a vented 500 mL rb flask and stirred at room temperature under the protection of a nitrogen atmosphere for 3 days. The red-orange liquid phase was decanted from the insoluble catalyst solids. The reaction was repeated to combine both batches. The excess 2,4,6,8-tetramethylcyclotetrasiloxane was removed by vacuum distillation (10 Torr / 36-38°C) and the remaining red-orange crude product was vacuum transferred from the residual catalyst by transferring from flask to flask. The collected colorless liquid was purified by vacuum distillation (1 Torr / 65°C) to give 128 g of 2-diethylamino-2,4,6,8-tetramethylcyclotetrasiloxane with a purity of 97% by GC analysis. GC-MS showed the following peaks: m / z=311 (M+), 297, 281, 266, 253, 239, 225, 209, 193, 179, 165, 148, 133, 119, 103, 86, 73.

[0118] Example 3. Synthesis of 2-ethylmethylamino-2,4,6,8-tetramethylcyclotetrasiloxane (hypothetical example) 2,4,6,8-Tetramethylcyclotetrasiloxane (3 equivalents), ethylmethylamine (1 equivalent), and Ru(CO) 12 Combine with the catalyst solids (0.01 equivalents) and stir with aeration at room temperature under the protection of a nitrogen atmosphere for 1-3 days. Decant the red-orange liquid phase from any insoluble catalyst solids. Remove excess 2,4,6,8-tetramethylcyclotetrasiloxane by vacuum distillation and vacuum transfer the remaining red-orange crude product from the residual catalyst by transferring from flask to flask. Purify the collected colorless liquid by vacuum distillation to obtain the desired product, 2-ethylmethylamino-2,4,6,8-tetramethylcyclotetrasiloxane.

[0119] Example 4. Synthesis of 2-isopropylamino-2,4,6,8-tetramethylcyclotetrasiloxane (hypothetical example) 2,4,6,8-Tetramethylcyclotetrasiloxane (3 equivalents), isopropylamine (0.3 equivalents), and Ru(CO) 12 The catalyst solids (0.01 equivalents) are combined and stirred under nitrogen atmosphere at room temperature for 1 hour with aeration. Another 0.3 equivalents of isopropylamine are added and the reaction mixture is stirred for another hour. Another 0.3 equivalents of isopropylamine are added and the reaction mixture is stirred overnight. The red-orange liquid phase is decanted from any insoluble catalyst solids. The excess 2,4,6,8-tetramethylcyclotetrasiloxane is removed by vacuum distillation and the remaining red-orange crude product is vacuum transferred from the residual catalyst by transferring from flask to flask. The collected colorless liquid is then purified by vacuum distillation to obtain the desired product 2-isopropylamino-2,4,6,8-tetramethylcyclotetrasiloxane.

[0120] Example 5. Synthesis of 1-dimethylamino-1,1,3,3,5,5,7,7-octamethyltetrasiloxane 1,1,3,3,5,5,7,7-octamethyltetrasiloxane (1.00 g of 80% pure material in octamethylcyclotetrasiloxane, 0.00283 mol), a 2.0 M solution of dimethylamine in THF (1.76 mL, 0.00352 mol), and Ru(CO) 12 (0.04g, 6.0×10 -5 The two aliquots (mol) were combined in a vented 20 mL scintillation vial and stirred at room temperature under the protection of a nitrogen atmosphere for 1 day. The resulting dark red reaction solution was analyzed by GC-MS and determined to contain 1-dimethylamino-1,1,3,3,5,5,7,7-octamethyltetrasiloxane as the major product. GC-MS showed the following peaks: m / z=325 (M+), 310 (M-15), 294, 281, 265, 251, 236, 207, 193, 177, 163, 148, 133, 119, 102, 88, 73.

[0121] Comparative Example 6a. Thermal atomic layer deposition of silicon oxide films using 2,4,6,8-tetramethylcyclotetrasiloxane (TMCTS) Atomic layer deposition of silicon oxide films was performed using the following precursor: TMCTS. The deposition was performed in a laboratory-scale ALD processing tool. The silicon precursor was delivered to the chamber by vapor draw. The deposition process and parameters are given in FIG. 2. Steps 1-6 were repeated for 200-250 cycles. Little actual film deposition was obtained in those depositions. The deposition process parameters and results are shown in Table 3.

[0122] [Table 5]

[0123] Example 6b. Thermal atomic deposition of silicon oxide films using 2-dimethylamino-2,4,6,8-tetramethylcyclotetrasiloxane Atomic layer deposition of silicon oxide films was performed using the following precursor: 2-dimethylamino-2,4,6,8-tetramethylcyclotetrasiloxane. The deposition was performed in a laboratory-scale ALD processing tool. The silicon precursor was transported to the chamber by vapor draw. The deposition process and parameters are given in Table 2. Steps 1-6 were repeated until the desired thickness was reached. Figure 1 shows the saturation curve of the GPC of 2-dimethylamino-2,4,6,8-tetramethylcyclotetrasiloxane versus the number of precursor pulses. It can be seen that the GPC increases with the precursor pulses and then saturates, indicating the ALD behavior of the precursor. The deposition process temperature, GPC and film properties are given in Table 4.

[0124] [Table 6]

[0125] Comparative Example 7a. PEALD Silicon Oxide Using TMCTS (2,4,6,8-Tetramethylcyclotetrasiloxane) in a Laminar Flow Reactor with 27.1 MHz Plasma Deposition was performed using TMCTS as silicon precursor and O2 plasma under the conditions given in Table 5. TMCTS was delivered to the chamber by vapor draw method and no carrier gas was used. Steps b-e were repeated multiple times to obtain the desired silicon oxide thickness for measurement. Film deposition parameters and deposition GPC and wafer non-uniformity are given in Table 6. Deposition wafers showed poor non-uniformity and GPC showed no saturation with increasing precursor pulses, indicating CVD deposition for TMCTS and therefore not suitable as an ALD precursor.

[0126] [Table 7]

[0127] [Table 8]

[0128] The non-uniformity data in Table 6 indicated that TMCTS is not suitable as a precursor for ALD processes via CVD.

[0129] Example 7b. PEALD Silicon Oxide Using 2-Dimethylamino-2,4,6,8-tetramethylcyclotetrasiloxane in a Laminar Flow Reactor with 27.1 MHz Plasma Deposition was performed using 2-dimethylamino-2,4,6,8-tetramethylcyclotetrasiloxane as the silicon precursor and O2 plasma under conditions as described above in Table 5. The precursor was delivered to the chamber using a carrier gas Ar flow of 200 sccm. Steps b-e were repeated multiple times to obtain the desired thickness of silicon oxide for measurement.

[0130] Figure 2 shows the GPC versus time of precursor pulse, and Figure 3 shows the GPC versus O2 plasma time for the precursor 2-dimethylamino-2,4,6,8-tetramethylcyclotetrasiloxane. From Figure 2, it can be seen that the GPC is nearly saturated at 4 seconds of precursor pulse. From Figure 3, it can be seen that the GPC decreases slightly using oxygen plasma times of 10 and 20 seconds versus 5 seconds of oxygen plasma time. The slightly decreased GPC indicates that the film densified during the longer oxygen plasma time, which is confirmed by the higher film density and lower WER of the film deposited with the longer oxygen plasma time. The results were consistent with ALD deposition behavior. The film deposition parameters and deposition GPC are shown in Table 7.

[0131] The film properties under different deposition conditions are shown in Table 8.

[0132] [Table 9]

[0133] [Table 10]

[0134] The conformality of the PEALD silicon oxide film deposited by 2-dimethylamino-2,4,6,8-tetramethylcyclotetrasiloxane was tested using TEM. The trench size was about 50 nm wide and about 600 nm deep. Figure 4 shows the TEM images for the top of the trench, the middle side of the trench, and the bottom of the trench. It can be seen that the film is highly conformal in the trench (i.e., excellent step coverage close to 100% for the middle or bottom of the trench), confirming the ALD behavior of the precursor. Unlike TMCTS, replacing one Si-H group in TMCTS with an organic amino group such as dimethylamino can turn TMCTS into an excellent ALD precursor with good step coverage as well as growth rate of more than 2.5 Å / cycle.

[0135] Example 7c. PEALD Silicon Oxide Using 2-Diethylamino-2,4,6,8-Tetramethylcyclotetrasiloxane in a Laminar Flow Reactor with 27.1 MHz Plasma Deposition was performed using 2-diethylamino-2,4,6,8-tetramethylcyclotetrasiloxane as the silicon precursor and O2 plasma under conditions as described above in Table 5. The precursor was delivered to the chamber using a 200 sccm flow of Ar as a carrier gas. Steps b through e were repeated multiple times to obtain the desired thickness of silicon oxide for measurement.

[0136] The film deposition parameters and deposition GPC are shown in Table 9. Conditions 1-6 show the deposition GPC versus time of precursor pulse at 100°C, from which it can be seen that the GPC becomes saturated with increasing precursor pulse. Conditions 11-16 show the deposition GPC versus time of precursor pulse at 300°C, from which it can be seen that the GPC also becomes saturated with increasing precursor pulse. This result was consistent with the behavior of ALD deposition. Conditions 8-10 show the deposition GPC versus oxygen plasma time at 100°C, from which it can be seen that the GPC was slightly decreased when using oxygen plasma times of 10 and 20 seconds versus oxygen plasma times of 5 seconds. The slightly decreased GPC indicated that the film densified during longer oxygen plasma times. The same phenomenon was also present for deposition at 300°C (see deposition conditions 18-19).

[0137] [Table 11]

[0138] Comparative Example 8a. PEALD Silicon Oxide Using TMCTS (2,4,6,8-Tetramethylcyclotetrasiloxane) in a Showerhead Reactor with a 13.56 MHz Plasma Deposition was performed using TMCTS as silicon precursor and O2 plasma in a showerhead reactor with 13.56 MHz plasma under the conditions given in Table 5. TMCTS was delivered to the chamber by vapor draw method and no carrier gas was used. Steps b to e were repeated multiple times to obtain the desired thickness of silicon oxide for measurement. Figure 5 shows GPC versus precursor pulse time. It can be seen that the GPC did not show saturation with increasing precursor pulse. The deposited film showed wafer non-uniformity of 4 to 11%. Figure 6 shows the conformality of silicon oxide film of TMCTS deposited with 16 second precursor pulse. It can be seen that the film is not conformal in the trench, i.e., the thickness of silicon oxide on the bottom of the trench is much larger than the top or middle of the trench, indicating that CVD has progressed especially on the bottom of the trench.

[0139] Example 8b.13 PEALD Silicon Oxide Using 2-Dimethylamino-2,4,6,8-tetramethylcyclotetrasiloxane in a Showerhead Reactor with a 56 MHz Plasma Deposition was performed using 2-dimethylamino-2,4,6,8-tetramethylcyclotetrasiloxane as silicon precursor and O2 plasma under the conditions given in Table 5, except that the deposition was performed at 300 °C in a showerhead chamber with 13.56 MHz plasma (100 W). The precursor was transported to the chamber using a carrier gas flow. Steps b to e were repeated to obtain the desired thickness of silicon oxide for measurement. Film deposition parameters and deposition GPC and wafer non-uniformity are shown in Table 10. Figure 7 shows the conformality of silicon oxide films deposited in a showerhead chamber. The films were highly conformal in the trench, indicating ALD deposition. Unlike TMCTS, replacing one Si-H group in TMCTS with an organic amino group such as dimethylamino could turn TMCTS into an excellent ALD precursor with good step coverage and growth rate of more than 2.5 Å / cycle.

[0140] [Table 12]

[0141] Example 8c. PEALD Silicon Oxide Using 1-Dimethylamino-1,1,3,3,5,5,7,7-Octamethyltetrasiloxane in a Showerhead Reactor with 13.56 MHz Plasma (Hypothetical Example) Deposition is performed using 1-dimethylamino-1,1,3,3,5,5,7,7-octamethyltetrasiloxane as silicon precursor and O2 plasma under conditions similar to those given in Table 5 in a showerhead chamber with a 13.56 MHz plasma at temperatures ranging from 100 to 300 °C. The precursor is transported to the chamber using a carrier gas flow. Steps b to e are repeated multiple times to obtain the desired thickness of silicon oxide for metrology. Unlike 1,1,3,3,5,5,7,7-octamethyltetrasiloxane, the replacement of one Si-H group with an organic amino group such as dimethylamino can turn an otherwise unreactive linear oligosiloxane into an excellent ALD precursor with good step coverage as well as growth rates of >2.5 Å / cycle.

[0142] Example 9: PEALD silicon oxide using 2-dimethylamino-2,4,6,8-tetramethylcyclotetrasiloxane in a laminar flow reactor with 27.1 MHz at 50°C Deposition was performed using 2-dimethylamino-2,4,6,8-tetramethylcyclotetrasiloxane as the silicon precursor and O2 plasma under conditions as described above in Table 5. The substrate temperature was 50°C. The precursor was transported into the chamber using a carrier gas Ar flow of 200 sccm. Steps b-e were repeated multiple times to obtain the desired thickness of silicon oxide for measurement. A 4 second precursor pulse, reactor pressure at 3 Torr, plasma power of 200 W, and plasma time of 5 seconds were used to obtain a GPC of 4.05 Å / cycle. The WER in 0.5 wt% HF was approximately 10 times higher than the etch rate of thermally grown silicon oxide.

[0143] While the present invention has been described with reference to certain preferred embodiments, those skilled in the art will recognize that various changes can be made in those elements and equivalents can be substituted without departing from the scope of the invention. Many modifications can also be made to adapt a particular situation or material to the teachings of the invention without departing from the essential scope thereof. Therefore, it is intended that the present invention not be limited to the particular embodiments, but rather to include all embodiments that come within the scope of the appended claims. The present disclosure also includes the following: [1] Formulas A, B, C and D: [ka] wherein: R 1 However, linear C1-C 10 Alkyl groups, branched C3-C 10 Alkyl groups, C3-C 10 Cyclic alkyl groups, C3-C 10 Heterocyclic groups, C3-C 10 Alkenyl groups, C3-C 10 Alkynyl groups and C4-C 10 aryl groups; R 2 But hydrogen, linear C1-C 10 Alkyl groups, branched C3-C 10 Alkyl groups, C3-C 10 Cyclic alkyl groups, C3-C 10 Heterocyclic groups, C3-C 10 Alkenyl groups, C3-C 10 Alkynyl groups and C4-C 10 aryl groups; R 1 and R 2 are either linked together to form a cyclic ring structure or are not linked together to form a cyclic ring structure; R 3~10 are each independently hydrogen, linear C1-C 10 Alkyl groups, branched C3-C 10 Alkyl groups, C3-C 10Cyclic alkyl groups, C2-C 10 Alkenyl groups, C2-C 10 Alkynyl groups and C4-C 10 aryl groups; X is a linear C1-C 10 Alkyl groups, branched C3-C 10 Alkyl groups, C3-C 10 Cyclic alkyl groups, C2-C 10 Alkenyl groups, C2-C 10 Alkynyl groups, C4-C 10 Aryl groups, C1-C 10 Acyl groups, amine groups (-NR 1 R 2 ), H, Cl, Br, I, F, C2~C 12 Carboxylate group, C1-C 10 selected from the group consisting of linear or branched alkoxy groups, trimethylsiloxy groups, dimethylsiloxy groups, methylsiloxy groups, and siloxy groups; R 1 and X are either linked together to form a cyclic ring or are not linked together to form a cyclic ring; in formula C, R 1~8 are all methyl groups, X cannot be a trimethylsiloxy group, and R 1~10 are all methyl groups, X cannot be a methyl or dimethylamino group. A composition comprising at least one organoamino-functionalized oligosiloxane compound. [2] The composition according to embodiment 1, comprising at least one compound selected from the group consisting of Formula A and Formula B. [3] The composition according to embodiment 1, comprising at least one compound selected from the group consisting of Formula C and Formula D. [4] The composition of claim 1, further comprising at least one selected from the group consisting of a solvent and a purge gas. [5] R 1~9 Each of is independently selected from hydrogen and a C1-C4 alkyl group. [6] The composition of embodiment 1, wherein the composition is substantially free of one or more impurities selected from the group consisting of halides, metal ions, metals, and combinations thereof. [7] The organic amino functionalized oligosiloxane compound is 2-dimethylamino-2,4,4,6,6-pentamethylcyclotrisiloxane, 2-diethylamino-2,4,4,6,6-pentamethylcyclotrisiloxane, 2-ethylmethylamino-2,4,4,6,6-pentamethylcyclotrisiloxane, 2-isopropylamino-2,4,4,6,6-pentamethylcyclotrisiloxane, 2-dimethylamino-2,4,4,6,6,8,8-heptamethylcyclotetrasiloxane, 2-diethylamino-2,4,4,6,6,8,8-heptamethylcyclotetrasiloxane, 2-ethylmethylamino-2,4,4,6,6,8,8-heptamethylcyclotetrasiloxane, 2-isopropylamino-2,4,4,6,6,8, 3. The composition of claim 2, wherein the is selected from the group consisting of 8-heptamethylcyclotetrasiloxane, 2-dimethylamino-2,4,6-trimethylcyclotrisiloxane, 2-diethylamino-2,4,6-trimethylcyclotrisiloxane, 2-ethylmethylamino-2,4,6-trimethylcyclotrisiloxane, 2-isopropylamino-2,4,6-trimethylcyclotrisiloxane, 2-dimethylamino-2,4,6,8-tetramethylcyclotetrasiloxane, 2-diethylamino-2,4,6,8-tetramethylcyclotetrasiloxane, 2-ethylmethylamino-2,4,6,8-tetramethylcyclotetrasiloxane, and 2-isopropylamino-2,4,6,8-tetramethylcyclotetrasiloxane. [8] The organic amino functionalized oligosiloxane compound is 1-dimethylamino-1,1,3,3,5,5-hexamethyl-5-methoxytrisiloxane, 1-dimethylamino-1,1,3,3,5,5,7,7-octamethyl-7-methoxytrisiloxane, 1-dimethylamino-1,1,3,3,5,5-hexamethyl-5-acetoxytrisiloxane, 1-dimethylamino-1,1,3,3,5,5,7,7-octamethyl-7-acetoxytrisiloxane, 1-dimethylamino-1,1,3,3,5,5,7,7,9,9,9-undecamethylpentasiloxane, 1-dimethylamino-1,1,3,3,5,5,7,7-octamethyltetrasiloxane, 1-dimethylamino 4. The composition of claim 3, wherein the at least one alkyl group is selected from the group consisting of 1,1,3,3,5,5,7,7,9,9-decamethylpentasiloxane, 1-dimethylamino-1,3,3,5,5,7,7,7-octamethyltetrasiloxane, 1-dimethylamino-1,3,3,5,5,7,7,9,9,9-decamethylpentasiloxane, 1-dimethylamino-3,3,5,5,7,7,7-heptamethyltetrasiloxane, 1-dimethylamino-3,3,5,5,7,7,9,9,9-nonamethylpentasiloxane, 1-dimethylamino-1,3,5,7,7,7-hexamethyltetrasiloxane, and 1-dimethylamino-1,3,5,7,9,9,9-heptamethylpentasiloxane. [9] Formulas A and B: [ka] 1. A method for producing an organoamino-functionalized oligosiloxane compound selected from the group consisting of: Formula (1) or (3): [ka] reacting a cyclotrisiloxane compound of formula (i) or a cyclotetrasiloxane compound of formula (iii) with an organic amine in the presence of a catalyst, as shown in formula (i) R 1 However, linear C1-C 10 Alkyl groups, branched C3-C 10Alkyl groups, C3-C 10 Cyclic alkyl groups, C3-C 10 Heterocyclic groups, C3-C 10 Alkenyl groups, C3-C 10 Alkynyl groups and C4-C 10 aryl groups; R 2 But hydrogen, linear C1-C 10 Alkyl groups, branched C3-C 10 Alkyl groups, C3-C 10 Cyclic alkyl groups, C3-C 10 Heterocyclic groups, C3-C 10 Alkenyl groups, C3-C 10 Alkynyl groups and C4-C 10 aryl groups; R 1 and R 2 are either linked together to form a cyclic ring structure or are not linked together to form a cyclic ring structure; R 3~9 are each independently hydrogen, linear C1-C 10 Alkyl groups, branched C3-C 10 Alkyl groups, C3-C 10 Cyclic alkyl groups, C2-C 10 Alkenyl groups, C2-C 10 Alkynyl groups and C4-C 10 aryl group.

[10] R 1~9 Each of is independently selected from hydrogen and a C1-C4 alkyl group.

[11] Formulas A and B: [ka] 1. A method for producing an organoamino-functionalized oligosiloxane compound selected from the group consisting of: Formula (2) or (4): [ka] reacting a chlorinated cyclotrisiloxane compound of formula (ii) or a chlorinated cyclotetrasiloxane compound of formula (iv) with an organic amine or a metal salt of an organic amine in the presence of a catalyst, as shown by the formula: R 1 However, linear C1-C 10 Alkyl groups, branched C3-C 10 Alkyl groups, C3-C 10 Cyclic alkyl groups, C3-C 10 Heterocyclic groups, C3-C 10 Alkenyl groups, C3-C 10 Alkynyl groups and C4-C 10 aryl groups; R 2 But hydrogen, linear C1-C 10 Alkyl groups, branched C3-C 10 Alkyl groups, C3-C 10 Cyclic alkyl groups, C3-C 10 Heterocyclic groups, C3-C 10 Alkenyl groups, C3-C 10 Alkynyl groups and C4-C 10 aryl groups; R 1 and R 2 are either linked together to form a cyclic ring structure or are not linked together to form a cyclic ring structure; R 3~9 are each independently hydrogen, linear C1-C 10 Alkyl groups, branched C3-C 10 Alkyl groups, C3-C 10 Cyclic alkyl groups, C2-C 10 Alkenyl groups, C2-C 10 Alkynyl groups and C4-C 10 aryl group.

[12] R 1~9 12. The method of claim 11, wherein each of is independently selected from hydrogen and a C1-C4 alkyl group.

[13] Formulas C and D: [ka] 1. A method for producing an organoamino-functionalized oligosiloxane compound selected from the group consisting of: Formula (v) or Formula (vi) [ka] with a compound selected from the group consisting of acetyl chloride, methyl iodide, trimethylchlorosilane, dimethylchlorosilane, methylchlorosilane, monochlorosilane, and organolithium compounds to form an intermediate compound; and thereafter reacting the intermediate compound with a compound selected from the group consisting of an organoaminochlorosilane, an organoamine, or a chlorosilane, wherein R 1 However, linear C1-C 10 Alkyl groups, branched C3-C 10 Alkyl groups, C3-C 10 Cyclic alkyl groups, C3-C 10 Heterocyclic groups, C3-C 10 Alkenyl groups, C3-C 10 Alkynyl groups and C4-C 10 aryl groups; R 2 But hydrogen, linear C1-C 10 Alkyl groups, branched C3-C 10 Alkyl groups, C3-C 10 Cyclic alkyl groups, C3-C 10 Heterocyclic groups, C3-C 10 Alkenyl groups, C3-C 10 Alkynyl groups and C4-C 10 aryl groups; R 3~10 are each independently hydrogen, linear C1-C 10 Alkyl groups, branched C3-C 10 Alkyl groups, C3-C 10 Cyclic alkyl groups, C2-C 10 Alkenyl groups, C2-C 10 Alkynyl groups and C4-C 10 aryl groups; X is a linear C1-C 10 Alkyl groups, branched C3-C10 Alkyl groups, C3-C 10 Cyclic alkyl groups, C2-C 10 Alkenyl groups, C2-C 10 Alkynyl groups, C4-C 10 Aryl groups, C1-C 10 Acyl groups, amine groups (-NR 1 R 2 ), H, Cl, Br, I, F, C2~C 12 Carboxylate group, C1-C 10 wherein the siloxy group is selected from the group consisting of linear or branched alkoxy groups, trimethylsiloxy groups, dimethylsiloxy groups, methylsiloxy groups, and siloxy groups.

[14] 1. A method for depositing a film comprising silicon and oxygen on a substrate, comprising: a) providing a substrate in a reactor; b) Formulas A, B, C, D and E [ka] wherein: R 1 However, linear C1-C 10 Alkyl groups, branched C3-C 10 Alkyl groups, C3-C 10 Cyclic alkyl groups, C3-C 10 Heterocyclic groups, C3-C 10 Alkenyl groups, C3-C 10 Alkynyl groups and C4-C 10 aryl groups; R 2 But hydrogen, linear C1-C 10 Alkyl groups, branched C3-C 10 Alkyl groups, C3-C 10 Cyclic alkyl groups, C3-C 10 Heterocyclic groups, C3-C 10 Alkenyl groups, C3-C 10 Alkynyl groups and C4-C 10 aryl groups; R 1 and R 2 are either linked together to form a cyclic ring structure or are not linked together to form a cyclic ring structure; R 3~10 are each independently hydrogen, linear C1-C 10 Alkyl groups, branched C3-C 10 Alkyl groups, C3-C 10 Cyclic alkyl groups, C2-C 10 Alkenyl groups, C2-C 10 Alkynyl groups and C4-C 10 aryl groups; X is a linear C1-C 10 Alkyl groups, branched C3-C 10 Alkyl groups, C3-C 10 Cyclic alkyl groups, C2-C 10 Alkenyl groups, C2-C 10 Alkynyl groups, C4-C 10 Aryl groups, C1-C 10 Acyl groups, amine groups (-NR 1 R 2 ), H, Cl, Br, I, F, C2~C 12 Carboxylate group, C1-C 10 selected from the group consisting of linear or branched alkoxy groups, trimethylsiloxy groups, dimethylsiloxy groups, methylsiloxy groups, or siloxy groups; R 1 and X are either linked to form a cyclic ring or not linked to form a cyclic ring; c) purging the reactor with a purge gas; d) introducing at least one of an oxygen-containing source and a nitrogen-containing source into the reactor; and e) purging the reactor with a purge gas, wherein steps b through e are repeated until a desired film thickness is deposited, and are conducted at one or more temperatures in the range of about 25 to 600° C.

[15] R 1~10 15. The method of claim 14, wherein each of is independently selected from hydrogen and a C1-C4 alkyl group.

[16] The at least one silicon precursor compound is selected from the group consisting of 2-dimethylamino-2,4,4,6,6-pentamethylcyclotrisiloxane, 2-diethylamino-2,4,4,6,6-pentamethylcyclotrisiloxane, 2-ethylmethylamino-2,4,4,6,6-pentamethylcyclotrisiloxane, 2-isopropylamino-2,4,4,6,6-pentamethylcyclotrisiloxane, 2-dimethylamino-2,4,4,6,6,8,8-heptamethylcyclotetrasiloxane, 2-diethylamino-2,4,4,6,6,8,8-heptamethylcyclotetrasiloxane, 2-ethylmethylamino-2,4,4,6,6,8,8-heptamethylcyclotetrasiloxane, 2-isopropylamino-2,4,4,6,6,8,8 15. The method of claim 14, wherein the isomer is selected from the group consisting of 2-heptamethylcyclotetrasiloxane, 2-dimethylamino-2,4,6-trimethylcyclotrisiloxane, 2-diethylamino-2,4,6-trimethylcyclotrisiloxane, 2-ethylmethylamino-2,4,6-trimethylcyclotrisiloxane, 2-isopropylamino-2,4,6-trimethylcyclotrisiloxane, 2-dimethylamino-2,4,6,8-tetramethylcyclotetrasiloxane, 2-diethylamino-2,4,6,8-tetramethylcyclotetrasiloxane, 2-ethylmethylamino-2,4,6,8-tetramethylcyclotetrasiloxane, and 2-isopropylamino-2,4,6,8-tetramethylcyclotetrasiloxane.

[17] The at least one silicon precursor compound is selected from the group consisting of 1-dimethylamino-1,1,3,3,5,5-hexamethyl-5-methoxytrisiloxane, 1-dimethylamino-1,1,3,3,5,5,7,7-octamethyl-7-methoxytrisiloxane, 1-dimethylamino-1,1,3,3,5,5-hexamethyl-5-acetoxytrisiloxane, 1-dimethylamino-1,1,3,3,5,5,7,7-octamethyl-7-acetoxytrisiloxane, 1-dimethylamino-1,1,3,3,5,5,7,7,7-nonamethyltetrasiloxane, 1-dimethylamino-1,1,3,3,5,5,7,7,9,9,9-undecamethylpentasiloxane, 1-dimethylamino-1,1,3,3,5,5,7,7-octamethyltetrasiloxane, 1-dimethylamino-1,1,3,3,5,5,7,7,9,9,9-undecamethylpentasiloxane, 1-dimethylamino-1,1,3,3,5,5,7,7-octamethyltetrasiloxane, 1-dimethylamino-1,1,3,3,5,5,7,7,9 15. The method of claim 14, wherein the alkyl group is selected from the group consisting of 1-dimethylamino-1,1,3,3,5,5,7,7,9,9-decamethylpentasiloxane, 1-dimethylamino-1,3,3,5,5,7,7,7-octamethyltetrasiloxane, 1-dimethylamino-1,3,3,5,5,7,7,9,9,9-decamethylpentasiloxane, 1-dimethylamino-3,3,5,5,7,7,7-heptamethyltetrasiloxane, 1-dimethylamino-3,3,5,5,7,7,9,9,9-nonamethylpentasiloxane, 1-dimethylamino-1,3,5,7,7,7-hexamethyltetrasiloxane, and 1-dimethylamino-1,3,5,7,9,9,9-heptamethylpentasiloxane.

[18] The following characteristics: density of about 2.1 g / cc or greater; wet etch rate of less than about 2.5 Å / sec when measured in a solution of dilute HF (0.5 wt% dHF) acid of 1:100 HF:water; about 1e-8 A / cm at 6 MV / cm or less 2 and a hydrogen impurity of less than about 5e20 at / cc as measured by secondary ion mass spectrometry (SIMS).

[19] A stainless steel container containing the composition of embodiment 1 above.

[20] 20. The stainless steel container of claim 19, further comprising an inert headspace gas selected from helium, argon, nitrogen, and combinations thereof. [twenty one] 15. The method of claim 14, wherein the silicon precursor compound further comprises at least one selected from the group consisting of a solvent and an inert gas.

Claims

1. 1. A method for depositing a silicon- and oxygen-containing film on a substrate at a temperature above 600° C. and at a growth rate of 2.0 Å / cycle or greater, comprising: a. providing a substrate in a reactor; b. Formulas A and B: 【Chemistry 1】 wherein: R 1 But linear C 1 ~C 10 Alkyl group, branched C 3 ~C 10 Alkyl group, C 3 ~C 10 Cyclic alkyl group, C 3 ~C 10 Heterocyclic group, C 3 ~C 10 Alkenyl group, C 3 ~C 10 Alkynyl groups, and C 4 ~C 10 aryl groups; R 2 is hydrogen, linear C 1 ~C 10 Alkyl group, branched C 3 ~C 10 Alkyl group, C 3 ~C 10 Cyclic alkyl group, C 3 ~C 10 Heterocyclic group, C 3 ~C 10 Alkenyl group, C 3 ~C 10 Alkynyl groups, and C 4 ~C 10 aryl groups; R 1 and R 2 are either linked together to form a cyclic ring structure or are not linked together to form a cyclic ring structure; R 3 to R 9 are each independently hydrogen, linear C 1 ~C 10 Alkyl group, branched C 3 ~C 10 Alkyl group, C 3 ~C 10 Cyclic alkyl group, C 2 ~C 10 Alkenyl group, C 2 ~C 10 Alkynyl groups, and C 4 ~C 10 introducing at least one compound selected from an aryl group into a reactor; c. purging the reactor with a purge gas to remove at least a portion of the unabsorbed precursor; d. introducing an oxygen-containing plasma source into the reactor; e. purging the reactor with a purge gas to remove at least a portion of the unreacted oxygen source, wherein steps b through e are repeated until a desired silicon-containing film thickness is deposited.

2. Each of R 2 to R 9 is independently hydrogen or C 1 ~C 4 The method of claim 1 , wherein the alkyl group is selected from the group consisting of alkyl groups.

3. The method of claim 1, wherein R 3-9 is not hydrogen.

4. The at least one compound is selected from the group consisting of 2-dimethylamino-2,4,4,6,6-pentamethylcyclotrisiloxane, 2-diethylamino-2,4,4,6,6-pentamethylcyclotrisiloxane, 2-ethylmethylamino-2,4,4,6,6-pentamethylcyclotrisiloxane, 2-isopropylamino-2,4,4,6,6-pentamethylcyclotrisiloxane, 2-dimethylamino-2,4,4,6,6,8,8-heptamethylcyclotetrasiloxane, 2-diethylamino-2,4,4,6,6,8,8-heptamethylcyclotetrasiloxane, 2-ethylmethylamino-2,4,4,6,6,8,8-heptamethylcyclotetrasiloxane, 2-isopropylamino-2,4,4,6,6,8,8-heptamethylcyclotetrasiloxane, 2. The method of claim 1, wherein the aryl group is selected from the group consisting of butamethylcyclotetrasiloxane, 2-dimethylamino-2,4,6-trimethylcyclotrisiloxane, 2-diethylamino-2,4,6-trimethylcyclotrisiloxane, 2-ethylmethylamino-2,4,6-trimethylcyclotrisiloxane, 2-iso-propylamino-2,4,6-trimethylcyclotrisiloxane, 2-dimethylamino-2,4,6,8-tetramethylcyclotetrasiloxane, 2-diethylamino-2,4,6,8-tetramethylcyclotetrasiloxane, 2-ethylmethylamino-2,4,6,8-tetramethylcyclotetrasiloxane, and 2-iso-propylamino-2,4,6,8-tetramethylcyclotetrasiloxane.

5. The silicon and oxygen containing film has a density of 2.1 g / cc or greater, a wet etch rate of 2.5 Å / sec or less when measured in a solution of dilute HF (0.5 wt % dHF) acid in 1:100 HF:water, and a dielectric constant of 1e-8 A / cm at 6 MV / cm or less. 2 10. The method of claim 1, wherein the silicon substrate exhibits one or more of the following: less than or equal to 1000 Watts per cubic centimeter; less than or equal to 5e20 at / cc of leakage current; less than or equal to 5e20 at / cc of hydrogen impurities as measured by SIMS; and combinations thereof.

6. 2. The method of claim 1, wherein the oxygen-containing plasma source is selected from the group consisting of water plasma, ozone plasma, oxygen plasma, oxygen / helium plasma, oxygen / argon plasma, nitrogen oxide plasma, carbon dioxide plasma, and mixtures thereof.

7. 10. The method of claim 1, further comprising subjecting the silicon and oxygen containing film to a post-deposition treatment selected from the group consisting of thermal annealing, plasma treatment, ultraviolet (UV) light treatment, laser treatment, electron beam treatment, and combinations thereof.

8. The method of claim 1 , wherein the growth rate is greater than 2.5 Å / cycle.

9. A method for depositing a silicon and oxygen containing film on a substrate at a temperature above 600° C., comprising: a. providing a substrate in a reactor; b. 2-dimethylamino-2,4,4,6,6-pentamethylcyclotrisiloxane, 2-diethylamino-2,4,4,6,6-pentamethylcyclotrisiloxane, 2-ethylmethylamino-2,4,4,6,6-pentamethylcyclotrisiloxane, 2-isopropylamino-2,4,4,6,6-pentamethylcyclotrisiloxane, 2-dimethylamino-2,4,4,6,6,8,8-heptamethylcyclotetrasiloxane, 2-diethylamino-2,4,4,6,6,8,8-heptamethylcyclotetrasiloxane, 2-ethylmethylamino-2,4,4,6,6,8,8-heptamethylcyclotetrasiloxane, 2-isopropylamino-2,4,4,6,6,8,8-heptamethylcyclotetrasiloxane introducing into the reactor at least one compound selected from the group consisting of 2-dimethylamino-2,4,6-trimethylcyclotrisiloxane, 2-diethylamino-2,4,6-trimethylcyclotrisiloxane, 2-ethylmethylamino-2,4,6-trimethylcyclotrisiloxane, 2-iso-propylamino-2,4,6-trimethylcyclotrisiloxane, 2-dimethylamino-2,4,6,8-tetramethylcyclotetrasiloxane, 2-diethylamino-2,4,6,8-tetramethylcyclotetrasiloxane, 2-ethylmethylamino-2,4,6,8-tetramethylcyclotetrasiloxane, and 2-iso-propylamino-2,4,6,8-tetramethylcyclotetrasiloxane; c. purging the reactor with a purge gas to remove at least a portion of the unabsorbed precursor; d. introducing an oxygen-containing plasma source into the reactor; e. purging the reactor with a purge gas to remove at least a portion of the unreacted oxygen source, wherein steps b through e are repeated until a desired silicon-containing film thickness is deposited.

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