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

Abstract

Disclosed herein are amino-functionalized linear and cyclic oligomeric siloxanes having at least two silicon atoms and two oxygen atoms and an organoamino group and methods for preparing the oligomeric siloxanes. Also disclosed herein are methods for depositing silicon- and oxygen-containing films using the organoamino-functionalized linear and cyclic oligomeric siloxanes.

Description

[0001] This application is a divisional application of a Chinese patent application with an application date of February 8, 2018, application number 201810128979.9, and invention name “Organoamino-functionalized linear and cyclic oligosiloxanes for depositing silicon-containing films”.

[0002] CROSS-REFERENCE TO RELATED APPLICATIONS

[0003] This application claims the benefit of priority under 35 U.S.C. §119(e) to U.S. Provisional Application Serial No. 62 / 456,297 filed on February 8, 2017 and U.S. Provisional Application Serial No. 62 / 574,952 filed on October 20, 2017, the entire contents of which are incorporated herein by reference. Technical Field

[0004] The present invention relates to organosilicon compounds that can be used to deposit films containing silicon and oxygen (e.g., silicon oxide, silicon oxycarbonitride, silicon oxycarbide, carbon-doped silicon oxide, and other films containing silicon and oxygen), methods of depositing silicon oxide-containing films using the compounds, and films obtained by the compounds and methods. Background Art

[0005] Novel organoamino-functionalized linear and cyclic oligosiloxane precursor compounds and compositions and methods containing the precursor compounds 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 a combination thereof are described herein. More specifically, 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 (including, for example, about 25° C. to about 300° C.) are described herein.

[0006] Atomic layer deposition (ALD) and plasma enhanced atomic layer deposition (PEALD) are processes for depositing conformal films such as silicon oxide at low temperatures (<500°C). In both ALD and PEALD processes, precursors and reactive gases (such as oxygen or ozone) are pulsed individually for a certain number of cycles to form a monolayer of silicon oxide at each cycle. However, silicon oxide deposited at low temperatures using these processes may contain a certain level of impurities, such as but not limited to carbon (C) or hydrogen (H), which may be harmful in certain semiconductor applications. To address this problem, one possible solution is to increase the deposition temperature to 500°C or higher. However, at these higher temperatures, conventional precursors used by the semiconductor industry tend to self-react, thermally decompose, and are deposited in a chemical vapor deposition (CVD) mode rather than an ALD mode. Compared to ALD deposition, CVD mode deposition has reduced conformality, particularly for high aspect ratio structures required in many semiconductor applications. In addition, compared to ALD mode deposition, CVD mode deposition has less control over film or material thickness.

[0007] It can be used to deposit nanostructured nanoparticles at relatively low temperatures (<300°C) and at relatively high growth per cycle (GPC> ) by atomic layer deposition (ALD) and plasma enhanced atomic layer deposition (PEALD) processes. Organoaminosilane and chlorosilane precursors for depositing silicon-containing films in 20% to 40% CO 2 / cycles are known in the art.

[0008] Examples of known precursors and methods are disclosed in the following publications, patents, and patent applications.

[0009] US Patent No. 7,084,076 B2 describes the use of halogen-substituted or NCO-substituted disiloxane precursors to deposit silicon oxide films using a base-catalyzed ALD process.

[0010] US Publication No. 2015087139 AA describes the use of amino-functionalized carbosilanes to deposit silicon-containing films by thermal ALD or PEALD processes.

[0011] US Patent No. 9,337,018 B2 describes the use of organoaminodisilanes for depositing silicon-containing films by thermal ALD or PEALD processes.

[0012] US Patent Nos. 8,940,648 B2, 9,005,719 B2, and 8,912,353 B2 describe the use of organoaminosilanes to deposit silicon-containing films by thermal ALD or PEALD processes.

[0013] US Publication No. 2015275355 AA describes the use of mono- and bis(organoamino)alkylsilanes to deposit silicon-containing films by thermal ALD or PEALD processes.

[0014] US Publication No. 2015376211 A describes the use of mono(organoamino)-substituted, halogen-substituted, and pseudohalido-substituted trisilylamines to deposit silicon-containing films by thermal ALD or PEALD processes.

[0015] Publication No. WO15105337 and US Pat. No. 9,245,740 B2 describe the use of alkylated trisilylamines to deposit silicon-containing films by thermal ALD or PEALD processes.

[0016] Publication No. WO15105350 describes the use of four-membered ring cyclodisilazanes having at least one Si-H bond for depositing silicon-containing films by thermal ALD or PEALD processes.

[0017] US Patent No. 7,084,076 B2 describes the use of halogen-substituted or NCO-substituted disiloxane precursors to deposit silicon oxide films using a base-catalyzed ALD process.

[0018] The disclosures of the above-identified patents and patent applications are incorporated herein by reference.

[0019] There is a need in the art for precursors and methods for depositing silicon oxide-containing films with high growth per cycle (GPC) to maximize throughput in semiconductor manufacturing facilities. Although some precursors can be deposited at > However, these precursors have disadvantages such as low-quality films (elemental contamination, low density, poor electrical properties, high wet etch rates), high process temperatures, the need for catalysts, being expensive, and producing low conformal films. Summary of the invention

[0020] The present invention solves the problems associated with conventional precursors and processes by providing silicon- and oxygen-containing precursors, particularly organoamino-functionalized linear and cyclic oligosiloxanes having at least two silicon and two oxygen atoms and an organoamino group for anchoring the oligosiloxane units to the substrate surface, as part of a process for depositing silicon- and oxygen-containing films. The polysilicon precursors disclosed in the present invention have novel structures compared to those described in the background section above, and thus may provide advantages in one or more aspects related to the cost or convenience of precursor synthesis, the physical properties of the precursor (including thermal stability, reactivity or volatility), the process for depositing silicon-containing films, or the properties of the deposited silicon-containing films.

[0021] The present invention discloses a composition comprising at least one organoamino-functional oligosiloxane compound selected from the group consisting of formula A, B, C, D and E:

[0022]

[0023] Where R 1 Select from C1 to C 10 Straight chain alkyl, C3 to C 10 Branched alkyl, C3 to C 10 Cyclic alkyl, C3 to C 10 Heterocyclic group, C3 to C 10 Alkenyl, C3 to C 10 Alkynyl and C4 to C 10 Aryl; R 2 Selected from hydrogen, C1 to C 10 Straight chain alkyl, C3 to C 10 Branched alkyl, C3 to C 10 Cyclic alkyl, C3 to C 10 Heterocyclic group, C3 to C 10 Alkenyl, C3 to C 10 Alkynyl and C4 to C 10 Aryl, where R 1 and R 2 Connected to form a cyclic ring structure or not connected to form a cyclic ring structure; R 3-10 are independently selected from hydrogen, C1 to C 10 Straight chain alkyl, C3 to C 10 Branched alkyl, C3 to C 10 Cyclic alkyl, C2 to C 10 Alkenyl, C2 to C 10 Alkynyl and C4 to C 10 Aryl; and X is selected from C1 to C 10 Straight chain alkyl, C3 to C 10 Branched alkyl, C3 to C 10 Cyclic alkyl, C2 to C 10 Alkenyl, C2 to C 10 Alkynyl, C4 to C 10 Aryl, C1 to C 10 Acyl, amine (-NR 1 R 2 ), H, Cl, Br, I, F, C2 to C 12 Carboxylate group, C1 to C 10 Straight-chain or branched alkoxy, trimethylsilyloxy, dimethylsilyloxy, methylsilyloxy and silyloxy, wherein R 1 and X are connected to form a cyclic ring or are not connected to form a cyclic ring, wherein if in formula C R 1-8are all methyl, then X cannot be trimethylsilyloxy, and if in formula D R 1-10 If all are methyl groups, then X cannot be methyl or dimethylamino.

[0024] Described herein are methods for depositing stoichiometric or non-stoichiometric silicon and oxygen-containing materials or films (e.g., but not limited to, silicon oxide, carbon-doped silicon oxide, silicon oxynitride films, or carbon-doped silicon oxynitride films) at relatively low temperatures (e.g., at one or more temperatures of 600° C. or less) 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), a plasma enhanced ALD-like process, or an ALD process using an oxygen-containing reactant source, a nitrogen-containing reactant source, or a combination thereof.

[0025] In one aspect, the present invention discloses a method for depositing a film comprising silicon and oxygen onto a substrate, the method comprising the steps of: (a) providing a substrate in a reactor; (b) introducing into the reactor at least one silicon precursor compound selected from the group consisting of formula A, B, C, D and E,

[0026]

[0027] Where R 1 Select from C1 to C 10 Straight chain alkyl, C3 to C 10 Branched alkyl, C3 to C 10 Cyclic alkyl, C3 to C 10 Heterocyclic group, C3 to C 10 Alkenyl, C3 to C 10 Alkynyl and C4 to C 10 Aryl; R 2 Selected from hydrogen, C1 to C 10 Straight chain alkyl, C3 to C 10 Branched alkyl, C3 to C 10 Cyclic alkyl, C3 to C 10 Heterocyclic group, C3 to C 10 Alkenyl, C3 to C 10 Alkynyl and C4 to C 10 Aryl, where R 1 and R 2 Connected to form a cyclic ring structure or not connected to form a cyclic ring structure; R 3-10 are independently selected from hydrogen, C1 to C 10 Straight chain alkyl, C3 to C 10 Branched alkyl, C3 to C 10 Cyclic alkyl, C2 to C10 Alkenyl, C2 to C 10 Alkynyl and C4 to C 10 Aryl; X is selected from C1 to C 10 Straight chain alkyl, C3 to C 10 Branched alkyl, C3 to C 10 Cyclic alkyl, C2 to C 10 Alkenyl, C2 to C 10 Alkynyl, C4 to C 10 Aryl, C1 to C 10 Acyl, amine (-NR 1 R 2 ), H, Cl, Br, I, F, C2 to C 12 Carboxylate group, C1 to C 10 A straight chain or branched alkoxy group, a trimethylsilyloxy group, a dimethylsilyloxy group, a methylsilyloxy group or a silyloxy group, wherein R 1 and X are connected to form an cyclic ring or are not connected to form an 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 the purge gas, wherein steps b to e are repeated until a film of a desired thickness is deposited; and wherein the method is performed at one or more temperatures in the range of about 25° C. to 600° C.

[0028] Methods of preparing the above compounds are also disclosed herein.

[0029] The embodiments of the present invention may be used alone or in combination with each other. BRIEF DESCRIPTION OF THE DRAWINGS

[0030] Figure 1 GPC of thermal ALD versus precursor pulse number of 2-dimethylamino-2,4,6,8-tetramethylcyclotetrasiloxane for an ozone process at 300°C is provided.

[0031] Figure 2 GPC of PEALD silica deposition versus precursor pulse time for 2-dimethylamino-2,4,6,8-tetramethylcyclotetrasiloxane is provided.

[0032] Figure 3 GPC of PEALD silicon oxide deposition versus O2 plasma exposure time for 2-dimethylamino-2,4,6,8-tetramethylcyclotetrasiloxane is provided.

[0033] Figure 4TEM images of PEALD silicon oxide films deposited from 2-dimethylamino-2,4,6,8-tetramethylcyclotetrasiloxane in a laminar flow reactor are provided, demonstrating excellent step coverage and that 2-dimethylamino-2,4,6,8-tetramethylcyclotetrasiloxane may be a good precursor for PEALD silicon oxide because it has anchoring groups.

[0034] Figure 5 GPC of PEALD silicon oxide deposition versus precursor pulse time for TMCTS in a showerhead chamber is provided, indicating that TMCTS is not suitable for atomic layer deposition.

[0035] Figure 6 TEM images of silicon oxide films deposited from TMCTS in a showerhead chamber are provided, showing that TMCTS is not suitable for good step coverage and thus further demonstrating its unsuitability as a precursor for atomic layer deposition.

[0036] Figure 7 TEM images of PEALD silicon oxide films deposited from 2-dimethylamino-2,4,6,8-tetramethylcyclotetrasiloxane in a showerhead chamber are provided, demonstrating excellent step coverage and that 2-dimethylamino-2,4,6,8-tetramethylcyclotetrasiloxane can be a good precursor for PEALD silicon oxide because it has anchoring groups. DETAILED DESCRIPTION

[0037] Unless otherwise noted herein or clearly contradictory to the context, the use of the terms "a", "an" and "the" and similar references in the context of describing the present invention (particularly in the context of the claims below) is interpreted as covering both the singular and the plural. Unless otherwise noted, the terms "comprising", "having", "including" and "containing" are interpreted as open terms (i.e., meaning "including but not limited to"). Unless otherwise noted herein, the recording of the numerical range herein is merely intended to be a shorthand method for referring to each individual numerical value falling within the range individually, and each individual numerical value is included in the specification as if it were stated individually herein. Unless otherwise noted herein or clearly contradictory to the context, all methods described herein may be performed in any suitable order. Unless otherwise stated, the use of any and all examples or exemplary language (e.g., "such as") provided herein is intended only to better illustrate the present invention, rather than to limit the scope of the present invention. No language in the specification should be interpreted as representing any unclaimed element as necessary for implementing the present invention.

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

[0039] The methods disclosed herein can be implemented using equipment known in the art. For example, the methods can use conventional reactors in the field of semiconductor manufacturing.

[0040] Without wishing to be bound by any theory or explanation, it is believed that the efficacy of the precursor compositions disclosed herein may vary with the number of silicon atoms and particularly silicon atom bonds. The precursors disclosed herein typically have 3 to 5 silicon atoms and 5 to 8 silicon-oxygen bonds.

[0041] The precursors disclosed herein have a different structure than those known in the art and are therefore able to perform better than conventional silicon-containing precursors and provide relatively high GPC, thereby producing higher quality films with favorable wet etch rates or with lower elemental contamination.

[0042] Disclosed herein is a composition for depositing a film selected from silicon oxide, carbon-doped silicon oxide, or silicon oxycarbonitride film using a vapor deposition process, the composition comprising a compound having Formula A, Formula B, Formula C, Formula D, or Formula E:

[0043]

[0044] Where R 1 Select from C1 to C 10 Straight chain alkyl, C3 to C 10 Branched alkyl, C3 to C 10 Cyclic alkyl, C3 to C 10 Heterocyclic group, C3 to C 10 Alkenyl, C3 to C 10 Alkynyl and C4 to C 10 Aryl; R 2 Selected from hydrogen, C1 to C 10 Straight chain alkyl, C3 to C 10 Branched alkyl, C3 to C 10 Cyclic alkyl, C3 to C 10 Heterocyclic group, C3 to C 10 Alkenyl, C3 to C 10 Alkynyl and C4 to C 10 Aryl, where R 1 and R 2 Connected to form a cyclic ring structure or not connected to form a cyclic ring structure; R 3-10 are independently selected from hydrogen, C1 to C 10 Straight chain alkyl, C3 to C 10 Branched alkyl, C3 to C 10 Cyclic alkyl, C2 to C 10 Alkenyl, C2 to C 10 Alkynyl and C4 to C 10 Aryl; and X is selected from C1 to C 10 Straight chain alkyl, C3 to C 10 Branched alkyl, C3 to C 10 Cyclic alkyl, C2 to C 10 Alkenyl, C2 to C 10 Alkynyl, C4 to C 10 Aryl, C1 to C 10 Acyl, amine (-NR 1 R 2 ), H, Cl, Br, I, F, C2 to C 12 Carboxylate group, C1 to C 10 Straight-chain or branched alkoxy, trimethylsilyloxy, dimethylsilyloxy, methylsilyloxy and silyloxy, wherein R 1 and X are connected to form a cyclic ring or are not connected to form a cyclic ring, wherein if in formula C R 1-8 are all methyl, then X cannot be trimethylsilyloxy, and if in formula D R 1-10 If all are methyl groups, then X cannot be methyl or dimethylamino.

[0045] In a preferred embodiment, under the above conditions, R 1-10At least one of is C1 to C4 alkyl. For formula A and B, preferred embodiments include those wherein R 1-9 Compounds each of which is a C1 to C4 alkyl group.

[0046] In the above formula and throughout the specification, the term "oligosiloxane" means a compound comprising at least two repeating -Si-O-siloxane units, preferably at least three repeating -Si-O-siloxane units, and may be a cyclic or linear structure, preferably a cyclic structure.

[0047] In the above formula and throughout the specification, the term "alkyl" means a straight or branched functional group having 1 to 10 carbon atoms. Exemplary straight chain alkyls include, but are not limited to, methyl, ethyl, propyl, butyl, pentyl, and hexyl. Exemplary branched chain alkyls include, but are not limited to, isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, tert-pentyl, isohexyl, and neohexyl. In certain embodiments, the alkyl may have one or more functional groups attached thereto, such as, but not limited to, an alkoxyl group, a dialkylamino group, or a combination thereof attached thereto. In other embodiments, the alkyl does not have one or more functional groups attached thereto. The alkyl may be saturated or unsaturated.

[0048] In the above formula and throughout the specification, the term "cyclic alkyl" refers to a cyclic functional group having 3 to 10 carbon atoms. Exemplary cyclic alkyl groups include, but are not limited to, cyclobutyl, cyclopentyl, cyclohexyl, and cyclooctyl.

[0049] In the above formulae and throughout the specification, 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.

[0050] In the above formula and throughout the specification, the term "dialkylamino" group, "alkylamino" group or "organoamino" group refers to a group having two alkyl groups bonded to a nitrogen atom or one alkyl group bonded to a nitrogen atom and having 1 to 10 or 2 to 6 or 2 to 4 carbon atoms. Examples include, but are not limited to, HNMe, HNBu t , NMe2, NMeEt, NEt2 and NPr i 2.

[0051] In the above formula and throughout the specification, the term "aryl" refers to an aromatic cyclic functional group having 4 to 10 carbon atoms, 5 to 10 carbon atoms, or 6 to 10 carbon atoms. Exemplary aryl groups include, but are not limited to, phenyl, benzyl, chlorobenzyl, tolyl, o-xylyl, 1,2,3-triazolyl, pyrrolyl, and furanyl.

[0052] Throughout the specification, the term "alkyl hydrocarbon" refers to a linear or branched C1 to C 20 Hydrocarbons, cyclic C6 to C 20Hydrocarbons. Exemplary hydrocarbons include, but are not limited to, heptane, octane, nonane, decane, dodecane, cyclooctane, cyclononane, and cyclodecane.

[0053] Throughout the specification, the term "alkoxy" refers to a C1 to C 10 -OR 1 Group, where R 1 As defined above. Exemplary alkoxy groups include, but are not limited to, methoxy, ethoxy, isopropoxy, n-propoxy, n-butoxy, sec-butoxy, tert-butoxy, and phenoxide.

[0054] Throughout the specification, the term "carboxylic acid ester" refers to a C2 to C 12 -OC(=O)R 1 Group, where R 1 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)Et), i Pr) and benzoate (-OC(=O)Ph).

[0055] Throughout the specification, the term "aromatic hydrocarbons" refers to C6 to C 20 Aromatic hydrocarbons. Exemplary aromatic hydrocarbons include, but are not limited to, toluene and mesitylene.

[0056] In the above formula and throughout the specification, the term "heterocycle" refers to a non-aromatic saturated monocyclic or polycyclic ring system having about 3 to about 10 ring atoms, preferably about 5 to about 10 ring atoms, wherein 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 the heterocycle indicates that at least one nitrogen, oxygen or sulfur atom is present as a ring atom, respectively. The heterocyclic group is optionally substituted.

[0057] Exemplary organoamino-functional linear and cyclic oligosiloxanes having Formula AE are listed in Table 1:

[0058] Table 1. Exemplary organoamino-functional linear and cyclic oligosiloxanes having formula AE, wherein R 1-10 Independently selected from hydrogen and C1 to C4 alkyl:

[0059]

[0060]

[0061]

[0062]

[0063] The compound having formula A or B can be synthesized, for example, by catalytic dehydrogenation coupling of cyclotrisiloxane or cyclotetrasiloxane with an organic amine (e.g., for cyclotrisiloxane, reaction formula (1); cyclotetrasiloxane can also be used as in reaction formula (3)) or by reaction of chlorinated cyclotrisiloxane with an organic amine or a metal salt of an organic amine (e.g., reaction formula 2; chlorinated cyclotetrasiloxane can also be used as in reaction formula (4)).

[0064]

[0065]

[0066] Preferably, the molar ratio of cyclotrisiloxane or cyclotetrasiloxane to organic amine in the reaction mixture is about 1 to 1.0, 1 to 1.5, 1 to 2, 1 to 3, 1 to 4, or 1 to 10.

[0067] The catalyst used in the method of the present invention is a catalyst that promotes the formation of silicon-nitrogen bonds in reaction formulas (1) and (3). Exemplary catalysts that can be used with the methods described herein include, but are not limited to, the following: alkaline earth metal catalysts; halogen-free main group, transition metal, lanthanide and actinide catalysts; and halogen-containing main group, transition metal, lanthanide and actinide catalysts.

[0068] Exemplary alkaline earth metal catalysts include, but are not limited to, the following: Mg[N(SiMe3)2]2, To M MgMe[To M =tri(4,4-dimethyl-2-oxazolinyl)phenylboronate], 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+Alkaline earth metal-amides, -imines, -alkyls, -hydrides and -silaalkyl complexes (M = Ca, Mg, Sr, Ba).

[0069] Exemplary halogen-free, main group, transition metal, lanthanide and actinide catalysts include, but are not limited to, the following: 1,3-diisopropyl-4,5-dimethylimidazol-2-ylidene, 2,2'-bipyridine, phenanthroline, B(C6F5)3, BR3 (R = linear, branched or cyclic C1 to C 10 Alkyl, C5 to C 10 Aryl or C1 to C 10 Alkoxy), AlR3 (R = straight chain, branched or cyclic C1 to C 10 Alkyl, C5 to C 10 Aryl or C1 to C 10 alkoxy), (C5H5)2TiR2 (R = alkyl, H, alkoxy, organic amino, silanyl), (C5H5)2Ti(OAr)2[Ar = (2,6-( i Pr)2C6H3)], (C5H5)2Ti(SiHRR')PMe3 (wherein R, R' are independently selected from H, Me, Ph), TiMe2(dmpe)2 (dmpe = 1,2-bis(dimethylphosphino)ethane), bis(phenyl)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(diisopropylphosphino)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, [tri(4,4-dimethyl-2-oxazolinyl)phenylborate]ZnH, (C5H5)2ZrR2 (R=alkyl, H, alkoxy, organic amino, silanyl), Ru3(CO) 12 ,[(Et3P)Ru(2,6-trimethylphenyl(mesityl)thiophenolate)][B[3,5-(CF3)2C6H3]4],[(C5Me5)Ru(R3P) x (NCMe) 3-x ] + (wherein R is selected from a linear, branched or cyclic C1 to C10 Alkyl and C5 to C 10 Aryl; x = 0, 1, 2, 3), Rh6(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, C6H 13 ), Pd / C, tris(dibenzylideneacetone)dipalladium(0), tetrakis(triphenylphosphine)palladium(0), Pd(II) acetate, (C5H5)2SmH, (C5Me5)2SmH, (THF)2Yb[N(SiMe3)2]2, (NHC)Yb(N(SiMe3)2)2[NHC=1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene)], Yb(η 2 -Ph2CNPh)(hmpa)3(hmpa=hexamethylphosphoramide), W(CO)6, Re2(CO) 10 ,Os3(CO) 12 , Ir4(CO) 12 , (acetylacetonato) 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 catalyst), bis(tri-tert-butylphosphine)platinum(0), Pt(cyclooctadiene)2, [(Me3Si)2N]3U][BPh4], [(Et2N)3U][BPh4], and other halogen-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 noble metals (such as ruthenium, platinum, palladium, rhodium, osmium) can also be attached to a support. The support is a solid with a high surface area. Typical support materials include, but are not limited to: alumina, MgO, zeolite, carbon, monolithic cordierite, diatomaceous earth, silica gel, silica / alumina, ZrO and TiO2. Preferred supports are carbon (e.g., platinum carbon, palladium carbon, rhodium carbon, ruthenium carbon), alumina, silica and MgO. The metal loading of the catalyst is in the range of about 0.01 wt % to about 50 wt %. The preferred range is about 0.5 wt % to about 20 wt %. The more preferred range is about 0.5 wt % to about 10 wt %. The catalyst that needs to be activated can be activated by many known methods. Heating the catalyst under vacuum is a preferred method. The catalyst can be activated before adding to the reaction vessel or before adding reactants to the reaction vessel. The catalyst can contain a promoter. Promoters are substances that are not catalysts themselves, but increase their efficiency (activity and / or selectivity) when mixed with active catalysts in small amounts. Promoters are usually metals such as Mn, Ce, Mo, Li, Re, Ga, Cu, Ru, Pd, Rh, Ir, Fe, Ni, Pt, Cr, Cu and Au and / or their oxides. They can be added to the reaction vessel alone, or they can be parts of the catalyst itself. For example, Ru / Mn / C (ruthenium carbon promoted by manganese) or Pt / CeO2 / Ir / SiO2 (platinum silicon oxide promoted by ceria and iridium). Some promoters can be used as catalysts by themselves, but they can improve the activity of the main catalyst when used in combination with the main catalyst. Catalysts can act as promoters for other catalysts. In this case, the catalyst can be called a bimetallic (or multimetallic) catalyst. For example, Ru / Rh / C can be called a ruthenium rhodium carbon bimetallic catalyst, or rhodium promoted ruthenium carbon. An active catalyst is a substance that acts as a catalyst in a specific chemical reaction.

[0070] Exemplary halogen, main group, transition metal, lanthanide and actinide containing 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, Cl), [Mn(CO)4Br]2, NiCl2, (C5H5)2ZrX2 (X = F, Cl), PdCl2, PdI2, CuCl, CuI, CuF2, CuCl2, C uBr2, Cu(PPh3)3Cl, ZnCl2, [(C6H6)RuX2]2 (X = Cl, Br, I), (Ph3P)3RhCl (Wilkinson's catalyst), [RhCl(cyclooctadiene)]2, di-μ-chloro-tetracarbonyl dirhodium (I), bis(triphenylphosphine)rhodium (I) carbonyl chloride, NdI2, SmI2, DyI2, (POCOP)IrHCl (POCOP = 2,6-(R2PO)2C6H3; R = i Pr, n Bu, Me), H2PtCl6·nH2O (Speier catalyst), PtCl2, Pt(PPh3)2Cl2, and other halogen-containing n+ Compound (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).

[0071] The molar ratio of catalyst to cyclotrisiloxane or cyclotetrasiloxane in the reaction mixture is in the range of 0.1 to 1, 0.05 to 1, 0.01 to 1, 0.005 to 1, 0.001 to 1, 0.0005 to 1, 0.0001 to 1, 0.00005 to 1, or 0.00001 to 1. In a 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.

[0072] In certain embodiments, the reaction mixture comprising cyclotrisiloxane or cyclotetrasiloxane, organic amine and catalyst also comprises an anhydrous solvent. Exemplary solvents may include but are not limited to straight chain, branched chain, cyclic or polyethers (e.g., tetrahydrofuran (THF), diethyl ether, diethylene glycol dimethyl ether and / or tetraethylene glycol dimethyl ether); straight chain, branched chain or cyclic alkanes, olefins, aromatic compounds and halogenated hydrocarbons (e.g., pentane, hexane, toluene and dichloromethane). The selection of one or more solvents (if added) may be affected by the compatibility of the reagents contained in the reaction mixture, the solubility of the catalyst and / or the separation process of the selected intermediate product and / or the final product. In other embodiments, the reaction mixture does not comprise a solvent.

[0073] In the methods described herein, the reaction between cyclotrisiloxane or cyclotetrasiloxane and the organic amine is carried out at one or more temperatures in the range of about 0°C to about 200°C, preferably 0°C 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. Suitable temperature ranges for the reaction can be determined by the physical properties of the reagents and optional solvents. Examples of specific reactor temperature ranges include, but are not limited to, 0°C to 80°C or 0°C to 30°C.

[0074] In certain embodiments of the methods described herein, the reaction pressure may be in the range of about 1 to about 115 psia or about 15 to about 45 psia. In some embodiments where the cyclotrisiloxane or cyclotetrasiloxane is a liquid at ambient conditions, the reaction is carried out at atmospheric pressure. In some embodiments where the cyclotrisiloxane or cyclotetrasiloxane is a gas at ambient conditions, the reaction is carried out at a pressure greater than 15 psia.

[0075] In some embodiments, one or more reagents can be introduced into the reaction mixture as liquid or steam.In the embodiment where one or more in the reagent are added as steam, non-reactive gas such as nitrogen or inert gas can be used as carrier gas to deliver steam to the reaction mixture.In the embodiment where one or more in the reagent are added as liquid, reagent can be added undiluted (neat), or can be diluted with solvent.Reagent is fed into the reaction mixture until the desired conversion ratio of the crude mixture or crude liquid containing the organic aminosilane product has been realized.In some embodiments, reaction can be carried out in a continuous manner by supplementing reactants and removing reaction product and crude liquid from the reactor.

[0076] The crude mixture comprising the compound of formula AE, catalyst and possible residual organic amine, solvent or undesirable product may require a separation process. Examples of suitable separation processes include, but are not limited to, distillation, evaporation, membrane separation, filtration, gas phase transfer, extraction, fractionation using a reverse phase column and combinations thereof.

[0077] The compound of formula C, D or E can be synthesized, for example, by ring-opening cyclotrisiloxane or cyclotetrasiloxane with, for example, acetyl chloride, methyl iodide, trimethylsilyl chloride or other types of chlorosilane reagents to produce halogen-substituted linear trisiloxane or tetrasiloxane, followed by reaction with an organic amine (e.g., reaction formula 5-7). Alternatively, the compound of formula C, D or E can be synthesized by reacting with R 1 R 2 NX substances, such as Me2NSiMe3 direct reaction and synthesis (e.g., reaction formula 8). Compounds with formula C, D or E can also be synthesized by ring-opening cyclotrisiloxane or cyclotetrasiloxane with an organic lithium reagent (e.g., methyl lithium or lithium amide), and then reacting with an organic aminochlorosilane or chlorosilane and synthesizing (e.g., reaction formula 9-10). These ring-opening reactions exemplified by reaction formulas 5-10 may require the presence of a catalyst. It should be noted that in which the halogenated oligosiloxane compound or intermediate is reacted with 2 equivalents of an organic amine HNR 1 R 2 In the reaction (Scheme 5-7), optionally only one equivalent of the organic amine HNR 1 R 2 It can be used in the presence of a tertiary amine such as Et3N, thus producing the tertiary amine hydrochloride as a salt by-product.

[0078]

[0079]

[0080] The synthetic methods illustrated in reaction schemes 5-10 can also be carried out using a cyclotetrasiloxane starting material having formula (vi):

[0081]

[0082] Schemes 1-10 are exemplary preparative chemistries and are not meant to be limited in any way to the preparation of compounds having Formula A, B, C, D, or E.

[0083] Silicon precursor compounds according to the present invention having formula A, B, C, D or E and compositions comprising silicon precursor compounds according to the present invention having formula A, B, C, D or E are preferably substantially free of halide ions. As used herein, the term "substantially free" means less than 5ppm (by weight) when it relates to halide ions (or halides) such as chlorides (i.e., chlorine-containing substances, such as HCl, or silicon compounds having at least one Si-Cl bond) and fluorides, bromides and iodides, preferably less than 3ppm by ICP-MS, more preferably less than 1ppm by ICP-MS, and most preferably 0ppm by ICP-MS. Chlorides are known to be used as decomposition catalysts for silicon precursor compounds having formula A. Significant levels of chloride in the final product can lead to degradation of the silicon precursor compound. The gradual degradation of the silicon precursor compound can directly affect the film deposition process, making it difficult for semiconductor manufacturers to meet the specifications of the film. In addition, the shelf life or stability is negatively affected by the higher degradation rate of the silicon precursor compound, thereby making it difficult to ensure a shelf life of 1-2 years. Therefore, the accelerated decomposition of the silicon precursor compound brings safety and performance issues related to the formation of these combustible and / or pyrophoric gaseous byproducts. The silicon precursor compound having formula A, B, C, D or E is preferably substantially free of metal ions, such as Li + 、Na + , K + Mg 2+ , Ca 2+ 、Al 3+ , Fe 2+ , Fe 3+ 、Ni 2 + Cr 3+ As used herein, the term "substantially free" as it relates to Li, Na, K, Mg, Ca, Al, Fe, Ni, Cr means less than 5 ppm (by weight), preferably less than 3 ppm, more preferably less than 1 ppm, and most preferably less than 0.1 ppm, as measured by ICP-MS. In some embodiments, the silicon precursor compound having formula A does not contain metal ions, such as Li + 、Na + , K + Mg 2+ , Ca 2+ 、Al 3+ , 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, noble metals such as 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.

[0084] In another embodiment, a method for depositing a film comprising silicon and oxygen onto a substrate is provided, the method comprising the steps of:

[0085] a) providing a substrate in a reactor;

[0086] b) introducing at least one silicon precursor compound into the reactor, wherein the at least one silicon precursor is selected from the formula AE:

[0087]

[0088] Where R 1 Independently selected from C1 to C 10 Straight chain alkyl, C3 to C 10 Branched alkyl, C3 to C 10 Cyclic alkyl, C3 to C 10 Heterocyclic group, C3 to C 10 Alkenyl, C3 to C 10 Alkynyl and C4 to C 10 Aryl; R 2 Selected from hydrogen, C1 to C 10 Straight chain alkyl, C3 to C 10 Branched alkyl, C3 to C 10 Cyclic alkyl, C3 to C 10 Heterocyclic group, C3 to C 10 Alkenyl, C3 to C 10 Alkynyl and C4 to C 10 Aryl, where R 1 and R 2 Connected to form a cyclic ring structure or not connected to form a cyclic ring structure; R 3-10 are independently selected from hydrogen, C1 to C 10 Straight chain alkyl, C3 to C 10 Branched alkyl, C3 to C 10 Cyclic alkyl, C2 to C 10 Alkenyl, C2 to C 10 Alkynyl and C4 to C 10 Aryl; X is selected from C1 to C 10 Straight chain alkyl, C3 to C 10 Branched alkyl, C3 to C 10 Cyclic alkyl, C2 to C 10 Alkenyl, C2 to C10 Alkynyl, C4 to C 10 Aryl, C1 to C 10 Acyl, amine (-NR 1 R 2 ), H, Cl, Br, I, F, C2 to C 12 Carboxylate group, C1 to C 10 A straight chain or branched alkoxy group, a trimethylsilyloxy group, a dimethylsilyloxy group, a methylsilyloxy group or a silyloxy group, wherein R 1 Connected to X to form a cyclic ring or not connected to form a cyclic ring;

[0089] c) purging the reactor with a purge gas;

[0090] d) introducing an oxygen-containing source into the reactor; and

[0091] e) purging the reactor with the purge gas,

[0092] wherein steps b to e are repeated until a film of desired thickness is deposited; and wherein the method is carried out at one or more temperatures in the range of about 25°C to 600°C.

[0093] The methods disclosed herein form a silicon oxide film comprising at least one of the following characteristics: a density of at least about 2.1 g / cc; a relative humidity of less than about 100% as measured in a dilute HF acid solution of 1:100 HF to water (0.5 wt % dHF); Wet etch rate; less than about 1e-8A / cm at up to 6MV / cm 2 leakage; and less than about 5e20 at / cc hydrogen impurities as measured by secondary ion mass spectrometry (SIMS).

[0094] In certain embodiments of the methods and compositions described herein, a layer of silicon-containing dielectric material is deposited on at least a portion of a substrate, for example, using a reaction chamber by a chemical vapor deposition (CVD) process. Suitable substrates include, but are not limited to, semiconductor materials such as gallium arsenide ("GaAs"), silicon, and silicon-containing compositions such as crystalline silicon, polycrystalline silicon, amorphous silicon, epitaxial silicon, silicon dioxide ("SiO2"), silicon glass, silicon nitride, fused silicon dioxide, 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 silicon carbide, 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. Still other layers may also be germanosilicates, aluminosilicates, copper, and aluminum, as well as diffusion barrier materials such as, but not limited to, TiN, Ti(C)N, TaN, Ta(C)N, Ta, W, or WN.

[0095] Deposition methods disclosed herein may involve one or more purge gases. The purge gas used to purge unconsumed reactants and / or reaction byproducts is an inert gas that does not react with the precursor. Exemplary purge gases include, but are not limited to, argon (Ar), nitrogen (N2), helium (He), neon, hydrogen (H2) and mixtures thereof. In certain embodiments, a purge gas such as Ar is supplied to the reactor for about 0.1 to 1000 seconds at a flow rate of about 10 to about 2000 sccm, thereby purging unreacted materials and any byproducts that may remain in the reactor.

[0096] A purge gas such as argon purges the unadsorbed excess complex from the process chamber. After sufficient purging, an oxygen source can be introduced into the reaction chamber to react with the adsorption surface, followed by another gas purge to remove the reaction byproducts from the reaction chamber. The process cycle can be repeated to achieve the desired film thickness. In some cases, pumping can replace the purge of the inert gas, or both can be used to remove unreacted silicon precursor.

[0097] Throughout the specification, the term "ALD or ALD-like" refers to a process including but not limited to the following processes: a) introducing individual reactants including a silicon precursor and a reactive gas into a reactor sequentially, such as a single wafer ALD reactor, a semi-batch ALD reactor or a batch furnace ALD reactor; b) exposing the individual reactants including a silicon precursor and a reactive gas to a substrate by moving or rotating the substrate to different sections of the reactor, and the various sections are separated by an inert gas curtain, i.e., a spatial ALD reactor or a roll-to-roll ALD reactor.

[0098] The method of the present invention is carried out by an ALD process using ozone or an oxygen-containing source comprising a plasma, wherein the plasma may further contain 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.

[0099] The oxygen-containing plasma source may be generated in situ, or remotely. In a particular embodiment, the oxygen-containing source comprises oxygen and is flowed or introduced with other reagents (such as, but not limited to, at least one silicon precursor and optionally an inert gas) during method steps b through d.

[0100] In certain embodiments, the compositions described herein—and used in the disclosed methods—also include a solvent. Exemplary solvents may include, but are not limited to, ethers, tertiary amines, alkyl hydrocarbons, aromatic hydrocarbons, tertiary amino ethers, and combinations thereof. In certain embodiments, the difference between the boiling point of the silicon precursor and the boiling point of the solvent is 40° C. or less. In some embodiments, the composition may be delivered by direct liquid injection into a reaction chamber for a silicon-containing film.

[0101] For those embodiments in which at least one silicon precursor having formula A to E is used in a composition comprising a solvent, the selected solvent or mixture thereof does not react with the silicon precursor. The amount of solvent in the composition by weight % is in the range of 0.5 wt % to 99.5 wt % or 10 wt % to 75 wt %. In this or other embodiments, the boiling point (bp) of the solvent is similar to the bp of the silicon precursor of formula A to E, or the difference between the bp of the solvent and the bp of the silicon precursor of formula A to E is 40°C or less, 30°C or less, or 20°C or less, or 10°C. Alternatively, the difference between the boiling points is within the range of any one or more of the following endpoints: 0, 10, 20, 30 or 40°C. Examples of suitable ranges of bp differences 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.

[0102] In certain embodiments, the silicon oxide or carbon-doped silicon oxide film deposited using the methods described herein is formed in the presence of an oxygen-containing source comprising ozone, water (H2O) (e.g., deionized water, purified water, and / or distilled water), oxygen (O2), oxygen plasma, NO, N2O, NO2, carbon monoxide (CO), carbon dioxide (CO2), and combinations thereof. The oxygen-containing source is passed through, for example, an in-situ or remote plasma generator to provide an oxygen-containing plasma source comprising oxygen, such as an oxygen plasma, a plasma comprising oxygen and argon, a plasma comprising oxygen and helium, an ozone plasma, a water plasma, a nitrous oxide plasma, or a carbon dioxide plasma. In certain embodiments, the oxygen-containing plasma source comprises an oxygen source gas introduced into the reactor at a flow rate of about 1 to about 2000 standard cubic centimeters (sccm) or about 1 to about 1000 sccm. The oxygen-containing plasma source may be introduced for a time of about 0.1 to about 100 seconds. In a particular embodiment, the oxygen-containing plasma source comprises water having a temperature of 10°C or higher. In embodiments where the film is deposited by a PEALD or plasma enhanced cyclic CVD process, depending on the volume of the ALD reactor, the precursor pulse can have a pulse duration greater than 0.01 seconds (e.g., about 0.01 to about 0.1 seconds, about 0.1 to about 0.5 seconds, about 0.5 seconds to about 10 seconds, about 0.5 seconds to about 20 seconds, about 1 second to about 100 seconds), and the oxygen-containing plasma source can have a pulse duration less than 0.01 seconds (e.g., about 0.001 to about 0.01 seconds).

[0103] In one or more of the above embodiments, the oxygen-containing plasma source is selected from oxygen plasma with or without an inert gas, water vapor plasma with or without an inert gas, nitrogen oxide (N2O, NO, NO2) plasma with or without an inert gas, carbon oxide (CO2, CO) plasma with or without an inert gas, and combinations thereof. In certain embodiments, the oxygen-containing plasma source further comprises an inert gas. In these embodiments, the inert gas is selected from argon, helium, nitrogen, hydrogen, or combinations thereof. In alternative embodiments, the oxygen-containing plasma source does not comprise an inert gas.

[0104] The corresponding steps of supplying precursors, oxygen sources, and / or other precursors, source gases, and / or reagents may be implemented by varying the time at which they are supplied to change the stoichiometric composition of the resulting dielectric film.

[0105] Energy is applied to at least one of the silicon precursors of formulas A to E, oxygen-containing sources, or combinations thereof to initiate a reaction and form a dielectric film or coating on the substrate. Such energy can be provided by, but is not limited to, heat, plasma, pulsed plasma, helicon plasma, high-density plasma, inductively coupled plasma, X-rays, electron beams, photons, remote plasma methods, and combinations thereof. In certain embodiments, a secondary RF radio frequency source can be used to change the plasma characteristics at the substrate surface. In embodiments where deposition involves plasma, the plasma generation process can include a direct plasma generation process (wherein the plasma is directly generated in the reactor) or a remote plasma generation process (wherein the plasma is generated outside the reactor and supplied to the reactor).

[0106] At least one silicon precursor can be delivered to the reaction chamber in various ways, such as plasma enhanced cyclic CVD or PEALD reactor or batch furnace reactor. In one embodiment, a liquid delivery system can be used. In alternative embodiments, a combined liquid delivery and flash treatment unit can be used, such as a turbo evaporator manufactured by MSP Corporation, Shoreview, MN, so that low volatility materials can be quantitatively (volumetrically) delivered, which results in repeatable delivery and deposition without thermal decomposition of the precursor. In liquid delivery formulations, the precursors described herein can be delivered in pure liquid form, or can be used in solvent formulations or compositions comprising them. Therefore, in some embodiments, the precursor formulation can include a solvent component with suitable properties (such as may be desired and advantageous in a given end-use application) to form a film on a substrate.

[0107] As previously described, the purity level of at least one silicon precursor is sufficiently high to be acceptable for reliable semiconductor manufacturing. In certain embodiments, at least one silicon precursor described herein contains less than 2 wt %, or less than 1 wt %, or less than 0.5 wt % of one or more of the following impurities: free amines, free halides or halogen ions, and higher molecular weight species. The higher purity levels of the silicon precursors described herein can be obtained by one or more of the following processes: purification, adsorption, and / or distillation.

[0108] In one embodiment of the methods described herein, a plasma enhanced cyclic deposition process, such as PEALD-like or PEALD, may be used, wherein deposition is performed using at least one silicon precursor and an oxygen plasma source. A PEALD-like process is defined as a plasma enhanced cyclic CVD process, but still provides highly conformal silicon and oxygen containing films.

[0109] In one embodiment of the present invention, a method for depositing a film comprising silicon and oxygen onto at least one surface of a substrate is described herein, wherein the method comprises the following steps:

[0110] a. providing a substrate in a reactor;

[0111] b. introducing into the reactor at least one silicon precursor having formula A to E as defined above;

[0112] c. purging the reactor with a purge gas;

[0113] d. introducing into the reactor an oxygen-containing source comprising a plasma; and

[0114] e. Purge the reactor with a purge gas.

[0115] In this method, steps b to e are repeated until a film of desired thickness is deposited on the substrate.

[0116] In this or other embodiments, it should be understood that the steps of the methods described herein can be performed in various orders, can be performed sequentially, can be performed simultaneously (e.g., during at least a portion of another step), and any combination thereof. The respective steps of supplying precursor and oxygen source gases can be performed, for example, by varying the duration of their supply to vary the stoichiometric composition of the resulting dielectric film. In addition, the purge time after the precursor or oxidant step can be minimized to <0.1 s, resulting in improved throughput.

[0117] In a particular embodiment, the method described herein deposits a high quality silicon and oxygen containing film on a substrate. The method comprises the following steps:

[0118] a. providing a substrate in a reactor;

[0119] b. introducing into the reactor at least one silicon precursor having Formulae A to E as described herein;

[0120] c. purging the reactor with a purge gas to remove at least a portion of the non-adsorbed precursor;

[0121] d. introducing an oxygen-containing plasma source into the reactor; and

[0122] e. purging the reactor with a purge gas to remove at least a portion of the unreacted oxygen source,

[0123] Steps b to e are repeated until a silicon-containing film of a desired thickness is deposited.

[0124] In another particular embodiment, the method described herein deposits a high quality silicon and oxygen containing film on a substrate at a temperature above 600° C. The method comprises the following steps:

[0125] a. providing a substrate in a reactor;

[0126] b. introducing into the reactor at least one organoaminopolysiloxane precursor having Formulas A to E as described herein;

[0127] c. purging the reactor with a purge gas to remove at least a portion of the non-adsorbed precursor;

[0128] d. introducing an oxygen-containing plasma source into the reactor; and

[0129] e. purging the reactor with a purge gas to remove at least a portion of the unreacted oxygen source,

[0130] Steps b to e are repeated until a silicon-containing film of a desired thickness is deposited.

[0131] It is believed that the compounds of formula A to E (particularly wherein R3-R 10 Organo-functionalized linear and cyclic oligosiloxane precursors of formulae C, D and E) which are not hydrogen are preferred for this process because they do not contain any Si-H groups, or the number of Si-H groups is limited, since Si-H groups can decompose at temperatures above 600° C. and can potentially lead to undesirable chemical vapor deposition. However, it is possible that under certain conditions, such as using short precursor pulses or low reactor pressures, this process can also be used at temperatures above 600° C. with oligosiloxanes of formulae A to E (where R 3-10 The invention relates to the preparation of organoamino-functionalized linear and cyclic oligomeric siloxane precursors in which either of the amino groups is hydrogen, without significant undesirable chemical vapor deposition.

[0132] Another method disclosed herein forms a carbon-doped silicon oxide film using a silicon precursor compound having a chemical structure represented by Formulas A to E as defined above plus an oxygen source.

[0133] Another exemplary method is as follows:

[0134] a. providing a substrate in a reactor;

[0135] b. contacting a vapor generated from at least one silicon precursor compound having a structure represented by Formulas A to E as defined above with or without a co-flowing oxygen source to chemically adsorb the precursor onto the heated substrate;

[0136] c. Purge any unadsorbed precursor;

[0137] d. introducing an oxygen source onto the heated substrate to react with the adsorbed precursor; and

[0138] e. Purge any unreacted oxygen source,

[0139] Steps b to e are repeated until the desired thickness is achieved.

[0140] In another specific embodiment, the method described herein deposits a high quality silicon oxynitride film on a substrate. The method comprises the following steps:

[0141] a. providing a substrate in a reactor;

[0142] b. introducing into the reactor at least one silicon precursor having Formulae A to E as described herein;

[0143] c. purging the reactor with a purge gas to remove at least a portion of the non-adsorbed precursor;

[0144] d. introducing a nitrogen-containing plasma source into the reactor; and

[0145] e. purging the reactor with a purge gas to remove at least a portion of the unreacted nitrogen source,

[0146] Steps b to e are repeated until a desired thickness of the oxygen-containing silicon nitride film is deposited.

[0147] Another exemplary method is as follows:

[0148] a. providing a substrate in a reactor;

[0149] b. contacting a vapor generated from at least one silicon precursor compound having a structure represented by Formulas A to E as defined above with or without a co-flowing nitrogen source to chemically adsorb the precursor onto the heated substrate;

[0150] c. Purge any unadsorbed precursor;

[0151] d. introducing a nitrogen source onto the heated substrate to react with the adsorbed precursor; and

[0152] e. Purge any unreacted nitrogen source,

[0153] Steps b to e are repeated until the desired thickness is achieved.

[0154] Solid silicon oxide, silicon oxynitride, carbon-doped silicon oxynitride, or carbon-doped silicon oxide can be deposited using various commercial ALD reactors such as single wafer, semi-batch, batch furnaces, or roll-to-roll reactors.

[0155] The processing temperatures of 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: about 0° C. to about 300° C.; or about 25° C. to about 300° C.; or about 50° C. to about 290° C.; or about 25° C. to about 250° C., or about 25° C. to about 200° C.

[0156] In another aspect, a method for depositing a film containing silicon and oxygen by flowable chemical vapor deposition (FCVD) is provided, the method comprising:

[0157] placing a substrate comprising surface features in a reactor, wherein the substrate is maintained at one or more temperatures in the range of about -20°C to about 400°C and the pressure of the reactor is maintained at 100 Torr or less;

[0158] introducing at least one compound selected from formulae A to E;

[0159] 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 feature;

[0160] annealing the film at one or more temperatures of about 100° C. to 1000° C. to coat at least a portion of the surface features; and

[0161] The substrate is treated with an oxygen source at one or more temperatures in a range of about 20° C. to about 1000° C. to form a silicon-containing film on at least a portion of the surface features.

[0162] In another aspect, a method for depositing a film containing silicon and oxygen by flowable chemical vapor deposition (FCVD) is provided, the method comprising:

[0163] placing a substrate comprising surface features in a reactor, wherein the substrate is maintained at one or more temperatures in the range of about -20°C to about 400°C and the pressure of the reactor is maintained at 100 Torr or less;

[0164] introducing at least one compound selected from formulae A to E;

[0165] 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 feature;

[0166] annealing the film at one or more temperatures of about 100° C. to 1000° C. to coat at least a portion of the surface features; and

[0167] The substrate is treated with an oxygen source at one or more temperatures in a range of about 20° C. to about 1000° C. to form a silicon-containing film on at least a portion of the surface features.

[0168] In certain embodiments, the oxygen source is selected from water vapor, water plasma, ozone, oxygen, oxygen plasma, oxygen / helium plasma, oxygen / argon plasma, nitrogen oxide plasma, carbon dioxide plasma, hydrogen peroxide, organic peroxides, and mixtures thereof. In other embodiments, the nitrogen source is selected from, for example, ammonia, hydrazine, monoalkylhydrazine, dialkylhydrazine, nitrogen, nitrogen / hydrogen, nitrogen / argon plasma, nitrogen / helium plasma, ammonia plasma, nitrogen plasma, nitrogen / hydrogen plasma, organic amines such as tert-butylamine, dimethylamine, diethylamine, isopropylamine, diethylamine plasma, dimethylamine plasma, trimethylamine plasma, ethylenediamine plasma, and alkoxyamines such as ethanolamine plasma, and mixtures thereof. In yet other embodiments, the nitrogen-containing source comprises ammonia plasma, a plasma comprising nitrogen and argon, a plasma comprising nitrogen and helium, or a plasma comprising hydrogen and nitrogen source gas. In this or other embodiments, the method steps are repeated until the surface features are filled with a silicon-containing film. In embodiments in which water vapor is used as an oxygen source in a flowable chemical vapor deposition process, the substrate temperature is in the range of about -20°C to about 40°C or about -10°C to about 25°C.

[0169] In yet another embodiment of the methods described herein, the film deposited by ALD, ALD-like, PEALD, PEALD-like or FCVD, or the film so deposited, is subjected to a (post-deposition) treatment step. The treatment step may 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, high temperature thermal annealing treatment; plasma treatment; ultraviolet (UV) light treatment; laser; electron beam treatment, and combinations thereof, to affect one or more properties of the film.

[0170] In another embodiment, a vessel or container for depositing a silicon-containing film containing one or more silicon precursor compounds described herein is provided. In a particular embodiment, the vessel includes at least one pressurizable vessel (preferably a stainless steel vessel having a design as disclosed in U.S. Pat. Nos. US7334595, US6077356, US5069244 and US5465766, the disclosures of which are incorporated herein by reference). The container may include glass (borosilicate or quartz glass) or 316, 316L, 304 or 304L type stainless steel alloy (UNS designations S31600, S31603, S30400, S30403) and is equipped with suitable valves and fittings to allow one or more precursors to be delivered to a reactor for a CVD or ALD process. In this or other embodiments, the silicon precursor is provided in a pressurizable vessel composed of stainless steel, and the purity of the precursor is 98 wt % or more or 99.5% or more, which is suitable for most semiconductor applications. The headspace of the vessel or container is filled with an inert gas selected from the group consisting of helium, argon, nitrogen and combinations thereof.

[0171] In certain embodiments, the gas line connecting the precursor tank to the reaction chamber is 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 other embodiments, a solution comprising at least one silicon precursor is injected into a vaporizer maintained at one or more temperatures for direct liquid injection.

[0172] A flow of argon and / or other gases may be used as a carrier gas to help deliver the vapor of at least one silicon precursor to the reaction chamber during the precursor pulse process. In some embodiments, the reaction chamber process pressure is about 50 mTorr to 10 Torr. In other embodiments, the reaction chamber process pressure may be up to 760 Torr (e.g., about 50 mTorr to about 100 Torr).

[0173] In a typical PEALD or PEALD-like process (eg, PECCVD process), a substrate, such as a silicon oxide substrate, is heated on a heater stage in a reaction chamber that is initially exposed to a silicon precursor to allow the complex to be chemically adsorbed onto the substrate surface.

[0174] Films deposited using silicon precursors of Formulas A to E described herein have improved properties, such as, but not limited to, a wet etch rate that is lower than the wet etch rate of the film prior to the treatment step, or a density that is higher than the density prior to the treatment step, compared to films deposited using previously disclosed silicon precursors under the same conditions. In a particular embodiment, the film so deposited is treated intermittently during the deposition process. These intermittent or mid-deposition treatments can be performed, for example, after each ALD cycle, after each certain number of ALD cycles (such as, but not limited to, one (1) ALD cycle, two (2) ALD cycles, five (5) ALD cycles, or after every ten (10) or more ALD cycles).

[0175] The precursors of formulae A to E exhibit / cycle or higher growth rate.

[0176] In embodiments where the film is treated with a high temperature annealing step, the annealing temperature is at least 100° C. or more above the deposition temperature. In this or other embodiments, the annealing temperature is in the range of about 400° C. to about 1000° C. In this or other embodiments, the annealing process can be performed in a vacuum (<760 Torr), an inert environment, or an oxygen-containing environment (such as H2O, N2O, NO2, or O2).

[0177] In embodiments where the film is UV treated, the film is exposed to a broad UV band, or a UV source having a wavelength in the range of about 150 nanometers (nm) to about 400 nm. In a particular embodiment, after the desired film thickness is achieved, the film so deposited is exposed to UV in a chamber different from the deposition chamber.

[0178] In embodiments where the film is treated with plasma, a passivation layer (such as SiO2 or carbon-doped SiO2) is deposited to prevent chlorine and nitrogen contaminants from penetrating into the film during subsequent plasma treatment. The passivation layer can be deposited using atomic layer deposition or cyclic chemical vapor deposition.

[0179] In embodiments where the film is treated with plasma, the plasma source is selected from hydrogen plasma, plasma containing hydrogen and helium, plasma containing hydrogen and argon. Hydrogen plasma reduces the dielectric constant of the film and increases damage resistance to subsequent plasma ashing processes while still keeping the overall carbon content nearly unchanged.

[0180] Without intending to be bound by a particular theory, it is believed that the silicon precursor compound having a chemical structure represented by Formulas A to E as defined above can be anchored by reacting an organic amino group with a hydroxyl group on the substrate surface to provide multiple Si-O-Si fragments per molecule of precursor, thereby increasing the growth rate of silicon oxide or carbon-doped silicon oxide compared to conventional silicon precursors having only one silicon atom such as bis(tert-butylamino)silane or bis(diethylamino)silane.

[0181] In certain embodiments, silicon precursors having formulas A to E as defined above may 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 alkoxides, metal amides, or volatile organometallic precursors are used to deposit metal-containing films using ALD or CVD processes (such as those described herein). Examples of suitable metal alkoxide precursors that can be used with the methods disclosed herein include, but are not limited to: Group 3 to 6 metal alkoxides, Group 3 to 6 metal complexes with both alkoxy and alkyl-substituted cyclopentadienyl ligands, Group 3 to 6 metal complexes with both alkoxy and alkyl-substituted pyrrolyl ligands, Group 3 to 6 metal complexes with both alkoxy and diketonate ligands; Group 3-6 metal complexes with both alkoxy and ketoester ligands.

[0182] Examples of suitable metal amide precursors that can be used with 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-butyliminotris(diethylamino)tantalum (TBTDET), tert-butyliminotris(dimethylamino)tantalum (TBTDET). Tantalum (MT), tert-butyliminotris(ethylmethylamino)tantalum (TBTEMT), ethyliminotris(diethylamino)tantalum (EITDET), ethyliminotris(dimethylamino)tantalum (EITDMT), ethyliminotris(ethylmethylamino)tantalum (EITEMT), tert-amyliminotris(dimethylamino)tantalum (TAIMAT), tert-amyliminotris(diethylamino)tantalum, penta(dimethylamino)tantalum, tert-amyliminotris(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 with the methods disclosed herein include, but are not limited to, Group 3 metal cyclopentadienyls or alkylcyclopentadienyls. Exemplary Group 3 to 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.

[0183] In certain embodiments, the silicon-containing films described herein have a dielectric constant of 6 or less, 5 or less, 4 or less, and 3 or less. In these or other embodiments, the film may have a dielectric constant of about 5 or less, or about 4 or less, or about 3.5 or less. However, it is contemplated that films having other dielectric constants (e.g., higher or lower) may be formed depending on the desired end use of the film. Examples of silicon-containing films formed using the silicon precursors and methods described herein having precursors of Formulas A to E have a formula Si x O y C z N v H w , wherein Si is in the range of about 10% to about 40%; O is in the range of about 0% to about 65%; C is in the range of about 0% to about 75% or about 0% to about 50%; N is in the range of about 0% to about 75% or about 0% to 50%; and H is in the range of about 0% to about 50% (atomic weight %), wherein x+y+z+v+w=100 atomic weight %, as determined, for example, by XPS or other methods. Another example of a silicon-containing film formed using the silicon precursors and methods of formulas A to E described herein is silicon oxynitride carbon, wherein the carbon content measured by XPS is 1 atomic % to 80 atomic %. Yet another example of a silicon-containing film formed using the silicon precursors and methods of formulas A to E described herein is amorphous silicon, wherein the sum of both nitrogen and carbon content measured by XPS is <10 atomic %, preferably <5 atomic %, and most preferably <1 atomic %.

[0184] As previously described, the methods described herein can be used to deposit silicon-containing films 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 carbon oxynitride, hydrogenated silicon carbon oxynitride, anti-reflective coatings, photoresists, germanium, germanium-containing, boron-containing, Ga / As, flexible substrates, organic polymers, porous organic and inorganic materials, metals such as copper and aluminum, and diffusion barriers 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.

[0185] The deposited films have applications including, but not limited to, computer chips, optical devices, magnetic information storage, coatings on support materials or substrates, microelectromechanical systems (MEMS), nanoelectromechanical systems, thin film transistors (TFT), light emitting diodes (LED), organic light emitting diodes (OLED), IGZO and liquid crystal displays (LCD). Potential uses of the resulting solid silicon oxide or carbon-doped silicon oxide include, but are not limited to, shallow trench insulation, interlayer dielectric layers, passivation layers, etch stop layers, portions of dual spacers, and sacrificial layers for patterning.

[0186] The methods described herein provide high quality silicon oxide, silicon oxynitride, carbon doped silicon oxynitride or carbon doped silicon oxide films. The term "high quality" refers to films that exhibit one or more of the following characteristics: a density of about 2.1 g / cc or more, 2.2 g / cc or more, 2.25 g / cc or more; as measured in a dilute HF acid solution of 1:100 HF to water (0.5 wt % dHF); or lower, or lower, or lower, or lower, or lower, or lower, or lower, Or lower wet etch rate; up to about 1 e-8 A / cm at 6 MV / cm 2 or less; and hydrogen impurities of about 5 e20 at / cc or less as measured by SIMS; and combinations thereof. With respect to etch rate, thermally grown silicon oxide films have an etch rate of about 100 % by weight in 0.5 wt% HF. The etching rate.

[0187] In certain embodiments, one or more silicon precursors having Formulas A through E described herein can be used to form films containing silicon and oxygen that are solid and non-porous or substantially non-porous.

[0188] Therefore, the present invention provides at least the following:

[0189] 1. A composition comprising at least one organoamino-functional oligosiloxane compound selected from the group consisting of formula A, B, C and D:

[0190]

[0191] in,

[0192] R 1 Select from C1 to C 10 Straight chain alkyl, C3 to C 10 Branched alkyl, C3 to C 10 Cyclic alkyl, C3 to C 10 Heterocyclic group, C3 to C 10 Alkenyl, C3 to C 10 Alkynyl and C4 to C 10 Aryl;

[0193] R 2 Selected from hydrogen, C1 to C 10 Straight chain alkyl, C3 to C 10 Branched alkyl, C3 to C 10 Cyclic alkyl, C3 to C 10 Heterocyclic group, C3 to C10 Alkenyl, C3 to C 10 Alkynyl and C4 to C 10 Aryl, where R 1 and R 2 connected to form an annular ring structure or not connected to form an annular ring structure;

[0194] R 3-10 are independently selected from hydrogen, C1 to C 10 Straight chain alkyl, C3 to C 10 Branched alkyl, C3 to C 10 Cyclic alkyl, C2 to C 10 Alkenyl, C2 to C 10 Alkynyl and C4 to C 10 aryl; and

[0195] X is selected from C1 to C 10 Straight chain alkyl, C3 to C 10 Branched alkyl, C3 to C 10 Cyclic alkyl, C2 to C 10 Alkenyl, C2 to C 10 Alkynyl, C4 to C 10 Aryl, C1 to C 10 Acyl, amine (-NR 1 R 2 ), H, Cl, Br, I, F, C2 to C 12 Carboxylate group, C1 to C 10 Straight-chain or branched alkoxy, trimethylsiloxy, dimethylsiloxy, methylsiloxy and siloxy,

[0196] Where R 1 and X are connected to form a cyclic ring or are not connected to form a cyclic ring, wherein if in formula C R 1-8 are all methyl, then X cannot be trimethylsilyloxy, and if in formula D R 1-10 If all are methyl groups, then X cannot be methyl or dimethylamino.

[0197] 2. The composition according to item 1, comprising at least one compound selected from formula A and formula B.

[0198] 3. The composition according to item 1, comprising at least one compound selected from formula C and formula D.

[0199] 4. The composition according to any one of items 1 to 3, further comprising at least one selected from a solvent and a purge gas.

[0200] 5. A composition according to item 2, wherein R 1-9 Each is independently selected from hydrogen and C1 to C4 alkyl.

[0201] 6. The composition according to any one of items 1 to 5, wherein the composition is substantially free of one or more impurities selected from halides, metal ions, metals, and combinations thereof.

[0202] 7. A composition according to item 2, wherein the organo-functional oligosiloxane 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-2,4,6-trimethylcyclotrisiloxane, 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.

[0203] 8. A composition according to item 3, wherein the organo-functional oligosiloxane 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-methoxytetrasiloxane, 1-dimethylamino-1,1,3,3,5,5-hexamethyl-5-acetoxytrisiloxane, 1-dimethylamino-1,1,3,3,5,5,7,7-octamethyl-7-acetoxytetrasiloxane, 1-dimethylamino-1,1,3,3,5,5,7,7-undecylpentasiloxane, 1-dimethylamino-1,1,3,3,5,5,7,7-octamethyl-7-acetoxytetrasiloxane, ,7,7-octamethyltetrasiloxane, 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-3,3,5,5,7,7,7-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.

[0204] 9. A method for preparing an organoamino-functional oligosiloxane compound selected from the group consisting of formula A and B:

[0205]

[0206] The method comprises the following steps:

[0207] As shown in reaction formula (1) or (3), a cyclotrisiloxane compound of formula (i) or a cyclotetrasiloxane compound of formula (iii) is reacted with an organic amine in the presence of a catalyst:

[0208]

[0209] in,

[0210] R 1 Select from C1 to C 10 Straight chain alkyl, C3 to C 10 Branched alkyl, C3 to C 10 Cyclic alkyl, C3 to C 10 Heterocyclic group, C3 to C 10 Alkenyl, C3 to C 10 Alkynyl and C4 to C 10 Aryl;

[0211] R 2Selected from hydrogen, C1 to C 10 Straight chain alkyl, C3 to C 10 Branched alkyl, C3 to C 10 Cyclic alkyl, C3 to C 10 Heterocyclic group, C3 to C 10 Alkenyl, C3 to C 10 Alkynyl and C4 to C 10 Aryl, where R 1 and R 2 connected to form an cyclic ring structure or not connected to form an cyclic ring structure; and

[0212] R 3-9 are independently selected from hydrogen, C1 to C 10 Straight chain alkyl, C3 to C 10 Branched alkyl, C3 to C 10 Cyclic alkyl, C2 to C 10 Alkenyl, C2 to C 10 Alkynyl and C4 to C 10 Aryl.

[0213] 10. The method according to item 9, wherein R 1-9 Each is independently selected from hydrogen and C1 to C4 alkyl.

[0214] 11. A method for preparing an organoamino-functional oligosiloxane compound selected from the group consisting of formula A and B:

[0215]

[0216] The method comprises the following steps:

[0217] As shown in reaction formula (2) or (4), a chlorinated cyclotrisiloxane compound of formula (ii) or a chlorinated cyclotetrasiloxane compound of formula (iv) is reacted with an organic amine or a metal salt of an organic amine in the presence of a catalyst:

[0218]

[0219]

[0220] in,

[0221] R 1 Select from C1 to C 10 Straight chain alkyl, C3 to C 10 Branched alkyl, C3 to C 10 Cyclic alkyl, C3 to C 10 Heterocyclic group, C3 to C 10 Alkenyl, C3 to C 10 Alkynyl and C4 to C 10 Aryl;

[0222] R 2 Selected from hydrogen, C1 to C 10 Straight chain alkyl, C3 to C 10 Branched alkyl, C3 to C 10 Cyclic alkyl, C3 to C 10 Heterocyclic group, C3 to C 10 Alkenyl, C3 to C 10 Alkynyl and C4 to C 10 Aryl, where R 1 and R 2 connected to form an cyclic ring structure or not connected to form an cyclic ring structure; and

[0223] R 3-9 are independently selected from hydrogen, C1 to C 10 Straight chain alkyl, C3 to C 10 Branched alkyl, C3 to C 10 Cyclic alkyl, C2 to C 10 Alkenyl, C2 to C 10 Alkynyl and C4 to C 10 Aryl.

[0224] 12. The method according to item 11, wherein R 1-9 Each is independently selected from hydrogen and C1 to C4 alkyl.

[0225] 13. A method for preparing an organoamino-functional oligosiloxane compound selected from the group consisting of formula C and D:

[0226]

[0227] The method comprises the following steps:

[0228] reacting a compound of formula (v) or (vi) with a compound selected from the group consisting of acetyl chloride, methyl iodide, trimethylchlorosilane, dimethylchlorosilane, methylchlorosilane, monochlorosilane and an organolithium compound to form an intermediate compound,

[0229] and

[0230] The intermediate compound is then reacted with a compound selected from an organic aminochlorosilane, an organic amine or a chlorosilane, wherein

[0231] R 1 Select from C1 to C 10 Straight chain alkyl, C3 to C 10 Branched alkyl, C3 to C 10 Cyclic alkyl, C3 to C 10 Heterocyclic group, C3 to C 10 Alkenyl, C3 to C 10 Alkynyl and C4 to C 10Aryl;

[0232] R 2 Selected from hydrogen, C1 to C 10 Straight chain alkyl, C3 to C 10 Branched alkyl, C3 to C 10 Cyclic alkyl, C3 to C 10 Heterocyclic group, C3 to C 10 Alkenyl, C3 to C 10 Alkynyl and C4 to C 10 Aryl;

[0233] R 3-10 are independently selected from hydrogen, C1 to C 10 Straight chain alkyl, C3 to C 10 Branched alkyl, C3 to C 10 Cyclic alkyl, C2 to C 10 Alkenyl, C2 to C 10 Alkynyl and C4 to C 10 aryl; and

[0234] X is selected from C1 to C 10 Straight chain alkyl, C3 to C 10 Branched alkyl, C3 to C 10 Cyclic alkyl, C2 to C 10 Alkenyl, C2 to C 10 Alkynyl, C4 to C 10 Aryl, C1 to C 10 Acyl, amine (-NR 1 R 2 ), H, Cl, Br, I, F, C2 to C 12 Carboxylate group, C1 to C 10 Straight-chain or branched alkoxy, trimethylsiloxy, dimethylsiloxy, methylsiloxy and siloxy.

[0235] 14. A method for depositing a film comprising silicon and oxygen onto a substrate, the method comprising the steps of:

[0236] a) providing a substrate in a reactor;

[0237] b) introducing into the reactor at least one silicon precursor compound selected from the group consisting of formula A, B, C, D and E,

[0238]

[0239] in,

[0240] R 1 Select from C1 to C 10 Straight chain alkyl, C3 to C 10 Branched alkyl, C3 to C10 Cyclic alkyl, C3 to C 10 Heterocyclic group, C3 to C 10 Alkenyl, C3 to C 10 Alkynyl and C4 to C 10 Aryl;

[0241] R 2 Selected from hydrogen, C1 to C 10 Straight chain alkyl, C3 to C 10 Branched alkyl, C3 to C 10 Cyclic alkyl, C3 to C 10 Heterocyclic group, C3 to C 10 Alkenyl, C3 to C 10 Alkynyl and C4 to C 10 Aryl, where R 1 and R 2 connected to form an annular ring structure or not connected to form an annular ring structure;

[0242] R 3-10 are independently selected from hydrogen, C1 to C 10 Straight chain alkyl, C3 to C 10 Branched alkyl, C3 to C 10 Cyclic alkyl, C2 to C 10 Alkenyl, C2 to C 10 Alkynyl and C4 to C 10 Aryl;

[0243] X is selected from C1 to C 10 Straight chain alkyl, C3 to C 10 Branched alkyl, C3 to C 10 Cyclic alkyl, C2 to C 10 Alkenyl, C2 to C 10 Alkynyl, C4 to C 10 Aryl, C1 to C 10 Acyl, amine (-NR 1 R 2 ), H, Cl, Br, I, F, C2 to C 12 Carboxylate group, C1 to C 10 A straight chain or branched alkoxy group, a trimethylsilyloxy group, a dimethylsilyloxy group, a methylsilyloxy group or a silyloxy group, wherein R 1 Connected to X to form a cyclic ring or not connected to form a cyclic ring;

[0244] c) purging the reactor with a purge gas;

[0245] d) introducing at least one of an oxygen-containing source and a nitrogen-containing source into the reactor; and

[0246] e) purging the reactor with the purge gas,

[0247] wherein steps b to e are repeated until a film of desired thickness is deposited; and wherein the method is carried out at one or more temperatures in the range of about 25°C to 600°C.

[0248] 15. The method according to item 14, wherein R 1-10 Each is independently selected from hydrogen and C1-C4 alkyl.

[0249] 16. A method according to item 14, wherein the at least one silicon precursor compound is selected from 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. Siloxane, 2-isopropylamino-2,4,4,6,6,8,8-heptamethylcyclotetrasiloxane, 2-dimethylamino-2,4,6-trimethylcyclotrisiloxane, 2-diethylamino-2,4,6-trimethylcyclotrisiloxane, 2-ethylmethylamino-2,4,6-trimethylcyclotrisiloxane, 2-isopropylamino-2,4,6-trimethylcyclotrisiloxane, 2-dimethylamino-2,4,6,8-tetramethylcyclotetrasiloxane, 2-diethylamino-2,4,6,8-tetramethylcyclotetrasiloxane, 2-ethylmethylamino-2,4,6,8-tetramethylcyclotetrasiloxane and 2-isopropylamino-2,4,6,8-tetramethylcyclotetrasiloxane.

[0250] 17. The method according to item 14, wherein the at least one silicon precursor compound is selected from 1-dimethylamino-1,1,3,3,5,5-hexamethyl-5-methoxytrisiloxane, 1-dimethylamino-1,1,3,3,5,5,7,7-octamethyl-7-methoxytetrasiloxane, 1-dimethylamino-1,1,3,3,5,5-hexamethyl-5-acetoxytrisiloxane, 1-dimethylamino-1,1,3,3,5,5,7,7-octamethyl-7-acetoxytetrasiloxane, 1-dimethylamino-1,1,3,3,5,5,7,7-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-octamethyl-7-acetoxytetrasiloxane, 1-dimethylamino-1,1,3,3,5,5,7,7-octamethyltetrasiloxane, 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-3,3,5,5,7,7,7-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.

[0251] 18. The method according to any one of items 14 to 17, wherein the silicon precursor compound further comprises at least one selected from a solvent and an inert gas.

[0252] 19. A film containing silicon and oxygen comprising at least one of the following characteristics: a density of at least about 2.1 g / cc; a carbonyl content of less than about 0.1 g / cc as measured in a dilute HF acid solution of 1:100 HF to water (0.5 wt % dHF); Wet etch rate; less than about 1e-8A / cm at up to 6MV / cm 2 leakage; and less than about 5e20 at / cc hydrogen impurities as measured by secondary ion mass spectrometry (SIMS).

[0253] 20. A stainless steel container containing the composition according to any one of items 1 to 8.

[0254] 21. The stainless steel container according to item 20, further comprising an inert headspace gas selected from the group consisting of helium, argon, nitrogen and combinations thereof.

[0255] The following examples are provided to illustrate certain aspects of the invention and should not be construed to limit the scope of the appended claims.

[0256] Working Example

[0257] Thermal atomic layer deposition of silicon oxide film was performed on a laboratory-scale ALD processing device. Silicon precursor was delivered to the chamber by vapor extraction. All gases (such as purge and reactant gases or precursors and oxygen sources) were preheated to 100°C before entering the deposition area. The flow rates of gases and precursors were controlled with an ALD diaphragm valve with high-speed actuation. The substrate used for deposition was a 12-inch long silicon strip. A thermocouple was connected to the sample holder to confirm the substrate temperature. Ozone was used as the oxygen source gas for deposition. The normal deposition process and parameters are shown in Table 2.

[0258] Table 2: Thermal atomic layer deposition of silicon oxide films using ozone as the oxygen source on a lab-scale ALD process Craftsmanship.

[0259]

[0260]

[0261] Plasma enhanced ALD (PEALD) was performed on a commercial side flow reactor (300mm PEALD equipment manufactured by ASM) equipped with a 27.1MHz direct plasma capability and a fixed spacing of 3.5mm between electrodes or a showerhead reactor (300mm PEALD equipment manufactured by ASM) equipped with a 13.56MHz direct plasma capability. The laminar flow chamber design utilizes an outer chamber and an inner chamber with independent pressure settings. The inner chamber is a deposition reactor in which all reactant gases (e.g., precursors, argon) are mixed in a manifold and delivered to the process reactor. Argon is used to maintain the reactor pressure in the outer chamber. The showerhead chamber has only one chamber, and it is usually operated at 2 Torr. The precursor is a liquid maintained at room temperature in a stainless steel bubbler and delivered to the chamber with an Ar carrier gas (usually set to a 200sccm flow) or steam suction. All depositions reported in this study were completed on 8-12Ohm-cm native oxide-containing Si substrates. The thickness and refractive index of the film are measured using a FilmTek 2000SE ellipsometer by fitting the reflection data from the film to a preset physical model (e.g., a Lorentz oscillator model). The growth rate per cycle is calculated by dividing the measured thickness of the resulting silicon oxide film by the total number of ALD / PEALD cycles. Wet etch rate (WER) measurements are performed using a 1:99 diluted hydrofluoric acid (HF) solution. Thermal oxide wafers are used as standards for each set of experiments to confirm the activity of the etching solution. Before starting to collect the WER of the bulk film, the sample is fully etched for 15 seconds to remove any surface layers. With this procedure, a typical thermal oxide wafer wet etch rate for a 1:99 dHF aqueous solution is All density measurements were measured by the X-ray reflectivity (XRR) method. Compositional analysis was performed using secondary ion mass spectroscopy (D-SIMS) or X-ray photoelectron spectroscopy (XPS).

[0262] Example 1a. Synthesis of 2-dimethylamino-2,4,6,8-tetramethylcyclotetrasiloxane.

[0263] A solution of 2-chloro-2,4,6,8-tetramethylcyclotetrasiloxane (prepared by the reaction of phosphorus pentachloride with an excess of 2,4,6,8-tetramethylcyclotetrasiloxane) containing 2.4 mmol in Et2O (5 mL) was added dropwise to 1 equivalent of dimethylamine and triethylamine in hexane. The resulting white slurry was stirred for 1 hour. The reaction mixture was filtered to remove solids and low-boilers 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.

[0264] Example 1b. Synthesis of 2-dimethylamino-2,4,6,8-tetramethylcyclotetrasiloxane.

[0265] At room temperature, THF (200 mL) / Ru3(CO) 12 To a stirred solution of 2-dimethylamino-2,4,6,8-tetramethylcyclotetrasiloxane (1.12 g, 0.00172 mol) and 2,4,6,8-tetramethylcyclotetrasiloxane (192 g, 0.792 mol) was added a dimethylamine solution (176 mL, 2.0 M solution) in THF in 4 portions, with a time interval of 1 hour for each portion. The reaction solution was stirred continuously overnight at room temperature. The solvent was removed under reduced pressure, and the crude product was purified by fractional distillation to provide 56 g of 2-dimethylamino-2,4,6,8-tetramethylcyclotetrasiloxane with a purity of 98% by GC analysis.

[0266] Example 1c. Thermal stability of 2-dimethylamino-2,4,6,8-tetramethylcyclotetrasiloxane.

[0267] 2-Dimethylamino-2,4,6,8-tetramethylcyclotetrasiloxane was heated at 80° C. for 7 days. The content of 2-dimethylamino-2,4,6,8-tetramethylcyclotetrasiloxane was measured to decrease from 96.41% to an average of 96.02%, demonstrating that 2-dimethylamino-2,4,6,8-tetramethylcyclotetrasiloxane has excellent thermal stability and is suitable as a precursor for a vapor deposition process.

[0268] Example 2. Synthesis of 2-diethylamino-2,4,6,8-tetramethylcyclotetrasiloxane.

[0269] 2,4,6,8-Tetramethylcyclotetrasiloxane (308 g, 1.28 mol), diethylamine (34.3 g, 0.469 mol) and Ru3(CO) 12 Catalyst solid (1.36g, 0.00213mol) is combined in an evacuated 500mL round-bottom flask and stirred at room temperature for three days under nitrogen atmosphere protection. The orange-red liquid phase is poured out from the insoluble catalyst solid. The reaction is repeated and two batches are merged. Excess 2,4,6,8-tetramethylcyclotetrasiloxane is removed by vacuum distillation (10 Torr / 36-38°C), and the remaining orange-red crude product is vacuum transferred from the residual catalyst by flask to flask. The collected colorless liquid is purified by vacuum distillation (1 Torr / 65°C) to provide 128g of 2-diethylamino-2,4,6,8-tetramethylcyclotetrasiloxane, and the purity is 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.

[0270] Example 3. Synthesis of 2-ethylmethylamino-2,4,6,8-tetramethylcyclotetrasiloxane (prophetic).

[0271] 2,4,6,8-Tetramethylcyclotetrasiloxane (3 equivalents), ethylmethylamine (1 equivalent) and Ru3(CO) 12 Catalyst solid (0.01 equivalent) merges, and under the protection of nitrogen atmosphere, stirs at room temperature for 1-3 days, exhausts simultaneously.Orange-red liquid phase is poured out from any insoluble catalyst solid.Excess 2,4,6,8-tetramethylcyclotetrasiloxane is removed by vacuum distillation, and the remaining orange-red crude product is vacuum transferred from residual catalyst by flask to flask transfer.Then the colorless liquid collected by vacuum distillation purification is provided to provide the desired product 2-ethylmethylamino-2,4,6,8-tetramethylcyclotetrasiloxane.

[0272] Example 4. Synthesis of 2-isopropylamino-2,4,6,8-tetramethylcyclotetrasiloxane (prophetic).

[0273] 2,4,6,8-Tetramethylcyclotetrasiloxane (3 equivalents), isopropylamine (0.3 equivalents) and Ru3(CO) 12Catalyst solid (0.01 equivalent) merges, and under the protection of nitrogen atmosphere, stirs at room temperature for 1 hour, exhausts simultaneously.Add 0.3 equivalent of isopropylamine again, and stir the reaction for 1 hour again.Add 0.3 equivalent of isopropylamine again, and make the reaction mixture stir overnight.Orange-red liquid phase pours out from any insoluble catalyst solid.Excess 2,4,6,8-tetramethylcyclotetrasiloxane is removed by vacuum distillation, and the remaining orange-red crude product is vacuum transferred from residual catalyst by flask to flask transfer.Then the colorless liquid collected by vacuum distillation purification is to provide the desired product 2-isopropylamino-2,4,6,8-tetramethylcyclotetrasiloxane.

[0274] Example 5. Synthesis of 1-dimethylamino-1,1,3,3,5,5,7,7-octamethyltetrasiloxane.

[0275] 1,1,3,3,5,5,7,7-octamethyltetrasiloxane (1.00 g of 80% pure octamethylcyclotetrasiloxane material, 0.00283 mol), a 2.0 M solution of dimethylamine in THF (1.76 mL, 0.00352 mol) and Ru3(CO) 12 (0.04 g, 6.0 × 10 -5 mol) were combined in an evacuated 20 mL scintillation tube and stirred at room temperature for 1 day under the protection of a nitrogen atmosphere. The resulting deep 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 main 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.

[0276] Comparative Example 6a: Thermal Atomic Layer Deposition of Silicon Oxide Film Using 2,4,6,8-Tetramethylcyclotetrasiloxane (TMCTS)

[0277] Atomic layer deposition of silicon oxide films was attempted using the following precursor: TMCTS. Deposition was performed on a lab scale ALD processing tool. The silicon precursor was delivered to the chamber by vapor pumping. The deposition process and parameters are provided in Table 2. Steps 1 to 6 were repeated for 200 to 250 cycles. For these depositions, almost no real film deposition was obtained. The process parameters and results of the deposition are provided in Table 3.

[0278] Table 3. Thermal ALD deposition parameters and deposition results using TMCTS.

[0279]

[0280] Example 6b: Thermal atomic layer deposition of silicon oxide films using 2-dimethylamino-2,4,6,8-tetramethylcyclotetrasiloxane.

[0281] Atomic layer deposition of silicon oxide films was performed using the following precursor: 2-dimethylamino-2,4,6,8-tetramethylcyclotetrasiloxane. Deposition was performed on a lab-scale ALD processing tool. The silicon precursor was delivered to the chamber by vapor pumping. The deposition process and parameters are provided in Table 2. Steps 1 to 6 were repeated until the desired thickness was reached. Figure 1 The saturation curve of the GPC of 2-dimethylamino-2,4,6,8-tetramethylcyclotetrasiloxane versus the number of precursor pulses is shown. 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 provided in Table 4.

[0282] Table 4. Thermal ALD deposition temperature of 2-dimethylamino-2,4,6,8-tetramethylcyclotetrasiloxane and ozone process GPC and membrane properties.

[0283]

[0284] Comparative Example 7a. PEALD silicon oxide using TMCTS (2,4,6,8-tetramethylcyclotetrasiloxane) in a laminar flow reactor with a 27.1 MHz plasma.

[0285] Deposition was performed with TMCTS and O2 plasma as silicon precursor under the conditions given in Table 5. TMCTS was delivered to the chamber by a vapor pumping method without using a carrier gas. Steps b to e were repeated multiple times to obtain the desired thickness of silicon oxide for metering. Table 6 shows the film deposition parameters and the deposition GPC and wafer uniformity. The deposited wafers showed poor uniformity and the GPC did not show saturation with increasing precursor pulses, indicating CVD deposition of TMCTS and therefore not suitable as an ALD precursor.

[0286] Table 5. Process for PEALD silicon oxide deposition in a commercial side stream PEALD reactor using TMCTS.

[0287]

[0288]

[0289] Table 6. PEALD silicon oxide film deposition parameters and deposition GPC and wafer uniformity using TMCTS.

[0290]

[0291] The uniformity data in Table 6 indicate that TMCTS undergoes CVD and is not suitable for use as a precursor for an ALD process.

[0292] Example 7b. PEALD of silicon oxide using 2-dimethylamino-2,4,6,8-tetramethylcyclotetrasiloxane in a laminar flow reactor with a 27.1 MHz plasma.

[0293] Deposition was performed using 2-dimethylamino-2,4,6,8-tetramethylcyclotetrasiloxane as a silicon precursor and O2 plasma under the conditions described in Table 5 above. The precursor was delivered to the chamber with a carrier gas Ar flow of 200 sccm. Steps b to e were repeated multiple times to obtain silicon oxide of the desired thickness for metering.

[0294] Figure 2 GPC showing relative to precursor pulse time, while Figure 3 GPC is shown for the precursor 2-dimethylamino-2,4,6,8-tetramethylcyclotetrasiloxane versus O2 plasma time. Figure 2 It can be seen that the GPC is almost saturated with a 4 second precursor pulse. Figure 3 As can be seen in Figure 7, the GPC is slightly reduced at 10 and 20 seconds of oxygen plasma time compared to 5 seconds of oxygen plasma time. The slightly reduced GPC indicates that the film is densified during the longer oxygen plasma time, which is confirmed by the lower WER and higher film density of the film deposited with more seconds of oxygen plasma time. The results are consistent with the ALD deposition behavior. Table 7 shows the film deposition parameters and deposition GPC.

[0295] Table 8 shows the film properties under different deposition conditions.

[0296] Table 7. PEALD silicon oxide film deposition parameters using 2-dimethylamino-2,4,6,8-tetramethylcyclotetrasiloxane and deposition GPC.

[0297]

[0298] Table 8. PEALD silicon oxide film deposition conditions and Membrane properties.

[0299]

[0300] The conformality of PEALD silicon oxide films deposited from 2-dimethylamino-2,4,6,8-tetramethylcyclotetrasiloxane was studied using TEM. The trench size was about 50 nm wide and about 600 nm deep. Figure 4 TEM images showing the top of the trench, the side of the middle of the trench, and the bottom of the trench. It can be seen that the film is very 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 of the Si-H groups in TMCTS with an organic amino group (such as dimethylamino) can transform TMCTS into a film with good step coverage and higher than Excellent ALD precursor with a growth rate of 1.144 W / cycle.

[0301] Example 7c. PEALD of silica using 2-diethylamino-2,4,6,8-tetramethylcyclotetrasiloxane in a laminar flow reactor with a 27.1 MHz plasma.

[0302] Deposition was performed using 2-diethylamino-2,4,6,8-tetramethylcyclotetrasiloxane as a silicon precursor and O2 plasma under the conditions described in Table 5 above. The precursor was delivered to the chamber with a carrier gas Ar flow of 200 sccm. Steps b to e were repeated multiple times to obtain the desired thickness of silicon oxide for metering.

[0303] Table 9 shows the film deposition parameters and deposition GPC. Conditions 1-6 show the deposition GPC relative to the precursor pulse time at 100°C, from which it can be seen that the GPC becomes saturated with increasing precursor pulses. Conditions 11-16 show the deposition GPC relative to the precursor pulse time at 300°C, and the GPC also becomes saturated with increasing precursor pulses. The results are consistent with the ALD deposition behavior. Conditions 8-10 show the deposition GPC relative to the oxygen plasma time at 100°C, from which it can be seen that the GPC is slightly reduced at oxygen plasma times of 10 seconds and 20 seconds compared to the oxygen plasma time of 5 seconds. The slightly reduced GPC indicates the densification of the film during the longer oxygen plasma time. The same phenomenon also exists for deposition at 300°C (see deposition conditions 18-19).

[0304] Table 9. PEALD silicon oxide film deposition parameters using 2-diethylamino-2,4,6,8-tetramethylcyclotetrasiloxane and deposition GPC.

[0305]

[0306]

[0307] Comparative Example 8a. PEALD silicon oxide using TMCTS (2,4,6,8-tetramethylcyclotetrasiloxane) in a showerhead reactor with a 13.56 MHz plasma.

[0308] Deposition was performed with TMCTS and O2 plasma as silicon precursor in a showerhead reactor with 13.56 MHz plasma under the conditions given in Table 5. TMCTS was delivered to the chamber by a vapor pumping method without using a carrier gas. Steps b to e were repeated multiple times to obtain the desired thickness of silicon oxide for metering. Figure 5 GPC is shown versus precursor pulse time. As can be seen, the GPC does not show saturation with increasing precursor pulses. The deposited films show a wafer uniformity of 4-11%. Figure 6The conformality of the TMCTS silicon oxide film deposited with a 16 second precursor pulse is shown. It can be seen that the film is not conformal in the trenches, i.e. the thickness of the silicon oxide on the bottom of the trench is much higher than at the top or middle of the trench, demonstrating that CVD occurs, especially on the bottom of the trench.

[0309] Example 8b. PEALD of silicon oxide using 2-dimethylamino-2,4,6,8-tetramethylcyclotetrasiloxane in a showerhead chamber with a 13.56 MHz plasma.

[0310] Deposition was performed with 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 delivered to the chamber with a carrier gas flow. Steps b to e were repeated multiple times to obtain the desired thickness of silicon oxide for metrology. Table 10 shows the film deposition parameters and deposition GPC and wafer uniformity. Figure 7 Figure 1 shows the conformality of silicon oxide deposited in the showerhead chamber. The film is very conformal in the trenches, indicating ALD deposition. Unlike TMCTS, replacing one of the Si-H groups in TMCTS with an organic amino group (such as dimethylamino) can transform TMCTS into a film with good step coverage and higher than Excellent ALD precursor with a growth rate of 1.144 W / cycle.

[0311] Table 10. PEALD Oxidation Using 2-Dimethylamino-2,4,6,8-Tetramethylcyclotetrasiloxane in a Showerhead Chamber Silicon film deposition parameters and deposition GPC.

[0312]

[0313] Example 8c. PEALD silicon oxide (prophetic) using 1-dimethylamino-1,1,3,3,5,5,7,7-octamethyltetrasiloxane in a showerhead chamber with a 13.56 MHz plasma.

[0314] Deposition was performed using 1-dimethylamino-1,1,3,3,5,5,7,7-octamethyltetrasiloxane as a silicon precursor and O2 plasma in a showerhead chamber with a 13.56 MHz plasma at temperatures ranging from 100°C to 300°C under conditions similar to those given in Table 5. The precursor was delivered to the chamber with a carrier gas flow. Steps b to e were repeated multiple times to obtain the desired thickness of silicon oxide for metering. Unlike 1,1,3,3,5,5,7,7-octamethyltetrasiloxane, replacing one Si-H group with an organic amino group (such as dimethylamino) can convert an otherwise non-reactive linear oligosiloxane into a polysiloxane with good step coverage and above 100 Å. Excellent ALD precursor with a growth rate of 1.144 W / cycle.

[0315] Example 9: PEALD of silicon oxide using 2-dimethylamino-2,4,6,8-tetramethylcyclotetrasiloxane at 50°C in a laminar flow reactor with a 27.1 MHz plasma.

[0316] Deposition was performed using 2-dimethylamino-2,4,6,8-tetramethylcyclotetrasiloxane as a silicon precursor and O2 plasma under the conditions described in Table 5 above. The substrate temperature was 50°C. The precursor was delivered to the chamber with a carrier gas Ar flow of 200 sccm. Steps b to e were repeated multiple times to obtain the desired thickness of silicon oxide for metering. With a precursor pulse of 4 seconds, a reactor pressure of 3 Torr, a plasma power of 200 W, and a plasma time of 5 seconds, a deposition rate of 1000 W was obtained. The WER in 0.5 wt% HF is about 10 relative to the etch rate of thermally grown silicon oxide.

[0317] Although the present disclosure has been described with reference to certain preferred embodiments, it will be appreciated by those skilled in the art that various changes may be made and elements thereof may be replaced by equivalents without departing from the scope of the present invention. In addition, many modifications may be made to adapt specific situations or materials to the teachings of the present invention without departing from the essential scope of the present invention. Therefore, it is intended that the present invention is not limited to particular embodiments, but that the present invention will include all embodiments falling within the scope of the appended claims.

Claims

1. A method for depositing a film containing silicon and oxygen by flowable chemical vapor deposition (FCVD), the method comprising: placing a substrate comprising surface features in a reactor, wherein the substrate is maintained at one or more temperatures in the range of -20°C to 400°C and the pressure of the reactor is maintained at 100 Torr or less; Introducing into the reactor at least one compound selected from formulae A to E: in, R 1 Select from C1 to C 10 Straight chain alkyl, C3 to C 10 Branched alkyl, C3 to C 10 Cyclic alkyl, C3 to C 10 Heterocyclic group, C3 to C 10 Alkenyl, C3 to C 10 Alkynyl and C4 to C 10 Aryl; R 2 Selected from hydrogen, C1 to C 10 Straight chain alkyl, C3 to C 10 Branched alkyl, C3 to C 10 Cyclic alkyl, C3 to C 10 Heterocyclic group, C3 to C 10 Alkenyl, C3 to C 10 Alkynyl and C4 to C 10 Aryl, where R 1 and R 2 connected to form an annular ring structure or not connected to form an annular ring structure; R 3-10 are independently selected from hydrogen, C1 to C 10 Straight chain alkyl, C3 to C 10 Branched alkyl, C3 to C 10 Cyclic alkyl, C3 to C 10 Alkenyl, C3 to C 10 Alkynyl and C4 to C 10 Aryl; X is selected from C1 to C 10 Straight chain alkyl, C3 to C 10 Branched alkyl, C3 to C 10 Cyclic alkyl, C2 to C 10 Alkenyl, C2 to C 10 Alkynyl, C4 to C 10 Aryl, C1 to C 10 Acyl, -NR 1 R 2 ,H,Cl,Br,I,F,C2 to C 12 Carboxylate group, C1 to C 10 a straight-chain or branched alkoxy group, a trimethylsiloxy group, a dimethylsiloxy group, a methylsiloxy group or a siloxy group, Where R 1 Connected to X to form a cyclic ring or not connected to form a cyclic ring; providing an oxygen source, a nitrogen source, or an oxygen source and 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 feature; annealing the film at one or more temperatures of 100°C to 1000°C to coat at least a portion of the surface features; and The substrate is treated with an oxygen source at one or more temperatures in the range of 20° C. to 1000° C. to form a film comprising silicon and oxygen on at least a portion of the surface features.

2. The method according to claim 1, wherein R 2-10 Each is independently selected from hydrogen and C1 to C4 alkyl.

3. The method according to claim 1, wherein 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. Siloxane, 2-isopropylamino-2,4,4,6,6,8,8-heptamethylcyclotetrasiloxane, 2-dimethylamino-2,4,6-trimethylcyclotrisiloxane, 2-diethylamino-2,4,6-trimethylcyclotrisiloxane, 2-ethylmethylamino-2,4,6-trimethylcyclotrisiloxane, 2-isopropylamino-2,4,6-trimethylcyclotrisiloxane, 2-dimethylamino-2,4,6,8-tetramethylcyclotetrasiloxane, 2-diethylamino-2,4,6,8-tetramethylcyclotetrasiloxane, 2-ethylmethylamino-2,4,6,8-tetramethylcyclotetrasiloxane and 2-isopropylamino-2,4,6,8-tetramethylcyclotetrasiloxane.

4. The method according to claim 1, wherein the at least one 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-methoxytetrasiloxane, 1-dimethylamino-1,1,3,3,5,5-hexamethyl-5-acetoxytrisiloxane, 1-dimethylamino-1,1,3,3,5,5,7,7-octamethyl-7-acetoxytetrasiloxane, 1-dimethylamino-1,1,3,3,5,5,7,7-nonamethyltetrasiloxane, 1-dimethylamino-1,1,3,3,5,5,7,7,9,9,9-undecamethylpentasiloxane, 1-dimethylamino-1,1,3,3,5,5,7,7,9,9,9-undecylpentasiloxane, Amino-1,1,3,3,5,5,7,7-octamethyltetrasiloxane, 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-3,3,5,5,7,7,7-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.

5. The method of claim 1, wherein the substrate is maintained at one or more temperatures in the range of -20°C to 40°C.

6. The method of claim 1, wherein the substrate is maintained at one or more temperatures in the range of -10°C to 25°C.

7. The process according to claim 1, wherein only an oxygen source is provided to the reactor, wherein the oxygen source is selected from the group consisting of water vapor, water plasma, ozone, oxygen, oxygen plasma, oxygen / helium plasma, oxygen / argon plasma, nitrogen oxide plasma, carbon dioxide plasma, hydrogen peroxide, organic peroxides and mixtures thereof.

8. The process according to claim 1, wherein only a nitrogen source is provided to the reactor, wherein the nitrogen source is selected from the group consisting of ammonia, hydrazine, nitrogen, nitrogen / hydrogen, nitrogen / argon plasma, nitrogen / helium plasma, ammonia plasma, nitrogen plasma, nitrogen / hydrogen plasma, tert-butylamine, dimethylamine, diethylamine, isopropylamine, diethylamine plasma, dimethylamine plasma, ethylenediamine plasma, ethanolamine plasma, and mixtures thereof.

9. The method of claim 8, wherein the nitrogen source is ammonia plasma, nitrogen / argon, nitrogen / helium plasma or nitrogen / hydrogen plasma.

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.

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