JP2023520226A - Cyclic oligosiloxanes with organoamino functional groups for the deposition of silicon-containing thin films - Google Patents

Abstract

Disclosed are cyclic oligosiloxanes having amino functional groups having at least 3 silicon atoms and 3 oxygen atoms and at least one organic amino group, and methods of making the oligosiloxanes. A method for depositing silicon- and oxygen-containing thin films using cyclic oligosiloxanes with organoamino functional groups is also disclosed. [Selection drawing] Fig. 1

Description

Related Art This continuation-in-part application is based on U.S. Provisional Application No. 16/838,997, filed Apr. 2, 2020 and U.S. Provisional Application No. 17/030, filed Sep. 23, 2020. Claim 187 benefits. The disclosures of Application Nos. 16/838,997 and 17/030,187 are incorporated herein by reference.

The present invention is an organosilicon that can be used to deposit silicon and oxygen containing thin films (e.g., silicon oxides, silicon oxycarbonitrides, silicon oxycarbides, carbon-doped silicon oxides, among other silicon and oxygen containing films). The present invention relates to compounds, methods of using compounds to deposit silicon oxide-containing thin films, and thin films resulting from said compounds and methods.

Novel cyclic oligosiloxane precursor compounds with organoamino functional groups and silicon oxides, including but not limited to, by thermal atomic layer deposition (ALD) or plasma enhanced atomic layer deposition (PEALD) methods, or combinations thereof Described herein are compositions and methods for depositing silicon-containing thin films such as silicon oxynitride, silicon oxycarbonitride, or carbon-doped silicon oxide. More specifically, compositions 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. and methods are described herein.

Atomic layer deposition (ALD) and plasma enhanced atomic layer deposition (PEALD) are methods used to deposit, for example, silicon oxide conformal thin films at low temperatures (<500° C.). In both ALD and PEALD processes, the precursor and reactive gas (such as oxygen or ozone) are individually pulsed in a specified number of cycles to form a monolayer of silicon oxide in each cycle. However, silicon oxides deposited at low temperatures using these methods may contain certain levels of impurities such as, but not limited to, carbon (C) or hydrogen (H), which may result in certain It can be harmful in semiconductor applications. To remedy this, one possible solution is to increase the deposition temperature above 500°C. However, at these high temperatures, conventional precursors used by the semiconductor industry tend to self-react, thermally decompose, and deposit in chemical vapor deposition (CVD) mode rather than ALD mode. CVD mode deposition is less conformal compared to ALD deposition, especially for the high aspect ratio structures required in many semiconductor applications. In addition, CVD mode deposition does not provide better control of thin film or material thickness than ALD mode deposition.

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

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

US Pat. No. 7,084,076 (B2) describes the use of halogen- or NCO-substituted disiloxane precursors for depositing silicon oxide thin films for use in base-catalyzed ALD processes.

US Patent Application Publication No. 2015/087139 AA describes the use of carbosilanes with amino functional groups for depositing silicon-containing thin films by thermal ALD or PEALD methods.

US Pat. No. 9,337,018 (B2) describes the use of organoaminodisilanes for depositing silicon-containing thin films by thermal ALD or PEALD methods.

US Pat. Nos. 8,940,648(B2) and 8,912,353(B2) describe the use of organoaminosilanes for depositing silicon-containing thin films by thermal ALD or PEALD methods. is described.

US Patent Application Publication No. 2015/275355 (AA) describes the use of mono- and bis(organoamino)alkylsilanes for depositing silicon-containing thin films by thermal ALD or PEALD methods.

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

WO 15/105337 and US Pat. No. 9,245,740 B2 describe the use of alkylated trisilylamines for depositing silicon-containing thin films by thermal ALD or PEALD methods. ing.

WO 15/105350 describes the use of four-membered ring cyclodisilazanes with at least one SH bond for depositing silicon-containing thin films by thermal ALD or PEALD methods.

US Pat. No. 7,084,076 (B2) describes the use of halogen- or NCO-substituted disiloxane precursors for depositing silicon oxide thin films for use in base-catalyzed ALD processes.

U.S. Patent Application Publication No. 2018/223047(A) discloses a direct amino functional group having at least two silicon atoms and two oxygen atoms and an organic amino group for depositing silicon and oxygen containing thin films. Chain and cyclic oligosiloxanes are disclosed.

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

Despite the above developments, there is a need in the art for precursors and methods for depositing silicon oxide-containing thin films at high growth per cycle (GPC) to maximize throughput in semiconductor fabrication facilities. Although certain precursors can be deposited with GPC of >2.0 Å/cycle, these precursors are associated with, among other things, low quality films (elemental impurities, low density, poor electrical properties, high wet etch rates), high It has drawbacks such as process temperature, requires a catalyst, is expensive, and produces low conformal thin films.

The present development relates to silicon- and oxygen-containing precursors, in particular cyclic oligosiloxanes with organoamino functional groups, containing at least three silicon atoms and three oxygen atoms and part of a method for depositing silicon- and oxygen-containing thin films. By providing a silicon- and oxygen-containing precursor, particularly a cyclic oligosiloxane having an organic amino functional group, which has at least one organic amino group that serves to anchor the cyclic oligosiloxane compound to the substrate surface as a to solve the problems associated with precursors and methods of The multi-silicon precursors disclosed in the present invention have a novel structure compared to those described in the background section above, thus reducing the cost or simplicity of precursor synthesis, thermal stability, It may provide advantages in one or more aspects of either the physical properties of the precursor, including reactivity or volatility, the method of depositing the silicon-containing thin film, or the properties of the deposited silicon-containing thin film.

から成る群から選択される化合物であって、 A composition comprising a cyclic oligosiloxane compound having at least one organoamino functional group, said compound having formulas AD:

A compound selected from the group consisting of

In Formulas A to D above, R ¹ is a linear C ₁ to C ₁₀ alkyl group, a branched C ₃ to C ₁₀ alkyl group, a C ₃ to C ₁₀ cyclic alkyl group, a C ₃ to C ₁₀ heterocyclic group. , C ₃ -C ₁₀ alkenyl groups, C ₃ -C ₁₀ alkynyl groups, and C ₄ -C ₁₀ aryl groups; R ² is hydrogen, C ₁ -C ₁₀ straight chain alkyl groups, branched chain C ₃ -C ₁₀ alkyl groups, C ₃ -C ₁₀ cyclic alkyl groups, C ₃ -C ₁₀ heterocyclic groups, C ₃ -C ₁₀ alkenyl groups, C ₃ -C ₁₀ alkynyl groups, and C ₄ -C ₁₀ are selected from the group consisting of aryl groups, wherein R ¹ and R ² are either joined to form a cyclic ring structure or are not joined to form a cyclic ring structure; R ^3-11 are , hydrogen, straight chain C ₁ -C ₁₀ alkyl groups, branched chain C ₃ -C ₁₀ alkyl groups, C ₃ -C ₁₀ cyclic alkyl groups, C ₂ -C ₁₀ alkenyl groups, C ₂ -C ₁₀ alkynyl groups, C ₄ -C ₁₀ aryl groups, and organic amino groups, NR ¹ R ² , R ¹ and R ² are each independently selected from the group consisting of as defined above; n=1, 2, or 3, and m = 2 or 3,
Compositions comprising the compounds are disclosed herein.

Plasma Enhanced ALD (PEALD), Plasma Enhanced Cyclic Chemical Vapor Deposition (PECCVD), Fluid Chemical Vapor Deposition (FCVD), Plasma Enhanced Fluid Chemical Vapor Deposition (PEFCVD), Plasma Enhanced ALD-like Process, or Oxygen-Containing Reactant, Nitrogen In an ALD process using the contained reactants, or combinations thereof, at relatively low temperatures, such as one or more temperatures below 600° C., including but not limited to silicon oxide, carbon-doped silicon oxide, silicon oxynitride thin films , or carbon-doped silicon oxynitride thin films, are described herein.

から成る群から選択される少なくとも１種のシリコン前駆体化合物であって、 In one aspect, a method of depositing a thin film comprising silicon and oxygen on a substrate, the method comprising: (a) providing a substrate in a reactor; (b) in the reactor; Formulas AD:

at least one silicon precursor compound selected from the group consisting of

In Formulas A to D above, R ¹ is a linear C ₁ to C ₁₀ alkyl group, a branched C ₃ to C ₁₀ alkyl group, a C ₃ to C ₁₀ cyclic alkyl group, a C ₃ to C ₁₀ heterocyclic group. , C ₃ -C ₁₀ alkenyl groups, C ₃ -C ₁₀ alkynyl groups, and C ₄ -C ₁₀ aryl groups; R ² is hydrogen, C ₁ -C ₁₀ straight chain alkyl groups, branched chain C ₃ -C ₁₀ alkyl groups, C ₃ -C ₁₀ cyclic alkyl groups, C ₃ -C ₁₀ heterocyclic groups, C ₃ -C ₁₀ alkenyl groups, C ₃ -C ₁₀ alkynyl groups, and C ₄ -C ₁₀ are selected from the group consisting of aryl groups, wherein R ¹ and R ² are either joined to form a cyclic ring structure or are not joined to form a cyclic ring structure; R ^3-11 are , hydrogen, straight chain C ₁ -C ₁₀ alkyl groups, branched chain C ₃ -C ₁₀ alkyl groups, C ₃ -C ₁₀ cyclic alkyl groups, C ₂ -C ₁₀ alkenyl groups, C ₂ -C ₁₀ alkynyl groups, C ₄ -C ₁₀ aryl groups, and organic amino groups, NR ¹ R ² , R ¹ and R ² are each independently selected from the group consisting of as defined above; n=1, 2, or 3, and m = 2 or 3,
(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 (d) the reaction. purging the vessel with said purge gas; repeating steps b through e until the desired thickness of the film has been deposited; and conducting said method at one or more temperatures ranging from about 25°C to 600°C. , process and
A method is disclosed herein comprising:

Also disclosed herein are methods of making the above compounds. Embodiments of the invention can be used singly or in combination with each other.

FIG. 1 shows bis(dimethylamino)-2,4,6,8-tetramethylcyclotetrasiloxane and 2-dimethylamino-2,4,6,8,10-pentamethylcyclopentasiloxane according to the invention and 1 is a graph of a GPC saturation curve versus precursor pulse time using a prior art BDEAS; FIG. 2 shows thin film GPC and WER versus O ₂ plasma power with bis(dimethylamino)-2,4,6,8-tetramethylcyclotetrasiloxane at 300° C. deposition according to the present invention. FIG. 3 shows thin film GPC and WER versus O ₂ plasma power with bis(dimethylamino)-2,4,6,8-tetramethylcyclotetrasiloxane at 100° C. deposition according to the present invention. FIG. 4 shows thin film GPC and WER versus O ₂ plasma time using bis(dimethylamino)-2,4,6,8-tetramethylcyclotetrasiloxane at 300° C. deposition according to the present invention. FIG. 5 shows thin film GPC and WER versus O ₂ plasma time using bis(dimethylamino)-2,4,6,8-tetramethylcyclotetrasiloxane at 100° C. deposition according to the present invention.

In the context of the description of the present invention (especially in the context of the claims that follow), the terms "a" and "an" and "the" and similar referents are used unless otherwise indicated herein or by context. Unless contradicted, it should be construed to include both the singular and the plural. Unless otherwise specified, the terms “comprising,” “having,” “including,” and “containing” are open-ended terms (i.e., “including but not limited to (meaning "without limitation"). Recitation of ranges of values herein is merely intended to serve as a shorthand method of referring to each individual value within the range, unless otherwise indicated herein, and each individual value are incorporated herein as if set forth individually herein. All methods described herein can be performed in any suitable order unless otherwise indicated herein or otherwise clearly contradicted by context. The use of any and all examples, or preferred language (e.g., "such as") provided herein is intended merely to better illustrate the invention, and may not otherwise appear in the claims. It is not proposed to limit the scope of the invention unless otherwise stated. No language in the specification should be construed as indicating any non-claimed element as essential to the practice of the invention.

at one or more temperatures of about 600° C. or less, or from about 25° C. to about 600° C., in embodiments from 25° C. to about 300° C., including but not limited to silicon oxide, carbon-doped silicon oxide thin films , silicon oxynitride, or carbon-doped silicon oxynitride thin films or combinations thereof, or compositions and methods related to the formation of materials containing silicon and oxygen. Describe. The thin films described herein may be deposited by, but not limited to, plasma-enhanced ALD (PEALD) or plasma-enhanced cyclic chemical vapor deposition (PECCVD), flow-enhanced chemical vapor deposition (FCVD), or plasma-enhanced flow-chemical deposition. It is deposited by a deposition method such as atomic layer deposition (ALD) or ALD-like methods such as vapor deposition (PEFCVD). Low temperature deposition (eg, one or more deposition temperatures ranging from about ambient temperature to 600° C.) methods described herein provide the following advantages: density of about 2.1 g/cc or greater, low chemical impurities, provide high conformality in thermal atomic layer deposition, plasma-enhanced atomic layer deposition (ALD) or plasma-enhanced ALD-like processes, the ability to tune the carbon content in the resulting thin film; It has an etch rate of 5 angstroms per second (Å/sec) or less when measured in 5 wt% diluted HF. 2 Å/sec in 0.5 wt % diluted HF, in addition to other characteristics such as, but not limited to, a density of about 1.8 g/cc or greater, or about 2.0 g/cc or greater, for carbon-doped silicon oxide thin films Greater than 1% carbon is desirable in order to tune the etch rate to values below.

The methods disclosed herein can be performed using equipment known in the art. For example, the method can use reactors commonly used in the semiconductor manufacturing field.

Without wishing to be bound by any theory or explanation, the effectiveness of the precursor compositions disclosed herein can vary as a function of the number of silicon atoms, particularly silicon atom bonds. The precursors disclosed herein typically have 3-8 silicon atoms and 6-16 silicon-oxygen bonds.

The precursors disclosed herein have different structures known in the art and thus can perform better than conventional silicon-containing precursors, provide relatively high GPCs, and High quality films are obtained, have favorable wet etch rates, or contain less elemental contamination.

を有する化合物であって、
前記式Ａ～Ｄ中、Ｒ^１は、直鎖Ｃ_１～Ｃ_１０アルキル基、分岐鎖Ｃ_３～Ｃ_１０アルキル基、Ｃ_３～Ｃ_１０環式アルキル基、Ｃ_３～Ｃ_１０複素環式基、Ｃ_３～Ｃ_１０アルケニル基、Ｃ_３～Ｃ_１０アルキニル基、及びＣ_４～Ｃ_１０アリール基から成る群から選択され；Ｒ^２は、水素、Ｃ_１～Ｃ_１０直鎖アルキル基、分岐鎖Ｃ_３～Ｃ_１０アルキル基、Ｃ_３～Ｃ_１０環式アルキル基、Ｃ_３～Ｃ_１０複素環式基、Ｃ_３～Ｃ_１０アルケニル基、Ｃ_３～Ｃ_１０アルキニル基、及びＣ_４～Ｃ_１０アリール基から成る群から選択され、Ｒ^１及びＲ^２は、結合して環式環構造を形成するか又は結合しないで環式環構造を形成しないかのいずれかであり；Ｒ^３～１１は、水素、直鎖Ｃ_１～Ｃ_１０アルキル基、分岐鎖Ｃ_３～Ｃ_１０アルキル基、Ｃ_３～Ｃ_１０環式アルキル基、Ｃ_２～Ｃ_１０アルケニル基、Ｃ_２～Ｃ_１０アルキニル基、Ｃ_４～Ｃ_１０アリール基、及び有機アミノ基、ＮＲ^１Ｒ^２、Ｒ^１及びＲ^２は上記に定義されている、から成る群から各々独立して選択され；ｎ＝１、２、又は３、及びｍ＝２又は３である、
化合物を含む、組成物を本明細書において開示する。 A composition for depositing a thin film selected from silicic acid, carbon-doped silicon oxide, or silicon carboxynitride thin films using vapor deposition, said composition comprising formulas A-D:

A compound having
In Formulas A to D above, R ¹ is a linear C ₁ to C ₁₀ alkyl group, a branched C ₃ to C ₁₀ alkyl group, a C ₃ to C ₁₀ cyclic alkyl group, a C ₃ to C ₁₀ heterocyclic group. , C ₃ -C ₁₀ alkenyl groups, C ₃ -C ₁₀ alkynyl groups, and C ₄ -C ₁₀ aryl groups; R ² is hydrogen, C ₁ -C ₁₀ straight chain alkyl groups, branched chain C ₃ -C ₁₀ alkyl groups, C ₃ -C ₁₀ cyclic alkyl groups, C ₃ -C ₁₀ heterocyclic groups, C ₃ -C ₁₀ alkenyl groups, C ₃ -C ₁₀ alkynyl groups, and C ₄ -C ₁₀ are selected from the group consisting of aryl groups, wherein R ¹ and R ² are either joined to form a cyclic ring structure or are not joined to form a cyclic ring structure; R ^3-11 are , hydrogen, straight chain C ₁ -C ₁₀ alkyl groups, branched chain C ₃ -C ₁₀ alkyl groups, C ₃ -C ₁₀ cyclic alkyl groups, C ₂ -C ₁₀ alkenyl groups, C ₂ -C ₁₀ alkynyl groups, C ₄ -C ₁₀ aryl groups, and organic amino groups, NR ¹ R ² , R ¹ and R ² are each independently selected from the group consisting of as defined above; n=1, 2, or 3, and m = 2 or 3,
Compositions comprising compounds are disclosed herein.

In preferred embodiments, at least one of R ^1-9 is a C ₁ -C ₄ alkyl group. Preferred embodiments include compounds of formulas AD, wherein each of R ^1-9 is either hydrogen or a C ₁ -C ₄ alkyl group.

In the above formula and throughout this specification, the term "oligosiloxane" denotes a compound containing at least two repeating -Si-O-siloxane units, preferably at least three repeating -Si-O-siloxane units, and a cyclic Alternatively, it may have a linear structure, preferably a cyclic structure.

In the above formulas and throughout this specification, the term "alkyl" denotes a straight or branched chain functional group having 1-10 carbon atoms. Preferred straight chain alkyl groups include, but are not limited to, methyl, ethyl, propyl, butyl, pentyl, and hexyl groups. Preferred branched chain alkyl groups include, but are not limited to, iso-propyl, iso-butyl, sec-butyl, tert-butyl, iso-pentyl, tert-pentyl, iso-hexyl, and neo-hexyl. In certain embodiments, an alkyl group may have one or more functional groups attached thereto such as, but not limited to, alkoxy groups, dialkylamino groups, or combinations thereof attached thereto. In other embodiments, an alkyl group does not have one or more functional groups attached to it. Alkyl groups can be saturated or unsaturated.

In the above formulas and throughout the specification, the term "cyclic alkyl" denotes a cyclic functional group having 3-10 carbon atoms. Preferred cyclic alkyl groups include, but are not limited to, cyclobutyl, cyclopentyl, cyclohexyl, and cyclooctyl groups.

In the above formulas and throughout this 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.

In the above formulas and throughout the specification, the terms "dialkylamino", "alkylamino", or "organoamino" groups refer to R ¹ R ² N- groups, wherein R ¹ is a linear C ₁ -C ₁₀ alkyl, branched C ₃ -C ₁₀ alkyl, C ₃ -C ₁₀ cyclic alkyl, C ₃ -C ₁₀ heterocyclic, C ₃ -C ₁₀ alkenyl, C ₃ -C 10 ₁₀ alkynyl groups, and C ₄ -C ₁₀ aryl groups; R ² is hydrogen, C ₁ -C ₁₀ straight chain alkyl groups, branched chain C ₃ -C ₁₀ alkyl groups, C ₃ -C ₁₀ is selected from the group consisting of cyclic alkyl groups, C ₃ -C ₁₀ heterocyclic groups, C ₃ -C ₁₀ alkenyl groups, C ₃ -C ₁₀ alkynyl groups, and C ₄ -C ₁₀ aryl groups. In some cases R ¹ and R ² are joined to form a cyclic ring structure, and in other cases R ¹ and R ² are not joined to form a cyclic ring structure. Preferred organic amino groups in which R ¹ and R ² combine to form a cyclic ring structure include pyrrolidino where R ¹ =propyl and R ² =Me, 1,2 where R ¹ =propyl and R ² =Et. -piperidino, 2,6-dimethylpiperidino where R ¹ =iso-propyl and R ² =sec-butyl, and 2,5-dimethylpyrrolidino where R ¹ =R ² =iso-propyl , but not limited to.

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

Throughout this specification, the term "alkyl hydrocarbon" refers to straight or branched chain _C1 - _C20 hydrocarbons, cyclic _C6 - _C20 hydrocarbons. Preferred hydrocarbons include, but are not limited to, heptane, octane, nonane, decane, dodecane, cyclooctane, cyclononane, and cyclodecane.

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

Throughout this specification, the term "carboxylate" refers to a _C2 - _C12 -OC(=O) ^R1 group, wherein ^R1 is as defined above. Preferred carboxylate groups include acetate (-OC(=O)Me), ethyl carboxylate (-OC(=O)Et), iso-propylcarboxylate (-OC(=O)iPr), and benzoate (- OC(=O)Ph), but not limited to;

Throughout this specification, the term "aromatic hydrocarbon" refers to _C6 - _C20 aromatic hydrocarbons. Preferred aromatic hydrocarbons include, but are not limited to toluene and mesitylene.

In the above formulas and throughout this specification, the term "heterocyclic" means from about 3 to about 10 ring atoms, wherein one or more of the atoms in the ring structure is an element other than carbon, such as nitrogen, oxygen or sulfur; Preferably, it refers to a non-aromatic saturated monocyclic or polycyclic ring structure of about 5 to about 10 ring atoms. Preferred heterocycles contain about 5 to about 6 ring atoms. The prefix aza, oxo or thio before heterocycle means that at least a nitrogen, oxygen or sulfur atom respectively is present as a ring atom. Heterocyclic groups may be optionally substituted.

Preferred organoamino functional cyclic oligosiloxanes having formulas AD are listed in Table 1:

Compounds having formulas A-D, for example, are subjected to catalytic dehydrocoupling reactions of cyclic oligosiloxanes having at least one Si—H bond with organic amines (e.g., formula 1 for cyclotetrasiloxane and others such as cyclopentasiloxane). 2) for large cyclic oligosiloxanes, or the reaction of chlorinated cyclic oligosiloxanes with organic amines or metal salts of organic amines (e.g., eq. 2 for cyclotetrasiloxanes), or organic aminosilanes and organic Catalytic hydrosilylation of imines with cyclic oligosiloxanes as described in U.S. Pat. No. 9,758,534 B2 for the synthesis of aminodisilanes, thereby replacing cyclic oligosiloxanes with silanes or disilanes. Can be synthesized by using

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

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

Preferred alkaline earth metal catalysts include: Mg[N(SiMe ₃ ) ₂ ] ₂ , ToMMgMe[ToM=tris(4,4-dimethyl-2-oxazolinyl)phenylborate], ToMMg-H, ToMMg- NR ₂ (R═H, alkyl, aryl) Ca[N(SiMe ₃ ) ₂ ] ₂ , [(dipp-nacnac)CaX(THF)] ₂ (dipp-nacnac=CH[(CMe)(2,6-iPr ₂ -C ₆ H ₃ N)] ₂ ; X═H, alkyl, carbosilyl, organic amino), Ca(CH ₂ Ph) ₂ , Ca(C ₃ H ₅ ) ₂ , Ca(α-Me ₃ Si-2- (Me ₂ N)-benzyl) ₂ (THF) ₂ , Ca(9-(Me ₃ Si)-fluorenyl)(α-Me ₃ Si-2-(Me ₂ N)-benzyl)(THF), [(Me _3TACD )3Ca3(μ3-H) ₂ ]+( _Me3TACD = _Me3 [12] _anN4 ), Ca(η2- _Ph2CNPh )(hmpa) ₃ (hmpa=hexamethylphosphoramide), Sr[ N(SiMe ₃ ) ₂ ] ₂ , dialkylmagnesium and other M ²⁺ alkaline earth metal-amides, -imines, -alkyls, -halides, and -carbosilyl complexes (M=Ca, Mg, Sr, Ba) but not limited to these.

Preferred halide-free, main group, transition metal, lanthanide, and actinide catalysts include: 1,3-di-iso-propyl-4,5-dimethylimidazo-2-ylidene, 2,2'-bipyridyl , phenanthroline, B(C ₆ F ₅ ) ₃ , BR ₃ (R=linear, branched, or cyclic C ₁ -C ₁₀ alkyl, C ₅ -C ₁₀ aryl, or C ₁ -C ₁₀ alkoxy ), AlR ₃ (R=linear, branched, or cyclic C ₁ -C ₁₀ alkyl group, C ₅ -C ₁₀ aryl group, or C ₁ -C ₁₀ alkoxy group), (C ₅ H ₅ ) ₂ TiR ₂ (R=alkyl, H, alkoxy, organic amino, carbosilyl), (C ₅ H ₅ ) ₂ Ti(OAr) ₂ [Ar=(2,6-(iPr) ₂ C ₆ H ₃ )], (C ₅ H ₅ ) ₂ Ti(SiHRR')PMe ₃ (wherein R, R' are each independently selected from H, Me and Ph), TiMe2(dmpe) ₂ (dmpe=1,2-bis(dimethyl _phosphino )ethane), bis(benzene)chromium(0), Cr(CO) ₆ , _Mn2 (CO) ₁₂ , Fe(CO) ₅ , _Fe3 (CO) ₁₂ , ( _C5H5 )Fe(CO ) ₂ Me, Co ₂ (CO) ₈ , Ni(II) acetate, nickel(II) acetylacetonate, Ni(cyclooctadiene) ₂ , [(dippe)Ni(μH)] ₂ (dippe=1, 2-bis(di-iso-propylphosphino)ethane), (R-indenyl)Ni(PR′ ₃ )Me (R=1-iPr, 1-SiMe ₃ , 1,3-(SiMe ₃ ) ₂ ; R '=Me, Ph), [{Ni(η-CH ₂ :CHSiMe ₂ ) ₂ O} ₂ {μ-(η-CH ₂ :CHSiMe ₂ ) ₂ O}], Cu(I) acetate, CuH, [Tris (4,4-dimethyl-2-oxazolinyl)phenylborate]ZnH, (C ₅ H ₅ ) ₂ ZrR ₂ (R=alkyl, H, alkoxy, organic amino, carbosilyl), Ru ₃ (CO) ₁₂ , [(Et _3P )Ru(2,6-dimesitylthiophenolate)][B[3,5- _{( CF3} ) _{2C6H3 ] 4} ], [( _C5Me5 )Ru _{( R3P} )x (NCMe) ₃ -x] ⁺ where R is selected from linear, branched or cyclic C ₁ -C ₁₀ alkyl groups and C ₅ -C ₁₀ aryl groups; x=0, 1, 2 , 3), Rh ₆ (CO) ₁₆ , tris(triphenylphosphine) rhodium(I) carbonyl hydride, Rh ₂ H ₂ (CO) ₂ (dppm) ₂ (dppm = bis(diphenylphosphino)methane, Rh ₂ (μ-SiRH) ₂ (CO) ₂ (dppm) ₂ (R=Ph, Et, C ₆ H 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( SiMe ₃ ) ₂ ) ₂ [NHC=1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene)], Yb(η2-Ph ₂ CNPh)(hmpa) ₃ (hmpa=hexamethylphospho amide), W(CO) ₆ , _Re2 (CO) ₁₀ , _Os3 (CO) ₁₂ , _Ir4 (CO) ₁₂ , (acetylacetonato)dicarbonyliridium(I), Ir(Me) ₂ (C _{5Me 5} )L (L = PMe ₃ , PPh ₃ ), [Ir(cyclooctadiene)OMe] ₂ , PtO ₂ (Adams catalyst), platinum carbon (Pt/C), ruthenium carbon (Ru/C), ruthenium -alumina, palladium on carbon, nickel on carbon, osmium on carbon, platinum(0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane (Kersted catalyst), bis(tri-tert-butylphosphine) Platinum(0), Pt(cyclooctadiene _{) 2} , [( _Me3Si ) _2N ] _3U ][BPh4], [( _Et2N ) _3U ][ _BPh4 ], and other halide-free ^Mn complex (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), but not limited to these. The catalysts listed above as well as pure noble metals such as ruthenium, platinum, palladium, rhodium and osmium can also be fixed on supports. A carrier is a solid with a high surface area. Typical support materials include: alumina, MgO, zeolites, carbon, monolithic cordierite, diatomaceous earth, silica gel, silica/alumina, ZrO, _TiO2 , metal organic frameworks (MOFs), and organic polymers such as polystyrene. include but are not limited to: Preferred supports are carbon (eg platinum on carbon, palladium on carbon, rhodium on carbon, ruthenium on carbon), alumina, silica and MgO. The metal loading of the catalyst ranges from about 0.01 weight percent to about 50 weight percent. A preferred range is from about 0.5 weight percent to about 20 weight percent. A more preferred range is from about 0.5 weight percent to about 10 weight percent. Catalysts requiring activation may be activated by several known methods. Heating the catalyst under vacuum is the preferred method. The catalyst may be activated in the reactor prior to addition to the reactor or prior to addition of the reactants. The catalyst may contain a co-catalyst. A co-catalyst is a substance that is not a catalyst per se, but increases its effectiveness (activity and/or selectivity) when mixed in small amounts with an active catalyst. The promoters are typically metals such as Mn, Ce, Mo, Li, Re, Ga, Cu, Ru, Pd, Rh, Ir, Fe, Ni, Pt, Cr, Cu and Au and/or their oxides. be. The cocatalyst can be added separately to the reactor or can be part of the catalyst itself. For example Ru/Mn/C (ruthenium carbon promoted by manganese) or Pt/CeO ₂ /Ir/SiO ₂ (platinum promoted by cerium oxide and iridium). Some co-catalysts can act as catalysts by themselves, but their use in combination with the main catalyst can improve the activity of the main catalyst. Catalysts may act as co-catalysts for other catalysts. In this context, the catalyst may be referred to as a bimetallic (or multimetallic) catalyst. For example, Ru/Rh/C can be referred to as either a ruthenium-rhodium-carbon bimetallic catalyst or a ruthenium-carbon promoted by rhodium. An active catalyst is a substance that acts as a catalyst in a specific chemical reaction.

Preferred halide-containing main group, transition metal, lanthanide and actinide catalysts include _BX3 ( _{X=F, Cl, Br, I), BF3.OEt2, AlX3 ( X} =F, Cl, Br, I ), ( _C5H5 ) _2TiX2 (X=F, _{CI), [Mn(CO)4Br]2 , NiCl2 , ( C5H5 ) 2ZrX2} (X=F, CI), _{PdCl 2} , PdI ₂ , CuCl, CuI, CuF _{2 , CuCl 2 ,} CuBr ₂ , Cu(PPh ₃ ) ₃ Cl, ZnCl ₂ , RuCl ₃ , [(C ₆ H ₆ )RuX ₂ ] ₂ (X=Cl, Br, I), (Ph ₃ P) ₃ RhCl (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=iPr, nBu _, Me), _H2PtCl6.nH2O ( _Spear 's catalyst), _PtCl2 , Pt( _PPh3 ) _2Cl2 , and other halide-containing Mn ⁺ 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 molar ratio of catalyst to cyclic oligosiloxane in the reaction mixture is 0.1-1, 0.05-1, 0.01-1, 0.005-1, 0.001-1, 0.0005-1 , 0.0001-1, 0.00005-1, or 0.00001-1. In one particular embodiment, 0.002 to 0.003 equivalents of catalyst are used per equivalent of cyclic oligosiloxane. In another particular embodiment, 0.001 equivalents of catalyst are used per equivalent of cyclic oligosiloxane.

In certain embodiments, the reaction mixture comprising the cyclic oligosiloxane organic amine and catalyst further comprises an anhydrous solvent. Preferred solvents include linear, branched, cyclic or polyethers (e.g. tetrahydrofuran (THF), diethyl ether, diglyme and/or tetraglyme); linear, branched or cyclic alkanes, alkenes, aromatics; and halogenated carbons such as pentane, hexane, toluene and dichloromethane, but are not limited thereto. The choice of one or more solvents, if added, is influenced by the compatibility with the reagents contained in the reaction mixture, the solubility of the catalyst, and/or the method of separation of the intermediate and/or final product chosen. may receive. In other embodiments, the reaction mixture is solvent-free.

In the methods described herein, the reaction of the cyclic oligosiloxane and the organic amine occurs at one or more temperatures ranging from about 0°C to about 200°C, preferably from 0°C to about 100°C. Preferred 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. A suitable temperature range for this reaction may be determined by the physical properties of the reagents and, if necessary, the solvent. Examples of specific reactor temperature ranges include, but are not limited to, 0°C to 80°C or 0°C to 30°C. In some embodiments it is preferred to maintain a reaction temperature between 20°C and 60°C.

In certain embodiments of the methods described herein, the reaction pressure is from about 1 to about 115 psia (6.89×10 ³ -7.93×10 ⁵ Pa) or from about 15 to about 45 psia (1. 03×10 ⁵ to 3.10×10 ⁵ Pa). In some embodiments in which the cyclic oligosiloxane is liquid under ambient conditions, the reaction is carried out at atmospheric pressure. In some embodiments where the cyclic oligosiloxane is a gas under ambient conditions, the pressure reduction reaction is carried out above 15 psia (1.03×10 ⁵ Pa).

In certain embodiments, one or more reagents may be introduced to the reaction mixture as liquids or vapors. In embodiments in which one or more of the reagents are added as a vapor, a non-reactive gas such as nitrogen or an inert gas may be used as the carrier gas to deliver the vapor to the reaction mixture. In embodiments in which one or more of the reagents are added as liquids, the reagents may be added neat or diluted with solvent. Reagents are fed to the reaction mixture until the desired conversion to crude mixture, or crude liquid, containing the organoaminosilane product is achieved. In certain embodiments, the reaction may be run continuously by replenishing the reactants and removing the reaction product and crude liquid from the reactor.

The crude mixture containing compounds of Formulas AD, catalyst, and any organic amine, solvent, or undesired products that may remain may require separation methods. Examples of suitable separation methods include, but are not limited to, distillation, evaporation, membrane separation, filtration, centrifugation, crystallization, gas phase transfer, extraction, fractionation using reverse columns, and combinations thereof. not.

Formulas 1-3 are preferred representative chemistries and are not intended to be limiting in any manner for the preparation of compounds having Formulas AD.

Silicon precursor compounds having formulas AD according to the present invention and compositions comprising silicon precursor compounds having formulas AD according to the present invention are preferably substantially free of halide ions. As used herein, for example, halide ions (or halides) such as chloride (i.e., chloride-containing species such as HCl or silicon compounds having at least one Si—Cl bond) as well as fluoride , bromide, and iodide when measured by plasma emission-mass spectrometry (ICP-MS), ion chromatography (IC), or any other analytical method; It means less than 5 ppm (by weight), preferably less than 3 ppm, more preferably less than 1 ppm, most preferably 0 ppm. Chlorides are known to act as decomposition catalysts for silicon precursor compounds having formulas AD. Significant levels of chloride in the final product can degrade the silicon precursor compound. Slow degradation of silicon precursor compounds can directly impact thin film deposition methods making it difficult for semiconductor manufacturing to meet thin film specifications. In addition, shelf life or stability is adversely affected by the higher degradation rate of silicon precursor compounds, making it difficult to guarantee a shelf life of 1-2 years. Accordingly, accelerated degradation of silicon precursor compounds presents safety and performance concerns associated with the purification of these combustible and/or pyrophoric gaseous by-products. Silicon precursor compounds having formulas AD are preferably metals such ^as Li ⁺ , Na ⁺ , K ⁺ , Mg ²⁺ , Ca ²⁺ , Al ³⁺ , Fe 2+ , Fe ²⁺ , Fe ³⁺ , Ni ²⁺ , Cr ³⁺ It is substantially free of ions, as well as other metal ions that may be derived from catalysts used in the synthesis of these compounds. As used herein, the term "substantially free" when referring to Li, Na, K, Mg, Ca, Al, Fe, Ni, Cr, and other metal impurities is , means less than 5 ppm (by weight), preferably less than 3 ppm, more preferably less than 1 ppm, most preferably 0.1 ppm as measured by ICP-MS. In some embodiments, the silicon precursor compounds having formulas AD are Li ⁺ , Na ⁺ , K ⁺ , Mg ²⁺ , Ca ²⁺ , Al ³⁺ , Fe ²⁺ , Fe ²⁺ , Fe ³⁺ , Ni ²⁺ , Cr It is substantially free of metal ions such as ³⁺ and other metal ions that may be derived from catalysts used in the synthesis of these compounds. As used herein, it relates to noble metals such as Li, Na, K, Mg, Ca, Al, Fe, Ni, Cr, and Ru, Rh, Pd, or Pt from catalysts used in the synthesis The term "free of" when used means less than 1 ppm, preferably 0.1 ppm (by weight) as determined by ICP-MS or other analytical method for metals determination.

の前駆体であって、前記式Ａ～Ｄ中、Ｒ^１は、直鎖Ｃ_１～Ｃ_１０アルキル基、分岐鎖Ｃ_３～Ｃ_１０アルキル基、Ｃ_３～Ｃ_１０環式アルキル基、Ｃ_３～Ｃ_１０複素環式基、Ｃ_３～Ｃ_１０アルケニル基、Ｃ_３～Ｃ_１０アルキニル基、及びＣ_４～Ｃ_１０アリール基から成る群から選択され；Ｒ^２は、水素、Ｃ_１～Ｃ_１０直鎖アルキル基、分岐鎖Ｃ_３～Ｃ_１０アルキル基、Ｃ_３～Ｃ_１０環式アルキル基、Ｃ_３～Ｃ_１０複素環式基、Ｃ_３～Ｃ_１０アルケニル基、Ｃ_３～Ｃ_１０アルキニル基、及びＣ_４～Ｃ_１０アリール基から成る群から選択され、Ｒ^１及びＲ^２は、結合して環式環構造を形成するか又は結合しないで環式環構造を形成しないかのいずれかであり；Ｒ^３～１１は、水素、直鎖Ｃ_１～Ｃ_１０アルキル基、分岐鎖Ｃ_３～Ｃ_１０アルキル基、Ｃ_３～Ｃ_１０環式アルキル基、Ｃ_２～Ｃ_１０アルケニル基、Ｃ_２～Ｃ_１０アルキニル基、Ｃ_４～Ｃ_１０アリール基、及び有機アミノ基、ＮＲ^１Ｒ^２、Ｒ^１及びＲ^２は上記に定義されている、から成る群から各々独立して選択され；ｎ＝１、２、又は３、及びｍ＝２又は３である、
前駆体から成る群から選択される、工程と；
ｃ）前記反応器をパージガスでパージする工程と；
ｄ）酸素含有原料を反応器に導入する工程と；
ｅ）前記反応器を前記パージガスでパージする工程と；
を含み、
薄膜の所望の厚さが堆積されるまで工程ｂから工程ｅを反復し；前記方法を、約２５℃～６００℃の範囲の１つ以上の温度で行う、
方法を提供する。 In another embodiment, a method of depositing a thin film comprising silicon and oxygen on a substrate, the method comprising:
a) providing a substrate in a reactor;
b) introducing into the reactor at least one silicon precursor compound, said at least one silicon precursor having formulas AD:

wherein R ¹ is a linear C ₁ -C 10 alkyl group, a branched C ₃ -C ₁₀ alkyl group, a C _{3 -C 10 cyclic} alkyl group, a C ₃ -C ₁₀ heterocyclic groups, C ₃ -C ₁₀ alkenyl groups, C ₃ -C ₁₀ alkynyl groups, and C ₄ -C ₁₀ aryl groups; R ² is hydrogen, C ₁ -C ₁₀ straight chain alkyl group, branched chain _C3 - _C10 alkyl group, _C3 - _C10 cyclic alkyl group, _C3 - _C10 heterocyclic group, _C3 - _C10 alkenyl group, _C3 - _C10 alkynyl group , and C ₄ -C ₁₀ aryl groups, wherein R ¹ and R ² either combine to form a cyclic ring structure or do not combine to form a cyclic ring structure Yes; R ^3-11 are hydrogen, straight chain C ₁ -C ₁₀ alkyl groups, branched chain C ₃ -C ₁₀ alkyl groups, C ₃ -C ₁₀ cyclic alkyl groups, C ₂ -C ₁₀ alkenyl groups, C ₂ -C ₁₀ alkynyl groups, C ₄ -C ₁₀ aryl groups, and organic amino groups, NR ¹ R ² , R ¹ and R ² are defined above; n= 1, 2, or 3, and m = 2 or 3,
a step selected from the group consisting of precursors;
c) purging the reactor with a purge gas;
d) introducing an oxygen-containing feedstock into the reactor;
e) purging the reactor with the purge gas;
including
repeating steps b through e until the desired thickness of the thin film is deposited; performing the method at one or more temperatures ranging from about 25°C to 600°C;
provide a way.

The methods disclosed herein form silicon oxide thin films that include at least one of the following properties: a density of at least about 2.1 g/cc; Wet etch rate of less than about 2.5 Å/sec when measured in a ^{.5 wt} . A silicon and oxygen containing thin film comprising at least one hydrogen impurity less than about 5×10 ²⁰ atoms/cc as determined by mass spectrometry (SIMS).

In certain embodiments of the methods and compositions described herein, a layer of silicon-containing dielectric is deposited on at least a portion of the substrate by, for example, chemical vapor deposition (CVD) using a reaction chamber. do. Suitable substrates include gallium arsenide (“GaAs”), silicon, as well as crystalline silicon, polysilicon, amorphous silicon, epitaxial silicon, silicon dioxide (“SiO ₂ ”), silicon glass, silicon nitride, fused silica, glass, Silicon-containing compositions such as, but not limited to, 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. Substrates are, for example, silicon, SiO ₂ , organosilicate glass (OSG), fluorosilicate glass (FSG), boron carbonitride, silicon carbide, hydrogenated silicon carbide, silicon nitride, hydrogenated silicon nitride, Additions such as 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. It may have layers. Still further layers include germanosilicates, aluminosilicates, copper and aluminum, and materials such as, but not limited to, TiN, Ti(C)N, TaN, Ta(C)N, Ta, W, or WN. Diffusion barrier materials are also possible.

The deposition methods disclosed herein may include one or more purge gases. The purge gas used to drive off unconsumed reactants and/or reaction byproducts is an inert gas that does not react with the precursors. Preferred purge gases include, but are not limited to, argon (Ar), nitrogen ( _N2 ), helium (He), neon, hydrogen ( _H2 ), and combinations thereof. In certain embodiments, a purge gas such as Ar is supplied to the reactor at a flow rate ranging from about 10 to about 2000 sccm (about 0.010 to about 2.000 L/min) for about 0.1 to 1000 seconds, and to purge unreacted materials and any by-products that may remain in the reactor.

A purge gas, such as argon, expels unabsorbed excess compounds from the process chamber. After sufficient purging, an oxygen source may be introduced into the reaction chamber to react with the absorbing surface, followed by a further gas purge to remove reaction byproducts from the chamber. The process cycle can be repeated to obtain the desired film thickness. In some cases, pumping can replace the purge with an inert gas, or both can be used to remove unreacted silicon precursor.

Throughout this specification, the term "ALD or ALD-like" refers to methods including, but not limited to: a) each reactant, including the silicon precursor and reactant gases, is processed in a single wafer ALD reactor; continuously introducing into a reactor such as a semi-batch ALD reactor or a batch furnace ALD reactor; The substrate is exposed by rotating and each compartment is separated by an inert gas curtain, i.e. space ALD reactor or roll-to-roll ALD reactor.

The method of the present invention is carried out by an ALD method using an oxygen-containing source containing ozone, or a plasma in which the plasma can further contain an inert gas such as one or more of: using or using an inert gas; oxygen plasma without or without inert gas, water vapor plasma with or without inert gas, nitrogen oxide (e.g., _N2O , NO, _NO2 ) plasma with or without inert gas, carbon oxide plasma with or without inert gas (eg, _CO2 , CO) plasma, and combinations thereof.

The oxygen-containing feedstock can be generated in situ or, alternatively, remotely. In one particular embodiment, the oxygen-containing source comprises oxygen, flows, or indefinitely in addition to at least one silicon precursor and optionally other reagents such as inert gases, steps b-d. introduced during the method through

In certain embodiments, the compositions described herein—and those used in the disclosed methods—further comprise a solvent. Preferred solvents include, but are not limited to ethers, tertiary amines, alkyl hydrocarbons, aromatic hydrocarbons, tertiary amino ethers, and combinations thereof. In certain embodiments, the difference between the boiling point of the silicon precursor and the boiling point of the solvent is 40° C. or less. In some embodiments, the composition can be delivered to the reactor chamber for silicon-containing thin films by direct liquid injection.

For those embodiments in which at least one silicon precursor having Formulas AD is used in a solvent-containing composition, the selected solvent or mixture thereof does not react with the silicon precursor. The amount of solvent in wt % in the composition ranges from 0.5 wt % to 99.5 wt % or from 10 wt % to 75 wt %. In this or other embodiments, the solvent has a boiling point (b.p.) similar to the boiling point of the silicon precursors of Formulas AD, and the boiling point of the solvent and the boiling point of the silicon precursors of Formulas AD are The difference is 40°C or less, 30°C or less, or 200°C or less, or 100°C. Alternatively, the boiling point difference ranges from any one or more of the following endpoints: 0, 10, 20, 30, or 40°C. b. p. Examples of suitable ranges for the difference include, but are not limited to, 0-40°C, 20-30°C, or 10-30°C. Examples of suitable solvents in the composition include ethers (1,4-dioxane, dibutyl ether, etc.), tertiary amines (pyridine, 1-methylpiperidine, 1-ethylpiperidine, N,N'-dimethylpiperidine, N,N,N',N'-tetramethylethylenediamine, etc. 9, nitriles (benzonitrile, etc.), alkyl hydrocarbons (octane, nonane, dodecane, ethylcyclohexane, etc.), aromatic hydrocarbons (toluene, mesitylene, etc.), Tertiary minoethers (bis(2-dimethylaminoethyl)ether), or combinations thereof, but are not limited thereto.

In certain embodiments, silicon oxide or carbon-doped silicon oxide thin films deposited using the methods described herein are treated with ozone, water (H ₂ O) (e.g., deionized water, pure water, and / or distilled water), hydrogen peroxide ( _H2O2 ), oxygen ( _O2 ), oxygen plasma _, NO, _N2O , _NO2 , carbon monoxide (CO), carbon dioxide ( _CO2 ) and these Formed in the presence of an oxygen-containing source comprising a combination. The oxygen-containing feedstock is passed through, for example, either an in-situ or remote plasma generator to generate an oxygen plasma, a plasma containing oxygen and argon, a plasma containing oxygen and helium, an ozone plasma, a water plasma, a nitrous oxide plasma, Alternatively, an oxygen-containing plasma source containing oxygen, such as a carbon dioxide plasma, may be provided. In certain embodiments, the oxygen-containing plasma source is about 1 to about 2000 standard cubic centimeters per minute (sccm) (about 0.001 to about 2.000 L/min) or about 1 to about 1000 sccm (about 0.001 to about 1.000 L/min), including the oxygen source gas introduced into the reactor. An oxygen-containing plasma source can be introduced for a time ranging from about 0.1 to about 100 seconds. In certain embodiments, the oxygen-containing plasma source comprises water having a temperature of 10° C. or higher. In embodiments that deposit thin films by PEALD or plasma-enhanced cyclic CVD methods, the precursor pulse is greater than 0.01 seconds (eg, about 0.01 to about 0.1 seconds, about 0.1 to about 0.5 seconds, about 0.5 to about 10 seconds, about 0.5 to about 20 seconds, about 1 to about 100 seconds), wherein the oxygen-containing plasma source is , has a pulse duration that is less than 0.01 seconds (eg, about 0.001 to about 0.01 seconds).

In one or more of the above embodiments, the oxygen-containing plasma source includes oxygen plasma with or without inert gas, water vapor plasma with or without inert gas, nitrogen oxides with or without inert gas (e.g. , N ₂ O, NO, NO ₂ ) plasma, carbon oxide (eg, CO ₂ , CO) plasma with or without 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 the group consisting of argon, helium, nitrogen, hydrogen, or combinations thereof. In an alternative embodiment, the oxygen-containing plasma source does not contain inert gas.

Each step of supplying precursors, oxygen sources, and/or other precursors, source gases, and/or reagents changes the stoichiometry of the resulting dielectric thin film. by changing the time to

Energy is applied to at least one of the silicon precursors of Formulas AD, the oxygen-containing source, or a combination thereof to induce a reaction to form a dielectric thin film or coating on the substrate. Such energy can be supplied by, but not limited to, thermal plasmas, pulsed plasmas, helicon plasmas, high density plasmas, inductively coupled plasmas, X-rays, E-beams, photons, remote plasma methods, and combinations thereof. In certain embodiments, a secondary RF frequency source can be used to modify the plasma properties at the substrate surface. In embodiments where the deposition includes plasma, the plasma generation process may include a direct plasma generation process in which the plasma is generated directly within the reactor, or a remote plasma generation process in which the plasma is generated outside the reactor and supplied to the reactor. It may also include developmental processes.

At least one silicon precursor may be delivered to a reaction chamber, such as a plasma-enhanced cyclic CVD or PEALD reactor, or a batch furnace reactor in various ways. In one embodiment, a liquid delivery system may be utilized. In alternative embodiments, low volatility materials are volumetrically delivered using, for example, a combined liquid delivery and flash vaporization process unit such as the turbo vaporizer manufactured by MSP Corporation of Shoreview, Minnesota. This allows for reproducible transport and deposition without pyrolysis of the precursor. For liquid delivery formulations, the precursors described herein may be delivered neat liquid or may be used in solvent formulations or compositions comprising same. Thus, in certain embodiments, precursor formulations may include solvent components of suitable properties as may be desirable and advantageous in a given end-use application to form a thin film on a substrate.

As previously mentioned, the purity level of the at least one silicon precursor is high enough 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 including: free amines, free halides or halogen ions, and higher molecular weight species. Higher purity levels of the silicon precursors described herein can be obtained by one or more of the following methods: purification, adsorption, and/or distillation.

One embodiment of the methods described herein may use plasma-enhanced cyclic chemical vapor deposition, such as PEALD-like or PEALD, using at least one silicon precursor and an oxygen plasma source. Deposition. PEALD-like methods, defined as plasma-enhanced cyclic CVD methods, also provide highly conformal silicon- and oxygen-containing thin films.

In one embodiment of the invention described herein for depositing a silicon and oxygen containing thin film on at least one surface of a substrate, the method comprises:
a. providing a substrate in a reactor;
b. introducing into the reactor at least one silicon precursor having formulas AD as defined above;
c. purging the reactor with a purge gas;
d. introducing a plasma containing an oxygen-containing feedstock into the reactor;
e. purging the reactor with a purge gas;
including. The method repeats steps b through e until the desired thickness of the thin film is deposited on the substrate.

In this or other embodiments, the steps of the methods described herein may be performed in various orders, sequentially, or simultaneously (e.g., at least part of another step). between), and combinations thereof. Each step of supplying a precursor, an oxygen source may be performed, for example, by varying the length of time for supplying these so as to alter the stoichiometry of the resulting dielectric thin film. . Additionally, the purge time after the precursor or oxidant steps can be minimized to <0.1 seconds to improve throughput.

In one particular embodiment, the methods described herein deposit high quality silicon and oxygen containing thin films on substrates. The method involves the following steps:
a. providing a substrate in a reactor;
b. introducing into the reactor at least one silicon precursor having formulas AD above;
c. purging the reactor with a purge gas to remove at least a portion of the unabsorbed precursor;
d. introducing an oxygen-containing plasma source into the reactor;
e. purging the reactor with a purge gas to remove at least a portion of the unreacted oxygen source;
and repeating steps b through e until the desired thickness of the silicon-containing thin film is deposited.

In another particular embodiment, the methods described herein deposit high quality silicon and oxygen containing thin films on substrates at temperatures greater than 600°C. The method involves the following steps:
a. providing a substrate in a reactor;
b. introducing into the reactor at least one silicon precursor having formulas AD above;
c. purging the reactor with a purge gas to remove at least a portion of the unabsorbed precursor;
d. introducing an oxygen-containing plasma source into the reactor;
e. purging the reactor with a purge gas to remove at least a portion of the unreacted oxygen source;
and repeating steps b through e until the desired thickness of the silicon-containing thin film is deposited.

Since Si—H groups can decompose at temperatures higher than 600° C. and can cause undesirable chemical vapor deposition, they either contain no Si—H groups, or the number of Si—H groups is In particular, cyclic oligosiloxane precursors with organoamino functional groups having formulas A-D, where R ³ -R ⁹ are not hydrogen, are believed to be preferred for this method. However, under certain conditions, such as using short precursor pulses or low reactor pressure, cyclic oligosiloxane precursors with organoamino functional groups having formulas A-D in which any of R ^3-9 are hydrogen are prepared. It is possible that the method can also be performed at temperatures above 600° C. without chemical vapor deposition, which is highly undesirable.

Another method disclosed herein uses a silicon precursor compound having a chemical structure represented by Formulas AD defined above plus an oxygen source to form a carbon-doped silicon oxide thin film.

Another preferred method is described as follows:
a. providing a substrate in a reactor;
b. Vapor generated from at least one silicon precursor compound having a chemical structure represented by Formulas AD defined above onto a heated substrate with or without contact with a co-flow of an oxygen source. chemically absorbing the precursor;
c. expelling any unabsorbed precursor;
d. introducing an oxygen source to the heated substrate to react with the absorbed precursor;
e. driving off any unreacted oxygen sources;
Repeat steps b through e until desired thickness is achieved.

In another particular embodiment, the methods described herein deposit high quality silicon oxynitride thin films on substrates. The method involves the following steps:
a. providing a substrate in a reactor;
b. introducing into the reactor at least one silicon precursor having formulas AD above;
c. purging the reactor with a purge gas to remove at least a portion of the unabsorbed precursor;
d. introducing a nitrogen-containing plasma source into the reactor;
e. purging the reactor with a purge gas to remove at least a portion of the unreacted nitrogen source, and repeating steps b through e until a desired thickness of silicon oxynitride-containing thin film is deposited.

Another preferred method is described as follows:
a. providing a substrate in a reactor;
b. Vapor generated from at least one silicon precursor compound having a chemical structure represented by Formulas A-D as defined above onto a heated substrate with or without contact with a co-flow of a nitrogen source. chemically absorbing the precursor;
c. expelling any unabsorbed precursor;
d. introducing a nitrogen source to the heated substrate to react with the absorbed precursor;
e. expelling any unreacted nitrogen sources;
Repeat steps b through e until desired thickness is achieved.

Various commercial ALD reactors, such as single-wafer, semi-batch, or batch furnaces or roll-to-roll reactors, are used to deposit solid acid-based silicon, silicon oxynitride, carbon-doped silicon oxynitride, or carbon-doped silicon oxide. can be used for

The process temperatures for the methods described herein are 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℃, 275℃, 300℃, 325℃, 350℃, 375℃, 400℃, 425℃, 450℃, 475℃, 500℃, 525℃, 550℃, 575℃, 600℃, 625℃, One or more of 650°C, 675°C, 700°C, 725°C, 750°C, 775°C, and 800°C is used. Preferred temperature ranges include: from about 0° C. to about 300° C.; or from about 25° C. to about 300° C.; or from about 50° C. to about 290° C.; Examples include, but are not limited to, about 200°C.

In another aspect, a method of depositing a silicic acid and oxygen containing thin film by fluidized chemical vapor deposition (FCVD), said method comprising:
A substrate containing surface features is placed in a reactor, the substrate is maintained at a temperature in the range of about −20° C. to about 400° C., and the pressure of the reactor is 100 Torr (1. 33×10 ⁵ Pa) or less;
introducing at least one compound selected from the group consisting of Formulas AD as defined herein;
providing an oxygen source within the reactor to react with the at least one compound to form a thin film covering at least a portion of the surface features;
annealing the thin film at one or more temperatures between about 100° C. and 1000° C. to cover at least a portion of the surface features;
treating the substrate with an oxygen source at one or more temperatures ranging from about 20° C. to about 1000° C. to form a silicon-containing thin film on at least a portion of the surface features;
A method is provided, comprising:

In another aspect, a method of depositing a silicic acid and oxygen containing thin film by fluidized chemical vapor deposition (FCVD), said method comprising:
A substrate containing surface features is placed in a reactor, the substrate is maintained at a temperature in the range of about −20° C. to about 400° C., and the pressure of the reactor is 100 Torr (1. 33×10 ⁵ Pa) or less;
introducing at least one compound selected from the group consisting of Formulas AD as defined herein;
providing a nitrogen source and/or an oxygen source within the reactor to react with the at least one compound to form a thin film covering at least a portion of the surface feature;
annealing the thin film at one or more temperatures between about 100° C. and 1000° C. to cover at least a portion of the surface features;
treating the substrate with an oxygen source at one or more temperatures ranging from about 20° C. to about 1000° C. to form a silicon-containing thin film on at least a portion of the surface features;
A method is provided, comprising:

In certain embodiments, the oxygen source includes water vapor, water plasma, ozone, oxygen, oxygen plasma, oxygen/helium plasma, oxygen/argon plasma, nitric oxide plasma, carbon dioxide plasma, hydrogen peroxide, organic peroxides, and It is selected from the group consisting of mixtures thereof. In other embodiments, the nitrogen source is, for example, ammonia, hydrazine, monoalkylhydrazine, dialkylhydrazine, nitrogen, nitrogen/hydrogen, nitrogen/argon plasma, nitrogen/helium plasma, ammonia plasma, nitrogen plasma, nitrogen/hydrogen plasma, selected from the group consisting of organic amines such as tert-butylamine, dimethylamine, diethylamine, isopropylamine, diethylamine plasma, dimethylamine plasma, trimethylplasma, trimethylamine plasma, ethylenediamine plasma, and alkoxyamines such as ethanolamine plasma, and mixtures thereof; be done. In still other embodiments, the nitrogen-containing source comprises an ammonia plasma, a plasma containing nitrogen and argon, a plasma containing nitrogen and helium, or a plasma containing hydrogen and a nitrogen source gas. In this or other embodiments, the method steps are repeated until the surface features are filled with the silicon-containing thin film. In embodiments in which water vapor is used as the oxygen source in fluid chemical vapor deposition, the substrate temperature ranges from about -20°C to about 40°C or -10°C to about 25°C.

In still further embodiments of the methods described herein, the thin film deposited or as-deposited from ALD, ALD-like, PEALD, PEALD-like or FCVD is subjected to a treatment step (post-deposition). . Treatment steps can be performed during at least a portion of the deposition step, after the deposition step, and combinations thereof. Preferred processing steps include, but are not limited to, treatment with high temperature thermal annealing to affect one or more properties of the thin film; plasma treatment; ultraviolet (UV) treatment; laser; electron beam treatment and combinations thereof. .

In another embodiment, described herein are baths or vessels for depositing silicon-containing thin films that include one or more silicon precursor compounds. In one particular embodiment, the vessel comprises at least one pressurizable vessel (preferably US Pat. No. 7,334,595; US Pat. No. 6,077,356; stainless steel having designs such as those disclosed in U.S. Pat. No. 5,069,244; and U.S. Pat. ). The vessel is glass (borosilicate or fused silica) or type 316, 316L, equipped with appropriate valves to allow delivery of one or more precursors to the reactor for CVD or ALD processes; Either 304 or 304L stainless steel alloys (UNS designations S31600, S31603, S30400, S30403) can be included. In this or other embodiments, the silicon precursor is supplied in a pressurizable vessel made of stainless steel and the purity of the precursor is greater than or equal to 98 wt% or greater than or equal to 99.5 wt% and is suitable for most semiconductor applications. suitable for The headspace of the vessel or vessel is filled with an inert gas selected from helium, argon, nitrogen and combinations thereof.

In certain embodiments, the gas lines leading from the precursor vessels to the reaction chamber are heated to one or more temperatures depending on process requirements, and the at least one silicon precursor vessel is heated to one or more temperatures for venting. to maintain. In other embodiments, a solution containing at least one silicon precursor is injected into a vaporizer maintained at one or more temperatures for direct liquid injection.

A flow of argon and/or other gas may be used as a carrier gas to help deliver at least one silicon precursor vapor to the reaction chamber between precursor pulses. In certain embodiments, the reaction chamber process pressure is between about 50 mTorr (66.5 Pa) and 10 mTorr (13.3 Pa). In other embodiments, the reaction chamber process pressure is 760 Torr (1.01×10 ⁶ Pa) or less (eg, from about 50 millitorr (66.5 Pa) to about 100 Torr (1.33×10 ⁵ Pa)). .

In a typical PEALD or PEALD-like process, such as a PECCVD process, a substrate, such as a silicon oxide substrate, is heated on a heater stage in a reaction chamber where it is first exposed to a silicon precursor to form a composite. Allows for chemical adsorption on surfaces.

Films deposited with silicon precursors having formulas AD described herein are not limited when compared to films deposited with previously disclosed silicon precursors under the same conditions. However, it has improved properties such as wet etch rate lower than the wet etch rate of the thin film prior to the processing step or density higher than the density prior to the processing step. In one particular embodiment, the as-deposited thin film is intermittently treated during the deposition method. These intermittent treatments or deposition intermediate treatments may be performed after each ALD cycle, for example, but not limited to, one (1) ALD cycle, two (2) ALD cycles, five (5) ALD cycles. , or after a certain number of ALD cycles, such as after ten (10) or more ALD cycles.

Precursors of Formulas AD exhibit growth rates of 2.0 Å/cycle or greater.

In embodiments where the thin film is treated with a high temperature annealing step, the annealing temperature is at least 100° C. or higher than the deposition temperature. In this or other embodiments, the annealing temperature ranges from about 400.degree. C. to about 1000.degree. In this or other embodiments, the annealing treatment is performed in a vacuum (<760 Torr (1.01×10 ⁶ Pa)), an inert environment, or an oxygen-containing environment (H ₂ O, N ₂ O, NO ₂ , O ₂ or ambient air, etc.).

In embodiments where the thin film is subjected to UV treatment, the thin film is exposed to broadband UV, or UV sources having wavelengths ranging from about 150 nanometers (nm) to about 400 nm. In one particular embodiment, the as-deposited thin film is exposed to UV in a chamber different from the deposition chamber after achieving the desired thin film thickness.

In embodiments where the thin film is plasma treated, a passivation layer such as _SiO2 or carbon-doped _SiO2 is deposited to prevent chlorine and nitrogen contamination from penetrating the thin film during subsequent plasma processing. The passivation layer can be deposited using atomic layer deposition or cyclic chemical vapor deposition.

In embodiments in which the thin film is treated with plasma, the plasma source is selected from the group consisting of hydrogen plasma, plasma containing hydrogen and helium, and plasma containing hydrogen and argon. Hydrogen plasma lowers the film dielectric constant and enhances damage resistance to subsequent plasma ashing processes while still keeping the carbon content in the bulk almost unchanged.

Without intending to be bound by any particular theory, a silicon precursor compound having a chemical structure represented by Formulas AD defined above is reacted with at least one organic amino group with hydroxyl groups on the substrate. , can be fixed by obtaining multiple Si--O--Si fragments per precursor molecule, thus conventional silanes such as bis(tert-butylamino)silane or bis(diethylamino)silane, which have only one silicon atom. It is believed to enhance the growth rate of silicon oxide or carbon-doped silicon oxide compared to silicon precursors. It is possible that silicon compounds having formulas AD with two or more organic amino groups can react with two or more adjacent hydroxyl groups on the substrate surface. It is also believed that the organoamino functional cyclic oligosiloxanes disclosed herein will exhibit higher deposition per cycle (GPC) due to the increased number of silicon atoms. For example, 2-dimethylamino-2,4,6,8,10- as a silicon ALD precursor compared to 2-dimethylamino-2,4,6,8-tetramethylcyclotetrasiloxane (4 silicon atoms). When using pentamethylcyclopentasiloxane (5 silicon atoms) it may be possible to obtain a higher GPC.

Without intending to be bound by any particular theory, 2,4,6-trimethylcyclotrisiloxane, 2,4,6,8-tetramethylcyclotetrasiloxane, and 2,4,6,8,10-pentamethyl Functionalization of cyclic oligosiloxane molecules, such as cyclopentasiloxane and other cyclic oligosiloxanes with organic amino groups, can increase the thermal stability of cyclic oligosiloxanes, giving them longer shelf life and less degradation. is believed to maintain high purity for a longer period of time. In some cases, more organic amino groups can provide the molecule with even greater thermal stability. For certain applications, the improved stability of the silicon precursors described herein having formulas AD makes them superior to the cyclic parent oligosiloxane precursors.

Without intending to be bound by any particular theory, 2,4,6-trimethylcyclotrisiloxane, 2,4,6,8-tetramethylcyclotetrasiloxane, and 2,4,6,8,10-pentamethyl Functionalization of cyclic oligosiloxane molecules, such as cyclopentasiloxane and other cyclic oligosiloxanes with organic amino groups, is particularly useful when the oxygen-containing reactant in the deposition process is a mild oxidant such as water or hydrogen peroxide. , could provide precursors that lead to greater levels of networking in the resulting silicon-containing thin films.

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

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

In certain embodiments, the silicon-containing thin 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 thin film may have a dielectric constant of about 5 or less, or about 4 or less, or about 3.5 or less. However, thin films having other dielectric constants (eg, higher or lower) can be formed depending on the desired end use of the thin film. Examples of silicon precursors having formulas A-D and silicon-containing thin films formed using the methods described herein have the composition Si _x O _y C _z N _v H _w , for example, XPS or as determined by other means, Si ranges from about 10% to about 40%; O ranges from about 0 atomic weight percent to about 65 atomic weight percent; C ranges from about 0 atomic weight percent to N ranges from about 0 atomic weight percent to about 75 atomic weight percent, or from about 0 atomic weight percent to 50 atomic weight percent; H ranges from about 0 atomic weight percent to about 50 atomic weight percent, with x+y+z+v+w=100 atomic weight percent. Another example of a silicon-containing thin film formed using the silicon precursors of Formulas A-D and the methods described herein is silicon carbon oxynitride, which has a carbon content of is 1 atomic % to 80 atomic %. Further, another example of a silicon-containing thin film formed using the silicon precursors of Formulas A-D and the methods described herein is amorphous silicon, where nitrogen and carbon The total content is <10 atomic %, preferably <5 atomic %, most preferably <1 atomic %.

As previously mentioned, the methods described herein may be used to deposit a silicon-containing thin film on at least a portion of a substrate. Examples of suitable _substrates include silicon, _SiO2 , _Si3N4 , OSG, FSG, silicon carbide, hydrogenated silicon oxycarbide, hydrogenated silicon oxynitride, silicon oxycarbonitride, hydrogenated silicon oxycarbonitride, Antireflective 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, but not limited to, TiN, Diffusion barrier layers such as, but not limited to, Ti(C)N, TaN, Ta(C)N, Ta, W, or WN. The thin film is compatible with various subsequent processing steps such as, for example, chemical mechanical planarization (CMP) and anisotropic etching techniques.

Deposited thin films include, but are not limited to, computer chips, optical devices, magnetic information storage, coatings on carrier materials or substrates, microelectromechanical systems (MEMS), nanoelectromechanical systems, thin film transistors (TFT), light emission. It has applications including diodes (LEDs), organic light emitting diodes (OLEDs), IGZO, and liquid crystal displays (LCDs). Potential applications of the resulting solid silicon oxide or carbon-doped silicon oxide include shallow trench insulators, interlayer dielectrics, passivation layers, etch stop layers, part of dual spacers, and sacrificial layers for patterning. include, but are not limited to.

The methods described herein provide high quality silicon oxide, silicon oxynitride, carbon-doped silicon oxynitride, or carbon-doped silicon oxide thin films. Advocated "high quality" includes the following characteristics: Density of about 2.1 g/cc or greater, 2.2 g/cc or greater, 2.25 g/cc or greater; 5% by weight dHF) diluted HF 2.5 Å/sec or less, 2.0 Å/sec or less, 1.5 Å/sec or less, 1.0 Å/sec or less, 0.5 Å/sec or less when measured in an acid solution; Wet etch rate of 0.1 Å/sec or less, 0.05 Å/sec or less, 0.01 Å/sec or less; electrical leakage of about 1×10 ⁻⁸ A/cm ^{2 or} less with an applied voltage of 6 MV/cm or less; when used, means a thin film exhibiting one or more of the following: hydrogen impurities less than or equal to about 5×10 ²⁰ atoms/cc; and combinations thereof. In terms of etch rate, thermally grown silicon oxide thin films have an etch rate of 0.5 A/sec in 0.5 wt% HF.

In certain embodiments, one or more silicon precursors having Formulas A-D described herein are used to be solid, non-porous, or substantially pore-containing. A silicon- and oxygen-containing thin film can be formed.

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

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

A solution of THF (200 mL), Ru ₃ (CO) ₁₂ (1.12 g, 0.00175 mol, 2.2 mol %) and 2,4,6,8-tetramethylcyclotetrasiloxane (192 g, 0.792 mol) at room temperature. To the stirred solution was added a solution of dimethylamine in THF (396 mL, 2.0 M solution, 2 eq) dropwise over 4 hours at room temperature. The reaction solution was kept stirring overnight at room temperature. The solvent is removed under reduced pressure and the crude product is purified by fractional distillation (6 torr (7.98×10 ³ Pa)/94° C.) to yield 2,4-bis(dimethylamino)-2,4,6, A mixture of 8-tetramethylcyclotetrasiloxane and 2,6-bis(dimethylamino)-2,4,6,8-tetramethylcyclotetrasiloxane was obtained. GC-MS showed the following peaks for both compounds: 326 (M ⁺ ), 311 (M−15), 282, 266, 252, 239, 225, 209, 193, 179, 165, 149, 141, 133. , 119, 111, 104, 89, 73, 58, 44.

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

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

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

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

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

Example 4. 2,4-bis(iso-propylamino)-2,4,6,8-tetramethylcyclotetrasiloxane and 2,6-bis(iso-propylamino)-2,4,6,8-tetra Synthesis of methylcyclotetrasiloxane.
2,4-Bis(iso-propylamino)-2,4,6,8-tetramethylcyclotetrasiloxane and 2 were prepared according to Example 1 except iso-propylamine was used instead of dimethylamine. ,6-bis(N-iso-propylamino)-2,4,6,8-tetramethylcyclotetrasiloxane was obtained. GC-MS showed the following peaks for both compounds: m/z = 356 (M ⁺ ), 341 (M-15), 325, 313, 296, 282, 253, 240, 223, 208, 193, 180, 164, 150, 141, 134, 120, 112, 103, 87, 74, 59, 44.

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

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

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

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

Example 7. Synthesis of 2-diethylamino-2,4,6,8,10-pentamethylcyclopentasiloxane.
Stirring THF (1 mL), Ru ₃ (CO) ₁₂ (0.010 g, 0.000016 mol) and 2,4,6,8,10-pentamethylcyclopentasiloxane (1.0 g, 0.0033 mol) at room temperature Diethylamine (0.22 g, 0.0030 mol) was added to the solution under nitrogen protection. The reaction solution was kept stirring overnight at room temperature. GC-MS determined that the solution contained 2-diethylamino-2,4,6,8,10-pentamethylcyclopentasiloxane as the major product. GC-MS showed the following mass peaks: m/z=371 (M ⁺ ), 357, 341, 327, 311, 300, 286, 268, 254, 240, 226, 210, 193, 179, 165, 149, 133, 116, 102, 86, 73, 59, 45.

Example 8. Synthesis of 2-(N-ethylmethylamino)-2,4,6,8,10-pentamethylcyclopentasiloxane.
Stirring THF (1 mL), Ru ₃ (CO) ₁₂ (0.010 g, 0.000016 mol) and 2,4,6,8,10-pentamethylcyclopentasiloxane (1.0 g, 0.0033 mol) at room temperature To the solution was added N-ethylmethylamine (0.17 g, 0.0029 mol) under nitrogen protection. The reaction solution was kept stirring overnight at room temperature. GC-MS determined that the solution contained 2-(N-ethylmethylamino)-2,4,6,8,10-pentamethylcyclopentasiloxane as the major product. GC-MS showed the following mass peaks: m/z=357 (M ⁺ ), 343, 327, 316, 300, 283, 273, 253, 239, 225, 209, 193, 179, 165, 149, 135, 116, 102, 88, 73, 59, 45.

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

Example 10. Synthesis of 2,4,6,8-tetrakis(methylamino)-2,4,6,8-tetramethylcyclotetrasiloxane from 2,4,6,8-tetramethylcyclotetrasiloxane and methylamine ( prophetic).
_2,4,6,8 - _{Tetramethylcyclotetra} Siloxane (100 g, 0.417 mol) is added dropwise over 4 hours at room temperature. The reaction solution is kept stirring overnight at room temperature. The solvent is removed under reduced pressure and the crude product is purified by fractional distillation to give the desired product, 2,4,6,8-tetrakis(methylamino)-2,4,6,8-tetramethylcyclotetrasiloxane. get

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

Example 12 Bis(dimethylamino)-2,4,6,8-tetramethylcyclotetrasiloxane (containing a mixture of 2,4- and 2,6-isomers in a laminar flow reactor containing a 27.1 MHz plasma ) with PEALD silicon oxide.

Plasma enhanced ALD (PEALD) was performed in a commercial side-flow reactor (300 mm PEALD tool manufactured by ASM) equipped with 27.1 MHz direct plasma capability with 3.5 mm fixed spacing between electrodes. The precursor was liquid heated to 62° C. in a stainless steel bubbler and delivered to the chamber using Ar carrier gas. All depositions reported in this study were performed on native oxide containing Si substrates. Film thickness and refractive index were measured using a FilmTek 2000SE ellipsometer. Wet etch rate (WER) measurements were performed by using a 1:99 (0.5 wt%) diluted hydrofluoric (HF) acid solution. Etch solution activity was confirmed using thermally oxidized wafers as standards for each set of experiments. All samples were etched for 15 minutes to remove any surface layers before starting bulk thin film WER collection. A typical thermal oxide wafer wet etch rate for a 1:99 (0.5 wt %) dHF aqueous solution was 0.5 Å/sec with this procedure.

Bis(dimethylamino)-2,4,6,8-tetramethylcyclotetrasiloxane (including mixtures of 2,4- and 2,6-isomers) as a silicon precursor and O ₂ plasma was used for the deposition. The silicon precursor was delivered to the chamber with a carrier gas Ar flow of 200 sccm (about 0.200 L/min). Steps b through e were repeated many times to obtain the desired thickness of silicon oxide for measurement.

Thin film deposition parameters and deposition GPC are shown in Table 3 for 100° C. deposition and Table 4 for 300° C. deposition. Depositions 1-6 and 13-18 show the GPC as a function of precursor pulse time deposition at 100°C and 300°C. FIG. 1 shows the saturation curve of bis(dimethylamino)-2,4,6,8-tetramethylcyclotetrasiloxane GPC versus the number of precursor pulses. It can be seen that the GPC increases with the precursor pulse and then saturates, indicating the ALD behavior of the precursor. A 100° C. deposition exhibits a higher GPC than a 300° C. deposition. BDEAS (bis(diethylamino)silane) deposition is shown in FIG. 1 for comparison. The BDEAS container was heated to 28°C and had an internal vapor pressure at 62°C similar to the bis(dimethylamino)-2,4,6,8-tetramethylcyclotetrasiloxane container. BDEAS was delivered to the chamber with a carrier gas Ar flow of 200 sccm (0.200 L/min). Bis(dimethylamino)-2,4,6,8-tetramethylcyclotetrasiloxane shows a much higher GPC than BDEAS. Depositions 7-12 and 19-24 show GPC and thin film relative WER at various deposition pressures, oxygen plasma times, or oxygen plasma powers. Figures 2 and 3 show the O2 plasma output at 300°C and 100°C deposition temperatures, respectively, when using bis(dimethylamino)-2,4,6,8-tetramethylcyclotetrasiloxane as _the silicon precursor. Thin film GPC and WER for . GPC decreased slightly with increasing oxygen plasma power, and WER decreased with increasing oxygen plasma power. Thin films deposited at high temperatures exhibit lower WER. Figures 4 and 5 plot O2 plasma time versus _O2 plasma time at 300°C and 100°C deposition, respectively, when bis(dimethylamino)-2,4,6,8-tetramethylcyclotetrasiloxane was used as the silicon precursor. Thin film GPC and WER are shown. GPC decreased slightly with increasing oxygen plasma time and WER decreased with increasing oxygen plasma time. A lower WER of a film indicates higher film quality.

Comparative Example 12a. PEALD Silicon Oxide with TMCTS (2,4,6,8-Tetramethylcyclotetrasiloxane) in a 27.1 MHz Plasma Laminar Flow Reactor

The deposition was performed using TMCTS as the silicon precursor and _O2 plasma reactant. TMCTS was delivered to the chamber by vapor inhalation and no carrier gas was used. Steps b through e of Table 2 were repeated a number of times to obtain the desired thickness of silicon oxide for measurement. Thin film deposition parameters and deposition GPC and wafer uniformity are shown in Table 5. The deposited wafer showed poor uniformity and GPC showed no saturation with increasing precursor pulses. This indicated CVD deposition for TMCTS and was therefore not suitable as an ALD precursor.

Comparative Example 12b. PEALD silicon oxide with BDEAS (bis(diethylamino)silane) in a 27.1 MHz plasma laminar flow reactor.

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

Example 13. PEALD silicon oxide with 2-dimethylamino-2,4,6,8,10-pentamethylcyclopentasiloxane in a 27.1 MHz plasma laminar flow reactor.
Deposition was carried out using 2-dimethylamino-2,4,6,8,10-pentamethylcyclopentasiloxane as the silicon precursor and an O ₂ plasma under the conditions described above in Table 2. The precursor was delivered to the chamber with a carrier gas Ar flow of 200 sccm (0.200 L/min). The vessel was heated to 50°C. Steps b through e were repeated many times to obtain the desired thickness of silicon oxide for measurement. The thin film deposition parameters and relative WER for deposition GPC, thin film RI and thermal oxide are shown in Tables 7 and 8. FIG. 1 shows the saturation curve of 2-dimethylamino-2,4,6,8,10-pentamethylcyclopentasiloxane GPC versus the number of precursor pulses. It can be seen that the GPC increases with the precursor pulse and then saturates, indicating the ALD behavior of the precursor. A 100° C. deposition exhibits a higher GPC than a 300° C. deposition. BDEAS (bis(diethylamino)silane) deposition is shown in FIG. 1 for comparison. Thin film GPC is very high with 2-dimethylamino-2,4,6,8,10-pentamethylcyclopentasiloxane precursor: approximately 3.6 Å/cycle at 300° C. deposition temperature and 100° C. deposition temperature. at approximately 4.6 Å/cycle. A higher _O2 plasma time or a longer _O2 plasma time reduces the growth rate and lowers the film relative WER, indicating improved film quality.

Example 14. Thermal ALD silicon oxide with 2-dimethylamino-2,4,6,8,10-pentamethylcyclopentasiloxane and ozone (prophetic).
Thermal atomic layer deposition of silicon oxide thin films is performed in a laboratory-scale ALD processing tool. A silicon precursor, 2-dimethylamino-2,4,6,8,10-pentamethylcyclopentasiloxane and ozone are delivered to the chamber by vapor inhalation. All gases (eg, purge and reactant gases or precursors and oxygen source) are preheated to 100° C. prior to entering the deposition zone. Gas and precursor flow rates are controlled with fast acting ALD diaphragm valves. The substrate used in the deposition is a 12 inch (30.48 cm) long silicon strip. A thermocouple is attached to the sample holder to check the substrate temperature. Deposition is performed using ozone as the oxygen source gas. Typical deposition methods and parameters are shown in Table 9. Repeat steps 1-6 until the desired thickness is achieved.

３００℃の堆積温度のため、堆積された薄膜のサイクル当たりの堆積量（ＧＰＣ）は、２．５Å／サイクルより大きいと期待される。純酸化ケイ素薄膜を、ＸＰＳにより測定されるとき、＜０．１原子％炭素及び＜０．１原子％窒素不純物を含んで形成する。１００℃の堆積温度のため、薄膜は、ＸＰＳにより測定されるとき、＞１０原子％の炭素含有率を含む炭素ドープ酸化ケイ素薄膜であると期待され、薄膜ＷＥＲは、１：９９（０．５質量％）希釈フッ化水素（ＨＦ）酸溶液を用いた熱酸化膜ＷＥＲより小さいと期待される。３００℃～６５０℃の温度における熱アニーリング又は水素プラズマ処理を用いて、薄膜は＜３．５のｋ値を有すると期待される。

For a deposition temperature of 300° C., the deposition per cycle (GPC) of the deposited thin film is expected to be greater than 2.5 Å/cycle. Pure silicon oxide thin films are formed containing <0.1 atomic % carbon and <0.1 atomic % nitrogen impurities as measured by XPS. For a deposition temperature of 100° C., the film is expected to be a carbon-doped silicon oxide film with a carbon content of >10 atomic % as measured by XPS, and the film WER is 1:99 (0.5 mass %) is expected to be smaller than that of the thermal oxide film WER using a dilute hydrofluoric (HF) acid solution. Using thermal annealing or hydrogen plasma treatment at temperatures between 300° C. and 650° C., the films are expected to have k values of <3.5.

Although the present disclosure has been described with reference to certain preferred embodiments, those skilled in the art will appreciate that various changes may be made and equivalents substituted for elements thereof without departing from the scope of the invention. will understand. In addition, many modifications may be made to adapt a particular situation or material to the teachings thereof without departing from the essential scope of the invention. Therefore, while the invention is not limited to any particular embodiment, it is intended that the invention will encompass all embodiments that fall within the scope of the appended claims.

Claims (14)

A composition comprising at least one cyclic oligosiloxane compound having an organic amino functional group, said compound having formulas AD:

is selected from the group consisting of:
R ¹ is linear C ₁ -C ₁₀ alkyl group, branched C ₃ -C ₁₀ alkyl group, C ₃ -C ₁₀ cyclic alkyl group, C ₃ -C ₁₀ heterocyclic group, C ₃ -C ₁₀ alkenyl C ₃ -C ₁₀ alkynyl groups, and C ₄ -C ₁₀ aryl groups;
R ² is hydrogen, C ₁ -C ₁₀ straight chain alkyl group, branched chain C ₃ -C ₁₀ alkyl group, C ₃ -C ₁₀ cyclic alkyl group, C ₃ -C ₁₀ heterocyclic group, C ₃ -C selected from the group consisting of ₁₀ alkenyl groups, C ₃ -C ₁₀ alkynyl groups, and C ₄ -C ₁₀ aryl groups;
R ¹ and R ² are either joined to form a cyclic ring structure or not joined to form a cyclic ring structure;
R ^3-11 are hydrogen, straight chain C ₁ -C ₁₀ alkyl groups, branched chain C ₃ -C ₁₀ alkyl groups, C ₃ -C ₁₀ cyclic alkyl groups, C ₂ -C ₁₀ alkenyl groups, C ₂ -C ₁₀ alkynyl groups, C ₄ -C ₁₀ aryl groups, and organic amino groups, NR ¹ R ² , R ¹ and R ² are defined above; n=1, 2 or 3, and m = 2 or 3,
A composition comprising a compound. 2. The composition of claim 1, wherein said composition further comprises at least one selected from the group consisting of solvent and purge gas. The composition of claim 1, wherein each of R ^3-9 is independently selected from the group consisting of hydrogen and C ₁ -C ₄ alkyl groups. The composition of claim 1, wherein R ¹ is selected from the group consisting of C ₃ -C ₁₀ cyclic alkyl groups and C ₄ -C ₁₀ aryl groups. 2. The composition of claim 1, wherein said composition is substantially free of one or more impurities selected from the group consisting of halides, metal ions, metals, and combinations thereof. The cyclic oligosiloxane compound having an organic amino functional group includes 2,4-bis(dimethylamino)-2,4,6-trimethylcyclotrisiloxane, 2,4-bis(dimethylamino)-2,4,6 ,6-tetramethylcyclotrisiloxane, 2,4-bis(dimethylamino)-2,4,6,8-tetramethylcyclotetrasiloxane, 2,4-bis(dimethylamino)-2,4,6,6 ,8,8-hexamethylcyclotetrasiloxane, 2,6-bis(dimethylamino)-2,4,6,8-tetramethylcyclotetrasiloxane, 2,6-bis(dimethylamino)-2,4,4 ,6,8,8-hexamethylcyclotetrasiloxane, 2-dimethylamino-2,4,6,8,10-pentamethylcyclopentasiloxane, 2-dimethylamino-2,4,4,6,6,8 , 8,10,10-nonamethylcyclopentasiloxane, 2,4-bis(methylamino)-2,4,6-trimethylcyclotrisiloxane, 2,4-bis(methylamino)-2,4,6, 6-tetramethylcyclotrisiloxane, 2,4-bis(methylamino)-2,4,6,8-tetramethylcyclotetrasiloxane, 2,4-bis(methylamino)-2,4,6,6, 8,8-hexamethylcyclotetrasiloxane, 2,6-bis(methylamino)-2,4,6,8-tetramethylcyclotetrasiloxane, 2,6-bis(methylamino)-2,4,4, 6,8,8-hexamethylcyclotetrasiloxane, 2-methylamino-2,4,6,8,10-pentamethylcyclopentasiloxane, 2-methylamino-2,4,4,6,6,8, 8,10,10-nonamethylcyclopentasiloxane, 2,4-bis(iso-propylamino)-2,4,6-trimethylcyclotrisiloxane, 2,4-bis(iso-propylamino)-2,4 , 6,6-tetramethylcyclotrisiloxane, 2,4-bis(iso-propylamino)-2,4,6,8-tetramethylcyclotetrasiloxane, 2,4-bis(iso-propylamino)-2 , 4,6,6,8,8-hexamethylcyclotetrasiloxane, 2,6-bis(iso-propylamino)-2,4,6,8-tetramethylcyclotetrasiloxane, 2,6-bis(iso -propylamino)-2,4,4,6,8,8-hexamethylcyclotetrasiloxane, 2-iso-propylamino-2,4,6,8,10-pentamethylcyclopentasiloxane, 2-iso- Propylamino-2,4,4,6,6,8,8,10,10-nonamethylcyclopentasiloxane, 2,4-bis(N-ethylmethylamino)-2,4,6-trimethylcyclotrisiloxane , 2,4-bis(N-ethylmethylamino)-2,4,6,6-tetramethylcyclotrisiloxane, 2,4-bis(N-ethylmethylamino)-2,4,6,8-tetra Methylcyclotetrasiloxane, 2,4-bis(N-ethylmethylamino)-2,4,6,6,8,8-hexamethylcyclotetrasiloxane, 2,6-bis(N-ethylmethylamino)-2 ,4,6,8-tetramethylcyclotetrasiloxane, 2,6-bis(N-ethylmethylamino)-2,4,4,6,8,8-hexamethylcyclotetrasiloxane, 2-(N-ethyl methylamino)-2,4,6,8,10-pentamethylcyclopentasiloxane, 2-(N-ethylmethylamino)-2,4,4,6,6,8,8,10,10-nonamethyl Cyclopentasiloxane, 2,4-bis(diethylamino)-2,4,6-trimethylcyclotrisiloxane, 2,4-bis(diethylamino)-2,4,6,6-tetramethylcyclotrisiloxane, 2,4 -bis(diethylamino)-2,4,6,8-tetramethylcyclotetrasiloxane, 2,4-bis(diethylamino)-2,4,6,6,8,8-hexamethylcyclotetrasiloxane, 2,6 -bis(diethylamino)-2,4,6,8-tetramethylcyclotetrasiloxane, 2,6-bis(diethylamino)-2,4,4,6,8,8-hexamethylcyclotetrasiloxane, 2-diethylamino -2,4,6,8,10-pentamethylcyclopentasiloxane, 2-diethylamino-2,4,4,6,6,8,8,10,10-nonamethylcyclopentasiloxane, 2,4,6 -tris(dimethylamino)-2,4,6-trimethylcyclotrisiloxane, 2,4,6,8-tetrakis(dimethylamino)-2,4,6,8-tetramethylcyclotetrasiloxane, 2,4, from the group consisting of 6-tris(methylamino)-2,4,6-trimethylcyclotrisiloxane, 2,4,6,8-tetrakis(methylamino)-2,4,6,8-tetramethylcyclotetrasiloxane The composition of claim 1, selected. A method of depositing a thin film comprising silicon and oxygen on a substrate, the method comprising:
a) providing a substrate in a reactor;
b) Formulas AD:

At least one silicon precursor compound selected from the group consisting of:
R ¹ is linear C ₁ -C ₁₀ alkyl group, branched C ₃ -C ₁₀ alkyl group, C ₃ -C ₁₀ cyclic alkyl group, C ₃ -C ₁₀ heterocyclic group, C ₃ -C ₁₀ alkenyl C ₃ -C ₁₀ alkynyl groups, and C ₄ -C ₁₀ aryl groups;
R ² is hydrogen, C ₁ -C ₁₀ straight chain alkyl group, branched chain C ₃ -C ₁₀ alkyl group, C ₃ -C ₁₀ cyclic alkyl group, C ₃ -C ₁₀ heterocyclic group, C ₃ -C selected from the group consisting of ₁₀ alkenyl groups, C ₃ -C ₁₀ alkynyl groups, and C ₄ -C ₁₀ aryl groups;
R ¹ and R ² are either joined to form a cyclic ring structure or not joined to form a cyclic ring structure;
R ^3-11 are hydrogen, straight chain C ₁ -C ₁₀ alkyl groups, branched chain C ₃ -C ₁₀ alkyl groups, C ₃ -C ₁₀ cyclic alkyl groups, C ₂ -C ₁₀ alkenyl groups, C ₂ -C ₁₀ alkynyl groups, C ₄ -C ₁₀ aryl groups, and organic amino groups, NR ¹ R ² , R ¹ and R ² are defined above; n=1, 2 or 3, and m = 2 or 3,
introducing at least one silicon precursor compound into the reactor;
c) purging the reactor with a purge gas;
d) introducing at least one of an oxygen-containing feedstock and a nitrogen-containing feedstock into the reactor;
e) purging the reactor with the purge gas;
including
repeating steps b through e until the desired thickness of the thin film is deposited; performing the method at one or more temperatures ranging from about 25°C to 600°C;
Method. 8. The method of claim 7, wherein each of R ^3-9 is independently selected from the group consisting of hydrogen and C ₁ -C ₄ alkyl groups. 8. The method of claim 7, wherein R ¹ is selected from the group consisting of C ₃ -C ₁₀ cyclic alkyl groups and C ₄ -C ₁₀ aryl groups. The at least one silicon precursor compound is 2,4-bis(dimethylamino)-2,4,6-trimethylcyclotrisiloxane, 2,4-bis(dimethylamino)-2,4,6,6- tetramethylcyclotrisiloxane, 2,4-bis(dimethylamino)-2,4,6,8-tetramethylcyclotetrasiloxane, 2,4-bis(dimethylamino)-2,4,6,6,8, 8-hexamethylcyclotetrasiloxane, 2,6-bis(dimethylamino)-2,4,6,8-tetramethylcyclotetrasiloxane, 2,6-bis(dimethylamino)-2,4,4,6, 8,8-hexamethylcyclotetrasiloxane, 2-dimethylamino-2,4,6,8,10-pentamethylcyclopentasiloxane, 2-dimethylamino-2,4,4,6,6,8,8, 10,10-nonamethylcyclopentasiloxane, 2,4-bis(methylamino)-2,4,6-trimethylcyclotrisiloxane, 2,4-bis(methylamino)-2,4,6,6-tetra Methylcyclotrisiloxane, 2,4-bis(methylamino)-2,4,6,8-tetramethylcyclotetrasiloxane, 2,4-bis(methylamino)-2,4,6,6,8,8 -hexamethylcyclotetrasiloxane, 2,6-bis(methylamino)-2,4,6,8-tetramethylcyclotetrasiloxane, 2,6-bis(methylamino)-2,4,4,6,8 ,8-hexamethylcyclotetrasiloxane, 2-methylamino-2,4,6,8,10-pentamethylcyclopentasiloxane, 2-methylamino-2,4,4,6,6,8,8,10 , 10-nonamethylcyclopentasiloxane, 2,4-bis(iso-propylamino)-2,4,6-trimethylcyclotrisiloxane, 2,4-bis(iso-propylamino)-2,4,6, 6-tetramethylcyclotrisiloxane, 2,4-bis(iso-propylamino)-2,4,6,8-tetramethylcyclotetrasiloxane, 2,4-bis(iso-propylamino)-2,4, 6,6,8,8-hexamethylcyclotetrasiloxane, 2,6-bis(iso-propylamino)-2,4,6,8-tetramethylcyclotetrasiloxane, 2,6-bis(iso-propylamino )-2,4,4,6,8,8-hexamethylcyclotetrasiloxane, 2-iso-propylamino-2,4,6,8,10-pentamethylcyclopentasiloxane, 2-iso-propylamino- 2,4,4,6,6,8,8,10,10-nonamethylcyclopentasiloxane, 2,4-bis(N-ethylmethylamino)-2,4,6-trimethylcyclotrisiloxane, 2, 4-bis(N-ethylmethylamino)-2,4,6,6-tetramethylcyclotrisiloxane, 2,4-bis(N-ethylmethylamino)-2,4,6,8-tetramethylcyclotetra siloxane, 2,4-bis(N-ethylmethylamino)-2,4,6,6,8,8-hexamethylcyclotetrasiloxane, 2,6-bis(N-ethylmethylamino)-2,4, 6,8-tetramethylcyclotetrasiloxane, 2,6-bis(N-ethylmethylamino)-2,4,4,6,8,8-hexamethylcyclotetrasiloxane, 2-(N-ethylmethylamino) -2,4,6,8,10-pentamethylcyclopentasiloxane, 2-(N-ethylmethylamino)-2,4,4,6,6,8,8,10,10-nonamethylcyclopentasiloxane , 2,4-bis(diethylamino)-2,4,6-trimethylcyclotrisiloxane, 2,4-bis(diethylamino)-2,4,6,6-tetramethylcyclotrisiloxane, 2,4-bis( diethylamino)-2,4,6,8-tetramethylcyclotetrasiloxane, 2,4-bis(diethylamino)-2,4,6,6,8,8-hexamethylcyclotetrasiloxane, 2,6-bis( diethylamino)-2,4,6,8-tetramethylcyclotetrasiloxane, 2,6-bis(diethylamino)-2,4,4,6,8,8-hexamethylcyclotetrasiloxane, 2-diethylamino-2, 4,6,8,10-pentamethylcyclopentasiloxane, 2-diethylamino-2,4,4,6,6,8,8,10,10-nonamethylcyclopentasiloxane, 2,4,6-tris ( dimethylamino)-2,4,6-trimethylcyclotrisiloxane, 2,4,6,8-tetrakis(dimethylamino)-2,4,6,8-tetramethylcyclotetrasiloxane, 2,4,6-tris selected from the group consisting of (methylamino)-2,4,6-trimethylcyclotrisiloxane, 2,4,6,8-tetrakis(methylamino)-2,4,6,8-tetramethylcyclotetrasiloxane 8. The method of claim 7. A silicon and oxygen containing thin film having the following properties: a density of at least about 2.1 g/cc; when measured in a diluted HF (0.5 wt% dHF) acid solution of 1:100 HF to water. , a wet etch rate of less than about 2.5 Å/sec; a current leakage of less than about 1×10 ⁻⁸ A/cm ² at 6 MV/cm or less; and about 5× as measured by secondary ion mass spectrometry (SIMS). A silicon and oxygen containing thin film containing at least one hydrogen impurity less than ¹⁰²⁰ atoms/cc. A stainless steel container containing the composition of claim 1. 13. The stainless steel container of Claim 12, further comprising an inert headspace gas selected from helium, argon, nitrogen and combinations thereof. 8. The method of claim 7, wherein the silicon precursor compound further comprises at least one selected from the group consisting of solvent and inert gas.

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