Silicon compound and method for depositing film using the same

Abstract

A composition and a chemical vapor deposition method for preparing a dielectric film are provided. A gaseous reagent comprising the composition is introduced into a reaction chamber in which a substrate is provided. The gaseous reagent comprises a silicon precursor, which comprises a silicon compound according to formula I defined herein. Energy is applied to the gaseous reagent in the reaction chamber to induce a reaction of the gaseous reagent and thereby deposit a film on the substrate. The film so deposited is suitable for its intended use without the need for applying an optional additional curing step to the film so deposited. A method for preparing the composition is also disclosed.

Description

[0001] This application is a divisional application of the invention patent application No. 201911296690.9, whose application date is August 9, 2019 and whose invention name is “Silicon compounds and methods for depositing films using silicon compounds”. The invention patent application No. 201911296690.9 is a divisional application of the invention patent application No. 201980002308.0, whose application date is August 9, 2019 and whose invention name is “Silicon compounds and methods for depositing films using silicon compounds”.

[0002] CROSS-REFERENCE TO RELATED APPLICATIONS

[0003] This application claims the benefit of U.S. Provisional Patent Application No. 62 / 717,454, filed on August 10, 2018, and U.S. Patent Application No. 16 / 532,657, filed on August 6, 2019, the disclosures of which are incorporated herein by reference in their entireties. Background Art

[0004] Compositions and methods for forming dielectric films using silicon compounds as structure-forming precursors are described herein. More specifically, compositions and methods for forming low dielectric constant films ("low-k" films or films having a dielectric constant of about 3.2 or less) are described herein, wherein the method used to deposit the films is a chemical vapor deposition (CVD) process. The low dielectric constant films produced by the compositions and methods described herein can be used, for example, as insulating layers in electronic devices.

[0005] The electronics industry utilizes dielectric materials as insulating layers between components of circuits and integrated circuits (ICs) and related electronic devices. Line dimensions are reduced to increase the speed and memory storage capacity of microelectronic devices (e.g., computer chips). As line dimensions decrease, the insulation requirements for interlayer dielectrics (ILDs) become much more stringent. Reducing spacing requires a lower dielectric constant to minimize the RC time constant, where R is the resistance of the wire and C is the capacitance of the insulating dielectric interlayer. The capacitance (C) is inversely proportional to the spacing and is directly proportional to the dielectric constant (k) of the interlayer dielectric (ILD). Conventional silicon dioxide (SiO2) CVD dielectric films made from SiH4 or TEOS (Si(CH2CH3)4, tetraethyl orthosilicate) and O2 have a dielectric constant k greater than 4.0. The industry has tried a variety of ways to produce silicon dioxide-based CVD films with lower dielectric constants, the most successful of which is to dope organic groups in the insulating silicon oxide film, thereby providing a dielectric constant of about 2.7 to about 3.5. Such organosilicon glasses are typically deposited as dense films (density of about 1.5 g / cm2) from organosilicon precursors (e.g., methylsilane or siloxane) and oxidants (e.g., O2 or N2O). 3). Organic silicon glass will be referred to herein as OSG. As the carbon content of OSG increases, the mechanical strength of the film, such as the hardness (H) and elastic modulus (EM) of the film, tends to decrease rapidly as the dielectric constant decreases.

[0006] A challenge that has been recognized in the industry is that films with lower dielectric constants generally have lower mechanical strength, which leads to enhanced defects in narrow pitch films, such as delamination, buckling, increased electromigration, as observed for wires made from copper embedded in dielectric films with reduced mechanical properties. Such defects can lead to premature dielectric breakdown or voiding of conductive copper lines, resulting in premature device failure. Carbon depletion in OSG films can also lead to one or more of the following problems: increased film dielectric constant; film etching and feature bowing during wet cleaning steps; moisture absorption into the film due to loss of hydrophobicity; pattern collapse of fine features during wet cleaning steps after pattern etching; and / or integration issues when depositing subsequent layers (such as, but not limited to, copper diffusion barriers such as Ta / TaN or advanced Co or MnN barrier layers).

[0007] Possible solutions to address one or more of these issues include using porous OSG membranes with increased carbon content but maintaining mechanical strength. Unfortunately, the relationship between increasing Si-Me content generally results in a decrease in mechanical properties, so membranes with more Si-Me will have a negative impact on mechanical strength (which is important for integration).

[0008] One solution proposed is to use the general formula R x (RO) 3-x Si(CH2) y S i z (OR) 3-z Ethylene or methylene bridged alkoxysilanes, wherein x = 0-3, y = 1 or 2, z = 0-3. The use of bridged materials is believed to avoid negative effects on mechanical properties by replacing bridging oxygen with a bridging carbon chain, because the network connectivity will remain the same. This arises from the following concept: replacing the bridging oxygen with a terminal methyl group will reduce the mechanical strength by reducing the network connectivity. In this way, 1-2 carbon atoms can be replaced by oxygen atoms to increase the C atom weight percentage (%) without reducing mechanical strength. However, due to the increased molecular weight of having two silicon groups, these bridged precursors usually have very high boiling points. The increase in boiling point can have a negative impact on the production process by making it difficult to transport chemical precursors as gas phase reagents into the reaction chamber without condensing them in the steam delivery line or process pump exhaust.

[0009]

[0006] Therefore, there is a need in the art for dielectric precursors that provide films with increased carbon content when deposited without suffering from the above-mentioned disadvantages. Summary of the invention

[0010] The methods and compositions described herein meet one or more of the above needs. The methods and compositions described herein use at least one silicon compound such as 2,2,5,5-tetramethyl-1-oxa-2-silacyclopentane or 2,5,5-trimethyl-2-ethoxy-1-oxa-2-silacyclopentane as a silicon precursor, which can be deposited as is for providing a low-k interlayer dielectric, or can be subsequently treated with a heat, plasma or UV energy source to change the film properties and, for example, provide chemical crosslinking to enhance mechanical strength. In addition, the film deposited using the silicon compound described herein as a silicon precursor contains a relatively high amount of carbon. In addition, the silicon compound described herein has a lower molecular weight (Mw) relative to the prior art silicon precursors such as bridging precursors (e.g., alkoxysilane precursors) that have two silicon groups in nature and have a higher MW and a higher boiling point, so that the silicon precursor has a boiling point of 250°C or less, more preferably 200°C or less, which is more convenient, for example, in a large-scale manufacturing process as described herein.

[0011] Described herein are dielectric films based on a single precursor comprising: Si v O w C x H y F z A material represented by wherein v+w+x+y+z=100%, v is 10-35 atomic%, w is 10-65 atomic%, x is 5-45 atomic%, y is 10-50 atomic%, and z is 0-15 atomic%, wherein the membrane has a volume porosity of 5.0-30.0% pores, a dielectric constant of 2.3-3.2, and mechanical properties such as a hardness of 1.0-7.0 gigapascals (GPa) and an elastic modulus of 4.0 to 40.0 GPa. In certain embodiments, the membrane comprises a higher carbon content (10-40%), as measured by X-ray spectroscopy (XPS); and exhibits a reduced carbon removal depth when exposed to, for example, O2 or NH3 plasma, as measured by examining the carbon content determined by XPS depth analysis.

[0012] In one aspect, a chemical vapor deposition method for producing a dielectric film is provided, comprising: providing a substrate into a reaction chamber; introducing a gaseous reagent into the reaction chamber, wherein the gaseous reagent comprises a silicon precursor, and the silicon precursor comprises a silicon compound having a structure of Formula I:

[0013]

[0014] Where R 1 Selected from hydrogen, straight or branched C1-C 10 Alkyl, straight chain or branched C2-C 10 Alkenyl, straight or branched C2-C10 Alkynyl, C3-C 10 Cycloalkyl, C3-C 10 Heterocycloalkyl, C5-C 10 Aryl and C3-C 10 Heteroaryl; R 2 is a C2-C4 alkanediyl group which, together with Si and oxygen atoms, forms a four-, five- or six-membered saturated cyclic ring having an optional alkyl substituent bonded to the ring; R 3 Selected from straight or branched C1-C 10 Alkyl, straight chain or branched C2-C 10 Alkenyl, straight or branched C2-C 10 Alkynyl, C3-C 10 Cycloalkyl, C3-C 10 Heterocycloalkyl, C5-C 10 Aryl, C3-C 10 Heteroaryl and alkoxy OR 4 , where R 4 Selected from linear branched C1-C 10 Alkyl, straight chain or branched C2-C 10 Alkenyl, straight or branched C2-C 10 an alkynyl group, at least one oxygen source; and applying energy to the gas reagent in the reaction chamber to induce the reaction of the gas reagent to deposit a film on the substrate. The film thus deposited can be used without additional treatment such as thermal annealing, plasma exposure or UV curing.

[0015] In another aspect, a composition for vapor deposition of a dielectric film is provided, comprising a silicon compound having the following formula I:

[0016]

[0017] Where R 1 Selected from hydrogen, straight or branched C1-C 10 Alkyl, straight chain or branched C2-C 10 Alkenyl, straight or branched C2-C 10 Alkynyl, C3-C 10 Cycloalkyl, C3-C 10 Heterocycloalkyl, C5-C 10 Aryl and C3-C 10 Heteroaryl; R 2 is a C2-C4 alkanediyl group which, together with Si and oxygen atoms, forms a four-, five- or six-membered saturated cyclic ring having an optional C1-C6 alkyl substituent; R 3 Selected from straight or branched C1-C 10 Alkyl, straight chain or branched C2-C 10 Alkenyl, straight or branched C2-C 10Alkynyl, C3-C 10 Cycloalkyl, C3-C 10 Heterocycloalkyl, C5-C 10 Aryl, C3-C 10 Heteroaryl and alkoxy OR 4 , where R 4 Selected from straight or branched C1-C 10 Alkyl, straight chain or branched C2-C 10 Alkenyl and straight or branched C2-C 10 Alkynyl.

[0018] According to another aspect, the composition is substantially free of at least one impurity selected from the group consisting of halides, organosilanes, and water.

[0019] According to another aspect of the present invention, there is provided a method for preparing a silicon compound represented by formula I:

[0020]

[0021] The method comprises:

[0022] According to reaction formula (1) or (2), alkoxysilane is hydrosilylated with an unsaturated alcohol in the presence of a catalyst in the presence or absence of a solvent, followed by cyclization, with a yield of 70% or more:

[0023]

[0024] Where R 1 Selected from hydrogen, straight or branched C1-C 10 Alkyl, straight chain or branched C2-C 10 Alkenyl, straight or branched C2-C 10 Alkynyl, C3-C 10 Cycloalkyl, C3-C 10 Heterocycloalkyl, C5-C 10 Aryl and C3-C 10 Heteroaryl; R 3 Selected from straight or branched C1-C 10 Alkyl, straight chain or branched C2-C 10 Alkenyl, straight or branched C2-C 10 Alkynyl, C3-C 10 Cycloalkyl, C3-C 10 Heterocycloalkyl, C5-C 10 Aryl and C3-C 10 Heteroaryl, and alkoxy OR 4 , where R 4 Selected from straight or branched C1-C 10 Alkyl, straight chain or branched C2-C 10 Alkenyl, straight or branched C2-C10 Alkynyl; and R 5 To R 8 Selected from hydrogen, straight or branched C1-C 10 alkyl. DETAILED DESCRIPTION

[0025] A chemical vapor deposition method for preparing a dielectric film is described herein, comprising: providing a substrate into a reaction chamber; introducing a gaseous reagent into the reaction chamber, wherein the gaseous reagent comprises a silicon precursor, and the silicon precursor comprises a silicon compound having a structure of Formula I:

[0026]

[0027] Where R 1 Selected from hydrogen, straight or branched C1-C 10 Alkyl, straight chain or branched C2-C 10 Alkenyl, straight or branched C2-C 10 Alkynyl, C3-C 10 Cycloalkyl, C3-C 10 Heterocycloalkyl, C5-C 10 Aryl and C3-C 10 Heteroaryl; R 2 is a C2-C4 alkanediyl group, which forms with Si and oxygen atoms a four-, five- or six-membered saturated ring having an optional alkyl substituent bonded to the ring; R 3 Selected from straight or branched C1-C 10 Alkyl, straight chain or branched C2-C 10 Alkenyl, straight or branched C2-C 10 Alkynyl, C3-C 10 Cycloalkyl, C3-C 10 Heterocycloalkyl, C5-C 10 Aryl, C3-C 10 Heteroaryl and alkoxy OR 4 , where R 4 Selected from straight or branched C1-C 10 Alkyl, straight chain or branched C2-C 10 Alkenyl, straight or branched C2-C 10 an alkynyl group, at least one oxygen source; applying energy to the gaseous reagent in the reaction chamber to induce a reaction of the gaseous reagent to deposit a film on the substrate. The film can be used as deposited, or can be subsequently treated with additional energy selected from thermal energy (annealing), plasma exposure, and UV curing to change the chemical properties of the film by increasing the mechanical strength of the film and producing a dielectric constant of less than 3.3.

[0028] Compared to prior art structure forming precursors such as diethoxymethylsilane (DEMS), the silicon compounds described herein provide unique properties that allow for the incorporation of higher carbon content in dielectric films with little impact on the mechanical properties of the low-k dielectric film. For example, DEMS has a mixed ligand system that includes two alkoxy groups, one silicon-methyl (Si-Me) and one silicon-hydride that provides a balance of reactive sites and allows for the formation of mechanically more robust films while maintaining the desired dielectric constant. The use of this silicon compound provides the following advantages: there are no silicon-methyl groups in the precursor that tend to reduce mechanical strength, while the carbon in the silicon heterocyclic ring provides carbon to the OSG film to reduce the dielectric constant and impart hydrophobicity.

[0029] The low-k dielectric film is an organosilicate glass ("OSG") film or material. Organosilicates are candidates for low-k materials. Since the type of organosilicate precursor has a large impact on the structure and composition of the film, it is beneficial to use a precursor that provides the desired film properties to ensure that the desired amount of carbon is added to achieve the desired dielectric constant without producing a mechanically unstable film. The methods and compositions described herein provide a means to produce low-k dielectric films with a desired balance of electrical and mechanical properties, as well as other beneficial film properties (such as high carbon content) to provide improved integrated plasma damage resistance.

[0030] In certain embodiments of the methods and compositions described herein, a layer of dielectric material containing silicon is deposited on at least a portion of a substrate using a reaction chamber by chemical vapor deposition (CVD) or plasma enhanced chemical vapor deposition (PECVD) process, preferably a PECVD process. Suitable substrates include, but are not limited to, semiconductor materials such as gallium arsenide ("GaAs"), silicon, and silicon-containing compositions such as crystalline silicon, polycrystalline silicon, amorphous silicon, epitaxial silicon, silicon dioxide ("SiO2"), silicon glass, silicon nitride, fused silicon dioxide, glass, quartz, borosilicate glass, and combinations thereof. Other suitable materials include chromium, molybdenum, and other metals commonly used in semiconductor, integrated circuit, flat panel display, and flexible display applications. The substrate may have additional layers such as silicon, SiO2, organosilicate glass (OSG), fluorosilicate glass (FSG), boron carbonitride, silicon carbide, hydrogenated silicon carbide, silicon nitride, hydrogenated silicon nitride, silicon carbonitride, hydrogenated silicon carbonitride, boron nitride, organic-inorganic composites, photoresists, organic polymers, porous organic and inorganic materials and composites, metal oxides such as aluminum oxide and germanium oxide. Still additional layers may also be germanosilicates, aluminosilicates, copper and aluminum, and diffusion barrier materials such as, but not limited to, TiN, Ti(C)N, TaN, Ta(C)N, Ta, W or WN.

[0031] In certain embodiments, a layer of a silicon-containing dielectric material is deposited on at least a portion of a substrate by introducing a gaseous reagent comprising at least one silicon precursor comprising a silicon compound without a porogen precursor into a reaction chamber. In another embodiment, a layer of a silicon-containing dielectric material is deposited on at least a portion of a substrate by introducing a gaseous reagent comprising at least one silicon precursor comprising a silicon compound and a hardening additive into a reaction chamber.

[0032] The methods and compositions described herein include silicon compounds having the following Formula I:

[0033]

[0034] Where R 1 Selected from hydrogen, straight or branched C1-C 10 Alkyl, straight chain or branched C2-C 10 Alkenyl, straight or branched C2-C 10 Alkynyl, C3-C 10 Cycloalkyl, C3-C 10 Heterocycloalkyl, C5-C 10 Aryl and C3-C 10 Heteroaryl; R 2 is a C2-C4 alkanediyl group which, together with Si and oxygen atoms, forms a four-, five- or six-membered saturated ring having an optional alkyl substituent bonded to the ring; R 3 Selected from straight or branched C1-C 10 Alkyl, straight chain or branched C2-C 10 Alkenyl, straight or branched C2-C 10 Alkynyl, C3-C 10 Cycloalkyl, C3-C 10 Heterocycloalkyl, C5-C 10 Aryl, C3-C 10 Heteroaryl and alkoxy OR 4 , where R 4 Selected from straight or branched C1-C 10 Alkyl, straight chain or branched C2-C 10 Alkenyl, straight or branched C2-C 10 Alkynyl.

[0035] In the above formula and throughout the specification, the term "alkyl" means a straight or branched functional group with 1 to 10 carbon atoms. Exemplary straight chain alkyls include, but are not limited to, methyl, ethyl, n-propyl, butyl, pentyl, and hexyl. Exemplary branched alkyls include, but are not limited to, isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, tert-pentyl, isohexyl, and neohexyl. In certain embodiments, the alkyl may have one or more functional groups connected thereto, such as, but not limited to, alkoxy groups such as methoxy, ethoxy, isopropoxy, and n-propoxy, dialkylamino groups such as dimethylamino, or combinations thereof. In other embodiments, the alkyl does not have one or more functional groups connected thereto. The alkyl may be saturated, or alternatively unsaturated.

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

[0037] In the above formula I and throughout the specification, the term "heterocycle" means a C3-C 10 Heterocycloalkyl groups, such as epoxy groups.

[0038] In the above formula I and throughout the specification, the term "alkenyl" denotes a group having one or more carbon-carbon double bonds and having 2 to 10 or 2 to 10 or 2 to 6 carbon atoms.

[0039] In the above formula I and throughout the specification, the term "alkynyl" denotes a group having one or more carbon-carbon triple bonds and having 3 to 10 or 2 to 10 or 2 to 6 carbon atoms.

[0040] In the above formula I and throughout the specification, the term "aryl" refers to an aromatic cyclic functional group having 5 to 10 carbon atoms or 6 to 10 carbon atoms. Exemplary aryl groups include, but are not limited to, phenyl, benzyl, chlorobenzyl, tolyl, and o-xylyl.

[0041] In the above formula I and throughout the specification, the term "heteroaryl" refers to a C3-C 10 Heterocyclic aryl groups, such as 1,2,3-triazolyl, pyrrolyl and furanyl.

[0042] In the above formula I, the substituent R 2 It is a C3-C6-carbon atom that forms a four-membered, five-membered, or six-membered ring with Si and oxygen atoms. 10 As will be appreciated by the skilled person, R 2It is a substituted or unsubstituted hydrocarbon chain, which is connected with Si and oxygen atom in formula I to form a ring together, wherein the ring is a four-membered, five-membered or six-membered ring. In these embodiments, the ring structure can be a saturated ring, such as a cycloalkyl ring. Exemplary saturated rings include but are not limited to silacyclobutane, silacyclopentane and silacyclohexane, preferably silacyclopentane, or alkyl such as methyl substituted silacyclopentane.

[0043] Throughout the specification, the term "alkoxy" refers to a group derived from an alcohol having at least one carbon atom. Exemplary alkoxy groups include, but are not limited to, methoxy, ethoxy, isopropoxy, and n-propoxy.

[0044] Throughout the specification, the term "oxygen source" refers to a gas including oxygen (O2), a mixture of oxygen and helium, a mixture of oxygen and argon, carbon dioxide, carbon monoxide, and combinations thereof.

[0045] Throughout the specification, the term "dielectric film" refers to a dielectric film containing silicon and oxygen atoms and having Si v O w C x H y F z A film composed of v+w+x+y+z=100%, v is 10-35 atomic%, w is 10-65 atomic%, x is 5-40 atomic%, y is 10-50 atomic%, and z is 0-15 atomic%.

[0046] In certain embodiments of Formula I, R 1 is selected from hydrogen, methyl and ethyl; R 3 is selected from the group consisting of methyl, ethyl, isopropyl, n-propyl, methoxy, ethoxy, isopropoxy and n-propoxy; and R 2 With Si and oxygen atoms, a four-membered, five-membered or six-membered saturated cyclic ring is formed. In some embodiments, the four-membered, five-membered or six-membered saturated cyclic ring with Si atoms may have at least one alkyl substituent, such as methyl, on the ring structure. Examples of these embodiments are as follows:

[0047]

[0048]

[0049]

[0050]

[0051] The silicon compound of formula I can be synthesized by, for example, hydrosilylation of alkoxysilane with an unsaturated alcohol in the presence of a catalyst with or without a solvent, followed by cyclization to produce 1-oxa-2-silacycloalkane having a five-membered or six-membered saturated cyclic ring (e.g., reaction formulas (1) and (2)) with a yield of 70% or more, preferably 80% or more. An example of a synthetic route is shown below:

[0052]

[0053] Where R 1 , R 3 and R 4 Same as above; R 5 To R 8 Selected from hydrogen, straight or branched C1-C 10 Alkyl, preferably hydrogen or methyl.

[0054] The silicon compounds described herein and methods and compositions including the silicon compounds are preferably substantially free of one or more impurities, such as, but not limited to, halide ions and water. As used herein, the term "substantially free" as it relates to each impurity, means 100 parts per million (ppm) or less, 50 ppm or less, 10 ppm or less, 5 ppm or less, 1 ppm or less of each impurity, such as, but not limited to, chloride or water.

[0055] The silicon compound of formula I according to the present invention and the composition of the silicon precursor compound of formula I according to the present invention are preferably substantially free of halides. As used herein, the term "substantially free" refers to less than 5ppm (weight) measured by ICP-MS when it relates to halide ions (or halides), such as chlorides (i.e., chlorine-containing substances, such as HCl or silicon compounds having at least one Si-Cl bond) and fluorides, bromides and iodides, preferably less than 3ppm measured by ICP-MS, more preferably less than 1ppm measured by ICP-MS, and most preferably 0ppm measured by ICP-MS. Chlorides are known to act as decomposition catalysts for silicon compounds of formula I. Significant levels of chloride in the final product can lead to degradation of silicon precursor compounds. The gradual degradation of silicon compounds can directly affect the film deposition process, making it difficult for semiconductor manufacturers to achieve film specifications. In addition, the higher degradation rate of silicon compounds of formula I has a negative impact on shelf life or stability, making it difficult to ensure a shelf life of 1-2 years. Therefore, the accelerated decomposition of silicon compounds having formula I raises safety and performance issues related to the formation of these flammable and / or pyrophoric gaseous byproducts. The silicon compounds having formula I are preferably substantially free of metal ions, such as Li + 、Na + , K + Mg2+ , Ca 2+ 、Al 3+ , Fe 2+ , Fe 2+ , Fe 3+ 、Ni 2+ Cr 3+ As used herein, the term "substantially free" as it relates to Li, Na, K, Mg, Ca, Al, Fe, Ni, Cr means less than 5 ppm (by weight), preferably less than 3 ppm, more preferably less than 1 ppm, and most preferably 0.1 ppm as measured by ICP-MS. In some embodiments, the silicon compound having Formula I or IA does not contain metal ions, such as Li + 、Na + , K + Mg 2+ , Ca 2+ 、Al 3+ , Fe 2+ , Fe 2+ , Fe 3+ 、Ni 2+ Cr 3+ . As used herein, the term "free of" metal impurities when it relates to Li, Na, K, Mg, Ca, Al, Fe, Ni, Cr, precious metals such as volatile Ru or Pt complexes from ruthenium or platinum catalysts used in the synthesis, refers to less than 1 ppm, preferably 0.1 ppm (by weight) as measured by ICP-MS or other analytical methods for measuring metals. The silicon compound of formula I is also preferably substantially free of water or organosilane impurities, such as alkoxysilanes from the starting materials or from by-products of the synthesis. As used herein, the term "substantially free" when it relates to water is less than 100 ppm (by weight), preferably less than 50 ppm, more preferably less than 10 ppm; the sum of all organosilane impurities such as methyltriethoxysilane or dimethyldiethoxysilane analyzed by gas chromatography (GC) is less than 1.0% by weight, preferably less than 0.5% by weight, preferably less than 0.1% by weight.

[0056] Substantially free of halide compositions according to the present invention can be obtained by (1) reducing or eliminating chloride sources during chemical synthesis, and / or (2) implementing effective purification methods to remove chloride from the crude product so that the final purified product is substantially free of chloride. Chloride sources can be reduced by using reagents (such as chlorosilanes, bromosilanes or iodosilanes) that do not contain halide during synthesis, thereby avoiding the production of by-products containing halide ions. In addition, the above reagents should be substantially free of chloride impurities so that the resulting crude product is substantially free of chloride impurities. In a similar manner, the synthesis should not use halide-based solvents, catalysts or solvents containing unacceptably high levels of halide contamination. The crude product can also be treated by various purification methods so that the final product is substantially free of halides such as chlorides. Such methods have been fully described in the prior art and can include, but are not limited to, purification processes such as distillation or adsorption. Distillation is generally used to separate impurities from the desired product by utilizing differences in boiling points. Adsorption can also be used to utilize the different adsorption characteristics of components to achieve separation so that the final product is substantially free of halide. Adsorbents, such as commercially available MgO-Al2O3 blends, can be used to remove halides, such as chlorides.

[0057] While prior art silicon-containing silicon precursors (e.g., DEMS) polymerize to form structures with -O-linkages (e.g., -Si-O-Si- or -Si-OC-) in the polymer backbone once energy is applied in the reaction chamber, it is believed that silicon compounds having Formula I polymerize to form structures in which some of the -O-bridges in the backbone are replaced with -CH2-methylene or -CH2CH2-ethylene bridges. In films deposited using DEMS as a structure-forming precursor (in which carbon is primarily present in the form of terminal Si-Me groups), there is a correlation between %Si-Me (which is directly related to %C) and mechanical strength, wherein replacement of the bridging Si-O-Si groups with two terminal Si-Me groups reduces mechanical properties because the network structure is disrupted. In the case of silicon compounds, it is believed that the cyclic structure is disrupted during film deposition or curing (to remove at least a portion or substantially all of the porogen precursor contained in the film so deposited) to form SiCH2Si or SiCH2CH2Si bridging groups. In this way, carbon can be introduced in the form of bridging groups so that the network structure is not destroyed from a mechanical strength perspective by increasing the carbon content of the film. Without intending to be bound by a particular theory, it is believed that this feature adds carbon to the film, which allows the film to be more resilient to carbon depletion of the porous OSG film caused by processes such as etching of the film, plasma ashing of the photoresist, and NH3 plasma treatment of the copper surface. Carbon depletion in the OSG film can lead to an increase in the defect dielectric constant of the film, as well as problems with film etching and feature bowing during wet cleaning steps, and / or integration problems when depositing copper diffusion barriers.

[0058] In certain embodiments of the methods and compositions included herein, the structure-forming precursor further comprises a hardening additive that will increase the mechanical strength. Examples of hardening additives include tetraalkoxysilane (Si(OR 9 ), where R 9 Selected from straight or branched C1-C 10 Alkyl, straight chain or branched C2-C 10 Alkenyl, straight or branched C2-C 10 Alkynyl, C3-C 10 Cycloalkyl, C3-C 10 Heterocycloalkyl, C5-C 10 Aryl and C3-C 10 Heteroaryl, such as tetraethoxysilane (TEOS) or tetramethoxysilane (TMOS). In embodiments where a hardening additive is used, the composition of the structure-forming portion comprises about 30 to about 95 weight % of a structure-forming precursor comprising an alkyl-alkoxysilicon heterocyclic compound having Formula I; about 5 to about 70 weight % of a hardening additive; and about 40 to about 95 weight % of a porogen precursor, such as α-terpinene or cyclooctane, of the total precursor stream.

[0059] Although the phrase "gaseous reagents" is sometimes used herein to describe reagents, the phrase is intended to encompass reagents delivered to the reactor directly as gases, delivered to the reactor as vaporized liquids, sublimated solids, and / or transported to the reactor by an inert carrier gas.

[0060] Additionally, the reagents may be delivered to the reactor individually from different sources or as a mixture. The reagents may be delivered to the reactor system by a variety of means, preferably using pressurized stainless steel containers equipped with appropriate valves and fittings to allow liquid delivery to the reactor.

[0061] In addition to the structure forming material (i.e., the compound of formula I), other materials can be introduced into the reaction chamber before, during and / or after the deposition reaction. Such materials include, for example, inert gases (e.g., He, Ar, N2, Kr, Xe, etc., which can be used as carrier gases for relatively low volatility precursors and / or which can promote the solidification of the material deposited in this way and provide a more stable final film) and reactive species such as oxygen-containing species (e.g., O2, O3 and N2O), gaseous or liquid organic substances, NH3, H2, CO2 or CO. In a specific embodiment, the reaction mixture introduced into the reaction chamber includes at least one oxidant selected from O2, N2O, NO, NO2, CO2, water, H2O2, ozone and combinations thereof. In alternative embodiments, the reaction mixture does not include an oxidant.

[0062] Energy is applied to the gaseous reagents to induce the gas reaction and form a film on the substrate. Such energy can be provided by, for example, plasma, pulsed plasma, spiral plasma, high density plasma, inductively coupled plasma, remote plasma, hot filament and thermal (i.e., non-hot filament) methods. A secondary RF source can be used to change the plasma characteristics at the substrate surface. Preferably, the film is formed by plasma enhanced chemical vapor deposition ("PECVD").

[0063] The flow rate of each of the gaseous reagents is preferably 10-5000 sccm per single 200 mm wafer, more preferably 30-1000 sccm. The individual rates are selected so as to provide the desired amounts of silicon, carbon, and oxygen in the film. The actual flow rates required may depend on the wafer size and chamber configuration, and are in no way limited to 200 mm wafers or single wafer chambers.

[0064] In some embodiments, the film is deposited at a deposition rate of about 50 nanometers (nm) per minute.

[0065] The pressure in the reaction chamber during deposition is about 0.01 to about 600 Torr or about 1 to 15 Torr.

[0066] The films are preferably deposited to a thickness of 0.002 to 10 microns, although the thickness can be varied as desired. Blanket films deposited on non-patterned surfaces have excellent uniformity, with thickness variations of less than 2% of 1 standard deviation across the substrate, with the edges reasonably excluded, e.g., the outermost 5 mm edge of the substrate is not included in the statistical calculation of uniformity.

[0067] Preferred embodiments of the present invention provide thin film materials having low dielectric constants and improved mechanical properties, thermal stability, and chemical resistance (to oxygen, aqueous oxidizing environments, etc.) relative to other porous low-k dielectric films deposited using other structure-forming precursors known in the art. The structure-forming precursors described herein comprising alkyl-alkoxysilicon heterocyclic compounds having Formula I provide for higher incorporation of carbon (preferably predominantly organic carbon-CH x , wherein x is 1-3), thereby using specific precursors or network forming chemicals to deposit the film. In certain embodiments, most of the hydrogen in the film is bonded to carbon.

[0068] Low-k dielectric films deposited according to the compositions and methods described herein contain: (a) from about 10 to about 35 atomic %, more preferably from about 20 to about 30 atomic % silicon; (b) from about 10 to about 65 atomic %, more preferably from about 20 to about 45 atomic % oxygen; (c) from about 10 to about 50 atomic %, more preferably from about 15 to about 40 atomic % hydrogen; (d) from about 5 to about 40 atomic %, more preferably from about 10 to about 45 atomic % carbon. The film may also contain from about 0.1 to about 15 atomic %, more preferably from about 0.5 to about 7.0 atomic % fluorine to improve one or more material properties. Smaller amounts of other elements may also be present in certain films of the present invention. OSG materials are considered low-k materials because their dielectric constant is less than the dielectric constant of the standard material traditionally used in the industry, namely, silicon glass.

[0069] The total porosity of the membrane can be from 0 to 15% or more, depending on the process conditions and the desired final membrane properties. The membranes of the present invention preferably have a density of less than 2.3 g / ml, or less than 2.0 g / ml or less than 1.8 g / ml. The total porosity of the OSG membrane can be affected by post-deposition treatments (including exposure to heat or UV curing, plasma sources). Although preferred embodiments of the present invention do not include the addition of porogens during film deposition, porosity can be induced by post-deposition treatments such as UV curing. For example, UV treatment can produce a porosity approaching about 15% to about 20%, preferably about 5% to about 10%.

[0070] The membranes of the present invention may also contain fluorine in the form of inorganic fluorine (eg, Si-F).When present, fluorine is preferably included in an amount of about 0.5 to about 7 atomic %.

[0071] The membranes of the present invention are thermally stable and have good chemical resistance. In particular, the average weight loss of the preferred membranes after annealing at 425°C isothermally under N2 is less than 1.0 wt% / hr. Moreover, the membranes preferably have an average weight loss of less than 1.0 wt% / hr isothermally under 425°C in air.

[0072] The films are suitable for a variety of uses. The films are particularly suitable for deposition on semiconductor substrates and are particularly suitable for use as, for example, insulating layers, interlayer dielectric layers and / or intermetallic dielectric layers. The films can form conformal coatings. The mechanical properties exhibited by these films make them particularly suitable for use in Al subtractive technology and Cu damascene or dual damascene technology.

[0073] The film is compatible with chemical mechanical planarization (CMP) and anisotropic etching, and is capable of adhering to a variety of materials such as silicon, SiO2, Si3N4, OSG, FSG, silicon carbide, hydrogenated silicon carbide, silicon nitride, hydrogenated silicon nitride, silicon carbonitride, hydrogenated silicon carbonitride, boronitride, antireflective coatings, photoresists, organic polymers, porous organic and inorganic materials, metals such as copper and aluminum, and diffusion barriers such as but not limited to TiN, Ti(C)N, TaN, Ta(C)N, Ta, W, WN, or W(C)N. The film is preferably capable of sufficient adhesion to at least one of the foregoing materials to pass conventional tensile testing, such as the ASTM D3359-95a tape tensile test. If there is no discernible film removal, the sample is considered to have passed the test.

[0074] Thus, in certain embodiments, the film is an insulating layer, an interlayer dielectric layer, an intermetallic dielectric layer, a capping layer, a chemical mechanical planarization (CMP) or etch stop layer, a barrier layer, or an adhesion layer in an integrated circuit.

[0075] Although the films described herein are uniformly deposited dielectric films, films such as those used in fully integrated structures may actually consist of multiple sandwich layers, such as thin layers deposited at the bottom or top containing little or no porogen, or layers may be deposited under conditions where there is a lower porogen precursor flow rate, or layers may be deposited, for example, at higher plasma powers, such that not all porogen precursors can be removed by UV treatment. These sandwich layers may be used to enhance secondary integration properties such as adhesion, etch selectivity, or electromigration performance.

[0076] Although the present invention is particularly suitable for providing films, and the products of the present invention are described herein primarily as films, the present invention is not limited thereto. The products of the present invention may be provided in any form capable of being deposited by CVD, such as coatings. Multi-layer assemblies and other types of objects that are not necessarily planar or thin, and numerous objects that are not necessarily used in integrated circuits. Preferably, the substrate is a semiconductor.

[0077] In addition to the OSG products of the present invention, the present disclosure also includes methods of making the products, methods of using the products, and compounds and compositions that can be used to make the products. For example, a method for making an integrated circuit on a semiconductor device is disclosed in U.S. Pat. No. 6,583,049, which is incorporated herein by reference.

[0078] The composition of the present invention may further include, for example, at least one pressurizable container (preferably stainless steel) equipped with suitable valves and fittings to allow the hardening additive and the silicon precursor of Formula I, such as DESCAP, to be delivered to the process reactor. The contents of the container may be premixed. Alternatively, for example, the hardening additive and the precursor may be kept in separate containers, or in a single container with a separation device for keeping the hardening additive and the precursor separate during storage. Such a container may also have a device for mixing the porogen and the precursor when necessary.

[0079] The preliminary (or so deposited) film can be further treated by a curing step, i.e., applying an additional energy source to the film, which may include thermal annealing, chemical treatment, in-situ or remote plasma treatment, photocuring (e.g., UV) and / or microwave treatment. Other in-situ or post-deposition treatments can be used to enhance material properties, such as hardness, stability (for shrinkage, for air exposure, for etching, for wet etching, etc.), integrity, uniformity and adhesion. Thus, as used herein, the term "post-treatment" means treating the film with energy (e.g., heat, plasma, photons, electrons, microwaves, etc.) or chemicals to remove porogens, and optionally, to enhance material properties.

[0080] The conditions under which post-treatment is performed can vary widely. For example, post-treatment can be performed under high pressure or under vacuum.

[0081] UV annealing is the preferred curing method and is generally carried out under the following conditions.

[0082] The environment can be inert (e.g., nitrogen, CO2, noble gases (He, Ar, Ne, Kr, Xe), etc.), oxidizing (e.g., oxygen, air, dilute oxygen environment, oxygen-rich environment, ozone, nitrous oxide, etc.), or reducing (dilute or concentrated hydrogen, hydrocarbons (saturated, unsaturated, linear or branched, aromatic), etc.). The pressure is preferably about 1 Torr to about 1000 Torr, more preferably atmospheric pressure. However, a vacuum environment can also be used for thermal annealing and any other post-treatment methods. The temperature is preferably 200-500°C, and the heating rate is 0.1 to 100°C / min. The total UV annealing time is preferably 0.01 minutes to 12 hours.

[0083] The chemical treatment of OSG film was performed under the following conditions.

[0084] Fluorination (HF, SIF4, NF3, F2, COF2, CO2F2, etc.), oxidation (H2O2, O3, etc.), chemical drying, methylation, or other chemical treatments that enhance the properties of the final material. The chemicals used in such treatments may be in solid, liquid, gaseous, and / or supercritical fluid states.

[0085] The supercritical fluid post-treatment for selective removal of porogens from organosilicate membranes was carried out under the following conditions.

[0086] Fluids can be carbon dioxide, water, nitrous oxide, ethylene, SF6 and / or other types of chemicals. Other chemicals can be added to the supercritical fluid to enhance the process. Chemicals can be inert (e.g., nitrogen, CO2, rare gases (He, Ar, Ne, Kr, Xe), etc.), oxidizing (e.g., oxygen, ozone, nitrous oxide, etc.) or reducing (e.g., dilute or concentrated hydrocarbons, hydrogen, plasma containing hydrogen, etc.). The temperature is preferably ambient temperature to 500° C. Chemicals can also include larger chemicals, such as surfactants. The total exposure time is preferably 0.01 minutes to 12 hours.

[0087] Plasma treatment for selective removal of labile groups and possible chemical modification of OSG films was performed under the following conditions.

[0088] The environment can be inert (nitrogen, CO2, noble gases (He, Ar, Ne, Kr, Xe), etc.), oxidative (e.g., oxygen, air, dilute oxygen environment, oxygen-rich environment, ozone, nitrous oxide, etc.), or reductive (e.g., dilute or concentrated hydrogen, hydrocarbons (saturated, unsaturated, linear or branched, aromatic), etc.). The plasma power is preferably 0-5000 W. The temperature is preferably approximately ambient temperature to about 500° C. The pressure is preferably 10 mTorr to atmospheric pressure. The total curing time is preferably 0.01 minutes to 12 hours.

[0089] UV curing for chemical crosslinking of organosilicate films is generally carried out under the following conditions.

[0090] The environment can be inert (e.g., nitrogen, CO2, noble gases (He, Ar, Ne, Kr, Xe), etc.), oxidizing (e.g., oxygen, air, dilute oxygen environment, oxygen-rich environment, ozone, nitrous oxide, etc.), or reducing (e.g., dilute or concentrated hydrocarbons, hydrogen, etc.). The temperature is preferably approximately ambient temperature to about 500°C. The power is preferably 0 to about 5000W. The wavelength is preferably IR, visible light, UV, or deep UV (wavelength <200nm). The total UV curing time is preferably 0.01 minutes to 12 hours.

[0091] Microwave post-treatment of organosilicate films is usually carried out under the following conditions.

[0092] The environment can be inert (e.g., nitrogen, CO2, noble gases (He, Ar, Ne, Kr, Xe), etc.), oxidizing (e.g., oxygen, air, dilute oxygen environment, oxygen-rich environment, ozone, nitrous oxide, etc.), or reducing (e.g., dilute or concentrated hydrocarbons, hydrogen, etc.). The temperature is preferably approximately ambient temperature to about 500°C. The power and wavelength are variable and adjustable for specific bonds. The total curing time is preferably 0.01 minutes to 12 hours.

[0093] Electron beam post-treatment for selective removal of porogens or specific chemicals from organosilicate films and / or to improve film properties is typically performed under the following conditions.

[0094] The environment can be vacuum, inert (e.g., nitrogen, CO2, noble gases (He, Ar, Ne, Kr, Xe), etc.), oxidizing (e.g., oxygen, air, dilute oxygen environment, oxygen-rich environment, ozone, nitrous oxide, etc.), or reducing (e.g., dilute or concentrated hydrocarbons, hydrogen, etc.). The temperature is preferably from room temperature to 500°C. The electron density and energy can vary and are adjustable for specific bonds. The total curing time is preferably from 0.001 minutes to 12 hours and can be continuous or pulsed. Additional guidance on the general use of electron beams can be obtained from publications such as: S. Chattopadhyay et al., Journal of Materials Science, 36 (2001) 4323-4330; G. Kloster et al., Proceedings of IITC, June 3-5, 2002, SF, CA; and U.S. Patent Nos. 6,207,555B1, 6,204,201B1 and 6,132,814A1. The use of electron beam treatment can provide porogen removal and film mechanical property enhancement through bond formation processes in the matrix.

[0095] Therefore, the present invention provides at least the following:

[0096] 1. A chemical vapor deposition method for preparing a dielectric film, the method comprising:

[0097] A gaseous reagent is introduced into a reaction chamber in which a substrate is provided, wherein the gaseous reagent comprises a silicon precursor comprising a silicon compound having the following Formula I:

[0098]

[0099] Where R 1 Selected from hydrogen, straight or branched C1-C 10 Alkyl, straight chain or branched C2-C 10 Alkenyl, straight or branched C2-C 10 Alkynyl, C3-C 10 Cycloalkyl, C3-C10 Heterocycloalkyl, C5-C 10 Aryl and C3-C 10 Heteroaryl; R 2 is a C2-C4 alkanediyl group which, together with Si and oxygen atoms, forms a four-, five- or six-membered saturated cyclic ring having an optional C1-C6 alkyl substituent; R 3 Selected from straight or branched C1-C 10 Alkyl, straight chain or branched C2-C 10 Alkenyl, straight or branched C2-C 10 Alkynyl, C3-C 10 Cycloalkyl, C3-C 10 Heterocycloalkyl, C5-C 10 Aryl, C3-C 10 Heteroaryl and alkoxy OR 4 , where R 4 Selected from straight or branched C1-C 10 Alkyl, straight chain or branched C2-C 10 Alkenyl and straight or branched C2-C 10 Alkynyl; and

[0100] Energy is applied to the gaseous reagents in the reaction chamber to induce a reaction of the gaseous reagents to deposit a film on the substrate.

[0101] 2. The method according to item 1, wherein the silicon precursor further comprises a hardening additive.

[0102] 3. The method according to claim 1, wherein the silicon compound comprises at least one selected from the group consisting of 2,2,5,5-tetramethyl-1-oxa-2-silacyclopentane, 2,5,5-trimethyl-2-ethoxy-1-oxa-2-silacyclopentane, 2,5,5-trimethyl-2-methoxy-1-oxa-2-silacyclopentane, 2,5,5-trimethyl-2-isopropoxy-1-oxa-2-silacyclopentane, 2,2-dimethyl-1-oxa-2-silacyclohexane, 2,2,6,6-tetramethyl-1-oxa-2-silacyclohexane, 2-methyl-2-ethoxy-1-oxa-2-silacyclohexane, 2,6,6-trimethyl-2-ethoxy-1-oxa-2-silacyclohexane, 2-methyl-2-methoxy-1-oxa-2-silacyclohexane, 2-Methyl-2-n-propoxy-1-oxa-2-silacyclohexane, 2,6,6-trimethyl-2-n-propoxy-1-oxa-2-silacyclohexane, 2-methyl-2-isopropoxy-1-oxa-2-silacyclohexane, 2,6,6-trimethyl-2-isopropoxy-1-oxa-2-silacyclohexane, 2,5,5-trimethyl-2-isopropyl-1-oxa-2-silacyclopentane, 2-methyl-2-isopropyl-1-oxa-2-silacyclopentane, 2-methyl-2-isopropyl-1-oxa-2-silacyclopentane, 2-methyl-2-isopropyl-1-oxa-2-silacyclohexane, 2,6,6-trimethyl-2-isopropyl-1-oxa-2-silacyclohexane, and combinations thereof.

[0103] 4. The method of clause 2, wherein the hardening additive comprises tetraethoxysilane.

[0104] 5. The method of clause 2, wherein the hardening additive comprises tetramethoxysilane.

[0105] 6. The method according to item 1, which is a plasma enhanced chemical vapor deposition method.

[0106] 7. A method according to item 1, wherein the gas reagent also contains at least one oxygen source selected from O2, N2O, NO, NO2, CO2, CO, water, H2O2, ozone and combinations thereof.

[0107] 8. The method of claim 1, wherein in the applying step, the reaction chamber contains at least one gas selected from the group consisting of He, Ar, N2, Kr, Xe, NH3, H2, CO2 and CO.

[0108] 9. The method according to item 1, further comprising the step of applying additional energy to the membrane.

[0109] 10. The method of item 9, wherein the additional energy is at least one selected from heat treatment, ultraviolet (UV) treatment, electron beam treatment, and gamma radiation treatment.

[0110] 11. A method according to item 10, wherein the UV treatment is performed during at least a portion of the heat treatment.

[0111] 12. The method of claim 1, wherein the gaseous reagent further comprises a porogen precursor; and

[0112] Wherein the step of applying energy to the gas reagent to deposit a film includes co-depositing a sacrificial porogen on the substrate.

[0113] 13. A composition for use in a deposition method for preparing a dielectric film, the composition comprising a silicon compound having the following formula I:

[0114]

[0115] Where R 1 Selected from hydrogen, straight or branched C1-C 10 Alkyl, straight chain or branched C2-C 10 Alkenyl, straight or branched C2-C 10 Alkynyl, C3-C 10 Cycloalkyl, C3-C 10 Heterocycloalkyl, C5-C 10 Aryl and C3-C 10 Heteroaryl; R 2 is a C2-C4 alkanediyl group which, together with Si and oxygen atoms, forms a four-, five- or six-membered saturated cyclic ring having an optional C1-C6 alkyl substituent; R 3 Selected from straight or branched C1-C 10 Alkyl, straight chain or branched C2-C 10 Alkenyl, straight or branched C2-C 10 Alkynyl, C3-C 10 Cycloalkyl, C3-C 10 Heterocycloalkyl, C5-C 10 Aryl, C3-C 10 Heteroaryl and alkoxy OR 4 , where R 4 Selected from straight or branched C1-C 10 Alkyl, straight chain or branched C2-C 10 Alkenyl and straight or branched C2-C 10 Alkynyl.

[0116] 14. The composition according to item 13, wherein the silicon compound is at least one selected from the group consisting of 2,2,5,5-tetramethyl-1-oxa-2-silacyclopentane, 2,5,5-trimethyl-2-ethoxy-1-oxa-2-silacyclopentane, 2,5,5-trimethyl-2-methoxy-1-oxa-2-silacyclopentane, 2,5,5-trimethyl-2-isopropoxy-1-oxa-2-silacyclopentane, 2,2-dimethyl-1-oxa-2-silacyclohexane, 2,2,6,6-tetramethyl-1-oxa-2-silacyclohexane, 2-methyl-2-ethoxy-1-oxa-2-silacyclohexane, 2,6,6-trimethyl-2-ethoxy-1-oxa-2-silacyclohexane, 2-methyl-2-methoxy-1-oxa-2-silacyclohexane, Oxa-2-silacyclohexane, 2,6,6-trimethyl-2-methoxy-1-oxa-2-silacyclohexane, 2-methyl-2-n-propoxy-1-oxa-2-silacyclohexane, 2,6,6-trimethyl-2-n-propoxy-1-oxa-2-silacyclohexane, 2-methyl-2-isopropoxy-1-oxa-2-silacyclohexane, 2,6,6-trimethyl-2-isopropoxy-1-oxa-2-silacyclohexane, 2,5,5-trimethyl-2-isopropyl-1-oxa-2-silacyclopentane, 2-methyl-2-isopropyl-1-oxa-2-silacyclopentane, 2-methyl-2-isopropyl-1-oxa-2-silacyclopentane, 2-methyl-2-isopropyl-1-oxa-2-silacyclohexane, 2,6,6-trimethyl-2-isopropyl-1-oxa-2-silacyclohexane, and combinations thereof.

[0117] 15. A method for preparing a silicon compound represented by formula I:

[0118]

[0119] The method comprises:

[0120] According to reaction formula (1) or (2), alkoxysilane is hydrosilylated with an unsaturated alcohol in the presence of a catalyst in the presence or absence of a solvent, followed by cyclization, with a yield of 70% or more:

[0121]

[0122] Where R 1 Selected from hydrogen, straight or branched C1-C 10 Alkyl, straight chain or branched C2-C 10 Alkenyl, straight or branched C2-C 10 Alkynyl, C3-C 10 Cycloalkyl, C3-C 10 Heterocycloalkyl, C5-C 10 Aryl and C3-C 10 Heteroaryl; R 3 Selected from straight or branched C1-C10 Alkyl, straight chain or branched C2-C 10 Alkenyl, straight or branched C2-C 10 Alkynyl, C3-C 10 Cycloalkyl, C3-C 10 Heterocycloalkyl, C5-C 10 Aryl and C3-C 10 Heteroaryl, and alkoxy OR 4 , where R 4 Selected from straight or branched C1-C 10 Alkyl, straight chain or branched C2-C 10 Alkenyl, straight or branched C2-C 10 Alkynyl; and R 5 To R 8 independently selected from hydrogen, straight or branched C1-C 10 alkyl.

[0123] 16. The method according to item 15, wherein the compound represented by formula I is selected from 2,2,5,5-tetramethyl-1-oxa-2-silacyclopentane, 2,5,5-trimethyl-2-ethoxy-1-oxa-2-silacyclopentane, 2,5,5-trimethyl-2-methoxy-1-oxa-2-silacyclopentane, 2,5,5-trimethyl-2-isopropoxy-1-oxa-2-silacyclopentane, 2,2-dimethyl-1-oxa-2-silacyclohexane, 2,2,6,6-tetramethyl-1-oxa-2-silacyclohexane, 2-methyl-2-ethoxy-1-oxa-2-silacyclohexane, 2,6,6-trimethyl-2-ethoxy-1-oxa-2-silacyclohexane, 2-methyl-2-methoxy-1-oxa-2-silacyclohexane, -silacyclohexane, 2,6,6-trimethyl-2-methoxy-1-oxa-2-silacyclohexane, 2-methyl-2-n-propoxy-1-oxa-2-silacyclohexane, 2,6,6-trimethyl-2-n-propoxy-1-oxa-2-silacyclohexane, 2-methyl-2-isopropoxy-1-oxa-2-silacyclohexane, 2,6,6-trimethyl-2-isopropoxy-1-oxa-2-silacyclohexane, 2,5,5-trimethyl-2-isopropyl-1-oxa-2-silacyclopentane, 2-methyl-2-isopropyl-1-oxa-2-silacyclopentane, 2-methyl-2-isopropyl-1-oxa-2-silacyclopentane, 2-methyl-2-isopropyl-1-oxa-2-silacyclohexane, 2,6,6-trimethyl-2-isopropyl-1-oxa-2-silacyclohexane and combinations thereof.

[0124] 17. A composition for vapor deposition of dielectric films comprising a silicon compound having the following formula I:

[0125]

[0126] Where R 1Selected from hydrogen, straight or branched C1-C 10 Alkyl, straight chain or branched C2-C 10 Alkenyl, straight or branched C2-C 10 Alkynyl, C3-C 10 Cycloalkyl, C3-C 10 Heterocycloalkyl, C5-C 10 Aryl and C3-C 10 Heteroaryl; R 2 is a C2-C4 alkanediyl group which, together with Si and oxygen atoms, forms a four-, five- or six-membered saturated cyclic ring having an optional C1-C6 alkyl substituent; R 3 Selected from straight or branched C1-C 10 Alkyl, straight chain or branched C2-C 10 Alkenyl, straight or branched C2-C 10 Alkynyl, C3-C 10 Cycloalkyl, C3-C 10 Heterocycloalkyl, C5-C 10 Aryl, C3-C 10 Heteroaryl and alkoxy OR 4 , where R 4 Selected from straight or branched C1-C 10 Alkyl, straight chain or branched C2-C 10 Alkenyl and straight or branched C2-C 10 alkynyl; and wherein the compound is substantially free of at least one impurity selected from the group consisting of halides, organosilane impurities, and water.

[0127] 18. The composition according to item 17, wherein the silicon compound is at least one selected from the group consisting of 2,2,5,5-tetramethyl-1-oxa-2-silacyclopentane, 2,5,5-trimethyl-2-ethoxy-1-oxa-2-silacyclopentane, 2,5,5-trimethyl-2-methoxy-1-oxa-2-silacyclopentane, 2,5,5-trimethyl-2-isopropoxy-1-oxa-2-silacyclopentane, 2,2-dimethyl-1-oxa-2-silacyclohexane, 2,2,6,6-tetramethyl-1-oxa-2-silacyclohexane, 2-methyl-2-ethoxy-1-oxa-2-silacyclohexane, 2,6,6-trimethyl-2-ethoxy-1-oxa-2-silacyclohexane, 2-methyl-2-methoxy-1-oxa-2-silacyclohexane, Oxa-2-silacyclohexane, 2,6,6-trimethyl-2-methoxy-1-oxa-2-silacyclohexane, 2-methyl-2-n-propoxy-1-oxa-2-silacyclohexane, 2,6,6-trimethyl-2-n-propoxy-1-oxa-2-silacyclohexane, 2-methyl-2-isopropoxy-1-oxa-2-silacyclohexane, 2,6,6-trimethyl-2-isopropoxy-1-oxa-2-silacyclohexane, 2,5,5-trimethyl-2-isopropyl-1-oxa-2-silacyclopentane, 2-methyl-2-isopropyl-1-oxa-2-silacyclopentane, 2-methyl-2-isopropyl-1-oxa-2-silacyclopentane, 2-methyl-2-isopropyl-1-oxa-2-silacyclohexane, 2,6,6-trimethyl-2-isopropyl-1-oxa-2-silacyclohexane, and combinations thereof.

[0128] 19. A composition according to item 17, wherein the halide comprises chloride ions.

[0129] 20. A composition according to item 19, wherein the chloride ion, if present, is present at a concentration of 50 ppm or less.

[0130] 21. A composition according to item 19, wherein the chloride ion, if present, is present at a concentration of 10 ppm or less.

[0131] 22. A composition according to item 19, wherein the chloride ion, if present, is present at a concentration of 5 ppm or less.

[0132] 23. A composition according to claim 19, wherein the composition has 0 ppm chloride ions.

[0133] 24. The composition of item 17, wherein the sum of all organosilane impurities is 1.0 wt% or less based on GC.

[0134] 25. The composition of item 17, wherein the sum of all organosilane impurities is 0.5 wt% or less based on GC.

[0135] The present invention will be described in more detail with reference to the following examples, but it should be construed that the present invention is not limited thereto.

[0136] Working Example 1

[0137] The synthesis of 2,5,5-trimethyl-2-ethoxy-1-oxa-2-silacyclopentane, wherein in the reaction formula (1), R 1 =Me, R 3 =OEt, R 4 =Et, R 5 =R 6 =Me

[0138] 1.50 mL of Karstedt catalyst (2% Pt in xylene) in 741.0 g (8.6 mol) of 2-methyl-3-butene-2-ol heated to 50° C. in a three-necked round-bottom flask equipped with an internal thermocouple and a reflux condenser was added dropwise via an additional funnel 1155.0 g (8.6 mol) of diethoxymethylsilane. There was an exotherm and the temperature of the mixture gradually increased to 85° C., at which point the heating was turned off. The temperature was maintained between 75-85° C. while the addition of DEMS was performed. Once the addition was complete, the reaction was allowed to cool back to room temperature and stirred overnight. The ethanol byproduct was removed by distillation at ambient pressure and heated to a vapor temperature of 153° C. The product was vacuum distilled at 93-94° C., 105-108 torr pressure, in an amount of 1235 g, with a purity of 97%. The yield was 82%.

[0139] Working Example 2

[0140] The synthesis of 2,2,5,5-tetramethyl-1-oxa-2-silacyclopentane, wherein in the reaction formula (1), R 1 =R 3 =Me, R 4 =Et, R 5 =R 6 =Me

[0141] 2.00mL Karstedt catalyst (2% Pt in xylene) in 1731.0g (20.1mol) 2-methyl-3-butene-2-ol heated to 50°C in a three-necked round-bottom flask equipped with an internal thermocouple and a reflux condenser was added dropwise via an addition funnel 2095.0g (20.1mol) dimethylethoxysilane. There was a gradual exotherm, and the reaction temperature reached 87°C, after which the temperature gradually decreased to 60°C. Increase the addition of DMES, at which point the temperature began to gradually increase, and then a sharp exotherm occurred, and the reaction mixture refluxed at 95°C. The second temperature spike was more intense than the first temperature spike. After the addition was complete, the reaction was cooled back to room temperature and stirred overnight. GC was run on the sample, showing that the ratio of product to diethoxydimethylsilane was 3:1. Ethanol and residual 2-methyl-3-butene-2-ol starting materials were removed by distillation at ambient pressure. Once the vapor temperature reached 107°C, removal was stopped. The product was distilled at ambient pressure in an amount of 566 g with a purity of 97%. The yield was 20%.

[0142] Working Example 3

[0143] The synthesis of 2,5,5-trimethyl-2-isopropyl-1-oxa-2-silacyclopentane, wherein in the reaction formula (1), R 1 =Me, R 3 = isopropyl, R 4 =Et, R 5 =R 6 =Me

[0144] To a single-necked round-bottom flask containing 24.6 g (186.0 mmol) of isopropylethoxymethylsilane in a mixture of 350 mL of hexane and THF was added 16.0 g (186.0 mmol) of 2-methyl-3-butene-2-ol, followed by 0.03 mL of Karstedt's catalyst (2% Pt in xylene). The reaction was stirred overnight. GC-MS indicated evidence of the desired product at m / z 172.

[0145] Working Example 4 (Membrane Example)

[0146] PECVD of Silicon-Containing Dielectric Films Using Dielectric 2,2,5,5-Tetramethyl-1-Oxa-2-Silacyclopentane

[0147] An exemplary film for 300 mm wafer processing was formed by a plasma enhanced CVD (PECVD) process using an Applied Materials Producer SE system that deposits the film on two wafers simultaneously. Therefore, the precursor and gas flow rates correspond to the flow rates required to deposit the film on two wafers simultaneously. The per-wafer RF power described is calibrated because each wafer processing station has its own independent RF power supply. Films are deposited from two different chemical precursors under different process conditions. The PECVD process generally includes the following basic steps: initial setup and stabilization of the gas flow, film deposition onto a silicon wafer substrate, and purging / evacuating the chamber before substrate removal. Experiments were performed on p-type Si wafers (resistivity range = 8-12 Ohm-cm).

[0148] Thickness and refractive index were measured on a SCI Film Tek 2000 reflectometer. Dielectric constant was determined on medium resistivity p-type wafers (range 8-12 ohm-cm) using the Hg probe technique. Mechanical properties (elastic modulus and hardness, GPa) were determined using nanoindentation, carbon content (atomic %) was determined by X-ray photoelectron spectroscopy, and SiO was determined by infrared spectroscopy. x The latter includes the silyl methyl density attributable to Si(CH3)1 and the disilyl methylene bridge density (SiCH2Si / SiO x *1E4).

[0149] Working Example 5 (Membrane Example)

[0150] Low dielectric constant films were deposited using a 2,2,5,5-tetramethyl-1-oxa-2-silacyclopentane precursor under the following conditions: total precursor flow rate was 2000 mg / min; oxygen flow rate was 15 sccm; deposition temperature was maintained at 390°C; RF power was varied from 230-500 W; pressure was maintained at 7.5 Torr; electrode spacing was maintained at 380 mils; He carrier gas flow for delivering the precursor to the process chamber was 1500 sccm. Table 1 below shows the film properties obtained from the 2,2,5,5-tetramethyl-1-oxa-2-silacyclopentane precursor at three different RF powers. The deposited films exhibited higher mechanical strength, higher dielectric constant, and higher network carbon, as obtained from the ratio of the integrated Si-CH2-Si band to the integrated Si-O band in the FTIR spectrum, Si-CH2-Si / SiO x The integration of higher network carbon density, such as Si-CH2-Si, is desirable because it reduces the depth at which film damage occurs during subsequent integration steps such as etching, ashing, planarization, and metallization.

[0151] Table 1: Film properties obtained from 2,2,5,5-tetramethyl-1-oxa-2-silacyclopentane precursor at three RF powers:

[0152]

[0153] Working Example 6 (Membrane Example)

[0154] PECVD of Silicon-Containing Dielectric Films Using Dielectric 2,5,5-Trimethyl-2-ethoxy-1-oxa-2-silacyclopentane

[0155] Low dielectric constant films were deposited using a 2,5,5-trimethyl-2-ethoxy-1-oxa-2-silacyclopentane precursor under the following conditions: total precursor flow rate varied from 2000-2500 mg / min; oxygen flow rate was 25-50 sccm; deposition temperature was maintained at 390°C; RF power varied from 315-515 W; pressure was maintained at 7.5 Torr; electrode spacing was maintained at 380 mils; He carrier gas flow for delivering the precursor to the process chamber was 1500 sccm. Table 2 below shows the film properties obtained from a 2,5,5-trimethyl-2-ethoxy-1-oxa-2-silacyclopentane precursor under three different process conditions. The deposited films exhibited similar mechanical strength and dielectric constant relative to 2,2,5,5-tetramethyl-1-oxa-2-silacyclopentane, but showed lower network carbon, as measured by Si-CH2-Si / SiO obtained from the ratio of the integrated Si-CH2-Si band to the integrated Si-O band in the FTIR spectrum. x The replacement of methyl groups with ethoxy groups reduces the amount of network carbon that can be incorporated into the membrane.

[0156] Table 2: Film properties obtained from 2,5,5-trimethyl-2-ethoxy-1-oxa-2-silacyclopentane precursor at three RF powers:

[0157]

[0158]

[0159] Although illustrated and described above with reference to certain specific embodiments and examples, the invention is not intended to be limited to the details shown. Rather, various changes may be made in the details within the scope and range of equivalents of the claims without departing from the spirit of the invention. It is expressly intended that all ranges broadly recited in this document include within their scope all narrower ranges that fall within the broader ranges.

Claims

1. A chemical vapor deposition method for preparing a dielectric film, the method comprising: A gaseous reagent is introduced into a reaction chamber in which a substrate is provided, wherein the gaseous reagent comprises a silicon precursor comprising a silicon compound having the following Formula I: Where R 1 Selected from hydrogen, straight or branched C1-C 10 Alkyl, straight chain or branched C2-C 10 Alkenyl, straight or branched C2-C 10 Alkynyl, C3-C 10 Cycloalkyl, C3-C 10 Heterocycloalkyl, C5-C 10 Aryl and C3-C 10 Heteroaryl; R 2 is a C2-C4 alkanediyl group which, together with Si and oxygen atoms, forms a four-, five- or six-membered saturated cyclic ring having an optional C1-C6 alkyl substituent; R 3 Selected from straight or branched C1-C 10 Alkyl, straight chain or branched C2-C 10 Alkenyl, straight or branched C2-C 10 Alkynyl, C3-C 10 Cycloalkyl, C3-C 10 Heterocycloalkyl, C5-C 10 Aryl, C3-C 10 Heteroaryl and alkoxy OR 4 , where R 4 Selected from straight or branched C1-C 10 Alkyl, straight chain or branched C2-C 10 Alkenyl and straight or branched C2-C 10 Alkynyl; and applying energy to the gaseous reagent in the reaction chamber to induce a reaction of the gaseous reagent to deposit a film on the substrate; The silicon compound having formula I is not 2,2-dimethyl-1-oxa-2-silacyclohexane. 2 . The method of claim 1 , wherein the silicon precursor further comprises a hardening additive.

3. The method according to claim 1, wherein the silicon compound comprises at least one selected from the group consisting of 2,2,5,5-tetramethyl-1-oxa-2-silacyclopentane, 2,5,5-trimethyl-2-ethoxy-1-oxa-2-silacyclopentane, 2,5,5-trimethyl-2-methoxy-1-oxa-2-silacyclopentane, 2,5,5-trimethyl-2-isopropoxy-1-oxa-2-silacyclopentane, 2,2,6,6-tetramethyl-1-oxa-2-silacyclohexane, 2-methyl-2-ethoxy-1-oxa-2-silacyclohexane, 2,6,6-trimethyl-2-ethoxy-1-oxa-2-silacyclohexane, 2-methyl-2-methoxy-1-oxa-2-silacyclohexane , 2,6,6-trimethyl-2-methoxy-1-oxa-2-silacyclohexane, 2-methyl-2-n-propoxy-1-oxa-2-silacyclohexane, 2,6,6-trimethyl-2-n-propoxy-1-oxa-2-silacyclohexane, 2-methyl-2-isopropoxy-1-oxa-2-silacyclohexane, 2,6,6-trimethyl-2-isopropoxy-1-oxa-2-silacyclohexane, 2,5,5-trimethyl-2-isopropyl-1-oxa-2-silacyclopentane, 2-methyl-2-isopropyl-1-oxa-2-silacyclopentane, 2-methyl-2-isopropyl-1-oxa-2-silacyclopentane, 2-methyl-2-isopropyl-1-oxa-2-silacyclohexane, 2,6,6-trimethyl-2-isopropyl-1-oxa-2-silacyclohexane and combinations thereof. The method of claim 2 , wherein the hardening additive comprises tetraethoxysilane. The method of claim 2 , wherein the hardening additive comprises tetramethoxysilane. The method according to claim 1 , which is a plasma enhanced chemical vapor deposition method.

7. The method according to claim 1, wherein the gaseous reagent further comprises at least one oxygen source selected from the group consisting of O2, N2O, NO, NO2, CO2, CO, water, H2O2, ozone and combinations thereof.

8. The method of claim 1, wherein in the applying step, the reaction chamber contains at least one gas selected from the group consisting of He, Ar, N2, Kr, Xe, NH3, H2, CO2, and CO.

9. The method of claim 1 further comprising the step of applying additional energy to the membrane.

10. The method of claim 9, wherein the additional energy is at least one selected from heat treatment, ultraviolet (UV) treatment, electron beam treatment, and gamma radiation treatment. The method according to claim 10 , wherein the UV treatment is performed during at least a portion of the heat treatment.

12. The method of claim 1, wherein the gaseous reagent further comprises a porogen precursor; and Wherein the step of applying energy to the gas reagent to deposit a film includes co-depositing a sacrificial porogen on the substrate.

13. A composition for use in a deposition method for preparing a dielectric film, the composition comprising a silicon compound having the following formula I: Where R 1 Selected from hydrogen, straight or branched C1-C 10 Alkyl, straight chain or branched C2-C 10 Alkenyl, straight or branched C2-C 10 Alkynyl, C3-C 10 Cycloalkyl, C3-C 10 Heterocycloalkyl, C5-C 10 Aryl and C3-C 10 Heteroaryl; R 2 is a C2-C4 alkanediyl group which, together with Si and oxygen atoms, forms a four-, five- or six-membered saturated cyclic ring having an optional C1-C6 alkyl substituent; R 3 Selected from straight or branched C1-C 10 Alkyl, straight chain or branched C2-C 10 Alkenyl, straight or branched C2-C 10 Alkynyl, C3-C 10 Cycloalkyl, C3-C 10 Heterocycloalkyl, C5-C 10 Aryl, C3-C 10 Heteroaryl and alkoxy OR 4 , where R 4 Selected from straight or branched C1-C 10 Alkyl, straight chain or branched C2-C 10 Alkenyl and straight or branched C2-C 10 Alkynyl; The silicon compound having formula I is not 2,2-dimethyl-1-oxa-2-silacyclohexane.

14. The composition according to claim 13, wherein the silicon compound is at least one selected from the group consisting of 2,2,5,5-tetramethyl-1-oxa-2-silacyclopentane, 2,5,5-trimethyl-2-ethoxy-1-oxa-2-silacyclopentane, 2,5,5-trimethyl-2-methoxy-1-oxa-2-silacyclopentane, 2,5,5-trimethyl-2-isopropoxy-1-oxa-2-silacyclopentane, 2,2,6,6-tetramethyl-1-oxa-2-silacyclohexane, 2-methyl-2-ethoxy-1-oxa-2-silacyclohexane, 2,6,6-trimethyl-2-ethoxy-1-oxa-2-silacyclohexane, 2-methyl-2-methoxy-1-oxa-2-silacyclohexane, 2-Methyl-2-n-propoxy-1-oxa-2-silacyclohexane, 2,6,6-trimethyl-2-n-propoxy-1-oxa-2-silacyclohexane, 2-methyl-2-isopropoxy-1-oxa-2-silacyclohexane, 2,6,6-trimethyl-2-isopropoxy-1-oxa-2-silacyclohexane, 2,5,5-trimethyl-2-isopropyl-1-oxa-2-silacyclopentane, 2-methyl-2-isopropyl-1-oxa-2-silacyclopentane, 2-methyl-2-isopropyl-1-oxa-2-silacyclopentane, 2-methyl-2-isopropyl-1-oxa-2-silacyclohexane, 2,6,6-trimethyl-2-isopropyl-1-oxa-2-silacyclohexane, and combinations thereof.

15. A method for preparing a silicon compound represented by formula I: The method comprises: According to reaction formula (1) or (2), alkoxysilane is hydrosilylated with an unsaturated alcohol in the presence of a catalyst in the presence or absence of a solvent, followed by cyclization, with a yield of 70% or more: Where R 1 Selected from hydrogen, straight or branched C1-C 10 Alkyl, straight chain or branched C2-C 10 Alkenyl, straight or branched C2-C 10 Alkynyl, C3-C 10 Cycloalkyl, C3-C 10 Heterocycloalkyl, C5-C 10 Aryl and C3-C 10 Heteroaryl; R 2 is a C2-C4 alkanediyl group which, together with Si and oxygen atoms, forms a four-, five- or six-membered saturated cyclic ring having an optional C1-C6 alkyl substituent; R 3 Selected from straight or branched C1-C 10 Alkyl, straight chain or branched C2-C 10 Alkenyl, straight or branched C2-C 10 Alkynyl, C3-C 10 Cycloalkyl, C3-C 10 Heterocycloalkyl, C5-C 10 Aryl and C3-C 10 Heteroaryl, and alkoxy OR 4 , where R 4 Selected from straight or branched C1-C 10 Alkyl, straight chain or branched C2-C 10 Alkenyl, straight or branched C2-C 10 Alkynyl; and R 5 To R 8 independently selected from hydrogen, straight or branched C1-C 10 alkyl; The silicon compound having formula I is not 2,2-dimethyl-1-oxa-2-silacyclohexane.

16. The method according to claim 15, wherein the compound represented by formula I is selected from 2,2,5,5-tetramethyl-1-oxa-2-silacyclopentane, 2,5,5-trimethyl-2-ethoxy-1-oxa-2-silacyclopentane, 2,5,5-trimethyl-2-methoxy-1-oxa-2-silacyclopentane, 2,5,5-trimethyl-2-isopropoxy-1-oxa-2-silacyclopentane, 2,2,6,6-tetramethyl-1-oxa-2-silacyclohexane, 2-methyl-2-ethoxy-1-oxa-2-silacyclohexane, 2,6,6-trimethyl-2-ethoxy-1-oxa-2-silacyclohexane, 2,5,5-trimethyl-2-methoxy-1-oxa-2-silacyclohexane, 2,5,5-trimethyl-2-isopropoxy-1-oxa-2-silacyclohexane, 6,6-trimethyl-2-methoxy-1-oxa-2-silacyclohexane, 2-methyl-2-n-propoxy-1-oxa-2-silacyclohexane, 2,6,6-trimethyl-2-n-propoxy-1-oxa-2-silacyclohexane, 2-methyl-2-isopropoxy-1-oxa-2-silacyclohexane, 2,6,6-trimethyl-2-isopropoxy-1-oxa-2-silacyclohexane, 2,5,5-trimethyl-2-isopropyl-1-oxa-2-silacyclopentane, 2-methyl-2-isopropyl-1-oxa-2-silacyclopentane, 2-methyl-2-isopropyl-1-oxa-2-silacyclopentane, 2-methyl-2-isopropyl-1-oxa-2-silacyclohexane, 2,6,6-trimethyl-2-isopropyl-1-oxa-2-silacyclohexane, and combinations thereof.

17. A composition for vapor deposition of dielectric films comprising a silicon compound having the following formula I: Where R 1 Selected from hydrogen, straight or branched C1-C 10 Alkyl, straight chain or branched C2-C 10 Alkenyl, straight or branched C2-C 10 Alkynyl, C3-C 10 Cycloalkyl, C3-C 10 Heterocycloalkyl, C5-C 10 Aryl and C3-C 10 Heteroaryl; R 2 is a C2-C4 alkanediyl group which, together with Si and oxygen atoms, forms a four-, five- or six-membered saturated cyclic ring having an optional C1-C6 alkyl substituent; R 3 Selected from straight or branched C1-C 10 Alkyl, straight chain or branched C2-C 10 Alkenyl, straight or branched C2-C 10 Alkynyl, C3-C 10 Cycloalkyl, C3-C 10 Heterocycloalkyl, C5-C 10 Aryl, C3-C 10 Heteroaryl and alkoxy OR 4 , where R 4 Selected from straight or branched C1-C 10 Alkyl, straight chain or branched C2-C 10 Alkenyl and straight or branched C2-C 10 Alkynyl; and wherein the compound is substantially free of at least one impurity selected from the group consisting of halides, organosilane impurities and water; The silicon compound having formula I is not 2,2-dimethyl-1-oxa-2-silacyclohexane.

18. The composition according to claim 17, wherein the silicon compound is at least one selected from the group consisting of 2,2,5,5-tetramethyl-1-oxa-2-silacyclopentane, 2,5,5-trimethyl-2-ethoxy-1-oxa-2-silacyclopentane, 2,5,5-trimethyl-2-methoxy-1-oxa-2-silacyclopentane, 2,5,5-trimethyl-2-isopropoxy-1-oxa-2-silacyclopentane, 2,2,6,6-tetramethyl-1-oxa-2-silacyclohexane, 2-methyl-2-ethoxy-1-oxa-2-silacyclohexane, 2,6,6-trimethyl-2-ethoxy-1-oxa-2-silacyclohexane, 2-methyl-2-methoxy-1-oxa-2-silacyclohexane, 2-Methyl-2-n-propoxy-1-oxa-2-silacyclohexane, 2,6,6-trimethyl-2-n-propoxy-1-oxa-2-silacyclohexane, 2-methyl-2-isopropoxy-1-oxa-2-silacyclohexane, 2,6,6-trimethyl-2-isopropoxy-1-oxa-2-silacyclohexane, 2,5,5-trimethyl-2-isopropyl-1-oxa-2-silacyclopentane, 2-methyl-2-isopropyl-1-oxa-2-silacyclopentane, 2-methyl-2-isopropyl-1-oxa-2-silacyclopentane, 2-methyl-2-isopropyl-1-oxa-2-silacyclohexane, 2,6,6-trimethyl-2-isopropyl-1-oxa-2-silacyclohexane, and combinations thereof.

19. The composition of claim 17, wherein the halide comprises chloride ions.

20. The composition of claim 19, wherein the chloride ion, if present, is present at a concentration of 50 ppm or less.

21. The composition of claim 19, wherein the chloride ion, if present, is present at a concentration of 10 ppm or less.

22. The composition of claim 19, wherein the chloride ion, if present, is present at a concentration of 5 ppm or less.

23. The composition of claim 19, wherein the composition has 0 ppm chloride ions.

24. The composition of claim 17, wherein the sum of all organosilane impurities is 1.0 wt% or less based on GC.

25. The composition of claim 17, wherein the sum of all organosilane impurities is 0.5 wt% or less based on GC.

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