Stabilized organosilane composition and method for forming compact low k film using the same

Abstract

A composition comprising: (a) a 1, 3-dialkoxy-1, 3-disilacyclobutane having the following formula I: wherein each R1 is independently a C1 to C10 linear or branched alkyl group, and each R2 is independently hydrogen or a C1 to C10 linear or branched alkyl group; and (b) a polymerization inhibitor. I

Description

Cross-reference to related applications

[0001] This application claims the benefit of U.S. Provisional Application 63 / 519,635, filed on August 15, 2023. Background Technology

[0002] This invention generally relates to stabilized organosilane compositions and the formation of dielectric films using stable compositions. More specifically, this invention relates to dielectric materials having low dielectric constants and enhanced mechanical properties, films comprising such dielectric materials, and methods for their preparation using stable compositions.

[0003] All references cited in this article, including publications, patent applications and patents, are incorporated herein by reference to the same extent that each reference is individually and specifically indicated as incorporated herein by reference and fully elaborated.

[0004] In the microelectronics industry, there has been a long-standing desire to increase circuit density in multi-level integrated circuit devices such as memory and logic chips to improve operating speed and reduce power consumption. US Patent 10,249,489 B2 discloses low-dielectric silicone films, particularly those formed using alkoxylated dimethylsilylalkane and alkoxylated dimethylsilylcycloalkane. Such low-dielectric materials are desirable for use as, for example, metal-front dielectric layers or interlayer dielectric layers.

[0005] One class of organosilanes that can be used in low-k applications is alkoxylated disiloxane. However, some of these compounds have boiling points that require heating the membrane precursor to sufficiently high temperatures to promote polymerization, which limits their use as stable and high-yield film-forming compounds.

[0006] US11393678 B discloses a method for depositing a high-hardness, low-k dielectric film. More specifically, it provides a method for processing a substrate. The method includes: (1) flowing a gas mixture containing a precursor into a processing volume of a processing chamber having a substrate, wherein the precursor is a silane derivative; (2) maintaining the substrate at a pressure ranging from about 0.1 mTorr to about 20 Torr and a temperature ranging from about 200° to about 500°; and (3) generating a plasma on a horizontal plane of the substrate to deposit a dielectric film on the substrate.

[0007] US5302734 A discloses the synthesis of alkoxy-1,3-disiloxane via pyrolysis.

[0008] US7381659 B discloses a method for reducing the tensile stress of a low-k dielectric layer, comprising depositing an organosilicon layer on a substrate having an associated initial tensile stress value. The layer is annealed in a reactive environment at a selected temperature for a selected duration to obtain a layer with a reduced tensile stress value relative to the initial tensile stress value after annealing.

[0009] US10249489 B describes a low-dielectric material for improving performance when used as an interlayer dielectric in integrated circuits, a film comprising the low-dielectric material, and a method for preparing the same. The formation of the organosilicon film involves chemical vapor deposition of at least one organosilicon precursor.

[0010] Interrante, LV et al. (1998), “Linear and hyperbranched polycarbosilanes with Si-CH2-Si bridging groups: a synthetic platform for the construction ofnovel functional polymeric materials.” Appl. Organomet. Chem .12(10 / 11):695-705 describes synthetic routes for linear and hyperbranched polycarbosilanes, which possess the characteristic "[SiH2CH2]". n "Composition formula. Linear [SiH2CH2]" n The polymer was prepared by ring-opening polymerization of substituted disiloxane.

[0011] There is a need to develop a composition containing stabilized cyclodisil-butane for vapor deposition of silicon-containing low-dielectric materials, because cyclodisil-butane disclosed in the prior art appears to potentially form polymeric substances during its delivery. Summary of the Invention

[0012] The compositions or formulations described herein and their methods of use overcome the problems of the prior art by depositing a silicon-containing film that provides the desired film properties on at least a portion of the substrate surface.

[0013] In one aspect, the present invention provides stabilized organosilane compositions that can be used to form dielectric films without polymerization to the point that the precursors lose their effectiveness. In another aspect, the present invention relates to dielectric materials having low dielectric constants and enhanced mechanical properties, films comprising such dielectric materials, and methods for their preparation using stabilized organosilane compositions.

[0014] The above-mentioned problems and other issues are overcome by including the following composition: (a) 1,3-dialkoxy-1,3-disilheycyclobutane having the following formula I: I Each R 1 Independently, they are C1 to C 10 Straight-chain or branched alkyl groups, and each R 2Independently hydrogen or C1 to C 10 Straight-chain or branched alkyl groups; and (b) Polymerization inhibitors, selected from: (i) Antioxidants or free radical scavengers; (ii)R 3 n R 4 m Si(OR 5 ) 4-n-m , where R 3 and R 4 Each is independently selected from hydrogen and C1 to C2. 10 Straight-chain or branched alkyl groups; and R 5 Selected from C1 to C 10 Straight-chain or branched alkyl; n is 0, 1, 2 or 3; m = 0, 1, 2, 3; (iii) Alkoxy-disiloxanes having the following formula Where R 6 Selected from straight-chain or branched C1 to C6 alkyl groups, preferably methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, or tert-butyl, and cyclic C5 to C6 alkyl groups; R 7 Selected from hydrogen and straight-chain or branched C1 to C5 alkyl groups; R 8-10 Each is independently selected from straight-chain or branched C1 to C5 alkyl groups, preferably methyl; and R 11 Selected from hydrogen, straight-chain or branched C1 to C5 alkyl groups, or OR 12 , where R 12 Selected from straight-chain or branched C1 to C5 alkyl groups; (iv) Alkoxy-carbosilanes having the following structure R 13 Selected from straight-chain or branched C1 to C6 alkyl groups, preferably methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, or tert-butyl, and cyclic C5 to C6 alkyl groups; R 14 Selected from hydrogen and straight-chain or branched C1 to C5 alkyl groups; R 15-17 Independently selected from straight-chain or branched C1 to C5 alkyl groups, preferably methyl; and R 18 Selected from hydrogen, straight-chain or branched C1 to C5 alkyl groups, or OR 19 , where R 19 Selected from straight-chain or branched C1 to C5 alkyl groups; and (v) Organoaminosilane R 20 n R 21 m Si(NR 22 R 23 )4-n-m , where R 20 and R 20 Each is independently selected from hydrogen and C1 to C2. 10 Straight-chain or branched alkyl groups; and R 22 and R 23 Selected from hydrogen, C1 to C 10 Straight-chain or branched alkyl; n is 0, 1, 2 or 3; m = 0, 1, 2 or 3.

[0015] In a preferred embodiment, the alkoxy group in any of the polymerization inhibitors (ii)-(v) is the same as the alkoxy group in 1,3-dialkoxy-1,3-disiloxane, to ensure that the chemical structure of 1,3-dialkoxy-1,3-disiloxane remains unchanged in the event of an alkoxy exchange reaction between the polymerization inhibitor and 1,3-dialkoxy-1,3-disiloxane.

[0016] The above and other problems are further solved by a chemical vapor deposition method for depositing an organosilicon film on at least a portion of a substrate, the method comprising: Provide the substrate within a vacuum chamber; The composition comprising (a) and (b) above is introduced into the vacuum chamber; and Energy is applied to a gaseous structure-forming composition in a vacuum chamber to induce a reaction of at least 1,3-dialkoxy-1,3-disilhexacyclobutane, thereby depositing a film on at least a portion of a substrate. Attached Figure Description

[0017] Figure 1 This is a graph depicting the precursor flow rate and corresponding piezoelectric control valve voltage associated with the evaporation of stabilized 1,3-dimethoxy-1,3-dimethyl-1,3-disilheycyclobutane (Figures A and C) and unstabilized 1,3-dimethoxy-1,3-dimethyl-1,3-disilheycyclobutane (Figures B and D) via the Horiba liquid source evaporation system.

[0018] Figure 2 This is a graph depicting the dielectric constants of films 1, 2, 3, and 4 deposited using stabilized 1,3-dimethoxy-1,3-dimethyl-1,3-disilhecyclobutane (black shaded pattern) and unstabilized 1,3-dimethoxy-1,3-dimethyl-1,3-disilhecyclobutane (solid black).

[0019] Figure 3 It is a graph depicting the hardness of films 1, 2, 3 and 4 deposited using stabilized 1,3-dimethoxy-1,3-dimethyl-1,3-disilhecyclobutane (black shaded pattern) and unstabilized 1,3-dimethoxy-1,3-dimethyl-1,3-disilhecyclobutane (solid black). Detailed Implementation

[0020] Unless otherwise stated herein or obviously contradicted by the context, the terms “a”, “an”, and “the,” and similar indicators used in the context of describing the invention (particularly in the context of the following claims) should be interpreted as covering both singular and plural. Unless otherwise stated, the terms “comprising,” “having,” “including,” and “containing” should be interpreted as open-ended terms (i.e., meaning “including but not limited to”). Unless otherwise stated herein, descriptions of numerical ranges herein are intended only as a way of abbreviating each individual value falling within that range, and each individual value is incorporated into this specification as if it were described separately herein. Unless otherwise stated herein or obviously contradicted by the context, all methods described herein may be performed in any suitable order. The use of any and all instances or exemplary language (e.g., “such as”) provided herein is intended only to better illustrate the invention and not to limit the scope of the invention, unless otherwise stated. No language in the specification should be construed as indicating that any unclaimed element is essential to the practice of the invention.

[0021] This document describes preferred embodiments of the invention, including the best mode known to the inventors for carrying out the invention. Variations of those preferred embodiments will become apparent to those skilled in the art upon reading the foregoing description. The inventors expect those skilled in the art to appropriately employ these variations, and the inventors intend to practice the invention in ways other than those specifically described herein. Therefore, the invention includes all modifications and equivalents of the subject matter described in the appended claims as permitted by applicable law. Furthermore, unless otherwise stated herein or clearly contradicted by the context, the invention covers any combination of the foregoing elements in all possible variations.

[0022] In the claims, letters may be used to identify the claimed method steps (e.g., a, b, and c). These letters are used to help designate the method steps and are not intended to indicate the order in which the claimed steps are performed, unless and only where such an order is specifically described in the claims.

[0023] In one aspect, the present invention provides a composition comprising: (a) 1,3-dialkoxy-1,3-disilheycyclobutane having the following formula I: I Each R 1 Independently, they are C1 to C 10 Straight-chain or branched alkyl groups, and each R 2 Independently hydrogen or C1 to C 10Straight-chain or branched alkyl groups; and (b) Polymerization inhibitors, selected from: (i) Antioxidants or free radical scavengers; (ii)R 3 n R 4 m Si(OR 5 ) 4-n-m , where R 3 and R 4 Each is independently selected from hydrogen and C1 to C2. 10 Straight-chain or branched alkyl groups; and R 5 Selected from C1 to C 10 Straight-chain or branched alkyl; n is 0, 1, 2 or 3; m = 0, 1, 2, 3; (iii) Alkoxy-disiloxanes having the following formula Where R 6 Selected from straight-chain or branched C1 to C6 alkyl groups, preferably methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, or tert-butyl, and cyclic C5 to C6 alkyl groups; R 7 Selected from hydrogen and straight-chain or branched C1 to C5 alkyl groups; R 8-10 Each is independently selected from straight-chain or branched C1 to C5 alkyl groups, preferably methyl; and R 11 Selected from hydrogen, straight-chain or branched C1 to C5 alkyl groups, or OR 12 , where R 12 Selected from straight-chain or branched C1 to C5 alkyl groups; (iv) Alkoxy-carbosilanes having the following structure R 13 Selected from straight-chain or branched C1 to C6 alkyl groups, preferably methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, or tert-butyl, and cyclic C5 to C6 alkyl groups; R 14 Selected from hydrogen and straight-chain or branched C1 to C5 alkyl groups; R 15-17 Independently selected from straight-chain or branched C1 to C5 alkyl groups, preferably methyl; and R 18 Selected from hydrogen, straight-chain or branched C1 to C5 alkyl groups, or OR 19 , where R 19 Selected from straight-chain or branched C1 to C5 alkyl groups; and (v) Organoaminosilane R 20 n R 21 m Si(NR 22 R 23 ) 4-n-m , where R20 and R 20 Each is independently selected from hydrogen and C1 to C2. 10 Straight-chain or branched alkyl groups; and R 22 and R 23 Selected from hydrogen, C1 to C 10 Straight-chain or branched alkyl; n is 0, 1, 2 or 3; m = 0, 1, 2 or 3.

[0024] In a preferred embodiment, the alkoxy group in any polymerization inhibitor (ii)-(v) is the same as the alkoxy group in 1,3-dialkoxy-1,3-disiloxane, to ensure that the chemical structure of 1,3-dialkoxy-1,3-disiloxane remains unchanged in the event of an alkoxy exchange reaction between the polymerization inhibitor and 1,3-dialkoxy-1,3-disiloxane.

[0025] According to an exemplary embodiment, for 1,3-dialkoxy-1,3-disilheycyclobutane (a), R 1 and R 2 Each is independently selected from hydrogen and C1 to C4 straight-chain or branched alkyl groups. Examples include 1,3-diethoxy-1,3-dimethyl-1,3-disilhecyclobutane, 1,3-dimethoxy-1,3-dimethyl-1,3-disilhecyclobutane, 1,3-di-n-propoxy-1,3-disilhecyclobutane, 1,3-diisopropoxy-1,3-dimethyl-1,3-disilhecyclobutane, 1,3-methoxy-1,3-diethyl-1,3-disilhecyclobutane, 1,3-dipropoxy-1,3-disilhecyclobutane, 1,3-diethoxy-1-methyl-1,3-disilhecyclobutane, and 1,3-diethoxy-1-ethyl-1,3-disilhecyclobutane, 1,3-diethoxy-1,3-disilhecyclobutane, and 1,3-dimethoxy-1,3-disilhecyclobutane.

[0026] The polymerization inhibitor (b) is used to stabilize 1,3-dialkoxy-1,3-disilhexacyclobutane and may be selected from (i), (ii), (iii), (iv) and combinations thereof. The concentration range of the polymerization inhibitor may be from about 1 ppm to about 50 wt%, or from about 1 ppm to about 40 wt%, or from about 1 ppm to about 30 wt%, or from about 1 ppm to about 20 wt%, or from about 1 ppm to about 10 wt%, or from about 1 ppm to about 5 wt%, or from about 1 ppm to about 2 wt%, or from about 1 ppm to about 1 wt%, or from about 1 ppm to about 0.5 wt%, or from about 1 ppm to about 0.1 wt%, or from 1 ppm to 100 ppm, or from 1 ppm to 50 ppm, or from 1 ppm to 10 ppm, depending on the polymerization inhibitor used.

[0027] Examples of antioxidants or free radical scavengers (i) include, but are not limited to, 2,6-di-tert-butyl-4-methylphenol (or BHT of butylated hydroxytoluene), 2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO), 2-tert-butyl-4-hydroxyanisole, 3-tert-butyl-4-hydroxyanisole, propyl 3,4,5-trihydroxybenzoate, 2-(1,1-dimethylethyl)-1,4-benzenediol, diphenylpicrylhydrazine, 4-tert-butylcatechol, N-methylaniline, p-methoxydiphenylamine, diphenylamine, N,N'-diphenyl-p-phenylenediamine, p-hydroxydiphenylamine, phenol, octadecyl-3-(3,5-di-tert-butyl-4-hydroxybenzene) Methylpropionate, tetra(methylene-(3,5-di-tert-butyl)-4-hydroxy-hydrogenated cinnamate)methane, phenothiazines, alkylmididine isoureas, thiodiethylene bis(3,5-di-tert-butyl-4-hydroxy-hydrogenated cinnamate, 1,2-bis(3,5-di-tert-butyl-4-hydroxy-hydrogenated cinnamoyl)hydrazine, tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane, cyclopentanetetramethylbis(octadecyl phosphite), 4,4'-thiobis(6-tert-butyl-m-cresol), 2,2'-methylenebis(6-tert-butyl-p-cresol), oxaloylbis(benzylidene hydrazine), and naturally occurring antioxidants such as unprocessed seed oils, wheat germ oils, tocopherols, and combinations thereof.

[0028] Examples of polymerization inhibitors (ii) include, but are not limited to, tetramethoxysilane, trimethoxysilane, tetraethoxysilane, triethoxysilane, dimethoxymethylsilane, diethoxymethylsilane, methoxydimethylsilane, and ethoxydimethylsilane.

[0029] Examples of polymerization inhibitors (iii) include, but are not limited to, 1,3-diethoxy-1,3-dimethyl-1,3-disiloxane and 1,3-diethoxy-tetramethyldisiloxane.

[0030] Examples of polymerization inhibitors (iv) include, but are not limited to, 2,4,4-triethoxy-2,4-disiloxane and 2,4-diethoxy-4-methyl-2,4-disiloxane.

[0031] Examples of polymerization inhibitors (v) include, but are not limited to, dimethylaminotrimethylsilane, diethylaminotrimethylsilane, bis(dimethylamino)dimethylsilane, tris(dimethylamino)methylsilane, dimethylaminodimethylsilane, and diethylaminodimethylsilane.

[0032] Throughout this invention, 1,3-dialkoxy-1,3-disilheycyclobutane can be cis-cis, trans-trans, or cis-trans isomers, and mixtures thereof. In this or other embodiments, the boiling point (bp) of the polymerization inhibitor is similar to that of 1,3-dialkoxy-1,3-disilheycyclobutane, or the difference between the bp of the polymerization inhibitor and that of 1,3-dialkoxy-1,3-disilheycyclobutane is 100°C or less, 40°C or less, 30°C or less, 20°C or less, 10°C or less, or 5°C or less. Alternatively, the difference between boiling points may be within any one or more of the following endpoints: 0, 10, 20, 30, 40°C, or 100°C. Examples of suitable ranges of boiling point differences include, but are not limited to, 0 to 100°C, 0 to 40°C, 1 to 10°C, or 1 to 5°C. Table 1 below lists some other exemplary polymerization inhibitors (b) and their corresponding boiling points.

[0033] Table 1: Exemplary Polymer Inhibitors Chemicals BP (C) 1,3-Diethoxy-1,3-dimethyl-1,3-disiloxane 185 2,4,4-Triethoxy-2,4-disilazane 240 1,3-Diethoxy-tetramethyldisiloxane 183 2,4-Diethoxy-4-methyl-2,4-disilazane 178 Tetraethoxysilane 168 sec-butoxy-pentamethyldisiloxane 161 Diethoxymethylsilane 98 An example of an organosilicon film deposited by the method of the present invention is a carbon-doped silicon oxide film. In the method of the present invention, a typical first step is to place a substrate comprising at least one surface feature in a reactor at a temperature of about 20°C to about 600°C, preferably 100°C to about 550°C, and most preferably 100°C to about 450°C. Suitable substrates include, but are not limited to, semiconductor materials such as gallium arsenide (“GaAs”), boron nitride (“BN”) silicon, and silicon-containing compositions such as crystalline silicon, polycrystalline silicon, amorphous silicon, epitaxial silicon, silicon dioxide (“SiO2”), silicon carbide (“SiC”), silicon carbide oxide (“SiOC”), silicon nitride (“SiN”), silicon carbonitride (“SiCN”), organosilicon glass (“OSG”), organofluorosilicate glass (“OFSG”), fluorosilicate glass (“FSG”), and other suitable substrates or mixtures thereof. The substrate may further include various layers on which the film is applied, such as, for example, antireflective coatings, photoresists, organic polymers, porous organic and inorganic materials, metals (such as copper, cobalt, ruthenium, tungsten, rhodium, and aluminum) or diffusion barrier layers (e.g., TiN, Ti, Ti(C)N, TaN, Ta(C)N, Ta, W, WN, TiSiN, TaSiN, SiCN, TiSiCN, TaSiCN, or W(C)N). The substrate may be a single-crystal silicon wafer, a silicon carbide wafer, an alumina (sapphire) wafer, a glass sheet, a metal foil, an organic polymer film, or a three-dimensional article of polymer, glass, silicon, or metal. The substrate may be coated with various materials known in the art, including silicon oxide films, silicon nitride films, amorphous carbon films, silicon carbide films, silicon oxynitride films, silicon carbide films, gallium arsenide films, gallium nitride films, etc. These coatings may completely cover the substrate, may be multiple layers of various materials, and may be partially etched to expose the underlying material layers. The surface may also have a photoresist material that has been patterned and developed to partially coat the substrate.

[0034] Examples of suitable deposition processes for the methods disclosed herein include, but are not limited to, thermochemical vapor deposition (CVD), plasma-enhanced CVD (PECVD), atomic layer deposition (ALD), and plasma-enhanced cyclic CVD (PECVD) processes. In one embodiment, a plasma-based (e.g., remotely generated or in-situ) CVD process is used to deposit the film. The term "reactor" as used herein includes, but is not limited to, a reaction chamber or a deposition chamber.

[0035] In some embodiments, the substrate may be exposed to one or more pre-deposition treatments, such as, but not limited to, plasma treatment, thermal treatment, chemical treatment, ultraviolet light exposure, electron beam exposure, and combinations thereof, to affect one or more properties of the film. These pre-deposition treatments may be performed in an atmosphere selected from inert, oxidizing, and / or reducing atmospheres.

[0036] Although the chemical reagents used herein may sometimes be described as “gaseous,” it should be understood that the chemical reagents may be delivered directly to the reactor as a gas, using carrier gases such as nitrogen, helium, or argon as vapor transport from vaporized or bubbling liquids, as vapor transport from sublimated solids, and / or delivered to the reactor via inert carrier gases.

[0037] In a preferred embodiment, the organosilicon film deposited by the method of the present invention is a dense organosilicon glass (OSG) film having a dielectric constant of about 2.8 to about 3.1 and a hardness of about 3.2 to about 4.5 gigapascals (GPa), as measured using an MTS Nano Indenter. This represents a significant reduction in dielectric constant compared to silicon dioxide films typically having a dielectric constant of about 3.8 to about 4.2 and a hardness of about 7 GPa.

[0038] The method of the present invention includes the following steps: introducing the composition defined above into a vacuum chamber and applying energy to the gaseous structure forming composition in the vacuum chamber to initiate a reaction of at least one organosilicon precursor, thereby depositing a film on at least a portion of a substrate.

[0039] The compositions described above and herein can be delivered to reaction chambers such as CVD or ALD reactors in various ways. In one embodiment, a liquid delivery system can be used. In alternative embodiments, a combination of liquid delivery and flash evaporation process units can be employed, such as a turbine evaporator manufactured, for example, by MSP Corporation of Shoreview, MN, to enable the metered delivery of low-volatility materials, resulting in reproducible delivery and deposition without thermal decomposition of the precursor. In liquid-delivered formulations, the precursors described herein can be delivered in net liquid form, or alternatively, can be used in solvent formulations or compositions containing them. Thus, in some embodiments, the precursor formulation may include a solvent component with suitable properties, such as those that may be desired and advantageous in a given end-use application, to form a film on a substrate.

[0040] In one particular embodiment, a plasma-enhanced chemical vapor deposition method for producing a low-k dielectric film includes: providing a substrate in a reaction chamber; introducing a gaseous composition comprising 1,3-dialkoxy-1,3-disilhexacyclobutane and at least one polymerization inhibitor, with or without an oxidant, into the reaction chamber; and applying energy to the gaseous composition in the reaction chamber to induce a reaction of the gaseous composition, thereby depositing a silicon-containing film on the substrate. The deposition process is typically performed on a heated substrate at temperatures ranging from 100°C to 600°C, or about 200°C to 550°C, or about 250°C to 450°C, or about 200°C to 400°C.

[0041] Oxidizing agents such as oxygen (O2), ozone (O3), nitrous oxide (N2O), nitric oxide (NO), nitrogen dioxide (NO2), dinitrogen tetroxide (N2O4), and / or hydrogen peroxide (H2O2) may be added.

[0042] One or more fluorine-providing gases may be used as additives in the reaction or in post-processing. Examples of fluorine-providing gases are NF3, F2, CF4, C2F6, C4F6, and C6F6.

[0043] In addition to the composition and optionally the oxygen-providing and fluorine-providing gases, additional materials may be loaded into the vacuum chamber before, during, and / or after the deposition reaction. Such materials include reactive substances such as gaseous or liquid organic substances, NH3, H2, CO2, CO, or fluorocarbons. Examples of organic substances are CH4, C2H6, C2H4, C2H2, C3H8, cyclopentane, cyclooctane, allenes, propylene, α-terpinene, p-cymene, benzene, naphthalene, toluene, and styrene.

[0044] Reagents (i.e., compositions, oxidants, etc.) can be loaded into the reactor individually or as mixtures from various sources. Reagents can be delivered to the reactor system in various ways, preferably using pressurized stainless steel containers equipped with appropriate valves and fittings to allow the delivery of liquids to the process reactor.

[0045] Energy is applied to a gaseous reagent to induce a gaseous reaction and form a film on at least a portion of a substrate. This energy can be provided, for example, by thermal, plasma, pulsed plasma, helical wave plasma, high-density plasma, inductively coupled plasma, and remote plasma methods. A secondary RF frequency source can be used to modify the plasma characteristics at the substrate surface. Preferably, the film is formed by plasma-enhanced chemical vapor deposition. Particularly preferred is capacitively coupled plasma generated at a frequency of 13.56 MHz. The plasma power is preferably from 0.02 to 7 W / cm². 2 More preferably 0.3 to 3 watts / cm 2 Based on the substrate surface area, using a carrier gas with low ionization energy to reduce the electron temperature in the plasma can be advantageous, which in turn leads to less fragmentation in the OSG precursor and pore-forming agent. Examples of this type of low-ionization gas include CO2, NH3, CO, CH4, Ar, Xe, and Kr.

[0046] In some embodiments where the energy is plasma energy, the plasma source is selected from, but not limited to, carbon source plasma, including hydrocarbon plasma, plasma containing hydrocarbons and helium, plasma containing hydrocarbons and argon, carbon dioxide plasma, carbon monoxide plasma, plasma containing hydrocarbons and hydrogen, plasma containing hydrocarbons and nitrogen sources, plasma containing hydrocarbons and oxygen sources, and mixtures thereof.

[0047] The flow rate of each gaseous reagent is preferably in the range of 10 to 5000 sccm per individual 200 mm wafer, more preferably 30 to 1000 sccm. A single rate is selected to provide the required amount of structure-forming agent and pore-forming agent in the film. The actual flow rate required may depend on the wafer size and chamber configuration, and is by no means limited to 200 mm wafers or single-wafer chambers.

[0048] In some implementations, the film is deposited at a rate of 50-250 nm / min.

[0049] The pressure in the vacuum chamber during deposition is preferably from 0.01 to 600 Torr, more preferably from 1 to 15 Torr.

[0050] Preferably, the film is deposited to a thickness of 0.002 to 10 micrometers, although the thickness can be varied as needed. The blanket-coated film deposited on the unpatterned surface has excellent uniformity, with a thickness variation of less than 2% over one standard deviation across the entire substrate, provided that reasonable edge exclusion is achieved, wherein, for example, the outermost 5 mm edge of the substrate is not included in the statistical calculation of uniformity.

[0051] In-situ or post-deposition treatments can be used to enhance material properties such as hardness, stability (to shrinkage, air exposure, etching, wet etching, etc.), integrity, uniformity, and adhesion. These treatments can be applied to the film before, during, and / or after pore-forming agent removal using the same or different methods employed for pore-forming agent removal. Therefore, the term "post-treatment," as used herein, refers to treating the film with energy (e.g., heat, plasma, photons, electrons, microwaves, etc.) or chemicals to remove pore-forming agents and optionally enhance material properties.

[0052] The conditions for post-processing can vary greatly. For example, post-processing can be carried out under high pressure or in a vacuum environment.

[0053] The thermal annealing is performed under the following conditions. The environment can be inert (e.g., nitrogen, CO2, rare gases (He, Ar, Ne, Kr, Xe), etc.), oxidizing (e.g., oxygen, air, depleted oxygen environment, oxygen-enriched environment, ozone, nitrous oxide, etc.), or reducing (diluted or concentrated hydrogen, hydrocarbons (saturated, unsaturated, straight-chain or branched, aromatic), etc.). The pressure is preferably about 1 Torr to about 1000 Torr, more preferably atmospheric pressure. However, a vacuum environment is also possible 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 annealing time is preferably 0.01 minutes to 12 hours.

[0054] Chemical treatment of OSG membranes can also be performed using fluorination (HF, SIF4, NF3, F2, COF2, CO2F2, etc.), oxidation (H2O2, O3, etc.), chemical drying, methylation, or other chemical treatments that enhance the final material properties. The chemicals used in these treatments can be in solid, liquid, gaseous, and / or supercritical fluid states.

[0055] In some embodiments, the OSG film is annealed, preferably by heating or radiation (i.e., photoannealing). In these embodiments, photoannealing is performed under the following conditions: The environment can be inert (e.g., nitrogen, CO2, rare gases (He, Ar, Ne, Kr, Xe), etc.), oxidizing (e.g., oxygen, air, depleted oxygen environment, oxygen-rich environment, ozone, nitrous oxide, etc.), or reducing (e.g., diluted or concentrated hydrocarbons, hydrogen, ammonia, etc.). The power can be in the range of 0 to 5000 W. The wavelength is preferably IR, visible light, UV, or deep UV (wavelength <200 nm). The temperature can be in the range of ambient temperature to 500°C. The pressure can be in the range of 10 mTorr to atmospheric pressure. The total curing time can be from 0.01 minutes to 12 hours.

[0056] The plasma treatment for chemical modification of OSG membranes is carried out under the following conditions. The environment can be inert (nitrogen, CO2, rare gases (He, Ar, Ne, Kr, Xe), etc.), oxidizing (e.g., oxygen, air, depleted oxygen environment, oxygen-enriched environment, ozone, nitrous oxide, etc.), or reducing (e.g., diluted or concentrated hydrogen, hydrocarbons (saturated, unsaturated, straight-chain or branched, aromatic), ammonia, etc.). The plasma power is preferably 0-5000 W, and the temperature is preferably ambient temperature to 500°C. The pressure is preferably 10 mTorr to atmospheric pressure. The total curing time is preferably 0.01 minutes to 12 hours.

[0057] Microwave post-treatment is performed under the following conditions. The environment can be inert (e.g., nitrogen, CO2, rare gases (He, Ar, Ne, Kr, Xe), etc.), oxidizing (e.g., oxygen, air, depleted oxygen environment, oxygen-rich environment, ozone, nitrous oxide, etc.), or reducing (e.g., diluted or concentrated hydrocarbons, hydrogen, etc.). The temperature is preferably ambient temperature to 500°C. The power and wavelength are variable and can be adjusted for specific bonds. The total curing time is preferably from 0.01 minutes to 12 hours.

[0058] Electron beam post-treatment is performed under the following conditions. The environment can be vacuum, inert (e.g., nitrogen, CO2, rare gases (He, Ar, Ne, Kr, Xe), etc.), oxidizing (e.g., oxygen, air, depleted oxygen environment, oxygen-enriched environment, ozone, nitrous oxide, etc.), or reducing (e.g., diluted or concentrated hydrocarbons, hydrogen, etc.). The temperature is preferably ambient temperature to 500°C. The electron density and energy can be varied and adjusted for specific bonds. The total curing time is preferably from 0.001 minutes to 12 hours and can be continuous or pulsed. Further guidance on the general use of electron beams is available in 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 pore-forming agent removal and enhancement of membrane mechanical properties through bond-forming processes in the matrix.

[0059] The invention will be described in more detail with reference to the following embodiments, but it should be understood that the invention is not intended to be limited thereto.

[0060] Example 1 - Stabilization of 1,3-diethoxy-1,3-dimethyl-1,3-disilhecyclobutane 1,3-Diethoxy-1,3-dimethyl-1,3-disilhexacyclobutane has a boiling point of 185 °C and must be heated above 100 °C to achieve sufficient vapor pressure for practical gas-phase transport. However, 1,3-Diethoxy-1,3-dimethyl-1,3-disilhexacyclobutane tends to polymerize when heated above 100 °C. More specifically, if heated to 120 °C for several days, net 1,3-diethoxy-1,3-dimethyl-1,3-disilhexacyclobutane will polymerize to form a gel. Thermogravimetric analysis (TGA) of 1,3-diethoxy-1,3-dimethyl-1,3-disilhexacyclobutane heated for 7 days showed significantly higher levels of non-volatile residues compared to the original material, which had undetectable levels of non-volatile residues. Thermogravimetric analysis of the polymer thermal degradation products can also be measured by GPC (gel permeation chromatography). In contrast, 1,3-diethoxy-1,3-dimethyl-1,3-disilheycyclobutane doped with butylated hydroxytoluene (BHT) or hydroquinone monomethyl ether (HQMME) (also known as 4-methoxy-phenol) showed significantly reduced or undetectable levels of nonvolatile residues by TGA. 1,3-diethoxy-1,3-dimethyl-1,3-disilheycyclobutane doped with organosilanes (such as DEMS or TEOS) also showed significantly reduced or undetectable levels of nonvolatile residues by TGA analysis. The thermal stability of 1,3-diethoxy-1,3-dimethyl-1,3-disilheycyclobutane significantly improved with antioxidants / free radical scavengers or with organosilanes such as those described herein, thus making it suitable for low-k applications.

[0061] Table 2 below provides a list of various compositions including 1,3-diethoxy-1,3-dimethyl-1,3-disilhecyclobutane (DEDMDSCB) and polymerization inhibitors. The compositions were aged at 120°C for 7 days or at 110°C for up to 26 days, and visually inspected after heat aging, and analyzed for NVR (non-volatile matter content) by TGA.

[0062] Table 2

[0063] 110℃ for 1 day 26 days at 110℃ Example 2 Further tests were conducted to evaluate other potential stabilizers for DEDMDSCB, including BTBAS (bis(tert-butyl)aminosilane), 1-methoxy,1,1,3,3-tetramethyldisiloxane, and 3,3,5,5-tetramethyl-2,6-dioxa-3,5-disiloxane. DEDMDSCB was incorporated into 0.5% by weight of BTBAS, 1-methoxy,1,1,3,3-tetramethyldisiloxane, or 3,3,5,5-tetramethyl-2,6-dioxa-3,5-disiloxane. The incorporated sample was heated to 120°C for 24 hours and then cooled to room temperature to examine for evidence of gel formation. If no gel formation was observed, the incorporated DEDMDSCB was reheated at 120°C for 6 days. After a total of 7 days at 120°C, the samples were assessed for any signs of gelation, degradation products, or the formation of non-volatile byproducts by visual inspection, GC, and TGA residue analysis.

[0064] Table 3 below provides a list of various compositions including DEDMDSCB and additives used as described above. The compositions were aged at 120°C for 7 days. Visual inspection of the ungelled compositions was performed by TGA analysis after 1 day and 7 days at 120°C.

[0065] Table 3

[0066] Example 3 The liquid precursor 1,3-dimethoxy-1,3-dimethyl-1,3-disilhexacyclic butane is evaporated using the Horiba Liquid Source Evaporation System (LSVS). This system consists of two components: a liquid flow meter and a heated evaporator (injector). Pressurized liquid is supplied to the liquid flow meter, and the measured liquid flow is then fed to the evaporator. The gas output from the evaporator is then supplied to a vacuum system. Piezoelectric control valves (0V = fully open, 120V = closed) in the evaporator open or close to regulate the liquid flow rate to its setpoint via a feedback loop. The evaporator temperature is typically set to the lowest temperature that results in a stable vapor delivery flow rate. For 1,3-dimethoxy-1,3-dimethyl-1,3-disilhexacyclic butane, an evaporator temperature of 110°C is used.

[0067] The degree of residue accumulation or blockage in the evaporator for a given precursor can be monitored by tracking the voltage of the piezoelectric control valve for a fixed liquid flow rate over time (i.e., as a function of the precursor mass). As residue accumulates in the piezoelectric valve, the valve must open further to maintain the same liquid flow rate. Therefore, if the voltage of the piezoelectric valve begins to drop rapidly (OV = fully open) for a fixed liquid flow rate, the evaporator is blocked.

[0068] To test the stability of 1,3-dimethoxy-1,3-dimethyl-1,3-disilhexacyclobutane over time in the Horiba LSVS, fixed liquid flow conditions (1,3-dimethoxy-1,3-dimethyl-1,3-disilhexacyclobutane = 600 mg / min; He = 700 sccm) were run at the start of the workday. During this daily standard, the liquid flow rate and piezoelectric voltage were recorded. After completing the daily standard, 1,3-dimethoxy-1,3-dimethyl-1,3-disilhexacyclobutane (500–1100 mg / min) was evaporated through the Horiba LSVS at various flow rates; evaporation times ranged from 72 to 380 seconds. After each evaporation run, the evaporator was purged with N2 before the next run. The variation in piezoelectric voltage over time during the daily standard was used to measure the degree of residue buildup (i.e., blockage) in the evaporator.

[0069] For both unstabilized and stabilized 1,3-dimethoxy-1,3-dimethyl-1,3-disilhecyclobutane, the stability of 1,3-dimethoxy-1,3-dimethyl-1,3-disilhecyclobutane was monitored by evaporation in a Horiba LSVS. Stabilized 1,3-dimethoxy-1,3-dimethyl-1,3-disilhecyclobutane was defined as a mixture of 99.5 wt% 1,3-dimethoxy-1,3-dimethyl-1,3-disilhecyclobutane and 0.5 wt% polymerization inhibitor (DEMS®). Results are shown in... Figure 1 The figure shows the precursor flow rate and piezoelectric valve voltage from daily standards as a function of the number of days (0 to 60) during the evaluation period. Figure 1 There are four figures. The top two figures (Figure A and Figure B) show the trend of the precursor flow rate, and the bottom two figures (Figure C and Figure D) show the trend of the piezoelectric valve voltage. Figure 1 The two figures on the right (Figures B and D) show the trend for using the original evaporator for unstabilized 1,3-dimethoxy-1,3-dimethyl-1,3-disilhexacyclic butane. Figure 1 The two graphs on the left (Figures A and C) show the trend of using the new evaporator for stabilized 1,3-dimethoxy-1,3-dimethyl-1,3-disilhexacyclic butane. A new evaporator is needed to test stabilized 1,3-dimethoxy-1,3-dimethyl-1,3-disilhexacyclic butane because the original evaporator became clogged after evaporating approximately 140 g of unstabilized 1,3-dimethoxy-1,3-dimethyl-1,3-disilhexacyclic butane.

[0070] Consider the data for unstabilized 1,3-dimethoxy-1,3-dimethyl-1,3-disilhexacyclic butane collected using the original syringe (Figures B and D). While the daily standard precursor flow for days 1–23 stabilized within the expected experimental error (Figure B), the decrease in the piezoelectric valve voltage required to maintain a stable flow (Figure D) indicates that residues accumulated in the piezoelectric valve as the unstabilized 1,3-dimethoxy-1,3-dimethyl-1,3-disilhexacyclic butane evaporated. This is clearly illustrated by considering the rapid decrease in the piezoelectric valve voltage each week (W1, W2, and W3). Data from the first week of testing (W1) show a rapid linear decrease in the piezoelectric valve voltage. In the second week of testing (W2), the unstabilized 1,3-dimethoxy-1,3-dimethyl-1,3-disilhexacyclic butane was run through the evaporator several hundred times, and the evaporator was left idle at temperature for 4 days. This clearly allowed the evaporator to recover slightly, as the initial valve voltage at the start of W2 (day 9) was higher than the valve voltage at the end of W1 (day 4). However, the initial valve voltage at the start of W2 was still much lower than the initial valve voltage at the start of W1, indicating residue accumulation in the piezoelectric control valve. Data from the second week of testing (W2) again showed a rapid linear decrease in the piezoelectric valve voltage. Limited data were collected during the third week of testing (W3) because the syringe became clogged after two more days of testing. Approximately 140 g of unstabilized 1,3-dimethoxy-1,3-dimethyl-1,3-disilhexacyclic butane was evaporated before the evaporator became clogged. These data clearly demonstrate that evaporating unstabilized 1,3-dimethoxy-1,3-dimethyl-1,3-disilhexacyclic butane readily leads to residue accumulation and clogging of the piezoelectric control valve in the Horiba LSVS.

[0071] This is Figure 1 The behavior of stabilized 1,3-dimethoxy-1,3-dimethyl-1,3-disilheycyclobutane, as shown in Figures A and C, is the opposite. Although the daily standard precursor flow was stable within the expected experimental error for days 39–58 (Figure A), only a small, gradual decrease in the piezoelectric valve voltage was observed (Figure C). Furthermore, the data in Figures A and C correspond to the evaporation of more than 200 g of stabilized 1,3-dimethoxy-1,3-dimethyl-1,3-disilheycyclobutane. These data clearly demonstrate that, relative to unstabilized 1,3-dimethoxy-1,3-dimethyl-1,3-disilheycyclobutane, stabilized 1,3-dimethoxy-1,3-dimethyl-1,3-disilheycyclobutane results in a significantly smaller rate of residue accumulation in the piezoelectric control valve.

[0072] In 300 mm AMAT Producer ®All evaporation and deposition experiments were performed on the SE, which deposited films simultaneously on two wafers. Therefore, the precursor and gas flow rates correspond to the flow rates required for simultaneous film deposition on both wafers. The stated per-wafer RF power is correct because each wafer processing station has its own independent RF power supply. The stated deposition pressure is correct because both wafer processing stations are maintained at the same pressure.

[0073] Thickness was measured using a Woollam M2000 spectroellipsometry. Dielectric constant was determined on medium resistivity p-type wafers (range 8–12 ohm-cm) using an Hg probe. Mechanical properties were determined using a KLA iNano Nano Indenter.

[0074] In the examples listed below, the same deposition conditions were used to deposit films with both unstabilized 1,3-dimethoxy-1,3-dimethyl-1,3-disilheycyclobutane and stabilized 1,3-dimethoxy-1,3-dimethyl-1,3-disilheycyclobutane.

[0075] Example 4: A dense OSG film 1 was deposited from unstabilized 1,3-dimethoxy-1,3-dimethyl-1,3-disilhecyclobutane and stabilized 1,3-dimethoxy-1,3-dimethyl-1,3-disilhecyclobutane.

[0076] For a 300 mm process, dense films were deposited using unstabilized 1,3-dimethoxy-1,3-dimethyl-1,3-disilheycyclobutane under the following process conditions. The unstabilized 1,3-dimethoxy-1,3-dimethyl-1,3-disilheycyclobutane precursor was fed into the reaction chamber via direct liquid injection (DLI) at a flow rate of 1100 mg / min, with a He carrier gas flow of 1500 standard cubic centimeters / minute (sccm), O2 at 10 sccm, a nozzle / heated substrate spacing of 400 mm, a substrate temperature of 400 °C, and a chamber pressure of 4.5 Torr, under a plasma of 300 W at 13.56 MHz. Stabilized 1,3-dimethoxy-1,3-dimethyl-1,3-disilheycyclobutane was used instead of the unstabilized 1,3-dimethoxy-1,3-dimethyl-1,3-disilheycyclobutane, and the same deposition conditions were used to deposit the dense film. As described above, various properties of the two films (e.g., dielectric constant (k) and hardness) are obtained, and in Figure 2 and Figure 3 It is shown graphically in the middle.

[0077] Example 5: Dense OSG was deposited using unstabilized 1,3-dimethoxy-1,3-dimethyl-1,3-disilhecyclobutane and stabilized 1,3-dimethoxy-1,3-dimethyl-1,3-disilhecyclobutane. (Film 2) For the 300 mm process, a dense film was deposited using unstabilized 1,3-dimethoxy-1,3-dimethyl-1,3-disilheycyclobutane under the following process conditions. The unstabilized 1,3-dimethoxy-1,3-dimethyl-1,3-disilheycyclobutane precursor was delivered to the reaction chamber via direct liquid injection (DLI) at a flow rate of 1100 mg / min, with a He carrier gas flow of 1000 standard cubic centimeters / minute (sccm), O2 at 100 sccm, a nozzle / heated substrate spacing of 300 mm, a substrate temperature of 400 °C, and a chamber pressure of 8.5 Torr, under which a 300 W 13.56 MHz plasma was applied. A stable 1,3-dimethoxy-1,3-dimethyl-1,3-disilheycyclobutane was used instead of the unstabilized 1,3-dimethoxy-1,3-dimethyl-1,3-disilheycyclobutane, and the same deposition conditions were used to deposit the dense film. As described above, various properties of the two films (e.g., dielectric constant (k) and hardness) are obtained, and in Figure 2 and Figure 3 It is shown graphically in the middle.

[0078] Example 6: Dense OSG was deposited using unstabilized 1,3-dimethoxy-1,3-dimethyl-1,3-disilhecyclobutane and stabilized 1,3-dimethoxy-1,3-dimethyl-1,3-disilhecyclobutane. (Film 3) For the 300 mm process, a dense film was deposited using unstabilized 1,3-dimethoxy-1,3-dimethyl-1,3-disilheycyclobutane under the following process conditions. The unstabilized 1,3-dimethoxy-1,3-dimethyl-1,3-disilheycyclobutane precursor was fed into the reaction chamber via direct liquid injection (DLI) at a flow rate of 1100 mg / min. A 13.56 MHz plasma at 400 W was applied using a He carrier gas flow rate of 1500 standard cubic centimeters / minute (sccm), 20 sccm of O2, a nozzle / heated substrate spacing of 330 mm, a substrate temperature of 400 °C, and a chamber pressure of 7.3 Torr. A dense film was then deposited using stabilized 1,3-dimethoxy-1,3-dimethyl-1,3-disilheycyclobutane instead of the unstabilized 1,3-dimethoxy-1,3-dimethyl-1,3-disilheycyclobutane under the same deposition conditions. As described above, various properties of the two films (e.g., dielectric constant (k) and hardness) are obtained, and in Figure 2 and Figure 3 It is shown graphically in the middle.

[0079] Example 7: Dense OSG was deposited using unstabilized 1,3-dimethoxy-1,3-dimethyl-1,3-disilhecyclobutane and stabilized 1,3-dimethoxy-1,3-dimethyl-1,3-disilhecyclobutane. (Film 4) For the 300 mm process, a dense film was deposited using unstabilized 1,3-dimethoxy-1,3-dimethyl-1,3-disilheycyclobutane under the following process conditions. The unstabilized 1,3-dimethoxy-1,3-dimethyl-1,3-disilheycyclobutane precursor was fed into the reaction chamber via direct liquid injection (DLI) at a flow rate of 1100 mg / min, with a He carrier gas flow of 1500 standard cubic centimeters / minute (sccm), O2 at 13 sccm, a nozzle / heated substrate spacing of 330 mm, a substrate temperature of 375 °C, and a chamber pressure of 7.3 Torr, under a plasma pressure of 400 W at 13.56 MHz. A stable 1,3-dimethoxy-1,3-dimethyl-1,3-disilheycyclobutane was used instead of the unstabilized 1,3-dimethoxy-1,3-dimethyl-1,3-disilheycyclobutane, and the same deposition conditions were used to deposit the dense film. As described above, various properties of the two films (e.g., dielectric constant (k) and hardness) are obtained, and in Figure 2 and Figure 3 It is shown graphically in the middle.

[0080] like Figure 2 and Figure 3 As shown, a comparison of the k and hardness of films 1, 2, 3, and 4 deposited using unstabilized and stabilized 1,3-dimethoxy-1,3-dimethyl-1,3-disilheycyclobutane indicates that, compared to the same films deposited using unstabilized 1,3-dimethoxy-1,3-dimethyl-1,3-disilheycyclobutane, stabilized 1,3-dimethoxy-1,3-dimethyl-1,3-disilheycyclobutane does not increase the k of the deposited films or decrease their mechanical properties. In fact, Figure 2 and Figure 3 The data indicate that, compared to films deposited using unstabilized 1,3-dimethoxy-1,3-dimethyl-1,3-disilheycyclobutane, films deposited using stabilized 1,3-dimethoxy-1,3-dimethyl-1,3-disilheycyclobutane have slightly lower k and slightly higher hardness.

[0081] Although the principles of the invention have been described above in conjunction with preferred embodiments, it should be clearly understood that this description is by way of example only and not as a limitation on the scope of the invention.

Claims

1. A composition comprising: (a) 1,3-dialkoxy-1,3-disilheycyclobutane according to formula I: Formula I wherein each R 1 independently is C1to C 10 linear or branched alkyl, and each R 2 independently is hydrogen or C1to C 10 linear or branched alkyl; and (b) Polymerization inhibitors, selected from: (i) Antioxidants or free radical scavengers; (ii) R 3 n R 4 m Si(OR 5 ) 4-n-m wherein R 3 and R 4 are each independently selected from the group consisting of hydrogen and C1to C 10 straight-chain or branched alkyl; and R 5 is selected from the group consisting of C1to C 10 straight-chain or branched alkyl; n is 0, 1, 2 or 3; m = 0, 1, 2, 3; (iii) Alkoxy-disiloxanes having the following formula Where R 6 Selected from straight-chain or branched C1 to C6 alkyl groups, preferably methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, or tert-butyl, and cyclic C5 to C6 alkyl groups; R 7 Selected from hydrogen and straight-chain or branched C1 to C5 alkyl groups; R 8-10 Each is independently selected from straight-chain or branched C1 to C5 alkyl groups, preferably methyl; and R 11 Selected from hydrogen, straight-chain or branched C1 to C5 alkyl groups, or OR 12 , where R 12 Selected from straight-chain or branched C1 to C5 alkyl groups; (iv) Alkoxy-carbosilanes having the following structure R 13 Selected from straight-chain or branched C1 to C6 alkyl groups, preferably methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, or tert-butyl, and cyclic C5 to C6 alkyl groups; R 14 Selected from hydrogen and straight-chain or branched C1 to C5 alkyl groups; R 15-17 Independently selected from straight-chain or branched C1 to C5 alkyl groups, preferably methyl; and R 18 Selected from hydrogen, straight-chain or branched C1 to C5 alkyl groups, or OR 19 , where R 19 Selected from straight-chain or branched C1 to C5 alkyl groups; and (v) Organoaminosilane R 20 n R 21 m Si(NR 22 R 23 ) 4-n-m , where R 20 and R 20 Each is independently selected from hydrogen and C1 to C2. 10 Straight-chain or branched alkyl groups; and R 22 and R 23 Selected from hydrogen, C1 to C 10 Straight-chain or branched alkyl; n is 0, 1, 2 or 3; m = 0, 1, 2 or 3.

2. The composition of claim 1, wherein for (a) 1,3-dialkoxy-1,3-disilheycyclobutane according to formula I, each R 1 Selected from methyl and ethyl, and R 2 It is a methyl group.

3. The composition of claim 1, wherein for (a) 1,3-dialkoxy-1,3-disilheycyclobutane according to formula I, each R 1 It is an ethyl group.

4. The composition of claim 1, wherein the polymerization inhibitor is selected from... (ii)R 3 n R 4 m Si(OR 5 ) 4-n-m , where R 3 R 4 and R 5 Substituents as defined; and (iv) The alkoxy-carbosilane having the following structure ， Where R 13 R 14 R 15 R 16 R 17 and R 18 Substituents are as defined.

5. The composition of claim 1, wherein the polymerization inhibitor (b) is (i) and is selected from 2,6-di-tert-butyl-4-methylphenol, butylhydroxytoluene, 2,2,6,6-tetramethyl-1-piperidinyloxy, 2-tert-butyl-4-hydroxyanisole, 3-tert-butyl-4-hydroxyanisole, propyl 3,4,5-trihydroxybenzoate, 2-(1,1-dimethylethyl)-1,4-benzenediol, diphenylpicrylhydrazine, 4-tert-butylcatechol, N-methylaniline, p-methoxydiphenylamine, diphenylamine, N,N'-diphenyl-p-phenylenediamine, p-hydroxydiphenylamine, phenol, octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl) Propionates, tetra(methylene-(3,5-di-tert-butyl)-4-hydroxy-hydrogenated cinnamate)methane, phenothiazines, alkylmididine isoureas, thiodiethylene bis(3,5-di-tert-butyl-4-hydroxy-hydrogenated cinnamate, 1,2-bis(3,5-di-tert-butyl-4-hydroxy-hydrogenated cinnamoyl)hydrazine, tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane, cyclopentanetetramethylbis(octadecyl phosphite), 4,4'-thiobis(6-tert-butyl-m-cresol), 2,2'-methylenebis(6-tert-butyl-p-cresol), oxaloylbis(benzylidene hydrazine), and naturally occurring antioxidants such as unprocessed seed oils, wheat germ oils, tocopherols, and combinations thereof.

6. The composition of claim 1, wherein the polymerization inhibitor (b) is (ii) and is selected from tetramethoxysilane, trimethoxysilane, tetraethoxysilane, triethoxysilane, dimethoxymethylsilane, diethoxymethylsilane, methoxydimethylsilane and ethoxydimethylsilane.

7. The composition of claim 1, wherein the polymerization inhibitor (b) is (iii) and is selected from 1,3-diethoxy-1,3-dimethyl-1,3-disiloxane and 1,3-diethoxy-tetramethyldisiloxane.

8. The composition of claim 1, wherein the polymerization inhibitor (b) is (iv) and is selected from 2,4,4-triethoxy-2,4-disilazane and 2,4-diethoxy-4-methyl-2,4-disilazane.

9. The composition of claim 1, wherein the polymerization inhibitor (b) is (v) and is selected from dimethylaminotrimethylsilane, diethylaminotrimethylsilane, bis(dimethylamino)dimethylsilane and tris(dimethylamino)methylsilane.

10. The composition of claim 1, wherein the boiling points of (a) 1,3-dialkoxy-1,3-disilhecyclobutane and (b) the polymerization inhibitor differ by 100°C or less.

11. The composition of claim 1, wherein any alkoxy group in any polymerization inhibitor (ii) to (v) is the same as any alkoxy group in 1,3-dialkoxy-1,3-disilhexacyclobutane according to formula I.

12. A chemical vapor deposition method for depositing an organosilicon film on at least a portion of a substrate, the method comprising: Provide the substrate within a vacuum chamber; The composition is introduced into the vacuum chamber, the composition comprising: (a) 1,3-dialkoxy-1,3-disilheycyclobutane having the following formula I: I Each R 1 Independently, they are C1 to C 10 Straight-chain or branched alkyl groups, and each R 2 Independently hydrogen or C1 to C 10 Straight-chain or branched alkyl groups; and (b) Polymerization inhibitors, selected from: (i) Antioxidants or free radical scavengers; (ii)R 3 n R 4 m Si(OR 5 ) 4-n-m , where R 3 and R 4 Each is independently selected from hydrogen and C1 to C2. 10 Straight-chain or branched alkyl groups; and R 5 Selected from C1 to C 10 Straight-chain or branched alkyl; n is 0, 1, 2 or 3; m = 0, 1, 2, 3; (iii) Alkoxy-disiloxanes having the following formula Where R 6 Selected from straight-chain or branched C1 to C6 alkyl groups, preferably methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, or tert-butyl, and cyclic C5 to C6 alkyl groups; R 7 Selected from hydrogen and straight-chain or branched C1 to C5 alkyl groups; R 8-10 Each is independently selected from straight-chain or branched C1 to C5 alkyl groups, preferably methyl; and R 11 Selected from hydrogen, straight-chain or branched C1 to C5 alkyl groups, or OR 12 , where R 12 Selected from straight-chain or branched C1 to C5 alkyl groups; (iv) Alkoxy-carbosilanes having the following structure R 13 Selected from straight-chain or branched C1 to C6 alkyl groups, preferably methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, or tert-butyl, and cyclic C5 to C6 alkyl groups; R 14 Selected from hydrogen and straight-chain or branched C1 to C5 alkyl groups; R 15-17 Independently selected from straight-chain or branched C1 to C5 alkyl groups, preferably methyl; and R 18 Selected from hydrogen, straight-chain or branched C1 to C5 alkyl groups, or OR 19 , where R 19 Selected from straight-chain or branched C1 to C5 alkyl groups; and (v) Organoaminosilane R 20 n R 21 m Si(NR 22 R 23 ) 4-n-m , where R 20 and R 20 Each is independently selected from hydrogen and C1 to C2. 10 Straight-chain or branched alkyl groups; and R 22 and R 23 Selected from hydrogen, C1 to C 10 Straight-chain or branched alkyl; n is 0, 1, 2 or 3; m = 0, 1, 2, 3; and Energy is applied to the gaseous structure-forming composition in the vacuum chamber to induce a reaction of at least the 1,3-dialkoxy-1,3-disilhexacyclobutane, thereby depositing a film on at least a portion of the substrate.

13. The method of claim 12, wherein for (a) 1,3-dialkoxy-1,3-disilheycyclobutane according to formula I, each R 1 Selected from methyl and ethyl, and R 2 It is a methyl group.

14. The method of claim 12, wherein the polymerization inhibitor (b) is (i) and is selected from 2,6-di-tert-butyl-4-methylphenol, butylhydroxytoluene, 2,2,6,6-tetramethyl-1-piperidinyloxy, 2-tert-butyl-4-hydroxyanisole, 3-tert-butyl-4-hydroxyanisole, propyl 3,4,5-trihydroxybenzoate, 2-(1,1-dimethylethyl)-1,4-benzenediol, diphenylpicrylhydrazine, 4-tert-butylcatechol, N-methylaniline, p-methoxydiphenylamine, diphenylamine, N,N'-diphenyl-p-phenylenediamine, p-hydroxydiphenylamine, phenol, octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl) Methylpropionate, tetra(methylene-(3,5-di-tert-butyl)-4-hydroxy-hydrogenated cinnamate)methane, phenothiazines, alkylmididine isoureas, thiodiethylene bis(3,5-di-tert-butyl-4-hydroxy-hydrogenated cinnamate, 1,2-bis(3,5-di-tert-butyl-4-hydroxy-hydrogenated cinnamoyl)hydrazine, tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane, cyclopentanetetramethylbis(octadecyl phosphite), 4,4'-thiobis(6-tert-butyl-m-cresol), 2,2'-methylenebis(6-tert-butyl-p-cresol), oxaloylbis(benzylidene hydrazine), and naturally occurring antioxidants such as unprocessed seed oils, wheat germ oils, tocopherols, and combinations thereof.

15. The method of claim 12, wherein the polymerization inhibitor (b) is (ii) and is selected from tetramethoxysilane, trimethoxysilane, tetraethoxysilane, triethoxysilane, dimethoxymethylsilane, and diethoxymethylsilane.

16. The method of claim 12, wherein the polymerization inhibitor (b) is (iii) and is selected from 1,3-diethoxy-1,3-dimethyl-1,3-disiloxane and 1,3-diethoxy-tetramethyldisiloxane.

17. The method of claim 12, wherein the polymerization inhibitor (b) is (iv) and is selected from 2,4,4-triethoxy-2,4-disilazane and 2,4-diethoxy-4-methyl-2,4-disilazane.

18. The method of claim 12, wherein the polymerization inhibitor (b) is (v) and is selected from dimethylaminotrimethylsilane, diethylaminotrimethylsilane, bis(dimethylamino)dimethylsilane, tris(dimethylamino)methylsilane, dimethylaminodimethylsilane and diethylaminodimethylsilane.

19. The method of claim 12, wherein the boiling points of (a) 1,3-dialkoxy-1,3-disilhexacyclobutane and (b) the polymerization inhibitor differ by 100°C or less.

20. The method of claim 12, wherein any alkoxy group in any polymerization inhibitor (ii) to (v) is the same as any alkoxy group in 1,3-dialkoxy-1,3-disilhexacyclobutane according to formula I.

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