Stabilized organosilane composition and method for forming a dense low-k film using the same

Abstract

The composition comprises (a) 1,3-dialkoxy-1,3-disilacyclobutane having the following formula I: JPEG2026528932000018.jpg29128[In the formula, each R 1 These are, independently, C1~C 10 It is a linear or branched alkyl group, and each R 2 These are independently hydrogen or C1-C 10 (b) containing a polymerization inhibitor.

Description

Technical Field

[0001] (Cross - Reference to Related Applications) This application claims the benefit of U.S. Provisional Patent Application No. 63 / 519,635, filed on August 15, 2023.

Background Art

[0002] The present invention generally relates to stabilized organosilane compositions and the formation of dielectric films using the stabilized compositions. More specifically, the present invention relates to dielectric materials having a low dielectric constant and enhanced mechanical properties, films containing such materials, and methods for manufacturing the same using a stable composition.

[0003] All references, including publications, patent applications, and patents cited herein, are hereby incorporated by reference in their entirety as if each reference were specifically and individually indicated to be incorporated by reference and were set forth in its entirety herein.

[0004] In the microelectronics industry, it is continuously desired to increase the circuit density in multi - level integrated circuit devices such as memory and logic chips to improve the operating speed and reduce power consumption. U.S. Patent No. 10249489 (B2) discloses low - dielectric - constant organosilicon films formed using, among other things, alkoxylated disilyl - alkanes and alkoxylated disilyl - cycloalkanes. Such low - dielectric - constant materials are desirable for use, for example, as pre - metal dielectric layers or inter - level dielectric layers.

[0005] One class of organosilanes useful for low - k applications is alkoxylated disilacyclobutanes. However, some of such compounds have boiling points that require heating the film precursor to a temperature high enough to promote polymerization, which limits the use of the precursor as a stable and high - yield film - forming compound.

[0006] U.S. Patent No. 1,1393,678(B) discloses a method for depositing a high-hardness, low-k dielectric film. More specifically, a method for processing a substrate is provided. The method includes (1) flowing a precursor-containing gas mixture into a processing volume of a processing chamber having a substrate, wherein the precursor is a silacic cyclobutane derivative; (2) maintaining the substrate at a pressure in the range of about 0.1 mtorr to about 20 torr and a temperature in the range of about 200° to about 500°; and (3) generating plasma at the substrate level to deposit a dielectric film on the substrate.

[0007] U.S. Patent No. 5,302,734(A) discloses the synthesis of alkoxy-1,3-disilacyclobutane by thermal decomposition.

[0008] U.S. Patent No. 7,381,659(B) discloses a method for reducing the tensile stress of a low-k dielectric layer, the method comprising the step of depositing an organosilicate layer on a substrate, the layer having an associated initial tensile stress value. The layer is annealed in a reactive environment at a temperature and duration selected to result in a layer having a tensile stress value lower than the initial tensile stress value after completion of annealing.

[0009] U.S. Patent No. 10249489(B) describes a low-dielectric material and a film containing the same for improving performance when used as an interlevel dielectric in an integrated circuit, as well as a method for manufacturing the same. The formation of this organosilicate film involves chemical vapor deposition (CVA) 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 of novel functional polymeric materials." Appl.Organomet.Chem.12(10 / 11):695-705.n This document describes the synthesis routes for both linear polycarbosilanes and ultrabranched polycarbosilanes having the chemical formula [SiH2CH2]. n The polymer was prepared by ring-opening polymerization of substituted disilacyclobutane.

[0011] Since the cyclodisibutanes disclosed to date appear to be capable of forming polymer species during their delivery, there is a need to develop compositions containing stabilized cyclodisibutanes for gas-phase deposition of silicon-containing low-dielectric materials. [Overview of the project]

[0012] The compositions or formulations described herein and methods of using them overcome the problems of the prior art by depositing a silicon-containing film on at least a portion of the substrate surface and providing desirable film properties.

[0013] In one aspect, the present invention provides a stabilized organosilane composition that can be used to form a dielectric film without polymerization occurring to the extent that the precursor loses its usefulness. In another aspect, the present invention relates to a dielectric material having a low dielectric constant and enhanced mechanical properties, a film containing the material, and a method for producing the same using a stable organosilane composition.

[0014] The above-mentioned problems and other problems are related to the composition, (a) 1,3-dialkoxy-1,3-disilacyclobutane having the following formula I: [ka] [In the formula, each R 1 These are, independently, C1~C 10 It is a linear or branched alkyl group, and each R 2 These are independently hydrogen or C1-C 10 [Straight-chain or branched-chain alkyl]; and (b) Polymerization inhibitor selected from the group consisting of the following: (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 hydrogen and C1-C 10 linear or branched alkyl; R 5 is selected from C1-C 10 linear or branched alkyl; n is 0, 1, 2, or 3; and m = 0, 1, 2, 3]; (iii) an alkoxy-disiloxane having the following formula[[ID=!24]] [[ID=!25]]

Chemical formula

Chemical formula

[0015] In a preferred embodiment, each of the polymerization inhibitors (ii) to (v) is the same as the alkoxy group in 1,3-dialkoxy-1,3-disilacyclobutane, ensuring that the chemical structure of 1,3-dialkoxy-1,3-disilacyclobutane does not change when an alkoxy exchange reaction occurs between the polymerization inhibitor and 1,3-dialkoxy-1,3-disilacyclobutane.

[0016] The above-mentioned problems and other problems relate to a chemical vapor deposition method for depositing an organosilicate film on at least a portion of a substrate, The process of providing a substrate in a vacuum chamber, A step of introducing a composition containing (a) and (b) above into a vacuum chamber, The problem is further solved by a method comprising the steps of applying energy to a gaseous structure-forming composition in a vacuum chamber to induce the reaction of at least 1,3-dialkoxy-1,3-disilacyclobutane and depositing a film on at least a portion of the substrate. [Brief explanation of the drawing]

[0017] [Figure 1] This graph shows the precursor flow rate and corresponding piezoelectric control valve voltage related to the vaporization of both stabilized 1,3-dimethoxy-1,3-dimethyl-1,3-disilacyclobutane (Panels A and C) and unstabilized 1,3-dimethoxy-1,3-dimethyl-1,3-disilacyclobutane (Panels B and D) through the Horiba liquid supply source vaporization system.

[0018] [Figure 2] This graph shows the dielectric constants of films 1, 2, 3, and 4 deposited using stabilized 1,3-dimethoxy-1,3-dimethyl-1,3-disilacyclobutane (black diagonal lines) and unstabilized 1,3-dimethoxy-1,3-dimethyl-1,3-disilacyclobutane (solid black).

[0019] [Figure 3] This graph shows the hardness of films 1, 2, 3, and 4 deposited using stabilized 1,3-dimethoxy-1,3-dimethyl-1,3-disilacyclobutane (black diagonal lines) and unstabilized 1,3-dimethoxy-1,3-dimethyl-1,3-disilacyclobutane (solid black). [Modes for carrying out the invention]

[0020] In the context describing the present invention (particularly in the context of the following claims), the use of the terms “a,” “an,” and “the,” and similar references, should be interpreted as encompassing both singular and plural forms unless otherwise indicated herein or explicitly refuted by the context. The terms “comprising,” “having,” “including,” and “containing” should be interpreted as open-ended terms (i.e., “listed, but not limited to”) unless otherwise indicated herein. Enumerations of value ranges herein are merely intended to serve as abbreviations to refer individually to each individual value falling within that range, unless otherwise indicated herein, and each individual value is incorporated herein as if it were individually listed herein. All methods described herein may be performed in any preferred order unless otherwise indicated herein or explicitly refuted by the context. Any and all examples or illustrative language provided herein (e.g., the use of "such as") is intended solely to better illustrate the invention and does not impose any limitation on the scope of the invention unless otherwise claimed. No language herein should be construed as indicating any unclaimed element essential to the practice of the invention.

[0021] Preferred embodiments of the present invention are described herein, including the best modes known to the inventors for carrying out the invention. Variations of these preferred embodiments may become apparent to those skilled in the art by reading the preceding description. The inventors anticipate that those skilled in the art will use such variations as needed, and the inventors intend that the invention may be carried out in ways other than those specifically described herein. Accordingly, the invention includes all variations and equivalents of the subject matter described in the claims appended herein, as permitted by applicable law. Furthermore, any combination of the above elements in all possible variations thereof is encompassed by the invention unless otherwise indicated herein or expressly rejected by the context.

[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 aid in the reference of the method steps and are not intended to indicate the order in which the claimed steps are performed, except to the extent that such an order is specifically stated in the claims.

[0023] In one embodiment, the present development is a composition, (a) 1,3-dialkoxy-1,3-disilacyclobutane having the following formula I: [ka] [In the formula, each R 1 These are, independently, C1~C 10 It is a linear or branched alkyl group, and each R 2 These are independently hydrogen or C1-C 10 [Straight-chain or branched-chain alkyl]; and (b) Polymerization inhibitor selected from the group consisting of the following: (i) Antioxidants or free radical scavengers; (ii)R 3 n R 4 m Si(OR5 ) 4-n-m [In the formula, R 3 and R 4 Each of them independently consists of hydrogen and C1-C 10 Selected from linear or branched alkyl groups; R 5 C1~C 10 Selected from linear or branched alkyl groups; n is 0, 1, 2, or 3; m = 0, 1, 2, or 3. (iii) Alkoxy-disiloxane having the following formula [ka] [In the formula, R 6 The C1-C6 alkyl groups are selected from linear or branched C1-C6 alkyl groups, preferably methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, or tert-butyl, and cyclic C5-C6 alkyl groups; R 7 R is selected from hydrogen and linear or branched C1-C5 alkyl groups; 8~10 Each is independently selected from linear or branched C1-C5 alkyl groups, preferably methyl groups; R 11 This includes hydrogen, linear or branched C1-C5 alkyl groups, or OR 12 [In the formula, R 12 [Selected from linear or branched C1-C5 alkyl groups]; (iv) Alkoxy-carbosilane having the following structure [ka] [In the formula, R 13 The C1-C6 alkyl groups are selected from linear or branched C1-C6 alkyl groups, preferably methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, or tert-butyl, and cyclic C5-C6 alkyl groups; R 14 R is selected from hydrogen and linear or branched C1-C5 alkyl groups; 15~17 These are independently selected from linear or branched C1-C5 alkyl groups, preferably methyl groups; R 18 This includes hydrogen, linear or branched C1-C5 alkyl groups, or OR 19 [In the formula, R 19[Selected from linear or branched C1-C5 alkyl groups]; and (v) Organoaminosilane R 20 n R 21 m Si(NR 22 R 23 ) 4-n-m [In the formula, R 20 and R 20 Each of them independently consists of hydrogen and C1-C 10 Selected from linear or branched alkyl groups; R 22 and R 23 is hydrogen, C1~C 10 Selected from linear or branched alkyl groups; n is 0, 1, 2, or 3; m = 0, 1, 2, or 3. A composition containing the following is provided.

[0024] In preferred embodiments, the alkoxy groups in each polymerization inhibitor (ii) to (v) are the same as the alkoxy groups in 1,3-dialkoxy-1,3-disilacyclobutane, ensuring that the chemical structure of 1,3-dialkoxy-1,3-disilacyclobutane does not change when an alkoxy exchange reaction occurs between the polymerization inhibitor and 1,3-dialkoxy-1,3-disilacyclobutane.

[0025] According to an exemplary embodiment, for 1,3-dialkoxy-1,3-disilacyclobutane (a), R 1 and R 2Each of these is independently selected from the group consisting of hydrogen and C1-C4 linear or branched alkyl groups. Examples include 1,3-diethoxy-1,3-dimethyl-1,3-disilacyclobutane, 1,3-dimethoxy-1,3-dimethyl-1,3-disilacyclobutane, 1,3-di-n-propoxy-1,3-disilacyclobutane, 1,3-di-iso-propoxy-1,3-dimethyl-1,3-disilacyclobutane, 1,3-methoxy-1,3-diethyl-1,3-disilacyclobutane, 1,3-dipropoxy-1,3-disilacyclobutane, 1,3-diethoxy-1-methyl-1,3-disilacyclobutane, and 1,3-diethoxy-1-ethyl-1,3-disilacyclobutane, 1,3-diethoxy-1,3-disilacyclobutane, and 1,3-dimethoxy-1,3-disilacyclobutane.

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

[0027] Examples of antioxidants or free radical scavengers (i) include, but are not limited to, 2,6-di-tert-butyl-4-methylphenol (or BHT in the case of butylhydroxytoluene), 2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO), 2-tert-butyl-4-hydroxyanisole, 3-tert-butyl-4-hydroxyanisole, 3,4,5-trihydroxybenzoate propyl ester, 2-(1,1-dimethylethyl)-1,4-benzenediol, diphenylpicrylhydrazyl, 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 Examples include propionates, tetrakis(methylene(3,5-di-tert-butyl)-4-hydroxyhydrocinnamate)methane, phenothiazines, alkylamide noisoureas, thiodiethylenebis(3,5-di-tert-butyl-4-hydroxyhydrocinnamate, 1,2-bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamoyl)hydrazine, tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane, cyclic neopentanetetraylbis(octadecyl phosphite), 4,4'-thiobis(6-tert-butyl-m-cresol), 2,2'-methylenebis(6-tert-butyl-p-cresol), oxalylbis(benzylidene hydrazide), and naturally occurring antioxidants such as raw seed oil, wheat germ oil, tocopherol, 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), though not limited to them, include 1,3-diethoxy-1,3-dimethyl-1,3-disiloxane and 1,3-diethoxy-tetramethyldisiloxane.

[0030] Examples of polymerization inhibitors (iv), though not limited to them, include 2,4,4-triethoxy-2,4-disilapentane and 2,4-diethoxy-4-methyl-2,4-disilapentane.

[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 the present invention, 1,3-dialkoxy-1,3-disilacyclobutane may be a cis-cis, trans-trans, or cis-trans isomer, or a mixture thereof. In this embodiment or other embodiments, the polymerization inhibitor has a bp (base point) similar to that of 1,3-dialkoxy-1,3-disilacyclobutane, or the difference between the bp of the polymerization inhibitor and the bp of 1,3-dialkoxy-1,3-disilacyclobutane 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 is a range from one or more of the following endpoints: 0, 10, 20, 30, 40, or 100°C. Examples of preferred ranges for the bp difference 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 additional exemplary polymerization inhibitors (b) and their corresponding boiling points.

[0033] [Table 1]

[0034] An example of an organosilicate film deposited by the method of the present invention is a carbon-doped silicon oxide film. In the method developed here, typically, the first step is to place a substrate having at least one surface feature into 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, polysilicon, amorphous silicon, epitaxial silicon, silicon dioxide ("SiO2"), silicon carbide ("SiC"), silicon oxycarbide ("SiOC"), silicon nitride ("SiN"), silicon carbonitride ("SiCN"), organosilicate glass ("OSG"), organofluorosilicate glass ("OFSG"), fluorosilicate glass ("FSG"), and other suitable substrates, or mixtures thereof. The substrate may further include various layers to which films are applied, such as anti-reflective coatings, photoresists, organic polymers, porous organic and inorganic materials, metals, such as copper, cobalt, ruthenium, tungsten, rhodium, and aluminum, or diffusion barrier layers, such as 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 aluminum oxide (sapphire) wafer, a glass sheet, a metal foil, an organic polymer film, or a polymer, glass, silicon, or metal three-dimensional article. The substrate may be coated with films of various materials well known in the art, such as silicon oxide, silicon nitride, amorphous carbon, silicon oxycarbide, silicon oxynitride, silicon carbide, gallium arsenide, gallium nitride, etc. These coatings may completely coat the substrate, consist of multiple layers of various materials, or be partially etched to expose the underlying material. The surface may also have a photoresist material on top, which is exposed and developed in a pattern to partially coat the substrate.

[0035] 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 (PECCVD) processes. In one embodiment, the film is deposited using a plasma-based (e.g., remotely generated or in situ) CVD process. As used herein, the term “reactor” includes, but is not limited to, a reaction chamber or a deposition chamber.

[0036] In certain embodiments, the substrate may be subjected to one or more pre-deposition treatments, including but not limited to plasma treatment, heat treatment, chemical treatment, ultraviolet exposure, electron beam exposure, and combinations thereof, in order to affect one or more properties of the film. These pre-deposition treatments may be carried out in an atmosphere selected from inert, oxidizing, and / or reducing.

[0037] Although chemical reagents used herein may sometimes be described as "gaseous," it should be understood that chemical reagents may be delivered directly to the reactor as a gas, delivered as vapors resulting from vaporizing a liquid or bubbling a liquid using a carrier gas such as nitrogen, helium, or argon, delivered as vapors from the sublimation of a solid, and / or transported into the reactor by an inert carrier gas.

[0038] In a preferred embodiment, the organosilicate film deposited by this method is a dense organosilicate 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 decrease in dielectric constant compared to a silicon dioxide film, which typically has a dielectric constant of about 3.8 to about 4.2 and a hardness of about 7 GPa.

[0039] The method developed in this project includes the steps of introducing the composition defined above into a vacuum chamber and applying energy to the gaseous structure-forming composition in the vacuum chamber to induce a reaction of at least one organosilicon precursor and deposit a film on at least a portion of the substrate.

[0040] The compositions described above and herein may be delivered to a reaction chamber, such as a CVD or ALD reactor, in a variety of ways. In one embodiment, a liquid delivery system can be utilized. In an alternative embodiment, a combination of liquid delivery and flash vaporization process units, such as a turbo vaporizer from MSP Corporation (Shoreview, MN), may be used to enable volumetric delivery of low-volatility materials, resulting in reproducible transport and deposition without thermal decomposition of the precursor. In liquid delivery formulations, the precursors described herein may be delivered in neat liquid form or used in a solvent formulation or a composition containing a solvent formulation. Thus, in a particular embodiment, the precursor formulation may contain a solvent component with suitable properties that may be desirable and advantageous in a given end-use application for forming a film on a substrate.

[0041] In one particular embodiment, a plasma-enhanced chemical vapor deposition method for producing a low-k dielectric film includes the steps of: providing a substrate in a reaction chamber; introducing a gaseous composition comprising 1,3-dialkoxy-1,3-disilacyclobutane and at least one polymerization inhibitor into the reaction chamber with or without an oxidizing agent; and applying energy to the gaseous composition in the reaction chamber to induce a reaction of the gaseous composition and deposit a silicon-containing film on the substrate. The deposition process is typically carried out on a heated pedestal 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.

[0042] 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), can be optionally added.

[0043] One or more fluorine feed gases can be used as additives during the reaction or post-treatment. Examples of fluorine feed gases include NF3, F2, CF4, C2F6, C4F6, and C6F6.

[0044] In addition to the composition, and optionally the oxygen and fluorine supply gases, additional materials may be introduced 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 include CH4, C2H6, C2H4, C2H2, C3H8, cyclopentane, cyclooctane, allene, propylene, α-terpinene, para-cymene, benzene, naphthalene, toluene, and styrene.

[0045] Reagents (i.e., compositions, oxidizing agents, etc.) can be delivered into the reactor separately from a separate source or as a mixture. Reagents can be delivered to the reactor system by any number of means, preferably using pressurized stainless steel containers equipped with appropriate valves and fittings that allow the liquid to be delivered to the process reactor.

[0046] Energy is applied to a gaseous reagent to induce a gaseous reaction, forming a film on at least a portion of the substrate. Such energy can be, for example, heat or plasma. 、It can be provided by pulsed plasma, helicon plasma, high-density plasma, inductively coupled plasma, and remote plasma methods. The plasma properties on the substrate surface can be modified using a secondary RF frequency source. Preferably, the film is formed by plasma chemical vapor deposition. It is particularly preferable to generate a capacitively coupled plasma at a frequency of 13.56 MHz. The plasma output is preferably 0.02 to 7 watts / cm², based on the surface area of ​​the substrate. 2 , more preferably 0.3 to 3 watts / cm² 2 Therefore, it can be advantageous to use a carrier gas with a low ionization energy in order to lower the electron temperature in the plasma (therefore reducing the decomposition of OSG precursors and pologens). Examples of this type of low-ionization gas include CO2, NH3, CO, CH4, Ar, Xe, and Kr.

[0047] In some embodiments where the energy is plasma energy, the plasma source is selected from, but is not limited to, the group consisting of carbon source plasmas, for example hydrocarbon plasmas, plasmas containing hydrocarbons and helium, plasmas containing hydrocarbons and argon, carbon dioxide plasmas, carbon monoxide plasmas, plasmas containing hydrocarbons and hydrogen, plasmas containing hydrocarbons and a nitrogen source, plasmas containing hydrocarbons and an oxygen source, and mixtures thereof.

[0048] The flow rate of each gaseous reagent is preferably in the range of 10 to 5000 sccm, more preferably 30 to 1000 sccm, per single 200 mm wafer. The individual rates are selected to provide the desired amounts of structure-forming and pore-forming agents into the film. The actual flow rates required may vary depending on the wafer size and chamber configuration and are by no means limited to a 200 mm wafer or a single wafer chamber.

[0049] In some embodiments, the film is deposited at a rate of 50 to 250 nm / min.

[0050] The pressure inside the vacuum chamber during deposition is preferably 0.01 to 600 torr, more preferably 1 to 15 torr.

[0051] The film is preferably deposited to a thickness of 0.002 to 10 microns, but this thickness can be changed as needed. Blanket films deposited on unpatterned surfaces exhibit excellent uniformity and, with reasonable edge exclusion (e.g., the outermost 5 mm edge of the substrate is not included in the statistical calculation of uniformity), have a thickness variation of less than 2% per standard deviation across the substrate.

[0052] In situ or post-deposition treatments may be used to improve material properties such as hardness, stability (against shrinkage, air exposure, etching, wet etching, etc.), integrity, uniformity, and adhesion. Such treatments can be applied to the film before, during, and / or after pologen removal, using the same or different means as those used for pologen removal. 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 pologens and optionally to improve material properties.

[0053] The conditions under which post-processing is performed can vary considerably. For example, post-processing can be carried out under high pressure or in a vacuum atmosphere.

[0054] Thermal annealing is carried out under the following conditions: The environment can be inert (e.g., nitrogen, CO2, noble gases (He, Ar, Ne, Kr, Xe), etc.), oxidizing (e.g., oxygen, air, dilution of oxygen, enrichment of oxygen, ozone, nitrous oxide, etc.), or reducing (dilution or concentration of 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 atmosphere is also possible for thermal annealing and any other post-treatment means. The temperature is preferably 200 to 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.

[0055] The chemical treatment of OSG films can also be carried out by fluorination (HF, SIF4, NF3, F2, COF2, CO2F2, etc.), oxidation (H2O2, O3, etc.), chemical drying, methylation, or other chemical treatments that improve the properties of the final material. The chemicals used in such treatments may be in the state of solid, liquid, gas, and / or supercritical fluid.

[0056] In certain embodiments, the OSG film is subjected to annealing treatment, preferably by heat or radiation (i.e., photoannealing). In these embodiments, photoannealing is performed under the following conditions: 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, rich oxygen environment, ozone, nitrous oxide, etc.), or reducing (e.g., diluted or concentrated hydrocarbons, hydrogen, ammonia, etc.). The power output can be in the range of 0 to 5000 W. The wavelength is preferably IR, visible, 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 in the range of 0.01 minutes to 12 hours.

[0057] Plasma treatment for chemical modification of OSG films is carried out under the following conditions. The environment can be inert (nitrogen, CO2, noble gases (He, Ar, Ne, Kr, Xe), etc.), oxidizing (e.g., oxygen, air, diluted oxygen environment, enriched oxygen environment, ozone, nitrous oxide, etc.), or reducing (e.g., diluted or concentrated hydrogen, hydrocarbons (saturated, unsaturated, linear or branched, aromatic), ammonia, etc.). The plasma output is preferably 0 to 5000 W. 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.

[0058] Microwave post-treatment is carried out under the following conditions: The environment can be inert (e.g., nitrogen, CO2, noble gases (He, Ar, Ne, Kr, Xe), etc.), oxidizing (e.g., oxygen, air, diluted oxygen environment, enriched oxygen environment, ozone, nitrous oxide, etc.), or reducing (e.g., diluted or concentrated hydrocarbons, hydrogen, etc.). The temperature is preferably ambient temperature ~ 500°C. The power and wavelength can be varied and adjusted for specific bonds. The total curing time is preferably 0.01 minutes to 12 hours.

[0059] Electron beam post-treatment is performed under the following conditions: The environment can be vacuum, inert (e.g., nitrogen, CO2, noble gases (He, Ar, Ne, Kr, Xe), etc.), oxidizing (e.g., oxygen, air, diluted oxygen environment, enriched oxygen environment, ozone, nitrous oxide, etc.), or reducing (e.g., diluted or concentrated hydrocarbons, hydrogen, etc.). The temperature is preferably ambient temperature ~ 500°C. Electron density and energy can be varied and adjusted for specific bonds. The total curing time is preferably 0.001 minutes to 12 hours and may be continuous or pulsed. Additional guidance on the use of electron beams in general 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. 6,207,555(B1), 6,204,201(B1), and 6,132,814(A1). The use of electron beam treatment can provide pologen removal and enhancement of the mechanical properties of films through bonding processes within the matrix.

[0060] The present invention will be described in more detail with reference to the following examples, but it should be understood that the present invention is not limited thereto. Example 1 - Stabilization of 1,3-diethoxy-1,3-dimethyl-1,3-disilacyclobutane

[0061] 1,3-diethoxy-1,3-dimethyl-1,3-disilacyclobutane has a boiling point of 185°C, and requires heating above 100°C to have a vapor pressure sufficient for practical gas-phase delivery. However, 1,3-diethoxy-1,3-dimethyl-1,3-disilacyclobutane tends to polymerize when heated above 100°C. More specifically, neat 1,3-diethoxy-1,3-dimethyl-1,3-disilacyclobutane polymerizes to form a gel when heated at 120°C for several days. Thermogravimetric analysis (TGA) of 1,3-diethoxy-1,3-dimethyl-1,3-disilacyclobutane heated for 7 days shows a significant level of non-volatile residue compared to the initial material, where non-volatile residues are undetectable. Polymer pyrolysis products can also be measured by GPC (gel permeation chromatography). In contrast, 1,3-diethoxy-1,3-dimethyl-1,3-disilacyclobutane spiked with butylated hydroxytoluene (BHT) or hydro(dydro)quinone monomethyl ether (HQMME) (also known as 4-methoxyphenol) shows significantly reduced or undetectable levels of non-volatile residue by TGA analysis. 1,3-diethoxy-1,3-dimethyl-1,3-disilacyclobutane spiked with organosilanes such as DEMS or TEOS also shows significantly reduced or undetectable levels of non-volatile residue by TGA analysis. Doping 1,3-diethoxy-1,3-dimethyl-1,3-disilacyclobutane with antioxidants / free radical scavengers or organosilanes as described herein substantially increases the thermal stability of 1,3-diethoxy-1,3-dimethyl-1,3-disilacyclobutane, making it practical for use in low-k applications.

[0062] Table 2 below provides a list of various compositions containing 1,3-diethoxy-1,3-dimethyl-1,3-disilacyclobutane (DEDMDSCB) and polymerization inhibitors. The compositions were aged at 120°C for 7 days or at 110°C for up to 26 days, visually inspected, and the NVR (non-volatile content) after thermal aging was analyzed by TGA.

[0063] [Table 2] * 110℃ for one day ** 26 days at 110℃ Example 2

[0064] Additional tests were performed to evaluate other possible stabilizers for DEDMDSCB, such as BTBAS (bis(tert-butyl)aminosilane), 1-methoxy,1,1,3,3-tetramethyldisiloxane, and 3,3,5,5-tetramethyl-2,6-dioxa-3,5-disilaheptane. DEDMDSCB was spiked with 0.5 wt% BTBAS (bis(tert-butyl)aminosilane), 1-methoxy,1,1,3,3-tetramethyldisiloxane, and 3,3,5,5-tetramethyl-2,6-dioxa-3,5-disilaheptane. The spiked samples were heated at 120°C for 24 hours and then allowed to cool to room temperature to examine for evidence of gel formation. If there was no sign of gel, the spiked DEDMDSCB was heated at 120°C for a further 6 days. After a total of 7 days at 120°C, the samples were evaluated by visual inspection, GC, and TGA residue analysis for any signs of gel formation, decomposition products, or non-volatile by-product formation.

[0065] Table 3 below provides a list of various compositions containing DEDMDSCB and the additives used above. The compositions were aged at 120°C for 7 days. Compositions that had not gelled were visually inspected after 1 day and 7 days at 120°C and evaluated by TGA analysis.

[0066] [Table 3] Example 3

[0067] The liquid precursor, 1,3-dimethoxy-1,3-dimethyl-1,3-disilacyclobutane, was vaporized using a Horiba liquid source vaporization system (LSVS). This system consists of two components: a liquid flow meter and a heated vaporizer (injector). Pressurized liquid is supplied to the liquid flow meter, the measured liquid flow is then supplied to the vaporizer, and the vaporized output is then supplied to the vacuum system. A piezoelectric control valve in the vaporizer (0V = fully open, 120V = closed) opens or closes to adjust the liquid flow rate to its set point via a feedback loop. The vaporizer temperature is typically set to the lowest temperature that provides a stable vapor flow rate. For 1,3-dimethoxy-1,3-dimethyl-1,3-disilacyclobutane, a vaporizer temperature of 110°C was used.

[0068] For a given precursor, the degree of residue buildup or blockage in the vaporizer can be monitored as a function of time (i.e., as a function of the mass of the vaporized precursor) by tracking the voltage of the piezoelectric control valve relative to the fixed liquid flow rate. When residue builds up in the piezoelectric valve, the valve needs to open further to maintain the same liquid flow rate. Therefore, if the voltage of the piezoelectric valve begins to decrease rapidly relative to the fixed liquid flow rate (0V = fully open), the vaporizer is blocked.

[0069] To test the stability of 1,3-dimethoxy-1,3-dimethyl-1,3-disilacyclobutane in the Horiba LSVS over time, a fixed liquid flow condition (1,3-dimethoxy-1,3-dimethyl-1,3-disilacyclobutane = 600 mg / min; He = 700 sccm) was applied at the start of each workday. During this daily standard, the liquid flow rate and piezoelectric voltage were recorded. After the daily standard was completed, 1,3-dimethoxy-1,3-dimethyl-1,3-disilacyclobutane (500-1100 mg / min) was vaporized through the Horiba LSVS at various flow rates. The vaporization time ranged from 72 to 380 seconds. After the vaporization cycle was completed, the vaporizer was purged with N2 before the next cycle. The degree of residue accumulation (i.e., blockage) in the vaporizer was measured using the change in piezoelectric voltage over time during the daily standard.

[0070] The vaporization stability of 1,3-dimethoxy-1,3-dimethyl-1,3-disilacyclobutane in the Horiba LSVS was monitored for both unstabilized and stabilized 1,3-dimethoxy-1,3-dimethyl-1,3-disilacyclobutane. Stabilized 1,3-dimethoxy-1,3-dimethyl-1,3-disilacyclobutane refers to a mixture of 99.5% by weight of 1,3-dimethoxy-1,3-dimethyl-1,3-disilacyclobutane and 0.5% by weight of polymerization inhibitor (DEMS®). The results are shown in Figure 1, which shows the precursor flow rate and piezoelectric valve voltage from the daily standard as a function of the number of days (0-60) during the evaluation period. Figure 1 has four panels. The top two panels (Panels A and B) show the trend of the precursor flow rate, and the bottom two panels (Panels C and D) show the trend of the piezoelectric valve voltage. The two panels on the right side of Figure 1 (Panels B and D) show the trend of unstabilized 1,3-dimethoxy-1,3-dimethyl-1,3-disilacyclobutane in the original vaporizer. The two panels on the left side of Figure 1 (Panels A and C) show the trend of stabilized 1,3-dimethoxy-1,3-dimethyl-1,3-disilacyclobutane in the new vaporizer. The original vaporizer became clogged after vaporizing approximately 140 g of unstabilized 1,3-dimethoxy-1,3-dimethyl-1,3-disilacyclobutane, so a new vaporizer was needed to test stabilized 1,3-dimethoxy-1,3-dimethyl-1,3-disilacyclobutane.

[0071] We examine the data for unstabilized 1,3-dimethoxy-1,3-dimethyl-1,3-disilacyclobutane collected with the initial injector (Panels B and D). While the daily standard precursor flow rates from days 1 to 23 are stable within the expected experimental error (Panel B), the decrease in piezoelectric valve voltage required to maintain a stable flow rate (Panel D) indicates that residue accumulated in the piezoelectric valve as the unstabilized 1,3-dimethoxy-1,3-dimethyl-1,3-disilacyclobutane vaporized. This is clearly demonstrated by considering the rapid decrease in piezoelectric valve voltage on a weekly basis (W1, W2, and W3). Data from week 1 of the test (W1) show a rapid linear decrease in piezoelectric valve voltage. In week 2 of the test (W2), N2 was circulated through the vaporizer hundreds of times before passing the unstabilized 1,3-dimethoxy-1,3-dimethyl-1,3-disilacyclobutane through the vaporizer, and the vaporizer was idled at a suitable temperature for 4 days. The initial valve voltage at the start of W2 (day 9) was higher than the valve voltage at the end of W1 (day 4), suggesting that the vaporizer had recovered somewhat. However, the initial valve voltage at the start of W2 was still much lower than that at the start of W1, indicating that residue accumulation remained within the piezoelectric control valve. Data from the second week of the test (W2) also shows a rapid linear decrease in the piezoelectric valve voltage. Data was limited in the third week of the test (W3) because the injector became blocked after two more days of testing. The vaporizer became blocked after approximately 140g of unstabilized 1,3-dimethoxy-1,3-dimethyl-1,3-disilacyclobutane was vaporized. These data clearly demonstrate that vaporizing unstabilized 1,3-dimethoxy-1,3-dimethyl-1,3-disilacyclobutane readily leads to residue accumulation and blockage of the piezoelectric control valve in the Horiba LSVS.

[0072] This should be compared with the behavior of stabilized 1,3-dimethoxy-1,3-dimethyl-1,3-disilacyclobutane shown in panels A and C of Figure 1. The daily standard precursor flow from days 39 to 58 is stable within the expected experimental error (panel A), but only a slight gradual decrease in the piezoelectric valve voltage (panel C) is observed. Furthermore, the data in panels A and C correspond to the vaporization of more than 200 g of stabilized 1,3-dimethoxy-1,3-dimethyl-1,3-disilacyclobutane. These data clearly demonstrate that the rate of residue accumulation in the piezoelectric controlled valve is significantly lower for stabilized 1,3-dimethoxy-1,3-dimethyl-1,3-disilacyclobutane compared to unstabilized 1,3-dimethoxy-1,3-dimethyl-1,3-disilacyclobutane.

[0073] All vaporization and deposition experiments were performed on a 300mm AMAT Producer® SE, which simultaneously deposits films on two wafers. Therefore, the precursor and gas flow rates correspond to the flow rates required to simultaneously deposit films on two wafers. Since each wafer processing station has its own independent RF power supply, the above-mentioned RF output for each wafer is correct. Since both wafer processing stations are maintained at the same pressure, the above-mentioned deposition pressure is correct.

[0074] Thickness was measured using a Woollam model M2000 spectroscopic ellipsometer. Dielectric constant was measured using an Hg probe on a p-type wafer with intermediate resistivity (in the range of 8-12 Ω-cm). Mechanical properties were measured using a KLA iNano Nano Indenter.

[0075] In the following examples, films were deposited using unstabilized 1,3-dimethoxy-1,3-dimethyl-1,3-disilacyclobutane and stabilized 1,3-dimethoxy-1,3-dimethyl-1,3-disilacyclobutane under the same deposition conditions. Example 4: Deposition of dense OSG and film 1 from unstabilized 1,3-dimethoxy-1,3-dimethyl-1,3-disilacyclobutane and stabilized 1,3-dimethoxy-1,3-dimethyl-1,3-disilacyclobutane

[0076] A dense film was deposited using unstabilized 1,3-dimethoxy-1,3-dimethyl-1,3-disilacyclobutane under the following process conditions for 300 mm processing. The unstabilized 1,3-dimethoxy-1,3-dimethyl-1,3-disilacyclobutane precursor was injected into the reaction chamber via direct liquid injection (DLI) at a flow rate of 1100 mg / min using a He carrier gas flow of 1500 standard cubic centimeters / min (sccm), 10 sccm of O2, a showerhead / heating pedestal spacing of 400 milliinches, a pedestal temperature of 400°C, and a chamber pressure of 4.5 Torr, to which a 300 watt 13.56 MHz plasma was applied. A dense film was deposited using stabilized 1,3-dimethoxy-1,3-dimethyl-1,3-disilacyclobutane instead of unstabilized 1,3-dimethoxy-1,3-dimethyl-1,3-disilacyclobutane under the same deposition conditions. The various attributes of these two films (e.g., dielectric constant (k) and hardness) were obtained as described above. These are shown graphically in Figures 2 and 3. Example 5: Deposition of dense OSG and film 2 from unstabilized 1,3-dimethoxy-1,3-dimethyl-1,3-disilacyclobutane and stabilized 1,3-dimethoxy-1,3-dimethyl-1,3-disilacyclobutane

[0077] A dense film was deposited using unstabilized 1,3-dimethoxy-1,3-dimethyl-1,3-disilacyclobutane under the following process conditions for 300 mm processing. The unstabilized 1,3-dimethoxy-1,3-dimethyl-1,3-disilacyclobutane precursor was injected into the reaction chamber via direct liquid injection (DLI) at a flow rate of 1100 mg / min using a He carrier gas flow of 1000 standard cubic centimeters / min (sccm), 100 sccm of O2, a showerhead / heating pedestal spacing of 300 milliinches, a pedestal temperature of 400°C, and a chamber pressure of 8.5 Torr, to which a 300 watt 13.56 MHz plasma was applied. A dense film was deposited using stabilized 1,3-dimethoxy-1,3-dimethyl-1,3-disilacyclobutane instead of unstabilized 1,3-dimethoxy-1,3-dimethyl-1,3-disilacyclobutane under the same deposition conditions. The various attributes of these two films (e.g., dielectric constant (k) and hardness) were obtained as described above. These are shown graphically in Figures 2 and 3.

[0078] Example 6: Deposition of dense OSG and film 3 from unstabilized 1,3-dimethoxy-1,3-dimethyl-1,3-disilacyclobutane and stabilized 1,3-dimethoxy-1,3-dimethyl-1,3-disilacyclobutane

[0079] A dense film was deposited using unstabilized 1,3-dimethoxy-1,3-dimethyl-1,3-disilacyclobutane under the following process conditions for 300 mm processing. The unstabilized 1,3-dimethoxy-1,3-dimethyl-1,3-disilacyclobutane precursor was injected into the reaction chamber via direct liquid injection (DLI) at a flow rate of 1100 mg / min using a He carrier gas flow of 1500 standard cubic centimeters / min (sccm), 20 sccm of O2, a showerhead / heating pedestal spacing of 330 milliinches, a pedestal temperature of 400°C, and a chamber pressure of 7.3 Torr, to which a 400 watt 13.56 MHz plasma was applied. A dense film was deposited using stabilized 1,3-dimethoxy-1,3-dimethyl-1,3-disilacyclobutane instead of unstabilized 1,3-dimethoxy-1,3-dimethyl-1,3-disilacyclobutane under the same deposition conditions. The various attributes of these two films (e.g., dielectric constant (k) and hardness) were obtained as described above. These are shown graphically in Figures 2 and 3.

[0080] Example 7: Deposition of dense OSG and film 4 from unstabilized 1,3-dimethoxy-1,3-dimethyl-1,3-disilacyclobutane and stabilized 1,3-dimethoxy-1,3-dimethyl-1,3-disilacyclobutane

[0081] A dense film was deposited using unstabilized 1,3-dimethoxy-1,3-dimethyl-1,3-disilacyclobutane under the following process conditions for 300 mm processing. The unstabilized 1,3-dimethoxy-1,3-dimethyl-1,3-disilacyclobutane precursor was injected into the reaction chamber via direct liquid injection (DLI) at a flow rate of 1100 mg / min using a He carrier gas flow of 1500 standard cubic centimeters / min (sccm), 13 sccm of O2, a showerhead / heating pedestal spacing of 330 milliinches, a pedestal temperature of 375°C, and a chamber pressure of 7.3 Torr, to which a 400 watt 13.56 MHz plasma was applied. A dense film was deposited using stabilized 1,3-dimethoxy-1,3-dimethyl-1,3-disilacyclobutane instead of unstabilized 1,3-dimethoxy-1,3-dimethyl-1,3-disilacyclobutane under the same deposition conditions. The various attributes of these two films (e.g., dielectric constant (k) and hardness) were obtained as described above. These are shown graphically in Figures 2 and 3.

[0082] As shown in Figures 2 and 3, a comparison of the k and hardness of films 1, 2, 3, and 4 deposited with unstabilized 1,3-dimethoxy-1,3-dimethyl-1,3-disilacyclobutane and stabilized 1,3-dimethoxy-1,3-dimethyl-1,3-disilacyclobutane shows that stabilized 1,3-dimethoxy-1,3-dimethyl-1,3-disilacyclobutane does not increase the k or decrease the mechanical properties of the as-deposited film compared to the same film deposited with unstabilized 1,3-dimethoxy-1,3-dimethyl-1,3-disilacyclobutane. In fact, the data in Figures 2 and 3 show that films deposited with stabilized 1,3-dimethoxy-1,3-dimethyl-1,3-disilacyclobutane have slightly lower k and slightly higher hardness compared to films deposited with unstabilized 1,3-dimethoxy-1,3-dimethyl-1,3-disilacyclobutane.

[0083] Although the principles of the present invention have been described above in relation to preferred embodiments, it should be clearly understood that this description is provided only as an example and does not limit the scope of the present invention.

Claims

1. A composition, (a) 1,3-dialkoxy-1,3-disilacyclobutane by formula I: 【Chemistry 1】 [In the formula, each R １ Independently, C １ ~C １０ It is a linear or branched alkyl group, and each R ２ These are, independently, hydrogen or C １ ~C １０ [Straight-chain or branched-chain alkyl]; and (b) Polymerization inhibitor selected from the group consisting of the following (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 hydrogen and C １ - C １０ linear or branched alkyl; R ５ is selected from C １ - C １０ linear or branched alkyl; n is 0, 1, 2, or 3; m = 0, 1, 2, or 3]; (iii) Alkoxy-disiloxane having the following formula 【Chemistry 2】 [In the formula, R ６ C is a straight or branched chain. １ ~C ６ Alkyl, preferably methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, or tert-butyl, and cyclic C ５ ~C ６ Selected from alkyl groups; R ７ These are hydrogen and straight-chain or branched-chain carbon atoms. １ ~C ５ Selected from alkyl groups; R ８～１０ Each of these is independently a linear or branched chain C １ ~C ５ Selected from alkyl, preferably methyl; R １１ This refers to hydrogen, straight-chain or branched-chain carbon. １ ~C ５ Alkyl, or OR １２ [In the formula, R １２ C is a straight or branched chain. １ ~C ５ Selected from alkyl groups; (iv) Alkoxy-carbosilane having the following structure 【Transformation 3】 [In the formula, R １３ C is a straight or branched chain. １ ~C ６ Alkyl, preferably methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, or tert-butyl, and cyclic C ５ ~C ６ Selected from alkyl groups; R １４ These are hydrogen and straight-chain or branched-chain carbon atoms. １ ~C ５ Selected from alkyl groups; R １５～１７ These are independently linear or branched chains C １ ~C ５ Selected from alkyl, preferably methyl; R １８ This refers to hydrogen, straight-chain or branched-chain carbon. １ ~C ５ Alkyl, or OR １９ [In the formula, R １９ C is a straight or branched chain. １ ~C ５ Selected from alkyl; and (v) Organoaminosilane R ２０ ｎ R ２１ ｍ Si(NR ２２ R ２３ ) ４－ｎ－ｍ [In the formula, R ２０ and R ２１ These are, independently, hydrogen and C １ ~C １０ Selected from linear or branched alkyl groups; R ２２ and R ２３ is hydrogen, C １ ~C １０ Selected from linear or branched alkyl groups; n is 0, 1, 2, or 3; m = 0, 1, 2, or 3. A composition containing the following:

2. Regarding the 1,3-dialkoxy-1,3-disilacyclobutane according to formula I above, each R １ R is selected from methyl and ethyl, ２ The composition according to claim 1, wherein is methyl.

3. Regarding the 1,3-dialkoxy-1,3-disilacyclobutane according to formula I above, each R １ The composition according to claim 1, wherein is ethyl.

4. The (b) polymerization inhibitor is (ii) R ３ ｎ R ４ ｍ Si ( OR ５ ) ４－ｎ－ｍ [In the formula, R ３ , R ４ , and R ５ The substituents are as defined; and (iv) Alkoxy-carbosilane having the following structure 【Chemistry 4】 [In the formula, R １３ , R １４ , R １５ , R １６ , R １７ and R １８ The substituents are as defined. A composition according to claim 1, selected from the following.

5. The polymerization inhibitor in (b) is (i), and is 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, 3,4,5-trihydroxybenzoate propyl ester, 2-(1,1-dimethylethyl)-1,4-benzenediol, diphenylpicrylhydrazyl, 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)propionate, tetrakis(methylene(3,5-di-te The composition according to claim 1, selected from the group consisting of rt-butyl)-4-hydroxyhydrocinnamate)methane, phenothiazine, alkylamide noisourea, thiodiethylenebis(3,5-di-tert-butyl-4-hydroxyhydrocinnamate, 1,2-bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamoyl)hydrazine, tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane, cyclic neopentanetetraylbis(octadecyl phosphite), 4,4'-thiobis(6-tert-butyl-m-cresol), 2,2'-methylenebis(6-tert-butyl-p-cresol), oxalylbis(benzylidene hydrazide), and naturally occurring antioxidants, such as raw seed oil, wheat germ oil, tocopherol, and combinations thereof.

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

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

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

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

10. The composition according to claim 1, wherein (a) 1,3-dialkoxy-1,3-disilacyclobutane and (b) polymerization inhibitor have boiling points that are 100°C or less apart.

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

12. A chemical vapor deposition method for depositing an organosilicate film on at least a portion of a substrate, The process of providing a substrate in a vacuum chamber; Inside the vacuum chamber, (a) 1,3-dialkoxy-1,3-disilacyclobutane having the following formula I: 【Transformation 5】 [wherein each R １ is independently C １ to C １０ linear or branched alkyl, and each R ２ is independently hydrogen or C １ to C １０ linear or branched alkyl]; and (b) Polymerization inhibitor selected from the group consisting of the following (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 hydrogen and C １ - C １０ linear or branched alkyl; R ５ is selected from C １ - C １０ linear or branched alkyl; n is 0, 1, 2, or 3; and m = 0, 1, 2, 3]; (iii) Alkoxy-disiloxane having the following formula 【Transformation 6】 [In the formula, R ６ C is a straight or branched chain. １ ~C ６ Alkyl, preferably methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, or tert-butyl, and cyclic C ５ ~C ６ Selected from alkyl groups; R ７ These are hydrogen and straight-chain or branched-chain carbon atoms. １ ~C ５ Selected from alkyl groups; R ８～１０ Each of these is independently a linear or branched chain C １ ~C ５ Selected from alkyl, preferably methyl; R １１ This refers to hydrogen, straight-chain or branched-chain carbon. １ ~C ５ Alkyl, or OR １２ [In the formula, R １２ C is a straight or branched chain. １ ~C ５ Selected from alkyl groups; (iv) Alkoxy-carbosilane having the following structure 【Transformation 7】 [In the formula, R １３ C is a straight or branched chain. １ ~C ６ Alkyl, preferably methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, or tert-butyl, and cyclic C ５ ~C ６ Selected from alkyl groups; R １４ These are hydrogen and straight-chain or branched-chain carbon atoms. １ ~C ５ Selected from alkyl groups; R １５～１７ These are independently linear or branched chains C １ ~C ５ Selected from alkyl, preferably methyl; R １８ This refers to hydrogen, straight-chain or branched-chain carbon. １ ~C ５ Alkyl, or OR １９ [In the formula, R １９ C is a straight or branched chain. １ ~C ５ Selected from alkyl; and (v) Organoaminosilane R ２０ ｎ R ２１ ｍ Si(NR ２２ R ２３ ) ４－ｎ－ｍ [In the formula, R ２０ and R ２１ These are, independently, hydrogen and C １ ~C １０ Selected from linear or branched alkyl groups; R ２２ and R ２３ is hydrogen, C １ ~C １０ Selected from linear or branched alkyl groups; n is 0, 1, 2, or 3; m = 0, 1, 2, or 3. A step of introducing a composition containing; A step of applying energy to the gaseous structure-forming composition in the vacuum chamber to induce at least the reaction of 1,3-dialkoxy-1,3-disilacyclobutane and deposit a film on at least a portion of the substrate, Methods that include...

13. The method according to claim 12, wherein, for 1,3-dialkoxy-1,3-disilacyclobutane according to formula I, each R1 is selected from methyl and ethyl, and R2 is methyl.

14. The polymerization inhibitor in (b) is (i), and is 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, 3,4,5-trihydroxybenzoate propyl ester, 2-(1,1-dimethylethyl)-1,4-benzenediol, diphenylpicrylhydrazyl, 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)propionate, tetrakis(methylene(3,5-di-te The method according to claim 12, selected from the group consisting of rt-butyl)-4-hydroxyhydrocinnamate)methane, phenothiazine, alkylamide noisourea, thiodiethylenebis(3,5-di-tert-butyl-4-hydroxyhydrocinnamate, 1,2-bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamoyl)hydrazine, tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane, cyclic neopentanetetraylbis(octadecyl phosphite), 4,4'-thiobis(6-tert-butyl-m-cresol), 2,2'-methylenebis(6-tert-butyl-p-cresol), oxalylbis(benzylidene hydrazide), and naturally occurring antioxidants, such as raw seed oil, wheat germ oil, tocopherol, and combinations thereof.

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

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

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

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

19. The method according to claim 12, wherein (a) 1,3-dialkoxy-1,3-disilacyclobutane and (b) polymerization inhibitor have boiling points that are 100°C or less apart.

20. The method according to 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-disilacyclobutane according to formula I.

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