Monoalkoxysilanes and high-density organic silica films made therefrom

Abstract

1. A method for producing a dense organosilicon film having improved mechanical properties, comprising the steps of: providing a substrate in a reaction chamber; introducing a gaseous composition comprising a novel monoalkoxysilane into the reaction chamber; and applying energy to the gaseous composition comprising the novel monoalkoxysilane in the reaction chamber to induce a reaction of the gaseous composition comprising the novel monoalkoxysilane to deposit an organosilicon film on the substrate, wherein the organosilicon film has a dielectric constant of about 2.80 to about 3.30, an elastic modulus of about 9 to about 32 GPa, and about 10 to about 30 at. % carbon as measured by XPS.

Description

[Technical Field]

[0001] Cross-reference of related applications This application claims the benefit of U.S. Provisional Patent Application No. 62 / 899824, filed on 13 September 2019. The disclosure of that application is incorporated herein by reference in its entirety.

[0002] This specification describes compositions and methods for forming high-density organic silica dielectric films using monoalkoxysilanes as precursors. More specifically, this specification describes compositions and chemical vapor deposition (CVD) methods for forming high-density films having a dielectric constant k ≥ 2.7, wherein the films have a higher modulus of elasticity and superior resistance to plasma-induced damage compared to films made from conventional precursors. [Background technology]

[0003] The electronics industry utilizes dielectric materials as insulating layers between circuits and components in integrated circuits (ICs) and related electronic devices. Wiring dimensions are reduced to increase the speed and memory storage capacity of microelectronic devices (e.g., computer chips). As wiring dimensions decrease, the insulation requirements for interlayer dielectrics (ILDs) become even more stringent. Reducing the spacing requires a lower dielectric constant to minimize the RC time constant, where R is the resistance of the conductive wiring and C is the capacitance of the insulating dielectric interlayer. Capacitance (C) is inversely proportional to the spacing and proportional to the dielectric constant (k) of the interlayer dielectric (ILD). Conventional silica (SiO2) CVD dielectric films manufactured from SiH4 or TEOS (Si(OCH2CH3)4, tetraethyl orthosilicate) and O2 have a dielectric constant k greater than 4.0. Various methods have been attempted in this industry to produce silica-based CVD films with lower dielectric constants, the most successful of which is doping with an insulating silicon oxide film with organic groups, providing a dielectric constant of approximately 2.7 to 3.5. This organosilica glass is typically made from an organosilicon precursor, such as methylsilane or siloxane, and an oxidizing agent, such as O2 or N2O, to produce a high-density film (approximately 1.5 g / cm³). 3 It is deposited as (density). In this specification, organic silica glass is referred to as OSG.

[0004] Patents, application publications, and publications in the field of porous ILDs by CVD methods include European Patent Application Publication No. 1119035 and U.S. Patent No. 6171945 (which describes a process for depositing OSG films from organosilicon precursors having unstable groups in the presence of N2O and optionally peroxides, and providing porous OSG with subsequent removal of unstable groups by thermal annealing); and U.S. Patents No. 6054206 and 6238751 (which describes removing essentially all organic groups from deposited OSG by oxidative annealing). This includes (which teaches removal to obtain porous inorganic SiO2); European Patent Application Publication No. 1037275 (which describes the deposition of a hydrogenated silicon carbide film, which is converted to porous inorganic SiO2 by subsequent treatment with an oxidizing plasma); and U.S. Patent No. 6,312,793, International Publication No. 00 / 24050 (which teaches the co-deposition of a film from an organosilicon precursor and an organic compound, and subsequent thermal annealing to provide a multiphase OSG / organic film in which some of the polymerized organic components are retained). In the latter reference, the final composition of the film is shown to be residual pologen and a large hydrocarbon film content of approximately 80-90 at%. Furthermore, the final film retains a network structure similar to SiO2, with some substitution of oxygen atoms for the organic groups.

[0005] U.S. Patent Application Publication No. 2011 / 10113184 discloses a type of material that can be used to deposit insulating films having dielectric constants of approximately k=2.4 to k=2.8 by a PECVD process. The material comprises a Si compound having two hydrocarbon groups that can bond to each other to form a cyclic structure with a Si atom, or a Si compound having one or more branched hydrocarbon groups. In the branched hydrocarbon group, the α-C carbon atom bonded to the Si atom constitutes a methylene group, and the β-C carbon atom bonded to the methylene group, or the γ-C carbon atom bonded to the β-C, is the branch point. Specifically, two of the alkyl groups bonded to Si include CH2CH(CH3)CH3, CH2CH(CH3)CH2CH3, CH2CH2CH(CH3)CH3, CH2C(CH3)2CH3, and CH2CH2CH(CH3)2CH3, and the third group bonded to silicon includes OCH3 and OC2H5. This method has various drawbacks. Firstly, the precursor structure requires a large alkyl group containing a branched alkyl group. Such molecules are costly to synthesize and, due to their inherently high molecular weight, typically have high boiling points and low volatility. High boiling points and low volatility make it difficult to efficiently transport such molecules in the gas phase, as required for the PECVD process. Furthermore, the high density of SiCH2Si groups in the low-k films disclosed in this method are formed after the deposited film is exposed to ultraviolet light irradiation (i.e., after the film is UV-cured). However, the formation of SiCH2Si groups after exposure to ultraviolet irradiation is well documented in the literature, for example, in Grill, A., “PECVD low and Ultralow Dielectric Constant Materials: From Invention and Research to Products,” J.Vac.Sci.Technol.B, 2016, 34, 020801-1 - 020801-4, and therefore cannot be a result solely of the deposition process. Finally, the reported dielectric constant values ​​in this method are low, below 2.8.Therefore, this method is closer to a coupled pologen method for generating porous low-k films than to a method for depositing high-density low-k films without post-deposition treatment (i.e., UV curing).

[0006] Plasma or process-induced damage (PID) in low-k films is caused by the removal of carbon from the film during plasma exposure, particularly during etching and photoresist stripping processes. This changes the plasma-damaged region from hydrophobic to hydrophilic. Exposure of hydrophilic SiO2, such as the damaged layer, to diluted HF-based wet post-chemical plasma treatment (with or without additives such as surfactants) causes an increase in the effective dielectric constant of the low-k film and rapid decomposition of the plasma-damaged layer. This leads to erosion of the surface in patterned low-k wafers. Process-induced damage and the resulting surface erosion in low-k films are significant problems that equipment manufacturers must address when incorporating low-k materials in ULSI interconnects. [Overview of the project] [Problems that the invention aims to solve]

[0007] Films with improved mechanical properties (higher modulus of elasticity, higher hardness) reduce wiring edge roughness in patterned features, reduce pattern collapse, result in greater internal mechanical stress at interconnections, and reduce defects caused by electromigration. Therefore, there is a demand for high-density, low-k films with excellent resistance to PID and the highest possible mechanical properties, preferably without requiring post-deposition treatment, such as UV curing, at a given dielectric constant. UV curing reduces processing volume, increases cost, and increases complexity, as well as reducing carbon content and introducing porosity into the film. Reduced carbon content and increased porosity lead to greater plasma-induced damage. The precursor in this invention is designed to deposit a high-density, low-k film with a dielectric constant of about 2.8 to 3.3, mechanical strength exceeding that of prior art precursors, and good resistance to plasma-induced damage, without requiring post-deposition treatment. [Means for solving the problem]

[0008] The methods and compositions described herein satisfy one or more of the requirements described above. Using monoalkoxysilane precursors, high-density, low-k films having a k value of about 2.8 to about 3.3 can be deposited without requiring post-deposition treatment, and such films exhibit unexpectedly high modulus / hardness and unexpectedly high resistance to plasma-induced damage.

[0009] In one embodiment, the present disclosure provides a method for producing a high-density organic silica film having improved mechanical properties, A step of providing the substrate into the reaction chamber; Equation (1) or (2): (1)R 1 R 2 MeSiOR 3 (In the formula, R 1 and R 2is independently selected from linear or branched C1-C5 alkyl, preferably methyl, ethyl, propyl, iso-propyl, butyl, sec-butyl or tert-butyl, R 3 is independently selected from linear or branched C1-C5 alkyl, preferably methyl, ethyl, propyl, iso-propyl, butyl, sec-butyl, iso-butyl or tert-butyl, more preferably iso-propyl, sec-butyl, iso-butyl and tert-butyl) (2)R 4 (Me)2SiOR 5 (wherein R 4 is selected from linear or branched C1-C5 alkyl, preferably methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl or tert-butyl, R 5 is selected from linear or branched C1-C5 alkyl, preferably methyl, ethyl, propyl (i.e., n-Pr or Pr-n), iso-propyl (i.e., i-Pr, Pr-i, iso-Pr, Pr-iso or Pr i [[]]) butyl (i.e., n-Bu, Bu-n or Bu n [[]]) sec-butyl (i.e., sec-Bu, Bu-sec, s-Bu, Bu-s or Bu s [[]]) iso-butyl (i.e., iso-Bu, Bu-iso, i-Bu, Bu-i or Bu i [[]]) or tert-butyl (tert-Bu, Bu-tert, t-Bu, Bu-t or Bu t [[]]), more preferably selected from iso-propyl, sec-butyl, iso-butyl and tert-butyl) The steps include introducing a gaseous composition containing a monoalkoxysilane having the structure given in the above formula into a reaction chamber (for the above formula, the alkyl group combination is selected such that the boiling point of the molecule is less than 200°C. In addition, for optimal performance, the R group is selected such that it forms a secondary or tertiary radical upon homolytic bond dissociation (e.g., SiO-R → SiO· + R·, where R is a secondary or tertiary radical, e.g., an isopropyl radical, a sec-butyl radical, or a tert-butyl radical)); and A process of applying energy to a gaseous composition containing monoalkoxysilane in a reaction chamber to induce a reaction in the gaseous composition containing monoalkoxysilane and deposit an organosilicon film on a substrate. The present invention provides a method comprising an organic silica film having a dielectric constant of about 2.8 to about 3.3 and an elastic modulus of about 9 to about 32 GPa.

[0010] In another embodiment, the present disclosure provides a method for producing a high-density organic silica film having improved mechanical properties, A step of providing the substrate into the reaction chamber; A step of introducing a gaseous composition containing a monoalkoxysilane into a reaction chamber; and A process of applying energy to a gaseous composition containing monoalkoxysilane in a reaction chamber to induce a reaction in the gaseous composition containing monoalkoxysilane and deposit an organic silica film on a substrate. The present invention provides a method comprising an organic silica film having a dielectric constant of approximately 2.8 to approximately 3.3, an elastic modulus of approximately 9 to approximately 32 GPa, and having approximately 10 at% to approximately 30 at% carbon as measured by XPS. [Brief explanation of the drawing]

[0011] [Figure 1] This graph shows the relationship between mechanical strength and the percentage of Si-Me groups in a thin film. [Figure 2] This chart shows GC-MS data for isopropyldimethylisopropoxysilane synthesized according to the method described in Example 1. [Figure 3] This graph shows the infrared spectrum of a high-density, low-k film formed from three precursors: di(ethyl)methyl-isopropoxysilane (DEMIPS), diethoxymethylsilane (DEMS®), and 1-methyl-1-isopropoxy-1-silacyclopentane (MPSCP). [Figure 4] This is a plot of dielectric constant against XPS carbon content for exemplary high-density low-k films deposited using di(ethyl)methyl-isopropoxysilane (DEMIPS) as a low-k precursor, compared to high-density low-k films deposited using diethoxymethylsilane (DEMS®) and 1-methyl-1-isopropoxy-1-silacyclopentane (MPSCP) as low-k precursors. [Modes for carrying out the invention]

[0012] A chemical vapor deposition method for producing a high-density organic silica film having improved mechanical properties, A step of providing the substrate into the reaction chamber; A step of introducing a gaseous composition containing a monoalkoxysilane, a gaseous oxidizing agent such as O2 or N2O, and an inert gas such as He into a reaction chamber; a step of applying energy to the gaseous composition containing the monoalkoxysilane in the reaction chamber to induce a reaction of the gaseous composition containing the monoalkoxysilane and deposit an organic silica film on a substrate. A method is described herein that includes an organic silica film having a dielectric constant of about 2.8 to about 3.3, an elastic modulus of about 9 to about 32 GPa, and about 10 at% to about 30 at% of carbon as measured by XPS, preferably a dielectric constant of about 2.9 to about 3.2, an elastic modulus of about 10 to about 29 GPa, and about 10 at% to about 30 at% of carbon as measured by XPS.

[0013] Furthermore, a method for producing a high-density organic silica film having improved mechanical properties, A step of providing the substrate into the reaction chamber; A step of introducing a gaseous composition containing a monoalkoxysilane, a gaseous oxidizing agent such as O2 or N2O, and an inert gas such as He into a reaction chamber; A process of depositing an organic silica film onto a substrate by applying energy to a gaseous composition containing a monoalkoxysilane. A method is also described herein in which the organic silica film comprises a dielectric constant of about 2.70 to about 3.3 and an elastic modulus of about 9 to about 32 GPa.

[0014] Compared to prior art structural precursors such as diethoxymethylsilane (DEMS®) and 1-isopropoxy-1-methyl-1-silacyclopentane (MESCP), monoalkoxysilanes offer unique properties that enable high-density organic silica films to achieve relatively low dielectric constants and exhibit remarkably superior mechanical properties. Although not constrained by theory, the monoalkoxysilanes of the present invention are R 1 and R 2 However, R is selected from the group consisting of ethyl, propyl, isopropyl, butyl, sec-butyl, or tert-butyl. 3However, when selected from the group consisting of methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, isobutyl, or tertbutyl, which provides more stable radicals compared to methyl disclosed in the prior art, such as Me3SiOMe or Me3SiOEt (Bayer, C. et al. "Overall Kinetics of SiOx Remote-PECVD using Different Organosilicon Monomers", 116-119, Surf.Coat.Technol., 874, (1999)), it is thought that stable radicals during plasma-enhanced chemical vapor deposition, such as CH3CH2·, (CH3)2CH·, and (CH3)3C· can be provided. In the plasma, higher-density, stable radicals such as CH3CH2·, (CH3)2CH·, and (CH3)3C· increase the possibility of extracting hydrogen atoms from terminal silicon methyl groups (Si-CH3) in the precursor (formation of SiCH2), promoting the formation of disilyl methylene groups (i.e., Si-CH2-Si moieties) in the as-deposited film. Perhaps, R 1 Me2SiOR 3 In molecules of this type, the higher density of terminal silicon methyl groups (two per silicon atom) in the precursor further facilitates the formation of high-density disilylmethylene groups (Si-CH2-Si) in the deposited film.

[0015] In organic chemistry, it is well known that generating a primary carbon radical (e.g., the ethyl radical CH3CH2·) requires more energy than generating a secondary carbon radical (e.g., the isopropyl radical (CH3)2CH·). This is due to the higher stability of the isopropyl radical compared to the ethyl radical. The same principle applies to the homolytic dissociation of oxygen-carbon bonds in silicon alkoxy groups; dissociating the oxygen-carbon bond in isopropoxysilane requires less energy than in ethoxysilane. Similarly, dissociating the silicon-carbon bond in isopropylsilane requires less energy than in ethylsilane. Bonds that require less energy to break are presumably more easily dissociated in a plasma. Therefore, Si-OPr i Si-OBu s Or Si-OBu t Monoalkoxysilanes containing the Si-OEt group can yield a higher density of SiO-type radicals in plasma compared to those containing the Si-OEt group. Similarly, Si-Et and Si-Pr i , Si-Bu s Or Si-Bu t Monoalkoxysilanes containing the Si-OEt group can yield a higher density of Si-type radicals in plasma compared to those containing only the Si-Me group. This is likely the case for monoalkoxysilanes containing Si-OPr. i Si-OBu s Or Si-OBu t The monoalkoxysilane containing the group contributes to the differentiated properties of the deposited material.

[0016] Some of the advantages over the prior art achieved by using monoalkoxysilanes as silicon precursors are, but are not limited to, the following: Ease of synthesis and low cost High modulus of elasticity / High hardness Wide range of XPS carbon High disilylmethylene density Includes.

[0017] Table 1 lists selected monoalkoxysilanes having formulas 1 and 2. While many compounds are disclosed, the most preferred molecules are those with an alkyl group (R) selected such that the boiling point of the molecule is less than 200°C (preferably less than 150°C). 1 , R 2 , R 3 , R 4 and R 5 It is a molecule having the combination of ). In addition, for optimal performance, R 1 , R 2 , R 3 , R 4 and R 5 The group, upon homolytic bond dissociation, has some or all of its members forming secondary or tertiary radicals (e.g., Si-R 2 →Si·+R 2 • or SiO-R 3 →SiO·+R 3 • Here, R 2 and R 3 The radicals can be selected to form a secondary or tertiary radical (for example, an isopropyl radical, a sec-butyl radical, a tert-butyl radical, or a cyclohexyl radical). The most preferred example is di-isopropylmethyl(iso-propoxy)silane, which has a predicted boiling point of 168°C at 760 Torr.

[0018] Table 1 List of exemplary monoalkoxysilanes having formulas 1 and 2 [Table 1-1] [Table 1-2] [Table 1-3] [Table 1-4] [Table 1-5]

[0019] Prior art silicon-containing structure-forming precursors, such as DEMS®, polymerize after excitation in a reaction chamber to form structures with -O-bonds in the polymer main chain (e.g., -Si-O-Si- or Si-OC-). Monoalkoxysilane compounds having formula (1) or formula (2), such as the DEMIPS molecule, polymerize to form structures in which a high proportion of -O-bridges in the main chain are replaced by -CH2-methylene or -CH2CH2-ethylene bridges. In films deposited using DEMS® as a structure-forming precursor where carbon mainly exists in the form of Si-Me groups, there is a relationship between %Si-Me (more directly related to %C) and mechanical strength; see, for example, the model work shown in Figure 1. Here, the substitution of bridged Si-O-Si groups with two terminal Si-Me groups reduces mechanical properties because the network structure collapses. In the case of monoalkoxysilane compounds of formula (1) or formula (2), it is thought that the precursor structure is destroyed during film deposition to form SiCH2Si or SiCH2CH2Si crosslinking groups. In this way, carbon in the form of crosslinking groups can be incorporated so as not to cause the network structure to collapse due to an increase in carbon content in the film, from the viewpoint of mechanical strength. Although not constrained by theory, this property leads to the addition of carbon to the film to make it more resilient to carbon depletion in high-density films caused by processes such as film etching, plasma ashing of photoresists, and NH3 plasma treatment of copper surfaces. Carbon depletion in high-density low-k films can lead to an increase in the effective dielectric constant of the film, problems associated with film etching, bending of features during wet cleaning processes, and / or integration problems when depositing copper diffusion barriers. Prior art structure-forming agents, such as MESCP, can deposit low-k films having very high density crosslinked SiCH2Si and / or SiCH2CH2Si groups, but these films also have very high Si-Me density and total carbon content, which ultimately limits the highest modulus achievable by this type of prior art low-k precursor.

[0020] Preferably, compositions comprising monoalkoxysilanes having formulas 1 and 2 according to the present invention, and monoalkoxysilane compounds having formulas 1 and 2 according to the present invention, are substantially free of halide ions. As used herein, the term “substantially free” means, with respect to halide ions (or halides), such as chlorides (i.e., chloride-containing species, such as HCl or silicon compounds having at least one Si-Cl bond), fluorides, bromides, and iodides, less than 5 ppm (by weight) as measured by ion chromatography (IC), preferably less than 3 ppm as measured by IC, more preferably less than 1 ppm as measured by IC, and most preferably 0 ppm as measured by IC. Chlorides are known to act as decomposition catalysts for silicon precursor compounds. Significant levels of chloride in the final product may decompose the silicon precursor compounds. Slow decomposition of silicon precursor compounds can directly affect the film deposition process, making it difficult for semiconductor manufacturers to meet film specifications. In addition, shelf life or stability is negatively affected by the faster decomposition rate of the silicon precursor compound, thereby making it difficult to guarantee a shelf life of 1-2 years. Therefore, the accelerated decomposition of the silicon precursor compound raises safety and performance concerns regarding the formation of these flammable and / or spontaneously combustible gaseous byproducts. Preferably, monoalkoxysilanes having formulas 1 and 2 contain metal ions, such as Li + kaNa + , K + Mg 2+ Ca 2+ , Al 3+ Fe 2+ Fe 2+ Fe 3+ Ni 2+ , Cr 3+It is substantially free of Li. When used herein, the term "substantially free" means less than 5 ppm (by weight), preferably less than 3 ppm, more preferably less than 1 ppm, and most preferably less than 0.1 ppm, when measured by ICP-MS, with respect to Li, Na, K, Mg, Ca, Al, Fe, Ni, and Cr. In some embodiments, the silicon precursor compound having formula A is free of metal ions, such as Li + kaNa + , K + Mg 2+ Ca 2+ , Al 3+ Fe 2+ Fe 2+ Fe 3+ Ni 2+ , Cr 3+ It does not contain. When used herein, the term “free from metal impurities” means less than 1 ppm, preferably less than 0.1 ppm (by weight) as measured by ICP-MS, and most preferably less than 0.05 ppm (by weight) as measured by ICP-MS or other analytical methods for measuring metals, with respect to Li, Na, K, Mg, Ca, Al, Fe, Ni, and Cr. In addition, preferably, when monoalkoxysilanes having formulas 1 and 2 are used as precursors for depositing silicon-containing films, they have a purity of 98 wt% or higher, preferably 99 wt% or higher, as measured by GC.

[0021] Low-k dielectric films are organic silica glass ("OSG") films or materials. Organic silicates are used in the electronics industry, for example, as low-k materials. Material properties depend on the chemical composition and structure of the film. Since the type of organosilicon precursor has a strong effect on the structure and composition of the film, it is beneficial to use a precursor that provides the required film properties to ensure that imparting the amount of porosity required to achieve the desired dielectric constant does not produce a mechanically unsound film. The methods and compositions described herein provide means for producing low-k dielectric films having a desired balance of electrical and mechanical properties, as well as other beneficial film properties such as a high carbon content, thereby providing improved integrated plasma resistance.

[0022] In certain embodiments of the methods and compositions described herein, a layer of silicon-containing dielectric material is deposited on at least a portion of a substrate via a chemical vapor deposition (CVD) process using a reaction chamber. Thus, the method includes the step of providing the substrate into the reaction chamber. Suitable substrates include, but are not limited to, semiconductor materials such as gallium arsenide ("GaAs"), silicon, and silicon-containing compositions such as crystalline silicon, polysilicon, amorphous silicon, epitaxial silicon, silicon dioxide ("SiO2"), silicon glass, silicon nitride, fused silica, glass, quartz, borosilicate glass, and combinations thereof. Other suitable materials include chromium, molybdenum, and other metals commonly used in semiconductor, integrated circuit, flat panel display, and flexible display applications. The substrate may have further layers, such as silicon, SiO2, organic silicate glass (OSG), fluorinated silicate glass (FSG), boron carbonitride, silicon carbide, hydrogenated silicon carbide, silicon nitride, hydrogenated silicon nitride, silicon carbonitride, hydrogenated silicon carbonitride, boron nitride, organic-inorganic composite materials, photoresists, organic polymers, porous organic and inorganic materials and composites, and metal oxides such as aluminum oxide and germanium oxide. Furthermore, the further layers may be germanosilicate, aluminosilicate, copper and aluminum, and diffusion barrier materials, such as, but not limited to, TiN, Ti(C)N, TaN, Ta(C)N, Ta, W, or WN.

[0023] Typically, the reaction chamber is, for example, a thermal CVD or plasma-enhanced CVD reactor, or a batch furnace type reactor in various ways. In one embodiment, a liquid transport system can be utilized. In a liquid transport formulation, the precursor described herein can be transported in undiluted liquid form, or alternatively, in a solvent formulation or composition containing the precursor described herein. Thus, in a particular embodiment, the precursor formulation may contain one or more solvent components having suitable features that may be desired and advantageous for forming a film on a substrate in a given end use.

[0024] The method disclosed herein includes the step of introducing a gaseous composition containing a monoalkoxysilane into a reaction chamber. In some embodiments, the composition may contain further reactants, such as oxygen-containing species, such as O2, O3, and N2O, gaseous or liquid organic substances, CO2, or CO. In one particular embodiment, the reaction mixture introduced into the reaction chamber contains at least one oxidizing agent selected from the group consisting of O2, N2O, NO, NO2, CO2, water, H2O2, ozone, and combinations thereof. In an alternative embodiment, the reaction mixture does not contain an oxidizing agent.

[0025] The compositions for depositing dielectric films described herein contain about 40 to about 100 wt% monoalkoxysilane.

[0026] In several embodiments, a gaseous composition containing a monoalkoxysilane can be used together with a curing additive to further increase the elastic modulus of the as-deposited film.

[0027] In several embodiments, the gaseous composition containing monoalkoxysilane is substantially free of halides, such as chlorides, or does not contain any halides.

[0028] In addition to monoalkoxysilanes, further materials can be introduced into the reaction chamber before, during, and / or after the deposition reaction. Such materials include, for example, inert gases (e.g., He, Ar, N2, Kr, Xe, etc., which can be used as carrier gases for less volatile precursors and / or to accelerate the curing of the deposited material to provide a more stable final film).

[0029] Any reagent used, including monoalkoxysilanes, can be transported into the reactor separately from another source or as a mixture. The reagents can be transported to the reactor system by any of many means, preferably using pressurized stainless steel containers equipped with suitable valves, which allow for the transport of liquids into the process reactor. Preferably, precursors are transported into the process vacuum chamber as gases, i.e., liquids must be vaporized before being transported into the process chamber.

[0030] The methods disclosed herein include the step of applying energy to a gaseous composition containing monoalkoxysilane in a reaction chamber to induce a reaction of the gaseous composition containing monoalkoxysilane and deposit an organic silica film on a substrate, wherein the organic silica film has a dielectric constant of about 2.8 to about 3.3 in some embodiments, 2.90 to 3.2 in other embodiments, and 3.0 to 3.2 in more preferred embodiments, an elastic modulus of about 9 to about 32 GPa, preferably 10 to 29 GPa, and about 10 to about 30 at% carbon as measured by XPS. Energy is applied to a gaseous reagent to induce a reaction of monoalkoxysilane and, if present, other reactants to form a film on the substrate. Such energy can be provided, for example, by plasma, pulsed plasma, helicon plasma, high-density plasma, inductively coupled plasma, remote plasma, hot filament, and thermal (i.e., non-filament) methods. The plasma properties on the substrate surface can be modified using a secondary RF frequency source. Preferably, the film is formed by plasma-enhanced chemical vapor deposition ("PECVD").

[0031] Preferably, the flow rate for each gaseous reagent is 10 to 5000 sccm, more preferably 30 to 3000 sccm, per single 300 mm wafer. The actual flow rate required may depend on the wafer size and chamber configuration and is by no means limited to 300 mm wafers or single wafer chambers.

[0032] In certain embodiments, the film is deposited at a deposition rate of approximately 5 to approximately 700 nanometers (nm) per minute. In other embodiments, the film is deposited at a deposition rate of approximately 30 to 200 nanometers (nm) per minute.

[0033] Typically, during deposition, the pressure in the reaction chamber is about 0.01 to about 600 torr or about 1 to 15 torr.

[0034] Preferably, the film is deposited to a thickness of 0.001 to 500 microns, but the thickness can be varied as required. Blanket films deposited on unpatterned surfaces exhibit excellent uniformity across the substrate with thickness variations of less than 3% / 1 standard deviation, with reasonable edge exclusion (e.g., the outermost 5 mm edge of the substrate is not included in the statistical calculation of uniformity).

[0035] In addition to the OSG products of the present invention, the present invention also includes processes for manufacturing the products, methods for using the products, and compounds and compositions useful for preparing the products. For example, a process for manufacturing integrated circuits on semiconductor devices is disclosed in U.S. Patent No. 6,583,049, which is incorporated herein by reference.

[0036] High-density organic silica films produced by the disclosed method exhibit good resistance to plasma-induced damage, particularly during etching and photoresist stripping processes.

[0037] High-density organic silica films produced by the disclosed method exhibit superior mechanical properties for a given dielectric constant compared to high-density organic silica films made from precursors that have the same dielectric constant but are not monoalkoxysilanes. Typically, the resulting (as-deposited) organic silica film has a dielectric constant of about 2.8 to about 3.3 in some embodiments, about 2.9 to about 3.2 in other embodiments, and about 3.0 to about 3.2 in yet another embodiment, an elastic modulus of about 9 to about 32 GPa, and about 10 to about 30 at% carbon as measured by XPS. In another embodiment, the resulting organic silica film has a dielectric constant of about 2.9 to about 3.2 in some embodiments, about 3.0 to about 3.20 in another embodiment, and an elastic modulus of about 9 to about 32 GPa. In yet another embodiment, the resulting organic silica film has an elastic modulus of about 10 to about 29 in some embodiments, about 11 to about 29 in another embodiment, and about 10 to about 30 at% carbon as measured by XPS.

[0038] The resulting high-density organic silica film may undergo a post-treatment process after deposition. 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 further improve the material properties.

[0039] The conditions under which post-processing is performed can be varied considerably. For example, post-processing may be carried out under high pressure or in a vacuum atmosphere.

[0040] UV annealing is a preferred method under the following conditions:

[0041] The environment may be inert (e.g., nitrogen, CO2, noble gases (He, Ar, Ne, Kr, Xe), etc.), oxidizing (e.g., oxygen, air, dilute oxygen environment, enriched oxygen environment, ozone, nitrous oxide, etc.), or reducing (dilute or concentrated hydrogen, hydrocarbons (saturated, unsaturated, linear or branched, aromatic), etc.). Preferably, the pressure is about 1 Torr to about 1000 Torr. However, a vacuum atmosphere is preferred for thermal annealing and any other post-treatment means. Preferably, the temperature is 200 to 500°C, with a temperature gradient of 0.1 to 100°C / min. Preferably, the total UV annealing time is 0.01 minutes to 12 hours.

[0042] The present invention is illustrated in more detail with reference to the following examples, but should not be understood as being limited to these examples. It is also recognized that using the precursors described in the present invention, it is possible to deposit porous low-k films having similar process advantages to existing porous low-k films (i.e., higher resistance to plasma-induced damage and higher modulus for a given dielectric constant value). [Examples]

[0043] Example 1: Synthesis of di(ethyl)methyl-isopropoxysilane In a 500 mL flask, Ru3(CO) 12 It was dissolved in 20 g of THF. Then, 200 g (3.33 mol) of IPA (isopropyl alcohol) was added. This solution was heated to 75°C. While stirring, 200 g (1.96 mol) of di(ethyl)methylsilane was added dropwise through an addition funnel. The reaction was exothermic, and hydrogen bubbles were observed. After the addition was complete, the reaction mixture was stirred at room temperature for 30 minutes. Excess IPA and THF were removed by distillation at atmospheric pressure. By fractional vacuum distillation, 250 g of di(ethyl)methyl-iso-propoxysilane (99.3% purity) with a boiling point of 63°C at 55 mmHg was prepared. The yield was 80%. GC-MS: 160(M+), 145, 131, 101, 88, 73, 61, 45.

[0044] Example 2: Synthesis of di(methyl)-iso-propyl-iso-propoxysilane 992 mL (1.98 mol) of 2 M isopropylmagnesium chloride in THF was added at room temperature to 303.0 g (1.98 mol) of di(methyl)-iso-propylchlorosilane in 1 L of hexane. The reaction mixture was slowly heated to 60°C. After the addition was complete, the mixture was cooled to room temperature and stirred overnight. The resulting light gray slurry was filtered. The solvent was removed by distillation. The product was distilled at atmospheric pressure. 218 g of di(methyl)iso-propyl-iso-propoxysilane with a boiling point of 134°C was prepared by fractional vacuum distillation. Figure 2 is a chart showing the GC-MS data of the synthesized di(methyl)iso-propyl-iso-propoxysilane. The yield was 69%. GC-MS: 160(M+), 145, 117, 101, 87, 75, 49, 45.

[0045] All of the following deposition experiments were performed on a 300 mm AMAT Producer® SE that simultaneously deposited films on two wafers. Therefore, the precursor and gas flow rates correspond to the flow rates required to deposit films on two wafers simultaneously. The stated per-wafer RF power is correct when each wafer processing station has its own independent RF power supply. The stated deposition pressure is correct when both wafer processing stations are held at the same pressure. The Producer® SE was equipped with a Producer® Nanocure chamber used for UV curing of specific films after the deposition process was complete.

[0046] While specific embodiments and examples have been illustrated and described above, the present invention is not intended to be limited to those shown. Rather, various modifications can be made in detail within the scope of the equivalents of the claims and without departing from the spirit of the invention. For example, all the scopes broadly described in this document are explicitly intended to include all the narrower scopes within that broader scope. The compounds disclosed in the present invention in formulas (1) and (2) can also be used as structuring agents for the deposition of porous, low-k films having high modulus of elasticity, high XPS carbon content, and high resistance to plasma-induced damage.

[0047] Thickness and refractive index were measured using a Woollam Model M2000 spectroscopic ellipsometer. Dielectric constant was determined using Hg probe technique for p-type wafers of moderate resistance (8–12 Ω·cm). FTIR spectra were measured using a Thermo Fisher Scientific Model iS50 spectrometer equipped with a nitrogen-purged Pike Technologies Map300 for processing 12-inch wafers. The relative density of crosslinked disilylmethylene groups in the film was calculated using the FTIR spectra. Terminal silicon methyl groups (i.e., Si-Me or Si(CH3)) in the film were determined by infrared spectroscopy. x The total density of (where x is 1, 2, or 3) is 1270 cm³. -1 Si(CH3) with the vicinity as the center x The area of ​​the infrared band is approximately 1250 cm². -1 ~920cm -1 of SiO x It is defined as 100 times the value obtained by dividing by the band area. When determined by infrared spectroscopy, the relative density of crosslinked disilylmethylene groups in the film (i.e., the density of SiCH2Si) is 1360 cm⁻¹. -1 The area of ​​the SiCH2Si infrared band centered in the vicinity is approximately 1250 cm². -1 ~920cm -1 of SiO xIt is defined as 10,000 times the value obtained by dividing by the band area. The mechanical properties were determined using a KLA iNano nanoindenter.

[0048] Composition data is obtained by X-ray photoelectron spectroscopy (XPS) using either PHI 5600 (73560, 73808) or Thermo K-Alpha (73846) and is provided in atomic weight percentages. The atomic weight percentage (%) values ​​recorded in the table do not include hydrogen.

[0049] For each precursor in the examples listed below, the deposition conditions were optimized to produce films with high mechanical properties at dielectric constants of 3.1 or 3.2.

[0050] Comparative Example 3: Deposition of a high-density diethoxymethylsilane (DEMS®)-based film. High-density, DEMS®-based films were deposited using the following process conditions for a 300 mm processing. The DEMS® precursor was transported into the reaction chamber via direct liquid injection (DLI) at a flow rate of 750 mg / min using a 1500 sccm He carrier gas stream, and a 300 watt 13.56 MHz plasma was applied at a chamber pressure of 10 Torr, a base temperature of 345°C, and a showerhead / heated base spacing of 380 mm-inches. Various properties of the film (e.g., dielectric constant (k), elastic modulus, hardness, density of various functional groups as determined by infrared spectroscopy, and atomic composition (%C, %O, and %Si) by XPS) were obtained as described above and are provided in Table 2.

[0051] Comparative Example 4: Deposition of a high-density diethoxymethylsilane (DEMS®)-based film. High-density, DEMS®-based films were deposited using the following process conditions for a 300 mm processing. The DEMS® precursor was transported into the reaction chamber via direct liquid injection (DLI) at a flow rate of 750 mg / min using a 2250 sccm He carrier gas stream, and a 13.56 MHz plasma at 200 watts was applied at a base temperature of 345°C, a chamber pressure of 10 Torr, and a showerhead / heated base spacing of 380 mm-inches. Various properties of the film (e.g., dielectric constant (k), elastic modulus, hardness, density of various functional groups as determined by infrared spectroscopy, and atomic composition (%C, %O, and %Si) by XPS) were obtained as described above and are provided in Table 3.

[0052] Comparative Example 5: Deposition of a high-density, 1-methyl-1-isopropoxy-1-silacyclopentane (MESCP)-based film. High-density, MPSCP-based films were deposited using the following process conditions for a 300 mm processing. The MPSCP precursor was transported into the reaction chamber via direct liquid injection (DLI) at a flow rate of 850 mg / min using a 750 sccm He carrier gas stream. A 13.56 MHz plasma at 225 watts was applied at a base temperature of 390°C, a chamber pressure of 7.5 Torr, and a showerhead / heated base spacing of 380 mm-inch. Various properties of the film (e.g., dielectric constant (k), elastic modulus, hardness, density of various functional groups as measured by infrared spectroscopy, and atomic composition (%C, %O, and %Si) by XPS) were obtained as described above and are provided in Table 2.

[0053] Comparative Example 6: Deposition of a high-density, 1-methyl-1-isopropoxy-1-silacyclopentane (MPSCP)-based film. A high-density MPSCP-based film was deposited using the following process conditions for a 300 mm processing. The MPSCP precursor was transported into the reaction chamber via direct liquid injection (DLI) at a flow rate of 850 mg / min using a 750 sccm He carrier gas stream. A 13.56 MHz plasma at 275 watts was applied at a base temperature of 390°C, a chamber pressure of 7.5 Torr, and a showerhead / heated base spacing of 380 mm-inches. Various properties of the film (e.g., dielectric constant (k), elastic modulus, hardness, density of various functional groups as measured by infrared spectroscopy, and atomic composition (%C, %O, and %Si) by XPS) were obtained as described above and are provided in Table 3.

[0054] Example 7: Deposition of a high-density, di(ethyl)methyl-isopropoxysilane (DEMIPS)-based film. High-density, di(ethyl)methyl-isopropoxysilane-based films were deposited using the following process conditions for a 300 mm processing. The di(ethyl)methyl-isopropoxysilane precursor was transported into the reaction chamber via direct liquid injection (DLI) at a flow rate of 850 mg / min using a 750 sccm He carrier gas flow, and a 13.56 MHz plasma at 225 watts was applied at a base temperature of 390°C, a chamber pressure of 7.5 Torr, and an O2 flow rate of 8 sccm with a showerhead / heated base spacing of 380 mm-inches. Various properties of the film (e.g., dielectric constant (k), elastic modulus, hardness, density of various functional groups as measured by infrared spectroscopy, and atomic composition (%C, %O, and %Si) by XPS) were obtained as described above and are provided in Table 2.

[0055] Example 8: Deposition of a high-density, di(ethyl)methyl-isopropoxysilane-based film High-density, di(ethyl)methyl-isopropoxysilane-based films were deposited using the following process conditions for a 300 mm processing. The di(ethyl)methyl-isopropoxysilane precursor was transported into the reaction chamber via direct liquid injection (DLI) at a flow rate of 850 mg / min using a 750 sccm He carrier gas flow, and a 13.56 MHz plasma at 275 watts was applied at a base temperature of 390°C, a chamber pressure of 7.5 Torr, and an O2 flow rate of 8 sccm with a showerhead / heated base spacing of 380 mm-inches. Various properties of the film (e.g., dielectric constant (k), elastic modulus, hardness, density of various functional groups as measured by infrared spectroscopy, and atomic composition (%C, %O, and %Si) by XPS) were obtained as described above and are provided in Table 3.

[0056] Table 2 below shows the processing conditions for depositing high-density low-k films in a 300 mm PECVD reactor using DEMIPS, DEMS®, and MPSCP as low-k precursors. The processing conditions for each of these deposits were adjusted to obtain a high elastic modulus at the dielectric constant of 3.1. Table 3 shows the infrared spectra of the high-density low-k films in Table 2. Si(CH3) in each film... x The relative densities of the group and the SiCH2Si group were calculated from the infrared spectrum described earlier.

[0057] A series of high-density, low-k dielectric films were deposited in a PECVD reactor using DEMIPS, DEMS®, or MPSCP as the low-k precursor under various process conditions: plasma power of 170–425 watts, chamber pressure of 7.5–10 Torr, substrate temperature of 345–390°C, O2 gas flow of 0–30 sccm, He carrier gas flow of 600–2250 sccm, precursor liquid flow of 0.75–2.0 g / min, and electrode spacing of 0.380 inches. Carbon content was measured by XPS as described herein. Figure 4 shows the relationship between the carbon content (at%) of high-density, DEMIPS, DEMS®, and MPSCP® films with different dielectric constants. As shown in Figure 4, the prior art or DEMS® low-k films had a narrow range of carbon content of about 17–22 at% as the dielectric constant increased from about 2.75 to about 3.45. Figure 4 also shows that prior art or MPSCP base k films had a wider range of carbon content, approximately 19–42 at% for the same dielectric constant range. DEMIPS films also have a wide range of carbon content, approximately 12–31 at% for the same dielectric constant, but symmetrically, the carbon content of DEMIPS films is lower than that of MPSCP-based films at the same dielectric constant. This demonstrates one of the key advantages of using the monoalkoxysilane compounds of formula (1) or formula (2) described herein as DEMIPS over using other prior art structuring agents for depositing high-density, low-k dielectric films with similar dielectric constant values, where the monoalkoxysilane precursor DEMIPS allows for a wide, adjustable range of carbon content, with less total carbon than prior art precursors such as MPSCP and more total carbon than prior art precursors such as DEMS®.

[0058] Table 2 provides a comparison of high-density low-k films with a dielectric constant of k=3.1 using DEMIPS, DEMS®, and MPSCP as low-k precursors. The processing conditions for the given films were adjusted to obtain a high modulus without post-treatment such as UV curing. Compared to prior art DEMS® and MPSCP-based films with low carbon content, the DEMIPS film has a significantly higher modulus (approximately +20%). Furthermore, the DEMIPS film has a higher carbon content (approximately +23%), a lower Si(CH3) group density (approximately -30%), and a higher SiCH2Si group density (approximately +40%) compared to the DEMS®-based film. Furthermore, the DEMIPS film has a lower carbon content (approximately -40%), a lower Si(CH3) group density (approximately -45%), and a lower SiCH2Si group density (approximately -40%) compared to the MPSCP-based film. This demonstrates a significant advantage of using the monoalkoxysilane compounds of formula (1) or formula (2) described herein as DEMIPS over the use of other prior art structuring agents for depositing high-density, low-k dielectric films with similar dielectric constants. Monoalkoxysilane precursors DEMIPS enable the deposition of low-k dielectric films with very high modulus, a wide tunable range of carbon content, low Si(CH3) group density, and high SiCH2Si group density. For the same dielectric constant, DEMIPS-based films have a higher total carbon content than prior art precursor-based films such as DEMS®, which result in films with a lower total carbon content, and a lower total carbon content than prior art precursor-based films such as MPSCP, which result in films with a higher total carbon content. This is a very important difference because the very high carbon content and high Si(CH3) density of prior art MPSCP-based films ultimately limit the maximum modulus that can be obtained using this type of precursor. On the other hand, prior art precursors such as DEMS (registered trademark), which result in films with low carbon content, incorporate carbon primarily as Si(CH3) groups in the oxide network structure instead of SiCH2Si, and therefore limit the maximum elastic modulus that can be obtained with this type of precursor.Furthermore, prior art precursors such as DEMS®, which have a low carbon content, exhibit limited resistance to plasma-induced damage (PID) due to their low carbon content. This demonstrates another significant advantage of using monoalkoxysilane compounds of formula (1) or formula (2) as described herein as DEMIPS compared to using other prior art structuring agents for depositing high-density, low-k dielectric films with similar dielectric constants. Monoalkoxysilane precursors DEMIPS enable the deposition of films with a high modulus, high resistance to plasma-induced damage due to their moderate carbon content, low Si(CH3) group density, and high SiCH2Si group density compared to prior art precursors such as DEMS®. In fact, the combination of high modulus, moderate carbon content, low Si(CH3) density, and high SiCH2Si density is expected to provide resistance to PID similar to that of prior art precursors such as MPSCP, resulting in the deposition of low-k films with a higher carbon content than DEMIPS-based films.

[0059] Table 2. Processing conditions for a selected film having a dielectric constant of 3.1, adjusted to obtain a high elastic modulus. [Table 2]

[0060] Table 3 provides a comparison of high-density low-k films with a dielectric constant of k=3.2 using DEMIPS, DEMS®, and MPSCP as low-k precursors. The processing conditions for the given films were adjusted to obtain high elastic modulus without post-treatment such as UV curing. Compared to prior art DEMS® and MPSCP-based films with low carbon content, the DEMIPS-based film has a significantly higher elastic modulus (approximately +16-20%). Furthermore, the DEMIPS film has a higher carbon content (approximately +57%), a lower Si(CH3) group density (approximately -20%), and a higher SiCH2Si group density (approximately +35%) compared to the DEMS®-based film. Furthermore, the DEMIPS film has a lower carbon content (approximately -33%), a lower Si(CH3) group density (approximately -41%), and a lower SiCH2Si group density (approximately -36%) compared to the MPSCP-based film. This demonstrates a significant advantage of using the monoalkoxysilane compounds of formula (1) or formula (2) described herein as DEMIPS over the use of other prior art structuring agents for depositing high-density, low-k dielectric films with similar dielectric constants. Monoalkoxysilane precursor DEMIPS enables the deposition of low-k dielectric films with very high modulus, a wide tunable range of carbon content, low Si(CH3) group density, and high SiCH2Si group density. For the same dielectric constant, DEMIPS-based films have a higher total carbon content than prior art precursor-based films such as DEMS®, and a lower total carbon content than prior art precursor-based films such as MPSCP. This is a crucial difference because the very high carbon content and high Si(CH3) density of prior art MPSCP-based films ultimately limit the maximum modulus that can be obtained using this type of precursor. On the other hand, prior art precursors such as DEMS (registered trademark), which result in films with low carbon content, incorporate carbon primarily as Si(CH3) groups in the oxide network structure instead of SiCH2Si, and therefore limit the maximum elastic modulus that can be obtained with this type of precursor.Furthermore, prior art precursors such as DEMS®, which have a low carbon content, have limited resistance to plasma-induced damage (PID) due to their low carbon content. This demonstrates another important advantage of using monoalkoxysilane compounds of formula (1) or formula (2) as described herein as DEMIPS compared to using other prior art structuring agents for depositing high-density, low-k dielectric films with similar dielectric constants. Monoalkoxysilane precursor DEMIPS allows for the deposition of films with higher modulus and higher resistance to expected induced damage compared to prior art precursors such as DEMS®. This is due to the higher carbon content and lower Si(CH3) in DEMIPS-based films compared to films deposited from prior art precursors such as DEMS®. x This is due to the density of the groups, and the higher density of SiCH2Si groups. In fact, it has a high modulus of elasticity, a moderate carbon content, and low Si(CH3) x The combination of high density and high SiCH2Si density is expected to provide resistance to PID similar to prior art precursors such as MPSCP, even though MPSCP-based films result in the deposition of low-k films with a higher carbon content than DEMIPS-based films.

[0061] Table 3. Processing conditions for a selected film having a dielectric constant of 3.2, adjusted to obtain a high elastic modulus. [Table 3] The following embodiments can be cited as examples of the present invention. (Note 1) A method for producing a high-density organic silica film having improved mechanical properties, A step of introducing the substrate into the reaction chamber; Equation (1) or (2): (1)R 1 R 2 MeSiOR 3 (In the formula, R 1 and R 2 However, C in a straight chain or branched chain 1 ~C 5 Alkyl, preferably independently selected from ethyl, propyl, isopropyl, butyl, sec-butyl or tert-butyl, R 3 However, C in a straight chain or branched chain 1 ~C 5 Alkyl, preferably selected from methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, isobutyl, or tert-butyl. (2)R 4 (Me) 2 SiOR 5 (In the formula, R 4 However, C in a straight chain or branched chain 1 ~C 5 Alkyl, preferably selected from ethyl, propyl, isopropyl, butyl, sec-butyl or tert-butyl, R 5 However, C in a straight chain or branched chain 1 ~C 5 Alkyl, preferably selected from ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, or tert-butyl. A step of introducing into the reaction chamber a gaseous composition comprising a monoalkoxysilane having the structure given in, which substantially does not contain one or more impurities selected from the group consisting of halides, water, metals and combinations thereof; and Application step: Applying energy to the gaseous composition containing monoalkoxysilane in the reaction chamber to induce a reaction in the gaseous composition containing monoalkoxysilane, thereby depositing an organic silica film on the substrate. A method comprising the following, wherein the organic silica film has a dielectric constant of about 2.8 to about 3.30 and an elastic modulus of about 9 to about 32 GPa. (Note 2) The method according to Appendix 1, wherein the gaseous composition containing a monoalkoxysilane does not contain a curing additive. (Note 3) The method described in Appendix 1, which is a chemical vapor deposition method. (Note 4) The method described in Appendix 1, which is a plasma-enhanced chemical vapor deposition method. (Note 5) The gaseous composition containing monoalkoxysilane is O 2 、N 2 O, NO, NO 2 CO 2 CO, water, H 2 O 2 The method according to Appendix 1, further comprising at least one oxidizing agent selected from the group consisting of ozone and combinations thereof. (Note 6) The method according to Appendix 1, wherein the gaseous composition containing a monoalkoxysilane is free of an oxidizing agent. (Note 7) The reaction chamber in the above application step contains He, Ar, and N 2 , Kr, Xe, CO 2 The method according to Appendix 1, comprising at least one gas selected from the group consisting of and CO. (Note 8) The method according to Appendix 1, wherein the organic silica film has a refractive index (RI) of approximately 1.3 to approximately 1.6 at 632 nm and a carbon content of approximately 10 at% to approximately 30 at% as measured by XPS. (Note 9) The method according to Appendix 1, wherein the organic silica film is deposited at a rate of approximately 5 nm / min to approximately 700 nm / min. (Note 10) The aforementioned organic silica film is composed of approximately 8 to approximately 30 SiCH 2 Si / SiO x×10 4 The method described in Appendix 8, having the IR ratio of the following. (Note 11) A composition for vapor deposition of dielectric films, comprising formula (1) or (2): (1)R 1 R 2 MeSiOR 3 (In the formula, R 1 and R 2 However, C in a straight chain or branched chain 1 ~C 5 Alkyl, preferably independently selected from ethyl, propyl, isopropyl, butyl, sec-butyl or tert-butyl, R 3 However, C in a straight chain or branched chain 1 ~C 5 Alkyl, preferably selected from methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, isobutyl, or tert-butyl. (2)R 4 (Me) 2 SiOR 5 (In the formula, R 4 However, C in a straight chain or branched chain 1 ~C 5 Alkyl, preferably selected from ethyl, propyl, isopropyl, butyl, sec-butyl or tert-butyl, R 5 However, C in a straight chain or branched chain 1 ~C 5 Alkyl, preferably selected from ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, or tert-butyl. A composition comprising a monoalkoxysilane having the structure given in, which substantially does not contain one or more impurities selected from the group consisting of halides, water, and metals. (Note 12) The aforementioned monoalkoxysilanes are di(ethyl)-methyl-methoxysilane, di(ethyl)-methyl-ethoxysilane, di(ethyl)-methyl-n-propoxysilane, di(ethyl)-methyl-iso-propoxysilane, di(ethyl)methyl(n-butoxy)silane, di(ethyl)methyl(sec-butoxy)silane, di(ethyl)methyl(tert-butoxy)silane, trimethyl(iso-propoxy)silane, trimethyl(iso-butoxy)silane, trimethyl(sec-butoxy)silane, trimethyl(n-butoxy)silane, trimethyl(ter t-butoxy)silane, di(propyl)methyl(methoxy)silane, di(propyl)methyl(ethoxy)silane, di(propyl)methyl(propoxy)silane, di(propyl)methyl(iso-propoxy)silane, di(n-propyl)methyl(butoxy)silane, di(n-propyl)methyl(sec-butoxy)silane, di(n-propyl)methyl(tert-butoxy)silane, di(n-propyl)methyl(iso-butoxy)silane, di(iso-propyl)methyl(methoxy)silane, di(iso-propyl)methyl(ethoxy)silane, di(iso- Propyl(methyl(propoxy)silane), di(iso-propyl)methyl(iso-propoxy)silane, di(iso-propyl)methyl(n-butoxy)silane, di(iso-propyl)methyl(sec-butoxy)silane, di(iso-propyl)methyl(tert-butoxy)silane, di(iso-propyl)methyl(iso-butoxy)silane, di(methyl)ethyl(methoxy)silane, di(methyl)ethyl(ethoxy)silane, di(methyl)ethyl(n-propoxy)silane, di(methyl)ethyl(n- Butoxysilane, di(methyl)ethyl(sec-butoxy)silane, di(methyl)-ethyl-tert-butoxysilane, di(methyl)ethyl(iso-butoxy)silane, di(methyl)n-propyl(methoxy)silane, di(methyl)n-propyl(ethoxy)silane, di(methyl)n-propyl(n-propoxy)silane, di(methyl)n-propyl(iso-propoxy)silane, di(methyl)n-propyl(butoxy)silane, di(methyl)n-propyl(sec-butoxy)silane, di(methyl)n-propyl(tert-butoxy)silane,Di(methyl)n-propyl(iso-butoxy)silane, di(methyl)iso-propyl(methoxy)silane, di(methyl)iso-propyl(ethoxy)silane, di(methyl)iso-propyl(n-propoxy)silane, di(methyl)iso-propyl(iso-propoxy)silane, di(methyl)iso-propyl(n-butoxy)silane, di(methyl)iso-propyl(sec-butoxy)silane, di(methyl)iso-propyl(tert-butoxy)silane, di(methyl)iso-propyl(iso -Butoxy)silane, di(methyl)n-butyl(methoxy)silane, di(methyl)n-butyl(ethoxy)silane, di(methyl)n-butyl(propoxy)silane, di(methyl)n-butyl(iso-propoxy)silane, di(methyl)n-butyl(n-butoxy)silane, di(methyl)-n-butyl(sec-butoxy)silane, di(methyl)n-butyl(tert-butoxy)silane, di(methyl)-n-butyl(iso-butoxy)silane, di(methyl)sec-butyl(methoxy)silane Di(methyl)sec-butyl(ethoxy)silane, di(methyl)sec-butyl(n-propoxy)silane, di(methyl)sec-butyl(iso-propoxy)silane, di(methyl)sec-butyl(n-butoxy)silane, di(methyl)sec-butyl(sec-butoxy)silane, di(methyl)sec-butyl(tert-butoxy)silane, di(methyl)sec-butyl(iso-butoxy)silane, di(methyl)tert-butyl(methoxy)silane, di(methyl)tert-butyl The composition according to Appendix 11, comprising at least one selected from the group consisting of ethyl(ethoxy)silane, di(methyl)tert-butyl(propoxy)silane, di(methyl)tert-butyl(iso-propoxy)silane, di(methyl)tert-butyl(n-butoxy)silane, di(methyl)tert-butyl(sec-butoxy)silane, di(methyl)tert-butyl(tert-butoxy)silane, di(methyl)tert-butyl(iso-butoxy)silane, and combinations thereof. (Note 13) The composition according to Appendix 11, wherein the halide contains chloride ions. (Note 14) The composition according to Appendix 13, wherein, if present, the chloride ions are present at a concentration of 50 ppm or less when measured by IC. (Note 15) The composition according to Appendix 13, wherein, if present, the chloride ions are present at a concentration of 10 ppm or less when measured by IC. (Note 16) The composition according to Appendix 13, wherein, if present, the chloride ions are present at a concentration of 5 ppm or less when measured by IC.

Claims

1. A method for producing an organic silica film, A step of introducing the substrate into the reaction chamber; Di(ethyl)-methyl-methoxysilane, di(ethyl)-methyl-ethoxysilane, di(ethyl)-methyl-n-propoxysilane, di(ethyl)-methyl-iso-propoxysilane, di(ethyl)methyl(n-butoxy)silane, di(ethyl)methyl(sec-butoxy)silane, di(ethyl)methyl(tert-butoxy)silane, trimethyl(iso-propoxy)silane, trimethyl(iso-butoxy)silane, trimethyl(sec-butoxy)silane, trimethyl(n-butoxy)silane, trimethyl(tert-butoxy)silane, di(propyl ) Methyl(methoxy)silane, di(propyl)methyl(ethoxy)silane, di(propyl)methyl(propoxy)silane, di(propyl)methyl(iso-propoxy)silane, di(n-propyl)methyl(butoxy)silane, di(n-propyl)methyl(sec-butoxy)silane, di(n-propyl)methyl(tert-butoxy)silane, di(n-propyl)methyl(iso-butoxy)silane, di(isopropyl)methyl(methoxy)silane, di(isopropyl)methyl(ethoxy)silane, di(isopropyl)methyl(propoxy)silane, di (Iso-propyl)methyl(iso-propoxy)silane, di(iso-propyl)methyl(n-butoxy)silane, di(iso-propyl)methyl(sec-butoxy)silane, di(iso-propyl)methyl(tert-butoxy)silane, di(iso-propyl)methyl(iso-butoxy)silane, di(methyl)ethyl(methoxy)silane, di(methyl)ethyl(ethoxy)silane, di(methyl)ethyl(n-propoxy)silane, di(methyl)ethyl(isopropoxy)silane, di(methyl)ethyl(n-butoxy)silane, di(methyl)ethyl(sec- Butoxysilane, di(methyl)-ethyl-tert-butoxysilane, di(methyl)ethyl(iso-butoxy)silane, di(methyl)n-propyl(methoxy)silane, di(methyl)n-propyl(ethoxy)silane, di(methyl)n-propyl(n-propoxy)silane, di(methyl)n-propyl(isopropoxy)silane, di(methyl)n-propyl(butoxy)silane, di(methyl)n-propyl(sec-butoxy)silane, di(methyl)n-propyl(tert-butoxy)silane, di(methyl)n-propyl(iso-butoxy)silane,Di(methyl)isopropyl(methoxy)silane, di(methyl)isopropyl(ethoxy)silane, di(methyl)isopropyl(n-propoxy)silane, di(methyl)isopropyl(isopropoxy)silane, di(methyl)isopropyl(n-butoxy)silane, di(methyl)isopropyl(sec-butoxy)silane, di(methyl)isopropyl(tert-butoxy)silane, di(methyl)isopropyl(isobutoxy)silane, di(methyl)n-butyl(methoxy)silane, di(methyl n-butyl(ethoxy)silane, di(methyl)n-butyl(propoxy)silane, di(methyl)n-butyl(iso-propoxy)silane, di(methyl)n-butyl(n-butoxy)silane, di(methyl)-n-butyl(sec-butoxy)silane, di(methyl)n-butyl(tert-butoxy)silane, di(methyl)-n-butyl(iso-butoxy)silane, di(methyl)sec-butyl(methoxy)silane, di(methyl)sec-butyl(ethoxy)silane, di(methyl)sec-butyl(n-propoxy) Silane, di(methyl)sec-butyl(iso-propoxy)silane, di(methyl)sec-butyl(n-butoxy)silane, di(methyl)sec-butyl(sec-butoxy)silane, di(methyl)sec-butyl(tert-butoxy)silane, di(methyl)sec-butyl(iso-butoxy)silane, di(methyl)tert-butyl(ethoxy)silane, di(methyl)tert-butyl(propoxy)silane, di(methyl)tert-butyl(iso-propoxy)silane, di(methyl)tert-butyl(n- A step of introducing a gaseous composition containing a monoalkoxysilane, which comprises at least one selected from the group consisting of butoxy)silane, di(methyl)tert-butyl(sec-butoxy)silane, di(methyl)tert-butyl(tert-butoxy)silane, di(methyl)tert-butyl(iso-butoxy)silane and combinations thereof, and which does not contain one or more impurities selected from the group consisting of halides, water, metals and combinations thereof, into the reaction chamber; and, Application step: Applying energy to the gaseous composition containing monoalkoxysilane in the reaction chamber to induce a reaction in the gaseous composition containing monoalkoxysilane, thereby depositing an organic silica film on the substrate. A method comprising the following, wherein the organic silica film has a dielectric constant of 2.8 to 3.30 and an elastic modulus of 9 to 32 GPa.

2. The method according to claim 1, wherein the gaseous composition containing a monoalkoxysilane does not contain a curing additive.

3. The method according to claim 1, which is a chemical vapor deposition method.

4. The method according to claim 1, which is a plasma-enhanced chemical vapor deposition method.

5. The method according to claim 1, wherein the gaseous composition containing a monoalkoxysilane does not contain an oxidizing agent.

6. The reaction chamber in the above application step is He, Ar, N 2 , Kr, Xe, CO 2 The method according to claim 1, comprising at least one gas selected from the group consisting of and CO.

7. The method according to claim 1, wherein the organic silica film has a carbon content of 10 at% to 30 at% when measured by XPS.

8. The method according to claim 1, wherein the organic silica film is deposited at a rate of 5 nm / min to 700 nm / min.

9. The aforementioned organic silica film is composed of 8 to 30 SiCH 2 Si / SiO x ×10 4 The method according to claim 7, having an IR ratio of

10. A composition for vapor deposition of an organic silica film having a dielectric constant of 2.8 to 3.3 and an elastic modulus of 9 to 32 GPa, comprising: di(ethyl)-methyl-methoxysilane, di(ethyl)-methyl-ethoxysilane, di(ethyl)-methyl-n-propoxysilane, di(ethyl)-methyl-iso-propoxysilane, di(ethyl)methyl(n-butoxy)silane, di(ethyl)methyl(sec-butoxy)silane, di(ethyl)methyl(tert-butoxy)silane, trimethyl(iso-propoxy)silane, trimethyl(iso-butoxy)silane, trimeth Sec-butoxysilane, Trimethyl(n-butoxy)silane, Trimethyl(tert-butoxy)silane, Di(propyl)methyl(methoxy)silane, Di(propyl)methyl(ethoxy)silane, Di(propyl)methyl(propoxy)silane, Di(propyl)methyl(iso-propoxy)silane, Di(n-propyl)methyl(butoxy)silane, Di(n-propyl)methyl(sec-butoxy)silane, Di(n-propyl)methyl(tert-butoxy)silane, Di(n-propyl)methyl(iso-butoxy)silane, Di(iso-propyl Methyl(methoxy)silane, di(iso-propyl)methyl(ethoxy)silane, di(iso-propyl)methyl(propoxy)silane, di(iso-propyl)methyl(iso-propoxy)silane, di(iso-propyl)methyl(n-butoxy)silane, di(iso-propyl)methyl(sec-butoxy)silane, di(iso-propyl)methyl(tert-butoxy)silane, di(iso-propyl)methyl(iso-butoxy)silane, di(methyl)ethyl(methoxy)silane, di(methyl)ethyl(ethoxy)silane, di(methyl)ethyl(ethoxy)silane ru(n-propoxy)silane, di(methyl)ethyl(iso-propoxy)silane, di(methyl)ethyl(n-butoxy)silane, di(methyl)ethyl(sec-butoxy)silane, di(methyl)-ethyl-tert-butoxysilane, di(methyl)ethyl(iso-butoxy)silane, di(methyl)n-propyl(methoxy)silane, di(methyl)n-propyl(ethoxy)silane, di(methyl)n-propyl(n-propoxy)silane, di(methyl)n-propyl(iso-propoxy)silane, di(methyl)n-propyl(butoxy)silane,Di(methyl)n-propyl(sec-butoxy)silane, di(methyl)n-propyl(tert-butoxy)silane, di(methyl)n-propyl(iso-butoxy)silane, di(methyl)iso-propyl(methoxy)silane, di(methyl)iso-propyl(ethoxy)silane, di(methyl)iso-propyl(n-propoxy)silane, di(methyl)iso-propyl(isopropoxy)silane, di(methyl)iso-propyl(n-butoxy)silane, di(methyl)iso-propyl(sec-butoxy)silane, di(methyl)iso-propyl Di(methyl)isopropyl(iso-butoxy)silane, di(methyl)n-butyl(methoxy)silane, di(methyl)n-butyl(ethoxy)silane, di(methyl)n-butyl(propoxy)silane, di(methyl)n-butyl(isopropoxy)silane, di(methyl)n-butyl(n-butoxy)silane, di(methyl)-n-butyl(sec-butoxy)silane, di(methyl)n-butyl(tert-butoxy)silane, di(methyl)-n-butyl(iso-butoxy)silane, di(methyl)sec-butyl Tyl(methoxy)silane, di(methyl)sec-butyl(ethoxy)silane, di(methyl)sec-butyl(n-propoxy)silane, di(methyl)sec-butyl(iso-propoxy)silane, di(methyl)sec-butyl(n-butoxy)silane, di(methyl)sec-butyl(sec-butoxy)silane, di(methyl)sec-butyl(tert-butoxy)silane, di(methyl)sec-butyl(iso-butoxy)silane, di(methyl)tert-butyl(ethoxy)silane, di(methyl)tert-butyl(propoxy)silane A composition comprising a monoalkoxysilane containing at least one selected from the group consisting of di(methyl)tert-butyl(iso-propoxy)silane, di(methyl)tert-butyl(n-butoxy)silane, di(methyl)tert-butyl(sec-butoxy)silane, di(methyl)tert-butyl(tert-butoxy)silane, di(methyl)tert-butyl(iso-butoxy)silane, and combinations thereof, wherein the monoalkoxysilane does not contain one or more impurities selected from the group consisting of halides, water, and metals.

11. The composition according to claim 10, wherein the halide contains chloride ions.

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