A composition for forming a carbon-doped silicon-containing film, a method for forming the composition, and a method and system for using the composition.

Abstract

The present invention provides a composition for forming a carbon-doped silicon-containing film, a method for forming the composition, and a method and system for using the composition. [Solution] The film-forming composition is based on the general formula (1): JPEG2026060924000014.jpg26170 (In the formula, Q 1 Q is a substituent selected from an acetoxy group, an acryloyloxy group, a C1-C6 alkoxy group, a silyloxy group, a gelmyloxy group, a phosphonooxy group, and an alkylamine group. 2 Q 3 , and Q 4 These are a hydrogen atom, a C1-C6 alkyl group, and Q, respectively. 1 The substituent is independently selected from the substituents. The invention includes a silicon precursor having a structure due to ). Methods for forming a film-forming composition, as well as methods and systems for depositing a carbon-doped silicon-containing film on a substrate using the film-forming composition, are also provided.

Description

[Technical Field]

[0001] (Cross-reference of related applications) This application claims the benefits of U.S. Provisional Patent Application No. 63 / 700,240, filed on 27 September 2024, which is incorporated herein by reference in its entirety.

[0002] This disclosure generally relates to the processing of semiconductor substrates. More specifically, this disclosure relates to compositions useful for forming carbon-doped silicon-containing films, as well as methods and systems for forming carbon-doped silicon-containing films on the surface of a substrate using these compositions. [Background technology]

[0003] Silicon oxycarbide (SiOC) is a promising low-κ exchange material for certain silicon oxide and silicon nitride layers in next-generation semiconductor devices. The carbon content of SiOC films reduces the dielectric constant by increasing porosity and / or polarization. The film composition should be optimized to yield a sufficiently low dielectric constant while maintaining the thermal and mechanical properties required for specific applications. Furthermore, such low-κ layers need to be able to be formed at temperatures consistent with the fabrication of the device structure, and, in some applications, using chemical vapor deposition (CVD) methods that provide conformal films with precise thickness control while maintaining high throughput.

[0004] Silicon oxycarbide films are generally formed using plasma-based CVD processes at relatively low temperatures, reducing the thermal budget in device manufacturing. The selection of chemical precursors used in the deposition method can significantly influence both process conditions and the material properties of the resulting layer. Improving low-κ material precursors for CVD processes is an ongoing research challenge. In this regard, this disclosure relates to precursor compositions for forming carbon-doped silicon-containing films that generally meet many of the requirements listed above, as well as methods and systems for using such precursor compositions.

[0005] All considerations, including the issues and solutions discussed in this section, are included in this disclosure solely for the purpose of providing context for this disclosure. Such considerations should not be construed as acknowledging that any of the information was publicly known or constitutes prior art at the time the invention was made. [Overview of the project] [Means for solving the problem]

[0006] This summary of the invention may present some concepts in a simplified form, which may be described in more detail below. This summary of the invention is not necessarily intended to identify the main or essential features of the claimed subject matter, nor is it intended to be used to limit the scope of the claimed subject matter.

[0007] One aspect of the present disclosure relates to a film-forming composition configured to form and / or suitable for forming a carbon-doped silicon-containing film. The film-forming composition is based on the general formula (1) (Chemical Formula 1) (wherein Q 1 Q is a substituent selected from an acetoxy group, an acryloyloxy group, a C1-C6 alkoxy group, a silyloxy group, a gelmyloxy group, a phosphonooxy group, and an alkylamine group. 2 Q 3 , and Q 4 These are a hydrogen atom, a C1-C6 alkyl group, and Q, respectively. 1 The substituent is independently selected from the same substituents. The material includes a silicon precursor having a structure due to ).

[0008] [ka]

[0009] In some embodiments, Q 1 The substituent is an acetoxy group. In some of these embodiments, Q 1 substituents and Q 3 The substituents are all acetoxy groups.

[0010] In some embodiments, the substituent of Q 1 is an acryloyloxy group. In some of these embodiments, the substituent of Q 1 and the substituent of Q 3 are both acryloyloxy groups. The acryloyloxy group may be selected from an acryloyloxy group or a methacryloyloxy group.

[0011] In some embodiments, the substituent of Q 1 is a C1-C6 alkoxy group. In some of these embodiments, the substituent of Q 1 and the substituent of Q 3 are both C1-C6 alkoxy groups. The C1-C6 alkoxy group may be selected from the group consisting of a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, and a butoxy group.

[0012] In some embodiments, the substituent of Q 1 is a silyloxy group. In some of these embodiments, the substituent of Q 1 and the substituent of Q 3 are both silyloxy groups. The silyloxy group may be a trimethylsilyloxy group.

[0013] In some embodiments, the substituent of Q 1 is a germyloxy group. In some of these embodiments, the substituent of Q 1 and the substituent of Q 3 are both germyloxy groups. The germyloxy group may be a trimethylgermyloxy group.

[0014] In some embodiments, the substituent of Q 1 is a phosphonooxy group. In some of these embodiments, the substituent of Q 1 and the substituent of Q 3 are both phosphonooxy groups. The phosphonooxy group may be a dimethylphosphonooxy group.

[0015] In some embodiments, Q 1 The substituent is an alkylamine group. In some of these embodiments, Q 1 substituents and Q 3 The substituents are all alkylamine groups. The alkylamine group may be selected from the group consisting of dimethylamine group, diethylamine group, and diisopropylamine group.

[0016] In some embodiments, substituent Q 1 and Q 3 The substituent Q is dependently selected from acetoxy group, acryloyloxy group, C1-C6 alkoxy group, silyloxy group, gelmyloxy group, phosphonooxy group, and alkylamine group. 2 and Q 4 The element is dependently selected from hydrogen atoms and C1-C6 alkyl groups.

[0017] In some embodiments, the silicon precursor is 1,3-diacetoxy-1,3-disilacyclobutane, 1,3-diacetoxy-1,3-dimethyl-1,3-disilacyclobutane, 1,3-diacryloxy-1,3-disilacyclobutane, 1,3-diacryloxy-1,3-dimethyl-1,3-disilacyclobutane, 1,3-dimethylacryloyloxy-1,3-disilacyclobutane, 1,3-dimethylacryloyloxy-1,3-dimethyl-1,3-disilacyclobutane, 1,3-diethoxy-1,3-disilacyclobutane, 1,3-diethoxy-1,3-dimethyl-1,3-disilacyclobutane, 1,3-bis(trimethylsilyloxy)- Selected from the group consisting of 1,3-disilacyclobutane, 1,3-bis(trimethylsilyloxy)-1,3-dimethyl-1,3-disilacyclobutane, 1,3-bis(trimethylgermyloxy)-1,3-disilacyclobutane, 1,3-bis(trimethylgermyloxy)-1,3-dimethyl-1,3-disilacyclobutane, 1,3-bis(dimethylphosphonooxy)-1,3-disilacyclobutane, 1,3-bis(dimethylphosphonooxy)-1,3-dimethyl-1,3-disilacyclobutane, 1,3-bis(diethylamine)-1,3-disilacyclobutane, and 1,3-bis(diethylamine)-1,3-dimethyl-1,3-disilacyclobutane.

[0018] In some embodiments, the film-forming composition is isomerically enriched. In some embodiments, at least 85% of the silicon precursor is in cis isomeric form, or at least 85% of the silicon precursor is in trans isomeric form. In some of these embodiments, at least 85% of the silicon precursor is in cis isomeric form, or at least 90% of the silicon precursor is in cis isomeric form, or at least 95% of the silicon precursor is in cis isomeric form, or at least 97% of the silicon precursor is in cis isomeric form, or at least 98% of the silicon precursor is in cis isomeric form, or at least 99% of the silicon precursor is in cis isomeric form, or at least 99.5% of the silicon precursor is in cis isomeric form. In some other embodiments of these embodiments, at least 85% of the silicon precursor is in trans isomer form, or at least 90% of the silicon precursor is in trans isomer form, or at least 95% of the silicon precursor is in trans isomer form, or at least 97% of the silicon precursor is in trans isomer form, or at least 98% of the silicon precursor is in trans isomer form, or at least 99% of the silicon precursor is in trans isomer form, or at least 99.5% of the silicon precursor is in trans isomer form.

[0019] In some embodiments, the film-forming composition has a purity of at least about 90% by weight, based on the weight of the silicon precursor. In some embodiments, the film-forming composition has a purity of at least about 95% by weight, or at least about 97% by weight, or at least about 98% by weight, or at least about 99% by weight, or at least about 99.5% by weight, or at least about 99.9% by weight.

[0020] Another aspect of the present disclosure relates to a method for forming a film-forming composition comprising a silicon precursor as described in any of the above paragraphs. The method comprises supplying a halogen-substituted 1,3-disilacyclobutane reactant comprising at least one halogen substituent, and Q 1 This includes replacing a substituent with a silicon precursor. The step of replacing at least one halogen substituent of the halogen-substituted 1,3-disilacyclobutane reactant may include contacting the halogen-substituted 1,3-disilacyclobutane reactant with an organometallic salt, the organometallic salt containing the Q1 substituent. 1 The substituents may be selected from the group consisting of acetoxy groups, acryloyloxy groups, C1-C6 alkoxy groups, silyloxy groups, gelmyloxy groups, phosphonooxy groups, and alkylamine groups.

[0021] In some of these embodiments, the organometallic salt is M(Q 1 ) n It has the general structure, where (i) M is a group I metal and n is an integer equal to 1, or (ii) M is a group II metal and n is an integer equal to 2.

[0022] In some embodiments, the organometallic salt is selected from the group consisting of metal acetates, metal acrylates, metal oxides, metal phosphates, metal silicon oxides, metal gelmyl oxides, and metal amides.

[0023] In some embodiments, the halogen-substituted 1,3-disilacyclobutane reactant is selected from the group consisting of 1-chloro-1,3-disilacyclobutane, 1-chloro-1,3,3-trimethyl-1,3-disilacyclobutane, 1,3-dichloro-1,3-disilacyclobutane, 1,3-dichloro-1,3-dimethyl-1,3-disilacyclobutane, 1,1,3,3-tetrachloro-1,3-disilacyclobutane, 1-bromo-1,3-disilacyclobutane, 1-bromo-1,3,3-trimethyl-1,3-disilacyclobutane, 1,3-dibromo-1,3-disilacyclobutane, 1,3-dibromo-1,3-dimethyl-1,3-disilacyclobutane, and 1,1,3,3-tetrabromo-1,3-disilacyclobutane.

[0024] In some embodiments, the method further includes separating a silicon precursor from a metal halide salt.

[0025] In certain embodiments, the step of supplying a halogen-substituted 1,3-disilacyclobutane reactant includes stereoselectively forming a 1,3-disilacyclobutane intermediate and reacting the 1,3-disilacyclobutane intermediate to form a halogen-substituted 1,3-disilacyclobutane reactant. In some of these embodiments, the 1,3-disilacyclobutane intermediate is a second 1,3-disilacyclobutane intermediate, and the method further includes stereoselectively forming a first 1,3-disilacyclobutane intermediate and forming a second 1,3-disilacyclobutane intermediate from the first 1,3-disilacyclobutane intermediate.

[0026] In some embodiments, the silicon precursor is formed such that at least 85% of the silicon precursor is in cis isomer form, or at least 85% of the silicon precursor is in trans isomer form. In some of these embodiments, at least 85% of the silicon precursor is in cis isomer form, or at least 90% of the silicon precursor is in cis isomer form, or at least 95% of the silicon precursor is in cis isomer form, or at least 97% of the silicon precursor is in cis isomer form, or at least 98% of the silicon precursor is in cis isomer form, or at least 99% of the silicon precursor is in cis isomer form, or at least 99.5% of the silicon precursor is in cis isomer form. In some other embodiments of these embodiments, at least 85% of the silicon precursor is in trans isomer form, or at least 90% of the silicon precursor is in trans isomer form, or at least 95% of the silicon precursor is in trans isomer form, or at least 97% of the silicon precursor is in trans isomer form, or at least 98% of the silicon precursor is in trans isomer form, or at least 99% of the silicon precursor is in trans isomer form, or at least 99.5% of the silicon precursor is in trans isomer form.

[0027] Another aspect of the present disclosure relates to a vapor delivery vessel comprising a film-forming composition comprising a silicon precursor as described in any of the relevant paragraphs above. The vapor delivery vessel comprises an outer wall enclosing a cavity for storing the film-forming composition and a gas outlet for allowing vapor of the film-forming composition to exit the cavity.

[0028] In some embodiments, the vapor delivery vessel further comprises a gas inlet and a conduit extending within a cavity to a fixed point. The conduit may extend within the cavity and into the film-forming composition to allow the carrier gas to pass through to the film-forming composition. Alternatively, the conduit may extend within the cavity to a point above the film formation to allow the carrier gas to pass over the surface of the film-forming composition.

[0029] In some embodiments, the steam delivery vessel further comprises a probe member. The probe member may comprise one or more temperature sensors and / or one or more level sensors and one or more pressure sensors.

[0030] In some embodiments, the outer walls and cavities of the steam delivery vessel are formed from stainless steel.

[0031] Another aspect of the present disclosure relates to a method for forming a carbon-doped silicon-containing film using a film-forming composition comprising a silicon precursor as described in any of the relevant paragraphs above. The method comprises supplying a substrate in a reaction space and exposing the surface of the substrate to vapors of the film-forming composition. In some embodiments, the method further comprises exposing the surface of the substrate to co-reactants.

[0032] In some embodiments, a method for forming a carbon-doped silicon-containing film includes performing one or more deposition cycles of a periodic deposition process, which includes exposing the surface of a substrate to a film-forming composition and exposing the surface of the substrate to a co-reacting material, thereby forming a carbon-doped silicon-containing film on the surface of the substrate. The exposure step may be repeated once or more times (n times). The periodic deposition process may include one or more of the ALD process and periodic CVD process.

[0033] In some embodiments, the co-reacting material includes a plasma species. The plasma species may be one or more of a hydrogen plasma species, a noble gas plasma species, a nitrogen plasma species, and an oxygen plasma species. In some of these embodiments, the co-reacting material is plasma. In some of these embodiments, the method further includes exposing the surface of a substrate to plasma. The plasma may be one or more of a hydrogen plasma, a noble gas plasma, a nitrogen plasma, and an oxygen plasma. In some embodiments, the plasma is one or more of a hydrogen plasma and a noble gas plasma.

[0034] In certain embodiments, the co-reacting material does not contain oxygen plasma species. In some of these embodiments, the surface of the substrate is not exposed to oxygen plasma or oxygen plasma species.

[0035] In certain embodiments, the surface of the substrate is directly exposed to the plasma. In certain other embodiments, the surface of the substrate is exposed to the plasma at a distance.

[0036] In some embodiments, the steps of exposing the surface of the substrate to a vapor of a film-forming composition and exposing the surface of the substrate to a co-reacting substance are performed sequentially. In some other embodiments, the steps of exposing the surface of the substrate to a vapor of a film-forming composition and exposing the surface of the substrate to a co-reacting substance overlap at least partially.

[0037] In some embodiments, the reaction space is purged after one or more of the following: the surface of the substrate is exposed to the vapor of the film-forming composition, and the surface of the substrate is exposed to co-reactants.

[0038] In some embodiments, the method further includes maintaining the temperature of the substrate at about 450°C or less during one or both exposure steps. The temperature of the substrate may be maintained at least at about 100°C to about 400°C or less, or at least at about 100°C to about 300°C or less, or at least at about 100°C to about 250°C or less.

[0039] Another aspect of the present disclosure relates to a system for forming a carbon-doped silicon-containing film using a film-forming composition comprising a silicon precursor as described in any of the relevant paragraphs above, in accordance with a method described in any of the relevant paragraphs above. The system may comprise a reaction space for containing a substrate and means for exposing the surface of the substrate to vapors of the film-forming composition. The system may further comprise means for exposing the surface of the substrate to co-reactants and, optionally, means for purging the reaction space after one or both exposure steps.

[0040] In some embodiments, the system comprises a reaction space for containing a substrate, a film-forming composition source for providing vapor of a forming composition which is in gas communication with the reaction space via a first valve, a co-reacting material source for providing co-reacting material which is in gas communication with the reaction space via a second valve, and a plasma generator.

[0041] In some embodiments, the system further comprises a controller operably connected to a first valve, a second valve, and a plasma generator, the controller being configured and programmed to control the supply of a film-forming composition into the reaction space, the supply of co-reactants into the reaction space, and the activation of the plasma generator. The controller may be programmed to repeat various process steps n times in order to deposit a carbon-doped silicon-containing film on the surface of the substrate.

[0042] In some embodiments, the plasma generator comprises a direct plasma unit. In some other embodiments, the plasma generator comprises a remote plasma unit.

[0043] In some embodiments, the reaction space comprises one or more heating elements thermally connected to the substrate, and one or more thermocouples for measuring and maintaining the temperature of the substrate at a set temperature. In some of these embodiments, a controller is operably connected to one or more heating elements and one or more thermocouples, and is configured and programmed to measure and control the temperature of at least one heating element to maintain the temperature of the substrate at a set temperature.

[0044] In some embodiments, the film-forming composition source includes a vapor delivery vessel containing the film-forming composition.

[0045] Another aspect of the present disclosure relates to carbon-doped silicon films formed using a film-forming composition comprising a silicon precursor as described in any of the relevant paragraphs above, and further formed using the methods and systems described in any of the relevant paragraphs above.

[0046] In some embodiments, the carbon-doped silicon film includes a silicon precursor and / or a portion or fragment of the silicon precursor.

[0047] In some embodiments, the carbon-doped silicon-containing film has a carbon content of at least about 5 atomic percent and about 50 atomic percent or less, or at least about 10% and about 50% or less, or at least about 20% and about 50% or less.

[0048] In some embodiments, the carbon-doped silicon-containing film has a dielectric constant (κ) of less than about 4.2, or less than about 4.0, or less than about 3.8, or less than about 3.5, or less than about 3.4, or less than about 3.3, or less than about 3.2, or less than about 3.1, or less than about 3.0, or less than about 2.9, or less than about 2.8, or less than about 2.7, or less than about 2.6, or less than about 2.5, or less than about 2.4, or less than about 2.3, or less than about 2.2, or less than about 2.1, or less than about 2.0.

[0049] In some embodiments, the carbon-doped silicon-containing film has a step coverage of about 80% or more, or about 90% or more. In some of these embodiments, the carbon-doped silicon-containing film has a step coverage of more than about 90% and less than about 110%, or about 95% or more and less than about 105%.

[0050] Those skilled in the art will readily see these and other embodiments from the detailed description of certain embodiments below and from further reference to the accompanying drawings. These embodiments or their components may be combined or applied separately as needed, unless otherwise stated. The present invention is not limited to any particular embodiment disclosed.

[0051] The accompanying drawings constitute part of this specification. The drawings are included to provide a further understanding of this disclosure and, together with the description, illustrate certain principles of this disclosure. The drawings illustrate exemplary embodiments of how this disclosure may be manufactured and used, and should not be construed as limiting this disclosure to only the exemplary and described embodiments. Naturally, elements in the drawings are illustrated for simplicity and clarity and are not necessarily drawn to actual size. The examples presented in this disclosure do not mean that they are the actual appearance of any particular material, structure, or device, but are merely idealized representations used to illustrate embodiments of this disclosure. For example, some dimensions of elements in the drawings may be exaggerated relative to other elements to help improve understanding of the illustrated embodiments of this disclosure. Further features and advantages will become apparent from the following more detailed description of the various aspects, embodiments, and configurations of this disclosure, as illustrated by the drawings referenced below. [Brief explanation of the drawing]

[0052] [Figure 1] Figure 1 shows an embodiment of a synthesis scheme for preferentially forming the trans isomer morphology of a silicon precursor. [Figure 2] Figure 2 shows another embodiment of a synthesis scheme for preferentially forming the trans isomer morphology of the silicon precursor. [Figure 3] Figure 3 shows an embodiment of a synthesis scheme for preferentially forming the cis isomer form of the silicon precursor. [Figure 4] Figure 4 is a process flow diagram of a method for forming a carbon-doped silicon-containing film according to an embodiment of the present disclosure. [Figure 5] Figure 5 is a schematic diagram of a semiconductor processing system suitable for forming a carbon-doped silicon-containing film according to an embodiment of the present disclosure. [Figure 6] Figure 6 is a perspective view of a vapor delivery vessel according to an embodiment of the present disclosure, showing a film-forming composition stored therein. [Modes for carrying out the invention]

[0053] The descriptions of embodiments of compositions, methods, and systems provided below are illustrative and intended for illustrative purposes only. The following descriptions are not intended to limit the scope of the disclosure or the claims. Furthermore, the enumeration of numerous embodiments having the described features is not intended to exclude other embodiments having additional features or incorporating different combinations of the described features. Unless otherwise stated, the exemplary embodiments or their components may be combined or applied separately. Headings provided herein, if any, are for convenience only and do not necessarily affect the scope or meaning of the claimed invention.

[0054] definition As used herein, “Atomic Layer Deposition” (ALD) refers to a deposition process in which a deposition cycle, e.g., multiple consecutive deposition cycles, takes place within a reaction space (e.g., one or more reaction chambers). Generally, in an ALD process, during each deposition cycle, a precursor is introduced into the reaction space and adsorbed onto the substrate surface, which may contain materials deposited in previous ALD cycles or other materials, and this adsorption forms up to one molecular layer of the precursor that does not readily react with additional excess precursors (i.e., a self-limiting reaction). Subsequently, in some examples, another precursor or reactant may be introduced into the reaction space to convert the adsorbed precursor onto the substrate surface into the desired material. Other reaction steps may be included in the deposition cycle. ALD can occur by a thermal process (thermal ALD) in which the reaction is facilitated by increasing the temperature of the substrate relative to the ambient temperature, or by a plasma-enhanced process (PE-ALD) or radical-enhanced process (RE-ALD) in which the reaction is facilitated through the use of energy plasma species. ALD, as used herein, may also mean processes represented by the relevant terms, such as chemical vapor deposition, atomic layer epitaxy (ALE), molecular beam epitaxy (MBE), gas source MBE, or organometallic MBE, and chemical beam epitaxy, when performed with alternating pulses of reactants.

[0055] As used herein, "chemical vapor deposition," abbreviated as "CVD," refers to a vapor deposition process in which a film is deposited on a substrate by exposing its surface to one or more gaseous precursors and reactants that react and / or decompose on the surface of the substrate to form a film. The precursors and / or reactants may be supplied simultaneously to the reaction space or in partially or completely separated pulses. In some embodiments, the precursors and / or reactants are supplied until a layer of the desired thickness is deposited. In some embodiments, a periodic CVD process can be used in multiple cycles to deposit a thin film of the desired thickness. In a periodic CVD process, the precursors and / or reactants may be supplied to the reaction space in non-overlapping, partially or completely overlapping pulses. CVD may be generated by a thermal process (thermal CVD) in which the reaction is facilitated by raising the temperature of the substrate relative to the ambient temperature, or by a plasma-enhanced process (PE-CVD) in which the reaction is facilitated using an energy plasma species.

[0056] As used herein, “cyclic deposition process” refers to the process of sequentially introducing precursors and / or reactants into a reaction space to deposit layers or films on or covering a substrate, and includes processing techniques such as ALD, cyclic chemical vapor deposition, and hybrid cyclic deposition processes, which include ALD components and cyclic chemical vapor deposition (CVD) components. In preferred embodiments, the cyclic deposition process disclosed herein refers to an ALD process.

[0057] As used herein, the interchangeable terms “film” or “layer” refer to a continuous, substantially continuous, or discontinuous material that extends perpendicular to the thickness direction and covers at least a portion of a surface. Films may be located on the lateral surfaces and / or sidewalls of recessed features of a surface. Films may include two-dimensional materials, three-dimensional materials, nanoparticles, partial or complete molecular layers, partial or complete atomic layers, and / or clusters of atoms or molecules. Films may be constructed from one or more indistinguishable monolayers or sub-monolayers to produce a uniform or substantially uniform material, the number of monolayers or sub-monolayers affecting the thickness of the film.

[0058] As used herein, “gas” refers to a state of matter consisting of atoms or molecules that has no defined volume or shape. Gases include vaporized solids and / or liquids, which may be called vapors. Depending on the context, gases may consist of a single gas or a mixture of gases.

[0059] As used herein, “precursor” means a compound that participates in a chemical reaction to form another compound or element, and a portion of the precursor (an element or group within the precursor) is incorporated into the compound or element resulting from the chemical reaction. The compound or element resulting from the chemical reaction may be a layer and / or film formed on the surface of a substrate.

[0060] As used herein, the term "purge" may refer to a procedure for removing vapor phase precursors, reactants, and / or vapor phase by-products from a substrate surface, for example, by evacuating the reaction space with a vacuum pump and / or by replacing the gas in the reaction space with an inert or nearly inert gas such as argon or nitrogen.

[0061] As used herein, “reactant” refers to a compound that participates in a chemical reaction to form another compound or element. In some examples, the reactant is a precursor. In other examples, the compound or element obtained from the chemical reaction does not contain any part or a significant part (an element or group in the reactant), and therefore the reactant is not a precursor.

[0062] As used herein, “substrate” refers to a base material(s) that may be used to form a device, circuit, material, or material layer, or a base material(s) on which a device, circuit, material, or material layer may be formed. “Substrate” may be continuous or discontinuous, rigid or flexible, solid or porous, or a combination thereof. The substrate may be in any form, such as powder, sheet, plate, or workpiece. A substrate in sheet form may extend outside the process / reaction chamber in which the deposition process takes place, and in some examples may move through the chamber, thereby allowing the process to continue until it reaches the edge of the substrate. A substrate in plate form may include wafers of various shapes and sizes. The substrate may be made from semiconductor materials, such as silicon, silicon germanium, silicon oxide, gallium arsenide, gallium nitride, and silicon carbide. The substrate may include one or more layers on top of a bulk material, for example, the substrate may include nitrides such as TiN, oxides, insulating materials, dielectric materials, conductive materials, metals (e.g., tungsten, ruthenium, molybdenum, cobalt, aluminum, or copper) or other metallic materials, crystalline materials, epitaxial, heteroepitaxial, and / or single-crystal materials. The substrate may include various topologies formed in or on at least a portion of the layers of the substrate, such as gaps, recesses, lines, trenches, vias, holes, or spaces between rising portions such as fins, and the like.

[0063] As used herein, “step coverage” refers to the percentage obtained by dividing the growth rate of the layer on the distal end face of the recess by the growth rate of that layer on the proximal end face of the recess. Step coverage provides a measure of layer suitability.

[0064] As used herein, “vapor delivery vessel” refers to a vessel configured for vapor delivery of a substance contained within the vessel. A vapor delivery vessel comprises an outer wall enclosing a cavity for storing and / or holding the substance, and a fluid outlet for allowing the vapor of the substance to exit the cavity. The substance contained in the cavity may be a composition suitable for vapor deposition. For example, the substance contained in the cavity may include one or more precursors. The substance contained in the cavity may be a homogeneous or heterogeneous mixture. The substance contained in the cavity may be in solid form, liquid form, gaseous form, or a combination thereof. A vapor delivery vessel may have a vapor extraction configuration, a carrier gas configuration, a double-wall configuration, a sublimation configuration, and / or other configurations.

[0065] As used herein, "wet etching rate," abbreviated as "WER," refers to the rate of material loss when a material is exposed to a liquid etching agent. For example, WER may refer to the loss of material from a layer, which can be determined by measuring the decrease in the thickness of the layer as a function of time. In some embodiments, WER may be measured by exposing the layer to diluted hydrofluoric acid (dHF).

[0066] The article "a" or "an" can, depending on the context, refer to a species or genus that includes multiple species. Thus, the terms "a / an," "one or more," and "at least one" can be used interchangeably in this specification.

[0067] The terms "comprising," "including," and "having" do not exclude the existence of other elements or components unless the context clearly indicates otherwise. "Comprising," "including," and "having" are interchangeable and include the meaning of "consisting of." However, the phrase "consisting of" indicates that no other features or components exist besides those stated, unless the context otherwise indicates.

[0068] When applied to values, the term "approximately" generally refers to a range of numbers considered equivalent to a list of values ​​(e.g., having the same function or result). In some examples, the term "approximately" may include numbers rounded to the nearest significant figure.

[0069] When applied to compositions, methods, systems, or structures, the term “essentially” generally means that additional components do not substantially modify the properties, characteristics, and / or functions of the composition, method, system, or structure.

[0070] When applied to compositions, methods, systems, or structures, the term “substantially” generally refers to a percentage of a value, property, feature, etc., that is at least about 70%, or at least about 80%, or at least about 90%, or at least about 95%, or at least about 97%, or at least about 98%, or at least about 99%, or at least about 99.5%, or at least about 99.9%, or more, or any percentage between about 70% and about 100%. In some embodiments, the term “substantially” means a percentage of about 85%, or about 90%, or about 95%, or about 97%, or about 98%, or about 99%, or about 99.5%, or about 99.9%.

[0071] The terms "on" or "over" can be used to describe relative positional relationships. For example, an element, membrane, or layer may be directly positioned on or covering at least a portion of another element, membrane, or layer, and may be in physical contact with it, or an element, membrane, or layer may be on or over another element, membrane, or layer, but may have one or more intervening elements, membranes, or layers between them. Thus, unless the term "directly" is used separately, the terms "on" or "over" are interpreted as relative concepts. Similarly, the terms "below," "below," or "below" describe relative positional relationships and should be interpreted as relative concepts unless otherwise indicated.

[0072] The terms “at least one,” “one or more,” and “and / or” are open-ended expressions that function as both conjunctions and disjunctions. For example, the expressions “at least one of A, B, and C,” “at least one of A, B, or C,” “one or more of A, B, and C,” and “one or more of A, B, or C,” as well as “A, B, and / or C,” mean A alone, B alone, C alone, a combination of A and B, a combination of A and C, a combination of B and C, or a combination of A, B, and C. Each of A, B, and C in the above expressions may be an element such as Q, Y, and Z, or Q1-X n Y1-Y m , and Z1-Z o When referring to classes of elements such as Q, Y, and Z, the term is intended to refer to a single element selected from Q, Y, and Z, a combination of elements selected from the same class (e.g., Q1 and Q2), and a combination of elements selected from two or more classes (e.g., Y1 and Z1).

[0073] All numerical ranges described throughout this disclosure include upper and lower limits, and it should be understood that any narrower numerical ranges included within such broad ranges are also deemed to be as if they were all explicitly described herein. For example, expressions such as “approximately 2 to approximately 4” or “2 to 4” include 2 and 4, and whole numbers and / or integers are in the range of approximately 2 to approximately 3, approximately 3 to approximately 4, and each possible range is based on real numbers (e.g., irrational and / or rational numbers), such as approximately 2.1 to approximately 3.9, approximately 2.1 to approximately 3.4, etc.

[0074] Standard abbreviations for the elements of the periodic table are used herein.

[0075] Throughout this disclosure, in certain places, compounds, functional groups of compounds, or substituents or ligands may be referred to by their chemical name (e.g., IUPAC name or common name), an abbreviated molecular formula, or both. Additionally or alternatively, compounds may be provided in stick form (skeletal structure) or partial stick form (skeletal structure) and may be represented by a structure in which hydrogen atoms may be omitted. If there is a discrepancy between the chemical name and / or molecular formula and / or structure and the identity of a compound, functional group, or substituent or ligand that cannot be clearly determined by a person skilled in the art, the structure shall prevail, followed by the molecular formula.

[0076] In this disclosure, any defined meaning does not necessarily exclude the ordinary and common meanings in some embodiments.

[0077] explanation Compositions configured to form and / or suitable for forming carbon-doped silicon-containing films are disclosed herein. The film-forming compositions include a 1,3-disilacyclobutane core and a silicon precursor having a structure comprising at least one substituent bonded to the silicon atom of the 1,3-disilacyclobutane core, selected from an acetoxy group, an acryloyloxy group, a C1-C6 alkoxy group, a silyloxy group, a gelmyloxy group, a phosphonooxy group, and an alkylamine group. Methods for preparing film-forming compositions, as well as deposition methods and systems for forming carbon-doped silicon-containing films using such compositions, are also disclosed herein.

[0078] As used herein, a carbon-doped silicon-containing film refers to a film containing silicon (Si), oxygen (O), and carbon (C). In some embodiments, a carbon-doped silicon-containing film contains one or more other elements in addition to Si, O, and C, such as nitrogen (N) and / or hydrogen (H). In some embodiments, a carbon-doped silicon-containing film contains silicon oxycarbide (SiOC) (which may also be called silicon carbon oxide (SiCO) in the literature). In some embodiments, a carbon-doped silicon-containing film consists of or essentially consists of silicon oxycarbide (SiOC). In some embodiments, a carbon-doped silicon-containing film contains silicon carbonitride (SiOCN). In some embodiments, a carbon-doped silicon-containing film consists of or essentially consists of silicon carbonitride (SiOCN). In some embodiments, a carbon-doped silicon-containing film may contain Si-C bonds and Si-O bonds, but not Si-N bonds. However, in some other embodiments, a carbon-doped silicon-containing film contains Si-C bonds, Si-O bonds, and Si-N bonds. In some embodiments, the ratio of Si-O bonds to Si-C bonds is about 1:1 to about 10:1. In some embodiments, the carbon-doped silicon film contains about 0.1% to about 70% carbon on an atomic basis. In some embodiments, the carbon-doped silicon film contains about 0.5% to about 60%, or about 1% to about 50%, or about 5% to about 50%, or about 10% to about 50%, or about 20% to about 50% carbon on an atomic basis. In some embodiments, the carbon-doped silicon film contains about 5% to about 70% oxygen on an atomic basis. In some embodiments, the carbon-doped silicon film contains about 10% to about 70%, or about 15% to about 50%, or about 20% to about 40% oxygen on an atomic basis. In some embodiments, the carbon-doped silicon film contains about 5% to about 50% silicon on an atomic basis. In some embodiments, the carbon-doped silicon-containing film contains about 10% to about 50%, or about 15% to about 40%, or about 20% to about 35% silicon on an atomic basis. In some embodiments, the carbon-doped silicon-containing film does not contain nitrogen.In some other embodiments, the carbon-doped silicon-containing film contains about 0.1% to about 50%, or about 0.1% to about 40%, or about 0.1% to about 30%, or about 0.1% to about 25%, or about 0.1% to about 20%, or about 0.1% to about 15%, or about 0.1% to about 10% of nitrogen on an atomic basis. In some embodiments, the carbon-doped silicon-containing film further contains hydrogen. In some embodiments, the carbon-doped silicon-containing film contains about 0.1% to about 35%, or about 0.1% to about 20%, or about 0.1% to about 15%, or about 0.1% to about 10%, or about 0.1% to about 5% of hydrogen on an atomic basis.

[0079] One aspect of the present disclosure relates to a film-forming composition suitable for forming a carbon-doped silicon-containing film. The film-forming composition comprises a silicon precursor having a structure comprising a 1,3-disilacyclobutane core and at least one substituent bonded to a silicon atom of the disilacyclobutane core, selected from an acetoxy group, an acryloyloxy group, a C1-C6 alkoxy group, a silyloxy group, a gelmyloxy group, a phosphonooxy group, and an alkylamine group. More specifically, in several embodiments, the silicon precursor is a compound of the general formula (1)(Chemical Formula 2)(wherein Q 1 Q is a substituent selected from an acetoxy group, an acryloyloxy group, a C1-C6 alkoxy group, a silyloxy group, a gelmyloxy group, a phosphonooxy group, and an alkylamine group. 2 Q 3 , and Q 4 Each of these substituents is independently selected from a hydrogen atom, a C1-C6 alkyl group, an acetoxy group, an acryloyloxy group, a C1-C6 alkoxy group, a silyloxy group, a gelmyloxy group, a phosphonooxy group, and an alkylamine group.

[0080] [ka]

[0081] Regarding general formula (1), the acetoxy group is represented by the chemical formula CH3C(=O)O. The acryloyloxy group is represented by the chemical formula H2C=C(R)C(=O)O, where R is a hydrogen atom or an alkyl group, typically a C1-C6 alkyl group, more typically a methyl group. Therefore, the acryloyloxy group may refer to acryloyloxy (H2C=CHC(=O)O), methacryloyloxy (H2C=C(CH3)C(=O)O), etc. The C1-C6 alkoxy group may have a linear or branched structure, such as methoxy (CH3O), ethoxy (C2H5O), isopropoxy (i-C3H7O), n-propoxy (n-C3H7O), butoxy (C4H9O), pentoxy (C5H 11 O), and hexoxy group (C6H 13 The silyloxy group may be selected from (O), typically from methoxy (CH3O) and ethoxy (C2H5O). The silyloxy group is represented by the chemical formula R3SiO, where each R is an independently selected alkyl group, typically a C1-C6 alkyl group, more typically a methyl group. A good example of a silyloxy group is trimethylsilyloxy ((CH3)3SiO). The gelmyloxy group is represented by the chemical formula R3GeO, where each R is an independently selected alkyl group, typically a C1-C6 alkyl group, more typically a methyl group. A good example of a gelmyloxy group is trimethylgelmyloxy ((CH3)3GeO). The phosphonooxy group is represented by the chemical formula (RO)2P(=O)O, where each R is an independently selected alkyl group, typically a C1-C6 alkyl group, more typically a methyl group. A good example of a phosphonooxy group is dimethylphosphonooxy ((CH3O)2P(=O)O). Alkylamine groups are represented by the chemical formula NR2, where each R is an independently selected alkyl group, typically a C1-C6 alkyl group. Suitable examples of alkylamine groups include dimethylamine (N(CH3)2), diethylamine (N(C2H5)2), and di-isopropylamine (N(i-C3H7)2). C1-C6 alkyl groups may have a linear or branched structure, such as methyl (CH3), ethyl (C2H5), propyl (C3H7), butyl (C4H9), and pentyl (C5H)11 ), and hexyl (C6H 13 They may be selected from ) and are typically selected from methyl (CH3) and ethyl (C2H5).

[0082] In some embodiments, Q 1 Q is a substituent selected from an acetoxy group, an acryloyloxy group, a C1-C6 alkoxy group, a silyloxy group, a gelmyloxy group, a phosphonooxy group, and an alkylamine group. 2 Q 3 , and Q 4 These are a hydrogen atom, a C1-C6 alkyl group, and Q, respectively. 1 A substituent independently selected from the same substituents. In some of these embodiments, Q 1 and Q 3 are the same substituent (i.e., Q 1 =Q 3 Therefore, in these embodiments, general formula (1) can be expressed as follows (Chemical Formula 3).

[0083] [ka]

[0084] Furthermore, in some of these embodiments, Q 1 and Q 3 Q is the same substituent. 2 and Q 4 These are the same substituent (i.e., Q 1 =Q 3 and Q 2 =Q 4 Therefore, in these embodiments, general formula (1) can be expressed as follows (Chemical Formula 4).

[0085] [ka]

[0086] In some embodiments, the silicon precursor has a structure according to general formula (1), where Q1 and Q 3 is subordinately selected from the group consisting of an acetoxy group, an acryloyloxy group, a C1-C6 alkoxy group, a siloxy group, a germyloxy group, a phosphonooxy group, and an alkylamine group, and Q 2 and Q 4 are each subordinately selected from the group consisting of a hydrogen atom and a C1-C6 alkyl group. For example, Q 1 and Q 3 may each be an acetoxy group, and Q 2 and Q 4 may each be subordinately selected from a hydrogen atom or a C1-C6 alkyl group. In another example, Q 1 and Q 3 may each be an acryloyloxy group, and Q 2 and Q 4 may each be subordinately selected from a hydrogen atom or a C1-C6 alkyl group. In yet another example, Q 1 and Q 3 may each be a C1-C6 alkoxy group, and Q 2 and Q 4 may each be subordinately selected from a hydrogen atom or a C1-C6 alkyl group. In yet another example, Q 1 and Q 3 may each be a silyloxy group, and Q 2 and Q 4 may each be subordinately selected from a hydrogen atom or a C1-C6 alkyl group. In yet another example, Q 1 and Q 3 may each be a germyloxy group, and Q 2 and Q 4 may each be subordinately selected from a hydrogen atom or a C1-C6 alkyl group. In yet another example, Q 1 and Q 3 may each be a phosphonooxy group, and Q 2 and Q 4 may each be subordinately selected from a hydrogen atom or a C1-C6 alkyl group. In yet another example, Q 1 and Q 3may each be an alkylamine group, Q 2 and Q 4 may each be independently selected from a hydrogen atom or a C1-C6 alkyl group.

[0087] Suitable examples of silicon precursors having the structure according to general formula (1) (where Q 1 =Q 3 and Q 2 =Q 4 ) include the structures shown in Table 1 (Table 1 and Table 2 below).

[0088]

Table 1

[0089]

Table 2

[0090] In certain embodiments of the present disclosure, the silicon precursor represented by general formula (1) may include both cis and trans isomers (Chemical Formula 5).

[0091]

Chemical Formula

[0092] In the cis isomeric form, both substituents Q 1 and Q[[ID=5​​​​One of the isomers is located at the axial position of the disilacyclobutane ring, and the other is located at the equatorial position of the disilacyclobutane ring. As a non-limiting example, the silicon precursors shown in Table 1 may be in cis-isomer and trans-isomer forms. Therefore, the film-forming composition may include a mixture of cis-isomers and trans-isomers. However, for certain applications, it may be desirable to have an isomerically pure composition or at least an isomerically concentrated composition. For example, in thin-film deposition applications, an isomerically pure (or isomerically concentrated) composition may provide a film with less variability in film structure. While we do not wish to be bound by any particular theory, isomers may interact differently with the substrate surface, which can lead to variations in film structure. This can be exacerbated if the ratio of the two isomers in the gas phase changes over time during film deposition due to slight differences in the vapor pressures of the two isomers. In this regard, in some embodiments, the film-forming composition comprises a silicon precursor having a structure according to general formula (1), which may be mainly in cis-isomer or trans-isomer form, or substantially in cis-isomer or trans-isomer form. In some of these embodiments, at least about 70% of the silicon precursor is in cis-isomer form, or at least about 75% of the silicon precursor is in cis-isomer form, or at least about 80% of the silicon precursor is in cis-isomer form, or at least about 85% of the silicon precursor is in cis-isomer form, or at least about 90% of the silicon precursor is in cis-isomer form, or at least about 95% of the silicon precursor is in cis-isomer form, or at least about 97% of the silicon precursor is in cis-isomer form, or at least about 98% of the silicon precursor is in cis-isomer form, or at least about 99% of the silicon precursor is in cis-isomer form, or at least about 99.5% of the silicon precursor is in cis-isomer form.In other words, in some embodiments, the ratio of cis-isomers to trans-isomers of the silicon precursor in the film-forming composition is at least about 70:30, or at least about 75:25, or at least about 80:20, or at least about 85:15, or at least about 90:10, or at least about 95:5, or at least about 97:3, or at least about 98:2, or at least about 99:1, or at least about 99.5:0.5. In some of these embodiments, the silicon precursor may be substantially in cis-isomer form, or essentially in cis-isomer form. Alternatively, in some of these embodiments, at least about 70% of the silicon precursor is in trans isomer form, or at least about 75% of the silicon precursor is in trans isomer form, or at least about 80% of the silicon precursor is in trans isomer form, or at least about 85% of the silicon precursor is in trans isomer form, or at least about 90% of the silicon precursor is in trans isomer form, or at least about 95% of the silicon precursor is in trans isomer form, or at least about 97% of the silicon precursor is in trans isomer form, or at least about 98% of the silicon precursor is in trans isomer form, or at least about 99% of the silicon precursor is in trans isomer form, or at least about 99.5% of the silicon precursor is in trans isomer form. In other words, in some embodiments, the ratio of trans isomers to cis isomers of the silicon precursor in the film-forming composition is at least about 70:30, or at least about 75:25, or at least about 80:20, or at least about 85:15, or at least about 90:10, or at least about 95:5, or at least about 97:3, or at least about 98:2, or at least about 99:1, or at least about 99.5:0.5. In some of these embodiments, the silicon precursor may be substantially in trans isomer form, or essentially in trans isomer form. Such isomerically pure or concentrated compositions can be advantageously formed using the methods disclosed herein.

[0093] According to certain embodiments of the present disclosure, a film-forming composition comprising a silicon precursor having a structure according to general formula (1) can be formed by contacting a halogen-substituted 1,3-disilacyclobutane reactant with an organometallic salt (for example, the metal salt comprising at least one organic group). In some embodiments, a method for forming a film-forming composition comprises supplying a halogen-substituted 1,3-disilacyclobutane reactant comprising at least one halogen substituent, and at least one halogen substituent of the halogen-substituted 1,3-disilacyclobutane reactant comprising Q 1 This includes forming a silicon precursor by replacing substituents with . Exemplary reactions are shown in formulas (1), (2), and (3) (Chemical Formula 6).

[0094] [ka]

[0095] In equations (1), (2), and (3), X represents a halogen such as chlorine (Cl), bromine (Br), and iodine (I), and Q 1 Q 2 Q 3 , and Q 4 The compound has the same substituent assignment as given by the general formula (1) above. The organometallic salt has structure M(Q 1 ) n The formula has the following properties, where M is a metal and n is typically an integer of 1 or 2 depending on the oxidation state of the metal. In the reactions shown in formulas (1), (2), and (3), the halogen group on the halogen-substituted 1,3-disilacyclobutane reactant is Q 1 The substituents are replaced with silicon precursors and metal halide salts (M(X) n ) forms. The silicon precursor may be separated from the metal halide salt, generally by filtration or decantation.

[0096] In some embodiments, the metal (M) of the organometallic salt is selected from Group I or Group II metals. In some embodiments, M is selected from Li, Na, K, Mg, Ca, Ni, Cu, Al, and Zn. In some embodiments, the organometallic salt is selected from the group consisting of metal acetates, metal acrylates, metal oxides, metal phosphates, metal silicon oxides, metal gelmyl oxides, and metal amides. Suitable non-limiting examples of organometallic salt reactants include lithium acetate (Li(OC(=O)CH3)), sodium acetate (Na(OC(=O)CH3)), magnesium acetate (Mg(OC(=O)CH3)2), lithium acrylate (Li(OC(=O)CHCH2)), sodium acrylate (Na(OC(=O)CHCH2)), magnesium acrylate (Mg(OC(=O)CHCH2)2), lithium methacrylate (Li(OC(=O)C(CH3)CH2)), and magnesium methacrylate (Mg(OC(=O)C(CH3)CH2)2). Examples include lithium dimethylamide (Li(N(CH3)2), lithium ethoxide (Li(OCH2CH3)), sodium ethoxide (Na(OCH2CH3)), magnesium ethoxide (Mg(OCH2CH3)2), lithium dimethyl phosphate (Li(OP(=O)(OCH3)2), sodium trimethylsiloxide (Na(OSi(CH3)3), and sodium trimethylgelmyl oxide (Na(OGe(CH3)3)), each of which is commercially available or can be readily synthesized using known methods reported in the literature.

[0097] As shown in formula (1), in some embodiments the halogen-substituted 1,3-disilacyclobutane reactant is monohalo-substituted, and referring to general formula (1), the reaction yields a silicon precursor, where Q 1 Q is selected from acetoxy group, acryloyloxy group, C1-C6 alkoxy group, silyloxy group, gelmyloxy group, phosphonooxy group, and alkylamine group. 2 Q 3 , and Q 4The alkyl group is independently selected from a hydrogen atom or a C1-C6 alkyl group. Suitable monohalo-substituted 1,3-disilacyclobutane reaction materials include 1-chloro-1,3-disilacyclobutane, 1-chloro-1,3,3-trimethyl-1,3-disilacyclobutane, 1-bromo-1,3-disilacyclobutane, and 1-bromo-1,3,3-trimethyl-1,3-disilacyclobutane, each of which is commercially available or can be readily synthesized using known methods reported in the literature.

[0098] As shown in formula (2), in some embodiments the halogen-substituted 1,3-disilacyclobutane reactant is tetrahalo-substituted, and referring to general formula (1), the reaction yields a silicon precursor, where Q 1 Q 2 Q 3 , and Q 4 The group is dependently selected from acetoxy, acryloyloxy, C1-C6 alkoxy, silyloxy, gelmyloxy, phosphonooxy, and alkylamine groups (i.e., Q 1 =Q 2 =Q 3 =Q 4 Suitable tetrahalo-substituted 1,3-disilacyclobutane reaction materials include 1,1,3,3-tetrachloro-1,3-disilacyclobutane and 1,1,3,3-tetrabromo-1,3-disilacyclobutane, each of which is commercially available or can be readily synthesized using known methods reported in the literature.

[0099] As shown in formula (3), in some embodiments the halogen-substituted 1,3-disilacyclobutane reactant is dihalo-substituted, and referring to general formula (1), the reaction yields a silicon precursor, where Q 1 and Q 3 The group is dependently selected from acetoxy, acryloyloxy, C1-C6 alkoxy, silyloxy, gelmyloxy, phosphonooxy, and alkylamine groups (i.e., Q 1 =Q 3 ), Q 2 and Q4 The isomer is selected from a hydrogen atom or a C1-C6 alkyl group. Suitable dihalosubstituted 1,3-disilacyclobutane reactants include 1,3-dichloro-1,3-disilacyclobutane, 1,3-dichloro-1,3-dimethyl-1,3-disilacyclobutane, 1,3-dibromo-1,3-disilacyclobutane, and 1,3-dibromo-1,3-dimethyl-1,3-disilacyclobutane, each of which is commercially available or can be readily synthesized using known methods reported in the literature. Examples of silicon precursors that can be formed from the reaction shown in formula (3) are provided in Table 1. As described above, such silicon precursors may be formed in cis-isomer and trans-isomer forms, resulting in a mixture of the two isomers, which may be undesirable for some applications. Therefore, in some embodiments, the film-forming composition containing the cis / trans isomer mixture may be purified to remove, or at least partially remove, one of the two isomers. A suitable separation method is chromatography. Additionally, or alternatively, such silicon precursors may be formed by modifying the synthetic route to preferentially form either trans or cis isomers. In this regard, the inventors of the present disclosure have designed synthetic routes for substantially forming disclosed film-forming compositions comprising silicon precursors in trans or cis isomeric form.

[0100] In some embodiments of the present disclosure, the silicon precursor is preferentially formed in cis-isomer or trans-isomer form. In some of these embodiments, the ratio of cis-isomers to trans-isomers of the silicon precursor in the film-forming composition is at least about 70:30, or at least about 75:25, or at least about 80:20, or at least about 85:15, or at least about 90:10, or at least about 95:5, or at least about 97:3, or at least about 98:2, or at least about 99:1, or at least about 99.5:0.5. In some of these embodiments, the ratio of trans isomers to cis isomers of the silicon precursor in the film-forming composition is at least about 70:30, or at least about 75:25, or at least about 80:20, or at least about 85:15, or at least about 90:10, or at least about 95:5, or at least about 97:3, or at least about 98:2, or at least about 99:1, or at least about 99.5:0.5. This can be achieved by forming a halogen-substituted 1,3-disilacyclobutane reactant from a 1,3-disilacyclobutane intermediate that is rich in stereoisomers, which are substantially in cis-isomer or substantially in trans-isomer form. Thus, in these embodiments, a method for forming a film-forming composition comprises stereoselectively forming a 1,3-disilacyclobutane intermediate, and then reacting the (stereoisomer-rich) 1,3-disilacyclobutane intermediate to form a halogen-substituted 1,3-disilacyclobutane reactant. As a result, halogen-substituted 1,3-disilacyclobutane reactants are substantially provided in cis-isomer form or substantially in trans-isomer form, based on the dominant stereoisomer of the 1,3-disilacyclobutane intermediate. 1 Subsequent reaction steps involving the exchange of substituents (for example, as shown in formula (3)) also substantially form the corresponding stereoisomers of the silicon precursor.

[0101] Figure 1 shows a general reaction sequence for preferentially forming the trans isomer form of the silicon precursor (1d) according to embodiments of the present disclosure. The silicon precursor (1d) has the structure described by general formula (1), where Q 1 =Q 3 and Q 2 =Q 4 In the reaction sequence, X represents a halogen such as chlorine (Cl), bromine (Br), and iodine (I), M represents a metal, n is an integer, and Q 1 and Q 2 The compound has the same substituent assignment as shown in the general formula (1) above. In the first step of reaction sequence 10, the 1,3-disilacyclobutane intermediate (1b) is formed via a stereoselective ring-forming reaction. The halo(halomethyl)oxysilane reactant (1a) contains bulky substituents (represented by OZ), and therefore the ring-forming reaction substantially forms a trans isomer of the 1,3-disilacyclobutane intermediate (1b). The formation of a cis isomer (not shown) of the 1,3-disilacyclobutane intermediate is sterically undesirable, and therefore any formation of the cis isomer form is minimal. Selection of bulky substituents on the halo(halomethyl)oxysilane reactant (1a) may be done to minimize or eliminate the formation of the cis isomer. Examples of bulky substituents include, but are not limited to, the triphenylmethoxy group, 1,1-bis(1,1-dimethylethyl)-2,2-dimethylpropoxy group, di-tert-butylphenoxy group, or adamantoxy group, as shown in the frame in Figure 1. In the next step of reaction sequence 11, the bulky substituents on the 1,3-disilacyclobutane intermediate (1b) are replaced by halogen atoms by reacting the 1,3-disilacyclobutane intermediate (1b) with a halogen exchange reagent such as boron trihalide (BX3) (e.g., boron tribromide) or acetyl halide (e.g., acetyl chloride). Reaction 11 results in the formation of dihalogen-substituted 1,3-disilacyclobutane (1c), which is substantially a trans isomer. In the final step of reaction sequence 12, the dihalogen-substituted 1,3-disilacyclobutane (1c) is converted to an organometallic salt (M(Q 1 ) n) is reacted with to form a silicon precursor (1d), which is essentially a trans isomer. In particular, reaction 12 for forming the silicon precursor (1d) from dihalogen-substituted 1,3-disilacyclobutane (1c) corresponds to formula (3) shown above.

[0102] Figure 2 shows a general reaction sequence for preferentially forming a trans isomer of a silicon precursor (2e) according to another embodiment of the present disclosure. In the reaction sequence shown, X represents a halogen such as chlorine (Cl), bromine (Br), and iodine (I), M represents a metal, n is an integer, and Q 1 and Q 2 The silicon precursor (2e) has the same substituent assignment as shown in the general formula (1) above. The silicon precursor (2e) has the structure described by the general formula (1), where Q 1 =Q 3 and Q 2 =Q 4 In the first step of reaction sequence 20, the first 1,3-disilacyclobutane intermediate (2b) is formed by reacting with 1,1,3,3-tetrahalo-1,3-disilacyclobutane (2a) (e.g., 1,1,3,3-tetrachloro-1,3-disilacyclobutane or 1,1,3,3-tetrabromo-1,3-disilacyclobutane) via a stereoselective exchange reaction. The co-reactant is a bulky substituent (M(OZ) in Figure 2) that replaces two of the halogen groups on 1,1,3,3-tetrahalo-1,3-disilacyclobutane (2a). nThe metal salt may contain (represented by ). The exchange reaction is stereoselective and substantially forms a trans isomer of the first 1,3-disilacyclobutane intermediate (2b). The formation of a cis isomer (not shown) of the first 1,3-disilacyclobutane intermediate is sterically undesirable, and therefore any formation of the cis isomer form is minimal. Selection of bulky substituents on the metal salt co-reactant may be done to minimize or eliminate the formation of cis isomers. Examples of bulky substituents include, but are not limited to, the triphenylmethoxy group, 1,1-bis(1,1-dimethylethyl)-2,2-dimethylpropoxy group, di-tert-butylphenoxy group, or adamantoxy group, shown in the frame in Figure 2. In the next step 21, the halogen group on the first 1,3-disilacyclobutane intermediate (2b) is exchanged for a hydrogen atom or a C1-C6 alkyl group, generally a methyl group, which collectively form Q 2 It is expressed as follows. Thus, the second 1,3-disilacyclobutane intermediate (2c) is formed from the first 1,3-disilacyclobutane intermediate (2b), and the second 1,3-disilacyclobutane intermediate (2c) is also substantially in trans isomer form. In the next step 22, the bulky substituent can be substituted by reacting the second 1,3-disilacyclobutane intermediate (2c) with a halogen exchange reagent such as boron trihalide (BX3) (e.g., boron tribromide) or acetyl halide (e.g., acetyl chloride). The reaction results in the formation of dihalogen-substituted 1,3-disilacyclobutane (2d), which is substantially in trans isomer form. In the final step of reaction sequence 23, the dihalogen-substituted 1,3-disilacyclobutane (2d) is converted to an organometallic salt (M(Q 1 ) n ) is reacted with to form a silicon precursor (2e), which is essentially a trans isomer. In particular, reaction 23, which forms the silicon precursor (2e) from dihalogen-substituted 1,3-disilacyclobutane (2d), corresponds to formula (3) shown above.

[0103] Figure 3 shows a typical reaction sequence for preferentially forming the cis isomer form of the silicon precursor (3e) according to embodiments of the present disclosure. In the reaction sequence, X represents a halogen such as chlorine (Cl), bromine (Br), and iodine (I), M represents a metal, n is an integer, and Q 1 and Q 2 The silicon precursor (3e) has the same substituent assignment as shown in the general formula (1) above. The silicon precursor (3e) has the structure described by the general formula (1), where Q 1 =Q 3 and Q 2 =Q 4 In the first step of reaction sequence 30, the first 1,3-disilacyclobutane intermediate (3b) is formed by reacting 1,1,3,3-tetrahalo-1,3-disilacyclobutane (3a) (e.g., 1,1,3,3-tetrachloro-1,3-disilacyclobutane or 1,1,3,3-tetrabromo-1,3-disilacyclobutane) via a stereoselective exchange reaction in the presence of a base (e.g., RNH2, where R is an alkyl group). The co-reactant may be a diol such as 1,2-ethenediol, 1,2-ethinediol, or hydroquinone, which are shown in the frame in Figure 3. The diol co-reactant replaces two of the halogen groups on 1,1,3,3-tetrahalo-1,3-disilacyclobutane (3a) with bridging substituents. The reaction substantially forms a cis isomer of the 1,3-disilacyclobutane intermediate (3b). Preferably, the reaction should be carried out under dilution conditions to minimize the linkage of two or more 1,1,3,3-tetrahalo-1,3-disilacyclobutane reactants. The formation of a trans isomer (not shown) of the first 1,3-disilacyclobutane intermediate is sterically undesirable, and therefore any formation of a trans isomer is minimal. In the following step 31, the halogen groups on the first 1,3-disilacyclobutane intermediate (3b) are replaced with hydrogen atoms or C1-C6 alkyl groups, generally methyl groups, which collectively form Q 2It is expressed as follows. Therefore, the second 1,3-disilacyclobutane intermediate (3c) is formed from the first 1,3-disilacyclobutane intermediate (3b), and the second 1,3-disilacyclobutane intermediate (3c) is also substantially in cis isomer form. In the next step 32, the bridging substituent may be substituted by reacting the second 1,3-disilacyclobutane intermediate (3c) with a halogen exchange reagent such as boron trihalide (BX3) (e.g., boron tribromide) or acetyl halide (e.g., acetyl chloride). The reaction results in the formation of dihalogen-substituted 1,3-disilacyclobutane (3d), which is substantially in cis isomer form. In the final step of reaction sequence 33, the dihalogen-substituted 1,3-disilacyclobutane (3d) is converted to an organometallic salt (M(Q 1 ) n ) is reacted with to form a silicon precursor (3e), which is essentially a cis isomer. In particular, reaction 33 for forming the silicon precursor (3e) from dihalogen-substituted 1,3-disilacyclobutane (3d) corresponds to formula (3) shown above.

[0104] Depending on the circumstances, one or more reactions for forming a film-forming composition may be carried out in an organic solvent, such as pentane, hexane, cyclohexane, benzene, toluene, xylene, diethyl ether, methyl tert-butyl ether, tetrahydrofuran, 1,4-dioxane, acetonitrile, triethylamine, pyridine, ethyl acetate, acetone, 1,2-dimethoxyethane, dimethyl sulfoxide, 2-butanone, methylene chloride, and mixtures thereof. Various reactions may be carried out at low temperatures, room temperature (about 18°C ​​to 25°C), or high temperatures. For example, in some embodiments, when a solvent is used, one or more reactions may be carried out above the freezing point of the solvent, or typically at low temperatures of at least about -80°C to a maximum of about 17°C. Additionally or alternatively, in some embodiments, one or more reactions may be carried out at near room temperature. Additionally or alternatively, in some embodiments, when a solvent is used, one or more reactions may be carried out up to the boiling point of the solvent, or typically at high temperatures of about 26°C to a maximum of about 200°C. The temperature of each reaction can be varied to optimize the distribution and yield of the products.

[0105] The film-forming composition may be purified using standard methods. The film-forming compositions disclosed herein may contain one or more impurities, which may be, in particular, the result of raw material sources, residual reactants and solvents and reaction by-products from the synthesis method, and / or trace elements in decomposition products. The film-forming composition may be purified, for example, by distillation or sublimation, extraction, and / or contact of the composition with an absorbent, as needed, among other methods. In some embodiments, the film-forming composition comprises at least about 90% by weight of silicon precursor, or at least about 95% by weight of silicon precursor, or at least about 97% by weight of silicon precursor, or at least about 98% by weight of silicon precursor, or at least about 99% by weight of silicon precursor, or at least about 99.5% by weight of silicon precursor, or at least about 99.99% by weight of silicon precursor, or at least about 99.99% by weight of silicon precursor. In some embodiments, the film-forming composition comprises a silicon precursor or is essentially composed of a silicon precursor. In some embodiments, the amount of impurities in the film-forming composition is less than about 5% by weight, or less than about 2% by weight, or less than about 1% by weight, or less than about 0.5% by weight, or less than about 0.1% by weight, or less than about 0.05% by weight, or less than about 0.01% by weight. In some embodiments, the amount of halogen-containing impurities in the film-forming composition is less than or equal to about 5%, or less than or equal to about 4%, or less than or equal to about 3%, or less than or equal to about 2%, or less than or equal to about 1%, or less than or equal to about 0.5%, or less than or equal to about 0.1%, or less than or equal to about 100 ppm, or less than or equal to about 10 ppm. In some embodiments, the amount of metal impurities in the film-forming composition is less than or equal to about 1%, or less than or equal to about 0.5%, or less than or equal to about 0.1%, or less than or equal to about 100 ppm, or less than or equal to about 10 ppm, or less than or equal to about 1 ppm, or less than or equal to about 100 ppb, or less than or equal to about 10 ppb. In some embodiments, the amount of carbon-containing impurities in the film-forming composition is about 5% or less, or about 4% or less, or about 3% or less, or about 2% or less, or about 1% or less, or about 0.5% or less, or about 0.1% or less, or about 100 ppm or less, or about 10 ppm or less.In some embodiments, the amount of silicon-containing impurities in the film-forming composition is about 5% or less, or about 4% or less, or about 3% or less, or about 2% or less, or about 1% or less, or about 0.5% or less, or about 0.1% or less, or about 100 ppm or less, or about 10 ppm or less. In certain other embodiments, the amount of germanium-containing impurities in the film-forming composition is about 5% or less, or about 4% or less, or about 3% or less, or about 2% or less, or about 1% or less, or about 0.5% or less, or about 0.1% or less, or about 100 ppm or less, or about 10 ppm or less. In certain other embodiments, the amount of phosphorus-containing impurities in the film-forming composition is about 5% or less, or about 4% or less, or about 3% or less, or about 2% or less, or about 1% or less, or about 0.1% or less, or about 100 ppm or less, or about 10 ppm or less. In certain other embodiments, the amount of nitrogen-containing impurities in the film-forming composition is about 5% or less, or about 4% or less, or about 3% or less, or about 2% or less, or about 1% or less, or about 0.5% or less, or about 0.1% or less, or about 100 ppm or less, or about 10 ppm or less.

[0106] In some embodiments of this disclosure, the film-forming composition is supplied into a vapor delivery vessel. The vapor delivery vessel is configured to store the film-forming composition and to supply a vapor stream of the film-forming composition from the vapor delivery vessel to an external environment, such as a substrate processing system or semiconductor processing apparatus for forming a carbon-doped silicon-containing film. The vapor delivery vessel is generally formed from a material that is non-reactive to the film-forming composition and, in some embodiments, may comply with U.S. Department of Transportation (DOT) regulations such as 49 CFR §178 (2021). In some embodiments, the vapor delivery vessel is formed from stainless steel (e.g., 316, 316L, 304, or 304L alloy). The configuration of the vapor delivery vessel may vary in different embodiments of this disclosure depending on the melting point and volatility of the silicon precursor and other factors. However, the vapor delivery vessel generally comprises an outer wall enclosing a cavity for storing the film-forming composition and a gas outlet to allow the vapor of the film-forming composition to exit the cavity. The gas outlet is seated within the outer wall of the vapor delivery vessel, communicates with the cavity of the vapor delivery vessel, and has at least one valve positioned above it to fluidly connect or disconnect the cavity to the external environment. In some embodiments, the vapor delivery vessel has one or more other fluid inlets or outlets in addition to the gas outlet. For example, the vapor delivery vessel has a fluid inlet seated within the outer wall of the vapor delivery vessel and communicating with the cavity of the vapor delivery vessel, and at the fluid inlet is provided with at least one valve for filling the vapor delivery vessel with a film-forming composition. Additionally or alternatively, the vapor delivery vessel has a fluid inlet seated within the outer wall of the vapor delivery vessel and communicating with the cavity of the vapor delivery vessel, and at the fluid inlet is provided with at least one valve for allowing a carrier gas to cover the surface of the film-forming composition and / or pass through the film-forming composition into the cavity of the vessel. Some or all of the valves at various inlets and outlets may be designed to withstand high temperatures (e.g., typically up to 100°C, 150°C, 200°C, or 250°C) to provide sufficient vapor pressure and withstand temperatures that may be required to prevent the film-forming composition from condensing within the valves and other components.In some embodiments, the vapor delivery vessel further comprises one or more probe members which may include one or more temperature sensors and / or one or more pressure sensors and / or one or more level sensors. Various level sensors for measuring the amount of film-forming composition in the cavity of the vapor delivery vessel are known in the art and include, but are not limited to, volume-based sensors, conductivity-based sensors, float-switch level sensors, tuned fork sensors, and ultrasonic sensors. In some embodiments, the vapor delivery vessel further comprises one or more heat transfer elements, such as fins, rods, and beads, to facilitate heat transfer from the vessel wall to the film-forming composition in the cavity, or vice versa. One or more heat transfer elements may form meandering or radial paths for holding the film-forming composition in the cavity and, optionally, covering the film-forming composition or directing the flow of carrier gas through the film-forming composition. Such configurations are particularly useful for delivering vapors of low-volatility liquid and solid compositions. If necessary, various design features described above can be combined to optimize the vapor flow of the film-forming composition from the vapor delivery vessel. An example of a suitable vapor delivery vessel is shown in Figure 6, which will be discussed in detail below.

[0107] Another aspect of this disclosure relates to a deposition method for forming a carbon-doped silicon-containing film using a film-forming composition comprising a silicon precursor disclosed herein. Preferred deposition methods include ALD or CVD, which include plasma-enhanced, radical-enhanced, and thermal methods. The method generally includes supplying a substrate into a reaction space (e.g., one or more reaction chambers), introducing a vapor of the film-forming composition into the reaction space, and exposing the surface of the substrate to the silicon precursor. The step of exposing the surface of the substrate to the silicon precursor composition results in the formation of an adsorbed silicon precursor-containing layer on the surface of the substrate. The adsorbed silicon precursor-containing layer may be physically adsorbed and / or chemically adsorbed on the surface of the substrate, and may be a whole or partial monolayer on the surface or on multiple monolayers. The adsorbed silicon precursor-containing layer may contain intact silicon precursor and / or a portion or fragment of silicon precursor. In some embodiments, a conversion step is used to convert the adsorbed silicon precursor-containing layer into a targeted carbon-doped silicon-containing layer. In some embodiments, the surface of the substrate is additionally exposed to a co-reacting material to form the targeted carbon-doped silicon-containing layer. In some embodiments, the surface of the substrate is further exposed to plasma to form a target carbon-doped silicon-containing layer. In some embodiments, the method for forming the carbon-doped silicon-containing film includes supplying the substrate into a reaction space and carrying out one or more deposition cycles of a periodic deposition process. The periodic deposition process may include one or more of an ALD process and a periodic CVD process.

[0108] Figure 4 shows a process flow diagram 400 of an exemplary embodiment for forming a carbon-doped silicon-containing film using a periodic deposition process. The method comprises supplying a substrate into a reaction space (410) and performing one or more deposition cycles of a periodic deposition process (420), the periodic deposition process (420) comprising: exposing the surface of the substrate to a film-forming composition containing a silicon precursor (as described above) (430) to form an adsorbed silicon precursor-containing layer on the surface of the substrate; optionally purging the reaction space (440); exposing the surface of the substrate to a co-reactant (450) to thereby form a carbon-doped silicon-containing film on the surface of the substrate; and optionally purging the reaction space (460) (or the surface of the substrate may be exposed to a co-reactant and then to the film-forming composition). Steps 430 and 450 having any of steps 440 and 460 constitute one deposition cycle. The method may include repeating the deposition cycle one or more times (n times) (470) in a periodic deposition process (420) to increase the uniformity and / or thickness of the carbon-doped silicon-containing film on the surface of the substrate. The periodic deposition process (420) may be terminated (480) once the desired uniformity and / or thickness of the carbon-doped silicon-containing film is reached.

[0109] In step 410, the substrate is supplied to the reaction space. The substrate loading / unloading mechanism is generally used to insert the substrate into the reaction space and, in embodiments where multiple reaction chambers are used, to transport the substrate between different reaction chambers in the reaction space. The substrate is not particularly limited and is generally as described above. In some embodiments, the substrate is one or more semiconductor wafers. For example, the substrate may be a silicon wafer such as a single-crystal silicon wafer (e.g., a p-type single-crystal silicon wafer). Alternatively, the substrate may include silicon-germanium (SiGe), single-crystal germanium, gallium arsenide, etc. The substrate may include one or more material layers present from one or more previous manufacturing steps, such as dielectric layers, insulating layers, metal layers, certain nitrides, sacrificial layers. In some embodiments, the substrate includes a hydroxyl-terminated surface, which can advantageously improve the deposition method described herein. The substrate may include various topologies, such as gaps, recesses, lines, trenches, vias, holes, or spaces between ridges formed in or on at least a portion of the layers of the substrate.

[0110] The reaction space is not particularly limited and may comprise one or more reaction chambers in a semiconductor processing system. In some embodiments, the semiconductor processing system is a cluster tool. In some embodiments, reaction chambers(s) in a fluidized reactor may be used. In some embodiments, reaction chambers(s) in a showerhead reactor may be used. In some embodiments, reaction chambers(s) in a divided reactor may be used. In some embodiments, reaction chambers(s) in a single-wafer reactor capable of mass production may be used. In other embodiments, reaction chambers(s) in a batch reactor may be used. In embodiments where a batch reactor is used, the reaction chambers may accommodate a large number of wafers, for example, the number of wafers may range from 10 to 200, or 50 to 150, or even 100 to 150.

[0111] In the methods disclosed herein, the surface of a substrate is exposed to (430) a film-forming composition (as described above) to result in the formation of a silicon precursor-containing layer adsorbed on the surface of the substrate. Exposure of the substrate surface to the film-forming composition (430) may include introducing vapor of the film-forming composition into the reaction space and bringing the surface of the substrate into contact with the vapor of the film-forming composition. The film-forming composition is typically supplied from a vapor delivery vessel containing the film-forming composition, connected to and in fluid communication with the reaction space, through one or more gas lines, valves, and flow controllers. The vapor delivery vessel, as well as one or more gas lines, valves, and flow controllers, may be heated to facilitate the flow of the film-forming composition from the vapor delivery vessel into the reaction space through one or more gas lines, valves, and flow controllers. The vapor pressure of the silicon precursor in the film-forming composition depends on the specific structure of the silicon precursor, and the temperature of the vapor delivery vessel can be adjusted (i.e., heated or cooled) to provide sufficient vapor pressure (typically about 1 Torr to 20 Torr at temperatures in the range of 25°C to 200°C) to facilitate the delivery of the film-forming composition into the reaction space. In some embodiments, a neat flow of film-forming composition vapor flows from the vapor delivery vessel into the reaction space through one or more gas lines, valves, and flow controllers. In other embodiments, the film-forming composition vapor may be introduced into the reaction space accompanied by a flow of an inert carrier gas (e.g., nitrogen and / or noble gases such as helium (He) and argon (Ar)).

[0112] In some embodiments, step 430, which involves exposing the surface of the substrate to the film-forming composition, includes pulsing the film-forming composition into the reaction space so as to cover the surface of the substrate. In embodiments in which the film-forming composition is pulsed on the surface of the substrate, the pulse time may be about 0.01 seconds to about 60 seconds, or about 0.1 seconds to about 30 seconds, or about 1 second to about 10 seconds. During the pulse, the flow rate of the film-forming composition may be less than about 2000 sccm, or less than about 1000 sccm, or less than about 500 sccm, or less than about 100 sccm. The flow rate may be, for example, about 500 sccm to about 1200 sccm, for example, about 600 sccm, or about 800 sccm, or about 1000 sccm. The pulse time may vary depending on the film-forming composition of interest, the reaction chamber configuration, and other process parameters (e.g., temperature, pressure, substrate, etc.) that can be independently selected to optimize the process.

[0113] A conversion step can be used to convert the adsorbed silicon precursor-containing layer into a target carbon-doped silicon-containing film. For example, the surface of the substrate may be further exposed to co-reactants (450). In some embodiments, the surface of the substrate is exposed to plasma species to form the target carbon-doped silicon-containing film. In some embodiments, the surface of the substrate is exposed to one or more of hydrogen plasma, noble gas plasma, nitrogen plasma, and oxygen plasma. The co-reactants may include one or more excited species and / or radical species that can be formed in situ in the reaction space using a direct plasma formed near or directly above the substrate (e.g., direct plasma). Alternatively, the co-reactants may include one or more excited species and / or radical species that can be formed either in situ in the reaction space at a spatially separated location from the substrate or upstream of the reaction space using a remote plasma (e.g., remote plasma). Remote plasma may be used to minimize or avoid exposure of the substrate surface to energy ion species. In either case, the plasma may be formed using a feed gas containing one or more of an inert gas and a reactive gas. A supply gas is supplied into the plasma unit, and the emitted plasma is activated. In some embodiments, the supply gas is supplied into the reaction space, and the emitted plasma is pulsed (i.e., on and off). The power for generating the plasma is variable in different embodiments of this disclosure. In some embodiments, the power for generating the plasma is about 10W to about 2,000W, typically about 20W to about 1,000W, or about 20W to about 500W, or about 20W to about 200W, or about 20W to about 100W.

[0114] In some embodiments, the substrate surface is exposed to one or more of a hydrogen plasma and / or a noble gas plasma. In some of these embodiments, the supply gas includes hydrogen (H2) and / or a noble gas selected from the group consisting of helium (He), neon (Ne), argon (Ar), krypton (Kr), xenon (Xe), and mixtures thereof. In some embodiments, the co-reacting material includes a hydrogen plasma species. In some embodiments, the substrate surface is exposed to a hydrogen plasma. Additionally or alternatively, in some embodiments, the co-reacting material includes a noble gas plasma species. In some embodiments, the substrate surface is exposed to a noble gas plasma. In these embodiments, the plasma may be used to activate an adsorbed silicon precursor-containing layer on the substrate surface and may not necessarily supply material to the deposited film, but may contribute to film growth in some situations. In some embodiments, the reactive gas may include a noble gas and H2, which are supplied at flow rates of about 20:1 to about 1:20, or about 10:1 to about 1:10, or about 5:1 to about 1:5, or about 1:2 to about 2:1, or about 1:1.

[0115] In some embodiments, the surface of the substrate is exposed to a nitrogen plasma. In certain embodiments, the co-reacting material includes nitrogen plasma species. In these cases, the supply gas may include a reactive gas containing one or more of nitrogen (N2), N2 / H2 mixtures, ammonia (NH3), aminoalkyl (NR3, where each R is independently H, alkyl, or aryl group), hydrazine (N2H4), and substituted hydrazines. Therefore, the co-reacting material may optionally include one or more of N2, NH3, aminoalkyl, hydrazine N2H4, substituted hydrazines, and excited species, radical species, and plasma species formed therefrom. In some embodiments, the co-reacting material includes nitrogen plasma species, for example, the co-reacting material may include one or more of activated nitrogen (N2), activated ammonia (NH3), nitrogen atoms (N), NH and NH2 radicals, and other NH-containing species generated during the plasma discharge. In some embodiments, the reactive gas may include N2 and H2, which are supplied in flow ratios (N2:H2) of about 20:1 to about 1:20, or about 10:1 to about 1:10, or about 5:1 to about 1:5, or about 1:2 to about 2:1, or about 1:1.

[0116] In some embodiments, the surface of the substrate is exposed to an oxygen plasma. In some embodiments, the co-reacting material may include an oxygen plasma species. In some embodiments, the reactive gas includes one or more of oxygen (O2), ozone (O3), water (H2O), hydrogen peroxide (H2O2), organic peroxides, alcohols, nitrogen dioxide (NO2), nitrous oxide (N2O), and nitric oxide (NO), and therefore the co-reacting material may optionally include one or more of oxygen (O2), ozone (O3), water (H2O), hydrogen peroxide (H2O2), organic peroxides, alcohols, nitrogen dioxide (NO2), nitrous oxide (N2O), nitric oxide (NO), and excited species, radical species, and plasma species formed therefrom. In some embodiments, the oxygen co-reacting material includes an oxygen plasma species, for example, the oxygen co-reacting material may include atomic oxygen (O), excited diatomic oxygen (e.g., singlet oxygen ( 1The co-reacting material may include one or more of the following: O2, ozone (O3), hydroxyl radical (OH), peroxyl radical (e.g., HO2), and nitric oxide (NO). In some other embodiments, the co-reacting material does not contain or substantially contains oxygen plasma species. In certain embodiments, the substrate is not exposed to the oxygen plasma. Therefore, the resulting film may have a higher carbon content and, consequently, a lower dielectric constant. Additionally or alternatively, in certain embodiments, damage to sublayers (e.g., conductive interlayers) on the substrate surface by the oxygen plasma can be prevented. Accordingly, a decrease in the electrical performance of the resulting device can be prevented.

[0117] In some embodiments, step 450, which exposes the surface of the substrate to a co-reactant, includes pulsing the co-reactant into a reaction space on the substrate surface. Pulsing can be achieved by controlling the flow of supply gas into the reaction space and activating a plasma discharge used to form the co-reactant. In embodiments in which the co-reactant is pulsed on the substrate, the pulse time may be about 0.01 seconds to about 60 seconds, or about 0.1 seconds to about 30 seconds, or about 1 second to about 10 seconds. During the pulse, the flow rate of the supply gas may be less than about 2000 sccm, or less than about 1000 sccm, or less than about 500 sccm, or less than about 100 sccm. The flow rate may be, for example, about 500 sccm to about 1200 sccm, for example, about 600 sccm, or about 800 sccm, or about 1000 sccm. The pulse duration may vary depending on other process parameters (e.g., temperature, pressure, substrate, etc.) that can be independently selected to optimize the process according to the target co-reactants, reaction chamber configuration, and intended application.

[0118] In some embodiments, the steps 430 for exposing the substrate surface to the film-forming composition and 450 for exposing the substrate surface to the co-reactant overlap at least partially. For example, in embodiments where the film-forming composition and / or co-reactant are pulsed on the substrate, the film-forming composition pulse and the co-reactant pulse may overlap at least partially. In some embodiments, the introduction of the film-forming composition and the co-reactant into the reaction space may occur simultaneously. In some embodiments, the introduction of the film-forming composition and the co-reactant into the reaction space may occur at least partially separately. For example, in embodiments where the film-forming composition and the co-reactant are pulsed on the substrate surface, the film-forming composition pulse and the co-reactant pulse may be at least partially separated. In some embodiments, the introduction of the film-forming composition and the co-reactant into the reaction space may occur completely separately. For example, in embodiments where the film-forming composition and the co-reactant are pulsed on the substrate surface, the film-forming composition pulse and the co-reactant pulse may be completely separated.

[0119] In some embodiments, the reaction space is purged between exposing the surface of the substrate to the film-forming composition (430) and exposing the surface of the substrate to a co-reactant (450). For example, an arbitrary purging step is shown in Figures 440 and 460. Purge can affect between pulses of two gases that react with each other. Purge can also affect between pulses of two gases that do not react with each other. For example, purging or purging may occur between a pulse of the film-forming composition and a pulse of the co-reactant. Purge can avoid or at least reduce gas-phase interactions between two gases that react with each other. It should be understood that purging can affect in time, space, or both. For example, in the case of temporal purging, the purging step can be used in a time series, for example, by supplying a first reactant to the reaction space, supplying a purging gas to the reaction space, supplying a second reactant to the reaction space, and the substrate on which the layer is deposited does not move. For example, in the case of spatial purging, the purging step may include moving the substrate from a first location (e.g., a first reaction chamber) where a first reactant is continuously supplied, through a purge gas curtain, to a second location (e.g., a second reaction chamber) where a second reactant is continuously supplied.

[0120] Various process steps may be repeated one or more times to grow a carbon-doped silicon-containing film on the surface of the substrate (470). The number of repeat cycles (n) is not particularly limited and depends on the growth per cycle (GPC) and the target film thickness. Typically, the film thickness may range from a few angstroms to several hundred microns. The number of repeat cycles (n) may be 1 to about 1,000, typically 1 to about 500, or 1 to about 200, or 1 to about 100, or 1 to about 50, or 1 to about 10. The GPC of the carbon-doped silicon film may be at least about 0.01 Å / cycle to about 10 Å / cycle or less. In certain embodiments, the GPC may vary depending on the exposure time of the substrate surface to the film-forming composition.In some embodiments, the GPC of the carbon-doped silicon film is at least about 0.05 Å / cycle to about 10 Å / cycle or less, or at least about 0.05 Å / cycle to about 8 Å / cycle or less, or at least about 0.05 Å / cycle to about 7 Å / cycle or less, or at least about 0.05 Å / cycle to about 6 Å / cycle or less, or at least about 0.05 Å / cycle to about 5 Å / cycle or less, or at least about 0.05 Å / cycle to about 4 Å / cycle or less, or at least about 0.05 Å / cycle to about 3 Å / cycle or less, or at least about 0.05 Å / cycle to about 2.5 Å / cycle or less, or at least about 0.05 Å / cycle to about 2.0 Å / cycle or less, or at least about 0.05 Å / cycle to about 1.5 Å / cycle or less, or at least about 0.05 Å / cycle to about 1 Å / cycle or less, or at least about 0.05 Å / cycle to about 0.5 Å / cycle or less , or at least approximately 0.1 Å / cycle to approximately 5 Å / cycle or less, or at least approximately 0.1 Å / cycle to approximately 4 Å / cycle or less, or at least approximately 0.1 Å / cycle to approximately 3 Å / cycle or less, or at least approximately 0.1 Å / cycle to approximately 2.5 Å / cycle or less, or at least approximately 0.1 Å / cycle to approximately 2.0 Å / cycle or less, or at least approximately 0.1 Å / cycle to approximately 1.5 Å / cycle or less, or at least approximately 0.1 Å / cycle to approximately 1 Å / cycle or less, or at least approximately 0.5 Å / cycle to approximately 5 Å / cycle or less, or at least approximately 0.5 Å / cycle to approximately 4 Å / cycle or less, or at least approximately 0.5 Å / cycle to approximately 3 Å / cycle or less, or at least approximately 0.5 Å / cycle to approximately 2.5 Å / cycle or less, or at least approximately 0.5 Å / cycle to approximately 2.0 Å / cycle or less, or at least approximately 0.5 Å / cycle to approximately 1.5 Å / cycle or less. In some embodiments, the GPC of the carbon-doped silicon-containing film is approximately 0.5 Å / cycle or more, or approximately 1 Å / cycle or more, or approximately 1.5 Å / cycle or more, or approximately 2 Å / cycle or more.In some embodiments, the GPC of carbon-doped silicon-containing films is approximately 0.5 Å / cycle, or approximately 1 Å / cycle, or approximately 1.5 Å / cycle, or approximately 2 Å / cycle, or approximately 2.5 Å / cycle, or approximately 3 Å / cycle, or approximately 3.5 Å / cycle, or approximately 4 Å / cycle, or approximately 4.5 Å / cycle, or approximately 5 Å / cycle, or approximately 5.5 Å / cycle, or approximately 6 Å / cycle, or approximately 6.5 Å / cycle, or approximately 7 Å / cycle. Typically, for ALD processes, the GPC is approximately 0.1 Å / cycle to approximately 3 Å / cycle, and for periodic CVD processes, the GPC can be higher depending on the exposure time of the substrate to the film-forming composition.

[0121] The method may further include maintaining the substrate temperature at a set temperature during the periodic deposition process (420). In some embodiments, the method includes maintaining the substrate temperature at a set temperature during one or both exposure steps (e.g., 430 and 450 in Figure 4). In some embodiments, the method includes maintaining the substrate temperature at approximately room temperature. In other embodiments, the method further includes heating the substrate to a temperature of at least about 40°C to about 500°C or less. In some embodiments, the method includes maintaining the substrate temperature at approximately 25°C to approximately 500°C, typically at approximately 100°C to approximately 450°C, or approximately 100°C to approximately 425°C, or approximately 100°C to approximately 400°C, or approximately 100°C to approximately 375°C, or approximately 100°C to approximately 350°C, or approximately 100°C to approximately 325°C, or approximately 100°C to approximately 300°C, or approximately 100°C to approximately 275°C, or approximately 100°C to approximately 250°C, or approximately 200°C to approximately 450°C, or approximately 200°C to approximately 425°C, or approximately 200°C to approximately 400°C, or approximately 200°C to approximately 375°C, or approximately 200°C to approximately 350°C. In some embodiments, the method is carried out while maintaining the substrate at a temperature of less than about 450°C, or less than about 425°C, or less than about 400°C, or less than about 375°C, or less than about 350°C, or less than about 325°C, or less than about 300°C, or less than about 275°C, or less than about 250°C, or less than about 225°C, or less than about 200°C, or less than about 175°C, or less than about 150°C. In some embodiments, the method includes maintaining the substrate temperature at approximately 25°C, or approximately 50°C, or approximately 75°C, or approximately 100°C, or approximately 125°C, or approximately 150°C, or approximately 175°C, or approximately 200°C, or approximately 225°C, or approximately 250°C, or approximately 275°C, or approximately 300°C, or approximately 325°C, or approximately 350°C, or approximately 375°C, or approximately 400°C, or approximately 425°C, or approximately 450°C.

[0122] In addition to controlling the temperature of the substrate, the methods of the present disclosure may be carried out in a reduced-pressure environment. In some embodiments, the methods further include controlling the pressure inside the reaction space during the periodic deposition process (420). The pressure inside the reaction space may be about 1 mTorr to about 760 Torr, or about 0.5 Torr to about 30 Torr, for example, about 10 Torr, or about 15 Torr, or about 20 Torr. In some embodiments, the pressure inside the reaction space during the periodic deposition process (420) is less than about 500 Torr, or the pressure inside the reaction chamber during the periodic deposition process (420) is about 0.1 Torr to about 500 Torr, or about 1 Torr to about 100 Torr, or about 1 Torr to about 20 Torr. In some embodiments, the pressure inside the reaction space during the periodic deposition process (420) is less than about 300 Torr, less than about 100 Torr, less than about 50 Torr, or less than about 10 Torr.

[0123] Another aspect of this disclosure relates to a system for forming carbon-doped silicon-containing films using the film-forming compositions and methods disclosed herein. In some embodiments, the system may comprise a semiconductor processing system comprising a reaction space (e.g., one or more reaction chambers) for housing a substrate. The semiconductor processing system may comprise one reaction chamber, two reaction chambers, three reaction chambers, four reaction chambers, or more. In some embodiments, the semiconductor processing system is a cluster tool. In some embodiments, reaction chambers(s) in a fluidized reactor may be utilized. In some embodiments, reaction chambers(s) in a showerhead reactor may be utilized. In some embodiments, reaction chambers(s) in a space-divided reactor may be utilized. In some embodiments, reaction chambers(s) in a mass-production-capable single-wafer reactor may be utilized. In other embodiments, reaction chambers(s) in a batch reactor may be utilized. The semiconductor processing system further comprises a film-forming composition source and means for exposing the surface of the substrate to vapor of the film-forming composition disclosed herein. The semiconductor processing system may further include means for exposing a substrate to a co-reacting substance, and optionally means for purging the reaction space during the exposure process.

[0124] Figure 5 shows an exemplary embodiment of a semiconductor processing system 500 according to the present disclosure. The film-forming composition and other gases disclosed herein are supplied into the reaction chamber 520 through an injector assembly 510. The injector assembly 510 is configured to supply vapor of the film-forming composition from a film-forming composition source 511 connected to the reaction chamber 520 via a first valve 515. The injector assembly 510 may further be configured to supply one or more other gases, for example, one or more co-reactants or feed gases for forming one or more co-reactants from a co-reactant source 512 connected to the reaction chamber 520 via a second valve 516, and / or one or more carrier gases from a carrier gas source 513 connected to the reaction chamber 520 via a third valve 517 (e.g., nitrogen and / or noble gases such as He, Ne, Ar, Kr, Xe, and combinations thereof). The injector assembly 510 further comprises one or more other gas sources 514 connected to the reaction chamber 520, for example via a fourth valve 518, for supplying purge gas, additional carrier gas, makeup gas, etc., and optionally various supply sources (511-514) and corresponding valves (515-518) and means (not shown) for heating the gas lines, thereby facilitating the introduction of the film-forming composition and other reactants into the reaction chamber 520.

[0125] In some embodiments, the film-forming composition source 511 includes a vapor delivery vessel containing the film-forming composition. Figure 6 shows a perspective view of an exemplary embodiment of the vapor delivery vessel 600 according to the present disclosure. The vapor delivery vessel 600 has an outer wall which may be generally cylindrical in shape, having a bottom portion 614 and an upper portion 612 connected by a cylindrical body 610 to surround a cavity 602 for storing the film-forming composition 604 inside. The vapor delivery vessel 600 further comprises a gas outlet 651, an optional gas inlet 631, an optional fluid inlet 641, and an optional probe member 660. The gas outlet 651 is seated on the upper part of the outer wall 612 and communicates with the cavity 602. The gas outlet 651 is configured to supply vapor of the film-forming composition from the cavity 602. In this regard, the gas outlet 651 may include one or more valves for opening and closing the gas outlet and for controlling the flow of vaporized film-forming composition 604 from the cavity 602. For example, the gas outlet 651 may have one or both of a manual valve 653 and an actuated valve 652 disposed along the gas outlet 651 on the outside of the container 600. The gas inlet 631 may also be seated on the upper part of the outer wall 612 and communicate with the cavity 602. The gas inlet 631 is configured to allow a carrier gas to flow into the cavity 602, either covering the surface of the film-forming composition 604 or passing through the film-forming composition 604, so as to entrain the vapor of the film-forming composition 604 in the carrier gas stream discharged from the gas outlet 651. In this regard, the gas inlet 631 may have a conduit extending into the cavity to a fixed point 632 either above the surface of the film-forming composition 604 or below the surface film-forming composition, as shown in Figure 6 (not shown). Furthermore, in this regard, the gas inlet 631 may have one or more valves for opening and closing the gas inlet 631 and for controlling the flow of carrier gas into the cavity 602. For example, the gas inlet 631 may have one or both of a manual valve 634 and an actuated valve 633 disposed along the gas inlet 631 on the outside of the container 600. The fluid inlet 641 may also be seated on the upper part of the outer wall 612 and communicate with the cavity 602.The fluid inlet 641 may be configured to replenish the vapor delivery vessel 600 with the film-forming composition 604. In this regard, the fluid inlet 641 may have a conduit 642 extending into the cavity 602, which in certain embodiments may be bent toward the outer wall 610 to reduce splashing, bubbles, and / or liquid level fluctuations of the film-forming composition during replenishment. Furthermore, in this regard, the fluid inlet 641 may have one or more valves for opening and closing the fluid inlet 641 and for controlling the flow of the film-forming composition 604 into the cavity 602. For example, the fluid inlet 641 may have one or both of a manual valve 644 and an operating valve 643 disposed on the outside of the vessel 600 along the fluid inlet 641. The probe member 660 may be seated in the upper part 612 of the outer wall and extend toward the bottom 614 into the cavity 602. In a particular example, the probe member 660 may be removably fixed within the probe member opening 661 so that the probe member 660 may be removed for cleaning and / or replacement as needed. The probe member 660 may include one or more temperature sensors 662 and / or one or more level sensors 663. One or more temperature sensors 662 and / or one or more level sensors 663 of the probe member 660, as well as various operating valves (633, 652, and 643), may each be configured so that they can be operably associated with the controller 580 (see Figure 5). Furthermore, the vapor delivery vessel 600 may be removably connected to the injector assembly 510 via one or more optional connectors, as shown in 630, 650, and 640 (see Figure 5), so that the vapor delivery vessel 600 can be removed from the injector assembly 510 for cleaning at a location away from the semiconductor processing system 500 (see Figure 5) and for filling with the film-forming composition (see Figure 5). Although the vapor delivery vessel 600 is shown and described herein as having a particular configuration, it should be understood and recognized that the vapor delivery vessel may include other elements and / or exclude certain elements described herein, or may have a different configuration, and may remain within the scope of this disclosure.For example, a steam delivery vessel may have other arrangements of inlets and outlets, including fewer or additional inlets and outlets, or other arrangements of valves, including fewer or additional valves.

[0126] Referring again to Figure 5, the film-forming composition and other gases flow into the reaction chamber 520 through a showerhead 521 positioned directly above the susceptor 523 on which the substrate 522 is placed. In some embodiments, the reaction chamber 520 further comprises one or more heating elements 524 that are in thermal communication with the substrate 522, and one or more thermocouples (not shown) for measuring and maintaining the temperature of the substrate at a set temperature. Unreacted gases and gaseous reaction byproducts are removed from the reaction chamber 520 through an exhaust line 560 connected to the external environment 570 via one or more optional vacuum pumps 562. A plasma generator 550 (e.g., an RF plasma generator, a microwave plasma generator, a capacitively coupled plasma generator, or an inductively coupled plasma generator) may be electrically connected to the showerhead 521, thereby biasing the showerhead 521 toward the susceptor 523 to form a plasma discharge between the two. In some cases, an ion trap (not shown) may be placed between the shower head 521 and the substrate 522 to restrict the plasma to the upper part of the reaction chamber 520, i.e., above the ion trap, thereby reducing the interaction of ion species with the substrate surface. For example, an electrically grounded mesh plate may be used as an ion trap.

[0127] The semiconductor processing system also includes a controller 580. The controller 580 generally includes a device interface 584, a processor 583, a user interface 585, and memory 581. The device interface 584 connects the processor 583 via a wired or wireless link to various elements of the vapor delivery vessel (e.g., one or more of 633, 652, 643, 662, and 663 in Figure 6) as well as one or more of the injector assembly 510, reaction chamber 520, plasma discharge 550, exhaust source 560, and / or other components (e.g., one or more heating elements 524 and thermocouples (not shown) for controlling the temperature of the substrate 522). The processor 583 is then operably connected to the user interface 585 to receive user inputs and / or supply user outputs, and also communicates with memory 581. The memory 581 may include a non-temporary machine-readable medium having a plurality of program modules 582 recorded thereon, which, when read by the processor 583, cause the processor 583 to perform a specific operation. These operations include a method for depositing a carbon-doped silicon-containing film (e.g., 400, see Figure 4) using the film-forming composition described above.

[0128] In some embodiments, the controller 580 is configured and programmed to perform a first and a second operation. In the first operation, the controller 580 opens a first valve 515 to allow vapor of the film-forming composition from the film-forming composition source 511 into the reaction chamber 520, thereby exposing the surface of the substrate to the film-forming composition, and after a set period, the controller 580 closes the first valve 515 to the film-forming composition source 511. In the second operation, the controller 580 opens a second valve 516 to allow co-reactant or co-reactant supply gas from a co-reactant source 512 into the reaction chamber 520, pulsing (turning on and then off) the plasma generator 550, thereby exposing the surface of the substrate 522 to the co-reactant. After another set period, the controller 580 closes the second valve 516 to the co-reactant source 512. In certain embodiments, the controller 580 is programmed to perform a first operation and a second operation, or vice versa, such that at least a portion of the first operation overlaps with at least a portion of the second operation, and as a result, the flow of the film-forming composition into the reaction chamber 520 overlaps at least partially with the flow of co-reacting material into the reaction chamber 520. In certain other embodiments, the controller 580 is programmed to perform a first operation followed by a second operation, or vice versa, so that the flow of the film-forming composition into the reaction chamber 520 and the flow of co-reacting material into the reaction chamber 520 do not overlap. The controller 580 may be programmed to repeat the first and second operations (n ​​times) to grow a carbon-doped silicon-containing film on the surface of the substrate 522.

[0129] As will be understood by those skilled in the art, the controller 580 may be configured and programmed to perform other operations. For example, the controller 580 may be operably connected to a purge gas source 514 and configured and programmed to open a fourth valve 518 to the purge gas source 514 to allow purge gas to flow into the reaction chamber 520, and then close the fourth valve 518 to the purge gas source 514 after a set period of time. In another example, the controller 580 may be operably connected to one or more heating elements 524 and one or more thermocouples (not shown) and configured and programmed to measure and control the temperature of at least one heating element 524 to maintain the temperature of the substrate 522 at a set temperature.

[0130] Furthermore, as will be understood by those skilled in the art, other configurations of semiconductor deposition systems are possible. For example, although the injector assembly 510 and reaction chamber 520 are shown and described herein as having a specific structure and flow configuration, other flow configurations and / or other mechanisms may be utilized for supplying various reactants and gases, as well as for housing the substrate and flowing gases over the substrate. Furthermore, other plasma generation configurations may be utilized. In some embodiments, a remote plasma may be generated using a remote plasma unit located upstream of the reaction chamber 520. Furthermore, although the controller 580 is shown and described herein as having a specific architecture, it should be understood and recognized that other controller architectures may be employed and remain within the scope of this disclosure.

[0131] Another aspect of this disclosure relates to a carbon-doped silicon-containing layer or film formed using a film-forming composition disclosed herein. Furthermore, the carbon-doped silicon-containing layer or film may be formed using the methods and systems described herein. In some embodiments, a carbon-doped silicon film is provided that is formed by contacting the surface of a substrate with a film-forming composition disclosed herein. In some of these embodiments, the carbon-doped silicon film includes a silicon precursor and / or a portion or fragment of the silicon precursor. The silicon precursor and / or a portion or fragment of the silicon precursor may be adsorbed onto the surface of the substrate. In some embodiments, a carbon-doped silicon-containing film is provided that is formed by the method described in Figure 4. In some embodiments, a carbon-doped silicon-containing film is provided that is formed by contacting the surface of a substrate with a film-forming composition disclosed herein and one or more of a hydrogen plasma, a noble gas plasma, a nitrogen plasma, and an oxygen plasma.

[0132] The disclosed film-forming compositions, as well as methods and systems for forming carbon-doped silicon-containing films using said film-forming compositions, may offer several advantages. In particular, the film-forming compositions may provide carbon-doped silicon-containing films having a high carbon content, generally about 1% to 70%, typically about 5% to 50%, or about 10% to 50%, or about 20% to 50%. While we do not wish to be bound by any particular theory, the high carbon content of the films may be attributable to the presence of Si-C-Si bonds in the silicon precursor structure, and in certain embodiments, CH3-Si bonds. Additionally or alternatively, in certain embodiments, the method for forming carbon-doped silicon-containing films excludes exposure of the substrate to an oxygen plasma. Instead, a hydrogen plasma and / or noble gas plasma can be used to form carbon-doped silicon-containing films while still maintaining acceptable GPC and / or throughput. As a result, in certain embodiments, the carbon-doped silicon-containing films may have a desired low dielectric constant. For example, in some embodiments, the carbon-doped silicon-containing film has a dielectric constant of less than about 4.2, or less than about 4.0, or less than about 3.8, or less than about 3.5, or less than about 3.4, or less than about 3.3, or less than about 3.2, or less than about 3.1, or less than about 3.0, or less than about 2.9, or less than about 2.8, or less than about 2.7, or less than about 2.6, or less than about 2.5, or less than about 2.4, or less than about 2.3, or less than about 2.2, or less than about 2.1, or less than about 2.0. Furthermore, in some embodiments, the carbon-doped silicon-containing film may also have good mechanical properties. For example, in some embodiments, the carbon-doped silicon-containing film may have a wet etching rate (WER) of less than 2.5 nm / min in 0.5% diluted hydrofluoric acid, or less than 2.0 nm / min in 0.5% diluted hydrofluoric acid, or less than 1.5 nm / min in 0.5% diluted hydrofluoric acid, or less than 1.0 nm / min in 0.5% diluted hydrofluoric acid, or less than 0.5 nm / min in 0.5% diluted hydrofluoric acid. Furthermore, in some embodiments, the carbon-doped silicon-containing film may also have good conformality.For example, in some embodiments, the carbon-doped silicon-containing film has a step coverage of about 80% or more, or about 90% or more. In some embodiments, the carbon-doped silicon-containing film has a step coverage of more than about 90% and less than about 110%, or about 95% or more and less than about 105%.

[0133] While specific embodiments and examples are disclosed herein, it will be understood by those skilled in the art that the disclosed compositions, methods, and systems extend beyond the specifically disclosed embodiments, encompassing all novel and non-obvious combinations and partial combinations of various compositions, methods, and systems, as well as all their equivalents. It will be understood that the compositions, methods, and systems described herein are essentially illustrative, and these specific embodiments or examples should not be considered restrictive, as numerous variations are possible. The specific methods and systems described herein may represent one or more of any number of process strategies. Therefore, the various operations illustrated may be performed in the order illustrated, in other orders, or omitted in some examples. Furthermore, various features of the disclosure are grouped together in one or more aspects, embodiments, and configurations for the purpose of streamlining the disclosure. Features of the aspects, embodiments, and configurations of the disclosure may be combined in alternative aspects, embodiments, and configurations other than those described above. The compositions, methods, and systems of the disclosure should not be interpreted as reflecting the intent required by the disclosure described in the claims, with respect to more features than those expressly described in each claim. Rather, as the following claims reflect, the embodiments of the invention are fewer than all the features of a single aforementioned disclosed embodiment and configuration. Accordingly, the following claims are incorporated into embodiments for carrying out the invention, each claim exists independently as a distinct embodiment of the disclosure, and the features enumerated in various dependent claims may be combined with each other in various combinations to form other embodiments of the disclosure as needed.

Claims

1. General formula (1): 【Chemistry 1】 (In the formula, Q １ is a substituent selected from the group consisting of an acetoxy group, an acryloyloxy group, a C １ -C ６ alkoxy group, a silyloxy group, a germyloxy group, a phosphonooxy group, and an alkylamine group, and Q ２ , Q ３ , and Q ４ are each a substituent independently selected from the group consisting of a hydrogen atom, a C １ -C ６ alkyl group, and the same substituent as Q １ ). A film-forming composition containing a silicon precursor having a structure according to

2. Q １ The film-forming composition according to claim 1, wherein the substituent is selected from the group consisting of an acetoxy group, an acryloyloxy group, a silyloxy group, a gelmyloxy group, and a phosphonooxy group.

3. The substituent Q １ and Q ３ However, acetoxy group, acryloyloxy group, C １ -C ６ The substituent Q is dependently selected from the group consisting of alkoxy groups, silyloxy groups, gelmyloxy groups, phosphonooxy groups, and alkylamine groups. ２ and Q ４ However, hydrogen atoms and C １ -C ６ The film-forming composition according to claim 1, wherein a group of alkyl groups is dependently selected, and at least 85% of the silicon precursor is in cis-isomer form, or at least 85% of the silicon precursor is in trans-isomer form.

4. The silicon precursor is 1,3-diacetoxy-1,3-disilacyclobutane, 1,3-diacetoxy-1,3-dimethyl-1,3-disilacyclobutane, 1,3-diacryloxy-1,3-disilacyclobutane, 1,3-diacryloxy-1,3-dimethyl-1,3-disilacyclobutane, 1,3-dimethylacryloyloxy-1,3-disilacyclobutane, 1,3-dimethylacryloyloxy-1,3-dimethyl-1,3-disilacyclobutane, 1,3-bis(trimethylsilyloxy)-1,3-disyl The film-forming composition according to claim 1, selected from the group consisting of lacyclobutane, 1,3-bis(trimethylsilyloxy)-1,3-dimethyl-1,3-disilacyclobutane, 1,3-bis(trimethylgelmyloxy)-1,3-disilacyclobutane, 1,3-bis(trimethylgelmyloxy)-1,3-dimethyl-1,3-disilacyclobutane, 1,3-bis(dimethylphosphonooxy)-1,3-disilacyclobutane, and 1,3-bis(dimethylphosphonooxy)-1,3-dimethyl-1,3-disilacyclobutane.

5. The film-forming composition according to claim 1, wherein the film-forming composition has a purity of at least 97% by weight.

6. General formula (1): 【Chemistry 2】 (In the formula, Q １ C is an acetoxy group, an acryloyloxy group, and １ -C ６ A substituent selected from the group consisting of alkoxy groups, silyloxy groups, gelmyloxy groups, phosphonooxy groups, and alkylamine groups, Q ２ Q ３ , and Q ４ These are a hydrogen atom and C, respectively. １ -C ６ Alkyl alkyl groups, and Q １ A vapor delivery container comprising a film-forming composition containing a silicon precursor having a structure due to a substituent independently selected from the group consisting of the same substituents as ).

7. General formula (1): 【Transformation 3】 (In the formula, Q １ C is an acetoxy group, an acryloyloxy group, and １ -C ６ A substituent selected from the group consisting of alkoxy groups, silyloxy groups, gelmyloxy groups, phosphonooxy groups, and alkylamine groups, Q ２ Q ３ , and Q ４ These are a hydrogen atom and C, respectively. １ -C ６ Alkyl alkyl groups, and Q １ A method for forming a film-forming composition comprising a silicon precursor having a structure with substituents independently selected from the group consisting of the same substituents as ), To supply a halogen-substituted 1,3-disilacyclobutane reactant containing at least one halogen substituent, The halogen-substituted 1,3-disilacyclobutane reactant is defined as Q １ The silicon precursor is formed by replacing the substituents of the above, Methods that include...

8. Replacing at least one halogen substituent of the halogen-substituted 1,3-disilacyclobutane reactant results in the halogen-substituted 1,3-disilacyclobutane reactant being M(Q) １ ) ｎ The method according to claim 7, comprising contacting an organometallic salt having a general structure with a silicon precursor and a metal halide salt, further comprising (i) M is a group I metal and n is an integer equal to 1, or (ii) M is a group II metal and n is an integer equal to 2, and separating the silicon precursor from the metal halide salt.

9. The method according to claim 7, wherein the halogen-substituted 1,3-disilacyclobutane reaction substance is selected from the group consisting of 1-chloro-1,3-disilacyclobutane, 1-chloro-1,3,3-trimethyl-1,3-disilacyclobutane, 1,3-dichloro-1,3-disilacyclobutane, 1,3-dichloro-1,3-dimethyl-1,3-disilacyclobutane, 1,1,3,3-tetrachloro-1,3-disilacyclobutane, 1-bromo-1,3-disilacyclobutane, 1-bromo-1,3,3-trimethyl-1,3-disilacyclobutane, 1,3-dibromo-1,3-disilacyclobutane, 1,3-dibromo-1,3-dimethyl-1,3-disilacyclobutane, and 1,1,3,3-tetrabromo-1,3-disilacyclobutane.

10. Q １ The method according to claim 7, wherein the substituent is selected from the group consisting of an acetoxy group, an acryloyloxy group, a silyloxy group, a gelmyloxy group, and a phosphonooxy group.

11. Q １ and Q ３ The substituents are an acetoxy group, an acryloyloxy group, and C １ -C ６ A group consisting of alkoxy groups, silyloxy groups, gelmyloxy groups, phosphonooxy groups, and alkylamine groups is selected dependently from the group Q ２ and Q ４ The substituents of are a hydrogen atom and C １ -C ６ The method according to claim 7, wherein a group consisting of alkyl groups is dependently selected, and at least 85% of the silicon precursor is in cis isomer form, or at least 85% of the silicon precursor is in trans isomer form.

12. The halogen-substituted 1,3-disilacyclobutane reactant is supplied. The stereoselective formation of a 1,3-disilacyclobutane intermediate, The 1,3-disilacyclobutane intermediate is reacted to form the halogen-substituted 1,3-disilacyclobutane reactant, The method according to claim 11, including the method described in claim 11.

13. The aforementioned 1,3-disilacyclobutane intermediate is a second 1,3-disilacyclobutane intermediate, The first 1,3-disilacyclobutane intermediate is to be formed stereoselectively, The formation of the second 1,3-disilacyclobutane intermediate from the first 1,3-disilacyclobutane intermediate, The method according to claim 12, further comprising:

14. A method for depositing a carbon-doped silicon-containing film, Supplying the substrate into the reaction space, The surface of the substrate is covered with general formula (1): 【Chemistry 4】 (In the formula, Q １ C is an acetoxy group, an acryloyloxy group, and １ -C ６ A substituent selected from the group consisting of alkoxy groups, silyloxy groups, gelmyloxy groups, phosphonooxy groups, and alkylamine groups, Q ２ Q ３ , and Q ４ These are a hydrogen atom and C, respectively. １ -C ６ Alkyl alkyl groups, and Q １ A method comprising exposing a silicon precursor having a structure due to a substituent independently selected from the group consisting of the same substituents as ) to vapor.

15. In the above general formula (1), Q １ The method according to claim 14, wherein the substituent is selected from the group consisting of an acetoxy group, an acryloyloxy group, a silyloxy group, a gelmyloxy group, and a phosphonooxy group.

16. In the above general formula (1), Q １ and Q ３ The substituents of are C １ -C ６ A group consisting of an alkoxy group, an acetoxy group, an acryloyloxy group, a silyloxy group, a gelmyloxy group, a phosphonooxy group, and an alkylamine group is selected dependently from the group Q ２ and Q ４ The substituents of are a hydrogen atom and C １ -C ６ The method according to claim 14, wherein a group consisting of alkyl groups is dependently selected, and at least 85% of the silicon precursor is in cis isomer form, or at least 85% of the silicon precursor is in trans isomer form.

17. The silicon precursor is 1,3-diacetoxy-1,3-silacyclobutane, 1,3-diacetoxy-1,3-dimethyl-1,3-disilacyclobutane, 1,3-diacryloxy-1,3-disilacyclobutane, 1,3-diacryloxy-1,3-dimethyl-1,3-disilacyclobutane, 1,3-dimethylacryloyloxy-1,3-disilacyclobutane, 1,3-dimethylacryloyloxy-1,3-dimethyl-1,3-disilacyclobutane, 1,3-bis(trimethylsilyloxy)-1,3-di The method according to claim 14, selected from the group consisting of silacyclobutane, 1,3-bis(trimethylsilyloxy)-1,3-dimethyl-1,3-disilacyclobutane, 1,3-bis(trimethylgelmyloxy)-1,3-disilacyclobutane, 1,3-bis(trimethylgelmyloxy)-1,3-dimethyl-1,3-disilacyclobutane, 1,3-bis(dimethylphosphonooxy)-1,3-disilacyclobutane, and 1,3-bis(dimethylphosphonooxy)-1,3-dimethyl-1,3-disilacyclobutane.

18. The method according to claim 14, further comprising exposing the surface of the substrate to a co-reacting substance, wherein the co-reacting substance is one or more of hydrogen plasma, noble gas plasma, nitrogen plasma, and oxygen plasma.

19. The method according to claim 18, wherein the co-reacting material is one or more of hydrogen plasma and noble gas plasma, and the co-reacting material does not contain an oxygen plasma species.

20. The method according to claim 18, wherein the surface of the substrate is sequentially exposed to the vapor of the film-forming composition, and the surface of the substrate is sequentially exposed to the co-reacting substance.

21. The method according to claim 18, wherein the surface of the substrate is exposed to the vapor of the film-forming composition and the surface of the substrate is exposed to the co-reacting substance, the method wherein these actions overlap at least partially.

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