Film forming compositions, methods of forming same, and methods and systems using same

Abstract

A film forming composition is provided. The film-forming composition includes a silicon precursor having a structure according to general formula (1): (1) wherein Q1 is a substituent selected from the group consisting of an acetoxy group, an acryloyloxy group, a C1 to C6 alkoxy group, a siloxy group, a germyl alkoxy group, a phosphinyloxy group, and an alkylamine group; q2, Q3, and Q4 are each a substituent independently selected from the group consisting of a hydrogen atom, a C1-C6 alkyl group, and a substituent group of Q1. Methods for forming the film-forming compositions and methods and systems for using the film-forming compositions to deposit carbon-doped silicon-containing films on a substrate are also provided.

Description

[0001] Cross-references to related applications

[0002] This application claims the benefit of U.S. Provisional Application 63 / 700,240, filed September 27, 2024, the entire contents of which are incorporated herein by reference. Technical Field

[0003] This disclosure generally relates to the processing of semiconductor substrates. More specifically, this disclosure relates to compositions that can be used to form carbon-doped silicon-containing films, and methods and systems for forming carbon-doped silicon-containing films on a substrate surface using the compositions. Background Technology

[0004] Silicon carbide oxide (SiOC) is a promising low-ħ substitution 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 produce a sufficiently low dielectric constant while maintaining the thermal and mechanical properties required for the specific application. Furthermore, this low-ħ layer must be able to be formed using chemical vapor deposition (CVD) methods that provide conformal films with precise thickness control at temperatures consistent with the fabrication of the device structure, and, in some applications, while maintaining high yield rates.

[0005] Plasma-based CVD processes are typically used to form silicon oxide films at relatively low temperatures to reduce the thermal budget during device fabrication. The choice of chemical precursors used in the deposition method can significantly influence process conditions and the material properties of the resulting layer. The search for improved low-k material precursors for CVD processes is an ongoing effort. In this regard, this disclosure generally relates to precursor compositions and methods and systems for forming carbon-doped silicon-containing films that meet many of the requirements listed above using said precursor compositions.

[0006] Any discussion set forth in this section (including discussions of problems and solutions) is included in this disclosure solely for the purpose of providing background information. Such discussion should not be construed as an admission that any information was known at the time of making this invention or otherwise constitutes prior art. Summary of the Invention

[0007] The present invention is presented in a simplified form, and the selected concepts are described in further detail below. This invention is not intended to necessarily identify key or essential features of the claimed subject matter, nor is it intended to limit the scope of the claimed subject matter.

[0008] One aspect of this disclosure relates to a film forming composition suitable for forming carbon-doped silicon-containing films. The film forming composition comprises a silicon precursor having a structure according to general formula (1):

[0009] (1)

[0010] Among them, Q 1 The substituent is selected from acetoxy, acryloyloxy, C1 to C6 alkoxy, silyloxy, germanyloxy, phosphonoyloxy, and alkylamine; and Q 2 Q 3 and Q 4 Each is independently selected from hydrogen atoms, C1-C6 alkyl groups, and Q. 1 Substituents of the same substituent group.

[0011] In some embodiments, Q 1 The substituent group is acetoxy. In some of these examples, Q 1 Substituents and Q 3 All substituents are acetoxy groups.

[0012] In some embodiments, Q 1 The substituent is acryloyloxy. In some of these examples, Q 1 Substituent groups and Q 3 All substituent groups are acryloyloxy groups. Acryloyloxy groups can be selected from acryloyloxy or methacryloyloxy groups.

[0013] In some embodiments, Q 1 The substituent groups are C1 to C6 alkoxy groups. In some of these examples, Q 1 Substituent groups and Q 3 The substituent groups are all C1 to C6 alkoxy groups. The C1 to C6 alkoxy groups can be selected from methoxy, ethoxy, n-propoxy, isopropoxy, and butoxy.

[0014] In some embodiments, Q 1 The substituent group is silyloxy. In some of these examples, Q 1 Substituent groups and Q 3 All substituent groups are silyloxy groups. The silyloxy group can be trimethylsilyloxy.

[0015] In some embodiments, Q 1 The substituent group is methylgermanyloxy. In some of these examples, Q 1 Substituent groups and Q 3 The substituent groups are all methylgermanyloxy groups. A methylgermanyloxy group can be trimethylgermanyloxy.

[0016] In some embodiments, Q 1 The substituent group is phosphonoyloxy. In some of these examples, Q 1 Substituent groups and Q3 All substituent groups are phosphonoyloxy groups. The phosphonoyloxy group can be dimethylphosphonoyloxy.

[0017] In some embodiments, Q 1 The substituent group is an alkylamine group. In some of these examples, Q 1 Substituents and Q 3 All substituent groups are alkylamino groups. The alkylamino group can be selected from dimethylamino, diethylamino, and diisopropylamino.

[0018] In some embodiments, the substituent group Q 1 and Q 3 The substituent group is selected from acetoxy, acryloyloxy, C1 to C6 alkoxy, siloxy, germanoxy, phosphonoyloxy, and alkylamine; and the substituent group Q 2 and Q 4 Relatedly selected from hydrogen atoms and C1-C6 alkyl groups.

[0019] In some embodiments, the silicon precursor is selected from 1,3-diacetoxy-1,3-disilcyclobutane, 1,3-diacetoxy-1,3-dimethyl-1,3-disilcyclobutane, 1,3-diaacryloxy-1,3-disilcyclobutane, 1,3-diaacryloxy-1,3-dimethyl-1,3-disilcyclobutane, 1,3-dimethacryloxy-1,3-disilcyclobutane, 1,3-dimethacryloxy-1,3-dimethyl-1,3-disilcyclobutane, 1,3-bis(di-) (trimethylsilyloxy)-1,3-disilcyclobutane, 1,3-bis(trimethylsilyloxy)-1,3-dimethyl-1,3-disilcyclobutane, 1,3-bis(trimethylgermanyloxy)-1,3-disilcyclobutane, 1,3-bis(trimethylgermanyloxy)-1,3-dimethyl-1,3-disilcyclobutane, 1,3-bis(dimethylphosphono)-1,3-disilcyclobutane and 1,3-bis(dimethylphosphono)-1,3-dimethyl-1,3-disilcyclobutane.

[0020] In some embodiments, the film-forming composition is rich in isomers. In some embodiments, at least 85% of the silicon precursor is in a cis isomer form or at least 85% of the silicon precursor is in a trans isomer form. In some of these embodiments, at least 85% of the silicon precursor is in a cis isomer form, or at least 90% of the silicon precursor is in a cis isomer form, or at least 95% of the silicon precursor is in a cis isomer form, or at least 97% of the silicon precursor is in a cis isomer form, or at least 98% of the silicon precursor is in a cis isomer form, or at least 99% of the silicon precursor is in a cis isomer form, or at least 99.5% of the silicon precursor is in a cis isomer form. In some other of these embodiments, at least 85% of the silicon precursor is in the trans isomer form, or at least 90% of the silicon precursor is in the trans isomer form, or at least 95% of the silicon precursor is in the trans isomer form, or at least 97% of the silicon precursor is in the trans isomer form, or at least 98% of the silicon precursor is in the trans isomer form, or at least 99% of the silicon precursor is in the trans isomer form, or at least 99.5% of the silicon precursor is in the trans isomer form.

[0021] 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.

[0022] Another aspect of this disclosure relates to a method for forming a film-forming composition comprising a silicon precursor as described in any of the preceding paragraphs. The method includes providing a halogen-substituted 1,3-disilcyclobutane reactant containing at least one halogen substituent; and reacting at least one halogen substituent of the halogen-substituted 1,3-disilcyclobutane reactant with Q… 1 The substituent groups are exchanged to form a silicon precursor. The step of exchanging at least one halogen substituent of the halogen-substituted 1,3-disilcyclobutane reactant may include contacting the halogen-substituted 1,3-disilcyclobutane reactant with an organometallic salt, wherein the organometallic salt contains Q... 1 Substituent groups. Q 1 The substituent group can be selected from acetoxy, acryloyloxy, C1 to C6 alkoxy, siloxy, germanoxy, phosphonoyloxy and alkylamine.

[0023] In some of these embodiments, the organometallic salt has M(Q) 1 ) n The general formula structure is given by (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.

[0024] In some embodiments, the organometal salt is selected from metal acetates, metal acrylates, metal oxides, metal phosphates, metal silicon oxides, metal germanium oxides, and metal amides.

[0025] In some embodiments, the halogen-substituted 1,3-disilcyclobutane reactant is selected from 1-chloro-1,3-disilcyclobutane, 1-chloro-1,3,3-trimethyl-1,3-disilcyclobutane, 1,3-dichloro-1,3-disilcyclobutane, 1,3-dichloro-1,3-dimethyl-1,3-disilcyclobutane, 1,1,3,3-tetrachloro-1,3-disilcyclobutane, 1-bromo-1,3-disilcyclobutane, 1-bromo-1,3,3-trimethyl-1,3-disilcyclobutane, 1,3-dibromo-1,3-disilcyclobutane, 1,3-dibromo-1,3-dimethyl-1,3-disilcyclobutane, and 1,1,3,3-tetrabromo-1,3-disilcyclobutane.

[0026] In some embodiments, the method further includes separating the silicon precursor from the metal halide salt.

[0027] In some embodiments, the step of providing the halogen-substituted 1,3-disilcyclobutane reactant includes stereoselectively forming a 1,3-disilcyclobutane intermediate; and reacting the 1,3-disilcyclobutane intermediate to form the halogen-substituted 1,3-disilcyclobutane reactant. In some of these embodiments, the 1,3-disilcyclobutane intermediate is a second 1,3-disilcyclobutane intermediate, and the method further includes stereoselectively forming a first 1,3-disilcyclobutane intermediate; and forming a second 1,3-disilcyclobutane intermediate from the first 1,3-disilcyclobutane intermediate.

[0028] In some embodiments, a silicon precursor is formed such that at least 85% of the silicon precursor is in a cis isomer form or at least 85% of the silicon precursor is in a trans isomer form. In some of these embodiments, at least 85% of the silicon precursor is in a cis isomer form, or at least 90% of the silicon precursor is in a cis isomer form, or at least 95% of the silicon precursor is in a cis isomer form, or at least 97% of the silicon precursor is in a cis isomer form, or at least 98% of the silicon precursor is in a cis isomer form, or at least 99% of the silicon precursor is in a cis isomer form, or at least 99.5% of the silicon precursor is in a cis isomer form. In some other of these embodiments, at least 85% of the silicon precursor is in the trans isomer form, or at least 90% of the silicon precursor is in the trans isomer form, or at least 95% of the silicon precursor is in the trans isomer form, or at least 97% of the silicon precursor is in the trans isomer form, or at least 98% of the silicon precursor is in the trans isomer form, or at least 99% of the silicon precursor is in the trans isomer form, or at least 99.5% of the silicon precursor is in the trans isomer form.

[0029] Another aspect of this disclosure relates to a vapor delivery container comprising a film-forming composition including a silicon precursor as described in any of the relevant paragraphs above. The vapor delivery container includes an outer wall surrounding a cavity for storing the film-forming composition and a gas outlet for allowing vapor of the film-forming composition to exit the cavity.

[0030] In some embodiments, the vapor delivery container further includes a gas inlet and a conduit extending into the cavity to a fixed point. The conduit may extend into the cavity and into the membrane forming composition to allow a carrier gas to pass through the membrane forming composition. Alternatively, the conduit may extend into the cavity to a point above the membrane forming to allow a carrier gas to pass over the surface of the membrane forming composition.

[0031] In some embodiments, the vapor delivery vessel further includes a probe component. The probe component may include one or more temperature sensors and / or one or more level sensors and one or more pressure sensors.

[0032] In some embodiments, the outer wall and cavity of the steam delivery container are formed of stainless steel.

[0033] Another aspect of this 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 includes: providing a substrate in a reaction space; and exposing the substrate surface to a vapor of the film-forming composition. In some embodiments, the method further includes exposing the substrate surface to a co-reactant.

[0034] In some embodiments, a method for forming a carbon-doped silicon-containing film includes performing one or more deposition cycles of a cyclic deposition process, the cyclic deposition process including exposing a surface of a substrate to a film-forming composition; and exposing a surface of the substrate to a co-reactant, thereby forming a carbon-doped silicon-containing film on the surface of the substrate. The exposure step may be repeated once or more (n) times. The cyclic deposition process may include one or more of an ALD process and a cyclic CVD process.

[0035] In some embodiments, the co-reactant comprises a plasma material. The plasma material may be one or more of hydrogen plasma, rare gas plasma, nitrogen plasma, and oxygen plasma. In some of these embodiments, the co-reactant 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 hydrogen plasma, rare gas plasma, nitrogen plasma, and oxygen plasma. In some embodiments, the plasma is one or more of hydrogen plasma and rare gas plasma.

[0036] In some embodiments, the co-reactants do not contain oxygen plasma material. In some of these embodiments, the surface of the substrate is not exposed to oxygen plasma or oxygen plasma material.

[0037] In some embodiments, the surface of the substrate is exposed to direct plasma. In some other embodiments, the surface of the substrate is exposed to remote plasma.

[0038] In some embodiments, the steps of exposing the substrate surface to the vapor of the film-forming composition and exposing the substrate surface to the co-reactant occur sequentially. In some other embodiments, the steps of exposing the substrate surface to the vapor of the film-forming composition and exposing the substrate surface to the co-reactant at least partially overlap.

[0039] In some embodiments, the reaction space is purged after exposing the surface of the substrate to the vapor of the film-forming composition and to one or more of the co-reactants.

[0040] In some embodiments, the method further includes maintaining the temperature of the substrate at no more than about 450°C during one or both of the exposure steps. The temperature of the substrate may be maintained at at least about 100°C and no more than about 400°C, or at least about 100°C and no more than about 300°C, or at least about 100°C and no more than about 250°C.

[0041] Another aspect of this 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 foregoing relevant paragraphs, according to the method described in any of the foregoing relevant paragraphs. The system may include a reaction space for containing a substrate and means for exposing the surface of the substrate to a vapor of the film-forming composition. The system may also include means for exposing the surface of the substrate to a co-reactant and, optionally, means for purging the reaction space after one or both of the exposure steps.

[0042] In some embodiments, the system includes: a reaction space for accommodating a substrate; a film-forming composition source for providing vapor of the film-forming composition, the film-forming composition source being in gas communication with the reaction space via a first valve; a co-reactant source for providing co-reactants, the co-reactant source being in gas communication with the reaction space via a second valve; and a plasma generator.

[0043] In some embodiments, the system further includes a controller operatively connected to the first valve, the second valve, and the plasma generator, wherein the controller is configured and programmed to control the supply of the film-forming composition to the reaction space, the supply of co-reactants to the reaction space, and the activation of the plasma generator. The controller may be programmed to repeat various process steps n times to deposit a carbon-doped silicon-containing film on the surface of the substrate.

[0044] In some embodiments, the plasma generator includes a direct plasma unit. In some other embodiments, the plasma generator includes a remote plasma unit.

[0045] In some embodiments, the reaction space includes one or more heating elements and one or more thermocouples in thermal communication with the substrate to measure the temperature of the substrate and maintain it at a set temperature. In some of these embodiments, a controller is operatively 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.

[0046] In some embodiments, the membrane forming composition source includes a vapor delivery container containing the membrane forming composition.

[0047] Another aspect of this disclosure relates to carbon-doped silicon films formed using film-forming compositions including silicon precursors as described in any of the foregoing relevant paragraphs, and further using the methods and systems described in any of the foregoing relevant paragraphs.

[0048] In some embodiments, the carbon-doped silicon film comprises a silicon precursor and / or a portion or fragment of a silicon precursor.

[0049] In some embodiments, the carbon content of the carbon-doped silicon film is at least about 5 atomic% and not more than about 50 atomic%, or at least about 10% and not more than about 50%, or at least about 20% and not more than about 50%.

[0050] In some embodiments, the dielectric constant (ĸ) of the carbon-doped silicon film is 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.

[0051] In some embodiments, the carbon-doped silicon-containing film has a stepped coverage of about 80% or more, or about 90% or more. In some of these embodiments, the carbon-doped silicon-containing film has a stepped coverage of about 90% or more and less than about 110%, or about 95% or more and less than about 105%.

[0052] These and other embodiments will become apparent to those skilled in the art from the following detailed description of certain embodiments and further reference to the accompanying drawings. Unless otherwise stated, these embodiments or components thereof may be combined, or they may be applied separately from each other where applicable. The invention is not limited to any particular embodiment disclosed. Attached Figure Description

[0053] The accompanying drawings form part of this specification. The drawings are included to provide a further understanding of this disclosure and, together with the specification, to explain certain principles of this disclosure. The drawings illustrate exemplary embodiments of how this disclosure can be made and used and should not be construed as limiting this disclosure to merely the examples shown and described. It should be understood that the elements in the drawings are shown for simplicity and clarity and are not necessarily drawn to scale. The illustrations presented herein are not intended to be actual views of any particular material, structure, or device, but are merely idealized representations used to describe embodiments of this disclosure. For example, the dimensions of some elements in the drawings may be exaggerated relative to other elements to aid in understanding the embodiments shown in this disclosure. Further features and advantages will become apparent from the following more detailed description of various aspects, embodiments, and configurations of this disclosure, as shown in the accompanying drawings referenced below.

[0054] Figure 1 An example of a synthesis scheme for preferentially forming the trans isomer form of a silicon precursor is shown.

[0055] Figure 2 Another embodiment of the synthesis scheme for preferentially forming the trans isomer form of the silicon precursor is shown.

[0056] Figure 3 An example of a synthesis scheme for preferentially forming the cis isomer form of the silicon precursor is shown.

[0057] Figure 4 This is a process flow diagram of a method for forming a carbon-doped silicon-containing film according to embodiments of the present disclosure.

[0058] Figure 5 This 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.

[0059] Figure 6 This is a perspective view of a vapor delivery container according to an embodiment of the present disclosure, showing a membrane forming composition stored therein. Detailed Implementation

[0060] The descriptions of embodiments of the compositions, methods, and systems provided below are exemplary only and intended for illustrative purposes. The following description is not intended to limit the scope of this disclosure or the claims. Furthermore, the description of multiple embodiments with indicative features is not intended to exclude other embodiments with additional features or other embodiments containing different combinations of said features. Unless otherwise stated, exemplary embodiments or components thereof may be combined or applied separately from each other. The headings provided herein (if any) are for convenience only and do not necessarily affect the scope or meaning of the claimed invention.

[0061] definition

[0062] As used herein, the abbreviation "ALD" for "atomic layer deposition" refers to a vapor-phase deposition process in which deposition cycles, such as multiple consecutive deposition cycles, are performed in a reaction space (e.g., one or more reaction chambers). Typically, in an ALD process, during each deposition cycle, a precursor is introduced into the reaction space and adsorbed onto a substrate surface, which may include previously deposited material from previous ALD cycles or other materials, thus forming at most a monolayer of the precursor that is not readily reacted with additional excess precursor (i.e., a self-limiting reaction). Subsequently, in some cases, another precursor or reactant may be introduced into the reaction space to convert the adsorbed precursor into the desired material on the substrate surface. Additional reaction steps may be included in the deposition cycle. ALD can occur via a thermal process (thermal ALD), where the reaction is promoted by increasing the substrate temperature relative to ambient temperature; or via a plasma-enhanced process (PE-ALD) or a radical-enhanced process (RE-ALD), where the reaction is promoted by using high-energy plasma materials. As used herein, ALD can also refer to processes specified by related 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.

[0063] As used herein, “chemical vapor deposition” (abbreviated as “CVD”) refers to a vapor-phase deposition process that deposits a film on a substrate by exposing the substrate surface to one or more gaseous precursors and reactants, which react and / or decompose on the substrate surface to form the film. The precursors and / or reactants may be provided simultaneously to the reaction space or in partially or completely separate pulses. In some embodiments, the precursors and / or reactants are provided until a layer of the desired thickness is deposited. In some embodiments, a cyclic CVD process may be used in combination with multiple cycles to deposit a thin film of the desired thickness. During a cyclic CVD process, the precursors and / or reactants may be provided to the reaction space in non-overlapping or partially or completely overlapping pulses. CVD can occur via a thermal process (thermal CVD), where the reaction is promoted by increasing the substrate temperature relative to ambient temperature; or via a plasma-enhanced CVD process, where a high-energy plasma material is used to promote the reaction.

[0064] As used herein, a “cyclic deposition process” refers to a method or process that includes sequentially introducing precursors and / or reactants into a reaction space to deposit a layer or film on or over a substrate, and includes processing techniques such as ALD, cyclic CVD, and hybrid cyclic deposition processes that include an ALD component and a cyclic CVD component. In a preferred embodiment, the cyclic deposition process disclosed herein refers to an ALD process.

[0065] As used herein, the interchangeable terms "membrane" or "layer" refer to a continuous, substantially continuous, or discontinuous material extending in a direction perpendicular to its thickness direction to cover at least a portion of a surface. A membrane may be positioned on a side surface and / or on sidewalls of recessed features of the surface. Membranes 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. A membrane may be constructed from one or more indistinguishable monolayers or sub-monolayers to produce a homogeneous or substantially homogeneous material, wherein the number of monolayers or sub-monolayers affects the membrane's thickness.

[0066] As used herein, “gas” refers to a state of matter consisting of atoms or molecules that have neither a defined volume nor a defined shape. Gases include evaporating solids and / or liquids and may be referred to as vapors. Depending on the circumstances, a gas may consist of a single gas or a mixture of gases.

[0067] As used herein, a "precursor" refers to a compound that participates in a chemical reaction to form another compound or element, wherein a portion of the precursor (an element or group within the precursor) is incorporated into the compound or element produced by the chemical reaction. The compound or element produced by the chemical reaction may be a layer and / or film formed on a substrate surface.

[0068] As used herein, the term “purging” can refer to, for example, the process of removing gaseous precursors, reactants and / or gaseous byproducts from a substrate surface by evacuating the reaction space with a vacuum pump and / or by replacing the gas in the reaction space with an inert or substantially inert gas (such as argon or nitrogen).

[0069] As used herein, "reactant" refers to a compound that participates in a chemical reaction to form another compound or element. In some cases, a reactant is a precursor. In other cases, the compound or element produced by the chemical reaction does not contain any part or significant portion of the reactant (the element or group within the reactant), and therefore the reactant is not a precursor.

[0070] As used herein, "substrate" refers to one or more underlying materials on which devices, circuits, materials, or material layers can be formed or on which they are formed. Substrates can be continuous or discontinuous; rigid or flexible; solid or porous; and combinations thereof. Substrates can be in any form, such as powder, sheet, plate, or workpiece. Sheet-form substrates can extend beyond the boundary of the process / reaction chamber where the deposition process occurs, and in some cases, move through the chamber such that the process continues until the end of the substrate is reached. Plate-form substrates can include wafers of various shapes and sizes. Substrates can be made of semiconductor materials, including, for example, silicon, silicon germanium, silicon oxide, gallium arsenide, gallium nitride, and silicon carbide. Substrates can include one or more layers covering a bulk material, such as nitrides (e.g., 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, such as gaps, grooves, lines, trenches, vias, holes, or spaces between raised portions (e.g., fins) formed in or on at least a portion of a layer of the substrate.

[0071] As used in this paper, “step coverage” refers to the growth rate of the layer on the distal surface of the recess divided by the growth rate of the layer on the proximal surface of the recess, expressed as a percentage. Step coverage provides a measure of the conformability of the layer.

[0072] As used herein, a “vapor delivery container” refers to a container configured for the vapor delivery of a substance contained within it. A vapor delivery container includes an outer wall and a fluid outlet; the outer wall surrounds a cavity for storing and / or retaining the substance, and the fluid outlet allows the vapor of the substance to exit the cavity. The substance contained within the cavity can be a composition suitable for vapor deposition. For example, the substance contained within the cavity may include one or more precursors. The substance contained within the cavity can be a homogeneous or heterogeneous mixture. The substance contained within the cavity can be in solid, liquid, gaseous, or a combination thereof. Vapor delivery containers may have vapor suction configurations, carrier gas configurations, double-wall configurations, sublimation configurations, and / or other configurations.

[0073] As used herein, the abbreviation "WER" for "wet etch rate" refers to the rate of material loss when the material is exposed to a liquid etchant. For example, WER can refer to material loss from a layer, which can be determined by measuring the decrease in layer thickness as a function of time. In some embodiments, WER can be measured by exposing the layer to dilute hydrofluoric acid (dHF).

[0074] The article “a” or “one” refers to a substance or a genus that includes multiple substances, depending on the context. Therefore, the terms “a / one,” “one or more,” and “at least one” are used interchangeably in this document.

[0075] The terms “comprising,” “including,” and “having” are open-ended and do not exclude the presence of other elements or components unless the context clearly indicates otherwise. “Comprising,” “including,” and “having” are used interchangeably and include the meaning of “consisting of.” However, unless the context clearly indicates otherwise, the phrase “consisting of” indicates that no other features or components exist besides those mentioned.

[0076] The term "approximately" applied to values ​​typically refers to a range of numbers that are considered equivalent to the value (e.g., having the same function or result). In some cases, the term "approximately" may include numerical values ​​rounded to the nearest significant figure.

[0077] The term "basic" when applied to compositions, methods, systems, or structures generally means that the additional components do not substantially alter the properties, characteristics, and / or functions of the composition, method, system, or structure.

[0078] The term "basic" applied to compositions, methods, systems, or structures generally refers to a proportion of a value, property, characteristic, etc., or conversely, a lack thereof, and 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 proportion between about 70% and about 100%. In some embodiments, the term "basic" means a proportion 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%.

[0079] The terms “on” or “above” are used to describe relative positional relationships. For example, an element, membrane, or layer may be directly positioned on or above at least a portion of another element, membrane, or layer and in physical contact with at least a portion of the other element, membrane, or layer; or alternatively, an element, membrane, or layer may be on or above another element, membrane, or layer, but with one or more inserted elements, membranes, or layers therebetween. Therefore, unless the term “directly” is used alone, the terms “on” or “above” will be interpreted as relative concepts. Similarly, it will be understood that the terms “below,” “lower layer,” or “below” describe relative positional relationships and, unless otherwise stated, should be interpreted as relative concepts.

[0080] The terms “at least one,” “one or more,” and “and / or” are open-ended expressions that are both conjunction and disjunctive in operation. For example, each of 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,” “one or more of A, B, or C,” and “A, B, and / or C” means a single A, a single B, a single C, A and B together, A and C together, B and C together, or A, B, and C together. When each of A, B, and C in the above expressions refers to an element, such as Q, Y, and Z, or an element category, such as Q1-X, this is also true. n Y1-Y m and Z1-Z o When used, this phrase is intended to refer to a single element selected from Q, Y, and Z, or a combination of elements selected from the same category (e.g., Q). 1 and Q 2 ) and combinations of elements selected from two or more categories (e.g., Y1 and Z1).

[0081] It should be understood that every numerical range given in this disclosure is considered to include the upper and lower limits, as well as every narrower numerical range falling within such a wider range, as all such narrower numerical ranges are explicitly stated herein. For example, the phrase “about 2 to about 4” or “2 to 4” includes 2 and 4, as well as integer and / or integer ranges of about 2 to about 3, about 3 to about 4, and every possible range based on real numbers (e.g., irrational and / or rational numbers), such as about 2.1 to about 3.9, about 2.1 to about 3.4, etc.

[0082] This article uses the standard abbreviations for elements in the periodic table.

[0083] Throughout this disclosure, chemical compounds, their functional groups or substituents or ligands may be referred to by their chemical names (e.g., IUPAC names or common names), abbreviated molecular formulas, or both. Alternatively or additionally, compounds may be shown by structures that may be provided in rod-like or partially rod-like form and may omit hydrogen atoms. In the event of a conflict between chemical names and / or molecular formulas and / or structures, where a person skilled in the art cannot definitively determine the characteristics of the compound, its functional groups or substituents or ligands, the structure shall prevail, followed by the molecular formula.

[0084] In this disclosure, the meaning of any definition is not necessarily excluded from its common and conventional meaning in some embodiments.

[0085] describe

[0086] This document discloses compositions configured for or suitable for forming carbon-doped silicon-containing films. The film-forming compositions comprise a silicon precursor having a structure comprising a 1,3-disilcyclobutane core and at least one substituent group bonded to a silicon atom of the 1,3-disilcyclobutane core and selected from acetoxy, acryloyloxy, C1-C6 alkoxy, silanoxy, germanoalkoxy, phosphonoyloxy, and alkylamine groups. This document also discloses methods for preparing the film-forming compositions and vapor deposition methods and systems for forming carbon-doped silicon-containing films using said compositions.

[0087] As used herein, a carbon-doped silicon-containing film refers to a film comprising silicon (Si), oxygen (O), and carbon (C). In some embodiments, in addition to Si, O, and C, the carbon-doped silicon-containing film also comprises one or more other elements, such as nitrogen (N) and / or hydrogen (H). In some embodiments, the carbon-doped silicon-containing film comprises silicon carbide (SiOC) (which may also be referred to in the literature as silicon carbide (SiCO)). In some embodiments, the carbon-doped silicon-containing film is composed of or substantially of silicon carbide (SiOC). In some embodiments, the carbon-doped silicon-containing film comprises silicon oxycarbonitride (SiOCN). In some embodiments, the carbon-doped silicon-containing film is composed of or substantially of silicon oxycarbonitride (SiOCN). In some embodiments, the carbon-doped silicon-containing film comprises Si-C bonds and Si-O bonds, and may not contain Si-N bonds. However, in some other embodiments, the carbon-doped silicon-containing film comprises Si-C bonds, Si-O bonds, and Si-N bonds. In some embodiments, the ratio of Si-O bonds to Si-C bonds is from about 1:1 to about 10:1. In some embodiments, the carbon-doped silicon-containing film comprises about 0.1% to about 70% carbon on an atomic basis. In some embodiments, the carbon-doped silicon-containing film comprises about 0.5% to about 60%, about 1% to about 50%, about 5% to about 50%, about 10% to about 50%, or about 20% to about 50% carbon on an atomic basis. In some embodiments, the carbon-doped silicon-containing film comprises about 5% to about 70% oxygen on an atomic basis. In some embodiments, the carbon-doped silicon-containing film comprises about 10% to about 70%, about 15% to about 50%, or about 20% to about 40% oxygen on an atomic basis. In some embodiments, the carbon-doped silicon-containing film comprises about 5% to about 50% silicon on an atomic basis. In some embodiments, the carbon-doped silicon-containing film comprises about 10% to about 50%, 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 comprises about 0.1% to about 50%, about 0.1% to about 40%, about 0.1% to about 30%, about 0.1% to about 25%, about 0.1% to about 20%, 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 comprises hydrogen. In some embodiments, the carbon-doped silicon-containing film comprises about 0.1% to about 35%, about 0.1% to about 20%, about 0.1% to about 15%, about 0.1% to about 10%, or about 0.1% to about 5% of hydrogen on an atomic basis.

[0088] One aspect of this disclosure relates to a film-forming composition suitable for forming carbon-doped silicon films. The film-forming composition comprises a silicon precursor having a structure comprising a 1,3-disilcyclobutane core and at least one substituent group bonded to a silicon atom of the disilcyclobutane core, the substituent being selected from acetoxy, acryloyloxy, C1 to C6 alkoxy, silanoxy, germanoalkoxy, phosphonoyloxy, and alkylamine groups. More specifically, in embodiments, the silicon precursor has a structure according to general formula (1):

[0089] (1)

[0090] Among them, Q 1 The substituent is selected from acetoxy, acryloyloxy, C1-C6 alkoxy, siloxy, germanoxy, phosphonoyloxy, and alkylamine; Q 2 Q 3 and Q 4 Each is a substituent independently selected from hydrogen atom, C1-C6 alkyl, acetoxy, acryloyloxy, C1-C6 alkoxy, siloxy, germanoxy, phosphonoyloxy, and alkylamine.

[0091] Regarding general formula (1): Acetoxy is represented by the chemical formula CH3C(=O)O. Acryloyloxy is represented by the chemical formula H2C=C(R)C(=O)O, where R is a hydrogen atom or an alkyl group, usually a C1-C6 alkyl group, and more usually a methyl group. Therefore, acryloyloxy can refer to acryloyloxy (H2C=CHC(=O)O), methacryloyloxy (H2C=C(CH3)C(=O)O), etc. C1-C6 alkoxy groups can have straight-chain or branched structures and are selected from methoxy (CH3O), ethoxy (C2H5O), isopropoxy (i-C3H7O), n-propoxy (n-C3H7O), butoxy (C4H9O), pentoxy (C5H9O), etc. 11 O) and hexyloxy (C6H) 13O), typically selected from methoxy (CH3O) and ethoxy (C2H5O). Silyoxy groups are represented by the chemical formula R3SO, where each R is an independently chosen alkyl group, typically C1-C6 alkyl, and more typically methyl. A suitable example of a siloxy group is trimethylsiloxy ((CH3)3SO). Germanyloxy groups are represented by the chemical formula R3GeO, where each R is an independently chosen alkyl group, typically C1-C6 alkyl, and more typically methyl. A suitable example of a Germanyloxy group is trimethylgermanyloxy ((CH3)3GeO). Phosphonoyloxy groups are represented by the chemical formula (RO)2P(=O)O, where each R is an independently chosen alkyl group, typically C1-C6 alkyl, and more typically methyl. A suitable example of a phosphonoyloxy group is dimethylphosphonoyloxy ((CH3O)2P(=O)O). Alkylamino groups are represented by the chemical formula NR2, where each R is an independently chosen alkyl group, typically C1-C6 alkyl. Suitable examples of alkylamine groups are dimethylamine (N(CH3)2), diethylamine (N(C2H5)2), diisopropylamine (N(i-C3H7)2), etc. C1-C6 alkyl groups can have straight-chain or branched structures and can be selected from methyl (CH3), ethyl (C2H5), propyl (C3H7), butyl (C4H9), pentyl (C5H9), etc. 11 ) and hexyl (C6H 13 ), usually selected from methyl (CH3) and ethyl (C2H5).

[0092] In some embodiments, Q 1 The substituent is selected from acetoxy, acryloyloxy, C1-C6 alkoxy, siloxy, germanoxy, phosphonoyloxy, and alkylamine; Q 2 Q 3 and Q 4 Each is independently selected from hydrogen atoms, C1-C6 alkyl groups, and Q. 1 Substituents of the same substituent group. In some of these examples, Q 1 and Q 3 They are the same substituent groups (i.e., Q). 1 =Q 3 Therefore, in these embodiments, general formula (1) can be expressed as:

[0093] .

[0094] Furthermore, in some of these embodiments, Q 1 and Q 3 They are the same substituent groups, Q 2 and Q 4 They are the same substituent groups (i.e., Q). 1 =Q 3 and Q 2 =Q4 Therefore, in these embodiments, general formula (1) can be expressed as:

[0095] .

[0096] In some embodiments, the silicon precursor has a structure according to general formula (1), wherein Q 1 and Q 3 Relevantly selected from acetoxy, acryloyloxy, C1-C6 alkoxy, siloxy, germanoxy, phosphonoyloxy, and alkylamine groups; Q 2 and Q 4 Each is specifically selected from hydrogen atoms and C1-C6 alkyl groups. For example, Q 1 and Q 3 Each can be an acetoxy group, Q 2 Both Q and Q4 can be relatedly selected from hydrogen atoms or C1-C6 alkyl groups. In another example, Q... 1 and Q 3 Each can be an acryloxy group, Q 2 and Q 4 Each can be selected from hydrogen atoms or C1-C6 alkyl groups. In yet another example, Q 1 and Q 3 Each can be a C1-C6 alkoxy group and Q 2 and Q 4 Each can be selected from hydrogen atoms or C1-C6 alkyl groups. In yet another example, Q 1 and Q 3 Each can be a silyloxy group, Q 2 and Q 4 Each can be selected from hydrogen atoms or C1-C6 alkyl groups. In yet another example, Q 1 and Q 3 Each can be a morganoalkoxy group, Q 2 and Q 4 Each can be selected from hydrogen atoms or C1-C6 alkyl groups. In yet another example, Q 1 and Q 3 Each can be a phosphonoyloxy group, Q 2 and Q 4 Each can be selected from hydrogen atoms or C1-C6 alkyl groups. In yet another example, Q 1 and Q 3 Each can be an alkylamine group, Q 2 and Q 4 Each can be selected from hydrogen atoms or C1-C6 alkyl groups.

[0097] It has a structure according to general formula (1) (where Q) 1 =Q 3 and Q 2 =Q4 Suitable examples of silicon precursors include those structures shown in Table 1.

[0098] Table 1—Exemplary silicon precursors according to general formula (1)

[0099]

[0100] 1,3-Diaacetoxy-1,3-disilcyclobutane

[0101]

[0102] 1,3-Diacryloyloxy-1,3-disilcyclobutane 1,3-Diacryloyloxy-1,3-dimethyl-1,3-disil Cyclobutane

[0103]

[0104] 1,3-Dimethacryloxy-1,3-disilcyclobutane 1,3-Dimethacryloxy-1,3-dimethyl- 1,3-Disilcyclobutane

[0105]

[0106] 1,3-Diethoxy-1,3-disilcyclobutane

[0107]

[0108] 1,3-Bis(trimethylsiloxy)-1,3-disilcyclobutane 3-Dimethyl-1,3-disilcyclobutane

[0109]

[0110] 1,3-Bis(trimethylgermanyloxy)-1,3-disilcyclobutane 3-Dimethyl-1,3-disilcyclobutane

[0111]

[0112] 1,3-Bis(dimethylphosphono)-1,3-disilcyclobutane Methyl-1,3-disilcyclobutane

[0113]

[0114] 1,3-Bis(diethylamine)-1,3-disilcyclobutane

[0115] In some embodiments of this disclosure, the silicon precursor according to general formula (1) may comprise cis and trans isomers.

[0116]

[0117] Ciss and trans

[0118] In the cis isomer form, the substituent Q 1 and Q 3 All are located at the axial or equatorial position of the disiloxane ring. In the trans isomer form, the substituent Q... 1 Or Q 3One of them is located in an axial position, while the other is located at the equatorial position of the disiloxane ring. As a non-limiting example, the silicon precursors shown in Table 1 can be in cis isomer form and trans isomer form. Thus, the film-forming composition may contain a mixture of cis and trans isomers. However, for some applications, it may be desirable to have a composition that is isomer-pure or at least isomer-rich. For example, for thin film deposition applications, an isomer-pure (or isomer-rich) composition can provide a film with less variability in film structure. It is not desirable to be bound by a particular theory, as the isomers can interact differently with the surface of the substrate, resulting in 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 small 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 predominantly or substantially in cis 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 the cis isomer to the trans isomer 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 predominantly or substantially in the cis isomer form. Alternatively, in some of these embodiments, at least about 70% of the silicon precursor is in the trans isomer form, or at least about 75% of the silicon precursor is in the trans isomer form, or at least about 80% of the silicon precursor is in the trans isomer form, or at least about 85% of the silicon precursor is in the trans isomer form, or at least about 90% of the silicon precursor is in the trans isomer form, or at least about 95% of the silicon precursor is in the trans isomer form, or at least about 97% of the silicon precursor is in the trans isomer form, or at least about 98% of the silicon precursor is in the trans isomer form, or at least about 99% of the silicon precursor is in the trans isomer form, or at least about 99.5% of the silicon precursor is in the trans isomer form.In other words, in some embodiments, the ratio of the trans isomer to the cis isomer 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 predominantly or substantially in the trans isomer form. Such isomer-pure or isomer-rich compositions can be advantageously formed using the methods disclosed herein.

[0119] According to certain embodiments of this disclosure, a film-forming composition comprising a silicon precursor having the structure of general formula (1) can be formed by contacting a halogen-substituted 1,3-disilcyclobutane reactant with an organometallic salt (e.g., the metal salt comprising at least one organic group). In some embodiments, the method for forming the film-forming composition comprises providing a halogen-substituted 1,3-disilcyclobutane reactant comprising at least one halogen substituent, and exchanging at least one halogen substituent of the halogen-substituted 1,3-disilcyclobutane reactant with a substituent group of Q1 to form a silicon precursor. Example reactions are shown in equations (1), (2), and (3).

[0120] Equation (1)

[0121] Equation (2)

[0122] Equation (3)

[0123] 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 It has the same substituent group distribution as given in general formula (1) above. The organometallic salt has the structure M(Q) 1 ) n Where M is a metal, and n is an integer, usually 1 or 2, depending on the oxidation state of the metal. In the reactions shown in equations (1), (2), and (3), the halogen group on the halogen-substituted 1,3-disilcyclobutane reactant is exchanged for Q. 1 Substituent groups are used to form silicon precursors and metal halide salts (M(X)). n Silicon precursors can typically be separated from metal halide salts by filtration or decantation.

[0124] 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 metal acetates, metal acrylates, metal oxides, metal phosphates, metal silicon oxides, metal germanium 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)), magnesium methacrylate (Mg(O)C(CH3)CH2)2), lithium methacrylate (Li(OC(=O)C(CH3)CH2)), and magnesium methacrylate (Mg(O)C(CH3)CH2)2). Lithium dimethylamino (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 trimethylsiloxane (Na(OSi(CH3)3)), and sodium trimethylgermanium oxide (Na(OGe(CH3)3)) are commercially available or can be readily synthesized using known methods reported in the literature.

[0125] As shown in equation (1), in some embodiments, the halogen-substituted 1,3-disilcyclobutane reactant is monohalogen-substituted, and referring to general formula (1), the reaction produces a silicon precursor, wherein Q 1 Selected from acetoxy, acryloyloxy, C1-C6 alkoxy, siloxy, germanoxy, phosphonoyloxy, and alkylamine groups; and Q 2 Q 3 and Q 4 The reactants are independently selected from hydrogen atoms or C1-C6 alkyl groups. Suitable monohalogenated 1,3-disilcyclobutane reactants include 1-chloro-1,3-disilcyclobutane, 1-chloro-1,3,3-trimethyl-1,3-disilcyclobutane, 1-bromo-1,3-disilcyclobutane, 1-bromo-1,3,3-trimethyl-1,3-disilcyclobutane, etc., which are commercially available or readily synthesized using known methods reported in the literature.

[0126] As shown in equation (2), in some embodiments, the halogen-substituted 1,3-disilcyclobutane reactant is tetrahalogen-substituted, and referring to general formula (1), the reaction produces a silicon precursor, wherein Q 1 Q 2 Q 3 and Q 4Relevantly selected from acetoxy, acryloyloxy, C1-C6 alkoxy, siloxy, germanoxy, phosphonoyloxy, and alkylamine (i.e., Q) 1 =Q 2 =Q 3 =Q 4 Suitable tetrahalogen-substituted 1,3-disilcyclobutane reactants include 1,1,3,3-tetrachloro-1,3-disilcyclobutane, 1,1,3,3-tetrabromo-1,3-disilcyclobutane, etc., which are commercially available or readily synthesized using known methods reported in the literature.

[0127] As shown in equation (3), in some embodiments, the halogen-substituted 1,3-disilcyclobutane reactant is dihalogen-substituted, and referring to general formula (1), the reaction produces a silicon precursor, wherein Q 1 and Q 3 Relevantly selected from acetoxy, acryloyloxy, C1-C6 alkoxy, siloxy, germanoxy, phosphonoyloxy, and alkylamine (i.e., Q) 1 =Q 3 );Q 2 and Q 4 Selected from hydrogen atoms or C1-C6 alkyl groups. Suitable dihalogen-substituted 1,3-disilcyclobutane reactants include 1,3-dichloro-1,3-disilcyclobutane, 1,3-dichloro-1,3-dimethyl-1,3-disilcyclobutane, 1,3-dibromo-1,3-disilcyclobutane, 1,3-dibromo-1,3-dimethyl-1,3-disilcyclobutane, etc., each of which is commercially available or readily synthesized using known methods reported in the literature. Exemplary silicon precursors that can be formed by the reaction shown in equation (3) are provided in Table 1. As mentioned above, such silicon precursors can be formed in cis isomer form and trans isomer form, resulting in a mixture of the two isomers, which may be undesirable for some applications. Therefore, in some embodiments, membrane-forming compositions comprising a mixture of cis / trans isomers may be purified to remove or at least partially remove one of the two isomers. Suitable separation methods may include chromatography. Alternatively, such silicon precursors can be formed by customizing synthetic routes to preferentially form either the trans or cis isomers. In this regard, the inventors of this disclosure have devised synthetic routes for substantially forming the disclosed film-forming compositions comprising the trans or cis isomer forms of the silicon precursors.

[0128] In some embodiments of this disclosure, the silicon precursor is preferably formed in either a cis or trans isomer. In some of these embodiments, the ratio of the cis 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 other embodiments of these examples, the ratio of the trans isomer to the cis isomer 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-disilcyclobutane reactant from a stereoisomer-rich 1,3-disilcyclobutane intermediate, which is substantially in either the cis or trans isomer form. Therefore, in these embodiments, the method for forming the film-forming composition includes stereoselectively forming a 1,3-disilcyclobutane intermediate and then reacting the (stereoisomer-rich) 1,3-disilcyclobutane intermediate to form a halogen-substituted 1,3-disilcyclobutane reactant. Therefore, based on the major stereoisomers of the 1,3-disilcyclobutane intermediate, halogenated 1,3-disilcyclobutane reactants are provided primarily in the cis isomer or primarily in the trans isomer. The halogen substituents of the halogenated 1,3-disilcyclobutane reactants are then reacted with Q... 1 The subsequent reaction steps involving the exchange of substituent groups (as shown in equation (3)) also substantially form the corresponding stereoisomers of the silicon precursor.

[0129] Figure 1 The general reaction sequence for preferentially forming a silicon precursor (1d) in the trans isomer form according to embodiments of the present disclosure is shown. The silicon precursor (1d) has a structure described by general formula (1), wherein 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 2The same substituent groups are assigned as given in general formula (1) above. In the first step of reaction sequence 10, a 1,3-disilcyclobutane intermediate (1b) is formed by a stereoselective ring-forming reaction. The halo(halomethyl)oxysilane reactant (1a) contains a large substituent (represented by OZ), and therefore, the ring-forming reaction essentially forms the trans isomer of the 1,3-disilcyclobutane intermediate (1b). The formation of the cis isomer of the 1,3-disilcyclobutane intermediate (not shown) is sterically unfavorable, and therefore, the formation of any cis isomer is rare. Large substituents on the halo(halomethyl)oxysilane reactant (1a) can be selected to minimize or eliminate the formation of the cis isomer. Examples of large substituents include, but are not limited to, triphenylmethoxy, 1,1-bis(1,1-dimethylethyl)-2,2-dimethylpropoxy, di-tert-butylphenoxy, or adamantylalkoxy, which are shown in Figure 1 In the box in the reaction sequence 11, the large substituent on the 1,3-disilcyclobutane intermediate (1b) is replaced by a halogen atom by reacting it with a halogen exchange agent such as boron trihalide (BX3) (e.g., boron tribromide), acetyl halide (e.g., acetyl chloride), etc. Reaction 11 results in the formation of dihalogen-substituted 1,3-disilcyclobutane (1c), which is essentially in the trans isomer form. In the final step of reaction sequence 12, the dihalogen-substituted 1,3-disilcyclobutane (1c) is reacted with an organometallic salt (M(Q)... 1 ) n The reaction forms a silicon precursor, which is also essentially in the form of a trans isomer (1d). Notably, reaction 12, in which 1,3-disilcyclobutane (1c) substituted with a dihalogen forms a silicon precursor (1d), corresponds to equation (3) shown above.

[0130] Figure 2 A general reaction sequence for preferentially forming the trans-isomer form of the silicon precursor (2e) according to another embodiment of this disclosure is shown. 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 It has the same substituent group distribution as given in general formula (1) above. The silicon precursor (2e) has the structure described by general formula (1), wherein Q 1 =Q 3 and Q 2 =Q 4In the first step of reaction sequence 20, the first 1,3-disilcyclobutane intermediate (2b) is formed by reacting 1,1,3,3-tetrahalo-1,3-disilcyclobutane (2a) (e.g., 1,1,3,3-tetrachloro-1,3-disilcyclobutane or 1,1,3,3-tetrabromo-1,3-disilcyclobutane) via a stereoselective exchange reaction. The co-reactant may contain a large substituent (from...) Figure 2 M (OZ) n The metal salt (represented by) is used to replace two of the halogen groups on 1,1,3,3-tetrahalo-1,3-disilcyclobutane (2a) with a large substituent. The exchange reaction is stereoselective, essentially forming the trans isomer of the first 1,3-disilcyclobutane intermediate (2b). The formation of the cis isomer of the first 1,3-disilcyclobutane intermediate (not shown) is sterically unfavorable, therefore, the formation of any cis isomer is rare. The large substituent on the metal salt co-reactant can be chosen to minimize or eliminate the formation of the cis isomer. Examples of large substituents include, but are not limited to, triphenylmethoxy, 1,1-bis(1,1-dimethylethyl)-2,2-dimethylpropoxy, di-tert-butylphenoxy, or adamantylalkoxy, which in Figure 2 The box in the diagram shows that in the next step 21, the halogen group on the first 1,3-disilcyclobutane intermediate (2b) is replaced with a hydrogen atom or a C1-C6 alkyl group, typically a methyl group, collectively referred to as Q. 2 Therefore, a second 1,3-disilcyclobutane intermediate (2c) is formed from the first 1,3-disilcyclobutane intermediate (2b), wherein the second 1,3-disilcyclobutane intermediate (2c) is also essentially in the trans isomer form. In the next step 22, the large substituent can be replaced by reacting the second 1,3-disilcyclobutane intermediate (2c) with a halogen exchange agent such as boron trihalide (BX3) (e.g., boron tribromide), acetyl halide (e.g., acetyl chloride), etc. This reaction results in the formation of a dihalogen-substituted 1,3-disilcyclobutane (2d) essentially in the trans isomer form. In the final step of reaction sequence 23, the dihalogen-substituted 1,3-disilcyclobutane (2d) is reacted with an organometallic salt (M(Q)). 1 ) n The reaction forms a silicon precursor (2e) that is also essentially in the form of a trans isomer. Notably, reaction 23, in which 1,3-disilcyclobutane (2d) substituted with a dihalogen forms a silicon precursor (2e), corresponds to equation (3) shown above.

[0131] Figure 3 The general reaction sequence for preferentially forming the cis isomer form of the silicon precursor (3e) according to embodiments of the present disclosure is illustrated. 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 Q2 It has the same substituent group distribution as given in general formula (1) above. The silicon precursor (3e) has the structure described by general formula (1), wherein Q 1 =Q 3 and Q 2 =Q 4 In the first step of reaction sequence 30, a first 1,3-disilcyclobutane intermediate (3b) is formed by reacting 1,1,3,3-tetrahalo-1,3-disilcyclobutane (3a) (e.g., 1,1,3,3-tetrachloro-1,3-disilcyclobutane or 1,1,3,3-tetrabromo-1,3-disilcyclobutane) via stereoselective exchange reaction in the presence of a base (e.g., RNH2, where R is an alkyl group). The co-reactant can be a diol, such as 1,2-ethylene glycol, 1,2-ethynyl glycol, or hydroquinone, which in… Figure 3 The box shows the reaction mixture. Two of the halogen groups on 1,1,3,3-tetrahalo-1,3-disilcyclobutane (3a) are replaced with bridging substituent groups. The reaction substantially forms the cis isomer of the 1,3-disilcyclobutane 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-disilcyclobutane reactants. The formation of the trans isomer of the first 1,3-disilcyclobutane intermediate (not shown) is sterically unfavorable, and therefore, the formation of any trans isomer is rare. In the next step 31, the halogen groups on the first 1,3-disilcyclobutane intermediate (3b) are exchanged for hydrogen atoms or C1-C6 alkyl groups, typically methyl, collectively referred to as Q. 2 Therefore, a second 1,3-disilcyclobutane intermediate (3c) is formed from the first 1,3-disilcyclobutane intermediate (3b), wherein the second 1,3-disilcyclobutane intermediate (3c) is also essentially in the cis isomer form. In the next step 32, the bridging substituent can be replaced by reacting the second 1,3-disilcyclobutane intermediate (3c) with a halogen exchange agent such as boron trihalide (BX3) (e.g., boron tribromide), acetyl halide (e.g., acetyl chloride), etc. This reaction results in the formation of a dihalogen-substituted 1,3-disilcyclobutane (3d) essentially in the cis isomer form. In the final step of reaction sequence 33, the dihalogen-substituted 1,3-disilcyclobutane (3d) is reacted with an organometallic salt (M(Q)). 1 ) n The reaction forms a silicon precursor (3e) that is also essentially in the cis isomer form. Notably, reaction 33, in which 1,3-disilcyclobutane (3d) substituted with a dihalogen forms the silicon precursor (3e), corresponds to equation (3) shown above.

[0132] Optionally, one or more reactions in the method for forming the film-forming composition can 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, dichloromethane, and mixtures thereof. Various reactions can be carried out at reduced temperatures, room temperature (~18-25°C), or elevated temperatures. For example, in some embodiments, one or more reactions can be carried out at reduced temperatures above the freezing point of the solvent (if a solvent is used), or typically at least about -80°C to about 17°C. Alternatively or alternatively, in some embodiments, one or more reactions can be carried out at about room temperature. Alternatively or alternatively, in some embodiments, one or more reactions can be carried out at elevated temperatures up to the boiling point of the solvent (if a solvent is used), or typically about 26°C to about 200°C. The temperatures of the individual reactions can be varied to optimize product distribution and yield.

[0133] Membrane-forming compositions can be purified using standard methods. The membrane-forming compositions disclosed herein may contain one or more impurities, which may result from trace elements in the feedstock source, residual reactants and solvents, and reaction byproducts and / or decomposition products from the synthetic process. Membrane-forming compositions can be purified, for example, using methods such as distillation or sublimation (if applicable), extraction, and / or contacting the composition with an adsorbent. In some embodiments, the membrane-forming composition comprises at least about 90 wt% of a silicon precursor, or at least about 95 wt% of a silicon precursor, or at least about 97 wt% of a silicon precursor, or at least about 98 wt% of a silicon precursor, or at least about 99 wt% of a silicon precursor, or at least about 99.5 wt% of a silicon precursor, or at least about 99.9 wt% of a silicon precursor, or at least about 99.99 wt% of a silicon precursor. In some embodiments, the membrane-forming composition consists of or is substantially composed of a silicon precursor. In some embodiments, the impurity content 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 halogen-containing impurity content in the film-forming composition is not more than about 5%, or not more than about 4%, or not more than about 3%, or not more than about 2%, or not more than about 1%, or not more than about 0.5%, or not more than about 0.1%, or not more than about 100 ppm, or not more than about 10 ppm. In some embodiments, the metal impurity content in the film-forming composition is not more than about 1%, or not more than about 0.5%, or not more than about 0.1%, or not more than about 100 ppm, or not more than about 10 ppm, or not more than about 1 ppm, or not more than about 100 ppb, or not more than about 10 ppb. In some embodiments, the carbon impurity content in the film-forming composition is no more than about 5%, or no more than about 4%, or no more than about 3%, or no more than about 2%, or no more than about 1%, or no more than about 0.5%, or no more than about 0.1%, or no more than about 100 ppm, or no more than about 10 ppm. In some embodiments, the silicon impurity content in the film-forming composition is no more than about 5%, or no more than about 4%, or no more than about 3%, or no more than about 2%, or no more than about 1%, or no more than about 0.5%, or no more than about 0.1%, or no more than about 100 ppm, or no more than about 10 ppm. In some other embodiments, the germanium impurity content in the film-forming composition is no more than about 5%, or no more than about 4%, or no more than about 3%, or no more than about 2%, or no more than about 1%, or no more than about 0.5%, or no more than about 0.1%, or no more than about 100 ppm, or no more than about 10 ppm. In some other embodiments, the phosphorus impurity content in the film-forming composition is no more than about 5%, or no more than about 4%, or no more than about 3%, or no more than about 2%, or no more than about 1%, or no more than about 0.1%, or no more than about 100 ppm, or no more than about 10 ppm.In some other embodiments, the nitrogen-containing impurities in the film-forming composition do not exceed about 5%, or about 4%, or about 3%, or about 2%, or about 1%, or about 0.5%, or about 0.1%, or about 100 ppm, or about 10 ppm.

[0134] In some embodiments of the invention, a film-forming composition is provided in a vapor delivery container. The vapor delivery container is configured to store the film-forming composition and to provide a vapor stream of the film-forming composition from the vapor delivery container to an external environment, such as to a substrate processing system or semiconductor processing apparatus for forming a carbon-doped silicon-containing film. The vapor delivery container is typically formed of a material that is not reactive to the film-forming composition and, in some embodiments, may comply with U.S. Department of Transportation (DOT) regulations, such as 49C.FR §178 (2021). In some embodiments, the vapor delivery container is formed of stainless steel (e.g., 316, 316L, 304, or an alloy of 304L). The type of vapor delivery container 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 container typically includes an outer wall that surrounds a cavity for storing the film-forming composition and a gas outlet for allowing vapor of the film-forming composition to exit the cavity. The gas outlet is located in the outer wall of the vapor delivery container and communicates with the cavity of the vapor delivery container, and has at least one valve positioned thereon to fluidly connect or disconnect the cavity from the external environment. In some embodiments, in addition to a gas outlet, the vapor delivery container includes one or more other fluid inlets or outlets. For example, the vapor delivery container may include a fluid inlet located in the outer wall of the vapor delivery container and communicating with a cavity of the vapor delivery container, and having at least one valve thereon for filling the vapor delivery container with a membrane forming composition. Alternatively or additionally, the vapor delivery container may include a fluid inlet located in the outer wall of the vapor delivery container and communicating with a cavity of the vapor delivery container, and having at least one valve thereon positioned for allowing carrier gas to flow into the cavity of the container, flow over and / or through the membrane forming composition. Some or all of the one or more valves disposed on the various inlets and outlets may be rated for high temperatures (e.g., typically up to 100°C, or up to 150°C, or up to 200°C, or up to 250°C) to withstand the temperatures that may be required, thereby providing sufficient vapor pressure and preventing condensation of the membrane forming composition within the valves and other components. In some embodiments, the vapor delivery container also includes 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 within the cavity of a vapor delivery container are known in the art, including but not limited to capacitance-based sensors, conductivity-based sensors, float switch level sensors, tuning fork sensors, and ultrasonic sensors. In some embodiments, the vapor delivery container further includes one or more heat transfer elements, such as fins, rods, beads, etc., to facilitate heat transfer from the container wall to the film-forming composition within the cavity and vice versa.One or more heat transfer elements can be arranged in a serpentine or radial path to hold the film-forming composition within the cavity and, in some cases, to guide the carrier gas to flow over or through the film-forming composition. This configuration is particularly useful for conveying vapors of low-volatility liquid and solid compositions. The various design features described above can be suitably combined to optimize the vapor flow of the film-forming composition from the vapor delivery vessel. Figure 6 An example of a suitable steam transport container is shown, which is discussed in detail below.

[0135] Another aspect of this disclosure relates to a vapor deposition method for forming carbon-doped silicon-containing films using the film-forming compositions disclosed herein, which include silicon precursors. Suitable vapor deposition methods include ALD or CVD, including plasma-enhanced, radical-enhanced, and thermal methods. This method typically includes providing a substrate in 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 substrate surface to the silicon precursor composition results in the formation of an adsorbed silicon precursor layer on the substrate surface. The adsorbed silicon precursor layer may be physically adsorbed and / or chemically adsorbed onto the surface of the substrate, and may be all or part of a monolayer or multiple monolayers on the surface. The adsorbed silicon precursor layer may contain a complete silicon precursor, and / or a portion or fragment of a silicon precursor. In some embodiments, a conversion step is employed to convert the adsorbed silicon precursor layer into a target carbon-doped silicon-containing layer. In some embodiments, the surface of the substrate is additionally exposed to a co-reactant to form the target carbon-doped silicon-containing layer. In some embodiments, the surface of the substrate is additionally exposed to plasma to form the target carbon-doped silicon-containing layer. In some embodiments, a method for forming a carbon-doped silicon-containing film includes providing a substrate in a reaction space and performing one or more deposition cycles of a cyclic deposition process. The cyclic deposition process may include one or more of an ALD process and a cyclic CVD process.

[0136] Figure 4A process flow diagram 400 illustrating an exemplary embodiment of forming a carbon-doped silicon-containing film using a cyclic deposition process is shown. The method includes providing a substrate in a reaction space 410 and performing one or more deposition cycles of a cyclic deposition process 420, including: exposing the surface of the substrate to a film-forming composition (as described above) 430 containing a silicon precursor to form an adsorbed silicon precursor 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 form a carbon-doped silicon-containing film on the surface of the substrate; and optionally purging the reaction space 460. (Alternatively, the substrate surface may be exposed to the co-reactant and then to the film-forming composition.) Steps 430 and 450, and optional steps 440 and 460, constitute a deposition cycle. The method may include repeating the deposition cycle 470 once or more (n) times in the cyclic deposition process 420 to increase the uniformity and / or thickness of the carbon-doped silicon-containing film on the substrate surface. Once the desired uniformity and / or thickness of the carbon-doped silicon-containing film is achieved, the cyclic deposition process 420 can be terminated 480.

[0137] In step 410, the substrate is provided to the reaction space. Typically, a substrate loading / unloading mechanism is used to insert the substrate into the reaction space, and in embodiments employing multiple reaction chambers, the substrate may optionally be transferred between the various reaction chambers within 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, such as dielectric layers, insulating layers, metal layers, certain nitrides, sacrificial layers, etc., presented from one or more prior manufacturing steps. In some embodiments, the substrate includes hydroxyl-terminated surfaces, and this can advantageously improve the deposition method described herein. The substrate may include various topological features or structures, such as gaps, recesses, lines, trenches, vias, holes, or spaces between raised portions formed within or on at least a portion of the layers of the substrate.

[0138] The reaction space is not particularly limited and may include one or more reaction chambers of a semiconductor processing system. In some embodiments, the semiconductor processing system is a cluster tool. In some embodiments, one or more reaction chambers in a flow reactor may be used. In some embodiments, one or more reaction chambers in a spray-head reactor may be used. In some embodiments, one or more reaction chambers in a space-separated reactor may be used. In some embodiments, one or more reaction chambers in a single-wafer reactor capable of high-volume manufacturing may be used. In other embodiments, one or more reaction chambers in a batch reactor may be used. In embodiments where a batch reactor is used, the reaction chamber can hold a large number of wafers, for example, the number of wafers may be in the range of 10 to 200, or 50 to 150, or even 100 to 150.

[0139] In the methods disclosed herein, the surface of a substrate is exposed to a film-forming composition (as described above) 430, resulting in the formation of an adsorbed silicon precursor layer on the substrate surface. Exposing the substrate surface to the film-forming composition 430 may include introducing vapor of the film-forming composition into a reaction space and contacting the substrate surface with the vapor of the film-forming composition. The film-forming composition is typically provided by a vapor delivery container containing the film-forming composition and is typically connected to and in fluid communication with the reaction space via one or more gas lines, valves, and flow controllers. The vapor delivery container and 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 container through one or more gas lines, valves, and flow controllers into the reaction space. The vapor pressure of the silicon precursor in the film-forming composition will depend on the specific structure of the silicon precursor, and the temperature of the vapor delivery container may be adjusted (i.e., heated or cooled) to provide sufficient vapor pressure (typically about 1-20 Torr in the temperature range of 25°C to 200°C) to facilitate the delivery of the film-forming composition to the reaction space. In some embodiments, a pure stream of the film-forming composition vapor flows from the vapor delivery container through one or more gas lines, valves, and flow controllers into the reaction space. In other embodiments, the membrane forming composition vapor can be entrained in an inert carrier gas (e.g., nitrogen and / or rare gases such as helium (He) and argon (Ar)) stream and introduced into the reaction space.

[0140] In some embodiments, the step of exposing the substrate surface to the film-forming composition 430 includes pulsed delivery of the film-forming composition into a reaction space above the substrate surface. In embodiments, when the film-forming composition is pulsed on the substrate surface, the pulse duration can be from about 0.01 seconds to about 60 seconds, or from about 0.1 seconds to about 30 seconds, or from about 1 second to about 10 seconds. During the pulse, the flow rate of the film-forming composition can 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 can be, for example, from about 500 sccm to about 1200 sccm, such as about 600 sccm, or about 800 sccm, or about 1000 sccm. The pulse duration can vary depending on the film-forming composition discussed, the reaction chamber configuration, and other process parameters (e.g., temperature, pressure, substrate, etc.), which can be independently selected to optimize the process.

[0141] A conversion step can be used to convert the adsorbed silicon precursor layer into a target carbon-doped silicon-containing film. For example, the surface of the substrate can be further exposed to co-reactant 450. In some embodiments, the surface of the substrate is exposed to plasma material 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, rare gas plasma, nitrogen plasma, and oxygen plasma. The co-reactant may include one or more stimulated and / or radical materials, which can be formed in situ in the reaction space using direct plasma formed near or directly above the substrate (e.g., direct plasma). Alternatively, the co-reactant including one or more stimulated and / or radical materials can be formed in situ in the reaction space at a location separated from the substrate space or upstream of the reaction space using remote plasma (e.g., remote plasma). Remote plasma can be used to minimize or avoid exposure of the substrate surface to high-energy ionic material. In either case, a feed gas including one or more inert and reactive gases can be used to form the plasma. The feed gas is supplied to the plasma unit, and the discharging plasma is activated. In some embodiments, the feed gas is supplied to the reaction space, and the discharging plasma is pulsed (i.e., turned on and off). The power used to generate plasma can vary in different embodiments of this disclosure. In some embodiments, the power used to generate plasma is about 10W to about 2000W, typically about 20W to about 1000W, or about 20W to about 500W, or about 20W to about 200W, or about 20W to about 100W.

[0142] In some embodiments, the surface of the substrate is exposed to one or more of a hydrogen plasma and a rare gas plasma. In some of these embodiments, the feed gas comprises hydrogen (H2) and / or a rare gas selected from helium (He), neon (Ne), argon (Ar), krypton (Kr), xenon (Xe), and mixtures thereof. In some embodiments, the co-reactant comprises a hydrogen plasma material. In some embodiments, the surface of the substrate is exposed to a hydrogen plasma. Alternatively or additionally, in some embodiments, the co-reactant comprises a rare gas plasma material. In some embodiments, the surface of the substrate is exposed to a rare gas plasma. In these embodiments, the plasma can be used to activate an adsorbed silicon precursor layer on the substrate surface and may not necessarily contribute material to the deposited film, but in some cases may contribute to film growth. In some embodiments, the reactive gas may comprise a rare gas and H2, wherein the rare gas and H2 are provided at a flow ratio 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.

[0143] In some embodiments, the surface of the substrate is exposed to nitrogen plasma. In some embodiments, the co-reactant comprises nitrogen plasma material. In these cases, the feed gas may comprise a reactive gas comprising one or more of nitrogen (N2), an N2 / H2 mixture, ammonia (NH3), an alkylamino group (NR3, wherein each R is independently H, alkyl, or aryl), hydrazine (N2H4), and substituted hydrazine; thus, the co-reactant may comprise one or more of N2, NH3, alkylamino, hydrazine N2H4, substituted hydrazine (if applicable), and excited material, radical material, and plasma material formed therefrom. In some embodiments, the co-reactant comprises nitrogen plasma material, for example, the co-reactant may comprise one or more of activated nitrogen (N2), activated ammonia (NH3), nitrogen atoms (N), NH and NH2 radicals, and other NH-containing materials generated during plasma discharge. In some embodiments, the reactive gas may comprise N2 and H2, wherein N2 and H2 are provided at a flow ratio (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.

[0144] In some embodiments, the surface of the substrate is exposed to oxygen plasma. In some embodiments, the co-reactant may comprise an oxygen plasma material. 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); therefore, the co-reactant may include 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) (if applicable), and the exciting material, free radical material, and plasma material formed therefrom. In some embodiments, the oxygen co-reactant comprises an oxygen plasma material; for example, the oxygen co-reactant may comprise atomic oxygen (O), excited diatomic oxygen (e.g., singlet oxygen), and other oxygen-generating materials. 1 One or more of the following: O2 (O2), ozone (O3), hydroxyl radicals (OH), peroxy radicals (e.g., HO2), and nitric oxide (NO). In some other embodiments, the co-reactants contain little or no oxygen plasma material. In some embodiments, the substrate is not exposed to oxygen plasma. Therefore, the resulting film may include a higher carbon content and thus may have a lower dielectric constant. Additionally or alternatively, in some embodiments, damage to sublayers (e.g., conductive intermediate layers) on the substrate surface by oxygen plasma can be prevented. Accordingly, low electrical performance of the resulting device can be prevented.

[0145] In some embodiments, the step of exposing the surface of the substrate to the co-reactant 450 includes pulsed the co-reactant into a reaction space above the substrate surface. The pulse can be achieved by controlling the flow of a feed gas into the reaction space and activating a plasma discharge for forming the co-reactant. In embodiments where the co-reactant is pulsed above the substrate, the pulse duration can be between about 0.01 seconds and about 60 seconds, or from about 0.1 seconds to about 30 seconds, or from about 1 second to about 10 seconds. During the pulse, the feed gas flow rate can 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 can be, for example, from about 500 sccm to about 1200 sccm, such as about 600 sccm, or about 800 sccm, or about 1000 sccm. The pulse duration can vary depending on the co-reactant discussed, the reaction chamber configuration, and other process parameters (e.g., temperature, pressure, substrate, etc.), which can be selected independently to optimize the process depending on the application discussed.

[0146] In some embodiments, the steps of exposing the surface of the substrate to the film-forming composition 430 and exposing the surface of the substrate to the co-reactant 450 at least partially overlap. For example, in embodiments where the film-forming composition and / or co-reactant are pulsed on the substrate, the film-forming composition pulses and co-reactant pulses may at least partially overlap. In some embodiments, introducing the film-forming composition into the reaction space and introducing the co-reactant into the reaction space may be simultaneous. In some embodiments, introducing the film-forming composition and co-reactant into the reaction space may be at least partially separate. For example, in embodiments where the film-forming composition and co-reactant are pulsed on the substrate surface, the film-forming composition pulses and co-reactant pulses may at least partially separate. In some embodiments, introducing the film-forming composition and co-reactant into the reaction space may be completely separate. For example, in embodiments where the film-forming composition and co-reactant are pulsed on the substrate surface, the film-forming composition pulses and co-reactant pulses may be completely separate.

[0147] 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 the co-reactant 450. For example, the optional purging step is performed in... Figure 4 The diagram is shown at 440 and 460. Purge may be performed between pulses of two gases that react with each other. Purge may also be performed between pulses of gases that do not react with each other. For example, purging may be provided between pulses of the film-forming composition and 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 may be performed temporally, spatially, or both. For example, in the case of temporal purging, the purging steps may be used, for example, in the temporal sequence of providing a first reactant to the reaction space, providing a purge gas to the reaction space, and providing a second reactant to the reaction space, wherein the substrate on which the layer is deposited does not move. For example, in the case of spatial purging, the purging steps may include moving the substrate from a first location (e.g., a first reaction chamber) where the first reactant is continuously supplied through a purge gas curtain to a second location (e.g., a second reaction chamber) where the second reactant is continuously supplied.

[0148] Various process steps can be repeated 470 times once or more to grow a carbon-doped silicon-containing film on the surface of a substrate. The number of cycles (n) is not particularly limited and depends on the growth per cycle (GPC) and the target film thickness. Typically, the film thickness can range from a few angstroms to several hundred micrometers. The number of cycles (n) can be between 1 and about 1000, typically between 1 and about 500, or between 1 and about 200, or between 1 and about 100, or between 1 and about 50, or between 1 and about 10. The GPC for the carbon-doped silicon film can be from at least about 0.01 Å / cycle to no more than about 10 Å / cycle. In some embodiments, the GPC can vary depending on the time the substrate surface is exposed 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 no more than about 10 Å / cycle, or at least about 0.05 Å / cycle to no more than about 8 Å / cycle, or at least about 0.05 Å / cycle to no more than about 7 Å / cycle, or at least about 0.05 Å / cycle to no more than about 6 Å / cycle, or at least about 0.05 Å / cycle to no more than about 5 Å / cycle, or at least about 0.05 Å / cycle to no more than about 4 Å / cycle, or at least about 0.05 Å / cycle to no more than about 3 Å / cycle, or at least about 0.05 Å / cycle to no more than about 2.5 Å / cycle, or at least about 0.05 Å / cycle to no more than about 2.0 Å / cycle, or at least about 0.05 Å / cycle to no more than about 1.5 Å / cycle, or at least about 0.05 Å / cycle to no more than about 1 Å / cycle, or at least about 0.05 Å / cycle to no more than about 0.5 Å / cycle. The loop, or at least about 0.1 Å / cycle to no more than about 5 Å / cycle, or at least about 0.1 Å / cycle to no more than about 4 Å / cycle, or at least about 0.1 Å / cycle to no more than about 3 Å / cycle, or at least about 0.1 Å / cycle to no more than about 2.5 Å / cycle, or at least about 0.1 Å / cycle to no more than about 2.0 Å / cycle, or at least about 0.1 Å / cycle to no more than about 1.5 Å / cycle, or at least about 0.1 Å / cycle to no more than about 1 Å / cycle, or at least about 0.5 Å / cycle to no more than about 5 Å / cycle, or at least about 0.5 Å / cycle to no more than about 4 Å / cycle, or at least about 0.5 Å / cycle to no more than about 3 Å / cycle, or at least about 0.5 Å / cycle to no more than about 2.5 Å / cycle, or at least about 0.5 Å / cycle to no more than about 2.0 Å / cycle, or at least about 0.5 Å / cycle to no more than about 1.5 Å / cycle. In some embodiments, the carbon-doped silicon-containing film has a GPC of about 0.5 Å / cycle or more, or about 1 Å / cycle or more, or about 1.5 Å / cycle or more, or about 2 Å / cycle or more.In some embodiments, the GPC for carbon-doped silicon films is about 0.5 Å / cycle, or about 1 Å / cycle, or about 1.5 Å / cycle, or about 2 Å / cycle, or about 2.5 Å / cycle, or about 3 Å / cycle, or about 3.5 Å / cycle, or about 4 Å / cycle, or about 4.5 Å / cycle, or about 5 Å / cycle, or about 5.5 Å / cycle, or about 6 Å / cycle, or about 6.5 Å / cycle, or about 7 Å / cycle. Typically, for ALD processes, the GPC is between about 0.1 Å / cycle and about 3 Å / cycle, while for cyclic CVD processes, the GPC can be higher, depending on the duration of substrate exposure to the film-forming composition.

[0149] The method may also include maintaining the substrate temperature at a set temperature during the cyclic deposition process 420. In some embodiments, the method includes an exposure step (e.g., Figure 4 During one or both of periods 430 and 450, the substrate temperature is maintained at a set temperature. 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 no more than about 500°C. In some embodiments, the method includes maintaining a substrate temperature of: about 25°C to about 500°C, typically about 100°C to about 450°C, or about 100°C to about 425°C, or about 100°C to about 400°C, or about 100°C to about 375°C, or about 100°C to about 350°C, or about 100°C to about 325°C, or about 100°C to about 300°C, or about 100°C to about 275°C, or about 100°C to about 250°C, or about 200°C to about 450°C, or about 200°C to about 425°C, or about 200°C to about 400°C, or about 200°C to about 375°C, or about 200°C to about 350°C. In some embodiments, the substrate is maintained at a temperature below about 450°C, or below about 425°C, or below about 400°C, or below about 375°C, or below about 350°C, or below about 325°C, or below about 300°C, or below about 275°C, or below about 250°C, or below about 225°C, or below about 200°C, or below about 175°C, or below about 150°C while performing the method. In some embodiments, the method includes maintaining the substrate temperature at about 25°C, or about 50°C, or about 75°C, or about 100°C, or about 125°C, or about 150°C, or about 175°C, or about 200°C, or about 225°C, or about 250°C, or about 275°C, or about 300°C, or about 325°C, or about 350°C, or about 375°C, or about 400°C, or about 425°C, or about 450°C.

[0150] In addition to controlling the substrate temperature, the method of this disclosure can be performed in a depressurized environment. In some embodiments, the method further includes controlling the pressure within the reaction space during the cyclic deposition process 420. The pressure within the reaction space can be between about 1 mTorr and about 760 Torr, or between about 0.5 Torr and about 30 Torr, for example, about 10 Torr, about 15 Torr, or about 20 Torr. In some embodiments, the pressure within the reaction space during the cyclic deposition process 420 is less than about 500 Torr, or the pressure within the reaction chamber during the cyclic deposition process 420 is between about 0.1 Torr and about 500 Torr, or between about 1 Torr and about 100 Torr, or between about 1 Torr and about 20 Torr. In some embodiments, the pressure within the reaction space during the cyclic 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.

[0151] 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 include a semiconductor processing system comprising a reaction space (e.g., one or more reaction chambers) for housing a substrate. The semiconductor processing system may include one, two, three, four, or more reaction chambers. In some embodiments, the semiconductor processing system is a cluster tool. In some embodiments, one or more reaction chambers in a flow reactor may be utilized. In some embodiments, one or more reaction chambers in a spray-head reactor may be utilized. In some embodiments, one or more reaction chambers in a space-separated reactor may be utilized. In some embodiments, one or more reaction chambers in a single-wafer reactor capable of high-volume fabrication may be utilized. In other embodiments, one or more reaction chambers in a batch reactor may be utilized. The semiconductor processing system also includes a film-forming composition source and means for exposing a substrate surface to the vapor of the film-forming composition disclosed herein. The semiconductor processing system may further include means for exposing the substrate to a co-reactant and optionally include means for purging the reaction space between exposure steps.

[0152] Figure 5An exemplary embodiment of a semiconductor processing system 500 according to the present disclosure is shown. The film-forming composition disclosed herein and other gases are provided into a reaction chamber 520 via an injector assembly 510. The injector assembly 510 is configured to provide vapor of the film-forming composition from a film-forming composition source 511, which is coupled to the reaction chamber 520 via a first valve 515. The injector assembly 510 may be further configured to provide one or more other gases, such as one or more co-reactants or feed gases, to form one or more co-reactants from a co-reactant source 512 coupled to the reaction chamber 520 via a second valve 516, and / or to provide one or more carrier gases (e.g., nitrogen and / or rare gases, such as He, Ne, Ar, Kr, Xe, and combinations thereof) from a carrier gas source 513 coupled to the reaction chamber 520 via a third valve 517. The injector assembly 510 may also include one or more other gas sources 514, for example connected to the reaction chamber 520 via a fourth valve 518, for providing purge gas, additional carrier gas, supplementary gas, etc., and means for heating (not shown) the various gas sources (511-514) and corresponding valves (515-518) and gas lines (if desired) to facilitate the introduction of the film-forming composition and other reactants into the reaction chamber 520.

[0153] In some embodiments, the membrane forming composition source 511 includes a vapor delivery container containing the membrane forming composition. Figure 6 A perspective view of an exemplary embodiment of a vapor delivery container 600 according to the present disclosure is shown. The vapor delivery container 600 includes an outer wall, which may generally be cylindrical, having a bottom 614 and a top 612 connected by a cylindrical body 610 to enclose a cavity 602 for storing a film-forming composition 604 therein. The vapor delivery container 600 also includes 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 located on the top portion of the outer wall 612 and communicates with the cavity 602. The gas outlet 651 is configured to provide vapor of the film-forming composition from the cavity 602. In this respect, the gas outlet 651 may include one or more valves for opening and closing the gas outlet and for controlling the flow of the evaporated film-forming composition 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 arranged along the exterior of the container 600. Gas inlet 631 may also be located in the top portion of outer wall 612 and communicate with cavity 602. Gas inlet 631 may be configured to allow carrier gas to flow into cavity 602, above or through membrane forming composition 604, to entrain vapor of membrane forming composition in the carrier gas stream exiting gas outlet 651. In this respect, gas inlet 631 may have a conduit extending into the cavity to fixation point 632, which is located above the surface of membrane forming composition (e.g., Figure 6 The gas inlet 631 may be located below the surface of the membrane forming composition (not shown), or alternatively, below the surface of the membrane forming composition. Furthermore, in this respect, the gas inlet 631 may have one or more valves for opening and closing the gas inlet 631 and for controlling the inflow 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 arranged along the exterior of the container 600. The fluid inlet 641 may also be located in the top portion of the outer wall 612 and communicate with the cavity 602. The fluid inlet 641 may be configured to refill the vapor delivery container 600 with the membrane forming composition 604. In this respect, the fluid inlet 641 may have a conduit 642 extending into the cavity 602, and in some embodiments, may be bent toward the outer wall 610 to reduce splashing, bubbling, and / or undulation of the horizontal membrane forming composition during refilling. Furthermore, in this respect, the fluid inlet 641 may have one or more valves for opening and closing the fluid inlet 641 and for controlling the inflow of the membrane forming composition 604 into the cavity 602. For example, fluid inlet 641 may have one or both of a manual valve 644 and an actuation valve 643 arranged along the outside of container 600. Probe member 660 may be located in the top portion 612 of the outer wall and extend toward the bottom portion 614 into cavity 602. In some examples, probe member 660 may be removably secured within probe member bore 661, allowing it to be removed as needed for cleaning and / or replacement. Probe member 660 may include one or more temperature sensors 662 and / or one or more level sensors 663. The one or more temperature sensors 662 and / or one or more level sensors 663 of probe member 660, along with various actuation valves (633, 652, and 643), may each be configured such that they are operatively associated with controller 580 (see [link to controller 580]). Figure 5 Furthermore, the vapor delivery container 600 can be removably connected to the injector assembly 510 via one or more optional connectors (as shown in 630, 650, and 640) (see [link to product]). Figure 5 This allows the vapor delivery container 600 to be connected to the injector assembly 510 (see [link]). Figure 5 Disconnect, for use at a distance of 500 from the semiconductor processing system (see...) Figure 5 The location is cleaned and filled with a membrane forming composition. While the vapor delivery container 600 is shown and described herein with a particular arrangement, it should be understood and recognized that the vapor delivery container may include other elements and / or exclude certain elements described herein, or have an alternative arrangement, still within the scope of this disclosure. For example, the vapor delivery container may include alternative arrangements of inlet and outlet, including having fewer or more inlets and outlets, or alternative arrangements of valves, including having fewer or more valves.

[0154] Return to reference Figure 5 The film-forming composition and other gases flow into the reaction chamber 520 through a spray head 521 positioned directly above a base 523 on which a substrate 522 rests. In some embodiments, the reaction chamber 520 further includes one or more heating elements 524 and one or more thermocouples (not shown) in thermal communication with the substrate 522 to measure and maintain 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 an external environment 570 via one or more optional vacuum pumps 562. A plasma generator 550 (e.g., an RF plasma generator, microwave plasma generator, capacitively coupled plasma generator, or inductively coupled plasma generator) may be electrically connected to the spray head 521, allowing the spray head 521 to be biased relative to the base 523 to form a plasma discharge between the two. Optionally, an ion trap (not shown) may be positioned between the spray head 521 and the substrate 522 to confine the plasma to the upper part of the reaction chamber 520 above the ion trap, thereby reducing the interaction between the ionic material and the substrate surface. For example, an electrically grounded grid may be used as the ion trap.

[0155] The semiconductor processing system also includes a controller 580. The controller 580 typically includes a device interface 584, a processor 583, a user interface 585, and a memory 581. The device interface 584 connects the processor 583 to various components of the vapor delivery vessel (e.g., [missing information]) via a wired or wireless link. Figure 6 The processor 583 includes one or more of 633, 652, 643, 662, and 663, and one or more of the injector assembly 510, reaction chamber 520, plasma discharge 550, exhaust source 560, and / or other components, such as one or more heating elements 524 and thermocouples (not shown) for controlling the temperature of the substrate 522. The processor 583 is then operatively connected to a user interface 585, for example, to receive user input and / or provide user output, and to communicate with a memory 581. The memory 581 may include a non-transitory machine-readable medium thereon on which a plurality of program modules 582 are recorded, which, when read by the processor 583, cause the processor 583 to perform certain operations. These operations include depositing a carbon-doped silicon-containing film using the above-described film forming composition (see, for example, [reference needed]). Figure 4 The operation of the 400 method.

[0156] In some embodiments, controller 580 is configured and programmed to perform a first operation and a second operation, etc. In the first operation, controller 580 opens a first valve 515 to allow vapor of the film-forming composition to flow from film-forming composition source 511 into reaction chamber 520, thereby exposing the substrate surface to the film-forming composition, and after a set time period, controller 580 closes the first valve 515 leading to film-forming composition source 511. In the second operation, controller 580 opens a second valve 516 to allow co-reactant or co-reactant feed gas from co-reactant source 512 to flow into reaction chamber 520 and causes plasma generator 550 to pulse (turn on and then off), thereby exposing the surface of substrate 522 to the co-reactant. After another set time period, controller 580 closes the second valve 516 leading to co-reactant source 512. In some embodiments, controller 580 is programmed to perform a first operation and a second operation, or vice versa, wherein at least a portion of the first operation overlaps with at least a portion of the second operation, such that the flow of the film-forming composition into reaction chamber 520 at least partially overlaps with the flow of the co-reactant into reaction chamber 520. In some other embodiments, controller 580 is programmed to perform the first operation sequentially, then the second operation, or vice versa, such that the flow of the film-forming composition into reaction chamber 520 and the flow of the co-reactant into reaction chamber 520 do not overlap. 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 substrate 522.

[0157] As those skilled in the art will understand, controller 580 can be configured and programmed to perform other operations. For example, controller 580 can be operatively connected to purge gas source 514 and configured and programmed to open a fourth valve 518 leading to purge gas source 514 to allow purge gas to flow into reaction chamber 520, and to close the fourth valve 518 leading to purge gas source 514 after a set time period. In another example, controller 580 can be operatively 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 substrate 522 at a set temperature.

[0158] Furthermore, as those skilled in the art will understand, other semiconductor deposition system configurations are possible. For example, although the implantation assembly 510 and reaction chamber 520 are shown and described herein with specific structural and flow configurations, other flow configurations and / or other mechanisms for providing various reactants and gases, as well as for containing the substrate and allowing gases to flow over the substrate, can be utilized. Additionally, other plasma generation configurations can be utilized. In some embodiments, a remote plasma unit located upstream of reaction chamber 520 can be used to generate remote plasma. Furthermore, although the controller 580 is shown and described herein with a specific architecture, it should be understood and recognized that other controller architectures can be employed and are still within the scope of this disclosure.

[0159] Another aspect of this disclosure relates to the formation of carbon-doped silicon-containing layers or films using the film formation compositions disclosed herein. Furthermore, carbon-doped silicon-containing layers or films can be formed using the methods and systems described herein. In some embodiments, a carbon-doped silicon film is provided formed by contacting the surface of a substrate with the film formation compositions disclosed herein. In some of these embodiments, the carbon-doped silicon film comprises a silicon precursor and / or a portion or fragment of a silicon precursor. The silicon precursor and / or a portion or fragment of a silicon precursor may be adsorbed onto the surface of the substrate. In some embodiments, a carbon-doped silicon film is provided formed by... Figure 4 The carbon-doped silicon-containing film is formed by the method described herein. In some embodiments, a carbon-doped silicon-containing film is provided by contacting a substrate surface with the film-forming composition disclosed herein and one or more of hydrogen plasma, rare gas plasma, nitrogen plasma, and oxygen plasma.

[0160] The disclosed film-forming compositions and the methods and systems for forming carbon-doped silicon-containing films using said film-forming compositions offer several advantages. In particular, the film-forming compositions can provide carbon-doped silicon-containing films with high carbon content, typically between about 1% and 70%, typically between about 5% and about 50%, or between about 10% and about 50%, or between about 20% and about 50%. While not wishing to be bound by a particular theory, the high carbon content of the film may be due to Si-C-Si bonds in the silicon precursor structure, and in some embodiments, the presence of CH3-Si bonds. Additionally or alternatively, in some embodiments, the method for forming carbon-doped silicon-containing films does not involve exposing the substrate to oxygen plasma. Instead, hydrogen plasma and / or rare gas plasma can be used to form carbon-doped silicon-containing films while still maintaining acceptable GPC and / or yield. Therefore, in some embodiments, the carbon-doped silicon-containing films can have a desired low dielectric constant. For example, in some embodiments, the dielectric constant of the carbon-doped silicon-containing film is 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 possess good mechanical properties. For example, in some embodiments, the carbon-doped silicon-containing film may have a wet etch rate (WER) of less than 2.5 nm / min in 0.5% dilute hydrofluoric acid, or less than 2.0 nm / min in 0.5% dilute hydrofluoric acid, or less than 1.5 nm / min in 0.5% dilute hydrofluoric acid, or less than 1.0 nm / min in 0.5% dilute hydrofluoric acid, or less than 0.5 nm / min in 0.5% dilute hydrofluoric acid. Furthermore, in some embodiments, the carbon-doped silicon-containing film may also exhibit good conformal properties. For example, in some embodiments, the carbon-doped silicon-containing film has a stepped coverage of about 80% or more, or about 90% or more. In some embodiments, the carbon-doped silicon-containing film has a stepped coverage of about 90% or more and less than about 110%, or about 95% or more and less than about 105%.

[0161] Although certain embodiments and examples have been disclosed herein, those skilled in the art will understand that the disclosed compositions, methods, and systems extend beyond the specific disclosed embodiments and include all novel and non-obvious combinations and sub-combinations of various compositions, methods, and systems, as well as any and all equivalents thereof. It should be understood that the compositions, methods, and systems described herein are exemplary in nature, and these specific embodiments or examples should not be considered limiting, as many variations are possible. The particular methods and systems described herein may represent one or more of any number of processing strategies. Therefore, the various actions shown may be performed in the order shown, in a different order, or in some cases omitted. Furthermore, for the purpose of simplifying this disclosure, various features of this disclosure are grouped together in one or more aspects, embodiments, and configurations. Features of aspects, embodiments, and configurations of this disclosure may be combined in alternative aspects, embodiments, and configurations other than those discussed above. The compositions, methods, and systems of this disclosure should not be construed as reflecting an intention to require more features than expressly recited in each claim. Rather, as reflected in the following claims, the inventive aspect lies in fewer than all features of a single foregoing aspect, embodiment, and configuration. Therefore, the following claims are incorporated herein by reference, wherein each claim is an independent embodiment of this disclosure, and the features recited in the various dependent claims may be suitably combined with each other in various combinations to form other embodiments of this disclosure.

Claims

1. A film-forming composition comprising a silicon precursor having a structure according to general formula (1): (1) in, Q 1 The substituent is selected from acetoxy, acryloyloxy, C1 to C6 alkoxy, silyloxy, germanyloxy, phosphonoyloxy, and alkylamine; and Q 2 Q 3 and Q 4 Each is independently selected from hydrogen atoms, C1-C6 alkyl groups, and Q. 1 Substituents of the same substituent group.

2. The film-forming composition according to claim 1, wherein, Q 1 The substituent groups are selected from acetoxy, acryloyloxy, silyloxy, germanyloxy, and phosphonooxy.

3. The film-forming composition according to claim 1, wherein, Substituent group Q 1 and Q 3 The substituent group is selected from acetoxy, acryloyloxy, C1 to C6 alkoxy, siloxy, germanoxy, phosphonoyloxy, and alkylamine; and the substituent group Q 2 and Q 4 The precursor is selected from hydrogen atoms and C1-C6 alkyl groups, and at least 85% of the silicon precursor is in the cis isomer form or at least 85% of the silicon precursor is in the trans isomer form.

4. The film-forming composition according to claim 1, wherein, The silicon precursor is selected from 1,3-diacetoxy-1,3-disilcyclobutane, 1,3-diacetoxy-1,3-dimethyl-1,3-disilcyclobutane, 1,3-diaacryloxy-1,3-disilcyclobutane, 1,3-diaacryloxy-1,3-dimethyl-1,3-disilcyclobutane, 1,3-dimethacryloxy-1,3-disilcyclobutane, 1,3-dimethacryloxy-1,3-dimethyl-1,3-disilcyclobutane, 1,3-bis(trimethyl) 1,3-bis(trimethylsilyloxy)-1,3-dimethyl-1,3-disilcyclobutane, 1,3-bis(trimethylgermanyloxy)-1,3-disilcyclobutane, 1,3-bis(trimethylgermanyloxy)-1,3-dimethyl-1,3-disilcyclobutane, 1,3-bis(dimethylphosphono)-1,3-disilcyclobutane and 1,3-bis(dimethylphosphono)-1,3-dimethyl-1,3-disilcyclobutane.

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

6. A vapor transport vessel comprising a membrane forming composition, the membrane forming composition comprising a silicon precursor having a structure according to general formula (1): (1) in, Q 1 The substituent is selected from acetoxy, acryloyloxy, C1 to C6 alkoxy, silyloxy, germanyloxy, phosphonoyloxy, and alkylamine; and Q 2 Q 3 and Q 4 Each is independently selected from hydrogen atoms, C1-C6 alkyl groups, and Q. 1 Substituents of the same substituent group.

7. A method for forming a film-forming composition, the film-forming composition comprising a silicon precursor having a structure according to general formula (1): (1) in, Q 1 The substituent is selected from acetoxy, acryloyloxy, C1 to C6 alkoxy, silyloxy, germanyloxy, phosphonoyloxy, and alkylamine; and Q 2 Q 3 and Q 4 Each is independently selected from hydrogen atoms, C1-C6 alkyl groups, and Q. 1 Substituents of the same substituent group, The method includes: Provides a halogenated 1,3-disilcyclobutane reactant containing at least one halogen substituent; and At least one halogen substituent of the halogen-substituted 1,3-disilcyclobutane reactant is reacted with Q 1 The substituent groups are exchanged to form silicon precursors.

8. The method according to claim 7, wherein, The step of exchanging at least one halogen substituent of a halogen-substituted 1,3-disilcyclobutane reactant comprises reacting the halogen-substituted 1,3-disilcyclobutane reactant with a reactant having the general formula M(Q) 1 ) n The method involves contacting an organometal salt to form the silicon precursor and the metal halide salt, wherein (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 wherein the method further includes separating the silicon precursor from the metal halide salt.

9. The method according to claim 7, wherein, The halogen-substituted 1,3-disilcyclobutane reactants are selected from 1-chloro-1,3-disilcyclobutane, 1-chloro-1,3,3-trimethyl-1,3-disilcyclobutane, 1,3-dichloro-1,3-disilcyclobutane, 1,3-dichloro-1,3-dimethyl-1,3-disilcyclobutane, 1,1,3,3-tetrachloro-1,3-disilcyclobutane, 1-bromo-1,3-disilcyclobutane, 1-bromo-1,3,3-trimethyl-1,3-disilcyclobutane, 1,3-dibromo-1,3-disilcyclobutane, 1,3-dibromo-1,3-dimethyl-1,3-disilcyclobutane, and 1,1,3,3-tetrabromo-1,3-disilcyclobutane.

10. The method according to claim 7, wherein, Q 1 The substituent groups are selected from acetoxy, acryloyloxy, silyloxy, germanyloxy, and phosphonooxy.

11. The method according to claim 7, wherein, Q 1 and Q 3 The substituent groups are relatedly selected from acetoxy, acryloyloxy, C1 to C6 alkoxy, siloxy, germanoxy, phosphonoyloxy, and alkylamino groups; and Q 2 and Q 4 The substituent groups are selected from hydrogen atoms and C1-C6 alkyl groups, and at least 85% of the silicon precursor is in the cis isomer form or at least 85% of the silicon precursor is in the trans isomer form.

12. The method according to claim 11, wherein, The steps for providing halogen-substituted 1,3-disilcyclobutane reactants include: Stereoselectively forming a 1,3-disilcyclobutane intermediate; and The 1,3-disilcyclobutane intermediate is reacted to form a halogen-substituted 1,3-disilcyclobutane reactant.

13. The method according to claim 12, wherein, The 1,3-disilcyclobutane intermediate is a second 1,3-disilcyclobutane intermediate, wherein the method further includes: Stereoselectively forming a first 1,3-disilcyclobutane intermediate; and The second 1,3-disilcyclobutane intermediate is formed from the first 1,3-disilcyclobutane intermediate.

14. A method for depositing a carbon-doped silicon film, the method comprising: Provide a substrate in the reaction space; The surface of the substrate is exposed to the vapor of the film-forming composition, which includes a silicon precursor having a structure according to general formula (1): (1) Among them, Q 1 The substituent is selected from acetoxy, acryloyloxy, C1 to C6 alkoxy, silyloxy, germanyloxy, phosphonoyloxy, and alkylamine; and Q 2 Q 3 and Q 4 Each is independently selected from hydrogen atoms, C1-C6 alkyl groups, and Q. 1 Substituents of the same substituent group.

15. The method according to claim 14, wherein, In general formula (1), Q 1 The substituent groups are selected from acetoxy, acryloyloxy, silyloxy, germanyloxy, and phosphonooxy.

16. The method of claim 14, wherein, In general formula (1), Q 1 and Q 3 The substituent groups are relatedly selected from acetoxy, acryloyloxy, C1 to C6 alkoxy, siloxy, germanoxy, phosphonoyloxy, and alkylamino groups; and Q 2 and Q 4 The substituent groups are selected from hydrogen atoms and C1-C6 alkyl groups, and at least 85% of the silicon precursor is in the cis isomer form or at least 85% of the silicon precursor is in the trans isomer form.

17. The method of claim 14, wherein, The silicon precursor is selected from 1,3-diacetoxy-1,3-disilcyclobutane, 1,3-diacetoxy-1,3-dimethyl-1,3-disilcyclobutane, 1,3-diaacryloxy-1,3-disilcyclobutane, 1,3-diaacryloxy-1,3-dimethyl-1,3-disilcyclobutane, 1,3-dimethacryloxy-1,3-disilcyclobutane, 1,3-dimethacryloxy-1,3-dimethyl-1,3-disilcyclobutane, 1,3-bis(trimethyl) 1,3-bis(trimethylsilyloxy)-1,3-dimethyl-1,3-disilcyclobutane, 1,3-bis(trimethylgermanyloxy)-1,3-disilcyclobutane, 1,3-bis(trimethylgermanyloxy)-1,3-dimethyl-1,3-disilcyclobutane, 1,3-bis(dimethylphosphono)-1,3-disilcyclobutane and 1,3-bis(dimethylphosphono)-1,3-dimethyl-1,3-disilcyclobutane.

18. The method according to claim 14, wherein, The method further includes exposing the surface of a substrate to a co-reactant, wherein the co-reactant is one or more of a hydrogen plasma, a rare gas plasma, a nitrogen plasma, and an oxygen plasma.

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

20. The method according to claim 18, wherein, The steps of exposing the surface of the substrate to the vapor of the film-forming composition and exposing the surface of the substrate to the co-reactant occur sequentially.

21. The method according to claim 18, wherein, The steps of exposing the surface of the substrate to the vapor of the film-forming composition and exposing the surface of the substrate to the co-reactant at least partially overlap.

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