Deposition and Etching of Silicon-Containing Layers

Abstract

A silicon-based film is conformally deposited on the feature and controllably etched using remote plasma. The silicon-based film may be an amorphous silicon layer or a doped silicon layer containing silicon oxide, silicon nitride, silicon carbide, silicon oxycarbide, silicon carbonitride, silicon oxynitride, or silicon oxycarbonitride. The silicon-based film is partially etched using remote plasma according to the desired depth and geometry by adjusting one or more of the following etching parameters: chamber pressure, substrate temperature, exposure time, RF power, gas composition, and relative concentration of the gas composition. Methods and apparatuses are also provided for depositing silicon-containing films having adjustable film composition and density, the silicon-containing films being formed by thermal atomic layer deposition or thermal chemical vapor deposition and treating the silicon-containing films with a densifying gas plasma.

Description

Incorporation by Reference

[0001] As part of this application, a PCT application form is filed simultaneously with this specification. Each application specified in this simultaneously filed PCT application form, for which this application claims benefit or priority, is incorporated herein by reference in its entirety for all purposes.

Background Art

[0002] Many semiconductor device fabrication processes involve the formation of silicon-based dielectric films. Silicon-based dielectric films can include films containing one element of silicon, or two elements such as silicon oxide, silicon carbide, or silicon nitride, or three elements such as silicon oxynitride, silicon oxycarbide, or silicon carbonitride, or four elements such as silicon oxycarbonitride. Depositing and etching silicon-based dielectric films according to the target depth and profile can be particularly difficult. The problems can also include gap filling of high aspect ratio features by silicon-based dielectric films.

[0003] The deposition of some silicon-based dielectric films involves thermal chemical vapor deposition (CVD) and / or thermal atomic layer deposition (ALD). Although thermal deposition is desirable for certain applications, the deposition conditions can be limited by the use of specific deposition precursors.

[0004] The background art provided here is intended to generally present the content of the present disclosure. Research by the inventors named at present within the scope described in this background art, as well as aspects of the description that cannot be separately regarded as prior art at the time of filing the application, are not recognized as prior art against the present disclosure, whether explicitly or implicitly.

Summary of the Invention

[0005] One aspect is a method of processing a substrate, which involves conformally depositing a silicon-containing film on one or more concave features of the substrate and etching at least a portion of the silicon-containing film to at least one of a desired depth and a desired profile by exposing the substrate to a remote plasma.

[0006] In various embodiments, the silicon-containing film includes an amorphous silicon layer. In various embodiments, conformally depositing the silicon-containing film includes flowing a silicon-containing precursor to adsorb on the surface of the substrate and thermally decomposing the silicon-containing precursor to form an amorphous silicon layer.

[0007] In various embodiments, the silicon-containing film includes silicon oxide, silicon nitride, silicon carbide, silicon oxycarbide, silicon carbonitride, silicon oxynitride, or silicon oxycarbonitride. In various embodiments, conformally depositing the silicon-containing film includes flowing a silicon-containing precursor to adsorb on the surface of the substrate, exposing the amorphous silicon layer to a plasma, and thermally decomposing the silicon-containing precursor to form an amorphous silicon layer in order to convert the amorphous silicon layer to silicon oxide, silicon nitride, silicon carbide, silicon oxycarbide, silicon carbonitride, silicon oxynitride, or silicon oxycarbonitride.

[0008] In various embodiments, conformally depositing the silicon-containing film includes depositing the silicon-containing film by thermal ALD or thermal CVD and treating the silicon-containing film with a densifying gas plasma.

[0009] In various embodiments, the remote plasma includes one or more plasma-activated species including radicals of hydrogen, halide, hydrocarbon, fluorocarbon, or combinations thereof. In various embodiments, the one or more plasma-activated species include radicals of hydrogen.

[0010] In various embodiments, at least one of a desired depth and a desired profile of the etching is based on one or more of the following etching parameters: chamber pressure, substrate temperature, exposure time, gas composition, relative concentration of the gas composition, and RF power. In various embodiments, the desired depth of the etching is adjusted according to the chamber pressure. In various embodiments, the desired depth of the etching is adjusted according to the substrate temperature. In various embodiments, the desired depth of the etching is adjusted according to the RF power. In various embodiments, the desired profile of the etching is adjusted according to the relative concentration of the gas composition.

[0011] In various embodiments, depositing a silicon-containing film and etching at least a portion of the silicon-containing film are performed in the same reaction chamber.

[0012] In various embodiments, the method further includes repeating the deposition and etching operations to partially or fully fill one or more recessed features of the substrate with a silicon-containing gap-fill material.

[0013] Another aspect is a method of processing a substrate, the method including flowing a silane-based precursor into a reaction chamber to adsorb to one or more recessed features of the substrate, the substrate being heated to thermally decompose the silane-based precursor and conformally deposit an amorphous silicon layer on one or more recessed features of the substrate. The method further includes generating a remote plasma including radicals of hydrogen, halide, hydrocarbon, fluorocarbon, or combinations thereof in a remote plasma chamber upstream of the reaction chamber, and exposing the substrate to the remote plasma to etch at least a portion of the silicon-containing layer in one or more recessed features to at least one of a desired depth and a desired profile by adjusting one or more of the following etching parameters in the reaction chamber: chamber pressure, substrate temperature, exposure time, gas composition of the remote plasma, relative concentration of the gas composition, and RF power.

[0014] In various embodiments, the silicon-containing layer includes an amorphous silicon layer.

[0015] In various embodiments, the silicon-containing film includes silicon oxide, silicon nitride, silicon carbide, silicon oxycarbide, silicon carbonitride, silicon oxynitride, or silicon oxycarbonitride.

[0016] In various embodiments, the remote plasma includes hydrogen radicals.

[0017] In various embodiments, the silane-based precursor includes silane, disilane, or trisilane.

[0018] In various embodiments, the method further includes repeating deposition and etching operations to partially or fully fill one or more recessed features of the substrate with a silicon-containing gap-fill material.

[0019] Another aspect is a method of processing a substrate housed in a process chamber, the method including introducing a silicon-containing precursor and a reactant into the process chamber at a substrate temperature of less than about 700° C. to form a silicon-containing film on the substrate without igniting a plasma, forming the silicon-containing film, and then performing a plasma treatment operation, the plasma treatment operation including stopping the flow of the silicon-containing precursor and the flow of the reactant, introducing a densification gas into the process chamber, and igniting a plasma to treat the silicon-containing film, and adjusting at least one of the silicon-containing precursor, the reactant, or the process conditions during the plasma treatment operation to change at least the composition or density of the silicon-containing film to form a treated silicon-containing film.

[0020] In various embodiments, the plasma treatment operation is performed after the silicon-containing film is formed to a thickness of about 1 Å to about 30 Å, or about 1 Å to about 20 Å.

[0021] In various embodiments, the method may also include stopping the plasma treatment operation and introducing a silicon-containing precursor and a reactant to form an additional silicon-containing film on the treated silicon-containing film.

[0022] In various embodiments, the silicon-containing precursor and the reactant are introduced simultaneously.

[0023] In various embodiments, the silicon-containing precursor and the reactant are introduced in temporally separated pulses.

[0024] In various embodiments, the method may also include purging the process chamber between forming the silicon-containing film and performing the plasma treatment operation.

[0025] In various embodiments, the silicon-containing film is selected from the group consisting of silicon carbide, silicon oxycarbide, silicon oxynitride, silicon oxynitride carbide, silicon carbonitride, and combinations thereof.

[0026] In various embodiments, the method further includes etching at least a portion of the silicon-containing film by exposing the substrate to a remote plasma.

[0027] In various embodiments and some of the above embodiments, the plasma is generated in situ.

[0028] In various embodiments and some of the above embodiments, the first and second plasmas are ignited using a single-frequency plasma generator.

[0029] In various embodiments and some of the above embodiments, the plasma is ignited using a dual-frequency plasma generator.

[0030] In various embodiments and in some of the above embodiments, the reactant is selected from the group consisting of oxygen, ozone, peroxide, nitrous oxide, nitric oxide, nitrogen, ammonia, hydrazine, and combinations thereof.

[0031] In various embodiments and in some of the above embodiments, the density of the silicon-containing film is at least about 2.0 g / cm 3 ~ about 2.6 g / cm 3 .

[0032] In various embodiments and in some of the above embodiments, the plasma treatment operation is performed at a temperature of less than about 700 °C. In various embodiments and in some of the above embodiments, the plasma treatment operation is performed at a temperature of less than about 650 °C.

[0033] In various embodiments and in some of the above embodiments, the silicon-containing film is formed in a feature having an aspect ratio of at least about 5:1.

[0034] In various embodiments and in some of the above embodiments, the silicon-containing film is deposited using thermal atomic layer deposition.

[0035] In various embodiments and in some of the above embodiments, the silicon-containing film is deposited using thermal chemical vapor deposition.

[0036] Another aspect is an apparatus for processing a substrate, the apparatus including one or more process chambers, each process chamber including a chuck, one or more gas inlets to the process chamber and associated flow control hardware, and a controller having at least one processor and a memory, the at least one processor and the memory being communicatively connected to each other, the at least one processor being at least operatively connected to the flow control hardware, the memory storing computer-executable instructions for controlling at least the flow control hardware to form a silicon-containing film on the substrate without igniting a plasma at a substrate temperature of less than about 700° C. and to process the silicon-containing film using a densification gas plasma.

[0037] These and other aspects are further described below with reference to the drawings.

Brief Description of the Drawings

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DETAILED DESCRIPTION OF THE INVENTION

[0051] In the following description, numerous specific details are set forth in order to provide a thorough understanding of the presented embodiments. The disclosed embodiments may be practiced without some or all of these specific details. In other instances, well-known process operations have not been described in detail so as not to unnecessarily obscure the disclosed embodiments. The disclosed embodiments are described in conjunction with specific embodiments, but it will be understood that the disclosed embodiments are not intended to be limiting.

[0052] In the present disclosure, the terms “semiconductor wafer,” “wafer,” “substrate,” “wafer substrate,” and “partially fabricated integrated circuit” are used interchangeably. Those skilled in the art will understand that the term “partially fabricated integrated circuit” can refer to a silicon wafer at any of many stages of integrated circuit fabrication. Wafers or substrates used in the semiconductor device industry typically have a diameter of 200 mm, or 300 mm, or 450 mm. The following detailed description assumes that the present disclosure is implemented on a wafer. However, the present disclosure is not so limited. The workpiece may be of various shapes, sizes, and materials. In addition to semiconductor wafers, other workpieces on which the present disclosure can be utilized include various articles such as printed circuit boards.

[0053] The substrate may include "features" or "trenches". As used herein, a "feature" may refer to a non-planar structure of a substrate, typically a surface that is modified in semiconductor device fabrication operations. Examples of features, which may also be referred to as "negative features" or "concave features", include trenches, holes, vias, gaps, concave regions, and the like. These terms may be used interchangeably in this disclosure. An example of a feature is a hole or via within a semiconductor substrate or within a layer on the substrate. Another example is a trench within the substrate or layer. Features typically have an aspect ratio (depth to lateral dimension). Features can be characterized by one or more of narrow and / or reentrant openings, constrictions within the feature, and high aspect ratios. A feature having a high aspect ratio can have an aspect ratio of depth to lateral dimension of about 10:1 or greater, about 15:1 or greater, about 20:1 or greater, about 25:1 or greater, about 30:1 or greater, about 40:1 or greater, about 50:1 or greater, or about 100:1 or greater. In various embodiments, a feature may have an underlying layer such as a barrier layer or an adhesion layer. Non-limiting examples of underlying layers include dielectric layers and conductive layers, such as silicon oxide, silicon nitride, undoped silicon carbide, oxygen-doped silicon carbide, nitrogen-doped silicon carbide, metal oxides, metal nitrides, metal carbides, and metal layers.

[0054] Features of the substrate can be of various types. In some embodiments, a feature can have straight sidewalls, positively sloped sidewalls, or negatively sloped sidewalls. In some embodiments, a feature may have sidewall topography or sidewall roughness that may result from an etching process that forms the feature. In some embodiments, a feature can have a feature opening that is larger at the top of the feature than at the bottom, or a feature can have a feature opening that is larger at the bottom of the feature than at the top.

[0055] Semiconductor manufacturing processes may involve the fabrication of silicon-containing films such as silicon carbonitride, silicon oxycarbonitride, silicon carbide, and silicon oxynitride. Such films are deposited on a patterned substrate and may form conformal films for various applications. Such films may also be deposited in a furnace. As devices are miniaturized and technology advances, higher quality, higher density, and more conformal films are desired. Certain silicon-containing films can be deposited on high aspect ratio features on a substrate. In some cases, but not limited to, deposition is carried out thermally for various reasons including reducing or eliminating damage to existing structures and / or materials on the substrate.

[0056] One technique for depositing a film is chemical vapor deposition (CVD), which can be thermal or plasma enhanced (e.g., also referred to as plasma enhanced CVD, PECVD). In CVD, the deposition reactants often react with each other on the surface of the substrate in the gas phase or vapor phase, thereby forming a film on the substrate.

[0057] Another technique for depositing a film is atomic layer deposition (ALD), which can also be thermal or plasma enhanced (e.g., also referred to as plasma enhanced ALD, PEALD). ALD is a technique that uses sequential self-limiting reactions to deposit thin layers of material. Unlike CVD, the ALD process deposits a film layer by layer using surface-mediated deposition reactions. As an example, a thermal ALD cycle can include the following operations: (i) delivery / adsorption of a precursor, (ii) purge of the precursor from the chamber, (iii) delivery of a second reactant, and (iv) purge of by-products from the chamber. The reaction between the adsorbed precursor and the second reactant on the surface of the substrate affects the composition and properties of the film, such as non-uniformity, stress, wet etching rate, dry etching rate, electrical properties (e.g., breakdown voltage and leakage current), etc.

[0058] In one example of an ALD process, a substrate surface including a collection of surface active sites is exposed to the gas phase distribution of a first precursor, such as a silicon-containing precursor, at a dosage provided to a chamber containing the substrate. Molecules of this first precursor are adsorbed onto the substrate surface, including chemisorbed species and / or physisorbed molecules of the first precursor. It should be understood that when a compound is adsorbed onto the substrate surface as described herein, the adsorption layer may include the compound as well as derivatives of the compound. For example, the adsorption layer of a silicon-containing precursor can include the silicon-containing precursor as well as derivatives of the silicon-containing precursor. After dosing with the first precursor, the chamber is evacuated to remove most or all of the first precursor remaining in the gas phase, thereby leaving most or all of the adsorbed species. In some embodiments, the chamber may not be completely evacuated. For example, it is possible to evacuate the reactor such that the partial pressure of the first precursor in the gas phase is low enough to reduce the reaction. A second reactant, such as a carbon-containing gas, is introduced into the chamber, whereby some of these molecules react with the first precursor adsorbed on the surface. In some processes, the second precursor reacts immediately with the adsorbed first precursor. In other embodiments, the second reactant reacts only after an activation source, such as heat, is applied. In some embodiments, the activation source is applied only when the second precursor is introduced. The exposure to the second reactant and the deposition precursor may be temporally separated, i.e., one is done after the other and not simultaneously. After exposure to the second reactant, the flow of the second reactant may be stopped, and then the chamber can be evacuated again to remove unreacted second reactant molecules. As described above, in some embodiments, the chamber may not need to be completely evacuated. Additional ALD cycles may be used to build up the film thickness.

[0059] In an embodiment of PEALD, the method includes plasma activation during exposure to a second reactant. As described herein, the ALD methods and apparatus described herein may be conformal film deposition (CFD) methods, which are generally described in U.S. Patent Application No. 13 / 084,399, entitled "PLASMA ACTIVATED CONFORMAL FILM DEPOSITION," filed Apr. 11, 2011 (currently U.S. Patent No. 8,728,956), and U.S. Patent Application No. 13 / 084,305, entitled "SILICON NITRIDE FILMS AND METHODS," filed Apr. 11, 2011, the disclosures of which are incorporated herein by reference in their entirety.

[0060] The ALD process can be used to deposit a particular film, but because certain processes involve the use of halogen-containing precursors, the process conditions under which the film can be deposited may be limited. For example, in some embodiments, due to thermodynamic constraints, deposition may only occur at temperatures above about 700° C., or above about 650° C.

[0061] Methods and apparatus are provided for depositing silicon-containing dielectric films by thermal ALD and / or CVD using halogen-free deposition precursors and adjustable film composition and densification. Silicon-containing films deposited using certain disclosed embodiments are high quality films. The silicon-containing films are deposited on a substrate, which may be a silicon wafer, such as a 200 mm wafer, 300 mm wafer, or 450 mm wafer, having one or more layers of material, such as a dielectric material, conductive material, or semiconductive material, deposited thereon. Non-limiting examples of layers that may be deposited on the substrate include dielectric layers and conductive layers, such as silicon oxide, silicon nitride, silicon carbide, metal oxides, metal nitrides, metal carbides, and metal layers. The substrate may be patterned to form features having an aspect ratio of from about 1:1 to about 60:1, or greater than about 1.5:1, or greater than about 4:1, or from about 1.5:1 to 60:1, or from about 1.5:1 to 40:1, or from about 1.5:1 to 20:1, such as about 5:1.

[0062] Films deposited in accordance with certain disclosed embodiments may be conformal. Conformality may be determined by step coverage. "Step coverage", as used herein, is calculated by dividing the average thickness of the deposited film on the sidewalls by the average thickness of the deposited film at the top of the feature and multiplying by 100 to obtain a percentage. Films deposited using certain disclosed embodiments can achieve step coverage of from about 70% to about 120% for features having an aspect ratio of from about 1:5 to about 1:50.

[0063] The method described herein is carried out at a temperature of less than about 700 °C, such as less than about 650 °C, from about 250 °C to about 350 °C, such as about 275 °C. It will be understood that the temperature described herein may refer to the temperature at which a pedestal holding a substrate can be set. The terms "substrate temperature", "pedestal temperature", and "temperature" may all refer to the temperature at which the pedestal is set. The temperature may also depend on the pressure in the chamber in which the semiconductor substrate is housed. The method may also be carried out in a process chamber having a chamber pressure of less than about 10 Torr, such as from about 2 Torr to about 10 Torr.

[0064] The manufacture of semiconductor devices typically involves forming one or more silicon-based thin films on a semiconductor substrate in an integrated fabrication process. The silicon-based thin films can include doped or undoped silicon oxide, doped or undoped silicon nitride, or doped or undoped silicon carbide. In the integrated circuit manufacturing industry, the technology nodes are continuously shrinking. For each technology node, the geometric shape of the device is also shrinking and the pitch is getting smaller. High aspect ratio gaps at such technology nodes may need to be filled with insulating materials such as low dielectric constant (low-k) insulating materials. Semiconductor integration operations may involve filling high aspect ratio gaps with low-k dielectric materials. This applies to shallow trench isolation, intermetal dielectric layers, passivation layers, etc. In another example, as the features of the device shrink laterally, unwanted conductive couplings may occur as conductive materials get closer and closer, leading to parasitic capacitance, signal propagation delay, and signal crosstalk due to capacitive effects. Low-k materials as interlayer dielectrics (ILDs) for conductive interconnects can reduce parasitic capacitance, signal delay, and signal crosstalk. In some applications, including fin field effect transistor (finFET) structures and dynamic random access memory (DRAM) bit structures, low-k materials are required as sidewall spacer materials.

[0065] Silicon nitride is often used as an insulating material in many integrated circuit applications because of its step coverage, thermal stability, etchability and etch resistance, as well as high breakdown voltage.

[0066] Silicon oxide has a low dielectric constant of about 4.0 and can significantly reduce the capacitance as an interlayer insulator for conductive interconnects.

[0067] Silicon carbide materials, including doped and undoped silicon carbide materials, can serve as insulating materials in integrated circuit applications that provide not only a low dielectric constant but also step coverage, thermal stability, wet etch resistance, dry etch selectivity to oxides / nitrides, and high breakdown voltage. For example, the properties of silicon carbide materials can be adjusted by incorporating oxygen atoms and / or nitrogen atoms. In some embodiments, an oxygen-doped silicon carbide film can serve as an insulating material in integrated circuit applications that provide a low dielectric constant, wet etch resistance to withstand device integration operations, and dry etch selectivity to oxides / nitrides.

[0068] Forming high-quality silicon-based thin films may have specific challenges, such as providing films with excellent step coverage, low dielectric constant, and / or high breakdown voltage. When a silicon-based thin film with desired properties and composition is formed, there may also be an additional challenge of conformally depositing the silicon-based thin film in high aspect ratio features. Conformal deposition may be desirable for gap filling in high aspect ratio features. The semiconductor manufacturing process often involves a gap filling process or a dielectric gap filling process. Typically, CVD and / or ALD methods are used to fill the features. However, with conventional techniques, undesirable seams or voids are often formed within the features. In some cases, the presence of seams and / or voids in gap filling can lead to increased resistance, contamination, loss of the filled material, performance degradation, and even device failure.

[0069] To avoid the formation of seams and voids during gap filling, the feature may be filled by a bottom-up filling process. Bottom-up filling can be performed with a silicon oxide film, but is more difficult with other silicon-based films. Conventional vapor deposition techniques such as CVD and ALD can be used to deposit silicon-based films on the feature. As the aspect ratio of the feature increases, a "bread-loafing" deposition effect can occur due to the mass transport limitation of the CVD gas-phase reaction, resulting in thicker deposition on the top surface and thinner deposition on the concave surface, so that the upper part of the feature opening closes before the feature can be completely filled. Unlike the CVD process, the ALD process uses a surface-mediated deposition reaction to deposit a film layer by layer, and such a film is typically conformal. ALD can deposit highly conformal films, but it may be difficult to deposit films on high aspect ratio features. The step coverage and uniformity of the film along the sidewalls depend, for example, on the transport of deposition precursors, reactant ions and / or radicals, and by-products. As the lateral dimension of the feature decreases, the transport and diffusion of deposition precursors and reactant species in the feature become increasingly difficult. Therefore, due to diffusion limitations, the upper part of the feature is exposed to more precursor and reactant species, and the bottom of the feature is exposed to fewer precursor and reactant species. This may result in the formation of seams and voids in high aspect ratio features. Various approaches can be employed in the gap filling of features with silicon-containing materials to avoid the formation of seams and / or voids.

[0070] Figures 1A-1C show schematic cross-sectional views of features of an exemplary substrate undergoing gap fill using directional etching in a dep-etch-dep process. The dep-etch-dep (deposition, etching, deposition) technique involves depositing a gap fill material, subsequently etch-backing a portion of the gap fill material to open a feature opening, and then redepositing the gap fill material to complete the gap fill or at least advance the gap fill process. Figure 1A shows an example of a feature 101 of a substrate 100 with a gap fill material 102a deposited on the feature 101. The gap fill material 102a may be deposited conformally along the top surface, sidewalls, and bottom surface of the feature 101. In some embodiments, the gap fill material 102a may be deposited using ALD.

[0071] Figure 1B shows an example of a feature 101 of the substrate 100 with the gap fill material 102a etch-backed. For example, the gap fill material 102a can be etch-backed to form a tapered profile. Thus, more of the gap fill material 102a is removed near the top of the feature 101 than at the bottom of the feature 101. The etching is configured to re-shape the gap fill material 102a such that more material can be filled into the feature 101. In this way, the profile of the feature 101 does not limit the diffusion of precursors and / or reactive species that reach the bottom and sidewalls of the feature 101 during subsequent deposition processes.

[0072] To reduce or eliminate the presence of voids and seams in gap filling, different types of etching can be applied between deposition cycles. It is possible to adjust the etching conditions and chemicals to perform non-conformal etching. In some cases, non-conformal etching preferentially removes more of the gap fill material 102a near the top surface of the feature 101 than the bottom surface of the feature 101. The etching chemical often includes fluorine-containing species, and the fluorine-containing etchant can include xenon difluoride (XeF2), molecular fluorine (F2), or nitrogen trifluoride (NF3). Other fluorine-containing etchants can include tetrafluoromethane (CF4), fluoromethane (CH3F), difluoromethane (CH2F2), tetrafluoroethylene (C2F4), hexafluoroethane (C2F6), octafluoropropane (C3F8), and sulfur hexafluoride (SF6). In certain embodiments, the fluorine-based etching can be plasma etching, whereby radicals and / or ions of the fluorine-containing species react with the gap fill material 102a to remove the gap fill material 102a. It is possible to control the fluorine-based etching to etch the silicon-based film and reshape the profile of the etched silicon-based film.

[0073] FIG. 1C shows an example of a feature 101 of a substrate 100 in which a gap fill material 102b is deposited to fill or substantially fill the feature 101. Although voids 103 can be formed by the deposition of the gap fill material 102b, the size of the voids 103 can be minimized by interrupting the deposition with one or more etching operations. The gap fill material 102b can be the same as the gap fill material 102a, and the feature 101 is filled or substantially filled with the combined gap fill materials 102a, 102b. In some embodiments, one or both of the gap fill material 102a and the gap fill material 102b include a silicon-based dielectric material such as silicon oxide, silicon nitride, silicon carbide, silicon oxycarbide, silicon carbonitride, silicon oxynitride, and silicon oxycarbonitride.

[0074] Fluorine-based etchants, such as fluorine radicals, can react chemically with silicon in a silicon-based film and selectively remove the silicon-based film. Therefore, fluorine-based etching is commonly used to etch silicon-containing layers. However, for several reasons, fluorine-based etching may not be desirable. First, fluorine-based chemicals may not be compatible with certain materials and layers in semiconductor fabrication processes and may cause unwanted reactions with fluorine-containing species. Second, fluorine-based etchants may leave residues on the sidewalls and other surfaces of the patterned substrate. The fluorine residues may be incorporated in an undesirable form in subsequent processing steps. Third, fluorine-based plasmas may leave an etched surface roughness, which may adversely affect device performance.

[0075] Figures 2A through 2C show cross-sectional schematic views of features of an exemplary substrate undergoing gap fill using an inhibitor chemical in a dep-etch-dep process. The inhibitor chemical can be used to cause the gap fill material to grow or form in the feature in a topographically different manner. For example, the inhibitor can react with the material to form a passivated surface that inhibits growth. The surface of the substrate may be more passivated in the field and upper regions of the feature, and may be less passivated as the distance from the feature increases. As a result, deposition on top of the feature is selectively inhibited, and deposition in the lower portion of the feature can proceed with less inhibition or without inhibition. FIG. 2A shows an example of a feature 201 of a substrate 200, where at least the field and upper regions of the feature 201 are exposed to a reactant that inhibits deposition / growth of the gap fill material. The reactant reacts with the substrate material to form a passivation layer 205 on the substrate 200. As an example, nitrogen gas (N2) or ammonia (NH3) can be used to form a passivation layer 205 consisting of a nitride. A gap fill material such as silicon dioxide (SiO2) nucleates at a slower rate on the nitride surface.

[0076] FIG. 2B shows an example of a feature 201 of a substrate 200, where a gap fill material 202a is deposited on the feature 201. The gap fill material 202a may be deposited along the top surface, sidewalls, and bottom surface of the feature 201. The passivation layer 205 selectively inhibits deposition / growth of the gap fill material 202a in the field and upper regions of the feature 201, such that the gap fill material 202a is deposited more on the sidewalls and bottom surface of the feature 201 than in the field and upper regions of the feature 201.

[0077] FIG. 2C shows an example of a feature 201 on a substrate 200, where a gap fill material 202b is deposited to fill or substantially fill the feature 201. Deposition of the gap fill material 202b may form a void 203, but the void 203 can be made small because an inhibiting chemical promotes bottom-up filling in the feature 201. The gap fill material 202b may be the same as the gap fill material 202a, and the feature 201 is filled or substantially filled with the combined gap fill materials 202a, 202b. In some embodiments, one or both of the gap fill material 202a and the gap fill material 202b include silicon-based dielectric materials such as silicon oxide, silicon nitride, silicon carbide, silicon oxycarbide, silicon carbonitride, silicon oxynitride, and silicon oxycarbonitride.

[0078] The inhibiting chemical can reduce the formation of seams and voids, but the inhibiting chemical is generally limited to specific types of chemicals and processes. In other words, different processes require different inhibiting chemicals. In addition to silicon oxide films, many inhibiting chemicals are often not suitable for restricting the deposition / growth of films of silicon nitride, silicon carbide, silicon oxycarbide, silicon carbonitride, silicon oxynitride, and silicon oxycarbonitride. In some cases, a particular inhibiting chemical may not be suitable for a particular deposition technique such as remote plasma CVD. Therefore, the application of inhibiting chemicals in gap filling may be limited to specific gap fill chemicals, deposition techniques, and even film properties.

[0079] This specification provides methods and apparatus related to controllably etching silicon-based films using remote plasma etching, where the silicon-based films are conformally deposited on high aspect ratio features of a substrate. The geometry and depth of the etching can be controlled by adjusting process parameters such as pressure, temperature, exposure time, gas flow rate, gas composition, and plasma power, among other process parameters. In some embodiments, the remote plasma etching uses a remote plasma gas flow containing one or more gas species, and the one or more gas species include hydrogen (H2). In some embodiments, the silicon-based film includes amorphous silicon (a-Si), or the silicon-based film includes silicon oxide, silicon nitride, silicon carbide, silicon oxycarbide, silicon carbonitride, silicon oxynitride, or silicon oxycarbonitride. After conformally depositing the silicon-based film, the silicon-based film is exposed to a remote plasma to controllably etch at least a portion of the silicon-based film. In some embodiments, the remote plasma removes a portion of the silicon-based film in the upper and sidewall regions of the silicon-based film to achieve a specific depth and / or profile. Optionally, the conformal deposition and controllable etching operations are repeated to fill high aspect ratio features in a gap fill process.

[0080] FIG. 3 shows a flowchart of an exemplary method of performing deposition and etching on features of a substrate, according to some embodiments. The operations of process 300 may be performed in a different order and / or with different, fewer, or additional operations. One or more of the operations of process 300 may be performed using the substrate processing apparatus shown in FIGS. 12 or 13. In some embodiments, the operations of process 300 may be implemented, at least in part, in accordance with software stored on one or more non-transitory computer-readable media.

[0081] In block 310 of process 300, a substrate is optionally provided to a process chamber. The substrate may be supported on a substrate support or pedestal within the process chamber. The substrate can be any wafer, semiconductor wafer, partially fabricated integrated circuit, printed circuit board, display screen, or other suitable workpiece. The substrate may be a patterned substrate having features. One or more features can be high aspect ratio features, and high aspect ratio features have a depth-to-width aspect ratio of about 10:1 or greater, about 15:1 or greater, about 20:1 or greater, about 25:1 or greater, about 30:1 or greater, about 40:1 or greater, about 50:1 or greater, or about 100:1 or greater. In some embodiments, one or more recessed features include high aspect ratio trenches within a 3D-NAND or logic device. Optionally, before or after providing the substrate to the process chamber, and before depositing and etching a silicon-containing layer on the substrate, the substrate can be cleaned. For example, diluted hydrogen fluoride (HF) can be used to remove contaminants or thin oxide layers on the substrate.

[0082] The process chamber provides a sealed space for depositing a silicon-containing layer on a substrate. In some cases, the process chamber is also used to etch the silicon-containing layer with remote plasma. By using the same process chamber for deposition and etching, substrate transfer is minimized and air breaks between operations are limited. The chamber walls in the process chamber may be fabricated from stainless steel, aluminum, plastic, ceramic, or other suitable materials. The process chamber can include a substrate support (e.g., a pedestal or an electrostatic chuck) on which the substrate is supported. In some embodiments, the process chamber can include one or more heating elements for controlling the temperature of the substrate, and the one or more heating elements may be infrared (IR) lamp light-emitting diodes (LEDs), or resistive heaters located on the substrate support. The process chamber can include one or more gas lines for feeding gas into the process chamber. For example, the one or more gas lines may include a showerhead for supplying process gas toward the substrate within the process chamber. In some embodiments, the process chamber may be coupled to a plasma generation chamber separate from the process chamber. The plasma generation chamber (e.g., a remote plasma chamber) may be an inductively coupled plasma (ICP) reactor, a capacitively coupled plasma (CCP) reactor, or a capacitively coupled plasma (CCP) reactor. In some cases, the process chamber further includes one or more gas outlets for exhausting gas, and these gas outlets may or may not be coupled to a vacuum pump to maintain a desired pressure within the process chamber. A process chamber for depositing a silicon-containing film (e.g., an amorphous silicon layer) may be the same as one for etching the silicon-containing film.

[0083] In block 320 of process 300, an amorphous silicon layer is optionally deposited on the recessed features of the substrate. Amorphous silicon (a-Si), in contrast to crystalline silicon, is non-crystalline and lacks long-range order. Techniques for depositing the amorphous silicon layer may include CVD, PECVD, ALD, PEALD, or other suitable deposition techniques. In some embodiments, the amorphous silicon layer is deposited by CVD via a thermal decomposition process. The thermal decomposition process is initiated by the activation of a heated precursor gas species, which is thermally decomposed into atoms and / or molecules for CVD deposition.

[0084] In some embodiments, the thickness of the amorphous silicon layer is controlled according to a predetermined deposition time, and a desired thickness can be achieved. In some embodiments, the deposition time can be from about 5 seconds to about 500 seconds, or from about 10 seconds to about 200 seconds. In some embodiments, the desired thickness of the amorphous silicon layer can be from about 0.5 nm to about 50 nm, or from about 1 nm to about 20 nm. The deposition time can correspond to the desired thickness of the amorphous silicon layer. The thickness may be controlled to allow radicals and / or ions to sufficiently penetrate the amorphous silicon layer from subsequent remote plasma etching or plasma treatment.

[0085] In some embodiments, the deposition of the amorphous silicon layer can be performed by flowing one or more silicon-containing precursors into the process chamber towards the substrate. The silicon-containing precursor is transported to the substrate surface, where it is adsorbed by the substrate to form a highly conformal amorphous silicon layer. In some embodiments, when forming an amorphous silicon layer by CVD, it may be necessary to control the deposition pressure in the range of 0.1 Torr to 30 Torr, or 0.5 Torr to about 10 Torr. The substrate temperature during the deposition of the amorphous silicon layer can be controlled to be about 300 °C to about 700 °C, or about 400 °C to about 650 °C. After deposition, the step coverage for the amorphous silicon layer may be at least about 85%. In some embodiments, the step coverage may be at least about 90% or at least about 95%.

[0086] In some embodiments in CVD or PECVD, the silicon-containing precursor can be continuously fed to the substrate until the desired thickness is obtained. In other embodiments in ALD or PEALD, an amorphous silicon layer can be formed by repeating (1) pulsing one or more silicon-containing precursors over a predetermined time, followed by (2) purging the excess precursor. In some embodiments, the amorphous silicon layer may not contain long-range order, and instead, the amorphous silicon layer may have a continuous random network of silicon atoms.

[0087] As described above, the amorphous silicon layer may be highly conformal. Without being limited by any theory, silicon-containing precursors having a low sticking coefficient may be capable of producing a highly conformal amorphous silicon layer. The term "sticking coefficient" is used to represent the ratio of the number of adsorbed species (e.g., fragments or molecules) that adsorb / attach to a surface to the total number of species that impinge on that surface during the same period. The symbol Sc may be used to indicate the sticking coefficient. The value of Sc is between 0 (meaning that none of the species attach) and 1 (meaning that all of the impinging species attach). Various factors, including the type of impinging species, surface temperature, surface coverage, details of the surface structure, and the kinetic energy of the impinging species, affect the sticking coefficient. Certain species are inherently more "sticky" than others, and are more likely to adsorb onto the surface each time the species impinge on the surface. These more sticky species have a larger sticking coefficient (all other factors being the same). In some cases, the sticking coefficient of the precursor (under the relevant deposition conditions) may be about 0.05 or less, such as about 0.001 or less.

[0088] In some embodiments, the silicon-containing precursor may include at least one or more Si-Si bonds and / or one or more Si-H bonds. Suitable silicon-containing precursors for use in accordance with the disclosed embodiments may include polysilane (H3Si-(SiH2) n -SiH3) where n≧0. Examples of silanes include silane (SiH4), disilane (Si2H6), trisilane (Si3H8), and organosilanes such as methylsilane, ethylsilane, isopropylsilane, t-butylsilane, dimethylsilane, diethylsilane, di-t-butylsilane, allylsilane, sec-butylsilane, texylsilane, isoamyldisilane, t-butyldisilane, di-t-butyldisilane, and the like. In some embodiments, one or more silicon-containing precursors include silane, disilane, or trisilane.

[0089] In some embodiments, the silicon-containing precursor can also include a halosilane. A halosilane contains at least one halogen group and may or may not contain hydrogen and / or carbon groups. Examples of halosilanes are iodosilane, bromosilane, chlorosilane, and fluorosilane. Specific chlorosilanes are tetrachlorosilane, trichlorosilane, dichlorosilane, monochlorosilane, chloroallylsilane, chloromethylsilane, dichloromethylsilane, chlorodimethylsilane, chloroethylsilane, t-butylchlorosilane, di-t-butylchlorosilane, chloroisopropylsilane, chlorosec-butylsilane, t-butyldimethylchlorosilane, texyldimethylchlorosilane, and the like.

[0090] In some embodiments, the silicon-containing precursor can also include an aminosilane. An aminosilane contains at least one nitrogen atom bonded to a silicon atom and may also contain hydrogen, oxygen, halogen, and carbon. Examples of aminosilanes are monoaminosilane, diaminosilane, triaminosilane, and tetraaminosilane (H3Si(NH2), H2Si(NH2)2, HSi(NH2)3, and Si(NH2)4, respectively), as well as substituted monoaminosilane, diaminosilane, triaminosilane, and tetraaminosilane, such as t-butylaminosilane, methylaminosilane, tert-butylsilaneamine, bis(tert-butylamino)silane (SiH2(NHC(CH3)3)2 (BTBAS), tert-butylsilylcarbamate, SiH(CH3)-(N(CH3)2)2, SiHCl-(N(CH3)2)2, (Si(CH3)2NH)3, diisopropylaminosilane, di-sec-butylaminosilane, and the like. A further example of an aminosilane is trisilylamine (N(SiH3)). In some embodiments, aminosilanes having two or more amine groups bonded to the central Si atom can be used. These may be less damaging than aminosilanes having only a single amine group bonded.

[0091] Further examples of silicon-containing precursors include trimethylsilane (3MS), ethylsilane, butasilane, pentasilane, octasilane, heptasilane, hexasilane, cyclobutasilane, 1-dimethylamino-1,1,5,5,5-pentamethyldisiloxane, cycloheptasilane, cyclohexasilane, cyclooctasilane, cyclopentasilane, 1,4-dioxa-2,3,5,6-tetrasilacyclohexane, diethoxymethylsilane (DEMS), diethoxysilane (DES), dimethoxymethylsilane, dimethoxysilane (DMOS), methyl-diethoxysilane (MDES), methyl-dimethoxysilane (MDMS), octamethoxydodecasiloxane (OMODDS), tert-butoxydisilane, tetramethylcyclotetrasiloxane (TMCTS), tetraoxymethylcyclotetrasiloxane (TOMCTS), triethoxysilane (TES), triethoxysiloxane (TRIES), and trimethoxysilane (TMS or TriMOS).

[0092] In addition to the precursor gas, an inert carrier gas or diluent gas can be flowed over the substrate. Examples of inert carrier gases or diluent gases include, but are not limited to, helium (He), neon (Ne), argon (Ar), krypton (Kr), xenon (Xe), and nitrogen (N2). In some embodiments, one or more gas mixtures of one or more source gases and an inert carrier gas or diluent gas may be provided to a remote plasma source.

[0093] As an example, the one or more silicon-containing precursors include silane, disilane, trisilane, or other silane-based precursors. The silane-based precursors can be flowed into the process chamber and adsorbed onto the exposed surface of the substrate. The silane-based precursors can be thermally decomposed under specific CVD operating conditions (e.g., 400°C to 650°C, 0.1 to 30 Torr) to form an amorphous silicon layer. Due to thermal decomposition, the silane-based precursors are decomposed into atoms and / or molecules and deposited on the surface of the heated substrate. Although plasma-based deposition processes can lead to non-conformal deposition of amorphous silicon, thermal decomposition of silane-based precursors at a sufficiently high temperature provides highly conformal deposition of amorphous silicon.

[0094] In block 330 of process 300, a silicon-containing film that is conformal to the shape of the recessed features of the substrate is formed. In some embodiments, the silicon-containing film is an amorphous silicon layer. Thus, the formation of the silicon-containing film that is conformal to the recessed features of the substrate in block 330 has already been achieved by the deposition of the amorphous silicon layer in block 320. In some other embodiments, the silicon-containing film includes two elements, three elements, four elements, or five or more elements. For example, the silicon-containing layer includes silicon oxide, silicon nitride, silicon carbide, silicon oxycarbide, silicon oxynitride, silicon carbonitride, or silicon oxycarbonitride. The formation of the multi-element silicon-containing film occurs by incorporating dopants (other than hydrogen) into the amorphous silicon layer deposited in block 320, thereby enabling the conversion of the amorphous silicon layer into a multi-element silicon-containing film in block 330. Alternatively, the multi-element silicon-containing film can be formed without necessarily depositing the amorphous silicon layer in block 320. In such a case, the multi-element silicon-containing film is conformally deposited by CVD, PECVD, ALD, PEALD, or other suitable deposition techniques. In one example, a silicon-carbon-containing film can be deposited on the substrate by remote plasma CVD. In another example, the multi-element silicon-containing film is conformally deposited by thermal ALD or thermal CVD, and then the silicon-containing film is treated with a densification gas plasma.

[0095] When the silicon-containing film is formed by conversion of an amorphous silicon layer, the amorphous silicon layer may be exposed to a gas plasma stream. The gas plasma stream may include one or more gas species including an oxygen-containing reactant such as oxygen (O2), ozone (O3), carbon monoxide (CO), carbon dioxide (CO2), nitrous oxide (N2O), or nitrogen dioxide (NO2), a carbon-containing reactant such as acetylene (C2H2), ethylene (C2H4), or propene (C3H6), a hydrogen-containing reactant such as hydrogen (H * ) or nitrogen-containing reactants such as nitrogen (N * ), oxygen radicals (O * ), carbon radicals (C * ), amine radicals (NH * , NH2 * ), or combinations thereof. In some embodiments, the gas plasma stream is a remote gas plasma stream. In some cases where the silicon-containing film is formed by conversion of an amorphous silicon layer, the amorphous silicon layer may be exposed to a temperature raised by flowing one or more gas species to the substrate, and the raised (high) temperature can be from about 200°C to about 650°C.

[0096] When the silicon-containing film is formed by CVD, PECVD, ALD, PEALD, or other suitable deposition techniques that do not involve the conversion of an amorphous silicon layer, the silicon-containing precursor can react in the gas phase to deposit the silicon-containing film. The silicon-containing precursor can react with one or more reactants in the gas phase to deposit the silicon-containing film. In some embodiments, the one or more reactants can include an oxygen-containing reactant, such as oxygen, ozone, carbon monoxide, carbon dioxide, nitrous oxide, nitrogen dioxide, or a mixture thereof. In some embodiments, the one or more reactants can include a carbon-containing reactant, such as acetylene, methane, ethylene, propene, or a mixture thereof. In some embodiments, the one or more reactants can include a nitrogen-containing reactant, such as nitrogen, ammonia, diazene, hydrazine, or a mixture thereof. The silicon-containing precursor can have one or more silicon-hydrogen (Si-H) bonds and / or one or more silicon-silicon (Si-Si) bonds. In some embodiments, the silicon-containing precursor can have one or more silicon-carbon (Si-C) bonds, one or more silicon-oxygen (Si-O) bonds, and / or one or more silicon-nitrogen (Si-N) bonds.

[0097] The silicon-containing film can be formed with excellent step coverage in the concave features of the substrate. The step coverage can be calculated by comparing the average thickness of the deposited film on the bottom, sidewall, or top of the feature to the average thickness of the deposited film on another part of the feature. For example, the step coverage can be calculated by dividing the average thickness of the deposited film on the sidewall by the average thickness of the deposited film at the top of the feature and multiplying by 100 to obtain a percentage. In some embodiments, the step coverage for the silicon-containing film can be at least about 85%. In some embodiments, the step coverage can be at least about 90% or at least about 95%. By depositing a silicon-containing film having excellent step coverage along the sidewalls of the concave features, a vertical structure can be formed.

[0098] In some cases, a silicon-containing film can be conformally deposited on a concave feature using remote plasma CVD such as remote hydrogen plasma CVD. The silicon-containing film may be formed by flowing a silicon-containing precursor into the process chamber through a first gas outlet and introducing hydrogen radicals generated from a remote plasma source into the process chamber through a second gas outlet. The first gas outlet may be located downstream from the second gas outlet. The hydrogen radicals react with the silicon-containing precursor in an environment adjacent to the substrate to deposit the silicon-containing film. Si-H bonds and / or Si-Si bonds are selectively cleaved by the hydrogen radicals and serve as reaction sites for forming bonds between the silicon-containing precursors. The cleaved bonds can also serve as sites for crosslinking during or after deposition. Bonding and crosslinking at the reaction sites can form the main backbone or matrix in the resulting silicon-containing film. In some embodiments, the hydrogen radicals become in a low-energy state or a ground state when reacting with the silicon-containing precursor in an environment adjacent to the substrate. It is possible to design the plasma processing apparatus to control the process conditions such that the hydrogen radicals relax from an excited state to a low-energy state or a ground state when reacting with the silicon-containing precursor. In this way, the hydrogen radicals can selectively cleave Si-H bonds and Si-Si bonds while generally retaining Si-O, Si-N, and Si-C bonds. In some embodiments, the hydrogen radicals may be fed together with an inert gas such as argon (Ar), helium (He), neon (Ne), krypton (Kr), or xenon (Xe). In some embodiments, one or more co-reactants can be flowed into the process chamber to react with the silicon-containing precursor to increase or decrease the carbon, oxygen, or nitrogen content of the silicon-containing film.Details regarding remote hydrogen plasma CVD processes for the deposition of silicon-containing films can be found in U.S. Patent No. 10,325,773 by Varadarajan et al. entitled "CONFORMAL DEPOSITION OF SILICON CARBIDE FILMS" filed on February 6, 2015, U.S. Patent Application No. 16 / 044,357 by Weimer et al. entitled "CONFORMAL DEPOSITION OF SILICON CARBIDE FILMS USING HETEROGENEOUS PRECURSOR INTERACTION" filed on July 24, 2018, and U.S. Patent Application No. 17 / 286,407 by Yuan et al. entitled "DOPED OR UNDOPED SILICON CARBIDE DEPOSITION AND REMOTE HYDROGEN PLASMA EXPOSURE FOR GAPFILL" filed on April 16, 2021, each of the above applications being incorporated by reference in its entirety for all purposes.

[0099] In some cases, the silicon-containing film may be conformally deposited on the concave features using ALD or PEALD. In some embodiments, the silicon-containing film is conformally deposited on the concave features using remote plasma ALD. ALD is a technique for depositing thin layers of material using sequential self-limiting reactions. Typically, an ALD cycle includes the operation of feeding and adsorbing at least one precursor to the substrate surface, and then reacting the adsorbed precursor with one or more reactants to form a partial film layer. As an example, a silicon nitride ALD cycle can include the following operations: (i) feeding / adsorbing a silicon-containing precursor, (ii) purging the silicon-containing precursor from the chamber, (iii) optionally exposing a nitrogen-containing reactant to a plasma, and (iv) purging excess reactant from the chamber. In some embodiments, the plasma reacts with the adsorbed silicon-containing precursor to deposit a silicon nitride film with nitrogen, ammonia, and / or hydrogen (N * , NH2 * , NH * , and / or H *) can contain radical species. In some cases, the plasma may be an in-situ plasma or a remote plasma. Pulses of various precursors and co-reactants may be used to deposit other types of films.

[0100] In some cases, the silicon-containing film is conformally deposited on the concave feature using thermal CVD or thermal ALD, and then the composition or density of the silicon-containing film can be changed by performing a plasma treatment that operates with a densification gas plasma. The thermal CVD or thermal ALD operation may be performed at a substrate temperature of less than about 700 °C or less than about 650 °C. The plasma treatment operation may be performed at a substrate temperature of less than about 700 °C or less than about 650 °C. The deposition of the silicon-containing film by thermal CVD or thermal ALD may proceed using a halogen-free silicon-containing precursor.

[0101] The silicon-containing film is deposited to a thickness that partially fills the concave feature. The silicon-containing film is continuously formed along the bottom, sidewalls, and top surface of the concave feature. In some embodiments, the thickness of the silicon-containing film is about 200 Å or less, about 0.5 Å to about 100 Å, about 1 Å to about 20 Å, or about 1 Å to about 10 Å.

[0102] In block 340 of process 300, at least a portion of the silicon-containing film is etched to at least one of a desired depth and a desired profile by exposure to a remote plasma. In some embodiments, the remote plasma is a remote hydrogen plasma. The remote plasma exposure is performed under conditions that achieve controlled etching of the silicon-containing film in the concave feature. In addition to or instead of densifying or treating the silicon-containing film, the remote plasma selectively removes a controlled amount of the silicon-containing film at or near the top of the concave feature and selectively removes another controlled amount of the silicon-containing film along the sidewalls of the concave feature. As used herein, "controlled etching" or "controlled amount" does not refer to an exact amount or value, but more broadly refers to the general shape of the silicon-containing film achieved by remote plasma exposure. Similarly, as used herein, "desired profile" and "desired depth" do not refer to an exact amount or value, but more broadly refer to an acquired profile close to the target profile and an acquired depth close to the target depth. In some cases, the desired profile or desired depth is within 1 nm of the target profile or target depth and is a profile or depth at any position within 5 degrees or 10 degrees of the target taper angle. Remote plasma etching preferentially removes more of the silicon-containing film at specific locations of the concave feature than at other locations of the concave feature. The extent to which the silicon-containing film is removed at various locations (i.e., top, bottom, sidewalls) of the concave feature is affected by the conditions of the remote plasma etching.

[0103] In some embodiments, the remote plasma is hydrogen (H * ), a halide (e.g., F * , Cl * ), a hydrocarbon (e.g., CH * ), a fluorocarbon (e.g., CF * ), an amine (e.g., NH *) and includes one or more plasma-activated species including radicals of these or combinations thereof. For example, the one or more plasma-activated species include hydrogen radicals. The plasma-activated species may be generated from one or more source gases. Exemplary source gases include, but are not limited to, hydrogen (H2), fluorine (F2), chlorine (Cl2), bromine (Br2), hydrogen fluoride (HF), hydrogen chloride (HCl), hydrogen bromide (HBr), nitrogen trifluoride (NF3), boron trichloride (BCl3), ammonia (NH3), methane (CH4), ethane (C2H6), acetylene (C2H2), ethylene (C2H4), propylene (C3H6), butene (C4H8), pentadiene (C5H8), hexene (C6H 12 ), propyne (C3H4), butyne (C4H6), pentyne (C5H8), toluene (C7H8), benzene (C6H6), tetrafluoromethane (CF4), octafluorocyclobutane (C4F8), hexafluorobutadiene (C4F6), and difluoromethane (CH2F2) may be mentioned. The one or more source gases are fed from a gas supply source to a remote plasma source. In some cases, the one or more source gases are supplied with an inert gas such as argon, helium, neon, krypton, or xenon. The one or more source gases are ignited to generate a plasma containing plasma-activated species. The plasma-activated species may include ions, radicals, charge-neutral substances, and other reactive species of the one or more source gases. The plasma-activated species are fed from the remote plasma source to the process chamber and can etch at least a part of the silicon-containing film. In some embodiments, the remote plasma source is located upstream of the process chamber.

[0104] Remote plasma etching is performed without feeding a silicon-containing precursor. Deposition of a silicon-containing film may involve feeding a silicon-containing precursor, but the flow of the silicon-containing precursor is stopped by remote plasma exposure for etching at least a portion of the silicon-containing film. Additionally or alternatively, remote plasma etching is performed without feeding any oxygen-containing species, any carbon-containing species, or any nitrogen-containing species. Some of the foregoing species may be used as dopants when converting an amorphous silicon layer to form a multi-element silicon-containing film, but such species are not flowed during remote plasma etching.

[0105] In some embodiments, deposition of the silicon-containing film is performed in the same process chamber as the remote plasma etching. Conformal deposition of the silicon-containing film can be performed in the process chamber, and etching of at least a portion of the silicon-containing film using remote plasma can also be performed in the process chamber. Thereby, deposition and etching can be performed in the same tool or chamber, so that deposition and etching are performed without introducing a vacuum break (e.g., an air break). A vacuum break can reduce throughput and cause oxidation of the substrate, increase electrical resistance, and decrease performance. In some cases, a plasma treatment operation using a densification gas plasma and remote plasma etching may be performed in the same process chamber.

[0106] One or both of the desired profile and the desired depth are achieved by adjusting one or more of the following etching parameters: chamber pressure, substrate temperature, exposure time, gas composition of the remote plasma, relative concentration of the gas composition, and RF power. By controlling one or more of the foregoing etching parameters, different types of etching profiles and etching depths can be obtained. Typically, conventional etching of a silicon-containing film involves a fluorine-based etchant that leaves undesirable residues, or conventional etching of a silicon-containing film may have control and directionality. The remote plasma etching of the present disclosure provides various etching profiles and depths depending on the conditions of the remote plasma. This enables the removal of the silicon-containing film on the controlled feature top and / or sidewalls.

[0107] In some embodiments, the depth of the remote plasma etching is adjusted according to the chamber pressure. The chamber pressure may be from about 0.01 Torr to about 10 Torr, from about 0.05 Torr to about 5 Torr, or from about 0.1 Torr to about 2 Torr. Generally speaking, the chamber pressure can be adjusted to obtain a more effective concentration of the etchant. By adjusting to a lower pressure, the etching rate increases and the etching depth becomes deeper. At high pressure, more silicon-containing film can be selectively etched near the top or in the vicinity of the concave feature than at the center and bottom or in the vicinity thereof, and at low pressure, more silicon-containing film can be etched at the top and center or in the vicinity of the concave feature than at the bottom or in the vicinity thereof.

[0108] In some embodiments, the depth of remote plasma etching is adjusted according to RF power. The RF power may be about 300 W to about 15 kW per station, about 500 W to about 10 kW per station, or about 1 kW to about 8 kW per station. Adjusting the RF power can increase the generation of hydrogen radical species, amine radical species, or other radical species. In some embodiments, the remote plasma source may be an inductively coupled plasma (ICP) reactor for the generation of radical species. By adjusting to a higher RF power, the concentration of the etchant increases and the etching depth becomes deeper. At low RF power, more silicon-containing film can be selectively etched in the upper part or near the upper part of the concave feature than in the central and bottom parts or near the bottom of the concave feature. At high RF power, more silicon-containing film can be selectively etched in the upper and central parts or near the upper and central parts of the concave feature than in the bottom part or near the bottom of the concave feature.

[0109] In some embodiments, the depth of remote plasma etching is adjusted according to the substrate temperature. The substrate temperature may be about 25°C to about 750°C, about 50°C to about 700°C, or about 200°C to about 650°C. Adjusting the temperature can increase the etching rate of the silicon-containing film. By adjusting to a lower temperature, the etching depth becomes deeper. At medium temperature, more silicon-containing film can be selectively removed in the upper part or near the upper part of the concave feature than in the central and bottom parts or near the bottom of the concave feature. At low temperature, more silicon-containing film can be selectively removed in the upper and central parts or near the upper and central parts of the concave feature than in the bottom part or near the bottom of the concave feature.

[0110] In some embodiments, the depth of remote plasma etching is adjusted according to the exposure time. The exposure time may be about 1 second to about 5 minutes, about 2 seconds to about 3 minutes, or about 5 seconds to about 2 minutes. It will be understood that the exposure time may vary depending on the dimensions of the concave feature. By adjusting to a longer exposure time, the etching depth becomes deeper.

[0111] In some embodiments, at least one of the depth and profile of remote plasma etching is adjusted according to the relative concentration of the gas composition. The gas composition may include source gases such as hydrogen, ammonia, one or more hydrocarbons, one or more fluorocarbons, one or more halides, or mixtures thereof. The gas composition may further include an inert gas such as argon, helium, neon, krypton, or xenon. For example, the gas composition may include a mixture of hydrogen and helium, or a mixture of hydrogen and argon. Adjusting the relative concentration of hydrogen and the inert gas can affect the etching depth and / or profile. In some embodiments, the flow rate ratio of hydrogen to the inert gas may be from about 1:10 to about 100:1, from about 1:2 to about 50:1, or from about 1:1 to about 20:1.

[0112] Whether increasing the concentration of the source gas increases or decreases the etching rate depends on the chemical substance of the source gas. Thus, an increase in the concentration of the source gas may or may not result in deeper etching. In the case of hydrogen and the inert gas, adjusting the concentration of the source gas to medium to low results in a deeper etching depth. At low source gas concentrations, more silicon-containing film can be selectively removed near the top or in the vicinity of the concave feature than at or near the center and bottom of the concave feature.

[0113] An increase or decrease in the source gas concentration relative to the inert gas concentration can potentially affect the profile of remote plasma etching. Other etching parameters such as chamber pressure, substrate temperature, RF power, exposure time, and gas composition may additionally or alternatively affect the profile of remote plasma etching. By controlling the deposition thickness and etching depth at each step, a final film profile with a desired taper can be formed. In some cases, it is possible to change the taper of the film in a concave feature by controlling the pressure or mean free path. For example, at low pressures, hydrogen radicals may diffuse deeper in the concave feature, and at high pressures, etching near the top of the concave feature may be more concentrated. Nevertheless, the combination of pressure, temperature, plasma power, exposure time, and gas composition can adjust the etching profile in the present disclosure. The etching profile can be described from the perspective of the shape of the silicon-containing film at various locations (i.e., top, bottom, sidewalls) of the concave feature. In some cases, the etching profile may have a taper, whereby the thickness of the silicon-containing film decreases as it approaches the top of the concave feature rather than the bottom. The degree of taper can be measured by the slope or angle with respect to a line perpendicular to the substrate surface from the upper region of the silicon-containing film in the concave feature. The slope or angle may be from 0 degrees to 60 degrees, from about 5 degrees to about 50 degrees, or from about 10 degrees to about 45 degrees. In some cases, the etching profile may have a rounded or sharp corner in the upper region of the silicon-containing film in the concave feature. In some cases, the etching profile may reflect notching, curvature, undercut, faceting, and other deviations from a vertically shaped film in the concave feature.

[0114] By operating various knobs of remote plasma etching, the etching depth and etching profile of remote plasma etching can be modified. In some embodiments, remote plasma etching removes more of the silicon-containing film near the opening of the concave feature than along the sidewalls and at the bottom of the concave feature. In some embodiments, remote plasma etching provides a tapered etching profile. For example, the tapered etching profile may be from about 30 degrees to about 70 degrees. In some embodiments, remote plasma etching removes at least 10%, at least 20%, at least 25%, at least 30%, at least 40%, or at least 50% of the silicon-containing film from the top of the concave feature. For example, remote plasma etching partially removes the silicon-containing film, such that about 10% to about 50% of the silicon-containing film is removed from the top of the concave feature.

[0115] In some embodiments, process 300 further includes repeating deposition and etching operations to fill or at least substantially fill the concave features. As used herein, being substantially filled with respect to filling the concave features may refer to having a silicon-containing gap fill material that occupies at least 98% of the volume of the concave features. The concave features can be filled without seams or voids. By controlling the shape and depth of remote plasma etching during the deposition operation, gap filling without seams or voids may be possible. After remote plasma etching at block 340, process 300 may be followed by deposition of an additional thickness of a silicon-containing film that serves as the gap fill material. The initially deposited silicon-containing film and any additional thickness of the silicon-containing film may constitute the silicon-containing gap fill material. The additional thickness of the silicon-containing film can partially or fully fill one or more concave features. Some embodiments of depositing the additional thickness of the silicon-containing film may be the same as depositing and forming the silicon-containing film at block 330. Thereafter, after process 300, another remote plasma etching may follow to shape the silicon-containing gap fill material according to at least one of a desired depth and a desired profile. Some embodiments of this remote plasma etching may be the same as the remote plasma etching at block 340. However, the etching parameters such as chamber pressure, substrate temperature, RF power, gas composition, and relative concentrations of the gas composition may be the same as or different from those at block 340. The deposition and etching operations may be repeated at least once, at least twice, at least three times, at least five times, at least eight times, or at least ten times before the final deposition of the silicon-containing gap fill material is performed to fill or at least substantially fill the concave features.

[0116] Figures 4A - 4B show schematic cross - sectional views of features of an exemplary substrate that is partially etched to a shallow depth using remote plasma, according to some embodiments. FIG. 4A shows an example of a feature 401 of a substrate 400, and a silicon - containing layer 402 is deposited on the feature 401. The silicon - containing layer 402 is conformally deposited along the top surface, sidewalls, and bottom surface of the feature 401. In some embodiments, the silicon - containing layer 402 is an amorphous silicon layer deposited by thermal CVD using a silane - based precursor that decomposes on the exposed surface of the substrate 400. In some embodiments, the silicon - containing layer 402 is a doped silicon layer such as silicon oxide, silicon nitride, silicon carbide, silicon oxycarbide, silicon carbonitride, silicon oxynitride, or silicon oxicarbonitride. The doped silicon layer may be deposited using any suitable deposition technique such as ALD, PEALD, CVD, PECVD, or other techniques. For example, the doped silicon layer may be deposited by remote plasma CVD. Alternatively, the doped silicon layer may be formed by converting an amorphous silicon layer, and the conversion is performed by exposing the amorphous silicon layer to a plasma stream containing gas species including carbon, nitrogen, and / or oxygen. Alternatively, the conversion may be performed by exposing the amorphous silicon layer to a high temperature (elevated temperature) while flowing gas species containing carbon, nitrogen, and / or oxygen, and the high temperature may be from about 200°C to about 650°C. In some embodiments, the silicon - containing layer 402 is deposited by thermal CVD or thermal ALD, followed by a plasma treatment operation using a densifying gas plasma. The plasma treatment operation can change at least the composition or density of the silicon - containing layer 402. The silicon - containing layer 402, which can include an amorphous silicon layer or a doped silicon layer, can be deposited with a step coverage of at least 85%, at least 90%, or at least 95% in the feature 401. The silicon - containing layer 402 only partially fills the feature 401.

[0117] FIG. 4B shows an example of a feature 401 on a substrate 400, where a silicon-containing layer 402 is partially etched. The substrate 400 may be exposed to a remote plasma under conditions that partially etch the silicon-containing layer 402 to a shallow depth. The remote plasma can remove the silicon-containing layer 402 to an etching depth that reaches about 1% to 50% of the depth from the top of the feature 401, about 5% to about 45% of the depth from the top of the feature 401, or about 10% to about 40% of the depth from the top of the feature 401. In some embodiments, the partially etched silicon-containing layer 402 may have a tapered profile. The remote plasma removes the silicon-containing layer 402 from the top of the feature 401 rather than from the center or bottom of the feature 401. The remote plasma can include one or more gas species including hydrogen, ammonia, one or more hydrocarbons, one or more fluorocarbons, one or more halides, or a mixture thereof. In some embodiments, the remote plasma includes hydrogen and an inert gas. In some embodiments, the remote plasma may be generated by a plasma source located upstream of the process chamber for depositing and etching the silicon-containing layer 402. The remote plasma controls etching parameters such as chamber pressure, substrate temperature, RF power, exposure time, gas composition, and / or relative concentration of the gas composition to perform the partial etching shown in FIG. 4B. By adjusting one or more of the aforementioned etching parameters, the silicon-containing layer 402 can be partially etched to a desired depth and / or profile in the feature 401. In some embodiments, the remote plasma for removing at least a portion of the silicon-containing layer 402 may proceed after performing a plasma treatment operation on the silicon-containing layer 402 using a densification gas plasma.

[0118] Figures 5A - 5B show schematic cross - sectional views of features of an exemplary substrate that is partially etched to a deep depth using remote plasma, according to some embodiments. Figure 5A shows an example of a feature 501 of a substrate 500, and a silicon - containing layer 502 is deposited on the feature 501. The silicon - containing layer 502 is conformally deposited along the top surface, sidewalls, and bottom surface of the feature 501. In some embodiments, the silicon - containing layer 502 is an amorphous silicon layer deposited by thermal CVD using a silane - based precursor that decomposes on the exposed surface of the substrate 500. In some embodiments, the silicon - containing layer 502 is a doped silicon layer such as silicon oxide, silicon nitride, silicon carbide, silicon oxycarbide, silicon carbonitride, silicon oxynitride, or silicon oxycarbonitride. The doped silicon layer may be deposited using any suitable deposition technique such as ALD, PEALD, CVD, PECVD, or other techniques. For example, the doped silicon layer may be deposited by remote plasma CVD. Alternatively, the doped silicon layer may be formed by converting an amorphous silicon layer, and the conversion is performed by exposing the amorphous silicon layer to a plasma stream containing gas species including carbon, nitrogen, and / or oxygen, or by exposing the amorphous silicon layer to a high temperature while flowing a gas species containing carbon, nitrogen, and / or oxygen over the substrate. In some embodiments, the doped silicon layer may be deposited by thermal CVD or thermal ALD, followed by a plasma treatment operation using a densification gas plasma. The silicon - containing layer 502, which can include an amorphous silicon layer or a doped silicon layer, can be deposited with a step coverage of at least 85%, at least 90%, or at least 95% in the feature 401. The silicon - containing layer 502 only partially fills the feature 501.

[0119] FIG. 5B shows an example of a feature 501 of a substrate 500, where a silicon-containing layer 502 is partially etched. The substrate 500 may be exposed to a remote plasma under conditions that partially etch the silicon-containing layer 502 to a deep depth. The remote plasma can remove the silicon-containing layer 502 to an etching depth that reaches about 40% to 95% of the depth from the top of the feature 501, about 50% to about 90% of the depth from the top of the feature 501, or about 60% to about 85% of the depth from the top of the feature 501. In some embodiments, the partially etched silicon-containing layer 502 may have a tapered profile. The silicon-containing layer 502 in FIG. 5B may be etched to a different depth and profile than the silicon-containing layer 402 in FIG. 4B. The remote plasma removes more of the silicon-containing layer 502 from the top of the feature 501 than from the bottom of the feature 501. The remote plasma can include one or more gas species including hydrogen, ammonia, one or more hydrocarbons, one or more fluorocarbons, one or more halides, or mixtures thereof. In some embodiments, the remote plasma includes hydrogen and an inert gas. In some embodiments, the remote plasma may be generated by a plasma source located upstream of the process chamber for depositing and etching the silicon-containing layer 502. The remote plasma controls etching parameters such as chamber pressure, substrate temperature, RF power, exposure time, gas composition, and / or relative concentration of the gas composition to perform the partial etching shown in FIG. 5B. By adjusting one or more of the aforementioned etching parameters, the silicon-containing layer 502 can be partially etched to a desired depth and / or profile in the feature 501.

[0120] Figures 6A - 6B show schematic cross - sectional views of features of an exemplary substrate partially etched on the top surface using remote plasma, according to some embodiments. Figure 6A shows an example of a feature 601 of substrate 600, where a silicon - containing layer 602 is deposited on the feature 601. The silicon - containing layer 602 is conformally deposited along the top surface, sidewalls, and bottom surface of the feature 601. In some embodiments, the silicon - containing layer 602 is an amorphous silicon layer deposited by thermal CVD using a silane - based precursor that decomposes on the exposed surface of the substrate 600. In some embodiments, the silicon - containing layer 602 is a doped silicon layer such as silicon oxide, silicon nitride, silicon carbide, silicon oxycarbide, silicon carbonitride, silicon oxynitride, or silicon oxycarbonitride. The doped silicon layer may be deposited using any suitable deposition technique such as ALD, PEALD, CVD, PECVD, or other techniques. For example, the doped silicon layer may be deposited by remote plasma CVD. Alternatively, the doped silicon layer may be formed by converting an amorphous silicon layer, and the conversion is performed by exposing the amorphous silicon layer to a plasma stream containing gas species including carbon, nitrogen, and / or oxygen, or by exposing the amorphous silicon layer to a high temperature while flowing a gas species containing carbon, nitrogen, and / or oxygen over the substrate. In some embodiments, the doped silicon layer may be deposited by thermal CVD or thermal ALD, followed by a plasma treatment operation using a densifying gas plasma. The silicon - containing layer 602, which can include the amorphous silicon layer or the doped silicon layer, can be deposited with a step coverage of at least 85%, at least 90%, or at least 95% in the feature 601. The silicon - containing layer 602 only partially fills the feature 601.

[0121] FIG. 6B shows an example of a feature 601 on a substrate 600, where a silicon-containing layer 602 is partially etched. The substrate 600 may be exposed to a remote plasma under conditions that partially etch the silicon-containing layer 602, whereby the silicon-containing layer 602 is substantially removed from the top surface of the feature 601 while the silicon-containing layer 602 along the sidewalls and bottom surface of the feature 601 is substantially retained. The silicon-containing layer 602 may be shaped such that the opening at the top surface of the feature 601 is larger than the opening at the central or bottom portion of the feature 601. The opening at the top surface of the feature 601 may be tapered as the silicon-containing layer 602 extends downward. The silicon-containing layer 602 in FIG. 6B is etched to a different depth and profile than the silicon-containing layer 502 in FIG. 5B and may be etched to a different depth and profile than the silicon-containing layer 402 in FIG. 4B. The remote plasma can include one or more gas species including hydrogen, ammonia, one or more hydrocarbons, one or more fluorocarbons, one or more halides, or mixtures thereof. In some embodiments, the remote plasma includes hydrogen and an inert gas. In some embodiments, the remote plasma may be generated by a plasma source located upstream of the process chamber for depositing and etching the silicon-containing layer 602. The remote plasma controls etching parameters such as chamber pressure, substrate temperature, RF power, exposure time, gas composition, and / or relative concentrations of the gas composition to perform the partial etching shown in FIG. 6B. By adjusting one or more of the foregoing etching parameters, the silicon-containing layer 602 can be partially etched to a desired depth and / or profile in the feature 601.

[0122] Figures 7A-7C show schematic cross-sectional views of features of an exemplary substrate undergoing gap fill in a dep-etch-dep process according to some embodiments. The operation of the gap fill may include more, fewer, or different operations than those shown in Figures 7A-7C. The operation of the gap fill can be implemented using a plasma processing apparatus as shown in Figures 12 and 13.

[0123] In FIG. 7A, a silicon-containing layer 702a of a first thickness is deposited on a feature 701 of a substrate 700. Although the substrate 700 shows only a single feature 701, it will be understood that the substrate 700 may have one or more features 701. In some embodiments, the silicon-containing layer 702a comprises amorphous silicon. In some other embodiments, the silicon-containing layer 702a comprises a doped silicon layer such as silicon oxide, silicon nitride, silicon carbide, silicon oxycarbide, silicon oxynitride, silicon carbonitride, or silicon oxycarbonitride. The silicon-containing layer 702a of the first thickness can be deposited using any suitable deposition technique. For example, if the silicon-containing layer 702a is amorphous silicon, the silicon-containing layer 702a may be deposited by thermal CVD using a silane-based precursor that thermally decomposes and adsorbs on the substrate surface at a high temperature. If the silicon-containing layer 702a is a doped silicon layer, the silicon-containing layer 702a may be deposited by ALD, PEALD, CVD, PECVD, or other techniques. Alternatively, the silicon-containing layer 702a may be formed by converting amorphous silicon, and the conversion is performed by exposing to a plasma stream containing carbon, nitrogen, and / or oxygen to form doped silicon, or by exposing to a high temperature while flowing a gas species containing carbon, nitrogen, and / or oxygen over the substrate to form doped silicon. In some embodiments, the silicon-containing layer 702a may be formed by thermal CVD or thermal ALD, and the silicon-containing layer 702a is exposed to a plasma treatment operation using a densifying gas plasma that affects the composition and / or density of the silicon-containing layer 702a. The silicon-containing layer 702a, which can comprise an amorphous silicon layer or a doped silicon layer, can be deposited with a step coverage of at least 85%, at least 90%, or at least 95% in the feature 701.

[0124] In FIG. 7B, a silicon-containing layer 702a of a first thickness is exposed to a remote plasma to partially etch the silicon-containing layer 702a. The etching is performed under conditions that increase the size of the opening at the upper surface of the feature 701. The remote plasma can etch the silicon-containing layer 702a to a shallow depth and leave no gap-fill material in the opening near the upper portion of the feature 701. The remote plasma can etch the silicon-containing layer 702a into a tapered profile that narrows as the silicon-containing layer 702a extends downward in the feature 701. The remote plasma can include one or more gas species including hydrogen, ammonia, one or more hydrocarbons, one or more fluorocarbons, one or more halides, or mixtures thereof. In some embodiments, the remote plasma includes hydrogen and an inert gas. In some embodiments, the remote plasma may be generated by a plasma source located upstream of the process chamber for depositing and etching the silicon-containing layer 702a. This enables the deposition cycle and the remote plasma etching cycle to be alternately performed in the same tool or chamber. As a result, deposition and etching can be performed without introducing a vacuum break (e.g., an air break) during the gap-fill process. The remote plasma controls etching parameters such as chamber pressure, substrate temperature, RF power, exposure time, gas composition, and / or relative concentration of the gas composition to perform the partial etching shown in FIG. 7B. By adjusting one or more of the foregoing etching parameters, the silicon-containing layer 702a can be partially etched to a desired depth and / or profile in the feature 701 for the gap-fill process.

[0125] In FIG. 7C, a silicon-containing layer 702b of a second thickness is deposited on a feature 701 of a substrate 700. The silicon-containing layer 702b of the second thickness is deposited on the silicon-containing layer 702a of the first thickness. Some aspects of depositing the second thickness may be the same as or at least similar to the aspects of depositing the first thickness. The silicon-containing layer 702b of the second thickness may be compositionally the same as the silicon-containing layer 702a of the first thickness, and the silicon-containing layers 702a, 702b serve as a gap-fill material. Depositing the first thickness, etching, and depositing the second thickness may be performed in the same tool or the same process chamber. Depositing the first thickness may be a thermal CVD process, etching the first thickness may be a remote plasma etching process, depositing the second thickness may be a thermal CVD process, and all of these may be performed in the same tool or the same process chamber. Depositing the first thickness may be a thermal CVD or thermal ALD process, the process may be a plasma process, etching the first thickness may be a remote plasma etching process, depositing the second thickness may be a thermal CVD or thermal ALD process, the process may be a plasma process, and all of these may be performed in the same tool or the same process chamber. The second thickness may have a step coverage of at least 85%, at least 90%, or at least 95%. In some cases, the silicon-containing layers 702a, 702b can fill or at least substantially fill the feature 701. As described in the present disclosure, interrupting the deposition operation with remote plasma etching can avoid seams and / or voids during gap filling or at least minimize the size of seams and / or voids. The deposition and remote plasma etching operations of the gap-fill material of the present disclosure can be repeated until the gap filling in FIG. 7C is completed.

[0126] As described above, aspects of the present disclosure can relate to depositing a silicon-containing layer on a feature and subsequently performing a controlled etching process using a remote plasma. However, whether or not an etching process follows the deposition of the silicon-containing layer on the feature, aspects of the present disclosure can relate to the deposition of the silicon-containing layer by thermal ALD and / or thermal CVD. Such deposition can be performed using a halogen-free deposition precursor. The silicon-containing layer can have an adjustable film composition and deposition. In some embodiments, the silicon-containing layer deposited by thermal ALD and / or thermal CVD is treated by exposure to a densification gas plasma. The deposition of the silicon-containing layer may be performed at a temperature of less than about 700 °C, such as less than about 650 °C, from about 250 °C to about 350 °C, such as about 275 °C.

[0127] FIG. 8A shows a process flow diagram illustrating operations that can be performed in accordance with certain disclosed embodiments. In operation 802, a patterned substrate can be provided to a process chamber that can be set to a chamber pressure of from about 0 Torr to about 30 Torr. The pressure may vary from operation to operation, may remain the same throughout all of the operations of FIG. 8A, or may be the same in two or more of the operations of FIG. 8A. Exemplary process chambers are further described below with respect to FIGS. 12 and 13. As described above, the substrate may be a silicon wafer having one or more dielectric, conductive, or semiconductive materials deposited thereon. The substrate may be patterned with features having an aspect ratio of from about 1:1 to about 60:1, or greater than about 1.5:1, or greater than about 4:1, or from about 1.5:1 to 60:1, or from about 1.5:1 to 40:1, or from about 1.5:1 to 20:1, such as about 5:1. When the patterned substrate is provided to the process chamber, the substrate can be subjected to a “temperature soak,” whereby the substrate is heated to a process temperature at which the operations described herein are received. For example, in some embodiments, the substrate may be heated to a temperature of less than about 700 °C, such as less than about 650 °C, from about 650 °C to about 400 °C, or about 275 °C.

[0128] In operation 804, the substrate is exposed to a silicon-containing deposition precursor and a reactant to form a thermally conformal silicon-containing film. In various embodiments, "halogen-free" means that the silicon-containing precursor molecule contains no halogen substituents at all. In various embodiments, the silicon-containing precursor is halogen-free. The silicon-containing deposition precursor may be any suitable silicon-containing precursor, such as those listed in the definitions herein and in the precursor section. In some embodiments, the halogen-free silicon-containing precursor has a decomposition temperature of less than about 700 °C, or less than about 650 °C. In some embodiments, the halogen-free silicon-containing deposition precursor is an aminosilane, or an alkylsilane, or a silazane. In some embodiments, the silicon-containing precursor is trimethylsilane. In some embodiments, the silicon-containing precursor is dimethylsilane. In some embodiments, the silicon-containing precursor is tetramethylsilane.

[0129] The deposition reactant selected depends on the film to be deposited. In various embodiments, the reactant may be an oxygen-containing gas, a carbon-containing gas, and / or a nitrogen-containing gas. Exemplary oxygen-containing gases include oxygen (O2), ozone (O3), peroxides such as hydrogen peroxide (H2O2), carbon monoxide (CO), carbon dioxide (CO2), nitrous oxide (N2O), nitrogen dioxide (NO2), and combinations thereof. The oxygen-containing reactant may help promote an increase in the oxygen content in the deposited film. Exemplary carbon-containing gases include CO, CO2, and combinations thereof. The carbon-containing reactant may help promote an increase in the carbon content in the deposited film. Exemplary nitrogen-containing gases include nitrogen (N2), ammonia (NH3), nitrous oxide (N2O), nitrogen dioxide (NO2), hydrazines such as hydrazine (N2H4), and combinations thereof. The nitrogen-containing reactant may help promote an increase in the nitrogen content in the deposited film.

[0130] Operation 804 may be performed by thermal CVD in some embodiments. In embodiments of thermal CVD, both the deposition precursor and the reactant may be continuously flowed into the process chamber containing the substrate.

[0131] Operation 804 may be performed by thermal ALD in some embodiments. In embodiments of thermal ALD, the flows of the deposition precursor and the reactant may be temporally separated, i.e., the reactant does not flow when the deposition precursor flows, and the deposition precursor does not flow when the reactant flows. Each exposure of the deposition precursor and the reactant may be referred to as a "pulse". In some embodiments, the "pulse" of the deposition precursor may be referred to as a "dose". The "pulse" of the reactant may be referred to as a "conversion", which may refer to converting the adsorbed precursor molecules into the film material. However, "conversion" assumes that the precursor is already adsorbed. It will be understood that in some embodiments, the pulse of the reactant may be performed even when the deposition precursor has not yet been pulsed or when precursor molecules have not been adsorbed onto the substrate. The temporally separated pulses may be pulsed in cycles such that each cycle includes one pulse of the deposition precursor and one pulse of the reactant.

[0132] FIG. 8B shows an exemplary process flow diagram of an operation that can be performed by thermal ALD as a deposition technique for performing operation 804 of FIG. 8A. In operation 804-a, the substrate is exposed to a halogen-free silicon-containing deposition precursor that may adsorb onto the substrate surface. In some embodiments, adsorption onto the surface of the substrate may form a thin layer of the silicon-containing precursor on the surface of the substrate. The thin layer may be less than a monolayer and may have a thickness of from about 0.5 Å to about 2.0 Å. During operation 804-a, a carrier gas may be flowed. The carrier gas can be used to co-flow with the silicon-containing precursor in some embodiments. The carrier gas may be an inert gas such as helium, argon, neon, and combinations thereof. The carrier gas may be routed such that the carrier gas is used to feed the deposition precursor gas into the process chamber. In some embodiments, the carrier gas may be provided to assist in the pressure and / or temperature control of the process chamber. In some embodiments, the carrier gas is used to ensure a more rapid delivery of gas to the process chamber. The carrier gas may be provided as a sweep gas to assist in the pressure and / or temperature control of the process chamber, the evaporation of liquid reactants, the more rapid delivery of reactants, and / or to remove process gases from the process chamber and / or process chamber piping.

[0133] In operation 804-b, the process chamber is optionally purged. Prior to purging, the flow of the halogen-free silicon-containing precursor can be stopped or diverted from the process chamber. The purge can remove silicon-containing precursors that did not adsorb onto the substrate surface. Purging the chamber can involve flowing a purge gas or sweep gas, which may be the carrier gas used in other operations or a different gas. In some embodiments, the purge may involve evacuating the chamber. Exemplary purge gases include argon, nitrogen, hydrogen, and helium. In some embodiments, operation 804-b may include one or more evacuation sub-steps for evacuating the process chamber. Alternatively, it will be appreciated that operation 804-b may be omitted in some embodiments. Operation 804-b can have any suitable duration, from about 0 seconds to about 60 seconds, such as about 0.01 seconds. In some embodiments, increasing the flow rate of one or more purge gases may decrease the duration of operation 804-b. For example, the flow rate of the purge gas can be adjusted according to the thermodynamic and / or geometric properties of the various reactants in the process chamber and / or the process chamber piping, and the duration of operation 804-b can be modified. In one non-limiting example, it is possible to adjust the duration of the purge step by adjusting the flow rate of the purge gas. This can shorten the deposition cycle time and improve the throughput of the substrate. After purging, the silicon-containing precursor molecules remain adsorbed on the substrate surface. In some embodiments, the purge gas is flowed into the chamber containing the substrate at a flow rate of about 100 sccm to about 5000 sccm.

[0134] In operation 804-c, the substrate is exposed to the reactant without plasma to form a silicon-containing film on the substrate surface. In some embodiments, this operation enables the reactant to react with the silicon-containing precursor molecules adsorbed thereon, converting the silicon-containing precursor molecules into the molecules of the silicon-containing film. This example of FIG. 8B involves adsorption prior to exposure to the reactant, although it will be understood that in some embodiments, the substrate may be exposed to the reactant and then to the silicon-containing precursor. Operation 804-c is performed without plasma, whereby the reaction between the silicon-containing precursor and the reactant is a thermal reaction.

[0135] In some embodiments, the reactant may be an oxygen-containing reactant or an oxidizing agent, as described above. In some embodiments, the silicon-containing precursor is an aminosilane and the reactant is an oxidizing agent. In such cases, the reaction between the aminosilane and the oxidizing agent is a thermal reaction, and thus no plasma is required to drive the reaction. In some embodiments, the reactant is flowed into the chamber containing the substrate at a flow rate of about 1 sccm to about 5000 sccm.

[0136] In operation 804-d, the chamber is optionally purged to remove residual by-products. Operation 804-d may be performed using any of the conditions described above with respect to operation 804-b.

[0137] It is determined whether a film of the desired thickness has been deposited. If not, operations 804-a to 804-d are repeated for a sufficient number of cycles to deposit a silicon-containing film of the desired thickness. Any suitable number of deposition cycles may be included in the ALD process to deposit a silicon-containing film of the desired film thickness. For example, using the disclosed embodiments, about 50 deposition cycles may be performed to deposit a silicon-containing film on the substrate. In some embodiments, the silicon-containing film is formed to a thickness of about 1 Å to about 30 Å.

[0138] Returning to FIG. 8A, in operation 806, the process chamber may optionally be purged. Operation 806 may be performed using any of the conditions described above with respect to operation 804-b of FIG. 8B. The purge may be used to remove deposition precursors and / or reactants from the chamber and / or from the processing region above the substrate surface.

[0139] In operation 808, after at least a portion of the silicon-containing film has been deposited, the silicon-containing film is exposed to a densification plasma either (1) without a precursor or reactant, or (2) with a densification gas. For example, the densification plasma can be generated by igniting a densification gas, which can include, but is not limited to, hydrogen (H2) gas, an oxygen-containing gas, a nitrogen-containing gas, and combinations thereof. The gas can be selected depending on the type of film being deposited and the reactants used during the deposition process. A general list of possible gases includes nitrogen only, ammonia only, nitrogen / ammonia mixtures, argon only, helium only, argon / helium mixtures, oxygen only, oxygen / nitrogen mixtures, hydrogen / oxygen mixtures, hydrogen only, hydrogen / nitrogen mixtures, and combinations thereof. Other noble gases can also be used.

[0140] Exposure to the densification plasma can change at least the composition or density of a portion of the silicon-containing film. The composition of the silicon-containing film refers to the relative amounts of silicon and oxygen, carbon, nitrogen, and hydrogen.

[0141] In some embodiments, even when nitrogen is used in operation 808 to form silicon nitride, operation 808 may involve exposure to a nitrogen plasma during post-processing to reduce the hydrogen content and densify the film.

[0142] In various embodiments, an oxygen-free plasma is used, i.e., oxygen (O2) gas or an oxygen-containing gas is not used to generate the plasma.

[0143] Operation 808 is performed for a specific duration sufficient to densify or process the silicon-containing film. In some embodiments, operation 808 is performed for a duration of about 10 seconds to about 60 seconds.

[0144] The plasma may be ignited at a plasma frequency of 13.56 MHz. In some embodiments, the plasma is generated using a dual-frequency radio frequency generator. In some embodiments, the plasma power is about 0 to about 6500 W per station, or about 100 W to about 6500 W during operation 808. In some embodiments, the plasma is generated using a single-frequency radio frequency generator. In various embodiments, the plasma power for the high-frequency plasma is about 400 W (0.1 W / cm 2 ) to about 5000 W (1.5 W / cm 2 ). In various embodiments, the plasma power for the low-frequency plasma is about 400 W (0.1 W / cm 2 ) to about 3000 W (1 W / cm 2) In some embodiments, the exposure to the plasma is performed in pulses. For example, instead of keeping the plasma on during operation 808, in some embodiments, operation 808 involves pulsing the plasma between an on state and an off state, or between a high state and a low state. The plasma may be pulsed at a pulse frequency of about 2 Hz to about 100 kHz with a duty cycle in the range of about 1% to about 95%. The duty cycle is defined as the duration during which the plasma is on during a period having a duration T. The duration T includes the duration of the pulse-on time (the duration during which the plasma is in the on state) and the duration of the plasma-off time (the duration during which the plasma is in the off state) for a given period. The pulse frequency is understood as 1 / T. For example, when the plasma pulsing period T = 100 μs, the frequency is 1 / T = 1 / 100 μs, i.e., 10 kHz. The duty cycle or duty ratio is the ratio or percentage during the period T when the plasma is in the on state, and thus the duty cycle or duty ratio is the pulse-on time divided by T. For example, when the plasma pulsing period T = 100 μs, if the pulse-on time is 70 μs (so the duration during which the plasma is on within the period is 70 μs) and the pulse-off time is 30 μs (so the duration during which the plasma is off within the period is 30 μs), the duty cycle is 70%. In some embodiments, the shortest RF on time during the pulse step can be as short as about 5 microseconds. In some embodiments, the shortest RF off time can be about 5 microseconds. Depending on the duty cycle and frequency, various combinations of RF on / RF off pulses can be implemented. For example, in some embodiments, this operation may be performed over a duration of about 0.01 milliseconds to about 60 seconds, or about 1 second to about 60 seconds, or about 0.01 milliseconds to about 5 milliseconds, or about 0.02 milliseconds to about 5 milliseconds, or about 0.05 milliseconds to about 5 milliseconds, or about 0.05 milliseconds to about 1.9 milliseconds, or about 0.5 milliseconds to about 1.9 milliseconds. During operation 808, the plasma may be pulsed hundreds to thousands of times depending on the total plasma duration.

[0145] During operation 808, the silicon-containing precursor and the reactant are not flowed.

[0146] The plasma may be generated in situ or within the chamber. In some embodiments, the plasma may be generated by a remote plasma generator to form plasma species, and then the plasma species may be fed into the process chamber through a showerhead. The plasma may be an inductively coupled plasma, or a capacitively coupled plasma, or a microwave plasma.

[0147] During operation 808 when the plasma is ignited, a densification gas or a combination of densification gases is flowed into the process chamber, thereby generating plasma species that may be capable of modifying and densifying the deposited film.

[0148] Operation 808 may be performed using the same substrate temperature as during operation 804. In some embodiments, operations 808 and 804 may be performed without breaking the vacuum. In some embodiments, operations 808 and 804 are performed in the same chamber.

[0149] In some embodiments, operations 808 and 804 are performed at different temperatures. In some embodiments, operations 808 and 804 are performed with an air break therebetween or in separate chambers.

[0150] The process conditions for densification may depend on the chemicals used to deposit the silicon-containing film, the thickness of the silicon-containing film, the topography of the substrate, the composition of the layer under the silicon-containing film, and other factors.

[0151] In operation 812, operations 804 - 810 may optionally be repeated in a number of cycles. In some embodiments, operation 808 is performed for every deposition thickness of the film in operation 804 of about 1 Å to about 30 Å, or about 1 Å to about 20 Å. That is, after depositing a silicon-containing film of at least about 1 Å to about 30 Å, or about 1 Å to about 20 Å in operation 804, operation 808 is performed.

[0152] The composition and properties of the silicon-containing film are adjusted by the selection of the chemicals, process conditions, and reaction mechanisms used during deposition in operation 804 and densification in operation 808. For example, in some embodiments, using a silicon-containing precursor with more Si-C bonds may result in more Si-C bonds in the resulting film. In some embodiments, when using a particular silicon-containing precursor, a lower temperature may be used, which may result in a film being formed at a lower deposition rate, which may affect the quality of the film. In some embodiments, by switching the gas flow and / or plasma conditions, more or fewer oxygen atoms, or more or fewer hydrogen atoms may be incorporated. In some embodiments, multiple gases are used as additive gases during deposition. For example, multiple gases may be used during the exposure of the reactants in the ALD process or during the deposition of the silicon-containing film by CVD, thereby allowing the film composition to be switched by incorporating more or specific molecules.

[0153] In some embodiments, a gradient film composition may be desirable. It is possible to achieve a gradient film by changing the gas composition during deposition and / or during processing and / or during different deposition cycles. A gradient film composition is defined as a film whose composition changes with the depth of the film or over different regions of the film, such as across the entire substrate surface. In one limiting example, the gradient film composition can include depositing at least about 1 Å to about 5 Å of SiCO with little or no nitrogen content and a carbon content of about 20%, and depositing at least about 1 Å to about 5 Å of SiCON with a nitrogen content of about 15% but a carbon content of only about 5%, and repeating these depositions alternately for at least about 20 cycles, resulting in a film having SiCON and SiCO.

[0154] Figure 9 is an exemplary pulse timing sequence diagram according to the disclosed embodiments. Figure 9 shows the stages in an exemplary process 900 for various process parameters such as reactant gas flow, densification gas flow, silicon-containing precursor flow, and plasma state. The lines indicate the timing at which the flows are turned on and off and the timing at which the plasma is turned on and off. This example shows an on / off flow and an on / off plasma state, but it will be understood that in some embodiments, the flow and / or plasma may be switched between a low position and a high position rather than an off position and an on position. Also, it will be understood that "off" does not refer to completely turning off the valve, and embodiments where the gas is bypassed may also be included. The various disclosed embodiments depend on process parameters including, but not limited to, the flow rate for densification, and the flow rates for reactant species, silicon-containing precursor gas, plasma conditions during processing, substrate temperature, and process chamber pressure. The example in Figure 9 refers to a CVD-based process where a silicon-containing film is thermally deposited by CVD and then plasma treated.

[0155] Process 900 includes two cycles, one cycle including a deposition stage 902A and a periodic plasma post-treatment stage 915A. Another cycle includes a deposition stage 902B and a periodic plasma post-treatment stage 915B. During deposition stage 902A, the flow of the densification gas (which can be H2) is turned off, the flow of the silicon-containing precursor gas is turned on, the flow of the reactant is turned on, and the plasma is turned off. This may refer to an example of an embodiment of operation 804 of FIG. 8A. During periodic plasma post-treatment stage 915A, the flow of the densification gas is turned on, the flow of the silicon-containing precursor is turned off, the flow of the reactant is turned off, and the plasma is turned on. This may refer to an example of an embodiment of operation 808 of FIG. 8A. Then, this cycle is repeated. In deposition stage 902B, the flow of the silicon-containing precursor gas is turned on, the flow of the reactant gas is turned on, the plasma is turned off, while the flow of the densification gas is turned off. In periodic plasma post-treatment stage 915B, the flow of the densification gas is turned on, the flow of the silicon-containing precursor gas is turned off, the flow of the reactant is turned off, and the plasma is turned on. This can be repeated over multiple cycles. Although not shown in FIG. 9, in some embodiments, the plasma post-treatment stage can involve flowing an oxygen-containing gas such as oxygen, or a nitrogen-containing gas such as nitrogen, or a mixture of both such as a mixture of oxygen gas and nitrogen gas, in addition to or instead of the flow of the hydrogen densification gas illustrated in FIG. 9. The plasma may be ignited while the densification gas is flowing.

[0156] Certain disclosed embodiments may utilize densification to achieve a particular film density. For example, for a film having a density of at least about 2.0 g / cm 3 to about 2.6 g / cm 3 , or a density of about 2.3 g / cc, the film may be densified using a plasma power of at least about 100 W to about 6500 W over a period of about 1 second to about 60 seconds.

[0157] Wafers or substrates used in the semiconductor device industry typically have diameters of 200 mm, or 300 mm, or 450 mm. Unless otherwise stated, the process details (e.g., flow rates, power levels, etc.) described herein relate to the processing of 300 mm diameter substrates, or processing chambers configured to process 300 mm diameter substrates, and can be scaled appropriately for other size substrates or chambers.

[0158] Experiment Test 1:

[0159] Silicon carboxynitride films were deposited with and without treating the films using silicon-containing precursors. The FTIR spectra for these two films are shown in Figure 10 using the specific precursors. Silicon carboxynitride films were deposited with and without treating the films using BTBAS and co-flowing oxygen gas. The FTIR spectra for these two films are shown in Figure 11. These results suggest that the H2 plasma treatment densified the films. The typical Si-O-Si stretching peak is at 1040 cm -1 ), and the Si–O bending peak is (820 cm -1 ), and the SiN peak is at 840 cm -1 The Si-C peak is at 810 cm -1 The peak for Si-C overlaps with the peaks for Si-O and Si-N, and is at 600 cm -1 ~1200cm -1 The more dense the film, the stronger the main peak becomes, e.g., the NH peak (3350 cm -1 ) decreased after densification.

[0160] Test 2:

[0161] Silicon-containing precursors were used to deposit silicon carboxynitride films with and without co-flow oxygen and with and without film treatment. The contents and densities (g / cc) of silicon, carbon, oxygen, and nitrogen are shown in Table 1 below. These results suggest that the gas chemistry used with the precursor and the use of treatment can affect the film composition and density. For example, the plasma treatment can be used to significantly densify the film.

[0162]

Table 1

[0163] Device One aspect of the present disclosure is an apparatus configured to achieve the methods described herein. In some embodiments, the apparatus is configured to achieve the film deposition methods described herein. In some embodiments, the apparatus is configured to achieve the film deposition methods and etching methods described herein. Suitable apparatuses include hardware for achieving process operations and a system controller having instructions for controlling the process operations according to the present disclosure. In some embodiments, the apparatus for performing the foregoing process operations can include a remote plasma source. The remote plasma source can provide milder reaction conditions compared to direct plasmas. An example of a suitable remote plasma apparatus is described in U.S. Patent Application No. 14 / 062,648, filed October 24, 2013, which application is incorporated herein by reference in its entirety for all purposes. In some embodiments, the apparatus for performing the foregoing process operations can include a pedestal for heating the substrate to a high temperature.

[0164] FIG. 12 shows a schematic diagram of an exemplary plasma processing apparatus having a remote plasma source according to some embodiments. It will be understood that the plasma processing apparatus of FIG. 12 can be used to deposit a silicon-containing layer and / or to etch a silicon-containing layer formed in a reaction chamber according to some embodiments. In some embodiments, a silicon-containing layer can be formed in the reaction chamber and then etched in the same reaction chamber using a remote plasma source without exposing the silicon-containing layer to the ambient atmosphere. In some embodiments, a silicon-containing layer can be formed in the reaction chamber and then a plasma treatment operation using a densification gas plasma is performed using a remote plasma source.

[0165] The plasma processing apparatus 1200 includes a reaction chamber 1210 having a showerhead 1220. Inside the reaction chamber 1210, a substrate 1230 is placed on a stage or pedestal 1235. In some embodiments, a heating / cooling element can be attached to the pedestal 1235. A controller 1240 is connected to the components of the plasma processing apparatus 1200 and can control the operation of the plasma processing apparatus 1200. For example, the controller 1240 may include instructions for controlling process conditions for the operation of the plasma processing apparatus 1200, such as temperature process conditions and / or pressure process conditions. In some embodiments, the controller 1240 may include instructions for controlling the flow rates of precursor gases, reactant gases, source gases, and / or carrier gases. The controller 1240 can include instructions for changing the flow rates of reactant gases, source gases, and / or carrier gases over time. The controller 1240 can include instructions for controlling chamber pressure, substrate temperature, RF power, exposure time, gas composition, and relative concentrations of gas compositions. A more detailed description of the controller 1240 is provided below.

[0166] During operation, gas or a gas mixture is introduced into reaction chamber 1210 via one or more gas inlets coupled to reaction chamber 1210. In some embodiments, more than two gas inlets are coupled to reaction chamber 1210. A first gas inlet 1255 can be coupled to reaction chamber 1210 and connected to container 1250, and a second gas inlet 1265 can be coupled to reaction chamber 1210 and connected to remote plasma source 1260. In some embodiments, the second gas inlet 1265 can provide a carrier gas to reaction chamber 1210. In embodiments including a remote plasma source, the feed lines for the precursors and radical species generated at the remote plasma source are separated. Thus, the precursors and radical species do not substantially interact before reaching substrate 1230. In some embodiments, the gas lines may be reversed, such that container 1250 can provide a precursor gas flow through second gas inlet 1265 and remote plasma source 1260 can provide ions and radicals through first gas inlet 1255, as will be appreciated.

[0167] One or more radical species may be generated in a remote plasma source 1260 and configured to enter the reaction chamber 1210 via a second gas inlet 1265. Any type of plasma source may be used in the remote plasma source 1260 to generate radical species. This includes, but is not limited to, inductively coupled plasma (ICP) sources, capacitively coupled plasma (CCP) sources, microwave plasma sources, DC plasma sources, and laser-generated plasma sources. An example of a capacitively coupled plasma may be a radio frequency (RF) plasma. The high frequency plasma can be configured to operate at 13.56 MHz or higher. An example of such a remote plasma source 1260 may be GAMMA (registered trademark) manufactured by Lam Research of Fremont, California. Another example of such a remote plasma source 1260 may be Astron (registered trademark) manufactured by MKS Instruments of Wilmington, Massachusetts, which can operate at 440 kHz and can be provided as a sub-unit bolted to a large device for processing one or more substrates in parallel. In some embodiments, a microwave plasma can be used as the remote plasma source 1260 (e.g., Astex (registered trademark) also manufactured by MKS Instruments). The microwave plasma can be configured to operate at a frequency of 2.45 GHz. The gas species provided to the remote plasma source 1260 may include hydrogen, nitrogen, oxygen, carbon, or other gases described elsewhere in this specification. In certain embodiments, hydrogen is provided with a carrier such as helium. As an example, hydrogen gas may be provided with a helium carrier at a hydrogen concentration of about 1 to 50 volume %.

[0168] The precursor can be provided to the container 1250 and supplied to the showerhead 1220 via the first gas inlet 1255. The showerhead 1220 distributes the precursor towards the substrate 1230 within the reaction chamber 1210. The substrate 1230 can be positioned below the showerhead 1220. It will be understood that the showerhead 1220 can have any suitable shape and may have any number and arrangement of ports for distributing the gas to the substrate 1230. The precursor can be supplied to the showerhead 1220 at a controlled flow rate and ultimately to the substrate 1230.

[0169] One or more radical species formed by the remote plasma source 1260 can be transported towards the substrate 1230 in the gas phase. One or more radical species can flow into the reaction chamber 1210 through the second gas inlet 1265. As shown in FIG. 12, it will be understood that the second gas inlet 1265 need not be lateral to the surface of the substrate 1230. In certain embodiments, the second gas inlet 1265 can be directly above the substrate 1230 or in other locations. The distance between the remote plasma source 1260 and the reaction chamber 1210 can be configured to provide mild reaction conditions, whereby the ionized species generated by the remote plasma source 1260 are substantially neutralized, but at least some of the radical species in the low-energy or ground state remain in the environment adjacent to the substrate 1230. Such low-energy radical species do not recombine to form stable compounds. The distance between the remote plasma source 1260 and the reaction chamber 1210 can be a function of the aggressiveness of the plasma (e.g., partially determined by the source RF power level), the density of the gas in the plasma (e.g., when the concentration of hydrogen atoms is high, a significant proportion of the hydrogen atoms may recombine to form H2 before reaching the reaction chamber 1210), and other factors. In some embodiments, the distance between the remote plasma source 1260 and the reaction chamber 1210 can be about 1 cm to 30 cm, such as about 5 cm or about 15 cm.

[0170] In some embodiments, a co-reactant or reactant other than the main silicon-containing precursor or hydrogen radicals may be introduced. In some embodiments, the co-reactant or reactant may be introduced during the deposition of the silicon-containing layer by thermal ALD or thermal CVD. In some embodiments, the co-reactant or reactant may be introduced during a plasma treatment operation to adjust the composition and / or density of the silicon-containing layer. In some embodiments, the co-reactant or reactant may be introduced during remote plasma etching. In some embodiments, the plasma processing apparatus 1200 is configured to introduce a co-reactant or reactant through a second gas inlet 1265. In some cases, the co-reactant or reactant is at least partially converted to a plasma. In some embodiments, the plasma processing apparatus 1200 is configured to introduce a co-reactant or reactant through a showerhead 1220 via a first gas inlet 1255. Examples of co-reactants or reactants include oxygen, nitrogen, ammonia, carbon dioxide, carbon monoxide, and the like. The flow rate of the co-reactant or reactant may vary over time and may result in a composition gradient in the gradient film.

[0171] In some embodiments, a gas plasma stream may be generated from a remote plasma source 1260. The gas plasma stream from the remote plasma source 1260 may include ions, radicals, charge-neutral particles, and other reactive species of the reactant gas. For example, the reactive species may include radical species of hydrogen, nitrogen, oxygen, carbon, or amine that may be supplied to the surface of the substrate 1230 for remote plasma etching.

[0172] FIG. 13 shows a schematic diagram of an exemplary plasma processing apparatus having a remote plasma source according to some embodiments. It will be understood that the reaction chamber of FIG. 13 can be used to deposit a silicon-containing layer, process a silicon-containing layer, and / or etch a silicon-containing layer formed in the reaction chamber according to some embodiments. In some embodiments, a silicon-containing layer may be formed in the reaction chamber and then etched within the same reaction chamber using a remote plasma source without exposing the silicon-containing layer to the ambient atmosphere. In some embodiments, a silicon-containing layer may be formed in the reaction chamber and then processed within the same reaction chamber using a remote plasma without exposing the silicon-containing layer to the ambient atmosphere.

[0173] The plasma processing apparatus 1300 includes a remote plasma source 1302 separated from a reaction chamber 1304. The remote plasma source 1302 is fluidly coupled to the reaction chamber 1304 via a gas distributor or showerhead 1306. In some embodiments, the showerhead 1306 includes an ion filter for filtering ions to limit damage to the substrate 1312 due to ion bombardment. Radical species and / or ions are generated within the remote plasma source 1302, and the radical species can be supplied to the reaction chamber 1304. Precursors such as silicon-containing precursors are supplied to the reaction chamber 1304 through a gas outlet 1308 positioned downstream of the remote plasma source 1302 and the showerhead 1306.

[0174] The substrate 1312 is supported on a substrate support structure or wafer pedestal 1314. The wafer pedestal 1314 can be configured with lift pins or other movable support members to position the substrate 1312 within a deposition / etch zone 1310. The substrate 1312 may be moved to a position close to the showerhead 1306 or a position far from the showerhead 1306. The wafer pedestal 1314 is shown in FIG. 13 with the substrate 1312 raised within the deposition / etch zone 1310.

[0175] In some embodiments, the wafer pedestal 1314 includes an electrostatic chuck 1316. The electrostatic chuck 1316 includes one or more electrostatic clamping electrodes 1318 embedded within the body of the electrostatic chuck 1316. In some embodiments, the one or more electrostatic clamping electrodes 1318 may be on the same plane or substantially on the same plane. The electrostatic clamping electrodes 1318 can be powered by a DC power source or a DC chuck voltage (e.g., from about 200V to about 2000V) such that the substrate 1312 can be held on the electrostatic chuck 1316 by electrostatic attraction. Power to the electrostatic clamping electrodes 1318 can be provided via a first electrical wire 1320. The electrostatic chuck 1316 can further include one or more heating elements 1322 embedded within the body of the electrostatic chuck 1316. The one or more heating elements 1322 may include a resistance heater. In some embodiments, the one or more heating elements 1322 are positioned under the one or more electrostatic clamping electrodes 1318. The one or more heating elements 1322 can be configured to heat the substrate 1312 to a temperature above about 450°C, above about 500°C, above about 550°C, above about 600°C, or above about 650°C. The one or more heating elements 1322 provide selective temperature control to the substrate 1312. Power to the one or more heating elements 1322 can be provided via a second electrical wire 1324.

[0176] Coil 1328 is disposed around remote plasma source 1302, which includes an outer wall (e.g., a quartz dome). Coil 1328 is electrically coupled to plasma generator controller 1332, which can be used to form and maintain a plasma within plasma region 334 via inductively coupled plasma generation. In some embodiments, plasma generator controller 1332 may include a power source for supplying power to coil 1328, and the power can be in the range of about 300 W to about 15 kW per station or in the range of about 1 kW to about 10 kW per station during plasma generation. In some embodiments, parallel plates or electrodes or antennas for capacitively coupled plasma generation can be used to generate a continuous supply of radicals via plasma excitation rather than inductively coupled plasma generation. Regardless of the mechanism used to ignite and maintain the plasma within plasma region 1334, radical species can be continuously generated using plasma excitation during film formation (e.g., film deposition) and / or remote plasma processing.

[0177] In some embodiments, hydrogen radicals (H * ), nitrogen radicals (N * ), oxygen radicals (O * ), carbon radicals (C * ), amine radicals (NH * , NH2 * ), or combinations thereof are generated in plasma region 1334 under substantially steady-state conditions during steady-state film deposition or remote plasma processing controlled by plasma generator controller 1332, although transient phenomena can occur at the start and end of film deposition and / or remote plasma etching. For example, hydrogen radicals can be generated in plasma region 1334. In another example, two or more different types of radicals such as nitrogen-containing radicals and hydrogen radicals can be generated in plasma region 1334. FIG. 13 shows nitrogen radicals (N * ), amine radicals (NH * , NH2 * ), and hydrogen radicals (H* ) is shown, but it should be understood that the foregoing radicals are merely illustrative and that other radicals may exist in addition to or instead of those illustrated in FIG. 13.

[0178] While the source gas is being supplied to the remote plasma source 1302, the supply of ions and radicals can be continuously generated within the plasma region 1334. The ions generated in the plasma region 1334 can be filtered by the ion filter of the showerhead 1306. In this way, while restricting ion bombardment, the radicals generated in the plasma region 1334 can be supplied to the substrate 1312 within the reaction chamber 1304. By filtering ions and / or photons, it is possible to reduce substrate damage, unwanted re-excitation of molecules, and / or selective destruction or decomposition of hydrocarbon precursors within the reaction chamber 1304.

[0179] The conditions within the remote plasma source 1302, including the composition of the source gas provided to the remote plasma source 1302 and the RF power supplied to the coil 1328, can be controlled to optimize the generation of the desired radical species in the plasma region 1334. In some embodiments, the source gas can include an oxygen-containing reactant such as oxygen (O2), ozone (O3), carbon monoxide (CO), carbon dioxide (CO2), or nitrogen dioxide (NO2), nitrous oxide (N2O), a carbon-containing reactant such as acetylene (C2H2), ethylene (C2H4), or propene (C3H6), a hydrogen-containing reactant such as hydrogen (H2) or methane (CH4), or a nitrogen-containing reactant such as nitrogen (N2), ammonia (NH3), diazene (N2H2), or hydrazine (N2H4), or a mixture thereof. In some embodiments, the source gas may include hydrogen gas. As an example, hydrogen radicals can be generated in the plasma region 1334, and the source gas of hydrogen gas can be provided to the remote plasma source 1302 to provide a gas plasma stream containing hydrogen radicals towards the substrate 1312 within the reaction chamber 1304.

[0180] In some embodiments, the source gas can be mixed with one or more additional gases. These one or more additional gases can be supplied to the remote plasma source 1302. In some embodiments, the source gas is mixed with one or more additional gases to form a gas mixture, and the one or more additional gases can include a carrier gas. Non-limiting examples of additional gases can include helium, neon, argon, krypton, and xenon. The one or more additional gases can support or stabilize the steady-state plasma conditions within the remote plasma source 1302, or assist in the transient plasma ignition or extinction processes. In FIG. 13, a source gas supply 1336 is fluidly coupled to the remote plasma source 1302 to supply the source gas. In some embodiments, source gas in an amount of about 5 sccm to about 10,000 sccm, or about 10 sccm to about 200 sccm, may be supplied from the source gas supply 1336. Additionally, an additional gas supply 1338 is fluidly coupled to the remote plasma source 1302 to supply one or more additional gases. The embodiment of FIG. 13 illustrates that the gas mixture of the source gas and one or more additional gases is introduced through separate gas outlets, but it will be understood that the gas mixture may be introduced directly into the remote plasma source 1302. That is, a premixed diluted gas mixture can be supplied to the remote plasma source 1302 through a single gas outlet.

[0181] Plasma-activated species 1342, such as excited nitrogen, hydrogen, carbon, oxygen, and / or amine radicals, flow out from the remote plasma source 1302 and into the reaction chamber 1304 through the showerhead 1306. The plasma-activated species 1342 within the showerhead 1306 and within the reaction chamber 1304 generally do not undergo continuous plasma excitation therein. The showerhead 1306 may have a plurality of gas ports that diffuse the flow of the plasma-activated species 1342 into the reaction chamber 1304. In some embodiments, the plurality of gas ports can be spaced apart from each other. In some embodiments, the plurality of gas ports can be arranged as an array of regularly spaced channels or through-holes that extend through a plate separating the remote plasma source 1302 and the reaction chamber 1304. The plurality of gas ports can smoothly disperse and diffuse the existing radicals (including the plasma-activated species 1342) from the remote plasma source 1302 into the deposition / etching zone 1310 of the reaction chamber 1304 while filtering ions.

[0182] Typical remote plasma sources are located far from the reaction vessel. As a result, the active species can be significantly reduced, for example, through radical annihilation and recombination via wall collision events. In contrast, in some embodiments, the dimensions of the plurality of gas ports are configured considering the mean free path or the gas flow residence time under typical processing conditions, and can assist the radicals to freely pass through the reaction chamber 1304. In some embodiments, the openings for the plurality of gas ports may occupy about 5% to about 20% of the exposed surface area of the showerhead 1306. In some embodiments, each of the plurality of gas ports may have an axial length to diameter ratio of about 3:1 to 10:1, or about 6:1 to about 8:1. Such an aspect ratio can reduce the wall collision frequency for the radical species passing through the plurality of gas ports while providing sufficient time for most of the excited state radical species to relax to the ground state radical species. In some embodiments, the dimensions of the plurality of gas ports may be configured such that the residence time of the gas passing through the showerhead 1306 is longer than the typical energy relaxation time of the excited state radical species.

[0183] By feeding the plasma-activated species 1342 from the showerhead 1306 into the reaction chamber 1304, the precursor 1344 (or other process gas) can be introduced into the reaction chamber 1304. The precursor 1344 can include a silicon-containing precursor such as silane. The precursor 1344 may be introduced via the gas outlet 1308, and the gas outlet 1308 may be fluidly coupled to the precursor source 1340. The gas outlet 1308 may include apertures spaced from each other such that the flow of the precursor 1344 can be introduced in a direction parallel to the plasma-activated species 1342 flowing from the showerhead 1306. In some embodiments, the gas outlet 1308 may be located downstream of the showerhead 1306. In some embodiments, the gas outlet 1308 is part of the showerhead 1306, such as a dual-plenum showerhead. The dual-plenum showerhead may provide separate outlets / passages for the plasma-activated species 1342 and the precursor 1344 to avoid mixing within the showerhead 1306. In this way, the precursor 1344 can flow into the reaction chamber 1304 through the showerhead 1306 without being exposed to the plasma in the remote plasma source 1302. The gas outlet 1308 may be located upstream of the deposition / etching zone 1310 and the substrate 1312. The deposition / etching zone 1310 is located inside the reaction chamber 1304 between the gas outlet 1308 and the substrate 1312.

[0184] In the film deposition process, a significant portion of the precursor 1344 can be prevented from mixing with the plasma-activated species 1342 within or adjacent to the showerhead 1306. In some embodiments, the precursor 1344 can be fed to the substrate 1312 during the dosing stage of the ALD cycle separately from the plasma-activated species 1342 that are fed to the substrate 1312 during the plasma exposure stage of the ALD cycle. The adsorbed precursor 1344 can react with the radicals of the plasma-activated species 1342 during the plasma exposure stage of the ALD cycle to deposit a film. In some embodiments, it is possible to continuously feed the precursor 1344 to the substrate 1312 to interact with the plasma-activated species 1342 within the deposition / etching zone 1310 and deposit a film by CVD. In some embodiments, the plasma-activated species 1342 can be fed to the substrate 1312 without feeding the precursor 1344 and can etch the film.

[0185] The gas can be removed from the reaction chamber 1304 through an outlet 1348 that is fluidly coupled to a pump (not shown). Thus, radical species or purge gas can be removed from the reaction chamber 1304.

[0186] In some embodiments, a thermal shield (not shown) may be positioned under the wafer pedestal 1314. The thermal shield serves as a heat insulator under the wafer pedestal 1314 to reduce heat loss due to thermal radiation, thereby reducing the amount of electrical power required to maintain the wafer pedestal 1314 at a specific high temperature and also preventing overheating of other components within the reaction chamber 1304 due to excessive heat radiated from the wafer pedestal 1314. For example, the thermal shield may be radially offset from the stem 1326 and may have a thin annular-shaped body with a high form factor relative to the lower surface of the electrostatic chuck 1316. Thus, the annular-shaped thermal shield can reduce radiative heat loss from the wafer pedestal 1314.

[0187] The electrostatic chuck 1316 of the wafer pedestal 1314 can chuck / detchuck the substrate 1312 in the plasma processing apparatus 1300 configured to operate at high temperatures. Such high temperatures may be above about 350°C, above about 400°C, above about 450°C, above about 500°C, or above about 550°C.

[0188] In some embodiments, the controller 1350 (e.g., a system controller) is operably communicative with the plasma processing apparatus 1300. In some embodiments, the controller 1350 includes a processor system 1352 (e.g., a microprocessor) configured to execute instructions held in a data system 1354 (e.g., a memory). In some embodiments, the controller 1350 is communicative with the plasma generator controller 1332 and can control plasma parameters and / or conditions within the remote plasma source 1302. In some embodiments, the controller 1350 is communicative with the wafer pedestal 1314 and can control the height of the pedestal, electrostatic chucking and electrostatic dechucking, as well as the temperature. In some embodiments, the controller 1350 can control other processing conditions, such as, among other processing conditions, in particular, RF power setting, frequency setting, duty cycle, pulse time, pressure within the reaction chamber 1304, pressure within the remote plasma source 1302, gas flow rate from the source gas supply section 1336, gas flow rates from additional gas supply sections 1338 and other sources, the temperature of the wafer pedestal 1314, as well as the temperature of the reaction chamber 1304.

[0189] The controller 1350 may include instructions for controlling process conditions for the operation of the plasma processing apparatus 1300. The controller 1350 typically includes one or more memory devices and one or more processors. The processor may include a CPU or computer, analog and / or digital input / output connections, a stepper motor controller board, and the like. Instructions for performing appropriate control operations are executed on the processor. These instructions can be stored in a memory device associated with the controller 1350 or provided via a network.

[0190] In certain embodiments, the controller 1350 controls all or most of the activities of the plasma processing apparatus 1300 described herein. For example, the controller 1350 can control all or most of the activities of the plasma processing apparatus 1300 associated with film deposition, film processing, and / or remote plasma etching. The controller 1350 can execute system control software that includes a series of instructions for controlling timing, gas composition, gas flow rate, chamber pressure, chamber temperature, RF power level, substrate position, substrate temperature, and / or other parameters. In some embodiments, other computer programs, scripts, or routines stored in a memory device associated with the controller 1350 can be used. In a multi-station reactor, the controller 1350 can include different or identical instructions for different apparatus stations, thus enabling the apparatus stations to operate independently or synchronously.

[0191] In some embodiments, the controller 1350 may include instructions configured to perform operations such as conformally depositing a silicon-containing film on the concave feature of the substrate 312, and exposing the substrate 1312 to plasma-activated species 1342 generated by the remote plasma source 1302 to etch the silicon-containing film to at least one of a desired depth and a desired profile. In some embodiments, exposing the substrate 1312 to plasma-activated species 1342 to etch the silicon-containing film to a desired depth and / or a desired profile is performed by adjusting one or more of the following parameters: chamber pressure, substrate temperature, exposure time, gas composition of the remote plasma, relative concentration of the gas composition, and RF power.

[0192] In some embodiments, the controller 1350 may include instructions configured to perform operations such as forming a silicon-containing film on the substrate 1312 without igniting plasma at a substrate temperature of less than about 700 °C and treating the silicon-containing film using a densification gas plasma. The silicon-containing film may be deposited using thermal ALD and / or thermal CVD. The controller 1350 can further include instructions configured to adjust at least one of a silicon-containing precursor, a reactant, or a process condition during plasma treatment to vary at least the composition or density of the silicon-containing film.

[0193] In some embodiments, the plasma processing apparatus 1300 may include a user interface associated with the controller 1350. The user interface can include a display screen, a graphical software display of the plasma processing apparatus 1300 and / or process conditions, and user input devices such as a pointing device, a keyboard, a touch screen, a microphone, and the like.

[0194] The computer program code for controlling the above operations can be written in any conventional computer-readable programming language (e.g., assembly language, C, C++, Pascal, Fortran, etc.). The compiled object code or script is executed by the processor to perform the tasks identified by the program.

[0195] Signals for monitoring the process may be provided by the analog and / or digital input connections of the controller 1350. Signals for controlling the process are output on the analog and digital output connections of the processing system.

[0196] Broadly, the controller 1350 may be defined as an electronic device having various integrated circuits, logic, memory, and / or software for receiving instructions, issuing instructions, controlling operations, enabling cleaning operations, enabling endpoint measurements, etc. The integrated circuits may include a chip in the form of firmware for storing program instructions, a digital signal processor (DSP), a chip defined as an application-specific integrated circuit (ASIC), and / or one or more microprocessors, i.e., a microcontroller that executes program instructions (e.g., software). The program instructions are instructions communicated to the controller 1350 in the form of various individual settings (or program files) that may define the operating parameters for executing a specific process on or for a semiconductor wafer or for a system. The operating parameters may, in some embodiments, be part of a recipe defined by a process engineer to implement one or more processing steps in the fabrication of one or more layers, materials (e.g., amorphous silicon), surfaces, circuits, and / or wafer dies.

[0197] In some embodiments, the controller 1350 may be part of a computer that is integrated or coupled with the system or otherwise network-connected to the system, or may be coupled to such a computer, or a combination thereof. For example, the controller 1350 may be within the "cloud" or may be all or part of the fab host computer system. This enables remote access to wafer processing. The computer can enable remote access to the system, monitor the current progress of the fabrication operation, consider the history of past fabrication operations, consider trends or performance criteria from multiple fabrication operations, change the parameters of the current process, set the processing steps following the current process, or initiate a new process. In some examples, a remote computer (e.g., a server) can provide a process recipe to the system through a network. Such a network may include a local network or the Internet. The remote computer may include a user interface that enables entry or programming of parameters and / or settings, and such parameters and / or settings are then communicated from the remote computer to the system. In some examples, the controller 1350 receives instructions in the form of data. Such data specifies the parameters for each processing step to be performed during one or more operations. It should be understood that the parameters may be specific to the type of process being performed and the type of tool that the controller 1350 is configured to interact with or control. Thus, as described above, the controller 1350 may be distributed, for example, by comprising one or more individual controllers that are network-connected to each other and cooperate towards a common purpose (such as the processes and controls described herein).As an example of a distributed controller for such purposes, one or more integrated circuits on a chamber, which are remotely located (e.g., at the platform level or as part of a remote computer) and communicate with one or more integrated circuits combined to control a process in the chamber, may be mentioned.

[0198] Definition and Precursors The terms "acyl" or "alkanoyl", when used interchangeably herein, represent a group of 1, 2, 3, 4, 5, 6, 7, 8 or more carbon atoms of linear, branched, cyclic configuration, saturated, unsaturated, and aromatic, and combinations thereof, or hydrogen, bonded to a parent molecular group via a carbonyl group as defined herein. This group is exemplified by formyl (-C(O)H), acetyl (Ac or -C(O)Me), propionyl, isobutyryl, butanoyl, etc. In some embodiments, the acyl group or alkanoyl group is -C(O)-R, where R is hydrogen, an aliphatic group, or an aromatic group as defined herein.

[0199] "Alkanoyloxy" means an alkanoyl group as defined herein bonded to a parent molecular group via an oxy group as defined herein. This group is exemplified by acetoxy (-OAc or -OC(O)Me). In some embodiments, the alkanoyloxy group is -OC(O)-R, where R is hydrogen, an aliphatic group, or an aromatic group as defined herein.

[0200] "Aliphatic" means at least 1 to 50 carbon atoms (C 1-50 ), e.g., 1 to 25 carbon atoms (C 1-25 ), or 1 to 10 carbon atoms (C 1-10means a hydrocarbon group having (), which includes alkanes (or alkyls), alkenes (or alkenyls), alkynes (or alkynyls), including their cyclic versions, and further includes straight-chain and branched-chain arrangements, as well as all stereoisomers and positional isomers. The aliphatic group is unsubstituted or substituted, for example, by a functional group described herein. For example, the aliphatic group can be substituted with one or more substituents described herein for alkyl.

[0201] "Aliphatic-carbonyl" means an aliphatic group that is coupled to or can be coupled to a compound disclosed herein, and the aliphatic group is coupled or becomes coupled via a carbonyl group (-C(O)-). In some embodiments, the aliphatic-carbonyl group is -C(O)-R, where R is an optionally substituted aliphatic group as defined herein.

[0202] "Aliphatic-carbonyloxy" means an aliphatic group that is coupled to or can be coupled to a compound disclosed herein, and the aliphatic group is coupled or becomes coupled via a carbonyloxy group (-OC(O)-). In some embodiments, the aliphatic-carbonyloxy group is -OC(O)-R, where R is an optionally substituted aliphatic group as defined herein.

[0203] "Aliphatic-oxy" means an aliphatic group that is coupled to or can be coupled to a compound disclosed herein, and the aliphatic group is coupled or becomes coupled via an oxy group (-C(O)-). In some embodiments, the aliphatic-oxy group is -O-R, where R is an optionally substituted aliphatic group as defined herein.

[0204] "Aliphatic-oxycarbonyl" means an aliphatic group that is coupled or can be coupled to a compound disclosed herein, and the aliphatic group is coupled or is to be coupled via an oxycarbonyl group (-C(O)O-). In some embodiments, the aliphatic-oxycarbonyl group is -C(O)O-R, where R is an optionally substituted aliphatic group as defined herein.

[0205] "Alkyl-aryl", "alkenyl-aryl", and "alkynyl-aryl" mean an alkyl group, an alkenyl group, or an alkynyl group, respectively, as defined herein, that is coupled (or bonded) or can be coupled (or bonded) to a parent molecular group via an aryl group as defined herein. The alkyl-aryl group, the alkenyl-aryl group, and / or the alkynyl-aryl group can be substituted or unsubstituted. For example, the alkyl-aryl group, the alkenyl-aryl group, and / or the alkynyl-aryl group can be substituted with one or more substituents described herein for alkyl and / or aryl. Exemplary unsubstituted alkyl-aryl groups are those having 7 to 16 carbons (C 7-16 alkyl-aryl), as well as those having an alkyl group having 1 to 6 carbons and an aryl group having 4 to 18 carbons (i.e., C 1-6 alkyl-C 4-18 aryl). Exemplary unsubstituted alkenyl-aryl groups are those having 7 to 16 carbons (C 7-16 alkenyl-aryl), as well as those having an alkenyl group having 2 to 6 carbons and an aryl group having 4 to 18 carbons (i.e., C 2-6 alkenyl-C 4-18 aryl). Exemplary unsubstituted alkynyl-aryl groups are those having 7 to 16 carbons (C 7-16 alkynyl-aryl), as well as those having an alkynyl group having 2 to 6 carbons and an aryl group having 4 to 18 carbons (i.e., C 2-6 alkynyl-C 4-18Those having an aryl group. In some embodiments, the alkyl-aryl group is -L-R, where L is an aryl group or an arylene group as defined herein, and R is an alkyl group as defined herein. In some embodiments, the alkenyl-aryl group is -L-R, where L is an aryl group or an arylene group as defined herein, and R is an alkenyl group as defined herein. In some embodiments, the alkynyl-aryl group is -L-R, where L is an aryl group or an arylene group as defined herein, and R is an alkynyl group as defined herein.

[0206] "Alkenyl" means an unsaturated monovalent hydrocarbon having at least 2 to 50 carbon atoms (C 2-50 ), for example 2 to 25 carbon atoms (C 2-25 ), or 2 to 10 carbon atoms (C 2-10 ), and at least one carbon-carbon double bond, and the unsaturated monovalent hydrocarbon can be obtained by removing one hydrogen atom from one carbon atom of the parent alkene. The alkenyl group can be branched, straight-chain, cyclic (e.g., cycloalkenyl), cis, or trans (e.g., E or Z). Exemplary alkenyls include optionally substituted C 2-24 alkyl groups having one or more double bonds. The alkenyl group can become monovalent or polyvalent (e.g., divalent) by removing one or more hydrogens to form a suitable bond to the parent molecular group or a suitable bond between the parent molecular group and another substituent. The alkenyl group can also be substituted or unsubstituted. For example, the alkenyl group can be substituted with one or more of the substituents described herein for alkyl. Non-limiting alkenyl groups include allyl (All), vinyl (VI), 1-butenyl, 2-butenyl, etc.

[0207] "Alkoxy" means -OR, where R is an optionally substituted aliphatic group as described herein. Exemplary alkoxy groups include, but are not limited to, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, t-butoxy, sec-butoxy, n-pentoxy, trihaloalkoxy such as trifluoromethoxy, and the like. The alkoxy group can be substituted or unsubstituted. For example, the alkoxy group can be substituted with one or more substituents as described herein for alkyl. Exemplary unsubstituted alkoxy groups include C 1-3 C 1-6 C 1-12 C 1-16 C 1-18 C 1-20 C 1-24 alkoxy groups.

[0208] "Alkoxyalkyl" means an alkyl group as defined herein substituted with an alkoxy group as defined herein. Exemplary unsubstituted alkoxyalkyl groups include 2 to 12 carbon (C 2-12 alkoxyalkyl), as well as those having an alkyl group having 1 to 6 carbons and an alkoxy group having 1 to 6 carbons (i.e., C 1-6 alkoxy-C 1-6 alkyl). In some embodiments, the alkoxyalkyl group is -L-O-R, where each of L and R is independently an alkyl group as defined herein.

[0209] "Alkoxycarbonyl" means -C(O)-OR, where R is an optionally substituted aliphatic group as described herein. In certain embodiments, the alkoxycarbonyl group is -C(O)-OAk, where Ak is an alkyl group as defined herein. The alkoxycarbonyl group can be substituted or unsubstituted. For example, the alkoxycarbonyl group can be substituted with one or more substituents as described herein for alkyl. Exemplary unsubstituted alkoxycarbonyl groups include C 2-3 C 2-6 C 2-7 C2-12 , C 2-16 , C 2-18 , C 2-20 , or C 2-24 An alkoxycarbonyl group may be mentioned.

[0210] "Alkyl" means a saturated monovalent hydrocarbon having at least 1 carbon atom to 50 carbon atoms (C 1-50 ), for example 1 to 25 carbon atoms (C 1-25 ), or 1 to 10 carbon atoms (C 1-10 ), and a saturated monovalent hydrocarbon can be obtained by removing one hydrogen atom from one carbon atom of a parent compound (for example, an alkane). An alkyl group can be branched, straight-chain, or cyclic (for example, cycloalkyl). Exemplary alkyls include methyl (Me), ethyl (Et), n-propyl (nPr), iso-propyl (iPr), n-butyl (nBu), iso-butyl (iBu), sec-butyl (sBu), tert-butyl (tBu), pentyl (Pe), n-pentyl (nPe), isopentyl (iPe), s-pentyl (sPe), neopentyl (neoPe), tert-pentyl (tPe), hexyl (Hx), heptyl (Hp), octyl (Oc), nonyl (Nn), decyl (De), dodecyl, tetradecyl, hexadecyl, eicosyl, tetracosyl, etc., and branched or unbranched saturated hydrocarbon groups having 1 to 24 carbon atoms. An alkyl group can also be substituted or unsubstituted. An alkyl group can become monovalent or polyvalent (for example, divalent) by removing one or more hydrogens to form an appropriate bond to a parent molecular group or an appropriate bond between a parent molecular group and another substituent. For example, an alkyl group can be substituted with 4 substituents in the case of an alkyl group of 1, 2, 3, or 2 or more carbons independently selected from the group consisting of: (1) C 1-6 alkoxy (for example, -O-R, where R is C 1-6 alkyl), (2) C 1-6 alkylsulfinyl (for example, -S(O)-R, where R is C 1-6 alkyl), (3) C 1-6 alkylsulfonyl (for example, -SO2-R, where R is C1-6 is alkyl), (4) amino (e.g., -NR 1 R 2 and R 1 and R 2 each independently is selected from hydrogen, aliphatic, heteroaliphatic, haloaliphatic, hal heteroaliphatic, aromatic, or any combination thereof as defined herein, or R 1 and R 2 can together with the nitrogen atom to which each is attached form a heterocyclyl group as defined herein), (5) aryl, (6) arylalkoxy (e.g., -O-L-R, where L is alkyl and R is aryl), (7) aroyl (e.g., -C(O)-R, where R is aryl), (8) azide (e.g., -N3), (9) cyano (e.g., -CN), (10) aldehyde (e.g., -C(O)H), (11)C 3-8 cycloalkyl, (12) halo, (13) heterocyclyl (e.g., a 5-, 6-, or 7-membered ring containing 1, 2, 3, or 4 non-carbon heteroatoms as defined herein), (14) heterocyclyloxy (e.g., -O-R, where R is heterocyclyl as defined herein), (15) heterocyclylcarbonyl (e.g., -C(O)-R, where R is heterocyclyl as defined herein), (16) hydroxyl (e.g., -OH), (17) N-protected amino, (18) nitro (e.g., -NO2), (19) oxo (e.g., =O), (20)C 1-6 thioalkoxy (e.g., -S-R, where R is alkyl), (21) thiol (e.g., -SH), (22) -CO2R 1 where R 1 is selected from the group consisting of (a) hydrogen, (b) C 1-6 alkyl, (c) C 4-18 aryl, and (d) C 4-18 aryl-C 1-6 alkyl (e.g., -L-R, where L is C 1-6 alkyl and R is C 4-18 aryl), (23) -C(O)NR 1 R 2 and R 1 and R2 Each of them is independently selected from the group consisting of (a) hydrogen, (b) C 1-6 alkyl, (c) C 4-18 aryl, and (d) C 4-18 aryl-C 1-6 alkyl (e.g., -L-R, where L is C 1-6 alkyl and R is C 4-18 aryl), (24) -SO2R 1 , where R 1 is selected from the group consisting of (a) C 1-6 alkyl, (b) C 4-18 aryl, and (c) C 4-18 aryl-C 1-6 alkyl (e.g., -L-R, where L is C 1-6 alkyl and R is C 4-18 aryl), (25) -SO2NR 1 R 2 , R 1 and R 2 each are independently selected from the group consisting of (a) hydrogen, (b) C 1-6 alkyl, (c) C 4-18 aryl, and (d) C 4-18 aryl-C 1-6 alkyl (e.g., -L-R, where L is C 1-6 alkyl and R is C 4-18 aryl), and (26) -NR 1 R 2 , R 1 and R 2 each are independently selected from the group consisting of (a) hydrogen, (b) an N-protecting group, (c) C 1-6 alkyl, (d) C 2-6 alkenyl, (e) C 2-6 alkynyl, (f) C 4-18 aryl, (g) C 4-18 aryl-C 1-6 alkyl (e.g., -L-R, where L is C 1-6 alkyl and R is C 4-18 aryl), (h) C 3-8 cycloalkyl, and (i) C 3-8 cycloalkyl-C 1-6 alkyl (e.g., -L-R, where L is C1-6 is alkyl, and R is C 3-8 selected from the group consisting of cycloalkyl). In one embodiment, there are also no two groups bonded to the nitrogen atom via a carbonyl group or a sulfonyl group. The alkyl group can be a primary, secondary, or tertiary alkyl group substituted with one or more substituents (e.g., one or more halo or alkoxy). In some embodiments, the unsubstituted alkyl group is C 1-3 , C 1-6 , C 1-12 , C 1-16 , C 1-18 , C 1-20 , or C 1-24 alkyl group.

[0211] "Alkylene", "alkenylene", or "alkynylene" each mean a polyvalent (e.g., divalent) form of the alkyl group, alkenyl group, or alkynyl group described herein. Exemplary alkylene groups include methylene, ethylene, propylene, butylene, etc. In some embodiments, the alkylene group is C 1-3 , C 1-6 , C 1-12 , C 1-16 , C 1-18 , C 1-20 , C 1-24 , C 2-3 , C 2-6 , C 2-12 , C 2-16 , C 2-18 , C 2-20 , or C 2-24 alkylene group. In other embodiments, the alkylene group is C 2-3 , C 2-6 , C 2-12 , C 2-16 , C 2-18 , C 2-20 , or C 2-24It is an alkylene group, alkenylene group, or alkynylene group. The alkylene group, alkenylene group, or alkynylene group can be branched or unbranched. The alkylene group, alkenylene group, or alkynylene group can also be substituted or unsubstituted. For example, the alkylene group, alkenylene group, or alkynylene group can be substituted with one or more substituents described herein for alkyl.

[0212] "Alkylsulfinyl" means an alkyl group as defined herein bonded to a parent molecular group via an -S(O)- group. In some embodiments, an unsubstituted alkylsulfinyl group is C 1-6 or C 1-12 alkylsulfinyl group. In other embodiments, the alkylsulfinyl group is -S(O)-R, where R is an alkyl group as defined herein.

[0213] "Alkylsulfinylalkyl" means an alkyl group as defined herein substituted by an alkylsulfinyl group. In some embodiments, an unsubstituted alkylsulfinylalkyl group is C 2-12 or C 2-24 alkylsulfinylalkyl group (e.g., C 1-6 alkylsulfinyl-C 1-6 alkyl or C 1-12 alkylsulfinyl-C 1-12 alkyl). In other embodiments, the alkylsulfinylalkyl group is -L-S(O)-R, where each of L and R is independently an alkyl group as defined herein.

[0214] "Alkylsulfonyl" means an alkyl group as defined herein bonded to a parent molecular group via an -SO2- group. In some embodiments, an unsubstituted alkylsulfonyl group is C 1-6 or C 1-12 alkylsulfonyl group. In other embodiments, the alkylsulfonyl group is -SO2-R, where R is optionally substituted alkyl (e.g., optionally substituted C as described herein1-12 (including alkyl, haloalkyl, or perfluoroalkyl).

[0215] “Alkylsulfonylalkyl” means an alkyl group as defined herein substituted by an alkylsulfonyl group. In some embodiments, an unsubstituted alkylsulfonylalkyl group is C 2-12 or C 2-24 an alkylsulfonylalkyl group (e.g., C 1-6 alkylsulfonyl-C 1-6 alkyl or C 1-12 alkylsulfonyl-C 1-12 alkyl). In other embodiments, an alkylsulfonylalkyl group is -L-SO2-R, where each of L and R is independently an alkyl group as defined herein.

[0216] “Alkynyl” means an unsaturated monovalent hydrocarbon having at least 2 to 50 carbon atoms (C 2-50 ), e.g., 2 to 25 carbon atoms (C 2-25 ), or 2 to 10 carbon atoms (C 2-10 ), and at least one carbon-carbon triple bond, and the unsaturated monovalent hydrocarbon can be obtained by removing one hydrogen atom from one carbon atom of the parent alkyne. The alkynyl group can be branched, straight-chain, or cyclic (e.g., cycloalkynyl). Exemplary alkynyls include an optionally substituted C 2-24 alkyl group having one or more triple bonds. The alkynyl group can be cyclic or acyclic and is exemplified by ethynyl, 1-propynyl, etc. The alkynyl group can become monovalent or polyvalent (e.g., divalent) by removing one or more hydrogens to form a suitable bond to the parent molecular group or a suitable bond between the parent molecular group and another substituent. The alkynyl group can also be substituted or unsubstituted. For example, the alkynyl group can be substituted with one or more of the substituents described herein for alkyl.

[0217] "Surrounding temperature" means a temperature in the range of 16°C to 26°C, such as 19°C to 25°C or 20°C to 25°C.

[0218] "Amide" means -C(O)NR 1 R 2 or -NHCOR 1 and each of R 1 and R 2 is independently selected from hydrogen, aliphatic, heteroaliphatic, aromatic, or any combination thereof as defined herein, or R 1 and R 2 can together with the nitrogen atom to which each is attached form a heterocyclyl group as defined herein.

[0219] "Amino" means -NR 1 R 2 and each of R 1 and R 2 is independently selected from hydrogen, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, optionally substituted heteroaromatic, optionally substituted silyl, or optionally substituted silyloxy, or any combination thereof, or R 1 and R 2 can together with the nitrogen atom to which each is attached form a heterocyclyl group as defined herein. In certain embodiments, each of R 1 and R 2 is independently H, optionally substituted alkyl, optionally substituted alkoxy, optionally substituted aryl, optionally substituted aryloxy, optionally substituted alkyl-aryl, optionally substituted aryl-alkyl, optionally substituted silyl, or optionally substituted silyloxy. In certain embodiments, R 1 and R 2 can together with the nitrogen atom to which each is attached form an optionally substituted heterocyclyl.

[0220] "Aminoalkyl" means an alkyl group as defined herein substituted by an amino group as defined herein. In some embodiments, the aminoalkyl group is -L-NR 1 R 2 wherein L is an alkyl group as defined herein, and R 1 and R 2 each independently is selected from hydrogen, aliphatic, heteroaliphatic, or aromatic as defined herein, or any combination thereof, or R 1 and R 2 together with the nitrogen atom to which each is attached can form a heterocyclyl group as defined herein. In other embodiments, the aminoalkyl group is -L-C(NR 1 R 2 )(R 3 )-R 4 wherein L is a covalent bond or an alkyl group as defined herein, and R 1 and R 2 each independently is selected from hydrogen, aliphatic, heteroaliphatic, or aromatic as defined herein, or any combination thereof, or R 1 and R 2 together with the nitrogen atom to which each is attached can form a heterocyclyl group as defined herein, and each of R 3 and R 4 is independently H or alkyl as defined herein.

[0221] "Aminooxy" means an oxy group as defined herein substituted by an amino group as defined herein. In some embodiments, the aminooxy group is -O-NR 1 R 2 wherein R 1 and R 2Each of which is independently selected from hydrogen, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, optionally substituted heteroaromatic, optionally substituted silyl, or optionally substituted silyloxy as defined herein, or any combination thereof, or R 1 and R 2 can together with the nitrogen atom to which each is attached form a heterocyclyl group as defined herein. In certain embodiments, each of R 1 and R 2 is independently H, optionally substituted alkyl, optionally substituted alkoxy, optionally substituted aryl, optionally substituted aryloxy, optionally substituted alkyl-aryl, optionally substituted aryl-alkyl, optionally substituted silyl, or optionally substituted silyloxy.

[0222] "Aromatic", unless otherwise specified, means a cyclic conjugated group or a moiety of 5 to 15 ring atoms having a monocyclic ring (e.g., phenyl) or a plurality of fused rings in which at least one ring is aromatic (e.g., naphthyl, indolyl, or pyrazolopyridinyl), i.e., at least one ring and optionally a plurality of fused rings have a continuous delocalized π-electron system. Typically, the number of out-of-plane π electrons corresponds to Hückel's rule (4n + 2). The point of attachment to the parent structure is typically through the aromatic portion of the fused ring system. The aromatic group is unsubstituted or substituted, for example, by a functional group as described herein. For example, the aromatic group can be substituted with one or more substituents as described herein for alkyl and / or aryl.

[0223] "Aryl-carbonyl" means an aryl group that is coupled to or can be coupled to a compound disclosed herein, and the aryl group is coupled or is to be coupled via a carbonyl group (-C(O)-). In some embodiments, the aryl-carbonyl group is -C(O)-R, where R is an optionally substituted aryl group as defined herein.

[0224] "Aryl-carbonyloxy" means an aryl group that is coupled to or can be coupled to a compound disclosed herein, and the aryl group is coupled or is to be coupled via a carbonyloxy group (-OC(O)-). In some embodiments, the aryl-carbonyloxy group is -OC(O)-R, where R is an optionally substituted aryl group as defined herein.

[0225] "Aryl-oxy" means an aryl group that is coupled to or can be coupled to a compound disclosed herein, and the aryl group is coupled or is to be coupled via an oxy group (-O-). In some embodiments, the aryl-oxy group is -O-R, where R is an optionally substituted aryl group as defined herein.

[0226] "Aryl-oxycarbonyl" means an aryl group that is coupled to or can be coupled to a compound disclosed herein, and the aryl group is coupled or is to be coupled via an oxycarbonyl group (-C(O)O-). In some embodiments, the aryl-carbonyl group is -C(O)O-R, where R is an optionally substituted aryl group as defined herein.

[0227] "Aryl" means having a single ring or a plurality of fused rings, at least 5 to 15 carbon atoms (C 5-15 ), for example 5 to 10 carbon atoms (C 5-10means an aromatic carbocyclic group containing ), and its fused ring may or may not be aromatic when the bonding point to the remaining positions of the compounds disclosed herein is through an atom of the aromatic carbocyclic group. The aryl group may be substituted with one or more groups other than hydrogen, such as aliphatic, heteroaliphatic, aromatic, other functional groups, or any combination thereof. Exemplary aryl groups include, but are not limited to, benzyl, naphthalene, phenyl, biphenyl, phenoxybenzene, and the like. The term aryl also includes heteroaryl, which is defined as a group containing an aromatic group having at least one heteroatom incorporated within the ring of the aromatic group. Examples of heteroatoms include, but are not limited to, nitrogen, oxygen, sulfur, and phosphorus. Similarly, the term non-heteroaryl, which is also included in the term aryl, defines a group containing an aromatic group that does not contain a heteroatom. The aryl group may be substituted or unsubstituted. The aryl group can be substituted with 1, 2, 3, 4, or 5 substituents independently selected from the group consisting of: (1) C 1-6 alkanoyl (e.g., -C(O)-R, where R is C 1-6 alkyl), (2) C 1-6 alkyl, (3) C 1-6 alkoxy (e.g., -O-R, where R is C 1-6 alkyl), (4) C 1-6 alkoxy-C 1-6 alkyl (e.g., -L-O-R, where each of L and R is independently C 1-6 alkyl), (5) C 1-6 alkylsulfinyl (e.g., -S(O)-R, where R is C 1-6 alkyl), (6) C 1-6 alkylsulfinyl-C 1-6 alkyl (e.g., -L-S(O)-R, where each of L and R is independently C 1-6 alkyl), (7) C 1-6 alkylsulfonyl (e.g., -SO2-R, where R is C 1-6 alkyl), (8) C 1-6 alkylsulfonyl-C 1-6 alkyl (e.g., -L-SO2-R, where each of L and R is independently C 1-6is alkyl), (9) aryl, (10) amino (e.g., -NR 1 R 2 , R 1 and R 2 each independently is selected from hydrogen, aliphatic, heteroaliphatic, haloaliphatic, haloheteroaliphatic, aromatic, or any combination thereof as defined herein, or R 1 and R 2 can together with the nitrogen atom to which each is attached form a heterocyclyl group as defined herein), (11)C 1-6 aminoalkyl (e.g., -L 1 -NR 1 R 2 or -L 2 -C(NR 1 R 2 )(R 3 )-R 4 , L 1 is C 1-6 alkyl, L2 is a covalent bond or C 1-6 alkyl, and each of R 1 and R 2 is independently selected from hydrogen, aliphatic, heteroaliphatic, haloaliphatic, haloheteroaliphatic, aromatic, or any combination thereof as defined herein, or R 1 and R 2 can together with the nitrogen atom to which each is attached form a heterocyclyl group as defined herein, and each of R 3 and R 4 is independently H or C 1-6 alkyl), (12) heteroaryl, (13)C 4-18 aryl-C 1-6 alkyl (e.g., -L-R, L is C 1-6 alkyl, and R is C 4-18 aryl), (14) aroyl (e.g., -C(O)-R, R is aryl), (15) azide (e.g., -N3), (16) cyano (e.g., -CN), (17)C 1-6 azidoalkyl (e.g., -L-N3, L is C 1-6is alkyl), (18) aldehyde (e.g., -C(O)H), (19) aldehyde-C 1-6 alkyl (e.g., -L-C(O)H, L is C 1-6 alkyl), (20) C 3-8 cycloalkyl, (21) C 3-8 cycloalkyl-C 1-6 alkyl (e.g., -L-R, L is C 1-6 alkyl and R is C 3-8 cycloalkyl), (22) halo, (23) C 1-6 haloalkyl (e.g., -L 1 -X or -L 2 -C(X)(R 1 )-R 2 , L 1 is C 1-6 alkyl, L 2 is a covalent bond or C 1-6 alkyl, X is fluoro, bromo, chloro, or iodo, and each of R 1 and R 2 is independently H or C 1-6 alkyl), (24) heterocyclyl (e.g., a 5-, 6-, or 7-membered ring containing 1, 2, 3, or 4 non-carbon heteroatoms as defined herein, etc.), (25) heterocyclyloxy (e.g., -O-R, R is heterocyclyl as defined herein), (26) heterocyclyloyl (e.g., -C(O)-R, R is heterocyclyl as defined herein), (27) hydroxyl (-OH), (28) C 1-6 hydroxyalkyl (e.g., -L 1 -OH or -L 2 -C(OH)(R 1 )-R 2 , L 1 is C 1-6 alkyl, L 2 is a covalent bond or alkyl, and each of R 1 and R 2 is independently H as defined herein or C 1-6 alkyl), (29) nitro, (30) C 1-6 nitroalkyl (e.g., -L1 -NO or -L 2 -C(NO)(R 1 )-R 2 、L 1 is C 1-6 alkyl, L 2 is a covalent bond or alkyl, R 1 and R 2 each is independently H or C 1-6 alkyl as defined herein), (31) N - protected amino, (32) N - protected amino - C 1-6 alkyl, (33) oxo (e.g., =O), (34) C 1-6 thioalkoxy (e.g., -S - R, R is C 1-6 alkyl), (35) thio - C 1-6 alkoxy - C 1-6 alkyl (e.g., -L - S - R, each of L and R is independently C 1-6 alkyl), (36) -(CH2) r CO2R 1 , r is an integer from 0 to 4, R 1 is selected from the group consisting of (a) hydrogen, (b) C 1-6 alkyl, (c) C 4-18 aryl, and (d) C 4-18 aryl - C 1-6 alkyl (e.g., -L - R, L is C 1-6 alkyl, R is C 4-18 aryl), (37) -(CH2) r CONR 1 R 2 , r is an integer from 0 to 4, each R 1 and R 2 is independently selected from the group consisting of (a) hydrogen, (b) C 1-6 alkyl, (c) C 4-18 aryl, and (d) C 4-18 aryl - C 1-6 alkyl (e.g., -L - R, L is C 1-6 alkyl, R is C 4-18 aryl), (38) -(CH2) r SO2R 1 , r is an integer from 0 to 4, R1 is selected from the group consisting of (a) C 1-6 alkyl, (b) C 4-18 aryl, and (c) C 4-18 aryl-C 1-6 alkyl (e.g., -L-R, where L is C 1-6 alkyl and R is C 4-18 aryl), (39)-(CH2) r SO2NR 1 R 2 , r is an integer from 0 to 4, and each of R 1 and R 2 is independently selected from the group consisting of (a) hydrogen, (b) C 1-6 alkyl, (c) C 4-18 aryl, and (d) C 4-18 aryl-C 1-6 alkyl (e.g., -L-R, where L is C 1-6 alkyl and R is C 4-18 aryl), (40)-(CH2) r NR 1 R 2 , r is an integer from 0 to 4, and each of R 1 and R 2 is independently selected from the group consisting of (a) hydrogen, (b) an N-protecting group, (c) C 1-6 alkyl, (d) C 2-6 alkenyl, (e) C 2-6 alkynyl, (f) C 4-18 aryl, (g) C 4-18 aryl-C 1-6 alkyl (e.g., -L-R, where L is C 1-6 alkyl and R is C 4-18 aryl), (h) C 3-8 cycloalkyl, and (i) C 3-8 cycloalkyl-C 1-6 alkyl (e.g., -L-R, where L is C 1-6 alkyl and R is C 3-8 cycloalkyl), and in one embodiment, there are no two groups bonded to the nitrogen atom via a carbonyl group or a sulfonyl group, (41) thiol (e.g., -SH), (42) perfluoroalkyl (e.g., -(CF2)n CF3, where n is an integer from 0 to 10), (43) perfluoroalkoxy (e.g., -O-(CF2) n CF3, where n is an integer from 0 to 10), (44) aryloxy (e.g., -O-R, where R is aryl), (45) cycloalkoxy (e.g., -O-R, where R is cycloalkyl), (46) cycloalkylalkoxy (e.g., -O-L-R, where L is alkyl and R is cycloalkyl), and (47) arylalkoxy (e.g., -O-L-R, where L is alkyl and R is aryl). In certain embodiments, the unsubstituted aryl group is C 4-18 C 4-14 C 4-12 C 4-10 C 6-18 C 6-14 C 6-12 or C 6-10 aryl group.

[0228] "Aryl-alkyl", "aryl-alkenyl", and "aryl-alkynyl" each mean an aryl group as defined herein that is coupled (or bonded) to or can be coupled (or bonded) to a parent molecular group via an alkyl group, alkenyl group, or alkynyl group as defined herein. An aryl-alkyl group, aryl-alkenyl group, and / or aryl-alkynyl group can be substituted or unsubstituted. For example, an aryl-alkyl group, aryl-alkenyl group, and / or aryl-alkynyl group can be substituted with one or more substituents as described herein for aryl and / or alkyl. Exemplary unsubstituted aryl-alkyl groups are those having 7 to 16 carbons (C 7-16 aryl-alkyl), as well as those having an aryl group with 4 to 18 carbons and an alkyl group with 1 to 6 carbons (i.e., C 4-18 aryl-C 1-6 alkyl). Exemplary unsubstituted aryl-alkenyl groups are those having 7 to 16 carbons (C 7-16Those of (aryl-alkenyl), and an aryl group having 4 to 18 carbons and an alkenyl group having 2 to 6 carbons (i.e., C 4-18 aryl-C 2-6 alkenyl). Exemplary unsubstituted aryl-alkynyl groups are those of 7 to 16 carbons (C 7-16 aryl-alkynyl), and an aryl group having 4 to 18 carbons and an alkynyl group having 2 to 6 carbons (i.e., C 4-18 aryl-C 2-6 alkynyl). In some embodiments, the aryl-alkyl group is -L-R, where L is an alkyl group or an alkylene group as defined herein, and R is an aryl group as defined herein. In some embodiments, the aryl-alkenyl group is -L-R, where L is an alkenyl group or an alkenylene group as defined herein, and R is an aryl group as defined herein. In some embodiments, the aryl-alkynyl group is -L-R, where L is an alkynyl group or an alkynylene group as defined herein, and R is an aryl group as defined herein.

[0229] "Arylene" means a polyvalent (e.g., divalent) form of an aryl group as described herein. Exemplary arylene groups include phenylene, naphthylene, biphenylene, triphenylene, diphenyl ether, acenaphthenylene, anthrylene, or phenanthrylene. In some embodiments, the arylene group is C 4-18 C 4-14 C 4-12 C 4-10 C 6-18 C 6-14 C 6-12 C 6-10 arylene group. The arylene group can be branched or unbranched. The arylene group can also be substituted or unsubstituted. For example, the arylene group can be substituted with one or more substituents as described herein for aryl.

[0230] "Aryloxy" means an aryl-alkyl group as defined herein, bonded to the parent molecular group through an oxygen atom. In some embodiments, the aryloxy group is -O-L-R, where L is an alkyl group as defined herein and R is an aryl group as defined herein.

[0231] "Aryloxy" means -OR, where R is an optionally substituted aryl group as described herein. In some embodiments, the unsubstituted aryloxy group is C 4-18 or C 6-18 aryloxy group. In other embodiments, R is an aryl group optionally substituted with alkyl, alkanoyl, amino, hydroxyl, etc.

[0232] "Aryloxycarbonyl" means an aryloxy group as defined herein, bonded to the parent molecular group through a carbonyl group. In some embodiments, the unsubstituted aryloxycarbonyl group is C 5-19 aryloxycarbonyl group. In other embodiments, the aryloxycarbonyl group is -C(O)O-R, where R is an aryl group as defined herein.

[0233] "Aroyl" means an aryl group bonded to the parent molecular group through a carbonyl group. In some embodiments, the unsubstituted aroyl group is C 7-11 aroyl or C 5-19 aroyl group. In other embodiments, the aroyl group is -C(O)-R, where R is an aryl group as defined herein.

[0234] "Aroyloxy" means an aroyl group as defined herein, bonded to the parent molecular group through an oxy group. In some embodiments, the unsubstituted aroyloxy group is C 5-19 aroyloxy group. In other embodiments, the aroyloxy group is -OC(O)-R, where R is an aryl group as defined herein.

[0235] "Azido" means an -N3 group.

[0236] "Alkyl azide" means an azide group bonded to a parent molecular group via an alkyl group as defined herein. In some embodiments, the alkyl azide group is -L-N3, where L is an alkyl group as defined herein.

[0237] "Azo" means an -N=N- group.

[0238] "Carbamoyl" means an amino group bonded to a parent molecular group via a carbonyl group as defined herein. In some embodiments, carbamoyl is -C(O)NR 1 R 2 group, where each of R 1 and R 2 is independently selected from hydrogen, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, optionally substituted heteroaromatic, optionally substituted silyl, or optionally substituted silyloxy as defined herein, or any combination thereof, or R 1 and R 2 can together with the nitrogen atom to which each is attached form a heterocyclyl group as defined herein.

[0239] "Carbamoyloxy" means a carbamoyl group as defined herein bonded to a parent molecular group via an n-oxy group as defined herein. In some embodiments, carbamoyl is -OC(O)NR 1 R 2 group, where each of R 1 and R 2 is independently selected from hydrogen, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, optionally substituted heteroaromatic, optionally substituted silyl, or optionally substituted silyloxy as defined herein, or any combination thereof, or R1 and R 2 can each, together with the nitrogen atom to which it is attached, form a heterocyclyl group as defined herein.

[0240] "Carboximidoyl" means a -C(NR)- group. In some embodiments, R is selected from hydrogen, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, optionally substituted heteroaromatic, optionally substituted silyl, optionally substituted alkyl, optionally substituted aryl, optionally substituted alkyl-aryl, or optionally substituted aryl-alkyl, optionally substituted silyloxy, or any combination thereof, as defined herein.

[0241] "Carbonyl" means a -C(O)- group and can also be represented as >C=O.

[0242] "Carboxyl" means a -CO2H group or its anion.

[0243] "Catalyst" means a compound that can catalyze a synthetic reaction, typically present in small amounts relative to the reactants, as readily understood by those skilled in the art. In some embodiments, the catalyst may include a transition metal coordination complex.

[0244] "Cyanato" means a -OCN group.

[0245] "Cyano" means a -CN group.

[0246] "Cycloaliphatic" means an aliphatic group as defined herein that is cyclic.

[0247] "Cycloalkoxy" means a cycloalkyl group as defined herein attached to a parent molecular group through an oxygen atom. In some embodiments, the cycloalkoxy group is -O-R, where R is a cycloalkyl group as defined herein.

[0248] "Cycloalkylalkoxy" means an -O-L-R group, where L is an alkyl or alkylene group as defined herein, and R is a cycloalkyl group as defined herein.

[0249] "Cycloalkyl", unless otherwise specified, means a monovalent saturated or unsaturated non-aromatic cyclic hydrocarbon group having 3 to 8 carbons, exemplified by cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, bicyclo[2.2.1]heptyl, etc. The cycloalkyl group can also be substituted or unsubstituted. For example, the cycloalkyl group can be substituted with one or more groups including those described herein for alkyl. Further, cycloalkyl can contain one or more double bonds and / or triple bonds.

[0250] "Cycloheteroaliphatic" means a cyclic heteroaliphatic group as defined herein.

[0251] "Disilanyl" means a group containing an Si-Si bond. In some embodiments, the disilanyl group is a -SiR S1 R S2 -SiR S3 R S4 R S5 or -SiR S1 R S2 -SiR S3 R S4 - group, where each of R S1 、R S2 、R S3 、R S4 、and R S5 is independently H, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, optionally substituted heteroaromatic, or optionally substituted amino.

[0252] "Disulfide" means -SSR, where R is selected from hydrogen, aliphatic, heteroaliphatic, haloaliphatic, haloheteroaliphatic, aromatic, or any combination thereof as defined herein.

[0253] "Electron-donating group" means a functional group capable of donating at least a part of its electron density to a ring directly bonded to the electron-donating group by resonance or the like.

[0254] "Electron-withdrawing group" means a functional group capable of receiving electron density from a ring directly bonded to the electron-withdrawing group by inductive electron withdrawal or the like.

[0255] "Halo" means F, Cl, Br, or I.

[0256] "Haloaliphatic" means an aliphatic group as defined herein, and one or more hydrogen atoms such as 1 to 10 hydrogen atoms are independently replaced by halogen atoms such as fluoro, bromo, chloro, or iodo.

[0257] "Haloalkyl" means an alkyl group as defined herein, and one or more hydrogen atoms such as 1 to 10 hydrogen atoms are independently replaced by halogen atoms such as fluoro, bromo, chloro, or iodo. In an independent embodiment, the haloalkyl can be a -C4 group, and each X can be independently selected from fluoro, bromo, chloro, or iodo. In some embodiments, the haloalkyl group is -L-X, where L is an alkyl group as defined herein and X is fluoro, bromo, chloro, or iodo. In other embodiments, the haloalkyl group is -L-C(X)(R 1 )-R 2 where L is a covalent bond or an alkyl group as defined herein, X is fluoro, bromo, chloro, or iodo, and each of R 1 and R 2 is independently H or alkyl as defined herein.

[0258] "Haloheteroaliphatic" means heteroaliphatic as defined herein, and one or more hydrogen atoms, such as 1 to 10 hydrogen atoms, are independently replaced by halogen atoms such as fluoro, bromo, chloro, or iodo.

[0259] "Heteroaliphatic" means an aliphatic group as defined herein, containing at least 1 heteroatom to 20 heteroatoms, such as 1 to 15 heteroatoms, or 1 to 5 heteroatoms, which can be selected from, but not limited to, oxygen, nitrogen, sulfur, silicon, boron, selenium, phosphorus, and their oxidized forms within the group. The heteroaliphatic group is unsubstituted or substituted, for example, by functional groups described herein. For example, the heteroaliphatic group can be substituted by one or more substituents described herein for alkyl.

[0260] "Heteroaliphatic-carbonyl" means a heteroaliphatic group that can be coupled to or can couple to a compound disclosed herein, and the heteroaliphatic group is coupled or is to be coupled via a carbonyl group (-C(O)-). In some embodiments, the heteroaliphatic-carbonyl group is -C(O)-R, where R is an optionally substituted heteroaliphatic group as defined herein.

[0261] "Heteroaliphatic-carbonyloxy" means a heteroaliphatic group that can be coupled to or can couple to a compound disclosed herein, and the heteroaliphatic group is coupled or is to be coupled via a carbonyloxy group (-OC(O)-). In some embodiments, the heteroaliphatic-carbonyloxy group is -OC(O)-R, where R is an optionally substituted heteroaliphatic group as defined herein.

[0262] "Heteroaliphatic-oxy" means a heteroaliphatic group that is coupled to or can be coupled to a compound disclosed herein, and the heteroaliphatic group is coupled or is to be coupled via an oxy group (-C(O)-). In some embodiments, the heteroaliphatic-oxy group is -O-R, where R is an optionally substituted heteroaliphatic group as defined herein.

[0263] "Heteroaliphatic-oxycarbonyl" means a heteroaliphatic group that is coupled to or can be coupled to a compound disclosed herein, and the heteroaliphatic group is coupled or is to be coupled via an oxycarbonyl group (-C(O)O-). In some embodiments, the heteroaliphatic-oxycarbonyl group is -C(O)O-R, where R is an optionally substituted heteroaliphatic group as defined herein.

[0264] "Heteroalkyl", "heteroalkenyl", and "heteroalkynyl" each mean an alkyl group, an alkenyl group, or an alkynyl group (which may be branched, straight-chain, or cyclic) as defined herein, and contain from at least 1 to 20 heteroatoms, such as 1 to 15 heteroatoms, or 1 to 5 heteroatoms, which can be selected from, but are not limited to, oxygen, nitrogen, sulfur, silicon, boron, selenium, phosphorus, and their oxidized forms within the group.

[0265] "Heteroalkylene", "heteroalkenylene", and "heteroalkynylene" each mean a polyvalent (e.g., divalent) form of a heteroalkyl group, a heteroalkenyl group, or a heteroalkynyl group as described herein.

[0266] "Heteroaromatic" means an aromatic group as defined herein, containing from at least 1 to 20 heteroatoms, such as from 1 to 15 heteroatoms, or from 1 to 5 heteroatoms, which can be selected, without limitation, from oxygen, nitrogen, sulfur, silicon, boron, selenium, phosphorus, and their oxidized forms within the group. The heteroaromatic group is unsubstituted or substituted, for example, by functional groups described herein. For example, the heteroaromatic group can be substituted with one or more substituents described herein for alkyl and / or aryl.

[0267] "Heteroaromatic-carbonyl" means a heteroaromatic group that is coupled or can be coupled to a compound disclosed herein, and the heteroaromatic group is coupled or becomes coupled via a carbonyl group (-C(O)-). In some embodiments, the heteroaromatic-carbonyl group is -C(O)-R, where R is an optionally substituted heteroaromatic group as defined herein.

[0268] "Heteroaromatic-carbonyloxy" means a heteroaromatic group that is coupled or can be coupled to a compound disclosed herein, and the heteroaromatic group is coupled or becomes coupled via a carbonyloxy group (-OC(O)-). In some embodiments, the heteroaromatic-carbonyloxy group is -OC(O)-R, where R is an optionally substituted heteroaromatic group as defined herein.

[0269] "Heteroaromatic-oxy" means a heteroaromatic group that is coupled or can be coupled to a compound disclosed herein, and the heteroaromatic group is coupled or becomes coupled via an oxy group (-O-). In some embodiments, the heteroaromatic-oxy group is -O-R, where R is an optionally substituted heteroaromatic group as defined herein.

[0270] "Heteroaromatic-oxycarbonyl" means a heteroaromatic group that is coupled to or can be coupled to a compound disclosed herein, and the heteroaromatic group is coupled or adapted to be coupled via an oxycarbonyl group (-C(O)O-). In some embodiments, the heteroaromatic-carbonyl group is -C(O)O-R, where R is an optionally substituted heteroaromatic group as defined herein.

[0271] "Heteroaryl" means an aryl group containing at least 1 to 6 heteroatoms, such as 1 to 4 heteroatoms, which can be selected from, but are not limited to, oxygen, nitrogen, sulfur, silicon, boron, selenium, phosphorus, and their oxidized forms within the ring. Such heteroaryl groups can have a monocyclic or multiple condensed rings, and the condensed rings may or may not be aromatic when the point of attachment is through an atom of the aromatic heteroaryl group and / or may contain heteroatoms. The heteroaryl group may be substituted with one or more groups other than hydrogen, such as aliphatic, heteroaliphatic, aromatic, other functional groups, or any combination thereof. Exemplary heteroaryls include a subset of the heterocyclyl groups defined herein that are aromatic, i.e., contain 4n+2 π electrons within a monocyclic or polycyclic ring system.

[0272] "Heteroarylene" means a polyvalent (e.g., divalent) form of a heteroaryl group as described herein.

[0273] "Heteroatom" means an atom other than carbon, such as oxygen, nitrogen, sulfur, silicon, boron, selenium, or phosphorus. In certain disclosed embodiments, such as when valence constraints do not permit, the heteroatom does not include a halogen atom.

[0274] "Heterocyclyl", unless otherwise specified, means a 5-, 6-, or 7-membered ring containing 1, 2, 3, or 4 non-carbon heteroatoms (independently selected from the group consisting of, for example, nitrogen, oxygen, phosphorus, sulfur, or halogen). The 5-membered ring has 0 to 2 double bonds, and the 6-membered and 7-membered rings have 0 to 3 double bonds. The term "heterocyclyl" also includes bicyclic, tricyclic, and tetracyclic groups, and any of the above heterocycles is condensed to one, two, or three rings independently selected from the group consisting of an aryl ring, a cyclohexane ring, a cyclohexene ring, a cyclopentane ring, a cyclopentene ring, and another monocyclic heterocycle such as indolyl, quinolyl, isoquinolyl, tetrahydroquinolyl, benzofuryl, benzothienyl. Heterocycles include thiiranyl, thietanyl, tetrahydrothienyl, thianyl, thiepanyl, aziridinyl, azetidinyl, pyrrolidinyl, piperidinyl, azepanyl, pyrrolyl, pyrrolinyl, pyrazolyl, pyrazolinyl, pyrazolidinyl, imidazolyl, imidazolinyl, imidazolidinyl, pyridyl, homopiperidinyl, pyrazinyl, piperazinyl, pyrimidinyl, pyridazinyl, oxazolyl, oxazolidinyl, oxazolidonyl, isoxazolyl, isoxazolidinyl, morpholinyl, thiomorpholinyl, thiazolyl, thiazolidinyl, isothiazolyl, isothiazolidinyl, indolyl, quinolinyl, isoquinolinyl, benzimidazolyl, benzothiazolyl, benzoxazolyl, furyl, thienyl, thiazolidinyl, isothiazolyl, isoindazolyl, triazolyl, tetrazolyl, oxadiazolyl, uracil, thiadiazolyl, pyrimidyl, tetrahydrofuranyl, dihydrofuranyl, dihydrothienyl, dihydroindolyl, tetrahydroquinolyl, tetrahydroisoquinolyl, pyranyl, dihydropyranyl, tetrahydropyranyl, dithiazolyl, dioxanyl, dioxinyl, dithianyl, trithianyl, oxazinyl, thiazinyl, oxothiolanyl, triazinyl, benzofuryl, benzothienyl, etc.

[0275] "Heterocyclyloxy" means a heterocyclyl group as defined herein, bonded to a parent molecular group through an oxygen atom. In some embodiments, the heterocyclyloxy group is -O-R, where R is a heterocyclyl group as defined herein.

[0276] "Heterocyclylcarbonyl" means a heterocyclyl group as defined herein, bonded to a parent molecular group through a carbonyl group. In some embodiments, the heterocyclylcarbonyl group is -C(O)-R, where R is a heterocyclyl group as defined herein.

[0277] "Hydrazino" means -NR 1 -NR 2 R 3 wherein each of R 1 and R 2 and R 3 is independently selected from hydrogen, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, optionally substituted heteroaromatic, optionally substituted silyl, or optionally substituted silyloxy, or any combination thereof, or the combination of R 1 and R 2 or the combination of R 2 and R 3 can together with the nitrogen atom to which each is attached form a heterocyclyl group as defined herein. In some embodiments, each of R 1 and R 2 and R 3 is independently H, optionally substituted alkyl, optionally substituted aryl, optionally substituted alkyl-aryl, or optionally substituted aryl-alkyl. In certain embodiments, R 2 and R 3 can together with the nitrogen atom to which each is attached form an optionally substituted heterocyclyl.

[0278] "Hydroxyl" means -OH.

[0279] "Hydroxyalkyl" means an alkyl group as defined herein substituted by one to three hydroxyl groups, provided that one or fewer hydroxyl groups may be attached to a single carbon atom of the alkyl group, and this group is exemplified by hydroxymethyl, dihydroxypropyl, etc. In some embodiments, the hydroxyalkyl group is -L-OH, where L is an alkyl group as defined herein. In other embodiments, the hydroxyalkyl group is -L-C(OH)(R 1 )-R 2 where L is a covalent bond or an alkyl group as defined herein, and each of R 1 and R 2 is independently H or alkyl as defined herein.

[0280] "Imidoyl" means a moiety containing a carboximideoyl group. In some embodiments, the imidoyl group is C(NR 1 )R 2 where each of R 1 and R 2 is independently selected from hydrogen, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, optionally substituted heteroaromatic, optionally substituted silyl, optionally substituted alkyl, optionally substituted aryl, optionally substituted alkyl-aryl, or optionally substituted aryl-alkyl, optionally substituted silyloxy, or any combination thereof as defined herein. In other embodiments, the imidoyl group is -C(NR 1 )H, -C(NR 1 )R Ak , or -C(NR N1 )R Ar where R 1is hydrogen, an optionally substituted aliphatic, an optionally substituted heteroaliphatic, an optionally substituted aromatic, an optionally substituted heteroaromatic, an optionally substituted silyl, an optionally substituted alkyl, an optionally substituted aryl, an optionally substituted alkyl-aryl, or an optionally substituted aryl-alkyl, or an optionally substituted silyloxy, and R Ak is an optionally substituted alkyl or an optionally substituted aliphatic, and R Ar is an optionally substituted aryl or an optionally substituted aromatic.

[0281] "Imino" means an -NR- group. In some embodiments, R is selected from hydrogen, an optionally substituted aliphatic, an optionally substituted heteroaliphatic, an optionally substituted aromatic, or an optionally substituted heteroaromatic. In certain embodiments, R is H, an optionally substituted alkyl, an optionally substituted alkoxy, an optionally substituted aryl, an optionally substituted aryloxy, an optionally substituted alkyl-aryl, or an optionally substituted aryl-alkyl.

[0282] "Isocyanato" means an -NCO group.

[0283] "Isocyano" means an -NC group.

[0284] "Ketone" means a compound containing a -C(O)R or such a group, where R is selected from aliphatic, heteroaliphatic, aromatic, or any combination thereof as defined herein. An example of a ketone can include R 1 C(O)R, where each of R and R 1 is independently selected from aliphatic, haloaliphatic, haloheteroaliphatic, heteroaliphatic, aromatic, aliphatic-aromatic, heteroaliphatic-aromatic, or any combination thereof as defined herein.

[0285] "Nitro" means a -NO2 group.

[0286] "Nitroalkyl" means an alkyl group as defined herein substituted by one to three nitro groups. In some embodiments, the nitroalkyl group is -L-NO, where L is an alkyl group as defined herein. In other embodiments, the nitroalkyl group is -L-C(NO)(R 1 )-R 2 , where L is a covalent bond or an alkyl group as defined herein, and each of R 1 and R 2 is independently H or alkyl as defined herein.

[0287] "Oxo" means the =O group.

[0288] "Oxy" means -O-.

[0289] "Perfluoroalkyl" means an alkyl group as defined herein having each hydrogen atom substituted by a fluorine atom. Exemplary perfluoroalkyl groups include trifluoromethyl, pentafluoroethyl, and the like. In some embodiments, the perfluoroalkyl group is -(CF2) n CF3, where n is an integer from 0 to 10.

[0290] "Perfluoroalkoxy" means an alkoxy group as defined herein having each hydrogen atom substituted by a fluorine atom. In some embodiments, the perfluoroalkoxy group is -O-R, where R is a perfluoroalkyl group as defined herein.

[0291] "Salt" means an ionic form of a compound or structure (e.g., any formula, compound, or composition described herein) that includes a cationic or anionic compound forming an electrically neutral compound or structure. Salts are well known in the art. For example, non-toxic salts are described in Berge S M et al., “Pharmaceutical salts,” J. Pharm. Sci. 1977 January; 66(1):1-19, and “Handbook of Pharmaceutical Salts: Properties, Selection, and Use,” Wiley-VCH, April 2011 (2nd rev. ed., eds. P. H. Stahl and C. G. Wermuth). Salts can be prepared separately during the final isolation and purification of the compounds of the invention in-situ, or by reacting the free base group with an appropriate organic acid (thereby forming an anion salt), or by reacting an acid group with an appropriate metal or organic salt (thereby forming a cation salt).Representative anion salts include acetate, adipate, alginate, ascorbate, aspartate, benzenesulfonate, benzoate, bicarbonate, bisulfate, bitartrate, borate, bromide, butyrate, camphorate, camphorsulfonate, chloride, citrate, cyclopentanepropionate, digluconate, dihydrochloride, diphosphate, dodecyl sulfate, edetate, ethanesulfonate, fumarate, glucoheptonate, gluconate, glutamate, glycerophosphate, hemisulfate, heptonate, hexanoate, hydrobromide, hydrochloride, hydroiodide, hydroxyethanesulfonate, hydroxynaphthoate, iodide, lactate, lactobionate, laurate, lauryl sulfate, malate, maleate, malonate, mandelate, mesylate, methanesulfonate, methyl bromide, methyl nitrate, methyl sulfate, mucate, 2-naphthalenesulfonate, nicotinate, nitrate, oleate, oxalate, palmitate, pamoate, pectinate, persulfate, 3-phenylpropionate, phosphate, picrate, pivalate, polygalacturonate, propionate, salicylate, stearate, subacetate, succinate, sulfate, tannate, tartrate, theophyllinate, thiocyanate, triethiodide, toluenesulfonate, undecanoate, valerate, etc. Representative cation salts include metal salts, such as alkali or alkaline earth salts, such as barium, calcium (e.g., calcium edetate), lithium, magnesium, potassium, sodium, etc.; other metal salts, such as aluminum, bismuth, iron, and zinc; and, without limitation, non-toxic ammonium, quaternary ammonium, and amine cations, including ammonium, tetramethylammonium, tetraethylammonium, methylamine, dimethylamine, trimethylamine, triethylamine, ethylamine, pyridinium, etc. Other cation salts include organic salts such as chloroprocaine, choline, dibenzylethylenediamine, diethanolamine, ethylenediamine, methylglucamine, and procaine, etc.Still other salts include ammonium, sulfonium, sulfoxonium, phosphonium, iminium, imidazolium, benzimidazolium, amidinium, guanidinium, phosphaziniuum, phosphazenium, pyridinium, etc., and other cationic groups described herein (e.g., optionally substituted isoxazolium, optionally substituted oxazolium, optionally substituted thiazolium, optionally substituted pyrrolium, optionally substituted furanium, optionally substituted thiophenium, optionally substituted imidazolium, optionally substituted pyrazolium, optionally substituted isothiazolium, optionally substituted triazolium, optionally substituted tetrazolium, optionally substituted furazanium, optionally substituted pyridinium, optionally substituted pyrimidinium, optionally substituted pyrazinium, optionally substituted triazinium, optionally substituted tetrazinium, optionally substituted pyridazinium, optionally substituted oxazinium, optionally substituted pyrrolidinium, optionally substituted pyrazolidinium, optionally substituted imidazolinium, optionally substituted isoxazolidinium, optionally substituted oxazolidinium, optionally substituted piperazinium, optionally substituted piperidinium, optionally substituted morpholinium, optionally substituted azepanium, optionally substituted azepinium, optionally substituted indolium, optionally substituted isoindolium, optionally substituted indolidinium, optionally substituted indazolium, optionally substituted benzimidazolium, optionally substituted isoquinolinium, optionally substituted quinolidinium, optionally substituted dehydroquinolidinium, optionally substituted quinolinium, optionally substituted isoindolinium, optionally substituted benzimidazolinium, and optionally substituted purinium).

[0292] "Silyl" means -SiR 1 R 2 R 3 or -SiR 1 R2 -group. In some embodiments, R 1 , R 2 , and R 3 are each, independently, H, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, optionally substituted heteroaromatic, or optionally substituted amino. In certain embodiments, R 1 , R 2 , and R 3 are each, independently, H, optionally substituted alkyl, optionally substituted alkoxy, optionally substituted aryl, optionally substituted aryloxy, optionally substituted alkyl-aryl, optionally substituted aryl-alkyl, or optionally substituted amino. In other embodiments, the silyl group is -Si(R) a (OR) b (NR2) c , where each R is, independently, H, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, or optionally substituted heteroaromatic, and each of a, b, and c is ≧0 and a + b + c = 3. In certain embodiments, each R is, independently, H, optionally substituted alkyl, optionally substituted aryl, optionally substituted alkyl-aryl, or optionally substituted aryl-alkyl.

[0293] "Silyloxy" means -OR, where R is an optionally substituted silyl group as described herein. In some embodiments, the silyloxy group is -O-SiR 1 R 2 R 3 , where R 1 , R 2 , and R 3 are each, independently, H, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, optionally substituted heteroaromatic, or optionally substituted amino. In certain embodiments, R 1 , R 2 , and R 3Each of them is independently H, optionally substituted alkyl, optionally substituted alkoxy, optionally substituted aryl, optionally substituted aryloxy, optionally substituted alkyl-aryl, optionally substituted aryl-alkyl, or optionally substituted amino. In other embodiments, the silyloxy group is -O-Si(R) a (OR) b (NR2) c wherein each R is independently H, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, or optionally substituted heteroaromatic, and each of a, b, and c is ≧0 and a + b + c = 3. In certain embodiments, each R is independently H, optionally substituted alkyl, optionally substituted aryl, optionally substituted alkyl-aryl, or optionally substituted aryl-alkyl.

[0294] "Sulfinyl" means a -S(O)- group.

[0295] "Sulfo" means a -S(O)2OH group.

[0296] "Sulfonyl" or "sulfonate" means a -S(O)2- group or -SO2R, where R is selected from hydrogen, aliphatic, heteroaliphatic, haloaliphatic, haloheteroaliphatic, aromatic, or any combination thereof as defined herein.

[0297] "Thioalkyl" means an alkyl group as defined herein bonded to the parent molecular group through a sulfur atom. Exemplary unsubstituted thioalkyl groups include C 1-6 thioalkyl. In some embodiments, the thioalkyl group is -S-R, where R is an alkyl group as defined herein.

[0298] "Thiol" means a -SH group.

[0299] One of ordinary skill in the art will recognize that the above definitions are not intended to include unacceptable substitution patterns (e.g., methyl substituted with five different groups, etc.). Such unacceptable substitution patterns will be readily recognized by one of ordinary skill in the art. Any functional group disclosed herein and / or defined above may be substituted or unsubstituted unless otherwise indicated.

[0300] As used herein, the term "about" means ±10% of the recited value. As used herein, this term modifies the recited value, a range of values, or the endpoints of one or more ranges.

[0301] As used herein, the terms "top", "bottom", "upper", "lower", "above", and "below" are used to provide a relative relationship between structures. The use of these terms does not imply or require that a particular structure must be located in a particular location within the device.

[0302] Other features and advantages of the invention will become apparent from the following description and claims.

[0303] In various embodiments, the silicon-containing precursor is a silane. Silanes include, but are not limited to, substituted and unsubstituted silanes, halosilanes, aminosilanes, organosilanes, alkylsilanes, alkylaminosilanes, and alkylhalosilanes. In certain embodiments, the silicon-containing precursor includes a halosilane precursor. In certain embodiments, the silicon-containing precursor includes an aminosilane precursor.

[0304] Aminosilanes contain at least one nitrogen atom bonded to a silicon atom and may also contain hydrogen, oxygen, halogen, and carbon. Examples of aminosilanes include mono-, di-, tri-, and tetra-aminosilanes (H3Si(NH2), H2Si(NH2)2, HSi(NH2)3, and Si(NH2)4, respectively), as well as substituted mono-, di-, tri-, and tetra-aminosilanes such as t-butylaminosilane, methylaminosilane, tert-butylsilaneamine, bis(tert-butylamino)silane (SiH2(NHC(CH3)3)2 (BTBAS), tert-butylsilylcarbamate, SiH(CH3)-(N(CH3)2)2, SiHCl-(N(CH3)2)2, (Si(CH3)2NH)3, di(sec-butylamino)silane (DSBAS), di(isopropylamino)silane (DIPAS), bis(diethylamino)silane (BDEAS), and the like. A further example of an aminosilane is trisilylamine (N(SiH3)3). In one example, the silicon-containing precursor is DIPAS. In another example, the silicon-containing precursor is BTBAS. In some embodiments, the silane precursor is a siloxane precursor. In some embodiments, the aminosilane is a siloxane. The siloxane precursor may be a disiloxane, or a trisiloxane, or a cyclic siloxane, or a tetrasiloxane. Cyclic siloxanes may include cyclotetrasiloxanes such as 2,4,6,8-tetramethylcyclotetrasiloxane (TMCTS), octamethylcyclotetrasiloxane (OMCTS), and heptamethylcyclotetrasiloxane (HMCTS). Other cyclic siloxanes may include, but are not limited to, cyclotrisiloxanes and cyclopentasiloxanes. In some embodiments, the silicon-containing deposition precursor is 1-dimethylamino-1,1,5,5,5-pentamethyldisiloxane. In some embodiments, the siloxane may have a three-dimensional or cage structure. Caged siloxanes have silicon atoms cross-linked to each other via oxygen atoms and form polyhedra or any 3D structure. An example of a caged siloxane precursor molecule is silsesquioxane.The cage siloxane structure is described in more detail in co-owned U.S. Patent No. 6,576,345 by Cleemput et al., the above application being incorporated herein by reference in its entirety for all purposes. In some embodiments, the siloxane may be linear. Linear siloxanes may include, but are not limited to, disiloxanes such as pentamethyldisiloxane (PMDSO), tetramethyldisiloxane (TMDSO), and hexamethyltrisiloxane. PMDSO and TMDSO can be used to form SiOC films.

[0305] The silicon-containing precursor can include one or more optionally substituted amino groups, thereby providing non-limiting aminosilanes. In one embodiment, the precursor has the formula (R’) 4-x Si(NR’’2) x where x is 1, 2, 3, or 4, each R’ is independently H, aliphatic, aliphatic-carbonyl, aliphatic-carbonyloxy, aliphatic-oxy, aliphatic-oxycarbonyl, heteroaliphatic, heteroaliphatic-carbonyl, heteroaliphatic-carbonyloxy, heteroaliphatic-oxy, heteroaliphatic-oxycarbonyl, aromatic, aromatic-carbonyl, aromatic-carbonyloxy, aromatic-oxy, aromatic-oxycarbonyl, heteroaromatic, heteroaromatic-oxy, amino, hydrazino, azide, hydroxyl, silyl, silyloxy, cyanato, isocyanato, cyano, or isocyano, any of which may be optionally substituted, each R’’ is independently H, aliphatic, heteroaliphatic, aromatic, heteroaromatic, or amino, any of which may be optionally substituted, or optionally two R’’s together with the nitrogen atom to which each is attached can form an optionally substituted heterocyclyl.

[0306] In another embodiment, the precursor has the formula (R’’2N) x (R’) 3-x Si-L-Si(R’) 3-x (NR’’2)x has the formula each x is independently 0, 1, 2, or 3, L is a linker, such as a covalent bond, an optionally substituted aliphatic, an optionally substituted heteroaliphatic, an optionally substituted aromatic, an optionally substituted heteroaromatic, oxy (-O-), imino, or silyl, each R’ is independently H, aliphatic, aliphatic - carbonyl, aliphatic - carbonyloxy, aliphatic - oxy, aliphatic - oxycarbonyl, heteroaliphatic, heteroaliphatic - carbonyl, heteroaliphatic - carbonyloxy, heteroaliphatic - oxy, heteroaliphatic - oxycarbonyl, aromatic, aromatic - carbonyl, aromatic - carbonyloxy, aromatic - oxy, aromatic - oxycarbonyl, heteroaromatic, heteroaromatic - oxy, amino, hydrazino, azide, hydroxyl, silyl, silyloxy, cyanato, isocyanato, cyano, or isocyano, any of which may be optionally substituted, each R’’ is independently H, aliphatic, heteroaliphatic, aromatic, heteroaromatic, or amino, any of which may be optionally substituted, or optionally two R’’s together with the nitrogen atom to which each is attached can form an optionally substituted heterocyclyl.

[0307] In certain embodiments, L is an optionally substituted imino such as -NR-, where R is H, an optionally substituted aliphatic, an optionally substituted alkyl, an optionally substituted alkenyl, an optionally substituted alkynyl, or an optionally substituted aromatic. In other embodiments, L is an optionally substituted silyl such as -SiR2-, where each R is independently H, an optionally substituted aliphatic, an optionally substituted alkyl, an optionally substituted alkenyl, an optionally substituted alkynyl, or an optionally substituted aromatic.

[0308] In one example, at least one x is not 0. In another embodiment, x can be 0 (e.g., when L contains a carbon atom or a heteroatom). In yet another embodiment, x is 0 and / or L contains optionally substituted aliphatic, optionally substituted alkylene, optionally substituted alkenylene, optionally substituted alkynylene, optionally substituted heteroaliphatic, optionally substituted heteroalkylene, optionally substituted heteroalkenylene, optionally substituted heteroalkynylene, optionally substituted aromatic, optionally substituted arylene, optionally substituted heteroaromatic, optionally substituted heteroarylene, oxy (-O-), imino, or silyl.

[0309] In certain embodiments, at least one R' or R'' is not H. The precursor can have any useful combination of R' groups bonded to one or more silicon atoms and amino groups (NR''2).

[0310] In some embodiments, R' is H, optionally substituted amino (e.g., -NR2), aliphatic-oxy (e.g., alkoxy or -OR), aliphatic-carbonyl (e.g., alkanoyl or -C(O)R), aliphatic-carbonyloxy (e.g., alkanoyloxy or -OC(O)R), aliphatic-oxycarbonyl (e.g., alkoxycarbonyl or -C(O)OR), silyl (e.g., -SiR3), aliphatic-oxy-silyl (e.g., alkoxysilyl or -Si(R) a (OR) b )、aminosilyl (e.g., -Si(R) a (NR2) b )、silyloxy (e.g., -O-SiR3), aliphatic-oxy-silyloxy (e.g., alkoxysilyloxy or -O-Si(R) a (OR) b )、aminosilyloxy (e.g., -O-Si(R) a (NR2) b) are aromatic (e.g., aryl), aromatic-oxy (e.g., aryloxy or -OR), hydroxyl (-OH), formyl (-C(O)H), etc. In certain embodiments, each R is independently H, optionally substituted aliphatic, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted heteroaliphatic, optionally substituted aromatic, optionally substituted aryl, and optionally substituted heteroaromatic, a ≧ 0, b ≧ 1, and a + b = 3. In some embodiments, two R groups can together with the nitrogen atom to which each is attached form an optionally substituted heterocyclyl. In other embodiments, each R is independently H, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, or optionally substituted aryl.

[0311] In other embodiments, R’’ is H, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted alkyl, optionally substituted silyl, or optionally substituted silyloxy. In some embodiments, R’’ is optionally substituted alkyl (e.g., Me, Et, nPr, iPr, sBu, or tBu). In other embodiments, R’’ is -SiR’3, -SiR3, -Si(R’) a (OR) b 、-Si(R) a (OR) b 、-Si(R’) a (NR2) b 、-Si(R’) a (NR2) b 、-Si(R’) a (OR) b (NR2) c 、-Si(R) a (OR) b (NR2) c 、-O-SiR’3、-O-SiR3、-O-Si(R’) a (OR) b 、-O-Si(R) a (OR) b 、-O-Si(R’)a (NR2) b 、 -O-Si(R)a(NR2) b )、 -O-Si(R’) a (OR) b (NR2) c 、 or -O-Si(R) a (OR) b (NR2) c where each R’ is independently H, aliphatic, heteroaliphatic, aromatic, heteroaromatic, amino, hydrazino, azido, hydroxyl, silyl, silyloxy, cyanato, isocyanato, cyano, or isocyano, any of which may be optionally substituted, and each R is independently H, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, or optionally substituted heteroaromatic, and each of a, b, and c is ≥0, with a + b + c = 3 or a + b = 3 (when c is absent). In certain embodiments, R is H, optionally substituted alkyl, optionally substituted alkenyl, or optionally substituted alkynyl.

[0312] The precursor can include at least one R’ group bonded to a silicon atom. In one embodiment, the precursor is (R’)(H) 3-x Si(NR’’2) xhaving the formula, where R’ and R’’ can be any of those described herein, and x is 1, 2, or 3. In another embodiment, the precursor has the formula (R’)(H)2Si(NR’’2), where R’ and R’’ can be any of those described herein. In one embodiment, the precursor has the formula (R’)(H)Si(NR’’2)2, where R’ and R’’ can be any of those described herein. In another embodiment, the precursor has the formula (R’)2(H)Si(NR’’2), where R’ and R’’ can be any of those described herein. In yet another embodiment, the precursor has the formula (R’)2Si(NR’’2)2, where R’ and R’’ can be any of those described herein. In one embodiment, the precursor has the formula (R’)3Si(NR’’2), where R’ and R’’ can be any of those described herein.

[0313] The precursor may lack an R’ group bonded to the silicon atom. In one embodiment, the precursor is (H) 4-x Si(NR’’2) x having the formula, where each R’’ can independently be any of those described herein, and x is 1, 2, 3, or 4. In another embodiment, the precursor is Si(NR’’2) x having the formula, where each R’’ can independently be any of those described herein. In certain embodiments, each R’’ is independently aliphatic, heteroaliphatic, aromatic, or heteroaromatic.

[0314] The precursor can contain one or more hydrogen atoms bonded to the silicon atom. In one embodiment, the precursor has the formula (H)3Si(NR’’2) or (H)2Si(NR’’2)2 or (H)Si(NR’’2)3, where each R’’ can independently be any of those described herein. In certain embodiments, each R’’ is independently aliphatic, heteroaliphatic, aromatic, heteroaromatic, or amino, any of which may optionally be substituted.

[0315] The precursor can include a heterocyclyl group having a nitrogen atom. In one embodiment, the formula has the formula H3Si-Het, where Het is an optionally substituted heterocyclyl containing at least one nitrogen atom. In certain embodiments, the precursor is [Chemical Formula] having the formula, and the heterocyclyl group can be optionally substituted (e.g., with any of the substituents described herein as substituents for alkyl), and n is 1, 2, 3, 4, or 5. In one embodiment, the formula has the formula R’3Si-Het, where Het is an optionally substituted heterocyclyl containing at least one nitrogen atom, and each R’ can independently be any of those described herein. In certain embodiments, the precursor is [Chemical Formula] having the formula, the heterocyclyl group can be optionally substituted (e.g., with any of the substituents described herein as substituents for alkyl), each R’ can independently be any of those described herein, and n is 1, 2, 3, 4, or 5.

[0316] Optionally, the precursor can have two or more silicon atoms, and the precursor can include an Si-Si bond. In certain embodiments, the precursor is (R’’2N) x (R’) 3-x Si-Si(R’) 3-x (NR’’2) xhaving the formula, and R’ and R’’ can be any of those described herein. In one embodiment, the precursor has the formula (R’’2N)(R’)2Si-Si(R’)2(NR’’2), and R’ and R’’ can be any of those described herein. In another embodiment, the precursor has the formula (R’’2N)2(R’)Si-Si(R’)(NR’’2)2, and R’ and R’’ can be any of those described herein. In yet another embodiment, the precursor has the formula (R’’2N)3Si-Si(NR’’2)3, and each R’’ can independently be any of those described herein.

[0317] The precursor can include different groups bonded to silicon atoms. In one example, the precursor is (R’’2N) x (R’) 3-x having the formula Si-SiH3, and R’ and R’’ can be any of those described herein.

[0318] The linker can be present between two silicon atoms. In one example, the precursor is (R’’2N) x (R’) 3-x Si-NR-Si(R’) 3-x (NR’’2) x having the formula, and R’ and R’’ can be any of those described herein, and R is H, optionally substituted aliphatic, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, or optionally substituted aromatic. In another example, the precursor is (R’’2N) x (H) 3-x Si-NR-Si(H) 3-x (NR’’2) x having the formula, and R, R’, and R’’ can be any of those described herein.

[0319] The precursor can include a combination of a linker having an R' group and a heteroatom. In one example, the precursor has the formula (R’)3Si-NR-Si(R’)3, and R and R’ can be any of those described herein. In another example, the precursor has the formula (R’)3Si-L-Si(R’)3, and L and R’ can be any of those described herein. In certain embodiments, L is oxy (-O-), optionally substituted imino (e.g., -NR-), or optionally substituted silyl (e.g., -SiR2-).

[0320] The precursor can include any useful combination of R' groups and NR’’2 groups in combination with two silicon atoms. In one example, the precursor has the formula (R’’2N)(R’)2Si-L-Si(R’)2(NR’’2) x and L, R’, and R’’ can be any of those described herein.

[0321] The precursor can include a heterocyclic group containing a silicon atom and a nitrogen atom. In one embodiment, the precursor is

Chemical formula

[0322] In another embodiment, the precursor is

Chemical formula

Chemical formula

Chemical formula

[0323] In any of the precursors herein, two R’’s can combine with the nitrogen atom to which each is attached to form an optionally substituted heterocyclyl.

[0324] The precursor is any of the following, for example, (R Ak )Si(NH2)(NR Ak 2)2, (R Ak )Si(NR Ak 2)3, (R Ak )2Si(NHR Ak 2)2, (R Ak )(H)Si(NHR Ak )2, (R Ak )3Si(NR Ak 2), (R Ak )3Si(NHR Ak ), H2Si(NHR Ak 2)2, (R Ak )(H)Si(NR Ak 2)2, HSi(NH2)(NR Ak 2)2, HSi(NR Ak 2)3, Si(NR Ak 2)4, (R’)(H)Si(NR’’2)2, (R’)2Si(NR Ak 2)2, (R’)2Si(N[SiH3]2)2, (R’)2Si(N[SiR’’3]2)2, or (R’)3Si(NHR Akcan include. In some embodiments, each of R’ and R’’ can independently be any as described herein (e.g., H, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted alkyl, optionally substituted alkenyl, or optionally substituted alkynyl). In other embodiments, each R Ak is independently H, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted alkyl, optionally substituted alkenyl, or optionally substituted alkynyl. In certain embodiments, R Ak is methyl (Me), ethyl (Et), n-propyl (nPr), iso-propyl (iPr), n-butyl (nBu), sec-butyl (sBu), iso-butyl (iBu), tert-butyl (tBu), etc.

[0325] Non-limiting examples of precursors include any of the following: methylaminotrimethylsilane (SiMe3[NHMe]), dimethylaminodimethylsilane (SiMe2H[NMe2]), dimethylaminotrimethylsilane (SiMe3[NMe2]), dimethylaminodiethylsilane (SiHEt2[NMe2]), dimethylaminotriethylsilane (SiEt3[NMe2]), ethylmethylaminodimethylsilane (SiHMe2[NMeEt]), ethylmethylaminotrimethylsilane (SiMe3[NMeEt]), ethylmethylaminodiethylsilane (SiHEt2[NMeEt]), ethylmethylaminotriethylsilane (SiEt3[NMeEt]), diethylaminomethylsilane (SiH2Me[NEt2]), diethylaminoethylsilane (SiH2Et[NEt2]), ethylaminotrimethylsilane (SiMe3[NHEt]), diethylaminodimethylsilane (SiHMe2[NEt2]), diethylaminodiethylsilane (SiHEt2[NEt2]), diethylaminotrimethylsilane (SiMe3[NEt2]), diethylaminotriethylsilane (SiEt3[NEt2]), iso-propylaminodimethylsilane (SiHMe2[NHiPr]), iso-propylaminotrimethylsilane (SiMe3[NHiPr]), iso-propylaminodiethylsilane (SiHEt2[NHiPr]), iso-propylaminotriethylsilane (SiEt3[NHiPr]), di-isopropylaminotrimethylsilane (SiMe3[NiPr2]), di-iso-propylaminosilane (SiH3[NiPr2], C6H 17NSi, or DIPAS), di-iso-propylaminomethylsilane (SiH2Me[NiPr2]), di-isopropylaminodimethylsilane (SiHMe2[NiPr2]), di-isopropylaminodiethylsilane (SiHEt2[NiPr2]), di-isopropylaminotriethylsilane (SiEt3[NiPr2]), n-propylaminotrimethylsilane (SiMe3[NHnPr]), di-sec-butylaminosilane (SiH3[NsBu2] or DSBAS), di-sec-butylaminomethylsilane (SiH2Me[NsBu2]), iso-butylaminotrimethylsilane (SiMe3[NHiBu]), n-butylaminotrimethylsilane (SiMe3[NHnBu]), tert-butylaminodimethylsilane (SiHMe2[NHtBu]), tert-butylaminotrimethylsilane (SiMe3[NHtBu]), tert-butylaminodiethylsilane (SiHEt2[NHtBu]), tert-butylaminotriethylsilane (SiEt3[NHtBu]), dicyclohexylaminosilane (SiH3[NCy2], Cy is cyclohexyl), N-propylisopropylaminosilane (SiH3[NiPrnPr]), N-methylcyclohexylaminosilane (SiH3[NMeCy]), N-ethylcyclohexylaminosilane (SiH3[NEtCy]), allylphenylaminosilane (SiH3[NAllPh]), N-isopropylcyclohexylaminosilane (SiH3[NiPrCy]), allylcyclopentylaminosilane (SiH3[NAllCp]), phenylcyclohexylaminosilane (SiH3[NPhCy]), cyclohexylaminotrimethylsilane (SiMe3[NHCy], Cy is cyclohexyl), pyrrolyltrimethylsilane (SiMe3[NHPy], Py is pyrrolyl), pyrrolidinotrimethylsilane (SiMe3[NHPyr], Pyr is pyrrolidinyl), piperidinotrimethylsilane (SiMe3[NHPip], Pip is piperidinyl), piperazinotrimethylsilane (SiMe3[NHPz], Pz is piperazinyl), imidazolyltrimethylsilane (SiMe3[NHIm], Im is imidazolyl),Bis(dimethylamino)silane (SiH2[NMe2]2 or BDMAS), bis(dimethylamino)methylsilane (SiMeH[NMe2]2), bis(dimethylamino)dimethylsilane (SiMe2[NMe2]2 or BDMADMS), bis(dimethylamino)diethylsilane (SiEt2[NMe2]2), bis(dimethylamino)methylvinylsilane (SiMeVi[NMe2]2), bis(ethylamino)dimethylsilane (SiMe2[NHEt]2), bis(ethylmethylamino)silane (SiH2[NMeEt]2), bis(ethylmethylamino)dimethylsilane (SiMe2[NMeEt]2), bis(ethylmethylamino)diethylsilane (SiEt2[NMeEt]2), bis(ethylmethylamino)methylvinylsilane (SiMeVi[NMeEt]2), bis(diethylamino)silane (SiH2[NEt2]2, C8H, 22N2Si, or BDEAS), bis(diethylamino)dimethylsilane (SiMe2[NEt2]2), bis(diethylamino)methylvinylsilane (SiMeVi[NEt2]2), bis(diethylamino)diethylsilane (SiEt2[NEt2]2), bis(iso-propylamino)dimethylsilane (SiMe2[NHiPr]2), bis(iso-propylamino)diethylsilane (SiEt2[NHiPr]2), bis(iso-propylamino)methylvinylsilane (SiMeVi[NHiPr]2), bis(di-iso-propylamino)silane (SiH2[NiPr2]2), bis(di-iso-propylamino)dimethylsilane (SiMe2[NiPr2]2), bis(di-iso-propylamino)diethylsilane (SiEt2[NiPr2]2), bis(di-iso-propylamino)methylvinylsilane (SiMeVi[NiPr2]2), bis(methylamino)silane (SiH2[NHMe]2), bis(sec-butylamino)silane (SiH2[NHsBu]2), bis(sec-butylamino)methylsilane (SiHMe[NHsBu]2), bis(sec-butylamino)ethylsilane (SiHEt[NHsBu]2), bis(tert-butylamino)silane (SiH2[NHtBu]2 or BTBAS), bis(tert-butylamino)dimethylsilane (SiMe2[NHtBu]2), bis(tert-butylamino)methylvinylsilane (SiMeVi[NHtBu]2), bis(tert-butylamino)diethylsilane (SiEt2[NHtBu]2), bis(1-imidazolyl)dimethylsilane (SiMe2[Im]2, Im is imidazolyl), tris(dimethylamino)silane (SiH[NMe2]3 or 3DMAS), tris(dimethylamino)phenylsilane (SiPh[NMe2]3), tris(dimethylamino)methylsilane (SiMe[NMe2]3), tris(dimethylamino)ethylsilane (SiEt[NMe2]3), tris(ethylmethylamino)silane (SiH[NEtMe]3), tris(diethylamino)silane (SiH[NEt2]3), tris(iso-propylamino)silane (SiH[NHiPr]3, C9H 25N3Si, or TIPAS), tris(dimethylamino)silylamide (Si[NMe2]3[NH2]), tetrakis(dimethylamino)silane (Si[NMe2]4), tetrakis(ethylmethylamino)silane (Si[NEtMe]4), tetrakis(diethylamino)silane (Si[NEt2]4), 1,2 - diethyl - tetrakis(diethylamino)disilane ([Et2N]2EtSi - SiEt[NEt2]2), 1,2 - dimethyl - tetrakis(dimethylamino)disilane ([Me2N]2MeSi - SiMe[NMe2]2), 1,2 - dimethyl - tetrakis(diethylamino)disilane ([Et2N]2MeSi - SiMe[NEt2]2), hexakis(methylamino)disilane ([MeHN]3Si - Si[NHMe]3), hexakis(ethylamino)disilazane ([EtHN]3Si - Si[NHEt]3), hexakis(dimethylamino)disilazane (Me2N - Si[Me2]2 - Si[NMe2]2 - NMe2), etc.

[0326] Conclusion In the foregoing description, numerous specific details are set forth in order to provide a thorough understanding of the presented embodiments. The disclosed embodiments may be practiced without some or all of these specific details. In other instances, well - known process operations have not been described in detail so as not to unnecessarily obscure the disclosed embodiments. The disclosed embodiments are described in conjunction with specific embodiments, but it will be understood that the disclosed embodiments are not intended to be limiting.

[0327] The foregoing embodiments have been described in some detail for purposes of clarity of understanding, but it will be apparent that certain changes and modifications may be practiced within the scope of the appended claims. Note that there are many other ways to implement the processes, systems, and apparatuses of this embodiment. Accordingly, this embodiment should be regarded as illustrative and not restrictive, and those embodiments should not be limited to the details described herein.

Claims

1. A method for processing a substrate, comprising: Conformally depositing a silicon-containing film on one or more concave features of the substrate; Etching at least a portion of the silicon-containing film to at least one of a desired depth and a desired profile by exposing the substrate to a remote plasma. A method comprising the above steps.

2. The method according to claim 1, wherein The silicon-containing film comprises an amorphous silicon layer.

3. The method according to claim 1, wherein The silicon-containing film comprises silicon oxide, silicon nitride, silicon carbide, silicon oxycarbide, silicon carbonitride, silicon oxynitride, or silicon oxycarbonitride.

4. The method according to claim 3, wherein Conformally depositing the silicon-containing film comprises: Flowing a silicon-containing precursor to adsorb on the surface of the substrate; Thermally decomposing the silicon-containing precursor to form an amorphous silicon layer; Exposing the amorphous silicon layer to a plasma to convert the amorphous silicon layer to silicon oxide, silicon nitride, silicon carbide, silicon oxycarbide, silicon carbonitride, silicon oxynitride, or silicon oxycarbonitride.

5. The method according to claim 1, wherein Conformally depositing the silicon-containing film comprises: Depositing the silicon-containing film by thermal ALD or thermal CVD; Processing the silicon-containing film using a densification gas plasma. A method comprising the above steps.

6. The method according to claim 1, wherein At least one of the desired depth and the desired profile of the etching is based on one or more of the following etching parameters: chamber pressure, substrate temperature, exposure time, gas composition, relative concentration of the gas composition, and RF power.

7. A method for processing a substrate, comprising: Flowing a silane-based precursor into a reaction chamber for adsorption on one or more concave features of the substrate, the substrate being heated to thermally decompose the silane-based precursor and conformally deposit an amorphous silicon layer on the one or more concave features of the substrate; Generating a remote plasma containing radicals of hydrogen, halide, hydrocarbon, fluorocarbon, or a combination thereof in a remote plasma chamber upstream of the reaction chamber. In the reaction chamber, by adjusting one or more of the following etching parameters: chamber pressure, substrate temperature, exposure time, gas composition of the remote plasma, relative concentration of the gas composition, and RF power, exposing the substrate to the remote plasma to etch at least a part of the silicon-containing layer in the one or more concave features to at least one of a desired depth and a desired profile. A method comprising this.

8. A method for processing a substrate housed in a process chamber, comprising: Introducing a silicon-containing precursor and a reactant into the process chamber at a substrate temperature of less than about 700 °C to form a silicon-containing film on the substrate without igniting a plasma. After forming the silicon-containing film, performing a plasma treatment operation, the plasma treatment operation comprising: Stopping the flow of the silicon-containing precursor and the flow of the reactant; Introducing a densification gas into the process chamber; Igniting a plasma to treat the silicon-containing film; and Adjusting at least one of the silicon-containing precursor, the reactant, or process conditions during the plasma treatment operation to change at least the composition or density of the silicon-containing film to form a treated silicon-containing film. A method comprising this.

9. The method according to claim 8, further comprising: Etching at least a part of the treated silicon-containing film to at least one of a desired depth and a desired profile by exposing the substrate to a remote plasma. A method comprising this.

10. An apparatus for processing a substrate, comprising: One or more process chambers, each process chamber comprising a chuck; One or more gas inlets to the process chamber and associated flow control hardware; A controller having at least one processor and a memory, the at least one processor and the memory being communicatively connected to each other, the at least one processor being at least operatively connected to the flow control hardware, and the memory controlling the at least one processor; Forming a silicon-containing film on the substrate without igniting a plasma at a substrate temperature of less than about 700 °C; Treating the silicon-containing film using a densification gas plasma. An apparatus that stores computer-executable instructions for at least controlling the flow control hardware as described above.

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