Attorney Docket No. 10948-1WO/LAMRP827WO MIXED MODE ATOMIC LAYER DEPOSITION/ CHEMICAL VAPOR DEPOSITION INCORPORATED BY REFERENCE [0001] A PCT Request Form is concurrently with this specification as part of the present application. Each application that the present application claims benefit of or priority to as identified in the concurrently filed PCT Request Form is incorporated by reference herein in its entirety and for all purposes. BACKGROUND [0002] Semiconductor fabrication processes involve deposition of materials over substrates having a variety of topographies, including high aspect ratio features. It is challenging to deposit certain materials with high conformality and increased throughput. [0003] The background description provided herein is for the purposes of generally presenting the context of the disclosure. Work of the presently named inventors, to the extent it is described in this background section, as well as aspects of the description that may not otherwise qualify as prior art at the time of filing, are neither expressly nor impliedly admitted as prior art against the present disclosure. SUMMARY [0004] One aspect involves a method for processing a semiconductor substrate housed in a chamber, the method including: introducing a deposition precursor and a deposition reactant in alternating pulses without purging the chamber between the alternating pulses to form at least a partial film on a surface of the semiconductor substrate, whereby the pulses partially overlap temporally. [0005] In various embodiments, the deposition precursor is flowed without igniting a plasma. [0006] In various embodiments, the deposition reactant includes a gas mixture having an oxidant and argon. In some embodiments, the oxidant includes one or more gases selected from the group consisting of oxygen, nitrous oxide, nitric oxide, carbon dioxide, carbon monoxide, peroxides, and ozone. [0007] In various embodiments, the plasma is pulsed during the flow of the deposition reactant. [0008] In various embodiments, the deposition precursor includes an aminosilane. In various embodiments, the deposition precursor includes bis(tertiarybutylamino)silane. [0009] In various embodiments, the semiconductor substrate includes one or more features. In some embodiments, the partial film is deposited superconformally into at least one of the one or more features. In some embodiments, the partial film is deposited subconformally into at least one of the one or more features. In some embodiments, at least one of the one or more features
Attorney Docket No. 10948-1WO/LAMRP827WO include smooth sidewalls. In some embodiments, at least one of the one or more features has an aspect ratio of up to about 50:1. [0010] In various embodiments, the plasma is generated by dual frequency plasma. [0011] In various embodiments, the plasma is generated by single frequency plasma. [0012] In various embodiments, plasma power of the plasma is about 100W to about 6500W for a 4-station process chamber. [0013] In various embodiments, the partial film includes material selected from the group consisting of silicon oxide, silicon nitride, silicon carbide, silicon oxynitride, silicon oxycarbide, silicon carbonitride, and silicon oxycarbonitride. [0014] Another aspect involves method for processing a semiconductor substrate, the method including: providing the semiconductor substrate to a process chamber; introducing a deposition precursor to the process chamber housing the semiconductor substrate for a first duration having a first end time at which the deposition precursor is no longer introduced; and without purging the chamber, and prior to the first end time, introducing a deposition reactant and igniting a plasma for a second duration having a second end time, the second end time being after the first end time, whereby the deposition precursor and plasma react to form at least a partial film on a surface of the semiconductor substrate. [0015] In various embodiments, the method also includes repeating introducing the deposition precursor for a third duration, whereby the deposition precursor is introduced for the third duration prior to the second end time. [0016] In various embodiments, the deposition precursor is flowed without igniting a plasma. [0017] In various embodiments, the deposition reactant includes a gas mixture having an oxidant and argon. In some embodiments, the oxidant includes one or more gases selected from the group consisting of oxygen, nitrous oxide, nitric oxide, carbon dioxide, carbon monoxide, peroxides, and ozone. [0018] In various embodiments, the plasma is pulsed during the flow of the deposition reactant. [0019] In various embodiments, the deposition precursor includes an aminosilane. In various embodiments, the deposition precursor includes bis(tertiarybutylamino)silane. [0020] In various embodiments, the semiconductor substrate includes one or more features. In some embodiments, the partial film is deposited superconformally into at least one of the one or more features. In some embodiments, the partial film is deposited subconformally into at least one of the one or more features. In some embodiments, at least one of the one or more features include smooth sidewalls. In some embodiments, at least one of the one or more features has an aspect ratio of up to about 50:1.
Attorney Docket No. 10948-1WO/LAMRP827WO [0021] In various embodiments, the plasma is generated by dual frequency plasma. [0022] In various embodiments, the plasma is generated by single frequency plasma. [0023] In various embodiments, plasma power of the plasma is about 100W to about 6500W for a 4-station process chamber. [0024] In various embodiments, the partial film includes material selected from the group consisting of silicon oxide, silicon nitride, silicon carbide, silicon oxynitride, silicon oxycarbide, and silicon carbonitride. [0025] Another aspect involves a method for processing a semiconductor substrate, the method including: (a) starting a flow of a deposition precursor to a process chamber housing the semiconductor substrate to cause the semiconductor substrate to be exposed to the deposition precursor; (b) stopping the flow of the deposition precursor to the process chamber; (c) prior to stopping the flow of the deposition precursor, starting a flow of a deposition reactant to the process chamber and igniting a plasma to generate a plasma species to cause the semiconductor substrate to be exposed to the plasma species; (d) repeating (a) while the semiconductor substrate is exposed to the plasma species; and (e) prior to repeating (b), stopping the flow of the deposition reactant to the process chamber and quenching the plasma, whereby the deposition precursor and plasma react to form at least a partial film on a surface of the semiconductor substrate. [0026] In various embodiments, the deposition precursor is flowed without igniting a plasma. [0027] In various embodiments, the deposition reactant includes a gas mixture having an oxidant and argon. In some embodiments, the oxidant includes one or more gases selected from the group consisting of oxygen, nitrous oxide, nitric oxide, carbon dioxide, carbon monoxide, peroxides, and ozone. [0028] In various embodiments, the plasma is pulsed during the flow of the deposition reactant. [0029] In various embodiments, the deposition precursor includes an aminosilane. In various embodiments, the deposition precursor includes bis(tertiarybutylamino)silane. [0030] In various embodiments, the semiconductor substrate includes one or more features. In some embodiments, the partial film is deposited superconformally into at least one of the one or more features. In some embodiments, the partial film is deposited subconformally into at least one of the one or more features. In some embodiments, at least one of the one or more features include smooth sidewalls. In some embodiments, at least one of the one or more features has an aspect ratio of up to about 50:1. [0031] In various embodiments, the plasma is generated by dual frequency plasma. [0032] In various embodiments, the plasma is generated by single frequency plasma. [0033] In various embodiments, plasma power of the plasma is about 100W to about 6500W for
Attorney Docket No. 10948-1WO/LAMRP827WO a 4-station process chamber. [0034] In various embodiments, the partial film includes material selected from the group consisting of silicon oxide, silicon nitride, silicon carbide, silicon oxynitride, silicon oxycarbide, silicon carbonitride, silicon oxycarbonitride. [0035] Another aspect involves an apparatus for processing substrates, the apparatus including: one or more process chambers, each process chamber including a chuck; one or more gas inlets into the process chambers and associated flow-control hardware; and a controller having at least one processor and a memory, whereby the at least one processor and the memory are communicatively connected with one another, the at least one processor is at least operatively connected with the flow-control hardware, and the memory stores computer-executable instructions for controlling the at least one processor to at least control the flow-control hardware to: cause introduction of a deposition precursor and a deposition reactant in alternating, partially temporally overlapping pulses without purging the chamber between the alternating partially temporally overlapping pulses. [0036] These and other aspects are described further below with reference to the drawings. BRIEF DESCRIPTION OF THE DRAWINGS [0037] Figure 1 is a process flow diagram depicting operations that may be performed in accordance with certain disclosed embodiments. [0038] Figure 2 shows timing schematic diagrams of a plasma-enhanced atomic layer deposition (PEALD) process, a timing diagram, and a film thickness diagram corresponding to a process that may be performed in accordance with certain disclosed embodiments. [0039] Figure 3 is a schematic diagram of an example process chamber for performing certain disclosed embodiments. [0040] Figure 4 is a schematic diagram of an example process tool for performing certain disclosed embodiments. [0041] Figure 5 is a schematic diagram of an example process tool for performing certain disclosed embodiments. [0042] Figure 6 is a hysteresis curve for a film deposited by PEALD and a film deposited using certain disclosed embodiments. [0043] Figure 7 is a graph of electric field current density for a film deposited by PEALD and a film deposited by certain disclosed embodiments. DETAILED DESCRIPTION [0044] In the following description, numerous specific details are set forth to provide a thorough understanding of the presented embodiments. The disclosed embodiments may be practiced
Attorney Docket No. 10948-1WO/LAMRP827WO without some or all of these specific details. In other instances, well-known process operations have not been described in detail to not unnecessarily obscure the disclosed embodiments. While the disclosed embodiments will be described in conjunction with the specific embodiments, it will be understood that it is not intended to limit the disclosed embodiments. [0045] Semiconductor fabrication processes involve depositing films for particular applications. One example method of depositing films is atomic layer deposition (ALD). Deposition of thin films using ALD is achieved through alternating inert gas purge-separated gas-solid surface reactions, resulting in cyclic, layer-by-layer film deposition. [0046] ALD may be used to deposit material such as silicon-containing material. In thermal ALD, the reaction between a silicon-containing precursor and a reactant forms a silicon-containing film. ALD is a technique that deposits thin layers of material using sequential self-limiting reactions. Typically, an ALD cycle includes operations to deliver and adsorb at least one reactant to the substrate surface, and then react the adsorbed reactant with one or more reactants to form the partial layer of film. As another example, a silicon oxide deposition cycle may include the following operations: (i) delivery/adsorption of a silane precursor, (ii) purging of the silane precursor from the chamber, (iii) delivery of an oxygen-containing gas, and (iv) purging of the oxygen-containing gas from the chamber. [0047] Unlike a chemical vapor deposition (CVD) technique, ALD processes use surface mediated deposition reactions to deposit films on a layer-by-layer basis. In one example of an ALD process, a substrate surface that includes a population of surface active sites is exposed to a gas phase distribution of a first precursor, such as a silicon-containing precursor, in a dose provided to a chamber housing a 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 the compound is adsorbed onto the substrate surface as described herein, the adsorbed layer may include the compound as well as derivatives of the compound. For example, an adsorbed layer of a silicon-containing precursor may include the silicon-containing precursor as well as derivatives of the silicon-containing precursor. After a first precursor dose, the chamber is then evacuated to remove most or all of the silicon-containing precursor remaining in gas phase so that mostly or only the adsorbed species remain. In some implementations, the chamber may not be fully evacuated. For example, the chamber may be evacuated such that the partial pressure of the first precursor in gas phase is sufficiently low to mitigate a reaction. A second reactant, such as an oxygen-containing reactant, is introduced to the chamber so that some of these molecules react with the silicon-containing precursor adsorbed on the surface. In some processes, the second reactant reacts immediately with the adsorbed silicon-containing precursor.
Attorney Docket No. 10948-1WO/LAMRP827WO The chamber may then be evacuated again to remove unbound second reactant molecules. As described above, in some embodiments the chamber may not be completely evacuated. Additional ALD cycles may be used to build film thickness. [0048] In certain embodiments, an ALD first precursor dose partially saturates the substrate surface. In some embodiments, the dose phase of an ALD cycle concludes before the precursor contacts the substrate to evenly saturate the surface. Typically, the precursor flow is turned off or diverted at this point, and only purge gas flows. By operating in this sub saturation regime, the ALD process reduces the cycle time and increases throughput. However, because precursor adsorption is not saturation limited, the adsorbed precursor concentration may vary slightly across the substrate surface. Examples of ALD processes operating in the sub-saturation regime are provided in U.S. Patent Application No. 14/061,587 (now U.S. Patent No. 9,355,839), filed October 23, 2013, titled “SUB-SATURATED ATOMIC LAYER DEPOSITION AND CONFORMAL FILM DEPOSITION,” which is incorporated herein by reference in its entirety. [0049] In some implementations, ALD methods may include plasma activation. In some implementations, ALD methods may not include plasma activation. As described herein, the ALD methods and apparatuses described herein may be conformal film deposition (CFD) methods, which are described generally in U.S. Patent Application No. 13/084,399 (now U.S. Patent No. 8,728,956), filed April 11, 2011, and titled “PLASMA ACTIVATED CONFORMAL FILM DEPOSITION,” and in U.S. Patent Application No. 13/084,305, filed April 11, 2011, and titled “SILICON NITRIDE FILMS AND METHODS,” which are herein incorporated by reference in their entireties. [0050] Plasma-enhanced ALD (PEALD) is a form of ALD that involves igniting a plasma during conversion of the adsorbed precursor layer to a film. In PEALD of oxide films, an oxygen-based plasma is used to convert the precursor ligands resulting from the gas-solid surface reaction with the precursor in a prior operation. Furthermore, in PEALD, the plasma can be left on after complete conversion of the surface ligands has taken place to densify the underlying film, thereby improving bulk material properties. However, one significant limitation to widespread adoption of PEALD is the low throughput compared to other techniques, which may be because of the temporally- separated and lengthy dose/RF/purging operations. There is also a higher degree of precursor waste in PEALD owing to the dose and purge operations, where excess dose is blocked from further surface reactions (an intrinsic feature of ALD chemistries) and pumped or purged away. [0051] PEALD is a subset of plasma-enhanced chemical vapor deposition (PECVD), where in PECVD similar chemistries and plasmas are used to deposit a film by continuous gas phase or gas- solid surface reactions. One of the benefits of PECVD is the higher deposition rate compared to
Attorney Docket No. 10948-1WO/LAMRP827WO PEALD. However, because the reactions can happen in the gas phase, particulates or contaminants may be higher in PECVD processes, and film growth is not easily controlled for thinner films. Furthermore, given that the precursor is subjected to a plasma, impurities from precursor ligand decomposition/breakdown can incorporate into the deposited film, resulting in inferior film properties as compared to PEALD. Additionally, films deposited by PECVD are often subconformal and results in thicker deposition of the film at or near the top of features. [0052] PEALD may be used to deposit linear oxides in nano through silicon via structures as devices continue to scale to smaller sizes. However, PEALD is still limited in present and future applications owing to its low throughput compared to other methods such as CVD (PECVD, sub- atomic chemical vapor deposition (SACVD), TEOS, etc.). [0053] Provided herein are methods and apparatuses that combine properties of PEALD and PECVD to target the excellent film quality of PEALD and possibly conformality and higher throughput of PECVD. The combined PEALD and PECVD process used herein may be referred to as “mixed mode ALD/CVD” or “MM-ALD/CVD.” MM-ALD/CVD combines aspects of PEALD and PECVD to improve wafer throughput and maintain or improve film material properties and conformality. MM-ALD/CVD is different from PEALD because it does not separate the RF and dose with inert gas purges, in favor of partially overlapping operations to achieve PECVD-like growth. MM-ALD/CVD is different from PECVD because it is not a continuous deposition process. While combining aspects of both processes, it separates itself from both techniques by its unique precursor dosing and RF exposure methodology. [0054] In certain disclosed embodiments, MM-ALD/CVD is performed by eliminating purge operations in a PEALD deposition cycle. For example, one embodiment may involve temporally alternating pulses between a dose (deposition precursor exposure) and RF (deposition reactant with plasma exposure) without purging between pulses. Eliminating purging has a particular advantage of reducing chemistry waste in that the chemistries introduced to the process chamber are used to form a film on the semiconductor substrate and no excess material is purged or removed. Purging and burst purges are described herein to refer to the same process, which may involve evacuating a chamber, flowing one or more purge gases, or both. In certain disclosed embodiments, MM-ALD/CVD is performed by eliminating purge operations and partially temporally overlapping the beginning of a dose with the end of an RF exposure, or partially temporally overlapping the beginning of an RF exposure with the end of a dose, or both. During the partial temporally overlap, the substrate is exposed to the dose and the reactant plasma simultaneously, resulting in PECVD-like deposition. However, because overlapping exposures temporally is not performed continuously, the cyclic nature of a PEALD-like process is
Attorney Docket No. 10948-1WO/LAMRP827WO maintained, which helps allow deposition of films that are more conformal than that of PECVD. [0055] Unlike PEALD which is limited by low throughput, PECVD-like overlapping of precursor injection (dose) and RF (plasma, such as oxygen-based plasma, nitrogen-containing plasma, and/or carbon-containing plasma) operations can help improve per-cycle and per-second deposition rate. MM-ALD/CVD involves alternating dose and plasma exposure operations, similar to ALD, but without purging operations and with some overlap between the dose and RF operations resulting in short bursts of PECVD. Certain disclosed embodiments allow the dose to penetrate features with a high aspect ratio and/or to spread across a wafer surface, even ones with complex topographies, as well as allow the plasma to densify the deposited film without simultaneous film deposition for improvement in material properties over both PEALD and PECVD. Additionally, in various embodiments, the precursor may be used more efficiently over conventional PEALD as it is consumed during the PECVD-like operation instead of being purged away. Furthermore, as compared to PEALD which may deposit superconformally (which is defined as having greater than about 100% step coverage) in vertical structures and PECVD which may deposit subconformally (which is defined as having less than about 100% step coverage), certain disclosed embodiments allow tuning of mixed mode ALD/CVD to achieve near perfect conformality. In some embodiments, superconformal deposition results in thinner deposition at or near the feature opening of a feature and thicker deposition at or near the bottom of the feature. In some embodiments, subconformal deposition results in thicker deposition at or near the feature opening of a feature and thinner deposition at or near the bottom of the feature. [0056] In various embodiments the per-angstrom RF budget may be increased, resulting in better material properties (lower wet etch rate, higher density, better electrical properties such as lower dielectric constant or lower leakage current). In some embodiments, not only is the throughput of the deposition process improved over PEALD, but the resulting material properties have also slightly improved over both PEALD and PECVD. [0057] Certain disclosed embodiments are capable of depositing highly conformal films. Conformality of films may be measured by the step coverage. Step coverage may be calculated by comparing the average thickness of a deposited film on a bottom, sidewall, or top of a trench to the average thickness of a deposited film on a bottom, sidewall, or top of a feature or trench. A “feature” of a substrate may be a via or contact hole, which may be characterized by one or more of narrow and/or re-entrant openings, constrictions within the feature, and a high aspect ratio. High aspect ratio may refer to features having an aspect ratio of at least about 10:1 or at least about 15:1 or at least about 20:1 or at least about 50:1 or at least about 100:1 or at least about 150:1 or at least about 200:1. The terms “trench” and “feature” may be used interchangeably in the present
Attorney Docket No. 10948-1WO/LAMRP827WO disclosure and will be understood to include any hole, via, or recessed region of a substrate. [0058] One example of step coverage may 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 it by 100 to obtain a percentage. Although ALD can deposit highly conformal films, deposition of films into high aspect ratio features becomes challenging. The step coverage and uniformity of film property along the sidewall depends on, among many factors, the transport of the deposition precursor, reactant ions and/or radicals (such as those generated by igniting a reactant gas with a plasma), and by-products. As the dimension of the trench is reduced, the transport becomes increasing difficult in the trench leading to formation of a seam and/or voids in high aspect ratio trenches. [0059] Figure 1 shows a process flow diagram depicting operations that may be performed using certain disclosed embodiments. In operation 102, a semiconductor substrate is provided to a process chamber. In some embodiments, the process chamber is a station within a multi-station chamber. Process conditions described herein are suitable for a single-wafer chamber. [0060] The process chamber may be set to a chamber pressure about 0.1 Torr to about 20 Torr. Such chamber pressures may be used throughout operations 104-112 as described herein. In some embodiments, chamber pressure may be different during different operations. The chamber pressure may also depend on the chemistries selected for various operations described herein. [0061] The substrate may be heated to a substrate temperature about 50°C to about 650°C during operations 104-108. It will be understood that substrate temperature as used herein refers to the temperature that the pedestal holding the substrate is set at and that in some embodiments, the substrate when provided to the process chamber on the pedestal may be heated to the desired substrate temperature prior to processing the substrate. The substrate temperature may be the same throughout operations 102-112 as described herein. [0062] The substrate may be any suitable substrate. The substrate may be a silicon wafer, e.g., a 200-mm wafer, a 300-mm wafer, including wafers having one or more layers of material, such as dielectric, conducting, or semi-conducting material deposited thereon. Non-limiting examples of under layers include dielectric layers and conducting layers, e.g., silicon oxides, silicon nitrides, silicon carbides, metal oxides, metal nitrides, metal carbides, and metal layers. In some embodiments, the substrate includes silicon oxide and silicon. In some embodiments, the substrate includes a partially fabricated 3D-NAND structure. [0063] In some embodiments, there are no features on the substrate. In some embodiments, the feature(s) may have an aspect ratio of at least about 1:1, at least about 2:1, at least about 4:1, at least about 6:1, at least about 10:1, or at least about 20:1, or at least about 50:1, or up to about
Attorney Docket No. 10948-1WO/LAMRP827WO 50:1. The feature(s) may also have a dimension near the opening, e.g., an opening diameter or line width of between about 10 nm to 500 nm, for example between about 25 nm and about 300 nm. Disclosed methods may be performed on substrates with feature(s) having an opening less than about 100 μm, or less than about 10 μm. A via, trench or other recessed feature may be referred to as an unfilled feature or a feature. According to various embodiments, the feature profile may narrow gradually and/or include an overhang at the feature opening. A re-entrant profile is one that narrows from the bottom, closed end, or interior of the feature to the feature opening. A re-entrant profile may be generated by asymmetric etching kinetics during patterning and/or the overhang due to non-conformal film step coverage in the previous film deposition, such as deposition of a diffusion barrier. In various examples, the feature may have a width smaller in the opening at the top of the feature than the width of the bottom of the feature. In some embodiments, the feature profile may have topography on the sidewalls of the feature; for example, there may be protrusions on a sidewall of the feature. In some embodiments, the feature profile may have one or more smooth sidewalls. [0064] In some embodiments, the substrate may be partially fabricated for forming a memory device. In some embodiments, exposed regions of the substrate include silicon-containing surfaces, including but not limited to low-k dielectric material, silicon oxide, silicon nitride, silicon oxynitride, silicon oxycarbide, silicon carbonitride, and silicon carbide. In some embodiments, exposed regions of the substrate include silicon oxynitride. [0065] In operation 104, a deposition precursor may be introduced to the process chamber without igniting a plasma. Operation 104 may be performed in a plasma-free environment. The deposition precursor is introduced without generating a plasma. The deposition precursor is introduced thermally. [0066] The deposition precursor is flowed to the process chamber through one or more inlets. In some embodiments, multiple deposition precursors may be introduced, or the deposition precursor may include a mixture of multiple gases. [0067] In some embodiments, the deposition precursor is flowed with a carrier gas. In some embodiments, the carrier gas is diverted prior to delivery of the deposition precursor to the process chamber. In some embodiments, the carrier gas is also delivered with the deposition precursor to the process chamber. In some embodiments, operation 104 involves introducing the deposition precursor after providing the semiconductor substrate before the desired material is deposited onto the semiconductor substrate. In some embodiments, operation 104 involves the first flow of deposition precursor to the process chamber. In some embodiments, the process chamber has an ambient environment that does not include any plasma species. Flow in operation 104 maybe
Attorney Docket No. 10948-1WO/LAMRP827WO referred to as a “dose.” During this “dose,” the substrate may be saturated with the deposition precursor, such as it might in ALD processes. The deposition precursor may be adsorbed to exposed surfaces of the semiconductor substrate. [0068] In some embodiments, the deposition precursor is a silicon-containing precursor. In various embodiments, the silicon-containing precursor is a silane. Non-limiting examples of silanes that may be used include but are not limited to substituted and unsubstituted silanes, halosilanes, aminosilanes, organosilanes, alkylsilanes, alkylaminosilanes, and alkylhalosilanes. Additional examples of silicon-containing precursors are included elsewhere herein such as in the Definitions and Precursors section. In some embodiments, the silicon-containing precursor is a halosilane such as one or more of the following: dichlorosilane (DCS), hexachlorodisilane (HCDS), tetrachlorosilane, or other chlorosilane precursors. [0069] In some embodiments, the silicon-containing precursor may be flowed at a flow rate of about 100 sccm to about 2000 sccm for a single-wafer chamber. The silicon-containing precursor may be flowed with an inert push gas, such as nitrogen gas or argon gas or a mixture of nitrogen and argon gas. The flow rate of the inert push gas may be about 300 sccm to about 1500 sccm for a single-wafer chamber. [0070] Operation 104 may be performed for a duration of about 0.1 second to about 100 seconds or about 0.1 second to about 5 seconds, or about 0.1 second to about 1 second. The duration may depend on the process conditions and semiconductor substrate topography. The duration may be selected so as to be sufficient to adsorb the deposition precursor onto exposed surfaces of the semiconductor substrate. The duration may be selected so as to not oversaturate the exposed surfaces of the semiconductor substrate with the deposition precursor. [0071] During operation 104, the process chamber may have a chamber pressure of about 0.1 Torr to about 20 Torr. In some embodiments, additional nitrogen gas may be introduced with the silicon-containing precursor and/or the inert push gas for dilution, for pressure stability, or both. The additional nitrogen gas may be flowed at a flow rate of about 500 sccm to about 2000 sccm for a single-wafer chamber. In one example, dichlorosilane is introduced to a chamber housing the substrate at a flow rate of about 1000 sccm for about 5 seconds at a chamber pressure of about 9.5 Torr in a plasma-free environment. [0072] In operation 106, after the deposition precursor flow begins and while the deposition precursor is flowing to the process chamber, flow of a deposition reactant to the process chamber is started and a plasma is ignited to form a reactant plasma species (e.g., a plasma species generated from igniting the deposition reactant). The reactant may be delivered to the process chamber with one or more inert gases, which may be carrier gases. In some embodiments, the carrier gas is
Attorney Docket No. 10948-1WO/LAMRP827WO diverted prior to delivery of the reactant to the process chamber. In some embodiments, the carrier gas is not diverted prior to delivery of the reactant to the process chamber. The inert gas may be argon in some embodiments. In some embodiments, argon is delivered prior to delivering the deposition reactant. In various embodiments, both the inert gas and the reactant are ignited in the plasma, which generates plasma species. In some embodiments, argon plasma is generated. [0073] During operation 106, the deposition reactant reacts with the saturated deposition precursor on a surface of the substrate, which results in a PEALD-like reaction. However, where the deposition precursor continues to flow, in some embodiments there may also be PECVD-like reactions taking place. [0074] The deposition reactant selected depends on the film to be deposited. In some embodiments, for depositing silicon oxide for example, an oxidant is used as the deposition reactant. Example oxidants include but are not limited to oxygen, nitrous oxide, nitric oxide, carbon dioxide, carbon monoxide, peroxides, ozone, and the like. In some embodiments, a mixture of oxidants may be used. For example, in some embodiments, a mixture of nitrous oxide and oxygen may be used. While oxygen-containing reactants are described herein, it will be understood that the deposition reactant may be another reactant, such as a nitrogen-containing reactant (for example for depositing nitrogen-containing films, such as silicon nitride), carbon- containing reactant (for example for depositing carbon-containing films, such as silicon carbide), or hydrogen or another reactant. More than one reactant may be used and relative amounts of each reactant may be used depending on the desired composition of the deposited film. For example, a mixture of oxygen-containing gases and nitrogen-containing gases may be used to form silicon oxynitride. In some embodiments, multiple deposition reactants may be sequentially introduced or introduced from one or more inlets to a process chamber housing the semiconductor substrate. In some embodiments, a mixture of hydrogen gas and/or other gases to form a reducing atmosphere may be used during deposition of silicon. [0075] The plasma may be generated using a single frequency plasma. The plasma may be generated using a dual frequency plasma. Microwave, inductively coupled, and/or capacitively coupled plasma may be used. The plasma may be generated remotely or in situ. [0076] In various embodiments, the plasma power used for a 4-station process chamber is about 100 W to about 6500 W which may be used in single frequency plasma or either the high frequency plasma or low frequency plasma in dual frequency plasma. In various embodiments, the plasma frequency is set to 0.4 MHz to about 27 MHz. The plasma generated in this operation may have a plasma power of about 100W to about 6500W. In various embodiments, the plasma may be an inductively coupled plasma or a capacitively coupled plasma. An inductively coupled plasma may
Attorney Docket No. 10948-1WO/LAMRP827WO be set at a plasma between about 100W to about 6500W. In some embodiments, a bias may be applied between about 0V and about 1000V. [0077] In some embodiments, the plasma both converts adsorbed deposition precursor, and ambient deposition precursor, to the film material and densifies the film material as it is being deposited onto a surface of the semiconductor substrate. Prolonged durations may be advantageous in some embodiments to allow further densification and improvement of some film characteristics. [0078] In some embodiments, after operation 104, operation 106 is performed in such way that the flow of deposition precursor is stopped, then the process chamber is optionally purged, and then the reactant flow begins and a plasma is ignited to form a reactant plasma species. In some embodiments, purging is performed between stopping the deposition precursor flow and beginning reactant flow. Purging may be performed by introducing one or more purge gases which may be inert gases into the process chamber. Example inert or purge gases include but are not limited to nitrogen gas and argon. Flow rate of the inert or purge gas during purging is about 1000 sccm to about 40000 sccm for a single-wafer chamber. Introduction of the inert or purge gas may be performed for a duration of about 0.1 second to about 10 seconds. During purging, the chamber pressure may be about 0.5 Torr to about 22 Torr. In one example, argon gas is introduced at a flow rate of about 10000 sccm for about 10 seconds at a chamber pressure of about 9.5 Torr. Purging is performed without igniting a plasma. Purging is performed in a plasma-free environment. [0079] In various embodiments, purging is not performed, and flow of the deposition precursor and flow the deposition reactant overlap partially. [0080] In operation 108, after a designated time (in which both the deposition precursor and the reactant are flowed), the deposition precursor flow is stopped while the deposition reactant continues to flow and plasma continues to be generated. Stopping of the deposition precursor flow may be referred to as ending a “dose” of the precursor. The remaining deposition precursor in the chamber may react with the deposition reactant in a PECVD-like reaction and the deposition precursor adsorbed on the semiconductor substrate surfaces may react with the deposition reactant in a PEALD-like reaction, thereby forming material on the substrate surface using a higher deposition rate than if using PEALD alone. [0081] The designated amount of time in which the deposition precursor and reactant flows overlap depends on the chemistries of the precursor and reactants used, particular application of the film being deposited, film topography, process conditions, and other factors. In some embodiments, the overlap time may be very short, such as about 0.5 seconds or less.
Attorney Docket No. 10948-1WO/LAMRP827WO [0082] In operation 110, after a designated time (in which the reactant is flowed while the deposition precursor is not flowed and plasma continues to be generated), flow of the deposition precursor is started again while the reactant is still flowing and plasma is still being generated. This is performed without stopping flow of the reactant and/or without an intervening purging operation between flow of the reactant and the repeated flow of the deposition precursor. Here, the deposition precursor is introduced into a stable plasma environment, which allows PECVD- like reactions between the deposition precursor and the reactant. Introducing the deposition precursor into a stable plasma environment may result in unexpectedly good results for forming high quality films that are surprisingly still conformal. [0083] In operation 112, the reactant flow is stopped and the plasma is no longer generated and/or the plasma species are no longer introduced to the plasma chamber while the deposition precursor is flowed. Operations 106-112 may be repeated in multiple cycles. In some embodiments, one cycle involves one dose and one RF plasma exposure. In some embodiments, a cycle is about 0.5 second to about 10 seconds, or about 0.5 second to about 1 second. In some embodiments, the duration of temporally partially overlapping between RF plasma and dose is about 0.001 second to about 0.1 second, or about 0.001 second to about 0.09 second, or about 0.01 second to about 0.9 second. [0084] In some embodiments, the duration in which the RF plasma is on is about 0.1 second to about 10 seconds. In some embodiments the RF plasma is on for about 0.2 second to about 0.7 seconds. The duration of the dose, the duration of overlap between dose and RF plasma, the duration of the RF plasma being on, and the duration of the overlap between the RF plasma and the dose depends on the deposition precursors, deposition reactant, RF plasma conditions, and the topography of the semiconductor substrate and any features that are to be filled with material deposited by certain disclosed embodiments. [0085] Figure 2 shows a comparison of timing schematics comparing a PEALD process 250 as compared to MM-ALD/CVD process 260. In PEALD process 250, three process conditions are depicted in horizontal lines – 201 represents when the purging is performed (e.g., “BP” represents “burst purge”), 203 represents when the dosing or the introduction of the deposition precursor occurs, and 205 represents when the plasma (or RF/radio frequency) is performed (which may be referred to as “conversion” of the precursor to the film in a PEALD cycle) with introduction of the deposition reactant. One PEALD cycle includes a dose, a burst purge, and an RF conversion operation. RFP refers to purging after RF conversion (e.g., “RF purge”). As shown, the cycle is then repeated with an additional dose, burst purge, then another RF conversion, etc. [0086] In MM-ALD/CVD process 260, three process conditions are also depicted in horizontal
Attorney Docket No. 10948-1WO/LAMRP827WO lines – 211 represents when purging is performed, 213 represents when the dosing or the introduction of the deposition precursor occurs, and 215 represents when the RF is introduced. As shown, purging is never performed. In this example, while RF conversion is on, the precursor is dosed with partial overlap; that is the RF is still on while the dose is introduced, but the RF is turned off while the dose is still on. Subsequently, the RF is turned on again while the dose is still on, then the dose is turned off while the RF continues to be on for an extended RF budget. The partial overlap between the dose and RF exposure results in PECVD-like deposition during that overlapping time. The graph 270 shows the relative deposition thickness during the corresponding timing schematic. The initial deposition thickness increases at curve 221a where the dose is introduced while RF is on. When the RF is stopped, the deposition still grows as shown in the curve 223, though at a slower pace, and subsequently when the RF is turned on again, growth increases rapidly resulting a curve 225. When the dose is subsequently stopped again, conversion and densification occurs as shown at dose capture 227. During dose capture 227, some residual deposition precursor remains in gas phase and can be captured in a PECVD-like gas phase and/or surface/solid reaction and converted into film material. Then as RF is on for an extended amount of time as shown in curve 229, film thickness growth does not increase as quickly. When the dose is then reintroduced again before stopping the RF, additional growth is shown in curve 221b. The cycle may subsequently repeat multiple times. Cycles are performed without any purging between dosing and RF conversion, and dose and RF conversion are partially overlapping at the beginning and end of each dose. Without being bound by a particular theory, it is believed that introducing a dose of a deposition precursor into an active plasma (such as at 221a) results in a center-high thickness (domed) profile on a substrate surface, and striking a plasma during the end of a dose of a precursor (such as at 225) results in PECVD-like deposition towards the outer wafer edges resulting in an edge-high (dished) profile. [0087] Certain disclosed embodiments surprisingly yielded films with better quality, higher density, improved leakage, reduced wet etch rate, improved adhesion, and reduced stress. Certain disclosed embodiments may be modified depending on the application of the process. For example, as noted above, in some embodiments, a purging operation may be performed after dose prior to introduction of the deposition reactant and igniting of the plasma which may be done in one or some or all cycles of MM-ALD/CVD. Another modification that may be performed is by modulating or tuning the dose gas mixture. For example, the flow rate ratio of one or more gases flowed during dose may be modified. For example, BTBAS may be used as a deposition precursor. During dose, BTBAS may be introduced with an inert gas, such as argon. The ratio of the flow rate of BTBAS to flow rate of argon may be modulated to achieve particular film characteristics.
Attorney Docket No. 10948-1WO/LAMRP827WO For example, in some embodiments, the ratio of flow rate of deposition precursor to flow rate of inert gas may be at least about 1:1, or at least about 1:2, or at least about 1:3, or at least about 1:10, or at least about 1:100, or about 1:1 to about 1:2, or about 1:2 to about 1:3, or about 1:1 to about 1:10, or about 1:1 to about 1:100, or about 1:2 to about 1:10, or about 1:2 to about 1:100, or about 1:10 to about 1:100. In some embodiments, a ratio of flow rate of deposition precursor to flow rate of inert gas (such as about 1:2 to about 1:3) can form a center-high deposition profile using certain disclosed embodiments because there may be more precursor molecules being converted where it is being introduced near the center of the showerhead. In some embodiments, a flow rate ratio of deposition precursor to flow rate of inert gas of about 1:10 or greater may result in uniform deposition by diluting the dose/plasma mixture. The film may be more uniform than if using a flow rate ratio of less than about 1:10. In some embodiments, a flow rate ratio of deposition precursor to flow rate of inert gas of about 1:100 or greater may improve step coverage by reducing gas-phase reactions by using highly diluted precursor mixtures. While such examples are described herein, it will be understood that such trends are not limiting and that certain flow rate ratios may also be used to modulate other properties of the deposited film besides uniformity and deposition profile. [0088] In some embodiments, a combination of MM-ALD/CVD with one or more of PEALD, ALD, PECVD, and/or CVD may be used. For example, for certain applications, initial deposition to fill a high aspect ratio feature may be performed using MM-ALD/CVD, but as the feature is filled, it may be suitable to use PECVD to fill the rest of the material. In some embodiments, a combination of performing PECVD or PEALD followed by MM-ALD/CVD may be used. For example, in some embodiments, a feature having protrusions on a sidewall of the feature may be filled by first performing PEALD to create a smoother sidewall, followed by performing MM- ALD/CVD to fill the rest of the feature. [0089] Certain disclosed embodiments may also be combined with other techniques, including but not limited to post-deposition treatment, such as plasma treatment. Additionally, in certain embodiments, a dose may be pulsed, or RF exposure may be pulsed, or both, depending on the application. In some embodiments, generation of the plasma during RF exposure is pulsed between turning the plasma on and turning the plasma off. In some embodiments, generation of the plasma during RF exposure is pulsed between low plasma power and high plasma power. In some embodiments, generation of the plasma during RF exposure is pulsed at a frequency lower than the RF frequency with varying duty cycles. The pulsing frequency may be about 0.00001 to 0.001 of the RF plasma frequency, with the duty cycle ranging from about 10% to about 90%.
Attorney Docket No. 10948-1WO/LAMRP827WO APPARATUS [0090] Figure 3 depicts a schematic illustration of an embodiment of a process station 300 having a process chamber body 302. In various embodiments, a single process station 300 is implemented in a tool such as shown in Figure 3. In some embodiments, a plurality of process stations 300 may be included in a low pressure process tool environment. For example, Figure 5 depicts an embodiment of a multi-station processing tool 500. In some embodiments, one or more hardware parameters of process station 300 including those discussed in detail below may be adjusted programmatically by one or more computer controllers 350. [0091] Process station 300 fluidly communicates with reactant delivery system 301a for delivering process gases to a showerhead 306. Reactant delivery system 301a includes a mixing vessel 304 for blending and/or conditioning process gases, such as a silicon-containing precursor gas, or oxygen-containing gas, or inert gas for delivery to showerhead 306. One or more mixing vessel inlet valves 320 may control introduction of process gases to mixing vessel 309. One or more valves 305 may control introduction of gases to the showerhead 306. [0092] As an example, the embodiment of Figure 3 includes a vaporization point 303 for vaporizing liquid reactant to be supplied to the mixing vessel 304. In some embodiments, vaporization point 303 may be a heated vaporizer. The saturated reactant vapor produced from such vaporizers may condense in downstream delivery piping. Exposure of incompatible gases to the condensed reactant may create small particles. These small particles may clog piping, impede valve operation, contaminate substrates, etc. Some approaches to addressing these issues involve purging and/or evacuating the delivery piping to remove residual reactant. However, purging the delivery piping may increase process station cycle time, degrading process station throughput. Thus, in some embodiments, delivery piping downstream of vaporization point 303 may be heat traced. In some examples, mixing vessel (not shown) may also be heat traced. In one non-limiting example, piping downstream of vaporization point 303 has an increasing temperature profile extending from approximately 30°C to approximately 55°C or from about 60°C to about 65°C at mixing vessel. [0093] In some embodiments, liquid precursor or liquid reactant may be vaporized at a liquid injector. For example, a liquid injector may inject pulses of a liquid reactant into a carrier gas stream upstream of the mixing vessel. In one embodiment, a liquid injector may vaporize the reactant by flashing the liquid from a higher pressure to a lower pressure. In another example, a liquid injector may atomize the liquid into dispersed microdroplets that are subsequently vaporized in a heated delivery pipe. Smaller droplets may vaporize faster than larger droplets, reducing a delay between liquid injection and complete vaporization. Faster vaporization may reduce a length
Attorney Docket No. 10948-1WO/LAMRP827WO of piping downstream from vaporization point 303. In one scenario, a liquid injector may be mounted directly to mixing vessel. In another scenario, a liquid injector may be mounted directly to showerhead 306. [0094] In some embodiments, a liquid flow controller (LFC) upstream of vaporization point 303 may be provided for controlling a mass flow of liquid for vaporization and delivery to process station 300. For example, the LFC may include a thermal mass flow meter (MFM) located downstream of the LFC. A plunger valve of the LFC may then be adjusted responsive to feedback control signals provided by a proportional-integral-derivative (PID) controller in electrical communication with the MFM. However, it may take one second or more to stabilize liquid flow using feedback control. This may extend a time for dosing a liquid reactant. Thus, in some embodiments, the LFC may be dynamically switched between a feedback control mode and a direct control mode. In some embodiments, this may be performed by disabling a sense tube of the LFC and the PID controller. [0095] Showerhead 306 distributes process gases toward substrate 312. In the embodiment shown in Figure 3, the substrate 312 is located beneath showerhead 306 and is shown resting on a pedestal 308. Showerhead 306 may have any suitable shape, and may have any suitable number and arrangement of ports for distributing process gases to substrate 312. [0096] In some embodiments, pedestal 308 may be raised or lowered to expose substrate 312 to a volume between the substrate 312 and the showerhead 306. It will be appreciated that, in some embodiments, pedestal height may be adjusted programmatically by a suitable computer controller 350. [0097] In another scenario, adjusting a height of pedestal 308 may allow a plasma density to be varied during plasma activation in the process in embodiments where a plasma is ignited. At the conclusion of the process phase, pedestal 308 may be lowered during another substrate transfer phase to allow removal of substrate 312 from pedestal 308. [0098] In some embodiments, pedestal 308 may be temperature controlled via heater 310. In some embodiments, the pedestal 308 may be heated to a temperature of about 25°C to about 650°C, or about 200°C to about 650°C, during deposition of silicon oxide films as described in disclosed embodiments. In some embodiments, the pedestal is set at a temperature of about 25°C to about 650°C, or about 200°C to about 300°C. In some embodiments, the same pedestal 308 is used for subsequent annealing. [0099] Further, in some embodiments, pressure control for process station 300 may be provided by butterfly valve 318. As shown in the embodiment of Figure 3, butterfly valve 318 throttles a vacuum provided by a downstream vacuum pump (not shown). However, in some embodiments,
Attorney Docket No. 10948-1WO/LAMRP827WO pressure control of process station 300 may also be adjusted by varying a flow rate of one or more gases introduced to the process station 300. [0100] In some embodiments, a position of showerhead 306 may be adjusted relative to pedestal 308 to vary a volume between the substrate 312 and the showerhead 306. Further, it will be appreciated that a vertical position of pedestal 308 and/or showerhead 306 may be varied by any suitable mechanism within the scope of the present disclosure. In some embodiments, pedestal 308 may include a rotational axis for rotating an orientation of substrate 312. It will be appreciated that, in some embodiments, one or more of these example adjustments may be performed programmatically by one or more suitable computer controllers 350. [0101] In some embodiments where plasma may be used as discussed above, showerhead 306 and pedestal 308 electrically communicate with a radio frequency (RF) power supply 314 and matching network 316 for powering a plasma. For example, plasma may be used for treating a silicon oxide surface prior to depositing silicon nitride. In some embodiments, the plasma energy may be controlled by controlling one or more of a process station pressure, a gas concentration, an RF source power, an RF source frequency, and a plasma power pulse timing. For example, RF power supply 314 and matching network 316 may be operated at any suitable power to form a plasma having a desired composition of radical species. Examples of suitable powers are about 100W to about 6500W for a single-station chamber. For a 4-station chamber, the plasma power may include four generators each powered up to about 100W, for a total of about 6500W. In some embodiments, during extended RF exposure, the substrate may be exposed to one or more oxygen- containing gases and optional inert gases while igniting a plasma using the RF power supply 314 and matching network 316. [0102] In some embodiments, the substrate may be exposed to a deposition reactant while igniting a plasma to convert and/or densify the film using plasma powers such as between about 500W and about 6500W per surface area of a 300mm wafer. The plasma may be generated remotely (such as in a remote plasma generator) or directly in a chamber housing the substrate (i.e. in situ). RF power supply 214 may provide RF power of any suitable frequency. In some embodiments, RF power supply 214 may be configured to control high- and low-frequency RF power sources independently of one another. Example low-frequency RF frequencies may include, but are not limited to, frequencies between 0 kHz and 500 kHz. Example high-frequency RF frequencies may include, but are not limited to, frequencies between 1.8 MHz and 2.45 GHz, or up to about 27 MHz, or greater than about 13.56 MHz, or greater than 27 MHz, or greater than 30 MHz, or greater than 60 MHz. It will be appreciated that any suitable parameters may be modulated discretely or continuously to provide plasma energy for the surface reactions.
Attorney Docket No. 10948-1WO/LAMRP827WO [0103] In some embodiments, the plasma may be monitored in-situ by one or more plasma monitors. In one scenario, plasma power may be monitored by one or more voltage, current sensors (e.g., VI probes). In another scenario, plasma density and/or process gas concentration may be measured by one or more optical emission spectroscopy sensors (OES). In some embodiments, one or more plasma parameters may be programmatically adjusted based on measurements from such in-situ plasma monitors. For example, an OES sensor may be used in a feedback loop for providing programmatic control of plasma power. It will be appreciated that, in some embodiments, other monitors may be used to monitor the plasma and other process characteristics. Such monitors may include, but are not limited to, infrared (IR) monitors, acoustic monitors, and pressure transducers. [0104] In some embodiments, instructions for a controller 350 may be provided via input/output control (IOC) sequencing instructions. In one example, the instructions for setting conditions for a process phase may be included in a corresponding recipe phase of a process recipe. In some cases, process recipe phases may be sequentially arranged, so that all instructions for a process phase are executed concurrently with that process phase. In some embodiments, instructions for setting one or more reactor parameters may be included in a recipe phase. For example, a first recipe phase may include instructions for setting a flow rate of a silicon-containing gas, instructions for setting a flow rate of a carrier gas (such as argon), and time delay instructions for the first recipe phase. A second recipe phase may include modulating or stopping a flow rate of an inert and/or a reactant gas, instructions for setting a flow rate of a carrier gas (such as argon), and time delay instructions for a second recipe phase. A third, subsequent recipe phase may include instructions for modulating or stopping a flow rate of an inert and/or a reactant gas, and instructions for modulating a flow rate of an oxygen-containing and time delay instructions for the third recipe phase. A fourth recipe phase may include instructions for modulating or stopping a flow rate of an inert and/or a reactant gas, instructions for modulating the flow rate of a carrier or purge gas, and time delay instructions for the fourth recipe phase. A fifth, subsequent recipe phase may include instructions for setting a flow rate of a nitridation or oxidation gas, instructions for optionally heating or igniting a plasma, and instructions for modulating a flow rate of a carrier or purge gas and time delay instructions for the fifth recipe phase. It will be appreciated that these recipe phases may be further subdivided and/or iterated in any suitable way within the scope of the disclosed embodiments. In some embodiments, the controller 350 may include any of the features described below with respect to system controller 450 of Figure 4 and system controller 529 of Figure 5. [0105] A process station may be included in a single-station chamber or single-chamber tool
Attorney Docket No. 10948-1WO/LAMRP827WO such as shown in Figure 4. Figure 4 depicts an example processing apparatus according to disclosed embodiments. Tool 400 includes a processing chamber 414 which includes a processing station 490 may process a wafer. The processing chamber 414 is configured to deposit silicon oxide, deposit silicon nitride, anneal substrates using thermal or plasma anneals, and the like. [0106] Tool 400 also includes a wafer transfer unit configured to transport wafers within the tool 400. Additional features of tool 400 will be discussed in greater detail below, and various features are discussed here with respect to some of the described techniques. In the depicted illustration, the wafer transfer unit includes a first robotic arm unit 426 in a first wafer transfer module and a second robotic arm unit 406 in a second wafer transfer module that may be considered an equipment front end module (EFEM) configured to received containers for wafers, such as a front opening unified module (FOUP) 408. The first robotic arm unit 426 is configured to transport a wafer between the processing chamber 414 and the second robotic arm unit via module 404 which may hold multiple wafers such as shown in module 402 with substrate 412. The second robotic arm unit 406 is configured to transport the wafer between a FOUP and module 404, or from module 402 to FOUP. After a wafer has been prepared in the module 404, the wafer transfer unit is able to transfer the wafer to first processing chamber 414 for deposition and optional anneal in situ. [0107] Similar to above, the first wafer transfer module may a vacuum transfer module (VTM). Airlock or module 404, also known as a loadlock, is shown and may be individually optimized to perform various fabrication processes. The tool 400 also includes a FOUP 408 that is configured to lower the pressure of the tool 400 to a vacuum or low pressure, e.g., between about 1 mTorr and about 10 Torr, and maintain the tool 400 at this pressure. This includes maintaining the processing chamber 414, and the first wafer transfer module at the vacuum or low pressure. The second wafer transfer module may be at a different pressure, such as atmospheric. As the wafer is transferred throughout the tool 400, it is therefore maintained at the vacuum or low pressure. [0108] In a further example, a substrate is placed in one of the FOUPs 408 and the second robot arm unit 406, or front-end robot, transfers the substrate from the FOUP 418 to an aligner, which allows the substrate to be properly centered before it is etched, or deposited upon, or otherwise processed. After being aligned, the substrate is moved by the second robot arm unit 406 into the airlock module 404. Because airlock modules have the ability to match the environment between an ATM and a VTM, the substrate is able to move between the two pressure environments without being damaged. From the airlock module 404, the substrate is moved by the first robot arm unit 426 through the first wafer transfer module, or VTM, and into the processing chamber 414. In order to achieve this substrate movement, the first robot arm unit 426 uses end effectors on each of its arms.
Attorney Docket No. 10948-1WO/LAMRP827WO [0109] Figure 4 also depicts an embodiment of a system controller 450 employed to control process conditions and hardware states of process tool 400. System controller 450 may include one or more memory devices 456, one or more mass storage devices 454, and one or more processors 452. Processor 452 may include a CPU or computer, analog and/or digital input/output connections, stepper motor controller boards, etc. In some embodiments, system controller 450 includes machine-readable instructions for performing operations such as those described above with respect to Figure 3 and below with respect to Figure 5. [0110] As described above, one or more process stations may be included in a multi-station processing tool. Figure 5 depicts an example processing apparatus according to disclosed embodiments. Tool 500 includes a first processing chamber 502 and a second processing chamber 504. The first processing chamber 502 includes a plurality of processing stations, four stations 580A–D, that each may process a wafer. The first processing chamber 502 is configured to perform plasma treatment operations on the wafers. The second processing chamber 504 is configured to perform deposition on the wafer and may be considered a deposition chamber. The second processing chamber 504 also includes a plurality of processing stations, four stations 582A–D, that each may process a wafer. The first and second processing chambers 502 and 504 may be considered multi-station processing chambers. [0111] Tool 500 also includes a wafer transfer unit configured to transport one or more wafers within the tool 500. Additional features of tool 500 will be discussed in greater detail below, and various features are discussed here with respect to some of the described techniques. In the depicted illustration, the wafer transfer unit includes a first robotic arm unit 508 in a first wafer transfer module 510 and a second robotic arm unit 512 in a second wafer transfer module 514 that may be considered an equipment front end module (EFEM) configured to received containers for wafers, such as a front opening unified module (FOUP) 516. The first robotic arm unit 508 is configured to transport a wafer between the first processing chamber 502 and the second processing chamber 504, and between the second the second robotic arm unit 512. The second robotic arm unit 512 is configured to transport the wafer between a FOUP and the first robotic arm unit 508. After a wafer has been treated in the first processing chamber 502, the wafer transfer unit is able to transfer the wafer from the first processing chamber 502, to the second processing chamber 504 where one or more layers of encapsulation material may be deposited on one or more wafers. [0112] Similar to above, the first wafer transfer module 510 may a vacuum transfer module (VTM). Airlock 520, also known as a loadlock or transfer module, is shown and may be individually optimized to perform various fabrication processes. The tool 500 also includes a
Attorney Docket No. 10948-1WO/LAMRP827WO FOUP 516 that is configured to lower the pressure of the tool 500 to a vacuum or low pressure, e.g., between about 1 mTorr and about 10 Torr, and maintain the tool 500 at this pressure. This includes maintaining the first and second processing chambers 502 and 504, and the first wafer transfer module 510 at the vacuum or low pressure. The second wafer transfer module 514 may be at a different pressure, such as atmospheric. As the wafer is transferred throughout the tool 500, it is therefore maintained at the vacuum or low pressure. For example, as the wafer is transferred from the first processing chamber 502, into the first wafer transfer module 510, and to the second processing chamber 504, the wafer is maintained at the vacuum or low pressure and not exposed to atmospheric pressure. [0113] In a further example, a substrate is placed in one of the FOUPs 518 and the second robot arm unit 512, or front-end robot, transfers the substrate from the FOUP 518 to an aligner, which allows the substrate to be properly centered before it is etched, or deposited upon, or otherwise processed. After being aligned, the substrate is moved by the second robot arm unit 512 into the airlock 520. Because airlock modules have the ability to match the environment between an ATM and a VTM, the substrate is able to move between the two pressure environments without being damaged. From the airlock 520, the substrate is moved by the first robot arm unit 508 through the first wafer transfer module 510, or VTM 510, and into the first processing chamber 502. In order to achieve this substrate movement, the first robot arm unit 508 uses end effectors on each of its arms. [0114] Figure 5 also depicts an embodiment of a system controller 529 employed to control process conditions and hardware states of tool 500. System controller 529 may include one or more memory devices (not shown), one or more mass storage devices (not shown), and one or more processors (not shown). Processors may include a CPU or computer, analog, and/or digital input/output connections, stepper motor controller boards, etc. [0115] In some embodiments, system controller 529 controls all of the activities of tool 500. System controller 529 executes system control software stored in mass storage device, loaded into memory device, and executed on processor. Alternatively, the control logic may be hard coded in the system controller 529. Applications Specific Integrated Circuits, Programmable Logic Devices (e.g., field-programmable gate arrays, or FPGAs) and the like may be used for these purposes. In the following discussion, wherever “software” or “code” is used, functionally comparable hard coded logic may be used in its place. System control software may include instructions for controlling the timing, mixture of gases, gas flow rates, chamber and/or station pressure, chamber and/or station temperature, wafer temperature, target power levels, RF power levels, substrate pedestal, chuck and/or susceptor position, and parameters of a particular process
Attorney Docket No. 10948-1WO/LAMRP827WO performed by tool 500. System control software may be configured in any suitable way. For example, various process tool component subroutines or control objects may be written to control operation of the process tool components used to carry out various process tool processes. System control software may be coded in any suitable computer readable programming language. [0116] In some embodiments, system control software may include input/output control (IOC) sequencing instructions for controlling the various parameters described above. Other computer software and/or programs stored on mass storage device and/or memory device associated with system controller 529 may be employed in some embodiments. Examples of programs or sections of programs for this purpose include a substrate positioning program, a process gas control program, a pressure control program, a heater control program, and a plasma control program. [0117] A substrate positioning program may include program code for process tool components that are used to load the substrate onto pedestal and to control the spacing between the substrate and other parts of tool 500. [0118] A process gas control program may include code for controlling gas composition (e.g., silicon-containing precursor gases, oxygen-containing gases, carrier gases, inert gases, and/or purge gases as described herein) and flow rates and optionally for flowing gas into one or more process stations prior to deposition in order to stabilize the pressure in the process station. A pressure control program may include code for controlling the pressure in the process station by regulating, for example, a throttle valve in the exhaust system of the process station, a gas flow into the process station, etc. [0119] A heater control program may include code for controlling the current to a heating unit that is used to heat the substrate. Alternatively, the heater control program may control delivery of a heat transfer gas (such as helium or nitrogen) to the substrate. [0120] A plasma control program may include code for setting RF power levels applied to the process electrodes in one or more process stations in accordance with the embodiments herein. [0121] A pressure control program may include code for maintaining the pressure in the reaction chamber in accordance with the embodiments herein. [0122] In some embodiments, there may be a user interface associated with system controller 529. The user interface may include a display screen, graphical software displays of the apparatus and/or process conditions, and user input devices such as pointing devices, keyboards, touch screens, microphones, etc. [0123] In some embodiments, parameters adjusted by system controller 529 may relate to process conditions. Non-limiting examples include process gas composition and flow rates, temperature, pressure, plasma conditions (such as RF bias power levels), etc. These parameters
Attorney Docket No. 10948-1WO/LAMRP827WO may be provided to the user in the form of a recipe, which may be entered utilizing the user interface. [0124] Signals for monitoring the process may be provided by analog and/or digital input connections of system controller 529 from various process tool sensors. The signals for controlling the process may be output on the analog and digital output connections of tool 500. Non-limiting examples of process tool sensors that may be monitored include mass flow controllers, pressure sensors (such as manometers), thermocouples, etc. Appropriately programmed feedback and control algorithms may be used with data from these sensors to maintain process conditions. [0125] System controller 529 may provide program instructions for implementing the above- described deposition processes. The program instructions may control a variety of process parameters, such as DC power level, RF bias power level, pressure, temperature, etc. The instructions may control the parameters to operate in-situ deposition of film stacks according to various embodiments described herein. [0126] The system controller 529 will typically include one or more memory devices and one or more processors configured to execute the instructions so that the apparatus will perform a method in accordance with disclosed embodiments. Machine-readable media containing instructions for controlling process operations in accordance with disclosed embodiments may be coupled to the system controller 529. [0127] In some implementations, the system controller 529 is part of a system, which may be part of the above-described examples. Such systems can include semiconductor processing equipment, including a processing tool or tools, chamber or chambers, a platform or platforms for processing, and/or specific processing components (a wafer pedestal, a gas flow system, etc.). These systems may be integrated with electronics for controlling their operation before, during, and after processing of a semiconductor wafer or substrate. The electronics may be referred to as the “controller,” which may control various components or subparts of the system or systems. The system controller 529, depending on the processing conditions and/or the type of system, may be programmed to control any of the processes disclosed herein, including the delivery of processing gases, temperature settings (e.g., heating and/or cooling), pressure settings, vacuum settings, power settings, radio frequency (RF) generator settings, RF matching circuit settings, frequency settings, flow rate settings, fluid delivery settings, positional and operation settings, wafer transfers into and out of a tool and other transfer tools and/or load locks connected to or interfaced with a specific system. [0128] Broadly speaking, the system controller 529 may be defined as electronics having various integrated circuits, logic, memory, and/or software that receive instructions, issue instructions,
Attorney Docket No. 10948-1WO/LAMRP827WO control operation, enable cleaning operations, enable endpoint measurements, and the like. The integrated circuits may include chips in the form of firmware that store program instructions, digital signal processors (DSPs), chips defined as application specific integrated circuits (ASICs), and/or one or more microprocessors, or microcontrollers that execute program instructions (e.g., software). Program instructions may be instructions communicated to the system controller 529 in the form of various individual settings (or program files), defining operational parameters for carrying out a particular process on or for a semiconductor wafer or to a system. The operational parameters may, in some embodiments, be part of a recipe defined by process engineers to accomplish one or more processing steps during the fabrication of one or more layers, materials, metals, oxides, silicon, silicon dioxide, surfaces, circuits, and/or dies of a wafer. [0129] The system controller 529, in some implementations, may be a part of or coupled to a computer that is integrated with, coupled to the system, otherwise networked to the system, or a combination thereof. For example, the system controller 529 may be in the “cloud” or all or a part of a fab host computer system, which can allow for remote access of the wafer processing. The computer may enable remote access to the system to monitor current progress of fabrication operations, examine a history of past fabrication operations, examine trends or performance metrics from a plurality of fabrication operations, to change parameters of current processing, to set processing operations to follow a current processing, or to start a new process. In some examples, a remote computer (e.g. a server) can provide process recipes to a system over a network, which 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, which are then communicated to the system from the remote computer. In some examples, the system controller 529 receives instructions in the form of data, which specify parameters for each of the processing operations to be performed during one or more operations. It should be understood that the parameters may be specific to the type of process to be performed and the type of tool that the system controller 529 is configured to interface with or control. Thus as described above, the system controller 529 may be distributed, such as by including one or more discrete controllers that are networked together and working towards a common purpose, such as the processes and controls described herein. An example of a distributed controller for such purposes would be one or more integrated circuits on a chamber in communication with one or more integrated circuits located remotely (such as at the platform level or as part of a remote computer) that combine to control a process on the chamber. [0130] Without limitation, example systems may include a plasma etch chamber or module, a deposition chamber or module, a spin-rinse chamber or module, a metal plating chamber or
Attorney Docket No. 10948-1WO/LAMRP827WO module, a clean chamber or module, a bevel edge etch chamber or module, a physical vapor deposition (PVD) chamber or module, a chemical vapor deposition (CVD) chamber or module, a MM-ALD/CVD chamber or module, an ALD chamber or module, an atomic layer etch (ALE) chamber or module, an ion implantation chamber or module, a track chamber or module, and any other semiconductor processing systems that may be associated or used in the fabrication and/or manufacturing of semiconductor wafers. [0131] As noted above, depending on the process step or steps to be performed by the tool, the system controller 529 might communicate with one or more of other tool circuits or modules, other tool components, cluster tools, other tool interfaces, adjacent tools, neighboring tools, tools located throughout a factory, a main computer, another controller, or tools used in material transport that bring containers of wafers to and from tool locations and/or load ports in a semiconductor manufacturing factory. [0132] An appropriate apparatus for performing the methods disclosed herein is further discussed and described in U.S. Patent Application Nos. 13/084,399 (now U.S. Patent No. 8,728,956), filed April 11, 2011, and titled “PLASMA ACTIVATED CONFORMAL FILM DEPOSITION”; and 13/084,305, filed April 11, 2011, and titled “SILICON NITRIDE FILMS AND METHODS,” each of which is incorporated herein in its entireties. [0133] The apparatus/process described herein may be used in conjunction with lithographic patterning tools or processes, for example, for the fabrication or manufacture of semiconductor devices, displays, LEDs, photovoltaic panels and the like. Typically, though not necessarily, such tools/processes will be used or conducted together in a common fabrication facility. Lithographic patterning of a film typically includes some or all of the following operations, each operation enabled with a number of possible tools: (1) application of photoresist on a workpiece, i.e., substrate, using a spin-on or spray-on tool; (2) curing of photoresist using a hot plate or furnace or UV curing tool; (3) exposing the photoresist to visible or UV or x-ray light with a tool such as a wafer stepper; (4) developing the resist so as to selectively remove resist and thereby pattern it using a tool such as a wet bench; (5) transferring the resist pattern into an underlying film or workpiece by using a dry or plasma-assisted etching tool; and (6) removing the resist using a tool such as an RF or microwave plasma resist stripper. EXPERIMENTAL EXPERIMENT 1 [0134] An experiment was conducted to evaluate dielectric properties of films deposited using certain disclosed embodiments and films deposited using plasma-enhanced atomic layer
Attorney Docket No. 10948-1WO/LAMRP827WO deposition (PEALD). Figure 6 shows the results. Curve 601 shows the capacitance for a silicon oxide film deposited using MM-ALD/CVD where dose and oxidizing plasma were alternated in partially overlapping pulses with no purging between the pulses, and curve 603 shows the capacitance for a silicon oxide film deposited using PEALD. The hysteresis curve for the film deposited by MM-ALD/CVD suggests that electrical defects were reduced in the film deposited using MM-ALD/CVD. EXPERIMENT 2 [0135] An experiment was conducted to evaluate electronic conduction behavior of films deposited using certain disclosed embodiments and films deposited using plasma-enhanced atomic layer deposition (PEALD). Figure 7 shows the results. Data 701 shows the current density versus applied electric field for a silicon oxide film deposited using MM-ALD/CVD where dose and oxidizing plasma were alternated in partially overlapping pulses with no purging between the pulses, and data 703 shows the electric field current density for a silicon oxide film deposited using PEALD. The results suggested that the current density was reduced for the film deposited by MM- ALD/CVD which suggested reduced electrical defects as compared to PEALD. DEFINITIONS AND PRECURSORS DEFINITIONS [0136] The term “acyl,” or “alkanoyl,” as used interchangeably herein, represents groups of 1, 2, 3, 4, 5, 6, 7, 8 or more carbon atoms of a straight, branched, cyclic configuration, saturated, unsaturated and aromatic, and combinations thereof, or hydrogen, attached to the parent molecular group through a carbonyl group, as defined herein. This group is exemplified by formyl (-C(O)H), acetyl (Ac or -C(O)Me), propionyl, isobutyryl, butanoyl, and the like. In some embodiments, the acyl or alkanoyl group is -C(O)-R, in which R is hydrogen, an aliphatic group, or an aromatic group, as defined herein. [0137] By “alkanoyloxy” is meant an alkanoyl group, as defined herein, attached to the parent molecular group through 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, in which R is hydrogen, an aliphatic group, or an aromatic group, as defined herein. [0138] By “aliphatic” is meant a hydrocarbon group having at least one carbon atom to 50 carbon atoms (C1-50), such as one to 25 carbon atoms (C1-25), or one to ten carbon atoms (C1- 10), and which includes alkanes (or alkyl), alkenes (or alkenyl), alkynes (or alkynyl), including cyclic versions thereof, and further including straight- and branched-chain arrangements, and all stereo and
Attorney Docket No. 10948-1WO/LAMRP827WO position isomers as well. An aliphatic group is unsubstituted or substituted, e.g., by a functional group described herein. For example, the aliphatic group can be substituted with one or more substitution groups, as described herein for alkyl. [0139] By “aliphatic-carbonyl” is meant an aliphatic group that is or can be coupled to a compound disclosed herein, wherein the aliphatic group is or becomes coupled through a carbonyl group (-C(O)-). In some embodiments, the aliphatic-carbonyl group is -C(O)-R, in which R is an optionally substituted aliphatic group, as defined herein. [0140] By “aliphatic-carbonyloxy” is meant an aliphatic group that is or can be coupled to a compound disclosed herein, wherein the aliphatic group is or becomes coupled through a carbonyloxy group (-OC(O)-). In some embodiments, the aliphatic-carbonyloxy group is -OC(O)- R, in which R is an optionally substituted aliphatic group, as defined herein. [0141] By “aliphatic-oxy” is meant an aliphatic group that is or can be coupled to a compound disclosed herein, wherein the aliphatic group is or becomes coupled through an oxy group (-C(O)- ). In some embodiments, the aliphatic-oxy group is -O-R, in which R is an optionally substituted aliphatic group, as defined herein. [0142] By “aliphatic-oxycarbonyl” is meant an aliphatic group that is or can be coupled to a compound disclosed herein, wherein the aliphatic group is or becomes coupled through an oxycarbonyl group (-C(O)O-). In some embodiments, the aliphatic-oxycarbonyl group is -C(O)O- R, in which R is an optionally substituted aliphatic group, as defined herein. [0143] By “alkyl-aryl,” “alkenyl-aryl,” and “alkynyl-aryl” is meant an alkyl, alkenyl, or alkynyl group, respectively and as defined herein, that is or can be coupled (or attached) to the parent molecular group through an aryl group, as defined herein. The alkyl-aryl, alkenyl-aryl, and/or alkynyl-aryl group can be substituted or unsubstituted. For example, the alkyl-aryl, alkenyl-aryl, and/or alkynyl-aryl group can be substituted with one or more substitution groups, as described herein for alkyl and/or aryl. Exemplary unsubstituted alkyl-aryl groups are of from 7 to 16 carbons (C7-16 alkyl-aryl), as well as those having an alkyl group with 1 to 6 carbons and an aryl group with 4 to 18 carbons (i.e., C1-6 alkyl-C4-18 aryl). Exemplary unsubstituted alkenyl-aryl groups are of from 7 to 16 carbons (C7-16 alkenyl-aryl), as well as those having an alkenyl group with 2 to 6 carbons and an aryl group with 4 to 18 carbons (i.e., C2-6 alkenyl-C4-18 aryl). Exemplary unsubstituted alkynyl-aryl groups are of from 7 to 16 carbons (C7-16 alkynyl-aryl), as well as those having an alkynyl group with 2 to 6 carbons and an aryl group with 4 to 18 carbons (i.e., C2-6 alkynyl-C4-18 aryl). In some embodiments, the alkyl-aryl group is -L-R, in which 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, in which L is an aryl group or an arylene group, as
Attorney Docket No. 10948-1WO/LAMRP827WO defined herein, and R is an alkenyl group, as defined herein. In some embodiments, the alkynyl- aryl group is -L-R, in which L is an aryl group or an arylene group, as defined herein, and R is an alkynyl group, as defined herein. [0144] By “alkenyl” is meant an unsaturated monovalent hydrocarbon having at least two carbon atom to 50 carbon atoms (C2-50), such as two to 25 carbon atoms (C2-25), or two to ten carbon atoms (C2-10), and at least one carbon-carbon double bond, wherein the unsaturated monovalent hydrocarbon can be derived from removing one hydrogen atom from one carbon atom of a parent alkene. An alkenyl group can be branched, straight-chain, cyclic (e.g., cycloalkenyl), cis, or trans (e.g., E or Z). An exemplary alkenyl includes an optionally substituted C2-24 alkyl group having one or more double bonds. The alkenyl group can be monovalent or multivalent (e.g., bivalent) by removing one or more hydrogens to form appropriate attachment to the parent molecular group or appropriate attachment between the parent molecular group and another substitution. The alkenyl group can also be substituted or unsubstituted. For example, the alkenyl group can be substituted with one or more substitution groups, as described herein for alkyl. Non-limiting alkenyl groups include allyl (All), vinyl (Vi), 1-butenyl, 2-butenyl, and the like. [0145] By “alkoxy” is meant -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, etc. The alkoxy group can be substituted or unsubstituted. For example, the alkoxy group can be substituted with one or more substitution groups, as described herein for alkyl. Exemplary unsubstituted alkoxy groups include C1-3, C1-6, C1-12, C1-16, C1-18, C1-20, or C1-24 alkoxy groups. [0146] By “alkoxyalkyl” is meant an alkyl group, as defined herein, which is substituted with an alkoxy group, as defined herein. Exemplary unsubstituted alkoxyalkyl groups include between 2 to 12 carbons (C2-12 alkoxyalkyl), as well as those having an alkyl group with 1 to 6 carbons and an alkoxy group with 1 to 6 carbons (i.e., C1-6 alkoxy-C1-6 alkyl). In some embodiments, the alkoxyalkyl group is -L-O-R, in which each of L and R is, independently, an alkyl group, as defined herein. [0147] By “alkoxycarbonyl” is meant -C(O)-OR, where R is an optionally substituted aliphatic group, as described herein. In particular embodiments, the alkoxycarbonyl group is -C(O)-OAk, in which 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 substitution groups, as described herein for alkyl. Exemplary unsubstituted alkoxycarbonyl groups include C2-3, C2-6, C2-7, C2-12, C2-16, C2-18, C2-20, or C2-24 alkoxycarbonyl groups.
Attorney Docket No. 10948-1WO/LAMRP827WO [0148] By “alkyl” is meant a saturated monovalent hydrocarbon having at least one carbon atom to 50 carbon atoms (C1-50), such as one to 25 carbon atoms (C1-25), or one to ten carbon atoms (C1- 10), wherein the saturated monovalent hydrocarbon can be derived from removing one hydrogen atom from one carbon atom of a parent compound (e.g., alkane). An alkyl group can be branched, straight-chain, or cyclic (e.g., cycloalkyl). An exemplary alkyl includes a branched or unbranched saturated hydrocarbon group of 1 to 24 carbon atoms, such as 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, and the like. The alkyl group can also be substituted or unsubstituted. The alkyl group can be monovalent or multivalent (e.g., bivalent) by removing one or more hydrogens to form appropriate attachment to the parent molecular group or appropriate attachment between the parent molecular group and another substitution. For example, the alkyl group can be substituted with one, two, three or, in the case of alkyl groups of two carbons or more, four substituents independently selected from the group consisting of: (1) C1-6 alkoxy (e.g., -O-R, in which R is C1-6 alkyl); (2) C1- 6 alkylsulfinyl (e.g., -S(O)-R, in which R is C1-6 alkyl); (3) C1-6 alkylsulfonyl (e.g., -SO2-R, in which R is C1-6 alkyl); (4) amino (e.g., -NR1R2, where each of R1 and R2 is, independently, selected from hydrogen, aliphatic, heteroaliphatic, haloaliphatic, haloheteroaliphatic, aromatic, as defined herein, or any combination thereof, or R1 and R2, taken together with the nitrogen atom to which each are attached, can form a heterocyclyl group, as defined herein); (5) aryl; (6) arylalkoxy (e.g., -O-L-R, in which L is alkyl and R is aryl); (7) aryloyl (e.g., -C(O)-R, in which R is aryl); (8) azido (e.g., -N3); (9) cyano (e.g., -CN); (10) aldehyde (e.g., -C(O)H); (11) C3-8 cycloalkyl; (12) halo; (13) heterocyclyl (e.g., as defined herein, such as a 5-, 6- or 7-membered ring containing one, two, three, or four non-carbon heteroatoms); (14) heterocyclyloxy (e.g., -O-R, in which R is heterocyclyl, as defined herein); (15) heterocyclyloyl (e.g., -C(O)-R, in which 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) C1-6 thioalkyl (e.g., -S-R, in which R is alkyl); (21) thiol (e.g., -SH); (22) -CO2R1, where R1 is selected from the group consisting of (a) hydrogen, (b) C1-6 alkyl, (c) C4- 18 aryl, and (d) C4-18 aryl-C1-6 alkyl (e.g., -L-R, in which L is C1-6 alkyl and R is C4-18 aryl); (23) -C(O)NR1R2, where each of R1 and R2 is, independently, selected from the group consisting of (a) hydrogen, (b) C1-6 alkyl, (c) C4-18 aryl, and (d) C4-18 aryl-C1-6 alkyl (e.g., -L-R, in which L is C1-6 alkyl and R is C4-18 aryl); (24) -SO2R1, where R1 is selected from the group consisting of (a) C1-6 alkyl, (b) C4-18 aryl, and (c) C4-18 aryl-C1-6 alkyl (e.g., -L-R, in which L is C1-6 alkyl and R is C4-18 aryl); (25) -SO2NR1R2, where each of R1 and R2 is, independently, selected from the group
Attorney Docket No. 10948-1WO/LAMRP827WO consisting of (a) hydrogen, (b) C1-6 alkyl, (c) C4-18 aryl, and (d) C4-18 aryl-C1-6 alkyl (e.g., -L-R, in which L is C1-6 alkyl and R is C4-18 aryl); and (26) -NR1R2, where each of R1 and R2 is, independently, selected from the group consisting of (a) hydrogen, (b) an N-protecting group, (c) C1-6 alkyl, (d) C2-6 alkenyl, (e) C2-6 alkynyl, (f) C4-18 aryl, (g) C4-18 aryl-C1-6 alkyl (e.g., -L-R, in which L is C1-6 alkyl and R is C4-18 aryl), (h) C3-8 cycloalkyl, and (i) C3-8 cycloalkyl-C1-6 alkyl (e.g., -L-R, in which L is C1-6 alkyl and R is C3-8 cycloalkyl), wherein in one embodiment no two groups are bound to the nitrogen atom through 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 a C1-3, C1-6, C1- 12, C1-16, C1-18, C1-20, or C1-24 alkyl group. [0149] By “alkylene,” “alkenylene,” or “alkynylene” is meant a multivalent (e.g., bivalent) form of an alkyl, alkenyl, or alkynyl group, respectively, as described herein. Exemplary alkylene groups include methylene, ethylene, propylene, butylene, etc. In some embodiments, the alkylene group is a C1-3, C1-6, C1-12, C1-16, C1-18, C1-20, C1-24, C2-3, C2-6, C2-12, C2-16, C2-18, C2-20, or C2-24 alkylene group. In other embodiments, the alkylene group is a C2-3, C2-6, C2-12, C2-16, C2-18, C2-20, or C2-24 alkenylene or alkynylene group. The alkylene, alkenylene, or alkynylene group can be branched or unbranched. The alkylene, alkenylene, or alkynylene group can also be substituted or unsubstituted. For example, the alkylene, alkenylene, or alkynylene group can be substituted with one or more substitution groups, as described herein for alkyl. [0150] By “alkylsulfinyl” is meant an alkyl group, as defined herein, attached to the parent molecular group through an -S(O)- group. In some embodiments, the unsubstituted alkylsulfinyl group is a C1-6 or C1-12 alkylsulfinyl group. In other embodiments, the alkylsulfinyl group is -S(O)- R, in which R is an alkyl group, as defined herein. [0151] By “alkylsulfinylalkyl” is meant an alkyl group, as defined herein, substituted by an alkylsulfinyl group. In some embodiments, the unsubstituted alkylsulfinylalkyl group is a C2-12 or C2-24 alkylsulfinylalkyl group (e.g., C1-6 alkylsulfinyl-C1-6 alkyl or C1-12 alkylsulfinyl-C1-12 alkyl). In other embodiments, the alkylsulfinylalkyl group is -L-S(O)-R, in which each of L and R is, independently, an alkyl group, as defined herein. [0152] By “alkylsulfonyl” is meant an alkyl group, as defined herein, attached to the parent molecular group through an -SO2- group. In some embodiments, the unsubstituted alkylsulfonyl group is a C1-6 or C1-12 alkylsulfonyl group. In other embodiments, the alkylsulfonyl group is -SO2- R, where R is an optionally substituted alkyl (e.g., as described herein, including optionally substituted C1-12 alkyl, haloalkyl, or perfluoroalkyl).
Attorney Docket No. 10948-1WO/LAMRP827WO [0153] By “alkylsulfonylalkyl” is meant an alkyl group, as defined herein, substituted by an alkylsulfonyl group. In some embodiments, the unsubstituted alkylsulfonylalkyl group is a C2-12 or C2-24 alkylsulfonylalkyl group (e.g., C1-6 alkylsulfonyl-C1-6 alkyl or C1-12 alkylsulfonyl-C1-12 alkyl). In other embodiments, the alkylsulfonylalkyl group is -L-SO2-R, in which each of L and R is, independently, an alkyl group, as defined herein. [0154] By “alkynyl” is meant an unsaturated monovalent hydrocarbon having at least two carbon atom to 50 carbon atoms (C2-50), such as two to 25 carbon atoms (C2-25), or two to ten carbon atoms (C2-10), and at least one carbon-carbon triple bond, wherein the unsaturated monovalent hydrocarbon can be derived from removing one hydrogen atom from one carbon atom of a parent alkyne. An alkynyl group can be branched, straight-chain, or cyclic (e.g., cycloalkynyl). An exemplary alkynyl includes an optionally substituted C2-24 alkyl group having one or more triple bonds. The alkynyl group can be cyclic or acyclic and is exemplified by ethynyl, 1-propynyl, and the like. The alkynyl group can be monovalent or multivalent (e.g., bivalent) by removing one or more hydrogens to form appropriate attachment to the parent molecular group or appropriate attachment between the parent molecular group and another substitution. The alkynyl group can also be substituted or unsubstituted. For example, the alkynyl group can be substituted with one or more substitution groups, as described herein for alkyl. [0155] By “ambient temperature” is meant a temperature ranging from 16°C to 26°C, such as from 19°C to 25°C or from 20°C to 25°C. [0156] By “amide” is mean -C(O)NR1R2 or -NHCOR1, where each of R1 and R2 is, independently, selected from hydrogen, aliphatic, heteroaliphatic, aromatic, as defined herein, or any combination thereof, or where R1 and R2, taken together with the nitrogen atom to which each are attached, can form a heterocyclyl group, as defined herein. [0157] By “amino” is meant -NR1R2, where each of R1 and R2 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 where R1 and R2, taken together with the nitrogen atom to which each are attached, can form a heterocyclyl group, as defined herein. In particular embodiments, each of R1 and R2 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 particular embodiments, R1 and R2 can be taken together, with the nitrogen atom to which each is attached, to form an optionally substituted heterocyclyl.
Attorney Docket No. 10948-1WO/LAMRP827WO [0158] By “aminoalkyl” is meant an alkyl group, as defined herein, substituted by an amino group, as defined herein. In some embodiments, the aminoalkyl group is -L-NR1R2, in which L is an alkyl group, as defined herein, and each of R1 and R2 is, independently, selected from hydrogen, aliphatic, heteroaliphatic, or aromatic, as defined herein, or any combination thereof; or R1 and R2, taken together with the nitrogen atom to which each are attached, can form a heterocyclyl group, as defined herein. In other embodiments, the aminoalkyl group is -L-C(NR1R2)(R3)-R4, in which L is a covalent bond or an alkyl group, as defined herein; each of R1 and R2 is, independently, selected from hydrogen, aliphatic, heteroaliphatic, or aromatic, as defined herein, or any combination thereof; or R1 and R2, taken together with the nitrogen atom to which each are attached, can form a heterocyclyl group, as defined herein; and each of R3 and R4 is, independently, H or alkyl, as defined herein. [0159] By “aminooxy” is meant an oxy group, as defined herein, substituted by an amino group, as defined herein. In some embodiments, the aminooxy group is -O-NR1R2, in which each of R1 and R2 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 R2, taken together with the nitrogen atom to which each are attached, can form a heterocyclyl group, as defined herein. In particular embodiments, each of R1 and R2 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. [0160] By “aromatic” is meant a cyclic, conjugated group or moiety of, unless specified otherwise, from 5 to 15 ring atoms having a single ring (e.g., phenyl) or multiple condensed rings in which at least one ring is aromatic (e.g., naphthyl, indolyl, or pyrazolopyridinyl); that is, at least one ring, and optionally multiple condensed rings, have a continuous, delocalized π-electron system. Typically, the number of out of plane π-electrons corresponds to the Huckel rule (4n+2). The point of attachment to the parent structure typically is through an aromatic portion of the condensed ring system. An aromatic group is unsubstituted or substituted, e.g., by a functional group described herein. For example, the aromatic group can be substituted with one or more substitution groups, as described herein for alkyl and/or aryl. [0161] By “aromatic-carbonyl” is meant an aromatic group that is or can be coupled to a compound disclosed herein, wherein the aromatic group is or becomes coupled through a carbonyl group (-C(O)-). In some embodiments, the aromatic-carbonyl group is -C(O)-R, in which R is an optionally substituted aromatic group, as defined herein.
Attorney Docket No. 10948-1WO/LAMRP827WO [0162] By “aromatic-carbonyloxy” is meant an aromatic group that is or can be coupled to a compound disclosed herein, wherein the aromatic group is or becomes coupled through a carbonyloxy group (-OC(O)-). In some embodiments, the aromatic-carbonyloxy group is -OC(O)- R, in which R is an optionally substituted aromatic group, as defined herein. [0163] By “aromatic-oxy” is meant an aromatic group that is or can be coupled to a compound disclosed herein, wherein the aromatic group is or becomes coupled through an oxy group (-O-). In some embodiments, the aromatic-oxy group is -O-R, in which R is an optionally substituted aromatic group, as defined herein. [0164] By “aromatic-oxycarbonyl” is meant an aromatic group that is or can be coupled to a compound disclosed herein, wherein the aromatic group is or becomes coupled through an oxycarbonyl group (-C(O)O-). In some embodiments, the aromatic-carbonyl group is -C(O)O-R, in which R is an optionally substituted aromatic group, as defined herein. [0165] By “aryl” is meant an aromatic carbocyclic group comprising at least five carbon atoms to 15 carbon atoms (C5-15), such as five to ten carbon atoms (C5-10), having a single ring or multiple condensed rings, which condensed rings can or may not be aromatic provided that the point of attachment to a remaining position of the compounds disclosed herein is through an atom of the aromatic carbocyclic group. Aryl groups 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 that contains an aromatic group that has 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. Likewise, the term non-heteroaryl, which is also included in the term aryl, defines a group that contains an aromatic group that does not contain a heteroatom. The aryl group can be substituted or unsubstituted. The aryl group can be substituted with one, two, three, four, or five substituents independently selected from the group consisting of: (1) C1-6 alkanoyl (e.g., -C(O)-R, in which R is C1-6 alkyl); (2) C1-6 alkyl; (3) C1-6 alkoxy (e.g., -O-R, in which R is C1-6 alkyl); (4) C1-6 alkoxy-C1-6 alkyl (e.g., -L-O-R, in which each of L and R is, independently, C1-6 alkyl); (5) C1-6 alkylsulfinyl (e.g., -S(O)-R, in which R is C1-6 alkyl); (6) C1-6 alkylsulfinyl-C1-6 alkyl (e.g., -L-S(O)-R, in which each of L and R is, independently, C1-6 alkyl); (7) C1-6 alkylsulfonyl (e.g., -SO2-R, in which R is C1-6 alkyl); (8) C1-6 alkylsulfonyl-C1-6 alkyl (e.g., -L-SO2-R, in which each of L and R is, independently, C1-6 alkyl); (9) aryl; (10) amino (e.g., - NR1R2, where each of R1 and R2 is, independently, selected from hydrogen, aliphatic, heteroaliphatic, haloaliphatic, haloheteroaliphatic, aromatic, as defined herein, or any combination
Attorney Docket No. 10948-1WO/LAMRP827WO thereof; or R1 and R2, taken together with the nitrogen atom to which each are attached, can form a heterocyclyl group, as defined herein); (11) C1-6 aminoalkyl (e.g., -L1-NR1R2 or -L2- C(NR1R2)(R3)-R4, in which L1 is C1-6 alkyl; L2 is a covalent bond or C1-6 alkyl; each of R1 and R2 is, independently, selected from hydrogen, aliphatic, heteroaliphatic, haloaliphatic, haloheteroaliphatic, aromatic, as defined herein, or any combination thereof; or R1 and R2, taken together with the nitrogen atom to which each are attached, can form a heterocyclyl group, as defined herein; and each of R3 and R4 is, independently, H or C1-6 alkyl); (12) heteroaryl; (13) C4-18 aryl-C1-6 alkyl (e.g., -L-R, in which L is C1-6 alkyl and R is C4-18 aryl); (14) aryloyl (e.g., -C(O)-R, in which R is aryl); (15) azido (e.g., -N3); (16) cyano (e.g., -CN); (17) C1-6 azidoalkyl (e.g., -L-N3, in which L is C1-6 alkyl); (18) aldehyde (e.g., -C(O)H); (19) aldehyde-C1-6 alkyl (e.g., -L-C(O)H, in which L is C1-6 alkyl); (20) C3-8 cycloalkyl; (21) C3-8 cycloalkyl-C1-6 alkyl (e.g., -L-R, in which L is C1-6 alkyl and R is C3-8 cycloalkyl); (22) halo; (23) C1-6 haloalkyl (e.g., -L1-X or -L2-C(X)(R1)- R2, in which L1 is C1-6 alkyl; L2 is a covalent bond or C1-6 alkyl; X is fluoro, bromo, chloro, or iodo; and each of R1 and R2 is, independently, H or C1-6 alkyl); (24) heterocyclyl (e.g., as defined herein, such as a 5-, 6- or 7-membered ring containing one, two, three, or four non-carbon heteroatoms); (25) heterocyclyloxy (e.g., -O-R, in which R is heterocyclyl, as defined herein); (26) heterocyclyloyl (e.g., -C(O)-R, in which R is heterocyclyl, as defined herein); (27) hydroxyl (-OH); (28) C1-6 hydroxyalkyl
which L1 is C1-6 alkyl; L2 is a covalent bond or alkyl; and each of R1 and R2 is, independently, H or C1-6 alkyl, as defined herein); (29) nitro; (30) C1-6 nitroalkyl (e.g., -L1-NO or -L2-C(NO)(R1)-R2, in which L1 is C1-6 alkyl; L2 is a covalent bond or alkyl; and each of R1 and R2 is, independently, H or C1-6 alkyl, as defined herein); (31) N-protected amino; (32) N-protected amino-C1-6 alkyl; (33) oxo (e.g., =O); (34) C1-6 thioalkyl (e.g., -S-R, in which R is C1-6 alkyl); (35) thio-C1-6 alkoxy-C1-6 alkyl (e.g., -L- S-R, in which each of L and R is, independently, C1-6 alkyl);
where r is an integer of from zero to four, and R1 is selected from the group consisting of (a) hydrogen, (b) C1-6 alkyl, (c) C4-18 aryl, and (d) C4-18 aryl-C1-6 alkyl (e.g., -L-R, in which L is C1-6 alkyl and R is C4-18 aryl); (37) -(CH2)rCONR1R2, where r is an integer of from zero to four and where each R1 and R2 is independently selected from the group consisting of (a) hydrogen, (b) C1-6 alkyl, (c) C4-18 aryl, and (d) C4-18 aryl-C1-6 alkyl (e.g., -L-R, in which L is C1-6 alkyl and R is C4-18 aryl); (38) -(CH2)rSO2R1, where r is an integer of from zero to four and where R1 is selected from the group consisting of (a) C1-6 alkyl, (b) C4-18 aryl, and (c) C4-18 aryl-C1-6 alkyl (e.g., -L-R, in which L is C1-6 alkyl and R is C4-18 aryl); (39) -(CH2)rSO2NR1R2, where r is an integer of from zero to four and where each of R1 and R2 is, independently, selected from the group consisting of (a) hydrogen, (b) C1-6 alkyl, (c) C4-18 aryl, and (d) C4-18 aryl-C1-6 alkyl (e.g., -L-R, in which L is
Attorney Docket No. 10948-1WO/LAMRP827WO C1-6 alkyl and R is C4-18 aryl); (40) -(CH2)rNR1R2, where r is an integer of from zero to four and where each of R1 and R2 is, independently, selected from the group consisting of (a) hydrogen, (b) an N-protecting group, (c) C1-6 alkyl, (d) C2-6 alkenyl, (e) C2-6 alkynyl, (f) C4-18 aryl, (g) C4-18 aryl- C1-6 alkyl (e.g., -L-R, in which L is C1-6 alkyl and R is C4-18 aryl), (h) C3-8 cycloalkyl, and (i) C3-8 cycloalkyl-C1-6 alkyl (e.g., -L-R, in which L is C1-6 alkyl and R is C3-8 cycloalkyl), wherein in one embodiment no two groups are bound to the nitrogen atom through a carbonyl group or a sulfonyl group; (41) thiol (e.g., -SH); (42) perfluoroalkyl (e.g., -(CF2)nCF3, in which n is an integer from 0 to 10); (43) perfluoroalkoxy (e.g., -O-(CF2)nCF3, in which n is an integer from 0 to 10); (44) aryloxy (e.g., -O-R, in which R is aryl); (45) cycloalkoxy (e.g., -O-R, in which R is cycloalkyl); (46) cycloalkylalkoxy (e.g., -O-L-R, in which L is alkyl and R is cycloalkyl); and (47) arylalkoxy (e.g., -O-L-R, in which L is alkyl and R is aryl). In particular embodiments, an unsubstituted aryl group is a C4-18, C4-14, C4-12, C4-10, C6-18, C6-14, C6-12, or C6-10 aryl group. [0166] By “aryl-alkyl,” “aryl-alkenyl,” and “aryl-alkynyl” is meant an aryl group, as defined herein, that is or can be coupled (or attached) to the parent molecular group through an alkyl, alkenyl, or alkynyl group, respectively, as defined herein. The aryl-alkyl, aryl-alkenyl, and/or aryl-alkynyl group can be substituted or unsubstituted. For example, the aryl-alkyl, aryl-alkenyl, and/or aryl-alkynyl group can be substituted with one or more substitution groups, as described herein for aryl and/or alkyl. Exemplary unsubstituted aryl-alkyl groups are of from 7 to 16 carbons (C7-16 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., C4-18 aryl-C1-6 alkyl). Exemplary unsubstituted aryl-alkenyl groups are of from 7 to 16 carbons (C7-16 aryl-alkenyl), as well as those having an aryl group with 4 to 18 carbons and an alkenyl group with 2 to 6 carbons (i.e., C4-18 aryl-C2-6 alkenyl). Exemplary unsubstituted aryl-alkynyl groups are of from 7 to 16 carbons (C7-16 aryl-alkynyl), as well as those having an aryl group with 4 to 18 carbons and an alkynyl group with 2 to 6 carbons (i.e., C4-18 aryl- C2-6 alkynyl). In some embodiments, the aryl-alkyl group is -L-R, in which 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, in which 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, in which L is an alkynyl group or an alkynylene group, as defined herein, and R is an aryl group, as defined herein. [0167] By “arylene” is meant a multivalent (e.g., bivalent) 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 a C4-18, C4-14, C4-12, C4-10, C6-18, C6-14, C6-12, or C6-10 arylene group. The arylene
Attorney Docket No. 10948-1WO/LAMRP827WO 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 substitution groups, as described herein for aryl. [0168] By “arylalkoxy” is meant an aryl-alkyl group, as defined herein, attached to the parent molecular group through an oxygen atom. In some embodiments, the arylalkoxy group is -O-L- R, in which L is an alkyl group, as defined herein, and R is an aryl group, as defined herein. [0169] By “aryloxy” is meant -OR, where R is an optionally substituted aryl group, as described herein. In some embodiments, an unsubstituted aryloxy group is a C4-18 or C6-18 aryloxy group. In other embodiments, R is an aryl group that is optionally substituted with alkyl, alkanoyl, amino, hydroxyl, and the like. [0170] By “aryloxycarbonyl” is meant an aryloxy group, as defined herein, that is attached to the parent molecular group through a carbonyl group. In some embodiments, an unsubstituted aryloxycarbonyl group is a C5-19 aryloxycarbonyl group. In other embodiments, the aryloxycarbonyl group is -C(O)O-R, in which R is an aryl group, as defined herein. [0171] By “aryloyl” is meant an aryl group that is attached to the parent molecular group through a carbonyl group. In some embodiments, an unsubstituted aryloyl group is a C7-11 aryloyl or C5-19 aryloyl group. In other embodiments, the aryloyl group is -C(O)-R, in which R is an aryl group, as defined herein. [0172] By “aryloyloxy” is meant an aryloyl group, as defined herein, that is attached to the parent molecular group through an oxy group. In some embodiments, an unsubstituted aryloyloxy group is a C5-19 aryloyloxy group. In other embodiments, the aryloyloxy group is -OC(O)-R, in which R is an aryl group, as defined herein. [0173] By “azido” is meant an -N3 group. [0174] By “azidoalkyl” is meant an azido group attached to the parent molecular group through an alkyl group, as defined herein. In some embodiments, the azidoalkyl group is -L-N3, in which L is an alkyl group, as defined herein. [0175] By “azo” is meant an -N=N- group. [0176] By “carbamoyl” is meant an amino group attached to the parent molecular group through a carbonyl group, as defined herein. In some embodiments, the carbamoyl is -C(O)NR1R2 group, where each of R1 and R2 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 where R1 and R2, taken together with the nitrogen atom to which each are attached, can form a heterocyclyl group, as defined herein.
Attorney Docket No. 10948-1WO/LAMRP827WO [0177] By “carbamoyloxy” is meant a carbamoyl group, as defined herein, attached to the parent molecular group through n oxy group, as defined herein. In some embodiments, the carbamoyl is -OC(O)NR1R2 group, where each of R1 and R2 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 where R1 and R2, taken together with the nitrogen atom to which each are attached, can form a heterocyclyl group, as defined herein. [0178] By “carbonimidoyl” is meant 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, as defined herein, or any combination thereof. [0179] By “carbonyl” is meant a -C(O)- group, which can also be represented as >C=O. [0180] By “carboxyl” is meant a -CO2H group or an anion thereof. [0181] By “catalyst” is meant a compound, usually present in small amounts relative to reactants, capable of catalyzing a synthetic reaction, as would be readily understood by a person of ordinary skill in the art. In some embodiments, catalysts may include transition metal coordination complex. [0182] By “cyanato” is meant a -OCN group. [0183] By “cyano” is meant a -CN group. [0184] By “cycloaliphatic” is meant an aliphatic group, as defined herein, that is cyclic. [0185] By “cycloalkoxy” is meant a cycloalkyl group, as defined herein, attached to the parent molecular group through an oxygen atom. In some embodiments, the cycloalkoxy group is -O-R, in which R is a cycloalkyl group, as defined herein. [0186] By “cycloalkylalkoxy” is meant a -O-L-R group, in which L is an alkyl group or an alkylene group, as defined herein, and R is a cycloalkyl group, as defined herein. [0187] By “cycloalkyl” is meant a monovalent saturated or unsaturated non-aromatic cyclic hydrocarbon group of from three to eight carbons, unless otherwise specified, and is exemplified by cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, bicyclo[2.2.1.heptyl], and the like. 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 may include one or more double bonds and/or triple bonds.
Attorney Docket No. 10948-1WO/LAMRP827WO [0188] By “cycloheteroaliphatic” is meant a heteroaliphatic group, as defined herein, that is cyclic. [0189] By “disilanyl” is meant a group containing an Si-Si bond. In some embodiments, the disilanyl group is a -SiRS1RS2-SiRS3RS4RS5 or -SiRS1RS2-SiRS3RS4- group, in which each of RS1, RS2, RS3, RS4, and RS5 is, independently, H, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, optionally substituted heteroaromatic, or optionally substituted amino. [0190] By “disulfide” is meant -SSR, where R is selected from hydrogen, aliphatic, heteroaliphatic, haloaliphatic, haloheteroaliphatic, aromatic, as defined herein, or any combination thereof. [0191] By “electron-donating group” is meant a functional group capable of donating at least a portion of its electron density into the ring to which it is directly attached, such as by resonance. [0192] By “electron-withdrawing group” is meant a functional group capable of accepting electron density from the ring to which it is directly attached, such as by inductive electron withdrawal. [0193] By “halo” is meant F, Cl, Br, or I. [0194] By “haloaliphatic” is meant an aliphatic group, as defined herein, in which one or more hydrogen atoms, such as one to 10 hydrogen atoms, independently is replaced with a halogen atom, such as fluoro, bromo, chloro, or iodo. [0195] By “haloalkyl” is meant an alkyl group, as defined herein, where one or more hydrogen atoms, such as one to 10 hydrogen atoms, independently is replaced with a halogen atom, such as fluoro, bromo, chloro, or iodo. In an independent embodiment, haloalkyl can be a -CX3 group, wherein each X independently can be selected from fluoro, bromo, chloro, or iodo. In some embodiments, the haloalkyl group is -L-X, in which 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)(R1)-R2, in which L is a covalent bond or an alkyl group, as defined herein; X is fluoro, bromo, chloro, or iodo; and each of R1 and R2 is, independently, H or alkyl, as defined herein. [0196] By “haloheteroaliphatic” is meant a heteroaliphatic, as defined herein, in which one or more hydrogen atoms, such as one to 10 hydrogen atoms, independently is replaced with a halogen atom, such as fluoro, bromo, chloro, or iodo. [0197] By “heteroaliphatic” is meant an aliphatic group, as defined herein, including at least one heteroatom to 20 heteroatoms, such as one to 15 heteroatoms, or one to 5 heteroatoms, which can be selected from, but not limited to oxygen, nitrogen, sulfur, silicon, boron, selenium, phosphorous, and oxidized forms thereof within the group. A heteroaliphatic group is
Attorney Docket No. 10948-1WO/LAMRP827WO unsubstituted or substituted, e.g., by a functional group described herein. For example, the heteroaliphatic group can be substituted with one or more substitution groups, as described herein for alkyl. [0198] By “heteroaliphatic-carbonyl” is meant a heteroaliphatic group that is or can be coupled to a compound disclosed herein, wherein the heteroaliphatic group is or becomes coupled through a carbonyl group (-C(O)-). In some embodiments, the heteroaliphatic-carbonyl group is -C(O)-R, in which R is an optionally substituted heteroaliphatic group, as defined herein. [0199] By “heteroaliphatic-carbonyloxy” is meant a heteroaliphatic group that is or can be coupled to a compound disclosed herein, wherein the heteroaliphatic group is or becomes coupled through a carbonyloxy group (-OC(O)-). In some embodiments, the heteroaliphatic-carbonyloxy group is -OC(O)-R, in which R is an optionally substituted heteroaliphatic group, as defined herein. [0200] By “heteroaliphatic-oxy” is meant a heteroaliphatic group that is or can be coupled to a compound disclosed herein, wherein the heteroaliphatic group is or becomes coupled through an oxy group (-C(O)-). In some embodiments, the heteroaliphatic-oxy group is -O-R, in which R is an optionally substituted heteroaliphatic group, as defined herein. [0201] By “heteroaliphatic-oxycarbonyl” is meant a heteroaliphatic group that is or can be coupled to a compound disclosed herein, wherein the heteroaliphatic group is or becomes coupled through an oxycarbonyl group (-C(O)O-). In some embodiments, the heteroaliphatic-oxycarbonyl group is -C(O)O-R, in which R is an optionally substituted heteroaliphatic group, as defined herein. [0202] By “heteroalkyl,” “heteroalkenyl,” and “heteroalkynyl” is meant an alkyl, alkenyl, or alkynyl group (which can be branched, straight-chain, or cyclic), respectively, as defined herein, including at least one heteroatom to 20 heteroatoms, such as one to 15 heteroatoms, or one to 5 heteroatoms, which can be selected from, but not limited to, oxygen, nitrogen, sulfur, silicon, boron, selenium, phosphorous, and oxidized forms thereof within the group. [0203] By “heteroalkylene,” “heteroalkenylene,” and “heteroalkynylene” is meant a multivalent (e.g., bivalent) form of a heteroalkyl, heteroalkenyl, or heteroalkynyl group, respectively, as described herein. [0204] By “heteroaromatic” is meant an aromatic group, as defined herein, including at least one heteroatom to 20 heteroatoms, such as one to 15 heteroatoms, or one to 5 heteroatoms, which can be selected from, but not limited to oxygen, nitrogen, sulfur, silicon, boron, selenium, phosphorous, and oxidized forms thereof within the group. A heteroaromatic group is unsubstituted or substituted, e.g., by a functional group described herein. For example, the heteroaromatic group can be substituted with one or more substitution groups, as described herein for alkyl and/or aryl.
Attorney Docket No. 10948-1WO/LAMRP827WO [0205] By “heteroaromatic-carbonyl” is meant a heteroaromatic group that is or can be coupled to a compound disclosed herein, wherein the heteroaromatic group is or becomes coupled through a carbonyl group (-C(O)-). In some embodiments, the heteroaromatic-carbonyl group is -C(O)-R, in which R is an optionally substituted heteroaromatic group, as defined herein. [0206] By “heteroaromatic-carbonyloxy” is meant a heteroaromatic group that is or can be coupled to a compound disclosed herein, wherein the heteroaromatic group is or becomes coupled through a carbonyloxy group (-OC(O)-). In some embodiments, the heteroaromatic-carbonyloxy group is -OC(O)-R, in which R is an optionally substituted heteroaromatic group, as defined herein. [0207] By “heteroaromatic-oxy” is meant a heteroaromatic group that is or can be coupled to a compound disclosed herein, wherein the heteroaromatic group is or becomes coupled through an oxy group (-O-). In some embodiments, the heteroaromatic-oxy group is -O-R, in which R is an optionally substituted heteroaromatic group, as defined herein. [0208] By “heteroaromatic-oxycarbonyl” is meant a heteroaromatic group that is or can be coupled to a compound disclosed herein, wherein the heteroaromatic group is or becomes coupled through an oxycarbonyl group (-C(O)O-). In some embodiments, the heteroaromatic-carbonyl group is -C(O)O-R, in which R is an optionally substituted heteroaromatic group, as defined herein. [0209] By “heteroaryl” is meant an aryl group including at least one heteroatom to six heteroatoms, such as one to four heteroatoms, which can be selected from, but not limited to, oxygen, nitrogen, sulfur, silicon, boron, selenium, phosphorous, and oxidized forms thereof within the ring. Such heteroaryl groups can have a single ring or multiple condensed rings, where the condensed rings may or may not be aromatic and/or contain a heteroatom, provided that the point of attachment is through an atom of the aromatic heteroaryl group. Heteroaryl groups may be substituted with one or more groups other than hydrogen, such as aliphatic, heteroaliphatic, aromatic, other functional groups, or any combination thereof. An exemplary heteroaryl includes a subset of heterocyclyl groups, as defined herein, which are aromatic, i.e., they contain 4n+2 pi electrons within the mono- or multicyclic ring system. [0210] By “heteroarylene” is meant a multivalent (e.g., bivalent) form of a heteroaryl group, as described herein. [0211] By “heteroatom” is meant an atom other than carbon, such as oxygen, nitrogen, sulfur, silicon, boron, selenium, or phosphorous. In particular disclosed embodiments, such as when valency constraints do not permit, a heteroatom does not include a halogen atom.
Attorney Docket No. 10948-1WO/LAMRP827WO [0212] By “heterocyclyl” is meant a 5-, 6- or 7-membered ring, unless otherwise specified, containing one, two, three, or four non-carbon heteroatoms (e.g., independently selected from the group consisting of nitrogen, oxygen, phosphorous, sulfur, or halo). The 5-membered ring has zero to two double bonds and the 6- and 7-membered rings have zero to three double bonds. The term “heterocyclyl” also includes bicyclic, tricyclic and tetracyclic groups in which any of the above heterocyclic rings is fused 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 heterocyclic ring, such as indolyl, quinolyl, isoquinolyl, tetrahydroquinolyl, benzofuryl, benzothienyl and the like. Heterocyclics 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, isoxazolidiniyl, morpholinyl, thiomorpholinyl, thiazolyl, thiazolidinyl, isothiazolyl, isothiazolidinyl, indolyl, quinolinyl, isoquinolinyl, benzimidazolyl, benzothiazolyl, benzoxazolyl, furyl, thienyl, thiazolidinyl, isothiazolyl, isoindazoyl, triazolyl, tetrazolyl, oxadiazolyl, uricyl, thiadiazolyl, pyrimidyl, tetrahydrofuranyl, dihydrofuranyl, dihydrothienyl, dihydroindolyl, tetrahydroquinolyl, tetrahydroisoquinolyl, pyranyl, dihydropyranyl, tetrahydropyranyl, dithiazolyl, dioxanyl, dioxinyl, dithianyl, trithianyl, oxazinyl, thiazinyl, oxothiolanyl, triazinyl, benzofuranyl, benzothienyl, and the like. [0213] By “heterocyclyloxy” is meant a heterocyclyl group, as defined herein, attached to the parent molecular group through an oxygen atom. In some embodiments, the heterocyclyloxy group is -O-R, in which R is a heterocyclyl group, as defined herein. [0214] By “heterocyclyloyl” is meant a heterocyclyl group, as defined herein, attached to the parent molecular group through a carbonyl group. In some embodiments, the heterocyclyloyl group is -C(O)-R, in which R is a heterocyclyl group, as defined herein. [0215] By “hydrazino” is meant -NR1-NR2R3, where each of R1, R2, and R3 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 where a combination of R1 and R2 or a combination of R2 and R3, taken together with the nitrogen atom to which each are attached, can form a heterocyclyl group, as defined herein. In some embodiments, each of R1, R2, or R3 is, independently, H, optionally substituted alkyl, optionally substituted aryl, optionally substituted alkyl-aryl, or optionally substituted aryl-alkyl. In particular embodiments,
Attorney Docket No. 10948-1WO/LAMRP827WO R2 and R3 can be taken together, with the nitrogen atom to which each is attached, to form an optionally substituted heterocyclyl. [0216] By “hydroxyl” is meant -OH. [0217] By “hydroxyalkyl” is meant an alkyl group, as defined herein, substituted by one to three hydroxyl groups, with the proviso that no more than one hydroxyl group may be attached to a single carbon atom of the alkyl group and is exemplified by hydroxymethyl, dihydroxypropyl, and the like. In some embodiments, the hydroxyalkyl group is -L-OH, in which L is an alkyl group, as defined herein. In other embodiments, the hydroxyalkyl group is -L-C(OH)(R1)-R2, in which L is a covalent bond or an alkyl group, as defined herein, and each of R1 and R2 is, independently, H or alkyl, as defined herein. [0218] By “imidoyl” is meant a moiety including a carbonimidoyl group. In some embodiments, the imidoyl group is C(NR1)R2, in which each of R1 and R2 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, as defined herein, or any combination thereof. In other embodiments, the imidoyl group is -C(NR1)H, -C(NR1)RAk, or -C(NRN1)RAr, in which R1 is 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, or optionally substituted silyloxy; RAk is an optionally substituted alkyl or an optionally substituted aliphatic; and RAr is an optionally substituted aryl or an optionally substituted aromatic. [0219] By “imino” is meant a -NR- group. In some embodiments, R is selected from hydrogen, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, or optionally substituted heteroaromatic. In particular embodiments, R is H, optionally substituted alkyl, optionally substituted alkoxy, optionally substituted aryl, optionally substituted aryloxy, optionally substituted alkyl-aryl, or optionally substituted aryl-alkyl. [0220] By “isocyanato” is meant a -NCO group. [0221] By “isocyano” is meant a -NC group. [0222] By “ketone” is meant -C(O)R or a compound including such a group, where R is selected from aliphatic, heteroaliphatic, aromatic, as defined herein, or any combination thereof. An example of a ketone can include R1C(O)R, in which each of R and R1 is, independently, selected
Attorney Docket No. 10948-1WO/LAMRP827WO from aliphatic, haloaliphatic, haloheteroaliphatic, heteroaliphatic, aromatic, aliphatic-aromatic, heteroaliphatic-aromatic, as defined herein, or any combination thereof. [0223] By “nitro” is meant an -NO2 group. [0224] By “nitroalkyl” is meant an alkyl group, as defined herein, substituted by one to three nitro groups. In some embodiments, the nitroalkyl group is -L-NO, in which L is an alkyl group, as defined herein. In other embodiments, the nitroalkyl group is -L-C(NO)(R1)-R2, in which L is a covalent bond or an alkyl group, as defined herein, and each of R1 and R2 is, independently, H or alkyl, as defined herein. [0225] By “oxo” is meant an =O group. [0226] By “oxy” is meant -O-. [0227] By “perfluoroalkyl” is meant an alkyl group, as defined herein, having each hydrogen atom substituted with a fluorine atom. Exemplary perfluoroalkyl groups include trifluoromethyl, pentafluoroethyl, etc. In some embodiments, the perfluoroalkyl group is -(CF2)nCF3, in which n is an integer from 0 to 10. [0228] By “perfluoroalkoxy” is meant an alkoxy group, as defined herein, having each hydrogen atom substituted with a fluorine atom. In some embodiments, the perfluoroalkoxy group is -O-R, in which R is a perfluoroalkyl group, as defined herein. [0229] By “salt” is meant an ionic form of a compound or structure (e.g., any formulas, compounds, or compositions described herein), which includes a cation or anion compound to form 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 in “Handbook of Pharmaceutical Salts: Properties, Selection, and Use,” Wiley-VCH, April 2011 (2nd rev. ed., eds. P. H. Stahl and C. G. Wermuth. The salts can be prepared in situ during the final isolation and purification of the compounds of the invention or separately by reacting the free base group with a suitable organic acid (thereby producing an anionic salt) or by reacting the acid group with a suitable metal or organic salt (thereby producing a cationic salt). Representative anionic salts include acetate, adipate, alginate, ascorbate, aspartate, benzenesulfonate, benzoate, bicarbonate, bisulfate, bitartrate, borate, bromide, butyrate, camphorate, camphorsulfonate, chloride, citrate, cyclopentanepropionate, digluconate, dihydrochloride, diphosphate, dodecylsulfate, 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, methylbromide, methylnitrate, methylsulfate, mucate, 2-naphthalenesulfonate,
Attorney Docket No. 10948-1WO/LAMRP827WO 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 salts, and the like. Representative cationic salts include metal salts, such as alkali or alkaline earth salts, e.g., barium, calcium (e.g., calcium edetate), lithium, magnesium, potassium, sodium, and the like; other metal salts, such as aluminum, bismuth, iron, and zinc; as well as nontoxic ammonium, quaternary ammonium, and amino cations, including, but not limited to ammonium, tetramethylammonium, tetraethylammonium, methylamine, dimethylamine, trimethylamine, triethylamine, ethylamine, pyridinium, and the like. Other cationic salts include organic salts, such as chloroprocaine, choline, dibenzylethylenediamine, diethanolamine, ethylenediamine, methylglucamine, and procaine. Yet other salts include ammonium, sulfonium, sulfoxonium, phosphonium, iminium, imidazolium, benzimidazolium, amidinium, guanidinium, phosphazinium, phosphazenium, pyridinium, etc., as well as 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 indolizinium, optionally substituted indazolium, optionally substituted benzimidazolium, optionally substituted isoquinolinum, optionally substituted quinolizinium, optionally substituted dehydroquinolizinium, optionally substituted quinolinium, optionally substituted isoindolinium, optionally substituted benzimidazolinium, and optionally substituted purinium). [0230] By “silyl” is meant a -SiR1R2R3 or -SiR1R2- group. In some embodiments, each of R1, R2, and R3 is, independently, H, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, optionally substituted heteroaromatic, or optionally substituted amino. In particular embodiments, each of R1, R2, and R3 is, independently,
Attorney Docket No. 10948-1WO/LAMRP827WO 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, in which each R is, independently, H, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, or optionally substituted heteroaromatic; each of a, b, and c ≥ 0; and a + b + c = 3. In particular embodiments, each R is, independently, H, optionally substituted alkyl, optionally substituted aryl, optionally substituted alkyl-aryl, or optionally substituted aryl-alkyl. [0231] By “silyloxy” is meant -OR, where R is an optionally substituted silyl group, as described herein. In some embodiments, the silyloxy group is -O-SiR1R2R3, in which each of R1, R2, and R3 is, independently, H, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, optionally substituted heteroaromatic, or optionally substituted amino. In particular embodiments, each of R1, R2, and R3 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, in which each R is, independently, H, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, or optionally substituted heteroaromatic; each of a, b, and c ≥ 0; and a + b + c = 3. In particular embodiments, each R is, independently, H, optionally substituted alkyl, optionally substituted aryl, optionally substituted alkyl-aryl, or optionally substituted aryl- alkyl [0232] By “sulfinyl” is meant an -S(O)- group. [0233] By “sulfo” is meant an -S(O)2OH group. [0234] By “sulfonyl” or “sulfonate” is meant an -S(O)2- group or a -SO2R, where R is selected from hydrogen, aliphatic, heteroaliphatic, haloaliphatic, haloheteroaliphatic, aromatic, as defined herein, or any combination thereof. [0235] By “thioalkyl” is meant an alkyl group, as defined herein, attached to the parent molecular group through a sulfur atom. Exemplary unsubstituted thioalkyl groups include C1-6 thioalkyl. In some embodiments, the thioalkyl group is -S-R, in which R is an alkyl group, as defined herein. [0236] By “thiol” is meant an -SH group. [0237] A person of ordinary skill in the art would recognize that the definitions provided above are not intended to include impermissible substitution patterns (e.g., methyl substituted with 5 different groups, and the like). Such impermissible substitution patterns are easily recognized by
Attorney Docket No. 10948-1WO/LAMRP827WO a person of ordinary skill in the art. Any functional group disclosed herein and/or defined above can be substituted or unsubstituted, unless otherwise indicated therein. [0238] As used herein, the term “about” means +/-10% of any recited value. As used herein, this term modifies any recited value, range of values, or endpoints of one or more ranges. [0239] 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 indicate or require that a particular structure must be located at a particular location in the apparatus. [0240] Other features and advantages of the invention will be apparent from the following description and the claims. SILICON-CONTAINING PRECURSORS [0241] 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 particular embodiments, the silicon- containing precursor includes a halosilane precursor. In particular embodiments, the silicon- containing precursor includes an aminosilane precursor. [0242] An aminosilane includes at least one nitrogen atom bonded to a silicon atom, but may also contain hydrogens, oxygens, halogens and carbons. Examples of aminosilanes are mono-, di-, tri- and tetra-aminosilane (H3Si(NH2)4, H2Si(NH2)2, HSi(NH2)3 and Si(NH2)4, respectively), as well as substituted mono-, di-, tri- and tetra-aminosilanes, for example, t-butylaminosilane, methylaminosilane, tert-butylsilanamine, bis(tertiarybutylamino)silane (SiH2(NHC(CH3)3)2 (BTBAS), tert-butyl silylcarbamate, 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. [0243] A silicon-containing precursor can include one or more optionally substituted amino groups, thereby providing a non-limiting amino silane. In one embodiment, the precursor has a formula of (Rʹ)4-xSi(NRʺ2)x, wherein: x is 1, 2, 3, or 4; each Rʹ 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,
Attorney Docket No. 10948-1WO/LAMRP827WO amino, hydrazino, azido, hydroxyl, silyl, silyloxy, cyanato, isocyanato, cyano, or isocyano, in which any of these may be optionally substituted; and each Rʺ is, independently, H, aliphatic, heteroaliphatic, aromatic, heteroaromatic, or amino, in which any of these may be optionally substituted; or optionally in which two Rʺ can be taken together, with the nitrogen atom to which each is attached, to form an optionally substituted heterocyclyl. [0244] In another embodiment, the precursor has a formula of (Rʺ2N)x(Rʹ)3-xSi−L−Si(Rʹ)3-x(NRʺ2)x, wherein: each x is, independently, 0, 1, 2, or 3; L is a linker, such as a covalent bond, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, optionally substituted heteroaromatic, oxy (-O-), imino, or silyl; each Rʹ 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, azido, hydroxyl, silyl, silyloxy, cyanato, isocyanato, cyano, or isocyano, in which any of these may be optionally substituted; and each Rʺ is, independently, H, aliphatic, heteroaliphatic, aromatic, heteroaromatic, or amino, in which any of these may be optionally substituted; or optionally in which two Rʺ can be taken together, with the nitrogen atom to which each is attached, to form an optionally substituted heterocyclyl. [0245] In particular embodiments, L is optionally substituted imino, such as -NR-, in which R is H, optionally substituted aliphatic, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, or optionally substituted aromatic. In other embodiments, L is optionally substituted silyl, such as -SiR2-, in which each R is, independently, H, optionally substituted aliphatic, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, or optionally substituted aromatic. [0246] In one instance, at least one x is not 0. In another embodiment, x can be 0 (e.g., if L includes a carbon atom or a heteroatom). In yet another embodiment, x is 0; and/or L includes optionally substituted aliphatic, optionally substituted alkylene, optionally substituted alkenylene, optionally substituted alkynylene, optionally substituted heteroaliphatic, optionally substituted heteroalkylene, optionally substituted heteroalkenylene, optionally substituted heteroalkynylene,
Attorney Docket No. 10948-1WO/LAMRP827WO optionally substituted aromatic, optionally substituted arylene, optionally substituted heteroaromatic, optionally substituted heteroarylene, oxy (-O-), imino, or silyl. [0247] In particular embodiments, at least one Rʹ or Rʺ is not H. The precursor can have any useful combination of Rʹ groups and amino groups (NRʺ2) attached to one or more silicon atoms. [0248] In some embodiments, Rʹ 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), aromatic (e.g., aryl), aromatic-oxy (e.g., aryloxy or -OR), hydroxyl (-OH), formyl (-C(O)H), and the like. In particular 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 be taken together, with the nitrogen atom to which each is attached, to 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. [0249] In other embodiments, Rʺ is H, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted alkyl, optionally substituted silyl, or optionally substituted silyloxy. In some embodiments, Rʺ is optionally substituted alkyl (e.g., Me, Et, nPr, iPr, sBu, or tBu). In other embodiments, Rʺ is -SiRʹ3, -SiR3, -Si(Rʹ)a(OR)b, -Si(R)a(OR)b, -Si(Rʹ)a(NR2)b, -Si(R)a(NR2)b, -Si(Rʹ)a(OR)b(NR2)c, -Si(R)a(OR)b(NR2)c, -O-SiRʹ3, -O-SiR3, -O-Si(Rʹ)a(OR)b, -O-Si(R)a(OR)b, -O-Si(Rʹ)a(NR2)b, -O-Si(R)a(NR2)b, -O-Si(Rʹ)a(OR)b(NR2)c, or -O-Si(R)a(OR)b(NR2)c in which each Rʹ is, independently, H, aliphatic, heteroaliphatic, aromatic, heteroaromatic, amino, hydrazino, azido, hydroxyl, silyl, silyloxy, cyanato, isocyanato, cyano, or isocyano, in which any of these may be optionally substituted; each R is, independently, H, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, or optionally substituted heteroaromatic; each of a, b, and c ≥ 0; and a + b + c = 3 or a + b = 3 (if c is not present). In particular embodiments, R is H, optionally substituted alkyl, optionally substituted alkenyl, or optionally substituted alkynyl. [0250] The precursor can include at least one Rʹ group attached to the silicon atom. In one embodiment, the precursor has a formula of (Rʹ)(H)3-xSi(NRʺ2)x, wherein Rʹ and Rʺ can be any
Attorney Docket No. 10948-1WO/LAMRP827WO described herein, and wherein x is 1, 2, or 3. In another embodiment, the precursor has a formula of (Rʹ)(H)2Si(NRʺ2), wherein Rʹ and Rʺ can be any described herein. In one embodiment, the precursor has a formula of (Rʹ)(H)Si(NRʺ2)2, wherein Rʹ and Rʺ can be any described herein. In another embodiment, the precursor has a formula of (Rʹ)2(H)Si(NRʺ2), wherein Rʹ and Rʺ can be any described herein. In yet another embodiment, the precursor has a formula of (Rʹ)2Si(NRʺ2)2, wherein Rʹ and Rʺ can be any described herein. In one embodiment, the precursor has a formula of (Rʹ)3Si(NRʺ2), wherein Rʹ and Rʺ can be any described herein. [0251] The precursor can lack an Rʹ group attached to the silicon atom. In one embodiment, the precursor has a formula of (H)4-xSi(NRʺ2)x, wherein each Rʺ can independently be any described herein, and wherein x is 1, 2, 3, or 4. In another embodiment, the precursor has a formula of Si(NRʺ2)x, wherein each Rʺ can independently be any described herein. In particular embodiments, each Rʺ is, independently, aliphatic, heteroaliphatic, aromatic, or heteroaromatic. [0252] The precursor can include one or more hydrogen atoms attached to the silicon atom. In one embodiment, the precursor has a formula of (H)3Si(NRʺ2) or (H)2Si(NRʺ2)2 or (H)Si(NRʺ2)3, wherein each Rʺ can independently be any described herein. In particular embodiments, each Rʺ is, independently, aliphatic, heteroaliphatic, aromatic, heteroaromatic, or amino, in which any of these may be optionally substituted. [0253] The precursor can include a heterocyclyl group having a nitrogen atom. In one embodiment, the formula has a formula of H3Si-Het, in which Het is an optionally substituted heterocyclyl including at least one nitrogen atom. In particular embodiments, the precursor has a formula of , in which the heterocyclyl group can be optionally substituted (e.g., with any substituent described herein as a substitution for alkyl), and wherein n is 1,2, 3, 4, or 5. In one embodiment, the formula has a formula of Rʹ3Si-Het, in which Het is an optionally substituted heterocyclyl including at least one nitrogen atom, and each Rʹ can independently be any described herein. In particular embodiments, the precursor has a formula of , in which the heterocyclyl group can be optionally substituted (e.g., with any substituent described herein as a substitution for alkyl); each Rʹ can independently be any described herein; and wherein n is 1,2, 3, 4, or 5. [0254] In some instances, the precursor can have two or more silicon atoms, in which the precursor can include a Si-Si bond. In a particular embodiment, the precursor has a formula of (Rʺ2N)x(Rʹ)3-xSi−Si(Rʹ)3-x(NRʺ2)x, wherein Rʹ and Rʺ can be any described herein. In one embodiment, the precursor has a formula of (Rʺ2N)(Rʹ)2Si−Si(Rʹ)2(NRʺ2), wherein Rʹ and Rʺ can be any described herein. In another embodiment, the precursor has a formula of (Rʺ2N)2(Rʹ)Si−
Attorney Docket No. 10948-1WO/LAMRP827WO Si(Rʹ)(NRʺ2)2, wherein Rʹ and Rʺ can be any described herein. In yet another embodiment, the precursor has a formula of (Rʺ2N)3Si−Si(NRʺ2)3, wherein each Rʺ can independently be any described herein. [0255] The precursor can include differing groups attached to the silicon atoms. In one instance, the precursor has a formula of (Rʺ2N)x(Rʹ)3-xSi−SiH3, wherein Rʹ and Rʺ can be any described herein. [0256] A linker can be present between two silicon atoms. In one instance, the precursor has a formula of (Rʺ2N)x(Rʹ)3-xSi−NR−Si(Rʹ)3-x(NRʺ2)x, wherein Rʹ and Rʺ can be any described herein, and in which R is H, optionally substituted aliphatic, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, or optionally substituted aromatic. In another instance, the precursor has a formula of (Rʺ2N)x(H)3-xSi−NR−Si(H)3-x(NRʺ2)x, wherein R, Rʹ, and Rʺ can be any described herein. [0257] The precursor can include a combination of Rʹ groups with a linker having a heteroatom. In one instance, the precursor has a formula of (Rʹ)3Si−NR−Si(Rʹ)3, wherein R and Rʹ can be any described herein. In another instance, the precursor has a formula of (Rʹ)3Si−L−Si(Rʹ)3, wherein L and Rʹ can be any described herein. In particular embodiments, L is oxy (-O-), optionally substituted imino (e.g., -NR-), or optionally substituted silyl (e.g., -SiR2-). [0258] The precursor can include any useful combination of Rʹ and NRʺ2 groups in combination with two silicon atoms. In one instance, the precursor has a formula of (Rʺ2N)(Rʹ)2Si−L−Si(Rʹ)2(NRʺ2)x, wherein L, Rʹ, and Rʺ can be any described herein. [0259] The precursor can include heterocyclic groups including the silicon and nitrogen atoms. In one embodiment, the precursor has a formula
wherein Rʹ and Rʺ can be any described herein, and wherein n is 1, 2, 3, or 4. [0260] In another embodiment, the precursor has a formula
wherein Rʹ and Rʺ can be any described herein, and wherein n is 1, 2, 3, or 4. In yet another embodiment, the precursor has a formula
which each Rʺ can independently be any described herein; and wherein n is 1,2, 3, or 4.
Attorney Docket No. 10948-1WO/LAMRP827WO In another embodiment, the precursor has a formula
wherein Rʹ and Rʺ can be any described herein, and wherein n is 1, 2, 3, or 4. In yet another embodiment, the precursor has a formula
, wherein Rʺ can independently be any described herein, and wherein n is 1, 2, 3, or 4. [0261] In any precursor herein, two Rʺ can be taken together, with the nitrogen atom to which each is attached, to form an optionally substituted heterocyclyl. [0262] Precursors can include any of the following, e.g., (RAk)Si(NH2)(NRAk2)2, (RAk)Si(NRAk 2)3, (RAk)2Si(NHRAk2)2, (RAk)(H)Si(NHRAk)2, (RAk)3Si(NRAk2), (RAk)3Si(NHRAk), H2Si(NHRAk2)2, (RAk)(H)Si(NRAk 2)2, HSi(NH2)(NRAk2)2, HSi(NRAk2)3, Si(NRAk2)4, (Rʹ)(H)Si(NRʺ Ak 2)2, (Rʹ)2Si(NR 2)2, (Rʹ)2Si(N[SiH3]2)2, (Rʹ)2Si(N[SiRʺ3]2)2, or (Rʹ)3Si(NHRAk). In some embodiments, each of Rʹ and Rʺ, independently, can be any 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 RAk is, independently, H, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted alkyl, optionally substituted alkenyl, or optionally substituted alkynyl. In particular embodiments, RAk is methyl (Me), ethyl (Et), n-propyl (nPr), iso-propyl (iPr), n-butyl (nBu), sec-butyl (sBu), iso-butyl (iBu), tert-butyl (tBu), and the like. [0263] Non-limiting examples of precursor 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
Attorney Docket No. 10948-1WO/LAMRP827WO (SiH3[NiPr2], C6H17NSi, 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], in which 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], in which Cy is cyclohexyl); pyrrolyltrimethylsilane (SiMe3[NHPy], in which Py is pyrrolyl); pyrrolidinotrimethylsilane (SiMe3[NHPyr], in which Pyr is pyrrolindyl); piperidino trimethylsilane (SiMe3[NHPip], in which Pip is piperidinyl); piperazinotrimethylsilane (SiMe3[NHPz], in which Pz is piperazinyl); imidazolyltrimethylsilane (SiMe3[NHIm], in which 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, C8H22N2Si, 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, in
Attorney Docket No. 10948-1WO/LAMRP827WO which 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, C9H25N3Si, 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)disilane ([EtHN]3Si−Si[NHEt]3); hexakis(dimethylamino)disilazane (Me2N−Si[NMe2]2− Si[NMe2]2−NMe2), and the like. [0264] In some embodiments, the silane precursor is a halosilane precursor. A halosilane precursor is defined as a precursor having at least one halogen-containing atom and at least one silicon atom. Halogens include chlorine, fluorine, bromine, and iodine. In some embodiments, the halosilane precursor includes a structure of formula (I): Si(X)4, wherein at least one X includes a halogen atom. [0265] For example, one halosilane is tetrachlorosilane or silicon tetrachloride (SiCl4). Another example of a chemical formula of a halosilane is SinXyHz where X is a halogen and H is hydrogen; n is an integer greater than or equal to 1 and is equal to the number of Si atoms in the molecule; in some embodiments, y is about 1 to about 4, and z is 4-y. Additional examples include but are not limited to SiHCl3, SiH2Cl2, and SiH3Cl. [0266] Examples of halosilanes are iodosilanes, bromosilanes, chlorosilanes and fluorosilanes. Specific chlorosilanes include but are not limited to tetrachlorosilane, trichlorosilane, dichlorosilane (DCS), monochlorosilane, chloroallylsilane, chloromethylsilane, dichloromethylsilane, chlorodimethylsilane, chloroethylsilane, t-butylchlorosilane, di-t- butylchlorosilane, chloroisopropylsilane, chloro-sec-butylsilane, t-butyldimethylchlorosilane, thexyldimethylchlorosilane, hexachlorodisilane (HCDS), and the like. [0267] In some embodiments, the halosilane is carbon-free. In some embodiments, the halosilane is an organic silicon-containing precursor. [0268] In some embodiments, the halosilane precursor (e.g., in formula (I)) has at least one optionally substituted C1-2 haloalkyl group. Non-limiting haloaliphatic groups include -CXyH3-y, wherein y is 1, 2, or 3, and wherein each X is, independently, halo (F, Cl, Br,
Attorney Docket No. 10948-1WO/LAMRP827WO or I); -CXzH2-zCXyH3-y, wherein z is 0, 1, or 2, wherein y is 0, 1, 2, or 3, and wherein each X is, independently, halo (F, Cl, Br, or I), in which at least one of z or y is not 0; or -CH2CXyH3-y, wherein y is 1, 2, or 3, and wherein each X is, independently, halo (F, Cl, Br, or I). Yet other non- limiting haloalkyl groups include fluoromethyl (-CH2F), difluoromethyl (-CHF2), trifluoromethyl (-CF3), chloromethyl (-CH2Cl), dichloromethyl (-CHCl2), trichloromethyl (-CCl3), bromomethyl (-CH2Br), dibromomethyl (-CHBr2), tribromomethyl (-CBr3), iodomethyl (-CH2I), diiodomethyl (-CHI2), triiodomethyl (-CI3), bromofluoromethyl (-CHFBr), chlorofluoromethyl (-CHFCl), fluoroiodomethyl (-CHFI), 2-fluoroethyl (-CH2CH2F), 2-chloroethyl (-CH2CH2Cl), 2-bromoethyl (-CH2CH2Br), 2-iodoethyl (-CH2CH2I), 2,2-difluoroethyl (-CH2CHF2), 2,2-dichloroethyl (- CH2CHCl2), 2,2-dibromoethyl (-CH2CHBr2), 2,2-diiodoethyl (-CH2CHI2), 2,2-fluoroiodoethyl (- CH2CHFI), and the like. In particular embodiments, the C1-2 haloalkyl includes β-halo-substituted ethyl. Yet other haloaliphatic groups include C1-4 haloalkyl, C2-4 haloalkenyl, and C2-4 haloalkynyl. CONCLUSION [0269] Although the foregoing embodiments have been described in some detail for purposes of clarity of understanding, it will be apparent that certain changes and modifications may be practiced within the scope of the appended claims. It should be noted that there are many alternative ways of implementing the processes, systems, and apparatus of the present embodiments. Accordingly, the present embodiments are to be considered as illustrative and not restrictive, and the embodiments are not to be limited to the details given herein.