Oxidizing plasma-free silicon oxide deposition

Abstract

Methods and apparatuses for depositing silicon-containing materials such as silicon oxide using an oxygen-free plasma are provided. Methods involve using a silicon-containing precursor having an oxygen atom and igniting an oxygen-free plasma to convert the silicon-containing precursor to silicon oxide.

Description

Attorney Docket No. LAMRP993WO-11549-1WO OXIDIZING PLASMA-FREE SILICON OXIDE DEPOSITION INCORPORATION BY REFERENCE

[0000] A PCT Request Form is filed 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

[0001] Certain semiconductor fabrication processes may involve formation of silicon-containing films such as silicon oxide films. It may be challenging to deposit such films selectively or without resulting in undesirable oxidation of other exposed surfaces during deposition.

[0002] 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

[0003] One aspect involves a method for processing substrates, the method including: providing a substrate; exposing the substrate to a silicon-containing precursor including an oxygen atom in a plasma-free environment, thereby forming a layer of the silicon-containing precursor on a surface of the substrate; and exposing the layer of the silicon-containing precursor to an oxygen-free plasma, such that exposing the layer of the silicon-containing precursor to the oxygen-free plasma converts the layer of the silicon-containing precursor to a silicon-containing material.

[0004] In various embodiments, the substrate includes a first exposed surface including dielectric material and a second exposed surface including a metal-containing material. In various embodiments, the layer of the silicon-containing precursor forms selectively on the first exposed surface relative to the second exposed surface.

[0005] In various embodiments, the silicon-containing precursor has a silicon to oxygen ratio of 1:2.

[0006] In various embodiments, the silicon-containing precursor includes at least one Si-O bond.

[0007] In various embodiments, the silicon-containing precursor includes a halogen substituent.

[0008] In various embodiments, the silicon-containing precursor includes an amino substituent.

[0009] In various embodiments, the oxygen-free plasma is generated by igniting a hydrogen gas.

[0010] In various embodiments, the oxygen-free plasma is generated by igniting a helium gas.

[0011] In various embodiments, the oxygen-free plasma is generated by igniting a gas mixture including helium and hydrogen.Attorney Docket No. LAMRP993WO-11549-1WO

[0012] In various embodiments, the silicon-containing precursor is delivered at a vapor pressure of about 0.1 Torr to about 15 Torr. In various embodiments, the silicon-containing precursor is delivered at a vapor pressure of about 1 Torr to about 5 Torr. In various embodiments, the silicon- containing precursor is delivered at a vapor pressure of greater than about 1 Torr.

[0013] In various embodiments and in any of the above described embodiments, the silicon- containing material may include silicon oxide.

[0014] In various embodiments and in any of the above described embodiments, the silicon- containing material may include silicon oxycarbide.

[0015] In various embodiments and in any of the above described embodiments, the silicon- containing material may include silicon oxynitride.

[0016] In various embodiments and in any of the above described embodiments, the silicon- containing material may include silicon carbonitride.

[0017] In various embodiments and in any of the above described embodiments, the silicon- containing material may include an amino group.

[0018] In various embodiments and in any of the above described embodiments, the silicon- containing material may include a halogen substituent.

[0019] In various embodiments and in any of the above described embodiments, the oxygen- free plasma is generated remotely.

[0020] In various embodiments and in any of the above described embodiments, the oxygen- free plasma is generated in situ.

[0021] In various embodiments and in any of the above described embodiments, the substrate is heated to a temperature of about 25°C to about 400°C.

[0022] 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, such that 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 silicon-containing precursor having an oxygen atom to the one or more process chambers, and cause generation of a plasma using an oxygen-free gas to convert the silicon-containing precursor to silicon oxide on a substrate held by the chuck.

[0023] 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 leastAttorney Docket No. LAMRP993WO-11549-1WO one processor and a memory, such that 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 the method of any of the above described embodiments.

[0024] These and other aspects are described further below with reference to the drawings. BRIEF DESCRIPTION OF THE DRAWINGS

[0025] Figure 1 is a process flow diagram depicting operations for a method in accordance with certain disclosed embodiments.

[0026] Figures 2A-2D are schematic illustrations of substrates undergoing operations described in accordance with certain disclosed embodiments.

[0027] Figures 3 and 4 are schematic diagrams of example process chambers for performing certain disclosed embodiments.

[0028] Figure 5 and 6 are schematic diagrams of example process tools for performing certain disclosed embodiments.

[0029] Figure 7 is a graph depicting growth rate of a film deposited in accordance with certain disclosed embodiments.

[0030] Figure 8 is an FTIR spectrum for a film deposited in accordance with certain disclosed embodiments. DETAILED DESCRIPTION

[0031] 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 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.

[0032] Semiconductor fabrication processes often involves deposition of films having silicon and oxygen atoms, such as silicon oxide. Sometimes, silicon oxide may be deposited using an oxygen-containing plasma, or a plasma generated by igniting oxygen gas (O2). However, sometimes the substrate that silicon oxide is deposited onto includes sensitive exposed surfaces, such as exposed metal-containing surfaces, and such plasma may be susceptible to damaging such surfaces. In some cases, damage may be because the metal-containing surface can be oxidized and it may not be desired to oxidize that surface. Example metal surfaces include but are not limited to copper, cobalt, tungsten, molybdenum, and ruthenium. This may also be the case inAttorney Docket No. LAMRP993WO-11549-1WO process flows that include selectively depositing silicon oxide on one region of the substrate relative to another region of the substrate (also known as “selective deposition”). Selective deposition of a material on a first region relative to or compared to a second region may be defined as the material having a higher deposition rate on the first region than on the second region. In some cases, the deposition rate may be so much higher that little or no deposition of the material is deposited on the second region. In some cases, it may be desirable to selectively deposit silicon oxide on a dielectric surface relative to a metal surface. Additionally, in some implementations, deposition using an oxygen-containing plasma may result in silicon oxide having particular properties, such as having a high dielectric constant. In some cases, it may not be desirable to form silicon oxide having a high dielectric constant.

[0033] Provided herein are methods and apparatuses for depositing silicon-containing materials using an oxygen-free plasma. Silicon-containing materials may include silicon oxide, silicon oxycarbide, silicon oxynitride, or silicon carbonitride. Certain disclosed embodiments can improve deposition processes by reducing the likelihood of oxidizing certain exposed surfaces that are susceptible to oxidation during the plasma exposure. For example, certain embodiments may be used for selectively depositing silicon oxide a first surface on a substrate relative to an exposed metal-containing surface of the substrate without oxidizing or damaging the metal-containing surface. Certain disclosed embodiments may be used for depositing silicon oxide having a low-k dielectric constant.

[0034] Techniques described herein involve atomic layer deposition (ALD). 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 silicon-containing precursor, (ii) purging of the silicon-containing precursor from the chamber, (iii) delivery of an oxygen-free gas and generation of a plasma, and (iv) purging of the oxygen-free gas from the chamber.

[0035] 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. ForAttorney Docket No. LAMRP993WO-11549-1WO 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 first 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 is introduced to the chamber so that some of these molecules react with the first precursor adsorbed on the surface. In some processes, the second reactant reacts immediately with the adsorbed first precursor. 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.

[0036] 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.

[0037] In some implementations, ALD methods may include plasma activation. However, in thermal ALD processes described herein, plasma is not ignited. 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.

[0038] Figure 1 is a process flow diagram depicting operations that may be performed in accordance with certain disclosed embodiments. In an operation 102, a substrate is provided. The substrate may be a silicon wafer, e.g., a 200-mm wafer, a 300-mm wafer, or a 450 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 other layers that may be present on the substrate surface include dielectric layers and conducting layers, e.g., silicon oxides, siliconAttorney Docket No. LAMRP993WO-11549-1WO nitrides, silicon carbides, metal oxides, metal nitrides, metal carbides, and metal layers. In some embodiments, the substrate includes silicon oxide and silicon.

[0039] In various embodiments, the substrate is provided to a process chamber. The process chamber may be set to a chamber pressure of about 10 mTorr to about 10 Torr, or about 1 Torr to about 3 Torr. Such chamber pressures may be used throughout operations 102-116 as described herein. The substrate may be heated to a substrate temperature of about 25°C to about 400°C, or about 200°C to about 300°C. 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 102-116 as described herein.

[0040] In some embodiments, the substrate may include multiple regions or multiple surfaces. For example, the substrate may include a first surface having a dielectric material, and a second surface having a metal material thereon. Example dielectric materials include but are not limited to silicon, silicon oxides, silicon nitrides, silicon carbides, silicon oxycarbides, silicon oxynitrides, silicon carbonitride, and combinations thereof. Example metal materials include but are not limited to copper, cobalt, tungsten, molybdenum, and ruthenium, alloys thereof, and combinations thereof. Figure 2A shows an example silicon substrate 201 with a dielectric material 203 and metal material 205 deposited thereon.

[0041] Returning to Figure 1, in an operation 104, the substrate is exposed to a silicon-containing precursor having an oxygen atom to form a layer of the precursor on the substrate surface. In some embodiments, forming the layer of the precursor is done selectively such that the precursor selectively or preferentially forms on a first surface of the substrate relative to second surface of the substrate. In some embodiments, forming the layer of the precursor on the substrate is formed non-selectively such that the precursor is formed on all or almost all exposed surfaces of the substrate.

[0042] Operation 104 may be performed under various process conditions. The process chamber may be set to a chamber pressure of about 10 mTorr to about 10 Torr, or about 1 Torr to about 3 Torr. In various embodiments, the silicon-containing precursor having an oxygen atom is introduced to the process chamber using a particular vapor pressure, such as about 0.1 Torr to about 15 Torr, or about 1 Torr to about 5 Torr, or greater than about 1 Torr of vapor pressure. In various embodiments, the silicon-containing precursor is heated or delivery through heated pipes or a different ampoule is used for delivering the silicon-containing precursor. The substrate may be heated to a substrate temperature of about 25°C to about 400°C, or about 200°C to about 300°C, or about 400°C. In various embodiments, the substrate is exposed to the silicon-containingAttorney Docket No. LAMRP993WO-11549-1WO precursor having an oxygen atom in a plasma-free environment.

[0043] The silicon-containing precursor having an oxygen atom may have a low melting point, a low boiling point, or both. An example low melting point is a melting point of less than about 50°C. An example low boiling point is a boiling point of less than about 100°C. The silicon- containing precursor having an oxygen atom includes at least one Si-O bond. The silicon- containing precursor having an oxygen atom may include only one silicon atom. The silicon- containing precursor having an oxygen atom may include only one silicon atom and at least one Si-O bond. The silicon-containing precursor having an oxygen atom may include only one silicon atom and two Si-O bonds. In various embodiments, to form stoichiometric silicon oxide (SiO2), the silicon-containing precursor selected may have a matching stoichiometric ratio such that at least one of the following is true: there is two oxygen atoms per silicon atom, or there is a silicon atom that is bound to two oxygen atoms each by a single bond. The silicon-containing precursor having an oxygen atom may also have other substituents, including a reactive substituent, such as but not limited to an amino group, a halogen, or an organic group. Example halogens include but are not limited to chlorine, bromine, and iodine. A reactive substituent is a compound that is capable of chemical adsorption onto the substrate surface. For example, a reactive substituent could enable adsorption onto the hydroxyl groups on a silicon oxide (SiO2) surface. Non-limiting examples of reactive substituents include amino groups, halogens, organic groups, and O- containing groups.

[0044] Example silicon-containing precursors having an oxygen atom include but are not limited to the following structures:N-allyl-aza-2,2-dimethoxysilacyclopentane

[0045] Additional precursors are further described herein in the Definitions and PrecursorsAttorney Docket No. LAMRP993WO-11549-1WO section.

[0046] While certain disclosed embodiments are described with respect to deposition of silicon oxide, other silicon-containing materials may be used using certain disclosed embodiments by selecting a precursor with particular properties or features.

[0047] The desired film composition (i.e. Si:O:C:N ratio) can be tuned by changing the Si:O:C:N ratio in the precursor. The desired Si:O:C:N ratio for each film type will depend on the application for using certain disclosed embodiments. For example, in some embodiments, certain disclosed embodiments could be used for deposition of low-k films, liners, gapfill, hard mask, diffusion barriers, and more.

[0048] In some embodiments, changing the deposited film composition (e.g. from SiOC to SiON) could likely be done both by changing the precursor or by changing the plasma conditions, or a combination of both.

[0049] For example, for deposition of silicon oxycarbide, the silicon-containing precursor may include a Si-O bond and a Si-C bond. In some embodiments, the silicon-containing precursor may have a Si-O bond to Si-C bond ratio of between about 3:1 to 1:3.

[0050] For deposition of silicon oxynitride, the silicon-containing precursor may include a Si-O bond and an Si-N bond. In some embodiments, the silicon-containing precursor may have a Si-O bond to Si-N bond ratio of between about 3:1 to 1:3.

[0051] For deposition of silicon carbonitride, the silicon-containing precursor may include a Si- N bond and an Si-C bond. In some embodiments, the silicon-containing precursor may have a Si- N bond to Si-C bond ratio of between about 3:1 to 1:3

[0052] In some embodiments, the precursor selected may also enable selective deposition. In some embodiments, the silicon-containing precursor may include an amide group which selectively or preferentially adsorbs or forms on an oxide surface (relative to a metal surface). The amide group reacts with Si-OH bonds on the surface of the oxide to adsorb and / or form a layer of the precursor onto the surface of the oxide. In some embodiments, for non-selective deposition, the precursor may also include an amide group.

[0053] Figure 2B shows an example silicon substrate 201 with a dielectric material 203 and metal material 205 deposited thereon whereby a silicon-containing precursor layer 207 is formed over the dielectric material 203 and metal material 205.

[0054] Returning to Figure 1, in an operation 106, the layer of the precursor is exposed to a plasma generated from igniting an oxygen-free gas. This operation may form an oxygen-free plasma that then reacts with the layer of the precursor to form silicon oxide on the substrate surface.

[0055] In various embodiments, prior to operation 106 and after operation 104, flow of the silicon-containing precursor is stopped. Prior to generating the plasma, flow of the oxygen-freeAttorney Docket No. LAMRP993WO-11549-1WO gas may begin. In various embodiments, operation 106 is performed while the silicon-containing precursor gas flow is diverted or not delivered to the process chamber housing the substrate.

[0056] In operation 106, the plasma may be generated using any suitable plasma source, such as but not limited to capacitively coupled plasma and inductively coupled plasma. In some embodiments, the plasma is generated remotely. In some embodiments, the plasma is generated in situ.

[0057] The oxygen-free gas may be an inert gas, such as argon, hydrogen, helium, neon, and combinations thereof. The oxygen-free gas may be helium in some embodiments. The oxygen- free gas may be hydrogen gas in some embodiments. The oxygen-free gas may be a mixture of helium and hydrogen in some embodiments. The usage of an oxygen-free gas reduces the likelihood of generating oxygen plasma species which may undesirably oxidize metal surfaces on the substrate.

[0058] Plasma may be generated using certain process conditions suitable for the oxygen-free gas used and the precursor used in operation 104. Certain plasma processing conditions, such as plasma power, plasma duration, and chemistry flows during plasma generation, may affect the film growth and film quality. In some embodiments, the plasma 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, an RF power supply and matching network may be operated at any suitable power to form a plasma having a desired composition of radical species. Examples of suitable powers are about 150W to about 6000W. The RF power supply may provide RF power of any suitable frequency. In some embodiments, the RF power supply 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 greater than about 13.56 MHz, or greater than 27 MHz, or greater than 40 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.

[0059] Figure 2C shows an example silicon substrate 201 having dielectric material 203 and metal material 205 deposited thereon whereby the layer of the silicon-containing precursor 207 having an oxygen atom from Figure 2B is converted to a silicon oxide film 209 after exposure to an oxygen-free plasma.

[0060] Purging may be performed before or after any operation in Figure 1. For example, purging may be performed after operation 104 and prior to operation 106 to remove silicon- containing precursors that did not form onto the substrate surface. Purging the chamber mayAttorney Docket No. LAMRP993WO-11549-1WO involve flowing a purge gas or a sweep gas, which may be a carrier gas used in other operations or may be a different gas. In some embodiments, purging may involve evacuating the chamber. The purge gas may be an inert gas in some embodiments. The purge gas may act as a sweep gas for removing process gases from the process chamber and / or process chamber plumbing. Example purge gases include argon, nitrogen, hydrogen, helium, neon, and combinations thereof. In some embodiments, purging may include one or more evacuation subphases for evacuating the process chamber. Purging may be omitted in some embodiments.

[0061] Operations 104 and 106 may be repeated in cycles. Any suitable number of deposition cycles may be included in an ALD process to deposit a desired film thickness of the deposited material. For example, about fifty deposition cycles may be performed to deposit a film on the substrate using disclosed embodiments.

[0062] While examples described herein refer to deposition of silicon oxide, it will be understood that certain disclosed embodiments may also be used to deposit silicon oxycarbide, silicon carbonitride, and other silicon-containing materials. Certain disclosed embodiments may eliminate usage of a catalyst, such as trimethylaluminum or pyridine, during deposition. Certain disclosed embodiments eliminate the usage of oxygen-containing plasma. Certain disclosed embodiments may be performed at certain higher deposition temperatures such as at least about 400°C, which can improve film quality.

[0063] As described elsewhere herein, certain disclosed embodiments may be used to form silicon oxide selectively on a dielectric surface relative to a metal surface. As shown in Figure 2D, silicon oxide 211 is formed selectively on the dielectric material 203 and no silicon oxide is on the metal surface 205. This may be achieved by using an inhibition process on the substrate prior to performing certain disclosed embodiments to block the metal surface. An example inhibition process may involve forming an inhibition material on the metal surface, or may involve depositing a metal mask on the metal surface such that the silicon-containing precursor preferentially forms on the dielectric surface and not on the metal mask. For example, the relative selectivity may be evaluated by rate of formation of the silicon-containing precursor on the substrate surface; the formation rate selectivity of dielectric to metal mask may be 100:1 or 1000:1 may be infinite (e.g., no silicon-containing precursor is formed on the metal mask).

[0064] An inhibition process may involve exposing the substrate to an inhibitor prior to performing certain disclosed embodiments. Example inhibitors include but are not limited to silanes (such as octylsilane, dodecylsilane, decylsilane, octadecylsilane, or butylsilane), aminosilanes (such as dimethylamino trimethylsilane, dimethylamino methylsilane, dimethylamino dimethyl silane, dimethylamino triethyl silane, diethylamino trimethylsilane, n-butyldimethyl(dimethylamino)silane, n-propyldimethyl(dimethylamino)silane, orAttorney Docket No. LAMRP993WO-11549-1WO triisopropyldimethylaminosilane), and halosilanes (such as hexachlorodisilane, dichlorodimethylsilane, n-propyltrichlorosilane, trichloro(octyl)silane, or n-octylmethyldichlorosilane), and other molecules (such as acetyl acetone, propargylamine, trimethylacetaldehyde, trimethylhexanal, or benzaldehyde). Such inhibitors may act to prevent deposition on one surface while allowing certain disclosed embodiments to deposit material on another surface. APPARATUS

[0065] Figure 3 depicts a schematic illustration of an embodiment of an atomic layer deposition (ALD) process station 300 having a process chamber body 302 for maintaining a low-pressure environment. A plurality of ALD process stations 300 may be included in a common low pressure process tool environment. For example, Figures 5 and 6 depict example embodiments of a multi- station processing tool 500 and tool 600. In some embodiments, one or more hardware parameters of ALD process station 300 including those discussed in detail below may be adjusted programmatically by one or more computer controllers 350.

[0066] ALD process station 300 fluidly communicates with reactant delivery system 301a for delivering process gases to a distribution 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, hydrogen gas, helium gas, for delivery to showerhead 306. One or more mixing vessel inlet valves 320 may control introduction of process gases to mixing vessel 309.

[0067] 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 304 may also be heat traced. In one non-limiting example, piping downstream of vaporization point 303 has an increasing temperature profile extending from approximately 100°C to approximately 150°C at mixing vessel 304.

[0068] 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, aAttorney Docket No. LAMRP993WO-11549-1WO 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 of piping downstream from vaporization point 303. In one scenario, a liquid injector may be mounted directly to mixing vessel 304. In another scenario, a liquid injector may be mounted directly to showerhead 306.

[0069] 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.

[0070] 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.

[0071] 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.

[0072] In another scenario, adjusting a height of pedestal 308 may allow a plasma density to be varied during plasma activation cycles 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.

[0073] 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 between about 25°C and about 400°C, or between about 200°C and about 300°C.

[0074] 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, pressure control of process station 300 may also be adjusted by varying a flow rate of one or moreAttorney Docket No. LAMRP993WO-11549-1WO gases introduced to the process station 300.

[0075] 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.

[0076] In some embodiments where plasma may be used as discussed above, such as for treating a silicon nitride surface, showerhead 306 and pedestal 308 electrically communicate with a radio frequency (RF) power supply 314 and matching network 316 for powering a plasma. 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 150W to about 6000W. RF power supply 314 may provide RF power of any suitable frequency. In some embodiments, RF power supply 314 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 greater than about 13.56 MHz, or greater than 27 MHz, or greater than 40 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.

[0077] 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.

[0078] In some embodiments, instructions for a controller 350 may be provided via input / outputAttorney Docket No. LAMRP993WO-11549-1WO 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 precursor gas having an oxygen atom, 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 instructions for setting a flow rate of an inert 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 a carrier or purge gas and time delay instructions for the third recipe phase. A fourth recipe phase may include instructions for modulating a flow rate of an oxygen-free gas, instructions for modulating the flow rate of a carrier or purge gas, generation of a plasma, and time delay instructions for the fourth recipe phase. A fifth, 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 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 460 of Figure 4.

[0079] Figure 4 shows a schematic view of an example processing tool 400 configured for depositing an inhibitor with a low vapor pressure onto a substrate. Processing tool 400 is configured as a CVD tool. Processing tool 400 includes a processing chamber 402 and a substrate support 404 within the processing chamber. Substrate support 404 is configured to support a substrate 406 disposed within processing chamber 402. Substrate support 404 may include a pedestal, a chuck, and / or any other suitable structure.

[0080] Processing chamber 402 further includes a substrate heater 408 configured to heat a substrate placed on substrate support 404. In other examples, a substrate heater may be located elsewhere within processing chamber 402, or may be omitted.

[0081] Processing tool 400 further includes a processing gas outlet 410. In some examples, processing gas outlet 410 may include a nozzle, showerhead, or other apparatus for introducing gas into processing chamber 402. Substrate support 404 can be raised and lowered to adjust the spacing between substrate 406 and processing gas outlet 410. In some examples, processing gas outlet 410 may include a heater.Attorney Docket No. LAMRP993WO-11549-1WO

[0082] Processing tool 400 further includes an ampoule 420 configured to hold a liquid phase processing chemical including a vapor pressure. Ampoule 420 is further configured to supply a flow of the vapor of the chemical in the ampoule by FOV. In some examples, the chemical includes an inhibitor configured to selectively deposit onto metal surfaces and inhibit oxide film growth. When ampoule 420 is holding a volume of liquid inhibitor, inhibitor in the gas phase occupies at least a portion of the ampoule. In other examples, ampoule 420 may hold a liquid phase processing chemical other than an inhibitor.

[0083] Ampoule 420 includes a FOV gas inlet 422 for flowing a carrier gas from a carrier gas source 423 into ampoule 420. Example carrier gases include N2, Ar, He, Ne, or Kr. FOV gas inlet 422 includes a mass flow controller 424 for controlling the flow of the carrier gas. In some examples, where carrier gas source 423 includes nitrogen, mass flow controller 424 is configured as a nitrogen mass flow controller. In other examples, mass flow controller 424 is configured for controlling the flow of a different carrier gas.

[0084] Ampoule 420 further includes a FOV gas outlet 426 for flowing gas out of ampoule 420. When a carrier gas is flowed through ampoule 420, the carrier gas flows over the surface of the liquid inhibitor and draws inhibitor gas through FOV gas outlet 426. Thus, the carrier gas flows with the inhibitor through FOV gas outlet 426.

[0085] Ampoule 420 further includes a bulkfill port 428 for refilling the ampoule with inhibitor from an inhibitor bulk source 430. In other examples, an ampoule may be refilled using a different method, such as by replacing a removable reservoir of inhibitor. Further, examples utilizing a liquid phase processing chemical other than an inhibitor, a bulk source of the liquid phase processing chemical other than the inhibitor may be included.

[0086] Processing tool 400 further includes an ampoule heater 434 for heating ampoule 420. Ampoule heater 434 may include any suitable configuration of one or more heating elements. In some examples, ampoule heater 434 may include a plurality of heating elements configured to apply heat to different locations on ampoule 420. As examples, ampoule heater 434 may include one or more of a cartridge heater, a ribbon heater, a jacket heater, a molded heater, or heating coil. In some examples, ampoule heater 434 includes a heater disposed below ampoule 420 and one or more heaters disposed around the sides of ampoule 420. In other examples, ampoule heater 434 may include any other suitable configuration.

[0087] As mentioned above, an inhibitor in liquid phase may have low vapor pressure. The vapor pressure of the inhibitor may increase with temperature. As one example, an inhibitor may have a vapor pressure of ≤ 10 torr at 60 ºC, ≤ 15 torr at 80ºC, ≤ 25 torr at 100ºC, and ≤ 50 torr at 120ºC. Other liquid phase processing chemicals, including other inhibitors, may have vapor pressures outside of these ranges. By heating ampoule 420, ampoule heater 434 increases theAttorney Docket No. LAMRP993WO-11549-1WO vapor pressure of the inhibitor. This allows the processing tool 400 to deliver more inhibitor in a flow of a carrier gas.

[0088] Processing tool 400 further includes a plurality of heated gas lines. More specifically, in this example, processing tool 400 includes a heated gas line 440A, a heated divert gas line 440B, and a heated maintenance vacuum line 440C. Heated gas line 440A, heated divert gas line 440B, and heated maintenance vacuum line 440C are respectively heated by gas line heaters 442A, 442B, 442C. The gas line heaters 442A, 442B, 442C are shown schematically as dashed lines. Gas line heaters 442A, 442B, 442C each may include any suitable configuration of one or more heating elements. As examples, gas line heaters 442A, 442B, 442C each may include one or more of a jacket heater, a ribbon heater, or a molded heater. Gas line heaters 442A, 442B, 442C may be controlled to respectively heat heated gas line 440A, heated divert gas line 440B, and heated maintenance vacuum line 440C to any suitable temperature or temperatures. The use of gas line heaters 442A, 442B, 442C helps to prevent vapor phase inhibitor from condensing on surfaces within heated gas line 440A, heated divert gas line 440B, and heated maintenance vacuum line 440C.

[0089] Heated gas line 440A is connected to FOV gas outlet 426. During operation, gas from FOV gas outlet 426 flows through heated gas line 440A to processing chamber 402. Gas line heater 442A is configured to heat heated gas line 440A. As mentioned above, by flowing gas through one or more heated gas lines, processing tool 400 may help avoid condensation of inhibitor within the heated gas lines.

[0090] Processing tool 400 further includes a divert valve system 444 disposed along heated gas line 440A. Heated divert gas line 440B is connected to divert valve system 444 and leads to an exhaust system 446. Gas line heater 442B is configured to heat heated divert gas line 440B. Exhaust system 446 is configured to receive gas outflowing from processing chamber 402 and / or one or more heated gas lines. In some examples, exhaust system 446 is configured to actively remove gas from processing chamber 402 and / or apply a partial vacuum. Exhaust system 446 may include any suitable hardware, including one or pumps.

[0091] Divert valve system 444 can be controlled to divert gas flow away from processing chamber 402 and flow gas through heated divert gas line 440B to exhaust system 446. Divert valve system 444 includes a first valve 444A and a second valve 444B. When gas is to be diverted to exhaust system 446, divert valve system 444 can be controlled to close first valve 444A and open second valve 444B without trapping gas. As such, divert valve system 444 may help avoid condensation of the inhibitor within gas lines or valves.

[0092] Heated maintenance vacuum line 440C is configured to remove gas from ampoule 420 to exhaust system 446. Removal of carrier gas and inhibitor vapor from ampoule 420 mayAttorney Docket No. LAMRP993WO-11549-1WO facilitate maintenance on ampoule 420. Gas line heater 442C is configured to heat heated maintenance vacuum line 440C. As mentioned above, exhaust system 446 may be configured to apply a partial vacuum to facilitate removal of gas from ampoule 420 and / or heated gas lines.

[0093] Processing tool 400 further includes a gas box 448 including one or more gas sources. In other examples, a gas box may be separate from processing tool 400. Processing tool 400 further includes a valve 450 for controlling a flow of one or more gases from gas box 448 into processing chamber 402. Gas box 448 may includes gas sources for one or more gases. In some examples, gas box 448 includes one or more inert gases for use as a carrier gas.

[0094] Processing tool 400 further includes a remote plasma system 452 configured to form a remote plasma to clean processing chamber 402. Radicals formed in the plasma may be introduced into processing chamber 402 through processing gas outlet 410. The radicals may help clean processing chamber 402 by reacting with deposited material on surfaces within processing chamber 402. Remote plasma system 452 also may be used to provide radicals for substrate processing.

[0095] Processing tool 400 further includes a main power source 454 for supplying power to components of processing tool 400, such as pumps, sensors, substrate heater 408, exhaust system 446, and valves 444A, 444B, 450. Processing tool 400 further includes an auxiliary power source 456 for supplying power to gas line heaters 442A, 442B, 442C. In some examples, gas line heaters may be powered by main power source 454 and auxiliary power source 456 may be omitted.

[0096] Processing tool 400 further includes a controller 460 for controlling operation of processing tool 400. Controller 460 is configured to control various functions of processing tool 400, such as operating substrate heater 408 to heat to a desired temperature.

[0097] Controller 460 is configured to control mass flow controller 424 to flow carrier gas into ampoule 420 at a desired flow rate. In some examples, controller 460 is configured to control mass flow controller 424 to flow nitrogen into ampoule 420 at a flow rate within a range of 6000 to 7500 standard cubic centimeters per minute (sccm). The carrier gas draws inhibitor out of ampoule 420 through FOV gas outlet 426. In some examples, the flow of nitrogen is controlled to achieve a flow of inhibitor through FOV gas outlet 426 that is within a range of 20 to 500 sccm. In other examples, any other suitable flow rates may be used. Flow rates may be dependent upon inhibitor vapor pressure and / or ampoule temperature.

[0098] Controller 460 is further configured to control components of ampoule 420. In some examples, controller 460 is configured to receive a signal from ampoule 420 indicating a liquid level of inhibitor in ampoule 420. In some examples, controller 460 is configured to output liquid level information to a display (not shown in FIG. 4). In some examples, controller 460 is configured to control a bulk fill system to fill ampoule 420 with inhibitor. For example, controllerAttorney Docket No. LAMRP993WO-11549-1WO 460 may control one or more pumps to pump inhibitor from inhibitor bulk source 430 into ampoule 420 through bulkfill port 428. In other examples, inhibitor may be added manually to ampoule 420. In some examples, controller 460 is configured to control ampoule 420 to fill with inhibitor based on a liquid level that is below a threshold value.

[0099] Controller 460 is further configured to control ampoule heater 434 to heat to a desired temperature. In some examples, ampoule heater may be controlled to heat an inhibitor or other liquid phase processing chemical to a temperature within a range of 60 to 130ºC. In more specific examples, ampoule heater may heat to a temperature within a range of 80 to 100ºC. In other examples, temperatures outside these ranges may be used. In the instance of an inhibition process, a temperature to which ampoule heater is heated depends upon a specific inhibitor contained in the ampoule and a desired vapor pressure.

[0100] Controller 460 is further configured to control gas line heaters 442A, 442B, 442C to respectively heat heated gas line 440A, heated divert gas line 440B, heated maintenance vacuum line 440C to desired temperatures. In some examples in which the chemical in the ampoule is an inhibitor, controller 460 may control one or more gas line heaters to heat to a temperature within a range of 600 to 630 ºC. Further, in some examples, gas line heaters 442A, 442B, 442C may heat the respective heated gas line 440A, heated divert gas line 440B, heated maintenance vacuum line 440C, to a temperature that is above a temperature of an ampoule heater.

[0101] Controller 460 is further configured to operate divert valve system 444 to direct inhibitor either to processing chamber 402 or to exhaust system 446. Controller 460 is further configured to operate exhaust system 446. Controller 460 is also configured to operate valve 450 and exhaust system 446 to purge processing chamber 402 by flowing an inert gas into processing chamber 402 and evacuating processing chamber 402. Controller 460 also may be configured to operate other components of processing tool 400 not shown here. Controller 460 may include any suitable computing system, examples of which are described below with reference to system controller 550 of Figure 5 and system controller 650 of Figure 6.

[0102] As described above, one or more process stations may be included in a multi-station processing tool. Figure 5 shows a schematic view of an embodiment of a multi-station processing tool 500 with an inbound load lock 502 and an outbound load lock 504, either or both of which may include a remote plasma source. A robot 506, at atmospheric pressure, is configured to move wafers from a cassette loaded through a pod 508 into inbound load lock 502 via an atmospheric port (not shown). A wafer or substrate is placed by the robot 506 on a pedestal 512 in the inbound load lock 502, the atmospheric port is closed, and the load lock is pumped down. Where the inbound load lock 502 includes a remote plasma source, the wafer may be exposed to a remote plasma treatment in the load lock prior to being introduced into one of the processing chambersAttorney Docket No. LAMRP993WO-11549-1WO such as processing chamber 514a. Further, the wafer also may be heated in the inbound load lock 502 as well, for example, to remove moisture and adsorbed gases. Next, a chamber transport port 516 to processing chamber 514a is opened, and another robot 526 places the wafer into the reactor on a pedestal 518 of a first station (labeled 1) of processing chamber 514a shown in the reactor for processing. While the embodiment depicted in Figure 5 includes load locks, it will be appreciated that, in some embodiments, direct entry of a wafer into a process station may be provided.

[0103] Each of the depicted processing chambers, such as processing chamber 514a, includes four process stations. Each station has a heated pedestal, and gas line inlets. It will be appreciated that in some embodiments, each process station may have different or multiple purposes. While the depicted processing chamber 514a includes four stations, it will be understood that a processing chamber according to certain disclosed embodiments may have any suitable number of stations. For example, in some embodiments, a processing chamber may have five or more stations, while in other embodiments a processing chamber may have three or fewer stations. Additionally, while the depicted processing tool 500 has three processing chambers 514a, 514b, and 514c, it will be understood that a processing tool according to certain disclosed embodiments may have any suitable number of processing chambers.

[0104] Figure 5 depicts an embodiment of a wafer handling system 590 for transferring wafers within processing chamber 514a. In some embodiments, wafer handling system 590 may transfer wafers between various process stations and / or between a process station and a load lock. It will be appreciated that any suitable wafer handling system may be employed. Non-limiting examples include wafer carousels and wafer handling robots. Figure 5 also depicts an embodiment of a system controller 550 employed to control process conditions and hardware states of process tool 500. System controller 550 may include one or more memory devices 556, one or more mass storage devices 554, and one or more processors 552. Processor 552 may include a CPU or computer, analog and / or digital input / output connections, stepper motor controller boards, etc.

[0105] In some embodiments, system controller 550 controls all of the activities of process tool 500. System controller 550 executes system control software 558 stored in mass storage device 554, loaded into memory device 556, and executed on processor 552. Alternatively, the control logic may be hard coded in the controller 550. 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 358 may include instructions for controlling the transfer of wafers into and out of a process chamber, rotating wafers within a process chamber, aligning wafers with the showerhead in a process chamber, transfer of wafers into and out of a process chamber, timing of gases out of particularAttorney Docket No. LAMRP993WO-11549-1WO regions of a showerhead, mixture of gases, amount of gas flow out of particular regions of a showerhead, chamber and / or station pressure, backside gas flow pressure out of particular regions of a showerhead, chamber and / or reactor temperature, wafer temperature, bias power, target power levels, RF power levels and type (such as single frequency or dual frequency or high frequency or low frequency), pedestal, chuck and / or susceptor position, and other parameters of a particular process performed by process tool 500. System control software 558 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 558 may be coded in any suitable computer readable programming language.

[0106] In some embodiments, system control software 558 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 554 and / or memory device 556 associated with system controller 550 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, electrostatic chuck power control program, and a plasma control program.

[0107] A substrate positioning program may include program code for process tool components that are used to load the substrate onto pedestal 518 and to control the spacing between the substrate and other parts of process tool 500. A process gas control program may include code for controlling gas composition (e.g., conditioning process gases, deposition gases, helium gas or other gas for backside flow, carrier gases, etc., 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, pressure of gas introduced to backside of a wafer during conditioning operations, etc.

[0108] A heater control program may include code for controlling the current to a heating unit that is used to heat the substrate for annealing operations described herein. Alternatively, the heater control program may control delivery of a heat transfer gas (such as helium) to the substrate. 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. A pressure control program may include code for maintaining the pressure in the reaction chamber in accordance with the embodiments herein.

[0109] In some embodiments, there may be a user interface associated with system controllerAttorney Docket No. LAMRP993WO-11549-1WO 550. 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.

[0110] In some embodiments, parameters adjusted by system controller 550 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 may be provided to the user in the form of a recipe, which may be entered utilizing the user interface.

[0111] Signals for monitoring the process may be provided by analog and / or digital input connections of system controller 550 from various process tool sensors. The signals for controlling the process may be output on the analog and digital output connections of process 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.

[0112] System controller 550 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 films according to various embodiments described herein.

[0113] The system controller 550 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 550.

[0114] In some implementations, the system controller 550 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 550, 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 and / or inhibitor gases, temperature settings (e.g., heating and / or cooling), pressure settings, vacuum settings, power settings, radio frequency (RF) generator settings, RF matching circuitAttorney Docket No. LAMRP993WO-11549-1WO 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.

[0115] Broadly speaking, the system controller 550 may be defined as electronics having various integrated circuits, logic, memory, and / or software that receive instructions, issue instructions, 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 550 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.

[0116] The system controller 550, 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 550 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 steps 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 550 receives instructions in the form of data, which specify parameters for each of the processing steps 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 550 is configured to interface with or control. Thus as described above, the system controller 550 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 theAttorney Docket No. LAMRP993WO-11549-1WO platform level or as part of a remote computer) that combine to control a process on the chamber.

[0117] 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 module, a clean chamber or module, a bevel edge etch chamber or module, a physical vapor deposition (PVD) chamber or module, a CVD or PECVD chamber or module, an ALD or PEALD 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.

[0118] As noted above, depending on the process step or steps to be performed by the tool, the system controller 550 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.

[0119] 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.

[0120] 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.

[0121] As described above, one or more process stations may be included in a multi-station processing tool. Figure 6 depicts an example processing apparatus according to disclosed embodiments. Tool 600 includes a first processing chamber 602 and a second processing chamber 604. The first processing chamber 602 includes a plurality of processing stations, four stationsAttorney Docket No. LAMRP993WO-11549-1WO 680A–D, that each may process a wafer. The first processing chamber 602 is configured to perform plasma operations on the wafers. The second processing chamber 604 is configured to perform deposition on the wafer and may be considered a deposition chamber. The second processing chamber 604 also includes a plurality of processing stations, four stations 682A–D, that each may process a wafer using a controller 690. The first and second processing chambers 602 and 604 may be considered multi-station processing chambers.

[0122] Tool 600 also includes a wafer transfer unit configured to transport one or more wafers within the tool 600. Additional features of tool 600 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 608 in a first wafer transfer module 610 and a second robotic arm unit 612 in a second wafer transfer module 614 that may be considered an equipment front end module (EFEM) configured to received containers for wafers, such as a front opening unified module (FOUP) 616. The first robotic arm unit 608 is configured to transport a wafer between the first processing chamber 602 and the second processing chamber 604, and between the second robotic arm unit 612. The second robotic arm unit 612 is configured to transport the wafer between a FOUP and the first robotic arm unit 608. After a wafer has been treated in the first processing chamber 602, the wafer transfer unit is able to transfer the wafer from the first processing chamber 602, to the second processing chamber 604 where one or more layers of encapsulation material may be deposited on one or more wafers.

[0123] Similar to above, the first wafer transfer module 610 may a vacuum transfer module (VTM). Airlock 620, also known as a loadlock or transfer module, is shown and may be individually optimized to perform various fabrication processes. The tool 600 also includes a FOUP 616 that is configured to lower the pressure of the tool 600 to a vacuum or low pressure, e.g., between about 1 mTorr and about 10 Torr, and maintain the tool 600 at this pressure. This includes maintaining the first and second processing chambers 602 and 604, and the first wafer transfer module 610 at the vacuum or low pressure. The second wafer transfer module 614 may be at a different pressure, such as atmospheric. As the wafer is transferred throughout the tool 600, it is therefore maintained at the vacuum or low pressure. For example, as the wafer is transferred from the first processing chamber 602, into the first wafer transfer module 610, and to the second processing chamber 604, the wafer is maintained at the vacuum or low pressure and not exposed to atmospheric pressure.

[0124] In a further example, a substrate is placed in one of the FOUPs 618 and the second robot arm unit 612, or front-end robot, transfers the substrate from the FOUP 618 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 612 into theAttorney Docket No. LAMRP993WO-11549-1WO airlock 620. 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 620, the substrate is moved by the first robot arm unit 608 through the first wafer transfer module 610, or VTM 610, and into the first processing chamber 602. In order to achieve this substrate movement, the first robot arm unit 608 uses end effectors on each of its arms.

[0125] Figure 6 also depicts an embodiment of a system controller 629 employed to control process conditions and hardware states of tool 600. System controller 629 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. EXPERIMENTAL EXPERIMENT 1

[0126] A substrate was exposed to various cycles of the following operations to form 250Å of silicon oxide: exposure to (dimethylamino)methylethoxysilane, purge, exposure to plasma generating using hydrogen and helium gas, and purge. The growth rate per cycle (GPC) is shown in Figure 7. The growth rate was measured to be about 0.2Å per cycle. EXPERIMENT 2

[0127] An FTIR spectrum was generated for the film from Experiment 1 and is shown in Figure 8. As shown, the FTIR shows Si-O and Si-N are in the as-converted film which suggests that the precursor stoichiometry having a 1:1 silicon to oxygen atom ratio might not necessarily allow for complete forming of silicon dioxide (which has a 1:2 Si:O ratio) thereby resulting in some Si-N formation. These results suggest that a precursor having a 1:2 Si:O ratio may be advantageous for forming silicon dioxide. DEFINITIONS AND PRECURSORS DEFINITIONS

[0128] 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.

[0129] 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 acetoxyAttorney Docket No. LAMRP993WO-11549-1WO (-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.

[0130] 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 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.

[0131] 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.

[0132] 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.

[0133] 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.

[0134] 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.

[0135] 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., C1-6alkyl-C4-18aryl). 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., C2-6alkenyl-C4-18aryl). ExemplaryAttorney Docket No. LAMRP993WO-11549-1WO 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., C2-6alkynyl-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 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.

[0136] 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.

[0137] 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 C1-24alkoxy groups.

[0138] 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., C1-6alkoxy-C1-6alkyl). 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.

[0139] 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,Attorney Docket No. LAMRP993WO-11549-1WO 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 C2-24alkoxycarbonyl groups.

[0140] 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) C1-6alkylsulfinyl (e.g., -S(O)-R, in which R is C1-6alkyl); (3) C1-6alkylsulfonyl (e.g., -SO2-R, in which R is C1-6 alkyl); (4) amino (e.g., -NR1R2, where each of R1and R2is, independently, selected from hydrogen, aliphatic, heteroaliphatic, haloaliphatic, haloheteroaliphatic, aromatic, as defined herein, or any combination thereof, or R1and 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) C3-8cycloalkyl; (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) C1-6thioalkyl (e.g., -S-R, in which R is alkyl); (21) thiol (e.g., -SH); (22) -CO2R1, where R1is selected from the group consisting of (a) hydrogen, (b) C1-6 alkyl, (c) C4-18aryl, and (d) C4-18aryl-C1-6alkyl (e.g., -L-R, in which L is C1-6alkyl and R is C4-18aryl); (23) -C(O)NR1R2, where each of R1and R2is, independently, selected from the group consisting of (a) hydrogen, (b) C1-6alkyl, (c) C4-18aryl, and (d) C4-18aryl-C1-6alkyl (e.g., -L-R, in which L isAttorney Docket No. LAMRP993WO-11549-1WO C1-6 alkyl and R is C4-18 aryl); (24) -SO2R1, where R1is selected from the group consisting of (a) C1-6alkyl, (b) C4-18aryl, and (c) C4-18aryl-C1-6alkyl (e.g., -L-R, in which L is C1-6alkyl and R is C4-18 aryl); (25) -SO2NR1R2, where each of R1and R2is, independently, selected from the group consisting of (a) hydrogen, (b) C1-6alkyl, (c) C4-18aryl, and (d) C4-18aryl-C1-6alkyl (e.g., -L-R, in which L is C1-6 alkyl and R is C4-18 aryl); and (26) -NR1R2, where each of R1and R2is, independently, selected from the group consisting of (a) hydrogen, (b) an N-protecting group, (c) C1-6alkyl, (d) C2-6alkenyl, (e) C2-6alkynyl, (f) C4-18aryl, (g) C4-18aryl-C1-6alkyl (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 C1-6alkyl and R is C3-8cycloalkyl), 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 C1-24alkyl group.

[0141] 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 alkenylene or alkynylene 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.

[0142] 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.

[0143] 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 C2-24alkylsulfinylalkyl group (e.g., C1-6alkylsulfinyl-C1-6alkyl or C1-12alkylsulfinyl-C1-12alkyl). 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.

[0144] 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 optionallyAttorney Docket No. LAMRP993WO-11549-1WO substituted C1-12 alkyl, haloalkyl, or perfluoroalkyl).

[0145] 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 C2-24alkylsulfonylalkyl group (e.g., C1-6alkylsulfonyl-C1-6alkyl or C1-12alkylsulfonyl-C1-12alkyl). 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.

[0146] 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.

[0147] 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.

[0148] By “amide” is mean -C(O)NR1R2or -NHCOR1, where each of R1and R2is, independently, selected from hydrogen, aliphatic, heteroaliphatic, aromatic, as defined herein, or any combination thereof, or where R1and R2, taken together with the nitrogen atom to which each are attached, can form a heterocyclyl group, as defined herein.

[0149] By “amino” is meant -NR1R2, where each of R1and R2is, 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 R1and 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 R1and R2is, 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, R1and R2can be taken together, with the nitrogen atom to which each is attached, to form an optionally substituted heterocyclyl.Attorney Docket No. LAMRP993WO-11549-1WO

[0150] 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 R1and R2is, independently, selected from hydrogen, aliphatic, heteroaliphatic, or aromatic, as defined herein, or any combination thereof; or R1and 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 R1and R2is, independently, selected from hydrogen, aliphatic, heteroaliphatic, or aromatic, as defined herein, or any combination thereof; or R1and R2, taken together with the nitrogen atom to which each are attached, can form a heterocyclyl group, as defined herein; and each of R3and R4is, independently, H or alkyl, as defined herein.

[0151] 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 R1and R2is, 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 R1and 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 R1and R2is, 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.

[0152] 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.

[0153] 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.

[0154] By “aromatic-carbonyloxy” is meant an aromatic group that is or can be coupled to aAttorney Docket No. LAMRP993WO-11549-1WO 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.

[0155] 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.

[0156] 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.

[0157] 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 C1-6alkyl); (2) C1-6alkyl; (3) C1-6alkoxy (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-C1-6alkyl (e.g., -L-S(O)-R, in which each of L and R is, independently, C1-6alkyl); (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, C1-6alkyl); (9) aryl; (10) amino (e.g., - NR1R2, where each of R1and R2is, independently, selected from hydrogen, aliphatic, heteroaliphatic, haloaliphatic, haloheteroaliphatic, aromatic, as defined herein, or any combination thereof; or R1and R2, taken together with the nitrogen atom to which each are attached, can form a heterocyclyl group, as defined herein); (11) C1-6aminoalkyl (e.g., -L1-NR1R2or -L2-Attorney Docket No. LAMRP993WO-11549-1WO C(NR1R2)(R3)-R4, in which L1is C1-6 alkyl; L2is a covalent bond or C1-6 alkyl; each of R1and R2is, independently, selected from hydrogen, aliphatic, heteroaliphatic, haloaliphatic, haloheteroaliphatic, aromatic, as defined herein, or any combination thereof; or R1and R2, taken together with the nitrogen atom to which each are attached, can form a heterocyclyl group, as defined herein; and each of R3and R4is, 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) C1-6azidoalkyl (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 C1-6alkyl); (20) C3-8cycloalkyl; (21) C3-8cycloalkyl-C1-6alkyl (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 L1is C1-6alkyl; L2is a covalent bond or C1-6alkyl; X is fluoro, bromo, chloro, or iodo; and each of R1and R2is, 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 (e.g., -L1-OH or -L2-C(OH)(R1)-R2, in which L1is C1-6 alkyl; L2is a covalent bond or alkyl; and each of R1and R2is, independently, H or C1-6 alkyl, as defined herein); (29) nitro; (30) C1-6nitroalkyl (e.g., -L1-NO or -L2-C(NO)(R1)-R2, in which L1is C1-6alkyl; L2is a covalent bond or alkyl; and each of R1and R2is, independently, H or C1-6 alkyl, as defined herein); (31) N-protected amino; (32) N-protected amino-C1-6alkyl; (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, C1-6alkyl); (36) -(CH2)rCO2R1, where r is an integer of from zero to four, and R1is selected from the group consisting of (a) hydrogen, (b) C1-6 alkyl, (c) C4-18aryl, and (d) C4-18aryl-C1-6alkyl (e.g., -L-R, in which L is C1-6alkyl and R is C4-18aryl); (37) -(CH2)rCONR1R2, where r is an integer of from zero to four and where each R1and R2is independently selected from the group consisting of (a) hydrogen, (b) C1-6alkyl, (c) C4-18aryl, 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 R1is selected from the group consisting of (a) C1-6alkyl, (b) C4-18aryl, and (c) C4-18aryl-C1-6alkyl (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 R1and R2is, 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 C1-6alkyl and R is C4-18aryl); (40) -(CH2)rNR1R2, where r is an integer of from zero to four and where each of R1and R2is, independently, selected from the group consisting of (a) hydrogen, (b) an N-protecting group, (c) C1-6alkyl, (d) C2-6alkenyl, (e) C2-6alkynyl, (f) C4-18aryl, (g) C4-18aryl-Attorney Docket No. LAMRP993WO-11549-1WO 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-C1-6alkyl (e.g., -L-R, in which L is C1-6alkyl and R is C3-8cycloalkyl), 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 C6-10aryl group.

[0158] 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 (C7-16aryl-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 (C7-16aryl-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- C2-6alkynyl). 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.

[0159] 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 C6-10arylene group. The arylene group can be branched or unbranched. The arylene group can also be substituted or unsubstituted. For example, the arylene group can be substituted with one or more substitution groups, as described herein for aryl.

[0160] By “arylalkoxy” is meant an aryl-alkyl group, as defined herein, attached to the parentAttorney Docket No. LAMRP993WO-11549-1WO 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.

[0161] 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 C4-18or C6-18aryloxy group. In other embodiments, R is an aryl group that is optionally substituted with alkyl, alkanoyl, amino, hydroxyl, and the like.

[0162] 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 C5-19aryloxycarbonyl group. In other embodiments, the aryloxycarbonyl group is -C(O)O-R, in which R is an aryl group, as defined herein.

[0163] 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.

[0164] 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.

[0165] By “azido” is meant an -N3 group.

[0166] 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.

[0167] By “azo” is meant an -N=N- group.

[0168] 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)NR1R2group, where each of R1and R2is, 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 R1and R2, taken together with the nitrogen atom to which each are attached, can form a heterocyclyl group, as defined herein.

[0169] 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)NR1R2group, where each of R1and R2is, independently, selected from hydrogen, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, optionally substituted heteroaromatic, optionally substituted silyl, or optionallyAttorney Docket No. LAMRP993WO-11549-1WO substituted silyloxy, as defined herein, or any combination thereof; or where R1and R2, taken together with the nitrogen atom to which each are attached, can form a heterocyclyl group, as defined herein.

[0170] 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.

[0171] By “carbonyl” is meant a -C(O)- group, which can also be represented as >C=O.

[0172] By “carboxyl” is meant a -CO2H group or an anion thereof.

[0173] 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.

[0174] By “cyanato” is meant a -OCN group.

[0175] By “cyano” is meant a -CN group.

[0176] By “cycloaliphatic” is meant an aliphatic group, as defined herein, that is cyclic.

[0177] 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.

[0178] 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.

[0179] 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.

[0180] By “cycloheteroaliphatic” is meant a heteroaliphatic group, as defined herein, that is cyclic.

[0181] By “disilanyl” is meant a group containing an Si-Si bond. In some embodiments, the disilanyl group is a -SiRS1RS2-SiRS3RS4RS5or -SiRS1RS2-SiRS3RS4- group, in which each of RS1, RS2, RS3, RS4, and RS5is, independently, H, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, optionally substituted heteroaromatic, orAttorney Docket No. LAMRP993WO-11549-1WO optionally substituted amino.

[0182] By “disulfide” is meant -SSR, where R is selected from hydrogen, aliphatic, heteroaliphatic, haloaliphatic, haloheteroaliphatic, aromatic, as defined herein, or any combination thereof.

[0183] 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.

[0184] 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.

[0185] By “halo” is meant F, Cl, Br, or I.

[0186] 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.

[0187] 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 R1and R2is, independently, H or alkyl, as defined herein.

[0188] 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.

[0189] 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 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.

[0190] 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.Attorney Docket No. LAMRP993WO-11549-1WO

[0191] 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.

[0192] 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.

[0193] 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.

[0194] 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.

[0195] By “heteroalkylene,” “heteroalkenylene,” and “heteroalkynylene” is meant a multivalent (e.g., bivalent) form of a heteroalkyl, heteroalkenyl, or heteroalkynyl group, respectively, as described herein.

[0196] 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.

[0197] 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.

[0198] 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 definedAttorney Docket No. LAMRP993WO-11549-1WO herein.

[0199] 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.

[0200] 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.

[0201] 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.

[0202] By “heteroarylene” is meant a multivalent (e.g., bivalent) form of a heteroaryl group, as described herein.

[0203] 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.

[0204] 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,Attorney Docket No. LAMRP993WO-11549-1WO 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.

[0205] 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.

[0206] 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.

[0207] By “hydrazino” is meant -NR1-NR2R3, where each of R1, R2, and R3is, 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 R1and R2or a combination of R2and 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 R3is, independently, H, optionally substituted alkyl, optionally substituted aryl, optionally substituted alkyl-aryl, or optionally substituted aryl-alkyl. In particular embodiments, R2and R3can be taken together, with the nitrogen atom to which each is attached, to form an optionally substituted heterocyclyl.

[0208] By “hydroxyl” is meant -OH.

[0209] 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 R1and R2is, independently, H or alkyl, as defined herein.

[0210] By “imidoyl” is meant a moiety including a carbonimidoyl group. In some embodiments,Attorney Docket No. LAMRP993WO-11549-1WO the imidoyl group is C(NR1)R2, in which each of R1and R2is, 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 R1is 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; RAkis an optionally substituted alkyl or an optionally substituted aliphatic; and RAris an optionally substituted aryl or an optionally substituted aromatic.

[0211] 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.

[0212] By “isocyanato” is meant a -NCO group.

[0213] By “isocyano” is meant a -NC group.

[0214] 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 R1is, independently, selected from aliphatic, haloaliphatic, haloheteroaliphatic, heteroaliphatic, aromatic, aliphatic-aromatic, heteroaliphatic-aromatic, as defined herein, or any combination thereof.

[0215] By “nitro” is meant an -NO2 group.

[0216] 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 R1and R2is, independently, H or alkyl, as defined herein.

[0217] By “oxo” is meant an =O group.

[0218] By “oxy” is meant -O-.

[0219] 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 nAttorney Docket No. LAMRP993WO-11549-1WO is an integer from 0 to 10.

[0220] 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.

[0221] 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, 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 substitutedAttorney Docket No. LAMRP993WO-11549-1WO 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).

[0222] By “silyl” is meant a -SiR1R2R3or -SiR1R2- group. In some embodiments, each of R1, R2, and R3is, 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 R3is, independently, H, optionally substituted alkyl, optionally substituted alkoxy, optionally substituted aryl, optionally substituted aryloxy, optionally substituted alkyl-aryl, optionally substituted aryl-alkyl, or optionally substituted amino. In other embodiments, the silyl group is -Si(R)a(OR)b(NR2)c, 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.

[0223] 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 R3is, 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 R3is, independently, H, optionally substituted alkyl, optionally substituted alkoxy, optionally substituted aryl, optionally substituted aryloxy, optionally substituted alkyl-aryl, optionally substituted aryl-alkyl, or optionallyAttorney Docket No. LAMRP993WO-11549-1WO 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

[0224] By “sulfinyl” is meant an -S(O)- group.

[0225] By “sulfo” is meant an -S(O)2OH group.

[0226] 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.

[0227] 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 C1-6thioalkyl. In some embodiments, the thioalkyl group is -S-R, in which R is an alkyl group, as defined herein.

[0228] By “thiol” is meant an -SH group.

[0229] 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 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.

[0230] 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.

[0231] 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.

[0232] Other features and advantages of the disclosed embodiments will be apparent from the following description and the claims. PRECURSORS

[0233] The film can be deposited using any useful silicon-containing precursor (Si-containing precursor). In some embodiments, the precursor includes a structure of formula (I): Si(Rʹ)4 (I), wherein at least one Rʹ includes an oxygen atom. In other embodiments, at least one Rʹ includes a heteroatom (e.g., nitrogen, oxygen, and / or silicon). In yet other embodiments, at least one Rʹ includes a carbon atom and a heteroatom (e.g., nitrogen, oxygen, and / or silicon). In particularAttorney Docket No. LAMRP993WO-11549-1WO embodiments, Rʹ does not include a halogen atom.

[0234] In other embodiments, the precursor includes a structure of formula (II): (Rʹ)3Si−[L−Si(Rʹ)2]−Rʹ (II), wherein at least one Rʹ includes an oxygen atom and L is a linker. In some embodiments, at least one Rʹ includes a heteroatom (e.g., nitrogen, oxygen, and / or silicon). In yet other embodiments, at least one Rʹ includes a carbon atom and a heteroatom (e.g., nitrogen, oxygen, and / or silicon). In particular embodiments, Rʹ does not include a halogen atom.

[0235] For formula (II), non-limiting linkers for L include a covalent bond, oxy (-O-), carbonyl (-C(O)-), optionally substituted carbonimidoyl (e.g., -C(NR)-), optionally substituted imino (e.g., -NR-), an optionally substituted alkylene, optionally substituted heteroalkylene, optionally substituted arylene, and the like.

[0236] For any formula herein (e.g., for formula (I) or (II)), Rʹ can be H, aliphatic, heteroaliphatic, aromatic, heteroaromatic, amino, hydrazino, azido, hydroxyl, silyl (e.g., aminosilyl, alkoxysilyl, and the like), silyloxy (e.g., aminosilyloxy, alkoxysilyloxy, and the like), cyanato (-OCN), isocyanato (-NCO), cyano (-CN), or isocyano (-NC), in which any of these may be optionally substituted.

[0237] In particular embodiments, at least one, two, three, four, or more Rʹ in any formula herein (e.g., for formula (I) or (II)) includes an optionally substituted aliphatic. Non-limiting aliphatic groups include alkyl, alkenyl, or alkynyl, including linear, branched, cyclic, saturated, or unsaturated forms thereof. Such groups can be unsubstituted or substituted, such as with one or more substituents described herein for alkyl. Further examples of aliphatic groups include methyl (Me), ethyl (Et), propyl (Pr), iso-propyl (iPr), cyclopropyl (cPr), butyl (Bu), sec-butyl (sBu), iso- butyl (iBu), tert-butyl (tBu), pentyl (Pe), tert-pentyl (tPe), allyl (All), vinyl (Vi), ethynyl, and the like.

[0238] In some embodiments, at least one, two, three, four, or more Rʹ in any formula herein (e.g., for formula (I) or (II)) includes an optionally substituted heteroaliphatic. A heteroaliphatic group can include any including one or more carbon atoms and one or more heteroatoms (e.g., oxygen, nitrogen, and the like).

[0239] Non-limiting heteroaliphatic groups includes aliphatic-carbonyl (e.g., alkanoyl or -C(O)RAk), aliphatic-carbonyloxy (e.g., alkanoyloxy or -OC(O)RAk), aliphatic-oxy (e.g., alkoxy or -ORAk), aliphatic-oxycarbonyl (e.g., alkoxycarbonyl or -C(O)ORAk), amino (e.g., -NRN1RN2), aromatic-carbonyl (e.g., aryloyl or -C(O)RAr), aromatic-carbonyloxy (e.g., aryloyloxy or - OC(O)RAr), aromatic-oxy (e.g., aryloxy or -ORAr), aromatic-oxycarbonyl (e.g., aryloxycarbonyl or -C(O)ORAr), imidoyl (e.g., -C(NRN1)H, -C(NRN1)RAk, or -C(NRN1)RAr), carbamoyl (e.g., -C(O)NRN1RN2), carbamoyloxy (e.g., -OC(O)NRN1RN2), carboxyl (-CO2H), formylAttorney Docket No. LAMRP993WO-11549-1WO (-C(O)H), heteroaromatic, heterocyclyl (e.g., optionally substituted furanyl, tetrahydrofuranyl, pyrrolidinyl, pyrrolyl, imidazolyl, pyrazolyl, triazolyl, piperidinyl, pyridinyl, pyrimidinyl, pyridazinyl, pyrazinyl, oxazolyl, morpholinyl, and the like), hydrazino (e.g., -NRN1-NRN2RN3), silyl (e.g., -SiRS1RS2RS3), and silyloxy (e.g., -O-SiRS1RS2RS3). Each of these groups can be optionally substituted with any substituent described herein (e.g., as described herein for alkyl). Heteroaliphatic groups can include linear, branched, cyclic (e.g., heterocyclyl), saturated, or unsaturated forms thereof.

[0240] Heteroaliphatic groups can include RAkand / or RArmoieties. In some embodiments, RAkis optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted cycloalkyl, optionally substituted heteroalkyl, optionally substituted heteroalkenyl, optionally substituted heteroalkynyl, or optionally substituted heterocyclyl. In other embodiments, RAris optionally substituted aromatic, optionally substituted heteroaromatic, optionally substituted aryl, or optionally substituted heteroaryl.

[0241] Nitrogen-containing groups (e.g., amino, imidoyl, etc.) can include RN1, RN2, and / or RN3moieties attached to a nitrogen atom. In some embodiments, each of RN1, RN2, and RN3is, independently, H, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, optionally substituted heteroaromatic, optionally substituted silyl, or optionally substituted silyloxy. In particular embodiments, RN1and RN2or RN2and RN3can be taken together, with the nitrogen atom to which each is attached, to form an optionally substituted heterocyclyl. Such nitrogen-containing groups can be included within other moieties, such as within silyl or silyloxy groups.

[0242] Silicon-containing groups (e.g., silyl, etc.) can include RS1, RS2, and / or RS3attached to a silicon atom. In some embodiments, each of RS1, RS2, and RS3is, independently, H, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, optionally substituted heteroaromatic, or optionally substituted amino. Such silicon-containing groups can be included within other moieties, such as within amino groups.

[0243] In some embodiments, the silyl group is an alkylsilyl group having one or more aliphatic groups attached to the silicon atom. In one instance, the alkylsilyl group is -Si(R)a(RAk)b, in which R is, independently, H, aromatic, heteroaromatic, amino, hydrazino, azido, hydroxyl, silyl (e.g., aminosilyl, alkoxysilyl, and the like), silyloxy (e.g., aminosilyloxy, alkoxysilyloxy, and the like), cyanato, isocyanato, cyano, or isocyano, in which any of these may be optionally substituted; RAkis optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted cycloalkyl, optionally substituted heteroalkyl, optionally substituted heteroalkenyl, optionallyAttorney Docket No. LAMRP993WO-11549-1WO substituted heteroalkynyl, or optionally substituted heterocyclyl; a ≥ 0; b ≥ 1; and a + b = 3. Yet other non-limiting alkylsilyl groups include -SiH2RAk, -SiH[RAk]2, or -Si[RAk]3, in which RAkis any provided herein.

[0244] In some embodiments, the silyl group is an alkoxysilyl group having one or more aliphatic groups attached to the silicon atom by way of an oxy (-O-) group. In one instance, the alkoxylsilyl group is -Si(R)a(ORAk)b, in which R is, independently, H, aromatic, heteroaromatic, amino, hydrazino, azido, hydroxyl, silyl (e.g., aminosilyl, alkoxysilyl, and the like), silyloxy (e.g., aminosilyloxy, alkoxysilyloxy, and the like), cyanato, isocyanato, cyano, or isocyano, in which any of these may be optionally substituted; RAkis optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted cycloalkyl, optionally substituted heteroalkyl, optionally substituted heteroalkenyl, optionally substituted heteroalkynyl, or optionally substituted heterocyclyl; a ≥ 0; b ≥ 1; and a + b = 3. Yet other non-limiting alkoxysilyl groups include -SiH2[ORAk], -SiH[ORAk]2, or -Si[ORAk]3, in which RAkis any described herein.

[0245] In other embodiments, the silyl group is an arylsilyl group having one or more aromatic groups attached to the silicon atom. In one instance, the arylsilyl group is -Si(R)a(RAr)b, in which R is, independently, H, aliphatic, heteroaliphatic, amino, hydrazino, azido, hydroxyl, silyl (e.g., aminosilyl, alkoxysilyl, and the like), silyloxy (e.g., aminosilyloxy, alkoxysilyloxy, and the like), cyanato, isocyanato, cyano, or isocyano, in which any of these may be optionally substituted; RAris optionally substituted aromatic, optionally substituted heteroaromatic, optionally substituted aryl, or optionally substituted heteroaryl; a ≥ 0; b ≥ 1; and a + b = 3. Yet other non-limiting arylsilyl groups include -SiH2RAr, -SiH[RAr]2, or -Si[RAr]3, in which RAris any described herein.

[0246] In yet other embodiments, the silyl group is an aryloxysilyl group having one or more aromatic groups attached to the silicon atom by way of an oxy (-O-) group. In one instance, the arylsilyl group is -Si(R)a(ORAr)b, in which R is, independently, H, aliphatic, heteroaliphatic, amino, hydrazino, azido, hydroxyl, silyl (e.g., aminosilyl, alkoxysilyl, and the like), silyloxy (e.g., aminosilyloxy, alkoxysilyloxy, and the like), cyanato, isocyanato, cyano, or isocyano, in which any of these may be optionally substituted; RAris optionally substituted aromatic, optionally substituted heteroaromatic, optionally substituted aryl, or optionally substituted heteroaryl; a ≥ 0; b ≥ 1; and a + b = 3. Yet other non-limiting aryloxysilyl groups include -SiH2[ORAr], -SiH[ORAr]2, or -Si[ORAr]3, in which RAris any described herein.

[0247] A silyl group can also include an aminosilyl having one or more optionally substituted amino groups attached to the silicon atom. In one instance, the aminosilyl group is -Si(R)a(NRN1RN2)b, in which R is, independently, H, aliphatic, heteroaliphatic, aromatic, heteroaromatic, hydrazino, azido, hydroxyl, silyl (e.g., aminosilyl, alkoxysilyl, and the like),Attorney Docket No. LAMRP993WO-11549-1WO silyloxy (e.g., aminosilyloxy, alkoxysilyloxy, and the like), cyanato, isocyanato, cyano, or isocyano, in which any of these may be optionally substituted; each of RN1and RN2is, independently, H, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, optionally substituted heteroaromatic, optionally substituted silyl, or optionally substituted silyloxy, in which RN1and RN2can be taken together, with the nitrogen atom to which each is attached, to form an optionally substituted heterocyclyl; a ≥ 0; b ≥ 1; and a + b = 3. Yet other non-limiting embodiments of aminosilyl groups include -SiH2[NRN1RN2], -SiH[RAk][NRN1RN2], -Si[RAk]2[NRN1RN2], -SiH[NRN1RN2]2, -Si[RAk][NRN1RN2]2, or -Si[NRN1RN2]3), such as -SiH2[NH2], -SiHRAk[NH2], -Si[RAk]2[NH2], -SiH2[NH(RAk)], -SiHRAk[NH(RAk)], -Si[RAk]2[NH(RAk)], -SiH2[N(RAk)2], -SiHRAk[N(RAk)2], -Si[RAk]2[N(RAk)2], -SiH[NH2]2, -SiRAk[NH2]2, -SiH[NH(RAk)]2, -SiRAk[NH(RAk)]2, -SiH[NH(RAk)][NH2], -SiRAk[NH(RAk)][NH2], -SiH[N(RAk)2]2, -SiRAk[N(RAk)2]2, -SiH[N(RAk)2][NH2], -SiRAk[N(RAk)2][NH2], -Si[NH2]3, -Si[N(RAk)2][NH2]2, -Si[N(RAk)2]2[NH2], -Si[N(RAk)2]3, -Si[NH(RAk)][NH2]2, -Si[NH(RAk)2]2[NH2], -Si[NH(RAk)]3, -Si[NH(RAk)][N(RAk)2]2, -Si[NH(RAk)]2[N(RAk)2], and the like, in which RAkis optionally substituted aliphatic, heteroaliphatic, alkyl, alkenyl, alkynyl, or alkoxy; and each of RN1and RN2is any described herein.

[0248] In some embodiments, the silyl group is -Si(Rʹ)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. In particular embodiments, each R is, independently, H, optionally substituted alkyl, optionally substituted aryl, optionally substituted alkyl-aryl, or optionally substituted aryl-alkyl.

[0249] In other embodiments, any of the silyl groups herein can be attached to the parent compound through an oxy bond. In some embodiments, the silyloxy group is -O- Si(Rʹ)a(OR)b(NR2)c, in which each Rʹis, 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. In particular embodiments, each R is, independently, H, optionally substituted alkyl, optionally substituted aryl, optionally substituted alkyl-aryl, or optionally substituted aryl-alkyl. Yet other non-limiting silyloxy groups include -O-Si(R)a(RAk)b, -O-Si(R)a(ORAk)b, -O-Si(R)a(RAr)b, -O- Si(R)a(ORAr)b, -O-Si(R)a(NRN1RN2)b, in which R is, independently, H, aromatic, heteroaromatic,Attorney Docket No. LAMRP993WO-11549-1WO amino, hydrazino, azido, hydroxyl, silyl (e.g., aminosilyl, alkoxysilyl, and the like), silyloxy (e.g., aminosilyloxy, alkoxysilyloxy, and the like), cyanato, isocyanato, cyano, or isocyano, in which any of these may be optionally substituted; RAkis optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted cycloalkyl, optionally substituted heteroalkyl, optionally substituted heteroalkenyl, optionally substituted heteroalkynyl, or optionally substituted heterocyclyl; RAris optionally substituted aromatic, optionally substituted heteroaromatic, optionally substituted aryl, or optionally substituted heteroaryl; each of RN1and RN2is, independently, H, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, optionally substituted heteroaromatic, optionally substituted silyl, or optionally substituted silyloxy, in which RN1and RN2can be taken together, with the nitrogen atom to which each is attached, to form an optionally substituted heterocyclyl; a ≥ 0; b ≥ 1; and a + b = 3. Yet other non-limiting silyloxy groups include alkylsilyloxy (e.g., -O-SiH2RAk, -O-SiH[RAk]2, or -O-Si[RAk]3); alkoxysilyloxy (e.g., -O-SiH2[ORAk], -O-SiH[ORAk]2, or -O-Si[ORAk]3); arylsilyloxy (e.g., -O-SiH2RAr, -O-SiH[RAr]2, or -O-Si[RAr]3); or aryloxysilyloxy (e.g., -O-SiH2[ORAr], -O-SiH[ORAr]2, or -O-Si[ORAr]3). In some embodiments, the silyl group is aminosilyloxy (e.g., -O-SiH2[NRN1RN2], -O-SiH[RAk][NRN1RN2], -O-Si[RAk]2[NRN1RN2], -O-SiH[NRN1RN2]2, -O-Si[RAk][NRN1RN2]2, or -O-Si[NRN1RN2]3).

[0250] Silyl and silyloxy group can have a mixed combination of aliphatic and aromatic groups. In one instance, the silyl group is -Si(R)a(RAk)b(RAr)cor -Si(R)a(ORAk)b(ORAr)c, in which R is, independently, H, aromatic, heteroaromatic, amino, hydrazino, azido, hydroxyl, silyl (e.g., aminosilyl, alkoxysilyl, and the like), silyloxy (e.g., aminosilyloxy, alkoxysilyloxy, and the like), cyanato, isocyanato, cyano, or isocyano, in which any of these may be optionally substituted; RAkis optionally substituted aliphatic (e.g., optionally substituted alkyl) or optionally substituted heteroaliphatic (e.g., optionally substituted alkoxy or optionally substituted amino); RAris optionally substituted aromatic or optionally substituted heteroaromatic; each of a, b, and c ≥ 0; and a + b + c = 3.

[0251] In another instance, the silyl group is -Si(R)a(NRAk2)b, -Si(R)a(NRAkRAr)b, or -Si(R)a(NRAr2)b, in which R is, independently, H, aromatic, heteroaromatic, amino, hydrazino, azido, hydroxyl, silyl (e.g., aminosilyl, alkoxysilyl, and the like), silyloxy (e.g., aminosilyloxy, alkoxysilyloxy, and the like), cyanato, isocyanato, cyano, or isocyano, in which any of these may be optionally substituted; each of RN1and RN2is, independently, H, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, optionally substituted heteroaromatic, optionally substituted silyl, or optionally substituted silyloxy, in which RN1and RN2can be taken together, with the nitrogen atom to which each is attached, to form anAttorney Docket No. LAMRP993WO-11549-1WO optionally substituted heterocyclyl; each of a and b ≥ 0; and a + b = 3.

[0252] In yet another instance, the silyloxy group is -O-Si(R)a(RAk)b(RAr)c, -O-Si(R)a(ORAk)b(ORAr)c, -O-Si(R)a(NRAk2)b, -O-Si(R)a(NRAkRAr)b, or -O-Si(R)a(NRAr2)b, in which R, RAk, and RArare any described herein; and a, b, and c are any described herein.

[0253] In some embodiments, at least one, two, three, four, or more Rʹ in any formula herein (e.g., for formula (I) or (II)) includes an optionally substituted aliphatic-oxy, heteroaliphatic-oxy, aromatic-oxy, or heteroaromatic-oxy. For instance, Rʹ can be -O-R, in which R is optionally substituted aliphatic (e.g., alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, or cycloalkynyl), optionally substituted heteroaliphatic (e.g., heteroalkyl, heteroalkenyl, heteroalkynyl, or heterocyclyl), optionally substituted aromatic (e.g., aryl), optionally substituted heteroaromatic (e.g., heteroaryl), optionally substituted aliphatic-carbonyl (e.g., alkanoyl or -C(O)RAk, in which RAkis optionally substituted aliphatic or any described herein), optionally substituted silyl (e.g., -SiRS1RS2RS3or -Si(Rʹ)a(OR)b(NR2)c, including any described herein), or optionally substituted amino (e.g., -NRN1RN2, including any described herein).

[0254] In particular embodiments, at least one, two, three, four, or more Rʹ in any formula herein (e.g., for formula (I) or (II)) includes an optionally substituted aromatic or optionally substituted heteroaromatic. Non-limiting aromatic and heteroaromatic groups include phenyl, benzyl, naphthyl, furanyl, pyrrolyl, imidazolyl, pyrazolyl, triazolyl, pyridinyl, pyrimidinyl, pyridazinyl, pyrazinyl, oxazolyl, and the like.

[0255] In particular embodiments, at least one, two, three, four, or more Rʹ in any formula herein (e.g., for formula (I) or (II)) includes an optionally substituted amino (e.g., -NH2, -NRN1H, or -NRN1RN2). In particular embodiments, each of RN1and RN2is, independently, H, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, optionally substituted heteroaromatic, optionally substituted amino, hydroxyl, 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, RN1and RN2can be taken together, with the nitrogen atom to which each is attached, to form an optionally substituted heterocyclyl.

[0256] Non-limiting instances of RN1and RN2can include H, aliphatic, alkyl (e.g., -RAk), alkenyl, alkynyl, aliphatic carbonyl (e.g., alkanoyl or -C(O)RAk), aliphatic-carbonyloxy (e.g., alkanoyloxy or -OC(O)RAk), aliphatic-oxy (e.g., alkoxy or -ORAk), aliphatic-oxycarbonyl (e.g., alkoxycarbonyl or -C(O)ORAk), amino (e.g., -NR2, in which each R is, e.g., H, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, or optionally substituted heteroaromatic), aromatic (e.g., aryl or -RAr), aromatic-carbonyl (e.g., aryloyl or -C(O)RAr),Attorney Docket No. LAMRP993WO-11549-1WO aromatic-carbonyloxy (e.g., aryloyloxy or -OC(O)RAr), aromatic-oxy (e.g., aryloxy or -ORAr), aromatic-oxycarbonyl (e.g., aryloxycarbonyl or -C(O)ORAr), imidoyl (e.g., -C(NR)H, -C(NR)RAk, or -C(NR)RAr, in which each R is, e.g., H, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, or optionally substituted heteroaromatic), carbamoyl (e.g., -C(O)NR2, in which each R is, e.g., H, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, or optionally substituted heteroaromatic), carbamoyloxy (e.g., -OC(O)NR2, in which each R is, e.g., H, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, or optionally substituted heteroaromatic), carboxyl (-CO2H), formyl (-C(O)H), heteroaromatic, heterocyclyl (e.g., optionally substituted furanyl, tetrahydrofuranyl, pyrrolidinyl, pyrrolyl, imidazolyl, pyrazolyl, triazolyl, piperidinyl, pyridinyl, pyrimidinyl, pyridazinyl, pyrazinyl, oxazolyl, morpholinyl, and the like), hydroxyl (-OH), silyl (e.g., -SiRS1RS2RS3or -Si(Rʹ)a(OR)b(NR2)c), and silyloxy (e.g., -O-SiRS1RS2RS3or -O-Si(Rʹ)a(OR)b(NR2)c). For any of these groups, where indicated, RAk, RAr, Rʹ, R, RS1, RS2, RS3, a, b, and c can be any described herein.

[0257] Yet other non-limiting amino groups include -NH2, -NHMe, -NMe2, -NHEt, -NMeEt, -NEt, -NHnPr, -NMenPr, -NnPr2, -NHiPr, -NMeiPr, -NiPr2, -NHsBu, -NMesBu, -NsBu2, -NHtBu, -NMetBu, -NtBu2, -N[SiH3]2, -N[Si(Me)3]2, -N[Si(Et)3]2, -NH[SiH3], -NH[Si(Me)3], -NH[Si(Et)3], -NMe[SiH3], -NMe[Si(Me)3], -NMe[Si(Et)3], -N[SiH2Me]2, -N[SiHMe2]2, -N[SiH2Et]2, -N[SiHEt2]2, -N[SiHMeEt]2, -NH[SiH2Me], -NH[SiHMe2], -NH[SiH2Et], -NH[SiHEt2]2, -NH[SiHMeEt], -NMe[SiH2Me], -NMe[SiHMe2], -NMe[SiH2Et], -NMe[SiHEt2]2, -NMe[SiHMeEt], and the like.

[0258] In particular embodiments, at least one, two, three, four, or more Rʹ in any formula herein (e.g., for formula (I) or (II)) includes an optionally substituted hydrazino (e.g., -NH-NH2or -NRN1-NRN2RN3). In particular embodiments, each of RN1, RN2, and RN3is, independently, H, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, optionally substituted heteroaromatic, optionally substituted amino, hydroxyl, 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, RN1and RN2or RN2and RN3can be taken together, with the nitrogen atom to which each is attached, to form an optionally substituted heterocyclyl. Yet other non-limiting hydrazino groups include -NH-NH2, -NMe-NH2, -NH-NHMe, -NH-NMe2, -NMe-NMe2, -NEt-NH2, -NH-NHEt, -NH-NEt2, -NMe-NEt2, and the like.

[0259] In some embodiments, at least one, two, three, four, or more Rʹ in any formula hereinAttorney Docket No. LAMRP993WO-11549-1WO (e.g., for formula (I) or (II)) includes an optionally substituted silyl. In one embodiment, silyl is -SiRS1RS2RS3, in which each of RS1, RS2, and RS3is, independently, H, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, optionally substituted heteroaromatic, optionally substituted amino, optionally substituted hydrazino, azido, hydroxyl, optionally substituted silyl, optionally substituted silyloxy, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted alkoxy, optionally substituted heteroalkyl, optionally substituted heteroalkenyl, optionally substituted heteroalkynyl, optionally substituted heterocyclyl, optionally substituted aryl, optionally substituted aryloxy, cyanato, isocyanato, cyano, isocyano, and the like. Non-limiting silyl groups include any described herein, such as -Si(R)a(RAk)b, -Si(R)a(ORAk)b, -Si(R)a(RAr)b, -Si(R)a(ORAr)b, -Si(R)a(NRN1RN2)b, -Si(Rʹ)a(OR)b(NR2)c, and the like. Yet other non-limiting silyl groups include -SiH3, -SiH2Me, -SiHMe2, -SiMe3, -Si(OH)3, -SiH2(OMe), -SiH(OMe)2, -Si(OMe)3, -SiH2(NH2), -SiHMe(NH2), -SiMe2(NH2), -SiH(NH2)2, -SiMe(NH2)2, -Si(NH2)3, -SiH2(NMe2), -SiH2(NMe2), -SiHMe(NMe2), -Si(Me)2(NMe2)2, -SiMe(NMe2)2, -Si(NMe2)3, -SiH2(NHMe), -SiHMe(NHMe), -SiH(NHMe)2, -SiMe(NHMe)2, -Si(NHMe)3, and the like.

[0260] In other embodiments, at least one, two, three, four, or more Rʹ in any formula herein (e.g., for formula (I) or (II)) includes an optionally substituted silyloxy. Non-limiting silyloxy groups include any described herein, such as -O-Si(R)a(RAk)b, -O-Si(R)a(ORAk)b, -O-Si(R)a(RAr)b, -O-Si(R)a(ORAr)b, -O-Si(R)a(NRN1RN2)b, -O-Si(Rʹ)a(OR)b(NR2)c, and the like. Yet other non- limiting silyloxy groups include -O-SiH3, -O-SiH2Me, -O-SiHMe2, -O-SiMe3, -O-Si(OH)3, -O-SiH2(OMe), -O-SiH(OMe)2, -O-Si(OMe)3, -O-SiH2(NH2), -O-SiHMe(NH2), -O-SiMe2(NH2), -O-SiH(NH2)2, -O-SiMe(NH2)2, -O-Si(NH2)3, -O-SiH2(NMe2), -O-SiH2(NMe2), -O-SiHMe(NMe2), -O-Si(Me)2(NMe2)2, -O-SiMe(NMe2)2, -O-Si(NMe2)3, -O-SiH2(NHMe), -O-SiHMe(NHMe), -O-SiH(NHMe)2, -O-SiMe(NHMe)2, -O-Si(NHMe)3, and the like.

[0261] In yet other embodiments, at least one, two, three, four, or more Rʹ in any formula herein (e.g., for formula (I) or (II)) includes azido (-N3), hydroxyl (-OH), cyanato (-OCN), isocyanato (-NCO), cyano (-CN), and / or isocyano (-NC).

[0262] The organic silicon-containing precursor may be selected from the group consisting of silane, disilane, trisilane, tetrasilane, amine-substituted versions of any of the foregoing silanes, and trisilylamine.

[0263] Examples of organic silicon-containing precursors include, but are not limited to, silanes, polysilanes, halosilanes, and aminosilanes. A silane contains hydrogen and / or carbon groups, but does not contain a halogen. A polysilane may have the formula (H3Si-(SiH2)n-SiH3), where n > 1. Examples of silanes include silane (SiH4), disilane (Si2H6), trisilane, tetrasilane and organo silanes such as methylsilane, ethylsilane, isopropylsilane, t-butylsilane, dimethylsilane, diethylsilane, di-Attorney Docket No. LAMRP993WO-11549-1WO t-butylsilane, allylsilane, sec-butylsilane, thexylsilane, isoamylsilane, t-butyldisilane, di-t- butyldisilane, tetra-ethyl-ortho-silicate (also known as tetra-ethoxy-silane or TEOS) and the like.

[0264] 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(isopropylamido)silane (DIPAS), bis(diethylamino)silane (BDEAS), and the like. A further example of an aminosilane is trisilylamine (N(SiH3)3).

[0265] Examples of silicon-containing precursors for depositing silicon carbide include siloxanes, alkyl silane or hydrocarbon-substituted silane, or a nitrogen-containing carbon-containing reactant. Examples of siloxanes include 2,4,6,8-tetramethylcyclotetrasiloxane (TMCTS), heptamethylcyclotetrasiloxane (HMCTS), silsesquioxane, disiloxanes, such as pentamethyldisiloxane (PMDSO) or tetramethyldisiloxane (TMDSO), and trisiloxanes such as hexamethyltrisiloxane or heptamethyltrisiloxane. Alkyl silanes include a central silicon atom with one or more alkyl groups bonded to it as well as one or more hydrogen atoms bonded to it. In some embodiments, any one or more of the alkyl groups contain 1-5 carbon atoms. The hydrocarbon groups may be saturated or unsaturated (e.g., alkene (e.g., vinyl), alkyne, and aromatic groups). Examples include but are not limited to trimethylsilane (3MS), triethylsilane, pentamethyl disilamethane ((CH3)2Si-CH2-Si(CH3)3), and dimethylsilane (2MS). Additionally, disilanes, trisilanes, or other higher silanes may be used in place of monosilanes. In some embodiments, one of the silicon atoms can have a carbon-containing or hydrocarbon group attached to it, and one of the silicon atoms can have a hydrogen atom attached to it. Example carbon-containing reactants including a nitrogen include methyl-substituted disilazanes and trisilazanes, such as tetramethyldisilazane and hexamethyl trisilazane.

[0266] Yet other examples of organic silicon-containing precursors can include siloxanes such as cyclotetrasiloxanes such as heptamethylcyclotetrasiloxane (HMCTS) and tetramethyl cyclotetrasiloxane. Other cyclic siloxanes can also include but are not limited to cyclotrisiloxanes and cyclopentasiloxanes. Other examples of suitable precursors include linear siloxanes such as, but not limited to, disiloxanes, such as pentamethyldisiloxane (PMDSO), tetramethyldisiloxane (TMDSO), hexamethyl trisiloxane, and heptamethyl trisiloxane. For undoped silicon carbide, examples of suitable precursors include monosilanes substituted with one or more alkyl, alkene, and / or alkyne groups containing, e.g., 1-5 carbon atoms. Examples include but are not limited to trimethylsilane (3MS), dimethylsilane (2MS), triethylsilane (TES), andAttorney Docket No. LAMRP993WO-11549-1WO pentamethyldisilamethane. Additionally, disilanes, trisilanes, or other higher silanes may be used in place of monosilanes. An example of one such disilane from the alkyl silane class is hexamethyldisilane (HMDS). Another example of a disilane from the alkyl silane class can include pentamethyldisilane (PMDS). Other types of alkyl silanes can include alkylcarbosilanes, which can have a branched polymeric structure with a carbon bonded to a silicon atom as well as alkyl groups bonded to a silicon atom. Examples include dimethyl trimethylsilyl methane (DTMSM) and bis-dimethylsilyl ethane (BDMSE). Examples of other suitable precursors include, e.g., alkyldisilazanes and possibly compounds including amino (-NH2) and alkyl groups separately bonded to one or more silicon atoms. Alkyldisilazanes include silizanes and alkyl groups bonded to two silicon atoms. An example includes 1,1,3,3-tetramethyldisilazane (TMDSN).

[0267] In the Si-containing precursors described herein, different kinds of Rʹ can be attached to the silicon atom. Further Si-containing precursors are described herein. AMINOSILANES

[0268] 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, 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.

[0269] 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-Attorney Docket No. LAMRP993WO-11549-1WO 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.

[0270] 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.

[0271] 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, optionally substituted aromatic, optionally substituted arylene, optionally substituted heteroaromatic, optionally substituted heteroarylene, oxy (-O-), imino, or silyl.

[0272] 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.

[0273] 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 optionallyAttorney Docket No. LAMRP993WO-11549-1WO substituted heterocyclyl. In other embodiments, each R is, independently, H, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, or optionally substituted aryl.

[0274] 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.

[0275] 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 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.

[0276] 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.

[0277] 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.Attorney Docket No. LAMRP993WO-11549-1WO

[0278] 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 anyherein 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.

[0279] 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− 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.

[0280] 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.

[0281] 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.

[0282] 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-).

[0283] The precursor can include any useful combination of Rʹ and NRʺ2groups in combinationAttorney Docket No. LAMRP993WO-11549-1WO 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.

[0284] The precursor can include heterocyclic groups including the silicon and nitrogen atoms. In one embodiment, the precursor has a , wherein Rʹ and Rʺ can be any described herein, and wherein n is 1, 2, 3, or

[0285] In another embodiment, the precursor has a Rʹ and Rʺ can be any described herein, and wherein n is 1, 2, 3, or theprecursor has a which each Rʺ can independently be any described herein; and wherein n is

[0286] In another embodiment, the precursor has a , wherein Rʹ and Rʺ can be any described herein, and wherein n is 1, 2, 3, orembodiment, the precursor has a , wherein Rʺ can independently be any described herein, and wherein n is

[0287] 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.

[0288] Precursors can include any of the following, e.g., (RAk)Si(NH2)(NRAk2)2, (RAk)Si(NRAk2)3, (RAk)2Si(NHRAk2)2, (RAk)(H)Si(NHRAk)2, (RAk)3Si(NRAk2), (RAk)3Si(NHRAk), H2Si(NHRAk2)2, (RAk)(H)Si(NRAk2)2, HSi(NH2)(NRAk2)2, HSi(NRAk2)3, Si(NRAk2)4, (Rʹ)(H)Si(NRʺ2)2, (Rʹ)2Si(NRAk2)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 RAkis, independently, H, optionally substituted aliphatic, optionally substituted heteroaliphatic,Attorney Docket No. LAMRP993WO-11549-1WO optionally substituted alkyl, optionally substituted alkenyl, or optionally substituted alkynyl. In particular embodiments, RAkis 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.

[0289] 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 (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]2or BDMADMS); bis(dimethylamino)diethylsilane (SiEt2[NMe2]2); bis(dimethylamino) methylvinylsilane (SiMeVi[NMe2]2); bis(ethylamino)dimethylsilane (SiMe2[NHEt]2);Attorney Docket No. LAMRP993WO-11549-1WO 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 which Im is imidazolyl); tris(dimethylamino)silane (SiH[NMe2]3or 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. ISOCYANATO SILANES

[0290] A silicon-containing precursor can include one or more isocyanato groups, thereby providing a non-limiting isocyanato silane. In one embodiment, the precursor has a formula of (Rʹ)4-xSi(NCO)x, wherein: x is 1, 2, 3, or 4; and 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-Attorney Docket No. LAMRP993WO-11549-1WO oxy, amino, hydrazino, azido, hydroxyl, silyl, silyloxy, cyanato, isocyanato, cyano, or isocyano, in which any of these may be optionally substituted.

[0291] In another embodiment, the precursor has a formula of (Rʹ)zSi(NCO)x(NRʺ2)y, wherein: x is 1, 2, 3, or 4; each of y and z is, independently, 0, 1, 2, or 3; x + y + z = 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, amino, hydrazino, azido, hydroxyl, silyl, silyloxy, cyanato, isocyanato, cyano, or isocyano, in which any of these may be optionally substituted; and

[0292] 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.

[0293] In yet another embodiment, the precursor has a formula of (NCO)x(Rʹ)3-xSi−L− Si(Rʹ)3-x(NCO)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 alkylene, optionally substituted alkenylene, optionally substituted alkynylene, optionally substituted heteroaliphatic, optionally substituted heteroalkylene, optionally substituted heteroalkenylene, optionally substituted heteroalkynylene, optionally substituted aromatic, optionally substituted arylene, optionally substituted heteroaromatic, optionally substituted heteroarylene, oxy (-O-), imino, or silyl; and 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.

[0294] 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.,Attorney Docket No. LAMRP993WO-11549-1WO -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.

[0295] 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)cin 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.

[0296] Precursors can include any of the following, e.g., (Rʹ)Si(NCO)(NRʺ2)2, (Rʹ)2Si(NCO)(NRʺ2), (Rʹ)2Si(NCO)(N[SiR3]2), or tetraisocyanatosilane (Si[NCO]4). 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 R is, independently, H, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted alkoxy, optionally substituted aromatic, optionally substituted heteroaromatic, optionally substituted aryl, or optionally substituted heteroaryl. AZIDO SILANES

[0297] A silicon-containing precursor can include one or more azido groups, thereby providingAttorney Docket No. LAMRP993WO-11549-1WO a non-limiting azido silane. In one embodiment, the precursor has a formula of (Rʹ)4-xSi(N3)x, wherein: x is 1, 2, 3, or 4; and 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.

[0298] In another embodiment, the precursor has a formula of (Rʹ)zSi(N3)x(NRʺ2)y, wherein: x is 1, 2, 3, or 4; each of y and z is, independently, 0, 1, 2, or 3; x + y + z = 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, amino, hydrazino, azido, hydroxyl, silyl, silyloxy, cyanato, isocyanato, cyano, or isocyano, in which any of these may be optionally substituted; and

[0299] 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.

[0300] In yet another embodiment, the precursor has a formula of (N3)x(Rʹ)3-xSi−L− Si(Rʹ)3-x(N3)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 alkylene, optionally substituted alkenylene, optionally substituted alkynylene, optionally substituted heteroaliphatic, optionally substituted heteroalkylene, optionally substituted heteroalkenylene, optionally substituted heteroalkynylene, optionally substituted aromatic, optionally substituted arylene, optionally substituted heteroaromatic, optionally substituted heteroarylene, oxy (-O-), imino, or silyl; and 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,Attorney Docket No. LAMRP993WO-11549-1WO 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.

[0301] 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.

[0302] 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)cin which each Rʹis, 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.

[0303] Precursors can include any of the following, e.g., (Rʹ)3Si(N3), (Rʹ)2Si(N3)2, (Rʹ)Si(N3)3, or Si(N3)(NRʺ2)3. 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). Non-limiting examples of precursors also include tris(dimethylamino)silylazide ([Me2N]3SiN3); di-tert-butylAttorney Docket No. LAMRP993WO-11549-1WO diazidosilane (tBu2Si(N3)2); ethylsilicon triazide (EtSi(N3)3); and the like. HYDRAZINO SILANES

[0304] A silicon-containing precursor can include one or more optionally substituted hydrazino groups, thereby providing a non-limiting hydrazino silane. In one embodiment, the precursor has a formula of (Rʹ)4-xSi(NRʺ-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, 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.

[0305] In another embodiment, the precursor has a formula of (NRʺ2-NRʺ)x(Rʹ)3-xSi−L−Si (Rʹ)3-x(NRʺ-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.

[0306] In yet another embodiment, the precursor has a formula of (Rʹ)4-xSi(NRʺ-L-NRʺ2)x, wherein: x is 1, 2, 3, or 4; and each L, Rʹ, and Rʺ can be any described herein.

[0307] In particular embodiments, L is optionally substituted imino, such as -NR-, in which RAttorney Docket No. LAMRP993WO-11549-1WO 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. In yet other embodiments, L is -NR-NR-, in which R is any described herein (e.g., R is H, optionally substituted aliphatic, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, or optionally substituted aromatic).

[0308] 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, optionally substituted aromatic, optionally substituted arylene, optionally substituted heteroaromatic, optionally substituted heteroarylene, oxy (-O-), imino, or silyl.

[0309] The precursor can include any useful combination of Rʹ and hydrazino groups. In one embodiment, the precursor has a formula of (Rʹ)3Si(NRʺ-L-NRʺ2) or (Rʹ)3Si(NRʺ-NRʺ2), wherein L, Rʹ, and Rʺ can be any described herein.

[0310] The precursor can include a plurality of hydrazino groups. In one embodiment, the precursor has a formula of (Rʹ)2Si(NRʺ-L-NRʺ2)2, (Rʹ)2Si(NRʺ-NRʺ2)2, or (Rʹ)2Si(NH-NHRʺ)2, wherein L, Rʹ, and Rʺ can be any described herein.

[0311] The precursor can include at least two silicon atoms. In one embodiment, the precursor has a formula of (NRʺ2-NRʺ)(Rʹ)2Si−Si(Rʹ)2(NRʺ-NRʺ2), wherein each Rʹ and Rʺ can be any described herein.

[0312] Non-limiting precursors can include bis(tert-butylhydrazino)diethylsilane (SiEt2[NH−NHtBu]2); tris(dimethylhydrazino)silane (SiH[NH−NMe2]3); and the like. SILOXANES AND DERIVATIVES THEREOF

[0313] A silicon-containing precursor can include one or more aliphatic-oxy, aromatic-oxy groups, and / or oxy groups, thereby providing a siloxane or a derivative thereof having one or more Si-O, O-Si-O, or Si-O-Si bonds. In one embodiment, the precursor has a formula of (Rʹ)4-xSi(OR‴)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,Attorney Docket No. LAMRP993WO-11549-1WO 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 R‴ is, independently, H, aliphatic, heteroaliphatic, aromatic, heteroaromatic, silyl, or silyloxy, in which any of these may be optionally substituted.

[0314] In another embodiment, the precursor has a formula of (R‴O)x(Rʹ)3-xSi−L− Si(Rʹ)3-x(OR‴)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 R‴ is, independently, H, aliphatic, heteroaliphatic, aromatic, heteroaromatic, silyl, or silyloxy, in which any of these may be optionally substituted.

[0315] 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. In other embodiments, L is −O−Lʹ−O−, in which Lʹ is optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, optionally substituted heteroaromatic, optionally substituted silyl (e.g., -SiR2-), optionally substituted alkylene (e.g., -(CH2)n-, in which n is 1 to 6), optionally substituted arylene, and the like. In yet other embodiments, L is oxy.

[0316] 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, optionally substituted aromatic, optionally substituted arylene, optionally substitutedAttorney Docket No. LAMRP993WO-11549-1WO heteroaromatic, optionally substituted heteroarylene, oxy (-O-), imino, or silyl.

[0317] 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.

[0318] In other embodiments, R‴ is H, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted alkyl, optionally substituted silyl, or optionally substituted silyloxy. In some embodiments, R‴ is optionally substituted alkyl (e.g., Me, Et, nPr, iPr, sBu, or tBu). In other embodiments, R‴ is -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 Rʹis, 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.

[0319] The precursor can include one or more hydrogen atoms attached to the silicon atom. In one embodiment, the precursor has a formula of H3Si(OR‴), H2Si(OR‴)2, or HSi(OR‴)3, wherein each R‴ can independently be any described herein.

[0320] The precursor can include any combination of Rʹ and OR‴ groups within the precursor. In one embodiment, the precursor has a formula of (Rʹ)3Si(OR‴), (Rʹ)2Si(OR‴)2, or (Rʹ)Si(OR‴)3, wherein each of Rʹ and R‴ can independently be any described herein. The precursor can includeAttorney Docket No. LAMRP993WO-11549-1WO alkyl groups, such as in the precursor having a formula of (RAk)3Si(ORAk), (RAk)2Si(ORAk)2, or (RAk)Si(ORAk)3, in which RAkis optionally substituted alkyl.

[0321] 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 (R‴O)x(Rʹ)3-xSi−Si(Rʹ)3-x(OR‴)x, wherein Rʹ and R‴ can be any described herein. In one embodiment, the precursor has a formula of (R‴O)(Rʹ)2Si−Si(Rʹ)2(OR‴), wherein Rʹ and R‴ can be any described herein.

[0322] 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−O−Si(Rʹ)3, wherein Rʹ can be any described herein. In another instance, the precursor has a formula of (Rʹ)3Si−O−Lʹ−O−Si(Rʹ)3, wherein Lʹ and Rʹ can be any described herein. In yet another instance, the precursor has a formula of (Rʹ)3Si−(OSiRʹ2)z−Rʹ, wherein Rʹ can be any described herein; and in which z is 1, 2, 3, 4, or more. In another instance, the precursor has a formula of (Rʹ)4-xSi−[(OSiRʹ2)z−Rʹ]x, wherein Rʹ can be any described herein; x is 1, 2, 3, or 4; and z is 1, 2, 3, 4, or more.

[0323] The precursor can include any useful combination of Rʹ and OR‴ groups in combination with two silicon atoms. In one instance, the precursor has a formula of (R‴O)x(Rʹ)3-xSi−O−Si(Rʹ)3-x(OR‴)x, wherein Rʹ and R‴ can be any described herein. In another instance, the precursor has a formula of (R‴O)x(Rʹ)3-xSi−O−Lʹ−O−Si(Rʹ)3-x(OR‴)x, wherein Lʹ, Rʹ, and R‴ can be any described herein.

[0324] Non-limiting precursors can include methoxydimethylsilane (SiHMe2[OMe]); ethoxydimethylsilane (SiHMe2[OEt]); iso-propoxydimethylsilane (SiHMe2[OiPr]); t- butoxydimethylsilane (SiHMe2[OtBu]); t-pentoxydimethylsilane (SiHMe2[OtPe]); phenoxy dimethylsilane (SiHMe2[OPh]); acetoxydimethylsilane (SiHMe2[OAc]); methoxytrimethylsilane (SiMe3[OMe]); ethoxytrimethylsilane (SiMe3[OEt]); iso-propoxytrimethylsilane (SiMe3[OiPr]); t-butoxytrimethylsilane (SiMe3[OtBu]); t-pentoxytrimethylsilane (SiMe3[OtPe]); phenoxy trimethylsilane (SiMe3[OPh]); acetoxytrimethylsilane (SiMe3[OAc]); methoxytriethylsilane (SiEt3[OMe]); ethoxytriethylsilane (SiEt3[OEt]); iso-propoxytriethylsilane (SiEt3[OiPr]); t- butoxytriethylsilane (SiEt3[OtBu]); t-pentoxytriethylsilane (SiEt3[OtPe]); phenoxytriethylsilane (SiEt3[OPh]); acetoxytriethylsilane (SiEt3[OAc]); dimethoxysilane (SiH2[OMe]2); diethoxysilane (SiH2[OEt]2); di-iso-propoxysilane (SiH2[OPr]2); di-tert-butoxysilane (SiH2[OtBu]2 or DTBOS); di-tert-pentoxysilane (SiH2[OtPe]2or DTPOS); diacetoxysilane (SiH2[OAc]2); dimethoxy dimethylsilane (SiMe2[OMe]2); diethoxydimethylsilane (SiMe2[OEt]2); di-iso-propoxy dimethylsilane (SiMe2[OPr]2); di-tert-butoxydimethylsilane (SiMe2[OtBu]2); diacetoxy dimethylsilane (SiMe2[OAc]2); dimethoxydiethylsilane (SiEt2[OMe]2); diethoxydiethylsilane (SiEt2[OEt]2); di-iso-propoxydiethylsilane (SiEt2[OiPr]2); di-tert-butoxydiethylsilaneAttorney Docket No. LAMRP993WO-11549-1WO (SiEt2[OtBu]2); diacetoxydiethylsilane (SiEt2[OAc]2); dimethoxydiphenylsilane (SiPh2[OMe]2); dimethoxydi-iso-propylsilane (Si[iPr]2[OMe]2); diethoxydi-iso-propylsilane (Si[iPr]2[OEt]2); di- iso-propoxydi-iso-propylsilane (Si[iPr]2[OiPr]2); di-tert-butoxydi-iso-propylsilane (Si[iPr]2[OtBu]2); diacetoxydi-iso-propylsilane (Si[iPr]2[OAc]2); dimethoxymethylvinylsilane (SiMeVi[OMe]2); diethoxymethylvinylsilane (SiMeVi[OEt]2); di-iso-propoxymethylvinylsilane (SiMeVi[OiPr]2); di-tert-butoxymethylvinylsilane (SiMeVi[OtBu]2); diacetoxymethylvinylsilane (SiMeVi[OAc]2); triethoxysilane (SiH[OEt]3or TES); trimethoxyethylsilane (SiEt[OMe]3); triethoxymethylsilane (SiMe[OEt]3); triethoxyphenylsilane (SiPh[OEt]3); tetramethoxysilane (Si[OMe]4); tetraethoxysilane (Si[OEt]4or TEOS); tetra-n-propoxysilane (Si[OnPr]4); tetra-iso- propoxysilane (Si[OiPr]4); tetra-n-butoxysilane (Si[OnBu]4); tetra-t-butoxysilane (Si[OtBu]4); tetramethyldisiloxane (O[SiHMe2]2or TMDO); hexamethyldisiloxane (O[SiMe3]2); hexaethyldisiloxane (O[SiEt3]2); hexapropyldisiloxane (O[SiPr3]2); hexaphenyldisiloxane (O[SiPh3]2); hexamethyltrisiloxane (Me2SiH-O-SiMe2-O-SiHMe2); and the like. MIXED SILANES INCLUDING OXYGEN AND NITROGEN

[0325] A silicon-containing precursor can include one or more optionally substituted amino groups with either aliphatic-oxy or aromatic-oxy groups, thereby providing a non-limiting mixed silane. In one embodiment, the precursor has a formula of (Rʹ)zSi(OR‴)x(NRʺ2)y, wherein: each of x and y is, independently, 1, 2, 3, or 4; z is 0, 1, or 2; x + y + z = 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, amino, hydrazino, azido, hydroxyl, silyl, silyloxy, cyanato, isocyanato, cyano, or isocyano, in which any of these may be optionally substituted; 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; and each R‴ is, independently, H, aliphatic, heteroaliphatic, aromatic, heteroaromatic, silyl, or silyloxy, in which any of these may be optionally substituted.

[0326] In another embodiment, the precursor has a formula of (Rʺ2N)y(R‴O)x(Rʹ)zSi−L− Si(Rʹ)z(OR‴)x(NRʺ2)y, wherein: each of x and y is more than 0 (e.g., 1 or 2);Attorney Docket No. LAMRP993WO-11549-1WO z is 0 or 1; x + y + z = 3; L is a linker, such as a covalent bond, optionally substituted aliphatic, optionally substituted alkylene, optionally substituted alkenylene, optionally substituted alkynylene, optionally substituted heteroaliphatic, optionally substituted heteroalkylene, optionally substituted heteroalkenylene, optionally substituted heteroalkynylene, optionally substituted aromatic, optionally substituted arylene, optionally substituted heteroaromatic, optionally substituted heteroarylene, oxy (-O-), imino, or silyl; 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; 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; and each R‴ is, independently, H, aliphatic, heteroaliphatic, aromatic, heteroaromatic, silyl, or silyloxy, in which any of these may be optionally substituted.

[0327] Non-limiting examples of Rʹ, Rʺ, and R‴ are described herein, e.g., such as for amino silane, siloxane, or derivatives thereof.

[0328] The precursor can include any combination of Rʹ, NRʺ2, and OR‴ groups. In one embodiment, the precursor has a formula of (Rʹ)Si(OR‴)2(NRʺ2) or (Rʹ)2Si(OR‴)2(NRʺ2), wherein each of Rʹ, Rʺ, and R‴ can independently be any described herein. In other embodiments, the precursor has a formula of (Rʹ)2Si(OR‴)(N[SiR3]2), wherein each of Rʹ and R‴ can independently be any described herein; and R is, independently, H, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, or optionally substituted heteroaromatic.

[0329] The precursor can include only amino and oxy-containing groups attached to the silicon atom. In one embodiment, the precursor has a formula of Si(OR‴)3(NRʺ2), Si(OR‴)2(NRʺ2)2, or Si(OR‴)(NRʺ2)3, wherein each of Rʺ and R‴ can independently be any described herein. Non- limiting precursors can include, e.g., diethoxy(iso-propylamino)silane (SiH[NHiPr][OEt]2); diethoxy(tert-butylamino)silane (SiH[NHtBu][OEt]2); diethoxy(tert-pentylamino)silane (SiH[NHtPe][OEt]2); di-tert-butoxy(methylamino)silane (SiH[NHMe][OtBu]2); di-tert-Attorney Docket No. LAMRP993WO-11549-1WO butoxy(ethylamino)silane (SiH[NHEt][OtBu]2); di-tert-butoxy(iso-propylamino)silane (SiH[NHiPr][OtBu]2); di-tert-butoxy(n-butylamino)silane (SiH[NHnBu][OtBu]2); di-tert- butoxy(sec-butylamino)silane (SiH[NHsBu][OtBu]2); di-tert-butoxy(iso-butylamino)silane (SiH[NHiBu][OtBu]2); di-tert-butoxy(tert-butylamino) silane (SiH[NHtBu][OtBu]2); di-tert- pentoxy(methylamino) silane (SiH[NHMe][OtPe]2); di-tert-pentoxy(ethylamino)silane (SiH[NHEt][OtPe]2); di-tert-pentoxy(iso-propylamino)silane (SiH[NHiPr][OtPe]2); di-tert- pentoxy(n-butylamino)silane (SiH[NHnBu][OtPe]2); di-tert-pentoxy(sec-butylamino)silane (SiH[NHsBu][OtPe]2); di-tert-pentoxy(iso-butylamino) silane (SiH[NHiBu][OtPe]2); di-tert- pentoxy(tert-butylamino)silane (SiH[NHtBu][OtPe]2); dimethoxy(phenylmethylamino)silane (SiH[NPhMe][OMe]2); diethoxy(phenylmethylamino)silane (SiH[NPhMe][OEt]2); dimethoxy(phenylmethylamino)methylsilane (SiMe[NPhMe][OMe]2); diethoxy (phenylmethylamino)methylsilane (SiEt[NPhMe][OEt]2); and the like. SILYL AMINES

[0330] A silicon-containing precursor can include one or more optionally substituted silyl groups attached to a nitrogen atom, thereby providing a non-limiting silyl amine. In one embodiment, the precursor has a formula of (Rʺ)3-yN(SiRʹ3)y, wherein: y is 1, 2, or 3; 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, amino, silyl, or silyloxy, 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.

[0331] In another embodiment, the precursor has a formula of (Rʹ3Si)y(Rʺ)2-yN−L− N(Rʺ)2-y(SiRʹ3)y, wherein: each y is, independently, 0, 1, or 2; 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-Attorney Docket No. LAMRP993WO-11549-1WO 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, optionally in which N−L−N, taken together, forms a multivalent heterocyclyl group.

[0332] In one instance, at least one y is not 0. In another embodiment, y can be 0 (e.g., if L includes a carbon atom or a heteroatom). In yet another embodiment, y 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, optionally substituted aromatic, optionally substituted arylene, optionally substituted heteroaromatic, optionally substituted heteroarylene, oxy (-O-), imino (e.g., -NR- or -N(SiR3)-), or silyl (e.g., -SiR2-), as well as combinations thereof (e.g., -SiR2-NR-, -NR-SiR2-, -SiR2-NR-SiR2- , 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.

[0333] 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 or -SiR2-L-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 optionallyAttorney Docket No. LAMRP993WO-11549-1WO substituted aryl. L can be any useful linker (e.g., a covalent bond, optionally substituted alkylene, optionally substituted heteroalkylene, oxy, imino, silyl, or the like).

[0334] 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)cin which each Rʹis, 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.

[0335] The precursor can include at least one Rʺ group attached to the nitrogen atom. In one embodiment, the precursor has a formula of (Rʺ)N(SiRʹ3)2or (Rʺ)2N(SiRʹ3), wherein Rʹ and Rʺ can be any described herein. In another embodiment, the precursor has a formula of (Rʺ)2N(SiH3) or (Rʺ)N(SiH3)2, wherein Rʺ can be any described herein. In particular embodiments, Rʹ is optionally substituted alkyl, amino, or alkoxy; and Rʺ is optionally substituted alkyl or amino, optionally wherein two Rʺ are taken together, with the nitrogen atom to which each are attached, to form a heterocyclyl.

[0336] The precursor can include at least one hydrogen atom attached to the nitrogen atom. In one embodiment, the precursor has a formula of (H)N(SiRʹ3)2, wherein Rʹ can be any described herein. In another embodiment, the precursor has a formula of (H)N(SiRAk3)2, wherein RAkcan be optionally substituted aliphatic, optionally substituted alkyl, optionally substituted alkenyl, or optionally substituted alkynyl.

[0337] The precursor can include three silicon atoms attached to the nitrogen atom. In one embodiment, the precursor has a formula of N(SiRʹ3)3, wherein Rʹ can be any described herein. In another embodiment, the precursor has a formula of N(SiH3)(SiRʹ3)2, wherein Rʹ can be any described herein. In yet another embodiment, the precursor has a formula of N(SiH3)(SiRAk3)2, wherein RAkcan be optionally substituted aliphatic, optionally substituted alkyl, optionally substituted alkenyl, or optionally substituted alkynyl.

[0338] The precursor can have two or more nitrogen atoms, in which the precursor includes a N-N bond. In one instance, the precursor has a formula of (Rʹ3Si)2N−N(SiRʹ3)2, wherein Rʹ canAttorney Docket No. LAMRP993WO-11549-1WO be any described herein.

[0339] A linker can be present between nitrogen atoms. In one instance, the precursor has a formula of (Rʹ3Si)(Rʺ)N−L−N(Rʺ)(SiRʹ3) or (Rʹ3Si)2N−L−N(SiRʹ3)2, wherein Rʹ and Rʺ can be any described herein. In some embodiments, L is a covalent bond, optionally substituted alkylene, optionally substituted heteroalkylene, -O-, -SiR2-, or -Si-. In particular embodiments, at least one of Rʺ is not H. In another instance, the precursor has a formula of (H3Si)(Rʺ)N−L−N(Rʺ)(SiH3), wherein Rʺ can be any described herein.

[0340] The linker can include a silicon atom. In one instance, the precursor has a formula of (Rʹ3Si)2N−SiRʹ2−N(SiRʹ3)2, wherein Rʹ can be any described herein. In another instance, the precursor has a formula of (Rʹ3Si)(Rʺ)N−SiRʹ2−N(Rʺ)(SiRʹ3) or (Rʹ3Si)2N−SiRʹ2−N(Rʺ)2, wherein Rʹ and Rʺ can be any described herein.

[0341] The linker can include a SiH2 group. In one instance, the precursor has a formula of (Rʹ3Si)2N−SiH2−N(SiRʹ3)2, wherein Rʹ can be any described herein. In another instance, the precursor has a formula of (Rʹ3Si)HN−SiH2−NH(SiRʹ3) or (Rʹ3Si)2N−SiH2−N(Rʺ)2, wherein Rʹ and Rʺ can be any described herein.

[0342] A plurality of nitrogen- and silicon-containing moieties may be present within the precursor. In one embodiment, the precursor has a formula of (Rʹ3Si)(Rʺ)N−SiRʹ2−N(Rʺ)− SiRʹ2−N(Rʺ)(SiRʹ3), wherein Rʹ and Rʺ can be any described herein.

[0343] Non-limiting precursors can include, e.g., 1,1,3,3-tetramethyldisilazane (NH[SiHMe2]2 or TMDS); 1,1,2,3,3-pentamethyldisilazane (NMe[SiHMe2]2); 1,1,1,3,3,3-hexamethyldisilazane (NH[SiMe3]2 or HMDS); heptamethyldisilazane (NMe[SiMe3]2); 1,1,1,3,3,3-hexamethyl-2- ethyldisilazane (NEt[SiMe3]2); 1,1,1,3,3,3-hexamethyl-2-isopropyldisilazane (NiPr[SiMe3]2); 1,1,1,3,3,3-hexaethyl-2-isopropyldisilazane (NiPr[SiEt3]2); 1,1,3,3-tetramethyl-2-isopropyl disilazane (NiPr[SiHMe2]2); 1,1,3,3-tetraethyl-2-isopropyldisilazane (NiPr [SiHEt2]2); 1,3- diethyltetramethyldisilazane (NH[SiMe2Et]2); 1,1,3,3-tetraethyldisilazane (NH[SiHEt2]2); 1,1,3,3- tetraethyl-2-methyldisilazane (NMe[SiHEt2]2); 1,1,1,3,3,3-hexaethyldisilazane (NH[SiEt3]2); 1,1,1,3,3,3-hexaethyl-2-methyldisilazane (NMe[SiEt3]2); 1,1,1,2,3,3,3-heptaethyldisilazane (NEt[SiEt3]2); 1,2,3-trimethyltrisilazane (N[SiH2Me]3); nonamethyltrisilazane (N[SiMe3]3); di- iso-propylsilylamine (NiPr2[SiH3]); diethylsilylamine (NEt2[SiH3]); diisopropylsilylamine (NiPr2[SiH3]); di-sec-butylsilylamine (NsBu2[SiH3]); di-tert-butylsilylamine (NtBu2[SiH3]); disilylmethylamine (NMe[SiH3]2); disilylethylamine (NEt[SiH3]2); disilylisopropylamine (NiPr[SiH3]2); disilyl-tert-butylamine (NtBu[SiH3]2); bis(trimethylsilyl) amine (NH[SiMe3]2); bis(triethylsilyl)amine (NH[SiEt3]2); and the like. SILAZANES AND DERIVATIVES THEREOF

[0344] A silicon-containing precursor can include one or more amino, silyl, and / or imino groups,Attorney Docket No. LAMRP993WO-11549-1WO thereby providing a silazane or a derivative thereof having one or more Si-N, N-Si-N, Si-N-Si, N- Si-Si, or N-Si-N-Si bonds. In one embodiment, the precursor has a formula of (Rʺ)3-yN(SiRʹ2−L−SiRʹ3)y, wherein: y is 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, as well as combinations thereof; 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, amino, silyl, or silyloxy, 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.

[0345] In another embodiment, the precursor has a formula of (Rʺ)3-yN(SiRʹ2−L−SiRʹ2−NRʺ2)y, wherein y is 1, 2, or 3; and each of L, Rʹ, and Rʺ can be any described herein.

[0346] In yet another embodiment, the precursor has a formula of (Rʺ)3-yN (SiRʹ2−L−NRʺ2)y, wherein y is 1, 2, or 3; and each of L, Rʹ, and Rʺ can be any described herein.

[0347] In one embodiment, the precursor has a formula of (Rʹ)4-xSi(NRʺ−L−SiRʹ3)x, wherein: x is 1, 2, 3, or 4; 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, as well as combinations thereof; 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, amino, silyl, or silyloxy, 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 optionallyAttorney Docket No. LAMRP993WO-11549-1WO substituted heterocyclyl.

[0348] In another embodiment, the precursor has a formula of (Rʺ2N)−(SiRʹ2−L)z−SiRʹ3, wherein z is 1, 2, or 3; and each of L, Rʹ, and Rʺ can be any described herein.

[0349] In some embodiments, 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, optionally substituted aromatic, optionally substituted arylene, optionally substituted heteroaromatic, optionally substituted heteroarylene, oxy (-O-), imino (e.g., -NR- or -N(SiR3)-), or silyl (e.g., -SiR2-), as well as combinations thereof (e.g., -SiR2-NR-, -NR-SiR2-, -SiR2-NR-SiR2-, 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.

[0350] 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., -SiR3or -SiR2-L-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. L can be any useful linker (e.g., a covalent bond, optionally substituted alkylene, optionally substituted heteroalkylene, oxy, imino, silyl, or the like).

[0351] 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,Attorney Docket No. LAMRP993WO-11549-1WO -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)cin which each Rʹis, 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.

[0352] The precursor can include one or more disilanyl groups and amino groups. In one embodiment, the precursor has a formula of Rʺ2N−SiRʹ2−SiRʹ3, wherein L, Rʹ, and Rʺ can be any described herein. In other embodiments, the precursor has a formula of Rʺ2N−SiH2−SiH3, wherein Rʺ is any described herein. In another embodiment, the precursor has a formula of (Rʺ)3-yN−(SiRʹ2−SiRʹ3)y, wherein y, Rʹ, and Rʺ can be any described herein. In yet another embodiment, the precursor has a formula of (Rʺ)3-yN−(SiH2−SiH3)y, wherein y and Rʺ can be any described herein.

[0353] The precursor can include a bivalent disilanyl group. In one embodiment, the precursor has a formula of Rʺ2N−SiRʹ2−SiRʹ2−L−NRʺ2, wherein L, Rʹ, and Rʺ can be any described herein. In another embodiment, the precursor has a formula of Rʺ2N−SiRʹ2−SiRʹ2−NRʺ2, wherein Rʹ and Rʺ can be any described herein.

[0354] A linker L can be present between two silyl group. In one embodiment, the precursor has a formula of Rʺ2N−SiRʹ2−L−SiRʹ3 or RʺN−(SiRʹ2−L−SiRʹ3)2, wherein L, Rʹ, and Rʺ can be any described herein. In another embodiment, the precursor has a formula of Rʺ2N−SiRʹ2−L− SiRʹ2−NRʺ2, wherein L, Rʹ, and Rʺ can be any described herein. In yet another embodiment, the precursor has a formula of (Rʺ)3-yN−(SiRʹ2−L−SiH3)y, wherein y, L, Rʹ, and Rʺ can be any described herein.

[0355] The precursor can include −SiH3as the silyl group. In one embodiment, the precursor has a formula of Rʺ2N−SiH2−SiH3, wherein Rʺ can be any described herein. In another embodiment, the precursor has a formula of (Rʺ)N−(SiH2−L−SiH3)2 or (Rʺ)2N−(SiH2−L−SiH3), wherein L and Rʺ can be any described herein.

[0356] The precursor can include a silyl-substituted amino group, such as, e.g., -NRʺ-SiRʹ3, in which Rʹ and Rʺ can be any described herein. In one embodiment, the precursor has a formula of (Rʹ)4-xSi(NRʺ−SiRʹ3)x or (Rʹ)4-xSi(NH−SiRʹ3)x, wherein x is 1, 2, 3, or 4; and in which Rʹ and Rʺ can be any described herein. In another embodiment, the precursor has a formula of H2Si(NRʺ−SiRʹ3)3, wherein Rʹ and Rʺ can be any described herein.

[0357] The precursor can include a bis-trisilylamino group, such as, e.g., -N(SiRʹ3)2in which RʹAttorney Docket No. LAMRP993WO-11549-1WO can be any described herein. In one embodiment, the precursor has a formula of Rʺ2N−SiRʹ2− N(SiRʹ3)2, in which Rʹ and Rʺ can be any described herein. In another embodiment, the precursor has a formula of Rʺ2N−SiH2−N(SiH3)2, in which Rʹ can be any described herein. In yet another embodiment, the precursor has a formula of (Rʹ3Si)2N−[SiRʹ2−N(SiRʹ3)]z(SiRʹ3), wherein z is 0, 1, 2, or 3; and in which Rʹ and Rʺ can be any described herein.

[0358] The precursor can include a linker L disposed between a silicon atom and a nitrogen atom. In one embodiment, the precursor has a formula of Rʺ2N−SiRʹ2−L−NRʺ2, wherein L, Rʹ, and Rʺ can be any described herein.

[0359] The precursor can include a linker L disposed between two nitrogen atoms. In one embodiment, the precursor has a formula of Rʹ3Si−SiRʹ2−NRʺ−L−NRʺ−SiRʹ2−SiRʹ3, wherein L, Rʹ, and Rʺ can be any described herein.

[0360] The linker can include a silylimino group, such as, e.g., -N(SiRʹ3)-, in which Rʹ can be any described herein. In one embodiment, the precursor has a formula of Rʺ2N−[SiRʹ2−N(SiRʹ3)]z−SiRʹ3 or Rʺ2N−[N(SiRʹ3)]z−SiRʹ3, in which z is 1, 2, 3, or more; and wherein Rʹ and Rʺ can be any described herein.

[0361] The linker can include both a silyl group and an imino group. In one embodiment, the precursor has a formula of Rʺ2N−[SiRʹ2−NRʺ]z−SiRʹ3, in which z is 1, 2, 3, or more; and wherein Rʹ and Rʺ can be any described herein.

[0362] Non-limiting precursors include, e.g., di-iso-propylaminodisilane ([iPr2N]-SiH2-SiH3); di-sec-butylaminodisilane ([sBu2N]-SiH2-SiH3); methylcyclohexylaminodisilane ([MeCyN]- SiH2-SiH3); methylphenylaminodisilane ([MePhN]-SiH2-SiH3); piperidinodisilane; 3,5- dimethylpiperidinodisilane; di-iso-propylaminotrisilylamine ([iPr2N]-SiH2-N[SiH3]2); diethyl aminotrisilylamine ([Et2N]-SiH2-N[SiH3]2); iso-propylaminotrisilylamine ([iPrHN]-SiH2- N[SiH3]2); and the like. MIXED AMINES INCLUDING SILICON AND OXYGEN

[0363] A silicon-containing precursor can include one or more amino groups substituted with a silyl group, thereby providing a non-limiting mixed amine. In one embodiment, the precursor has a formula of (Rʺ)3-yN[Si(OR‴)xRʹ3-x]y, wherein: each of x and y is, independently, 1, 2, or 3; 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;Attorney Docket No. LAMRP993WO-11549-1WO 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; and each R‴ is, independently, H, aliphatic, heteroaliphatic, aromatic, heteroaromatic, silyl, or silyloxy, in which any of these may be optionally substituted.

[0364] Non-limiting examples of Rʹ, Rʺ, and R‴ are described herein, e.g., such as for amino silane, siloxane, silyl amine, or derivatives thereof.

[0365] The precursor can include any combination of Rʺ groups and silicon-containing groups. In one embodiment, the precursor has a formula of (Rʺ)3-yN[Si(ORAk)xRAk3-x]y or (RAk)3-yN [Si(ORAk)xRAk3-x]y, in which Rʺ, x, and y is any described herein; and wherein RAkis H, optionally substituted aliphatic, or optionally substituted heteroaliphatic. In particular embodiments, RAkis H, optionally substituted alkyl, optionally substituted alkylene, or optionally substituted alkynyl. In other embodiments, the precursor has a formula of (Rʺ)3-yN [Si(ORAk)xH3-x]y or (Rʺ)3-yN[Si(ORAk)H(RAk)]y, in which Rʺ, RAk, x, and y is any described herein.

[0366] The precursor can include two silicon-containing groups. In one embodiment, the precursor has a formula of (Rʺ)N[Si(ORAk)xRAk3-x]2 or (RAk)N[Si(ORAk)xRAk3-x]2, in which Rʺ, RAk, x, and y is any described herein. In particular embodiments, x is 1 or 2.

[0367] The precursor can include a hydrogen atom attached to the nitrogen atom. In one embodiment, the precursor has a formula of (H)3-yN[Si(ORAk)xRAk3-x]yor (H)3-yN[Si(ORAk)xH3-x]yor (H)3-yN[Si(ORAk)H(RAk)]y, in which RAk, x, and y is any described herein. In particular embodiments, x is 1 or 2.

[0368] Non-limiting precursors include, e.g., bis(dimethoxysilyl)amine (NH[Si(OMe)2H]2); bis(diethoxysilyl)amine (NH[Si(OEt)2H]2); N-iso-propylbis(diethoxysilyl)amine (NiPr[Si(OEt)2H]2); bis(methoxymethylsilyl)amine (NH[Si(OMe)MeH]2); tris(dimethoxysilyl) amine (N[Si(OMe)2H]3); tris(methoxymethylsilyl)amine (N[Si(OMe)MeH]3); tris(diethoxysilyl) amine (N[Si(OEt)2H]3); tris(trimethoxysilyl)amine (N[Si(OMe)3]3); and the like. CYCLIC SILAZANES

[0369] A silicon-containing precursor can include a cyclic group having one or more nitrogen atoms. In one embodiment, the precursor has a formula of [NRʺ−(SiRʹ2)n]z, wherein: z is 1, 2, 3, 4, 5, or more; n is 1, 2, or 3; 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,Attorney Docket No. LAMRP993WO-11549-1WO 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, amino, silyl, or silyloxy, 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.

[0370] In one embodiment, the precursor has a formula of [NRʺ−(SiRʹ2)n−L−(SiRʹ2)n]z, wherein: z is 1, 2, 3, 4, 5, or more; each n is, independently, 1, 2, or 3; each L is, independently, a linker, such as a covalent bond, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, optionally substituted heteroaromatic, oxy (-O-), imino, or silyl, as well as combinations thereof; 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, amino, silyl, or silyloxy, 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.

[0371] In another embodiment, the precursor has a formula of [NRʺ−L−NRʺ−(SiRʹ2)n]z, wherein: z is 1, 2, 3, 4, 5, or more; each n is, independently, 1, 2, or 3; and in which Rʹ and Rʺ can be any described herein.

[0372] In yet another embodiment, the precursor has a formula of [L−(SiRʹ2)n]z, wherein: z is 1, 2, 3, 4, 5, or more; each n is, independently, 1, 2, or 3; L is imino (e.g., -NR-), optionally substituted aliphatic, optionally substituted heteroaliphatic, or combinations thereof; and in which Rʹ can be any described herein. In particular embodiments, if L does not include a heteroatom, then Rʹ includes one or more heteroatoms (e.g., nitrogen atoms).

[0373] In one embodiment, the precursor has a , wherein Rʹ and Rʺ can be any described herein, and wherein n is 1, 2, 3, or 4.Attorney Docket No. LAMRP993WO-11549-1WO

[0374] In another embodiment, the precursor has a formula of , wherein Rʹ and Rʺcan be any described herein, and wherein n is 1, 2, 3, or 4.

[0375] In yet another embodiment, the precursor has a formula of , wherein Rʺ and R‴ can be any described herein, and wherein n is 1, 2, 3, or 4. In eachR‴ is, independently, H, aliphatic, heteroaliphatic, aromatic, or silyloxy, in which any of these may be optionally substituted.

[0376] In one embodiment, the precursor has a formula of , wherein Rʹ can includea heteroatom (e.g., a nitrogen atom, such as in optionally substituted amino, azido, isocyanato, or optionally substituted hydrazino), and wherein n is 1, 2, 3, or 4.

[0377] In some embodiments, 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, optionally substituted aromatic, optionally substituted arylene, optionally substituted heteroaromatic, optionally substituted heteroarylene, oxy (-O-), imino (e.g., -NR- or -N(SiR3)-), or silyl (e.g., -SiR2-), as well as combinations thereof (e.g., -SiR2-NR-, -NR-SiR2-, -SiR2-NR-SiR2-, 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.

[0378] In other embodiments, L is an optionally substituted alkylene, and at least one Rʹ includes an optionally substituted heteroaliphatic, optionally substituted amino, optionally substituted aliphatic-oxy, or optionally substituted alkoxy.

[0379] In some embodiments, each Rʹ is, independently, H, optionally substituted aliphatic, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted aromatic, or optionally substituted aryl. In other embodiments, each Rʹ is, independently, optionally substituted heteroaliphatic, optionally substituted amino, or optionally substituted alkoxy.

[0380] In other embodiments, each Rʺ is, independently, H, optionally substituted aliphatic, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted silyl, optionally substituted amino, optionally substituted aromatic,Attorney Docket No. LAMRP993WO-11549-1WO optionally substituted aryl, optionally substituted heteroaromatic, or optionally substituted heteroaryl.

[0381] Non-limiting precursors include 1,3,3-trimethylcyclodisilazane ([NH−SiMe2][NH−SiMeH]); hexamethylcyclotrisilazane ([NH−SiMe2]3); octamethylcyclotetrasilazane ([NH−SiMe2]4); and the like. CYCLIC SILOXANES

[0382] A silicon-containing precursor can include a cyclic group having one or more oxygen atoms. In one embodiment, the precursor has a formula of [L−(SiRʹ2)n]z, wherein: z is 1, 2, 3, 4, 5, or more; n is 1, 2, or 3; L is an oxygen-containing linker (e.g., oxy or heteroalkylene); and 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.

[0383] In one embodiment, the precursor has a formula of [O−Lʹ−O−(SiRʹ2)n]z, wherein: z is 1, 2, 3, 4, 5, or more; n is 1, 2, or 3; each Lʹ is, independently, a linker, such as optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, optionally substituted heteroaromatic, optionally substituted silyl (e.g., -SiR2-), optionally substituted alkylene (e.g., -(CH2)n-, in which n is 1 to 6), and optionally substituted arylene; and in which Rʹ is any described herein.

[0384] In another embodiment, the precursor has a formula of [O−(SiRʹ2)n−L−(SiRʹ2)n]z, wherein: z is 1, 2, 3, 4, 5, or more; each n is, independently, 1, 2, or 3; each L is, independently, a linker, such as a covalent bond, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, optionally substituted heteroaromatic, oxy (-O-), imino, or silyl, as well as combinations thereof; and in which Rʹ is any described herein.

[0385] In yet another embodiment, the precursor has a formula of [L−(SiRʹ2)n]z, wherein: z is 1, 2, 3, 4, 5, or more; each n is, independently, 1, 2, or 3; L is oxy (-O-), optionallyAttorney Docket No. LAMRP993WO-11549-1WO substituted aliphatic, optionally substituted heteroaliphatic, or combinations thereof; and in which Rʹ can be any described herein. In particular embodiments, if L does not include a heteroatom, then Rʹ includes one or more heteroatoms (e.g., oxygen atoms).

[0386] In one embodiment, the precursor has a formula of , wherein Rʹ can be any described herein, and wherein n is 1, 2, 3, or 4.

[0387] In another embodiment, the precursor has a formula of , wherein Rʹ and Rʺcan be any described herein, and wherein n is 1, 2, 3, or 4.

[0388] In yet another embodiment, the precursor has a formula , wherein R‴ can be any described herein, and wherein n is 1, 2, 3, or 4. Ineach R‴ is, independently, H, aliphatic, heteroaliphatic, aromatic, heteroaromatic, silyl, or silyloxy, in which any of these may be optionally substituted.

[0389] In one embodiment, the precursor has a formula of , wherein Rʹ can includea heteroatom (e.g., an oxygen atom, such as inaliphatic-oxy, aliphatic- oxycarbonyl, aliphatic-carbonyl, aliphatic-carbonyloxy, optionally substituted alkoxy, optionally substituted alkoxycarbonyl, optionally substituted alkanoyl, optionally substituted alkanoyloxy, and the like), and wherein n is 1, 2, 3, or 4.

[0390] In some embodiments, each Rʹ is, independently, H, optionally substituted aliphatic, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted aminoalkyl, optionally substituted aromatic, or optionally substituted aryl. In other embodiments, each Rʹ is, independently, optionally substituted heteroaliphatic, optionally substituted amino, or optionally substituted alkoxy.

[0391] Non-limiting precursors include, e.g., tetramethylcyclotetrasiloxane ([OSiHMe]4 or TMCTS); hexamethylcyclotetrasiloxane ([OSiMe2OSiHMe]2or HMCTS); octamethyl cyclotetrasiloxane ([OSiMe2]4, C8H24O4Si4, or OMCTS); decamethylcyclopentasiloxane ([OSiMe2]5or C10H30O5Si5); 2-dimethylamino-2,4,4,6,6-pentamethylcyclotrisiloxane ([OSiMe2]2[OSiMe(NMe2)]); 2-dimethylamino-2,4,4,6,6,8,8-heptamethylcyclotetrasiloxane ([OSiMe2]3[OSiMe(NMe2)]); and the like. AMINO SILOXANE AND DERIVATIVES THEREOF

[0392] A silicon-containing precursor can include siloxane or a derivative thereof and having one or more amino substitutions, thereby providing a siloxane or a derivative thereof having oneAttorney Docket No. LAMRP993WO-11549-1WO or more Si-O, O-Si-O, or Si-O-Si bonds and having one or more -NR2 substitutions. In one embodiment, the precursor has a formula of (Rʺ)3-yN[SiRʹ2−(OSiRʹ2)z−Rʹ]y, wherein: y is 1, 2, or 3; z is 1, 2, 3, or more; 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.

[0393] In another embodiment, the precursor has a formula of (Rʺ)3-yN [(SiRʹ2−O)z−SiRʹ3]y, wherein Rʹ, Rʺ, y, and z can be any described herein.

[0394] The precursor can include an optionally substituted amino group with an optionally substituted silyl group. In one embodiment, the precursor has a formula of Rʺ2N−SiRʹ2−(OSiRʹ2)z−Rʹ or Rʺ2N−SiRʹ2−O−SiRʹ3, wherein Rʹ, Rʺ, and z can be any described herein. In another embodiment, the precursor has a formula of Rʺ2N(SiRʹ2−O)z−SiRʹ3, wherein Rʹ, Rʺ, and z can be any described herein.

[0395] The precursor can include two optionally substituted amino group. In one embodiment, the precursor has a formula of Rʺ2N−SiRʹ2−(OSiRʹ2)z−NRʺ2, wherein Rʹ, Rʺ, and z can be any described herein.

[0396] In some embodiments, Rʹ is H, optionally substituted aliphatic, optionally substituted alkyl, optionally substituted alkenyl, or optionally substituted alkynyl. In other embodiments, Rʺ is H, optionally substituted aliphatic, optionally substituted alkyl, optionally substituted alkenyl, or optionally substituted alkynyl. In particular embodiments, z is 1, 2, or 3.

[0397] Non-limiting precursors can include, e.g., 1-dimethylamino-pentamethyldisiloxane (Me2N−SiMe2−OSiMe3); 1-diethylamino-pentamethyldisiloxane (Et2N−SiMe2−OSiMe3); 1- ethylmethylamino-pentamethyldisiloxane (EtMeN−SiMe2−OSiMe3); 1,3-bis(dimethylamino) tetramethyldisiloxane (Me2N−SiMe2−OSiMe2−NMe2); 1-dimethylamino-heptamethyltrisiloxane (Me2N−SiMe2−[OSiMe2]2−Me); 1,5-bis(dimethylamino) hexamethyltrisiloxane (Me2N−SiMe2−[OSiMe2]2−NMe2); and the like. SILANOLS, INCLUDING ALKYL SILANOLS OR ALKOXY SILANOLSAttorney Docket No. LAMRP993WO-11549-1WO

[0398] A silicon-containing precursor can include one or more hydroxyl groups, thereby providing a non-limiting silanol. In one embodiment, the precursor has a formula of (Rʹ)4-xSi(OH)x, wherein: x is 1, 2, 3, or 4; and 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.

[0399] In other embodiments, the precursor has a formula of (Rʹ)zSi(OH)x(OR‴)y, wherein: x is 1, 2, 3, or 4; each of y and z is, independently, 0, 1, 2, or 3; x + y + z = 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, amino, hydrazino, azido, hydroxyl, silyl, silyloxy, cyanato, isocyanato, cyano, or isocyano, in which any of these may be optionally substituted; and each R‴ is, independently, H, aliphatic, heteroaliphatic, aromatic, heteroaromatic, silyl, or silyloxy, in which any of these may be optionally substituted.

[0400] The precursor can have one hydroxyl group. In one embodiment, the precursor has a formula of (Rʹ)3Si(OH), in which each Rʹ can be any described herein. In another embodiment, the precursor has a formula of Si(OH)(OR‴)3, in which each R‴ can be any described herein. In particular embodiments, R‴ is optionally substituted alkyl (e.g., Me, Et, nPr, iPr, sBu, or tBu), in which the optionally substituted alkyl is linear, branched, substituted, or unsubstituted.

[0401] Non-limiting precursors include, e.g., tri(t-butoxy)silanol (SiOH[OtBu]3); tri(t- pentoxy)silanol (SiOH[OtPe]3); and the like. CARBONYLOXY SILANES

[0402] A silicon-containing precursor can include one or more optionally substituted aliphatic- carbonyloxy groups, thereby providing a non-limiting carbonyloxy silane. In one embodiment, the precursor has a formula of (Rʹ)4-xSi(OC(O)-R^)x, wherein: x is 1, 2, 3, or 4; each Rʹ is, independently, H, aliphatic, aliphatic-carbonyl, aliphatic-oxy, aliphatic-Attorney Docket No. LAMRP993WO-11549-1WO oxycarbonyl, heteroaliphatic, heteroaliphatic-carbonyl, heteroaliphatic-oxy, heteroaliphatic- oxycarbonyl, aromatic, aromatic-carbonyl, 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 R^ is, independently, H, aliphatic, heteroaliphatic, aromatic, heteroaromatic, amino, or aminooxy, in which any of these may be optionally substituted.

[0403] In another embodiment, the precursor has a formula of (R^-C(O)O)x(Rʹ)3-xSi−L−Si(Rʹ)3-x(OC(O)-R^)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-oxy, aliphatic- oxycarbonyl, heteroaliphatic, heteroaliphatic-carbonyl, heteroaliphatic-oxy, heteroaliphatic- oxycarbonyl, aromatic, aromatic-carbonyl, 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 R^ is, independently, H, aliphatic, heteroaliphatic, aromatic, heteroaromatic, amino, or aminooxy, in which any of these may be optionally substituted.

[0404] 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-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.

[0405] In some embodiments, R^ is H, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted alkoxy, optionally substitutedAttorney Docket No. LAMRP993WO-11549-1WO aryloxy, optionally substituted amino, or optionally substituted aminooxy.

[0406] Non-limiting precursors include those having a formula of (Rʹ)2Si(OC(O)-R^)2, wherein Rʹ and R^ can be any described herein. CONCLUSION

[0407] 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.

Claims

Attorney Docket No. LAMRP993WO-11549-1WO CLAIMS What is claimed is:

1. A method for processing substrates, the method comprising: providing a substrate; exposing the substrate to a silicon-containing precursor comprising an oxygen atom in a plasma-free environment, thereby forming a layer of the silicon-containing precursor on a surface of the substrate; and exposing the layer of the silicon-containing precursor to an oxygen-free plasma, wherein exposing the layer of the silicon-containing precursor to the oxygen-free plasma converts the layer of the silicon-containing precursor to a silicon-containing material.

2. The method of claim 1, wherein the substrate comprises a first exposed surface comprising dielectric material and a second exposed surface comprising a metal- containing material.

3. The method of claim 2, wherein the layer of the silicon-containing precursor forms selectively on the first exposed surface relative to the second exposed surface.

4. The method of claim 1, wherein the silicon-containing precursor has a silicon to oxygen ratio of 1:

2.

5. The method of claim 1, wherein the silicon-containing precursor comprises at least one Si-O bond.

6. The method of claim 1, wherein the silicon-containing precursor comprises a halogen substituent.

7. The method of claim 1, wherein the silicon-containing precursor comprises an amino substituent.

8. The method of claim 1, wherein the oxygen-free plasma is generated by igniting a hydrogen gas.

9. The method of claim 1, wherein the oxygen-free plasma is generated by igniting a helium gas.

10. The method of claim 1, wherein the oxygen-free plasma is generated by igniting a gasAttorney Docket No. LAMRP993WO-11549-1WO mixture comprising helium and hydrogen.

11. The method of claim 1, wherein the silicon-containing precursor is delivered at a vapor pressure of about 0.1 Torr to about 15 Torr.

12. The method of any of claims 1-11, wherein the silicon-containing material comprises silicon oxide.

13. The method of any of claims 1-3 or 5-11, wherein the silicon-containing material comprises silicon oxycarbide.

14. The method of claim 13, wherein the silicon-containing precursor has a Si-O bond to Si- C bond ratio of about 3:1 to 1:

3.

15. The method of any of claims 1-3 or 5-11, wherein the silicon-containing material comprises silicon oxynitride.

16. The method of claim 1, wherein the silicon-containing precursor has a Si-O bond to Si-N bond ratio of about 3:1 to 1:

3.

17. The method of any of claims 1-11, wherein the oxygen-free plasma is generated remotely.

18. The method of any of claims 1-11, wherein the oxygen-free plasma is generated in situ.

19. The method of any of claims 1-11, wherein the substrate is heated to a temperature of about 25°C to about 400°C.

20. A method for processing substrates, the method comprising: providing a substrate; exposing the substrate to a silicon-containing precursor comprising a carbon atom and a nitrogen atom in a plasma-free environment, thereby forming a layer of the silicon- containing precursor on a surface of the substrate; and exposing the layer of the silicon-containing precursor to an oxygen-free plasma, wherein exposing the layer of the silicon-containing precursor to the oxygen-free plasma converts the layer of the silicon-containing precursor to a silicon-containing material.

21. The method of claim 20, wherein the silicon-containing material comprises silicon carbonitride.Attorney Docket No. LAMRP993WO-11549-1WO 22. An apparatus for processing substrates, the apparatus comprising: one or more process chambers, each process chamber comprising 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, wherein 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 silicon-containing precursor having an oxygen atom to the one or more process chambers, and cause generation of a plasma using an oxygen-free gas to convert the silicon-containing precursor to silicon oxide on a substrate held by the chuck.

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