Passivation during silicon etch

Abstract

Methods and apparatuses for etching silicon and / or germanium material relative to a contrast material using an etching plasma generated from an etching gas mixture and an additive are provided herein. Methods include etching polysilicon relative to oxide material using an etching plasma generated from an etching gas mixture and a silicon halide gas as an additive.

Description

Attorney Docket No. LAM1P062WO-11987-1WO PASSIVATION DURING SILICON ETCH 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 their entireties and for all purposes. BACKGROUND

[0001] Fabrication of semiconductors involves many kinds of processing. One type of processing involves depositing materials on the surface of a substrate. Another type of processing involves etching materials from the surface of the substrate.

[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 having a polysilicon material over a contrast material; generating a plasma using a gas mixture to a process chamber housing the substrate, the gas mixture including a halogen- containing gas, a carbon-containing gas, and one or more additives; and exposing the substrate to the plasma to selectively etch the polysilicon material relative to the contrast material, whereby the one or more additives includes a silicon-containing gas.

[0004] In various embodiments, the silicon-containing gas includes silicon tetrafluoride. In some embodiments, the silicon-containing gas is silicon tetrafluoride.

[0005] In various embodiments, the silicon-containing gas includes a silane. In some embodiments, the silicon-containing gas is a silane.

[0006] In various embodiments, the halogen-containing gas includes nitrogen trifluoride. In some embodiments, the halogen-containing gas is nitrogen trifluoride. In various embodiments, the halogen-containing gas comprises carbon tetrafluoride. In various embodiments, the halogen- containing gas is nitrogen-free.

[0007] In various embodiments, the carbon-containing gas includes methane. In some embodiments, the carbon-containing gas is methane.

[0008] In various embodiments, the gas mixture further includes hydrogen gas.

[0009] In various embodiments, the gas mixture further includes a dilution gas.

[0010] In various embodiments, the plasma is pulsed.Attorney Docket No. LAM1P062WO-11987-1WO

[0011] In various embodiments, the method also includes biasing the substrate during exposure of the substrate to the plasma.

[0012] In various embodiments, the silicon-containing gas is flowed at a flow rate of about 1 sccm to about 150 sccm.

[0013] In various embodiments, the substrate further includes a patterned SiGe material underlying the contrast material.

[0014] In various embodiments, the contrast material is a dielectric material.

[0015] In various embodiments, the contrast material is selected from the group consisting of oxygen-containing material, nitrogen-containing material, and carbon-containing material. For example, in some embodiments, the contrast material is silicon oxide.

[0016] In various embodiments, the plasma is generated remotely.

[0017] In various embodiments, the substrate is exposed to the plasma for at least 120 seconds.

[0018] In various embodiments, the substrate is exposed to the plasma for a duration sufficient to etch at least about 1000Å of polysilicon.

[0019] Another aspect involves a method for processing substrates, the method including: providing a substrate having a germanium material over a contrast material; generating a plasma using a gas mixture to a process chamber housing the substrate, the gas mixture including a halogen-containing gas, a carbon-containing gas, and one or more additives; and exposing the substrate to the plasma to selectively etch the germanium material relative to the contrast material, whereby the one or more additives includes a germanium-containing gas.

[0020] 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; a plasma generator; and a controller having at least one processor and a memory, whereby the at least one processor and the memory are communicatively connected with one another, the at least one processor is at least operatively connected with the flow-control hardware, and the memory stores computer- executable instructions for controlling the at least one processor to at least control the flow-control hardware to: cause generation of a plasma in the plasma generator using a gas mixture to a process chamber housing the substrate, the gas mixture including a halogen-containing gas, a carbon- containing gas, and a silicon-containing additive gas; and cause delivery of the plasma to the one or more process chambers to etch a substrate in the one or more process chambers using the plasma.

[0021] These and other aspects are described further below with reference to the drawings. BRIEF DESCRIPTION OF THE DRAWINGS

[0022] Figure 1 a flow chart describing a method of etching a semiconductor substrate inAttorney Docket No. LAM1P062WO-11987-1WO accordance with certain disclosed embodiments.

[0023] Figures 2A, 2B, and 3 are schematic illustrations of an example of a substrate undergoing operations that may be performed in accordance with certain disclosed embodiments.

[0024] Figure 4 depicts a cross-sectional side view of an example apparatus in accordance with disclosed embodiments.

[0025] Figure 5 depicts a cross-sectional side view of an example apparatus in accordance with disclosed embodiments. DETAILED DESCRIPTION

[0026] 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.

[0027] Semiconductor fabrication processes can sometimes involve etching a silicon-containing material, such as removing of dummy silicon material in a replacement gate process. For example, a partially fabricated semiconductor substrate may include an epitaxially-deposited a fin-shaped silicon-containing material or structure; such as an epitaxially deposited silicon fin, or an epitaxially deposited silicon-germanium fin, or an epitaxially deposited silicon and silicon- germanium fin. In some embodiments, the structure is not fin-shaped. In some embodiments, the structure is a positive feature. The positive feature may have particular chemical composition. In some cases, the feature includes an epitaxially-deposited material such as silicon (Si), or silicon germanium (SiGe), or a stack thereof, or a stack comprising layers of such materials in alternating layers thereof. The epitaxially deposited material may be crystalline.

[0028] A contrast material may be formed over the epitaxially-deposited material. The contrast material may be formed to act as a buffer over the epitaxially-deposited material. Some examples of contrast material include but are not limited to dielectric materials, such as oxygen-containing material, nitrogen-containing material, carbon-containing material, oxides, nitrides, oxycarbides, oxynitrides, oxycarbonitrides, carbonitrides, and combinations thereof. Examples include oxides (e.g., silicon oxide, tin oxide, etc.), nitrides (e.g., silicon nitride, tantalum nitride, titanium nitride, etc.), carbides (e.g., silicon carbide, etc.), carbonitrides (e.g., silicon carbonitride, etc.), carboxides (e.g., silicon carboxide, etc.), etc. In some cases, the contrast material may be a dielectric material such as a high-k dielectric material or a low-k dielectric material. Generally, high-k dielectric materials are dielectric materials that have a high dielectric constant relative to silicon dioxide, and low-k dielectric materials are dielectric materials that have a low dielectric constant relative toAttorney Docket No. LAM1P062WO-11987-1WO silicon oxide. Silicon oxide has a dielectric constant of about 3.7-3.9. As such, high-k dielectric materials typically have a dielectric constant greater than about 3.9, while low-k dielectric materials typically have a dielectric constant lower than about 3.7. Examples of low-k dielectric materials include carbon-doped silicon oxides, fluorine-doped silicon oxides, as well as spin-on organic polymeric dielectric materials such as polyimides, polynorbenes, and benzocyclobutenes. Examples of high-k dielectric materials include hafnium silicate, zirconium silicate, hafnium dioxide, and zirconium dioxide.

[0029] The contrast material may be referred to as a contrast material because it helps protect the underlying material on the fin-shaped material from being etched, since the fin-shaped material may have similar chemical composition as the polysilicon material. A polysilicon material may be over the contrast material, filling spaces between the fins. The polysilicon material may be sacrificial material or may be referred to as a “dummy” material. The polysilicon material may be amorphous. The polysilicon material may be non-crystalline. While polysilicon is described herein, it will be understood that other amorphous materials may be used, and other amorphous silicon-containing materials may be used for the polysilicon.

[0030] The materials exposed on the substrate may be selected in various combinations and provided in various structures, as desired for a particular application. The techniques described herein are widely applicable to many different applications.

[0031] It may be desirable to selectively remove the polysilicon material from the substrate without substantially etching the contrast material, and without etching the epitaxially-deposited fin-shaped material. Because the contrast material may be “soft” material or be susceptible to etching, etching the polysilicon material may be done in such way so as to prevent the contrast material from being etched too quickly, as once it is etched the epitaxially-deposited fin-shaped material is likely to be etched as well, resulting in a “pitting” effect where sections of the fin- shaped material are removed, resulting in defects, nonuniform etching, and unusable structures on the wafer.

[0032] Provided herein are methods and apparatuses for etching polysilicon material selectively relative to the contrast material without substantially etching the contrast material and without substantially etching the epitaxially-deposited fin material. A first material being etched “selectively” to a second material as used herein means the first material etches at a rate faster than the second material. In some cases, “selectively etching” the first material etches the first material much faster than the second material such that the etch rate of the second material is small, negligible, or zero. Certain disclosed embodiments have the capability of extending the etch contrast to numerous times greater than currently achievable using certain etch chemistries. Certain disclosed embodiments have various applications, such as, but not limited to, 3D-NAND,Attorney Docket No. LAM1P062WO-11987-1WO 3D DRAM, advancing packaging, gate all around, CFET, and others.

[0033] Certain disclosed embodiments involve using an additive when using plasma etching to etch the polysilicon material. The additive may be selected based on the etchants used as well as the material being etched. The additive may include a halogen-containing gas. The additive may include a silicon-containing gas. The additive may be silicon-containing and halogen-containing. The additive may be a halide. The additive may be a silicon halide. The additive may assist in passivating surfaces of the substrate, including surfaces of the contrast material, during etching of the polysilicon to prevent the contrast material from being etched. The additive may form a volatile material during etching. The additive may form a salt during etching.

[0034] Figure 1 shows a process flow diagram depicting operations that may be performed in accordance with certain disclosed embodiments. Operation 190 involves providing a substrate in a reaction chamber. The reaction chamber may be set to a chamber pressure of about 200 mTorr to about 5 Torr, or about 500 mTorr to about 1500 mTorr in various embodiments. In some embodiments, the chamber pressure is the same throughout the operations performed in Figure 1. In some embodiments, the chamber pressure may be varied.

[0035] The substrate includes one or more materials thereon that are to be removed. The substrate may include a fin-shaped structure or feature, which may be made of epitaxially- deposited material, or may be a crystalline material. In some embodiments, the feature may be silicon. In some embodiments, the feature may be crystalline silicon. In some embodiments, the feature may be silicon-germanium. In some embodiments, the feature may be crystalline silicon- germanium. In some embodiments, the feature includes both silicon and silicon-germanium. In some embodiments, the feature includes epitaxially deposited Si / SiGe.

[0036] There may be a contrast material over the feature. The contrast material may be a dielectric material. The dielectric material may be an oxide, nitride, or any of the dielectric materials described above.

[0037] Over the dielectric material, there may be a dummy or sacrificial layer made of silicon- containing materials. Examples include amorphous silicon, such as polysilicon. The dummy or sacrificial layer may be non-crystalline. The dummy or sacrificial layer may be amorphous.

[0038] During operation 192, the substrate is exposed to an etching plasma in the reaction chamber. The etching plasma may be generated by igniting a gas mixture including a halogen- containing etching gas, one or more additional gases, and a passivation gas.

[0039] The halogen-containing etching gas may be a fluorine-containing gas. The halogen- containing etching gas is nitrogen-free. The halogen-containing etching gas may include nitrogen trifluoride. The halogen-containing gas may be CF4, F2, ClF3, PF3, or PF5. The halogen-containing gas may be chlorine-containing. The halogen-containing etching gas may be flowed at a particularAttorney Docket No. LAM1P062WO-11987-1WO flow rate, such as about 10 sccm to about 1000 sccm, or about 20 sccm to about 80 sccm, or about 20 sccm to about 50 sccm.

[0040] The one or more additional gases may include hydrogen gas. Hydrogen may be flowed at a flow rate of about 5 sccm to about 5000 sccm, or about 200 sccm to about 700 sccm.

[0041] The passivation gas may be a carbon-containing gas. The passivation gas may be methane. The passivation gas may be flowed at a flow rate of about 1 sccm to about 250 sccm, or about 50 sccm to about 200 sccm.

[0042] An inert gas may optionally be flowed with the gas mixture. Example inert gases include but are not limited to He, Ar, Ne, Xe, and combinations thereof. The inert gas may be used as a carrier gas. The inert gas may be used as a dilution gas. The inert gas may be flowed at a flow rate of 0 sccm (no inert gas) to about 5000 sccm, or about 1000 sccm to about 3000 sccm.

[0043] The etching plasma may be generated to perform what is referred to herein as a “main etch” which may refer to bulk etching of most of the polysilicon material. Without being bound by a particular theory, it is believed that the passivation gas passivates surfaces of the substrate during etching to control or modulate the etching so that the etching of the polysilicon does not penetrate that of the dielectric contrast material. During “main etch,” the polysilicon can be etched. As the remaining amount of polysilicon is reduced and the surface of the polysilicon approaches the surface of the contrast material, it may become critical to control the etching so as to not etch the contrast material.

[0044] Without being bound by a particular theory, it is believed that during etching using this gas mixture, Si is being etched and SiF4 is produced from reacting polysilicon with NF3. SiF4 can combine with NH3and HF to form (NH4)2SiF6which can be removed from the gas phase without deposition onto the film surface. The CH4 passivates the oxide surface thereby forming CN and CHxwhich are volatile. However, as etching continues and the contrast material is exposed to the etching chemistry, there is less polysilicon remaining on the substrate and thus SiF4 is not generated, so HF and NH3continuously etch and can overcome the CH4passivation effect and reduce the thickness of a C-containing passivation layer on the oxide, thereby reducing the passivation effect and causing undesirable etch of the contrast material which then causes pitting.

[0045] The plasma in operation 192 may be generated using a remote plasma or an in-situ plasma. The plasma may be an inductively coupled plasma. The plasma may be a transformer coupled plasma. The plasma may be a capacitively coupled plasma. The plasma may be generated using a single frequency plasma. The plasma may be generated using a dual frequency plasma. The plasma may be generated using a power of about 200 W to about 300 W, or about 700 W to about 900 W. The plasma may be generated at a particular frequency. The frequency may be about 500 Hz to about 1500 Hz, or about 1000 Hz.Attorney Docket No. LAM1P062WO-11987-1WO

[0046] The plasma may be pulsed in some embodiments. Pulsing may be performed using a particular duty cycle. It will be understood that plasma pulsing may involve repetitions of periods, each of which may last a duration T. The duration T includes the duration for pulse ON time (the duration for which the plasma is in an ON state) and the duration for plasma OFF time (the duration from which the plasma is in an OFF state) during a given period. The pulse frequency will be understood as 1 / T. For example, for a plasma pulsing period T = 100 µs, frequency is 1 / T = 1 / 100µs, or 10 kHz. The duty cycle or duty ratio is the fraction or percentage in a period T during which the plasma is in the ON state such that duty cycle or duty ratio is pulse ON time divided by T. For example, for a plasma pulsing period T = 100 µs, if a pulse ON time is 70 µs (such that the duration for which the plasma is in an ON state in a period is 70 µs) and a pulse OFF time is 30 µs (such that the duration for which the plasma is in an OFF state in a period is 30 µs), the duty cycle is 70%. In various embodiments, the plasma is pulsed using a duty cycle of about 30% to about 70%, or about 50%.

[0047] Exposure to the plasma may be performed for any suitable duration, such as about 10 seconds to about 500 seconds, or about 50 seconds to about 200 seconds.

[0048] The substrate may be biased during etching. The substrate may be processed in a chamber where the substrate is placed on an electrostatic chuck, such that the electrostatic chuck may also bias the substrate. The bias may be applied to the substrate using a particular bias voltage, which may be measured in Vb units. It will be understood that the unit “Vb” or “Vb” or “Vbias” is a unit of volts, and “b” or “bias” is used to characterize that the power is for the bias power. As such, the bias power during etching may be set at less than about 100 Vb, or less than about 80 Vb, or about 50 Vbto 80 Vb.

[0049] In operation 193, an additive is introduced which assists in etching one or more materials on the substrate. The additive may be introduced with the plasma. The additive may be introduced to the remote plasma generator with the other gases in operation 192 to generate plasma species that are delivered to the process chamber. The additive may be a non-vapor. The additive may, in some embodiments, not be injected downstream of the plasma generator. The additive may be delivered via a mass flow controller. The additive may be introduced together with the gas mixture used to generate the etching plasma such that there may be at least some overlap between introduction of a plasma generated from igniting the additive source to the reaction chamber and introduction of the etching plasma into the reaction chamber. The plasma conditions used to generate the plasma in operation 192 may be the same plasma conditions as in operation 193.

[0050] The additive may have a flow rate of greater than 0 sccm up to about 5000 sccm, or about 1 sccm to about 1000 sccm or about 1 sccm to about 500 sccm or about 1 sccm to about 100 sccm, or about 1 sccm to about 20 sccm.Attorney Docket No. LAM1P062WO-11987-1WO

[0051] In various embodiments, the additive is a silicon-containing gas. In various embodiments, the additive is a halogen-containing gas. In various embodiments, the additive is SiF4, or SiCl4, or SiH4.

[0052] In some embodiments, SiF4is added to the reaction mixture during etching to remove NH3 and HF from gas phase and prevent oxide damage from NH4F deposition.

[0053] In some embodiments, instead of adding an additive source, nitrogen is removed from the reaction mixture so there is no NH3formation in the plasma. In some embodiments, the halogen-containing gas used in the etching gas is nitrogen-free. Without being bound by a particular theory, it is believed that without NH3, there is no deposited NH4F or (NH4)2SiF6layer to attack dielectric film and thus prevent pitting defects from forming. Possible sources of F source without N include CF4, F2, ClF3, PF3, PF5, etc.

[0054] Figures 2A, 2B, and 3 show example schematic illustrations of substrates undergoing various disclosed embodiments. Figure 2A shows a fin-shaped structure 201 (such as a Si or SiGe material), a contrast material 203 (such as oxide) over the fin-shaped structure 201, and polysilicon material 205. As the main etch is performed (such as operation 192 of Figure 1), Figure 2B shows passivation layer 207 (such as CH4 or CHx is formed) over the substrate as the polysilicon is etched. When the etching is performed with an additive, etching does not damage the oxide, resulting in Figure 3, which shows an un-damaged oxide 301 with the fin-shaped structure 303 underlying it, without any pitting effect.

[0055] Certain disclosed embodiments may be used to etch polysilicon relative to contrast material such as dielectric material. In some embodiments, methods herein may be used to etch polysilicon relative to silicon-germanium material. Certain disclosed embodiments are capable of extending the etch selectivity such that much more polysilicon material may be etched without etching the contrast material as compared to etch processes that do not include the additive. For example, without the additive, after about 1350 Å of polysilicon is etched, continued etching without the additive results in pitting effects. In contrast, when the additive is added, little pitting appears on the substrate even after etching about 5000Å of polysilicon, which suggests certain disclosed embodiments may extend over five times that of existing etching techniques.

[0056] Certain disclosed embodiments may be suitable for etching many other types of material. The additive may be selected depending on the main etch chemistry and the material being etched. For example, if the material being etched is germanium and not polysilicon, and the etch chemistry is a halogen-containing chemistry, the additive used during etching of germanium may be a germanium halide gas. The additive may be selected as long as it is capable of passivation through the uptake or transformation of active etch species. Example active etch species may include NH3 and HF. The additive may be used as a transforming agent to enable passivation, or may be usedAttorney Docket No. LAM1P062WO-11987-1WO to extend the process window for existing passivation approaches during etching of polysilicon material. APPARATUS

[0057] Figure 4 is an example of a substrate processing chamber 400 shown for selectively etching polysilicon on a substrate. The substrate processing chamber 400 includes a lower chamber region 402 and an upper chamber region 404. The lower chamber region 402 is defined by chamber sidewall surfaces 408, a chamber bottom surface 410 and a lower surface of a gas distribution device 414. The upper chamber region 104 is defined by an upper surface of the gas distribution device 414 and an inner surface of a dome 418. In some examples, the dome 418 is spherical, although a cylindrical upper chamber region with a flat top and flat inductive coil(s) can also be used.

[0058] A substrate support 422 is arranged in the lower chamber region 404. In some examples, the substrate support 422 includes an electrostatic chuck (ESC), although other types of substrate supports can be used. A substrate 426 is arranged on an upper surface of the substrate support 422 during the etching process. In some examples, a temperature of the substrate 426 may be controlled by a heater plate 425, an optional cooling plate with flow channels (not shown) and / or one or more sensors 427, although any other suitable substrate heaters may be used.

[0059] In some examples, the gas distribution device 414 includes a showerhead (for example, a plate 428 having a plurality of spaced holes 429). The plurality of spaced holes 429 extend from the upper surface of the plate 428 to the lower surface of the plate 428. In some examples, the plurality of holes has a diameter from 0.1” to 0.75”, although other sizes may be used. In some examples, the plate 428 is made of a conducting material such as aluminum. In other examples, the plate 428 is made of a non-conducting material such as ceramic and includes an embedded electrode.

[0060] In some examples, radially outer ends of the gas distribution device 414 may extend upwardly and may define a gas flow channel 434. The gas flow channel 434 is in fluid communication with a plurality of holes 436 for directing gas from the gas flow channel 434 into the upper chamber region 404. In some examples, the plurality of holes 436 direct gas flow from the gas flow channel 434 at an acute radially-inward angle relative to the upper surface of the plate 428 as shown by reference number 438.

[0061] An inductive coil 440 is arranged around an outer portion of the dome 418. When energized, the inductive coil 440 creates an electromagnetic field inside of the dome 418. A gas diffuser 442 disburses feed gas or a feed gas mixture from a gas delivery system 450-1. In some examples, the gases may be directed into the upper chamber region using the diffuser 442 and / or the plurality of holes 436.Attorney Docket No. LAM1P062WO-11987-1WO

[0062] In some examples, the gas delivery system 450-1 includes one or more gas sources 452, one or more valves 454, one or more mass flow controllers (MFCs) 456, and a mixing manifold 458, although other types of gas delivery systems may be used. Another gas delivery system 450- 2 may be used to supply a feed gas or a feed gas mixture to the gas flow channel 434 (in addition to or instead of feed gas from the gas diffuser 442). Gases such as the etching gases, passivation gases, additional gases, and additive gases may be delivered using one or more MFCs 456.

[0063] A plasma generator 470 may be used to generate RF power that is output to the inductive coil 440. Plasma is generated in the upper chamber region 404. In some examples, the plasma generator 470 includes an RF source 472 and a matching network 474. The matching network 474 matches an impedance of the RF source 472 to the impedance of the inductive coil 440. In some examples, the gas distribution device 414 is grounded. A valve 478 and a pump 480 may be used to control pressure inside of the lower and upper chamber regions 402, 404 and to evacuate reactants from the lower and upper chamber regions 402, 404, respectively.

[0064] A controller 476 communicates with the gas delivery systems 450-1 and 450-2, the valve 478, the pump 480, the heater plate 425, and / or the plasma generator 470 to control flow of process gas, purge gas, RF plasma and chamber pressure. In some implementations, a controller 476 is part of a system, which may be part of the above-described examples. Such systems can comprise 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 controller 476, depending on the processing requirements and / or the type of system, may be programmed to control any of the processes disclosed herein, including the delivery of processing gases, temperature settings (e.g., heating and / or cooling), pressure settings, vacuum settings, power settings, radio frequency (RF) generator settings, RF matching circuit settings, frequency settings, flow rate settings, fluid delivery settings, positional and operation settings, wafer transfers into and out of a tool and other transfer tools and / or load locks connected to or interfaced with a specific system.

[0065] Broadly speaking, the controller 476 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.,Attorney Docket No. LAM1P062WO-11987-1WO software). Program instructions may be instructions communicated to the controller 476 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.

[0066] The controller 476, 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 controller 476 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 controller 476 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 controller 476 is configured to interface with or control. Thus as described above, the controller 476 may be distributed, such as by comprising one or more discrete controllers that are networked together and working towards a common purpose, such as the processes and controls described herein. An example of a distributed controller for such purposes would be one or more integrated circuits on a chamber in communication with one or more integrated circuits located remotely (such as at the platform level or as part of a remote computer) that combine to control a process on the chamber.

[0067] 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 chemical vapor deposition (CVD) chamber or module, an atomic layer deposition (ALD) chamber or module, an atomic layer etch (ALE) chamber or module, an ion implantation chamber or module, a track chamber or module, and any other semiconductor processing systems that may be associated or used in the fabrication and / or manufacturing of semiconductor wafers.Attorney Docket No. LAM1P062WO-11987-1WO

[0068] As noted above, depending on the process step or steps to be performed by the tool, the controller 476 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.

[0069] Plasma zones 490 are created in the upper chamber region 404. References numbers 490, 492 and 494 illustrate flow of process gases from the gas diffuser 442.

[0070] In some examples, plasma is sustained inside the dome 418 by the inductive coil, which is located on an atmospheric side of the dome 418. Feed gas is introduced from the top of the chamber using the gas diffuser 442 and / or the holes 436 and plasma is confined within the dome 418 using the gas distribution device 414, which is grounded. Cold plasma diffuses through the gas distribution device 414 and reacts with the substrate 426 located in the lower chamber region 402.

[0071] Confining the plasma in the dome 418 allows volume recombination of plasma species and effusing desired etchant species through the gas distribution device 414. In some examples, there is no bias applied to the substrate 426. As a result, there is no active sheath on the substrate 426 and ions are not hitting the substrate with any finite energy. Some amount of the ions will diffuse out of the plasma region through the gas distribution device 414. However, the amount of plasma that diffuses is an order of magnitude lower than the plasma located inside the dome 418. Most of the ions in the plasma are lost by volume recombination at high pressures. Surface recombination loss at the upper surface of the gas distribution device 414 also lowers ion density below the gas distribution device 414.

[0072] In other examples, an RF bias is supplied to the substrate support. An RF bias generator 484 selectively provides an RF bias to the substrate support. A matching network (not shown) may be used between the RF bias generator 484 and the substrate support.

[0073] The RF power applied to the inductive coil and the RF bias may have the same or different frequencies or power levels. In some examples, both the RF power applied to the inductive coil and the RF bias are at 43.56MHz, although other frequencies may be used. For example only, the RF bias may be supplied at a frequency such as 2MHz, 27MHz or another frequency while the RF applied to the inductive coil is supplied at a frequency of 43.56MHz. In some examples, the RF power applied to the inductive coil may be in a range from 2kW to 5kW. In other examples, the RF power applied to the inductive coil may be in a range from 2kW to 2.5kW. In some examples, the RF bias power may be supplied at a range from 200W to 4kW, although other power levels may be used.Attorney Docket No. LAM1P062WO-11987-1WO

[0074] Figure 5 shows a schematic illustration of an example plasma processing apparatus that generates plasma comprising high-energy ions and radicals according to some other implementations. The plasma processing apparatus 500 includes a remote plasma source 550 and a processing chamber 525 separate from the remote plasma source 550. The remote plasma source 550 is configured to generate a remote plasma 560. The remote plasma 560 may be an inductively- coupled plasma comprising high-energy ions and radicals. The high-energy ions and radicals of the remote plasma 560 may be introduced through a showerhead 554. A substrate 520 may be supported on a substrate support 510.

[0075] Process gases 502 may be supplied to the remote plasma source 550 via a gas distributor 552. One or more valves may control introduction of the process gases 502 into the remote plasma source 550. The remote plasma source 550 may be a container of any suitable shape, such as dome-shaped, conical-shaped, or cylindrical-shaped. Coils 556 may surround at least a portion of the container of the remote plasma source 550. The coils 556 may be in electrical communication with an RF power source for generating the remote plasma 560 in the remote plasma source 550. The remote plasma 560 may be ignited by energizing the coils 556 to form activated species 504, which may include high-energy ions and radicals. The activated species 504 pass through the showerhead 554 towards the substrate 520. The activated species 504 of the remote plasma 560 may be used to etch one or more materials from the substrate 520, treat the substrate 520, deposit a film on the substrate 520, or clean internal surfaces of the processing chamber 525.

[0076] In some implementations, an in situ plasma 530 may be generated between the showerhead 554 and the substrate support 510, where the in situ plasma may be a capacitively- coupled plasma. A gas or gas mixture 506 may be introduced into the processing chamber 525. An electric field may be generated between the showerhead 554 and the substrate support 510, and ionization of the gas or gas mixture 506 may ignite the in situ plasma 530 to form activated species including high-energy ions and radicals. In some implementations, the in situ plasma 530 may be used to etch one or more materials from the substrate 520, treat the substrate 520, deposit a film on the substrate 520, or clean internal surface of the processing chamber 525.

[0077] The plasma processing apparatus 500 may further include a controller 540. The controller 540 may be programmed to control various processes performed by the plasma processing apparatus 500, including delivery of gases, temperature settings, pressure settings, vacuum settings, power settings, RF generator settings, RF matching circuit settings, frequency settings, flow rate settings, fluid delivery settings, positional and operation settings, substrate transfers in and out of a tool and / or load locks, etc. EXPERIMENTAL

[0078] An experiment was conducted on various substrates using the following conditions andAttorney Docket No. LAM1P062WO-11987-1WO yielded the following results: Table 1. Conditions and Results Substrate # Conditions Amount of Si etched Additive? Observation g g g g ingo . DEFINITIONS AND PRECURSORS DEFINITIONS

[0080] 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.

[0081] By “alkanoyloxy” is meant an alkanoyl group, as defined herein, attached to the parent molecular group through an oxy group, as defined herein. This group is exemplified by acetoxy (-OAc or -OC(O)Me). In some embodiments, the alkanoyloxy group is -OC(O)-R, in which R is hydrogen, an aliphatic group, or an aromatic group, as defined herein.

[0082] 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 functionalAttorney Docket No. LAM1P062WO-11987-1WO group described herein. For example, the aliphatic group can be substituted with one or more substitution groups, as described herein for alkyl.

[0083] 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.

[0084] 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.

[0085] 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.

[0086] 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.

[0087] 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., C2-6 alkenyl-C4-18 aryl). Exemplary unsubstituted alkynyl-aryl groups are of from 7 to 16 carbons (C7-16alkynyl-aryl), as well as those having an alkynyl group with 2 to 6 carbons and an aryl group with 4 to 18 carbons (i.e., C2-6 alkynyl-C4-18aryl). 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-Attorney Docket No. LAM1P062WO-11987-1WO 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.

[0088] 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.

[0089] 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.

[0090] 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 (C2-12alkoxyalkyl), as well as those having an alkyl group with 1 to 6 carbons and an alkoxy group with 1 to 6 carbons (i.e., C1-6 alkoxy-C1-6 alkyl). In some embodiments, the alkoxyalkyl group is -L-O-R, in which each of L and R is, independently, an alkyl group, as defined herein.

[0091] By “alkoxycarbonyl” is meant -C(O)-OR, where R is an optionally substituted aliphatic group, as described herein. In particular embodiments, the alkoxycarbonyl group is -C(O)-OAk, in which Ak is an alkyl group, as defined herein. The alkoxycarbonyl group can be substituted or unsubstituted. For example, the alkoxycarbonyl group can be substituted with one or more substitution groups, as described herein for alkyl. Exemplary unsubstituted alkoxycarbonyl groups include C2-3, C2-6, C2-7, C2-12, C2-16, C2-18, C2-20, or C2-24alkoxycarbonyl groups.

[0092] 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-Attorney Docket No. LAM1P062WO-11987-1WO 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) C1-6alkoxy (e.g., -O-R, in which R is C1-6alkyl); (2) C1-6 alkylsulfinyl (e.g., -S(O)-R, in which R is C1-6 alkyl); (3) C1-6 alkylsulfonyl (e.g., -SO2-R, in which R is C1-6alkyl); (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) C1-6 thioalkyl (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) C1-6alkyl, (c) C4-18 aryl, and (d) C4-18 aryl-C1-6 alkyl (e.g., -L-R, in which L is C1-6 alkyl and R is C4-18 aryl); (23) -C(O)NR1R2, where each of 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); (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)Attorney Docket No. LAM1P062WO-11987-1WO C1-6 alkyl, (d) C2-6 alkenyl, (e) C2-6 alkynyl, (f) C4-18 aryl, (g) C4-18 aryl-C1-6 alkyl (e.g., -L-R, in which L is C1-6alkyl and R is C4-18aryl), (h) C3-8cycloalkyl, and (i) C3-8cycloalkyl-C1-6alkyl (e.g., -L-R, in which L is C1-6 alkyl and R is C3-8 cycloalkyl), wherein in one embodiment no two groups are bound to the nitrogen atom through a carbonyl group or a sulfonyl group. The alkyl group can be a primary, secondary, or tertiary alkyl group substituted with one or more substituents (e.g., one or more halo or alkoxy). In some embodiments, the unsubstituted alkyl group is a C1-3, C1-6, C1-12, C1-16, C1-18, C1-20, or C1-24alkyl group.

[0093] 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 C2-24alkylene group. In other embodiments, the alkylene group is a C2-3, C2-6, C2-12, C2-16, C2-18, C2-20, or C2-24alkenylene 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.

[0094] 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.

[0095] By “alkylsulfinylalkyl” is meant an alkyl group, as defined herein, substituted by an alkylsulfinyl group. In some embodiments, the unsubstituted alkylsulfinylalkyl group is a C2-12or C2-24 alkylsulfinylalkyl group (e.g., C1-6 alkylsulfinyl-C1-6 alkyl or C1-12 alkylsulfinyl-C1-12 alkyl). In other embodiments, the alkylsulfinylalkyl group is -L-S(O)-R, in which each of L and R is, independently, an alkyl group, as defined herein.

[0096] By “alkylsulfonyl” is meant an alkyl group, as defined herein, attached to the parent molecular group through an -SO2- group. In some embodiments, the unsubstituted alkylsulfonyl group is a C1-6 or C1-12 alkylsulfonyl group. In other embodiments, the alkylsulfonyl group is -SO2- R, where R is an optionally substituted alkyl (e.g., as described herein, including optionally substituted C1-12 alkyl, haloalkyl, or perfluoroalkyl).

[0097] 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.Attorney Docket No. LAM1P062WO-11987-1WO

[0098] 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.

[0099] 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.

[0100] 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.

[0101] 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.

[0102] 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 whichAttorney Docket No. LAM1P062WO-11987-1WO 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.

[0103] 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.

[0104] 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.

[0105] 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.

[0106] By “aromatic-carbonyloxy” is meant an aromatic group that is or can be coupled to a compound disclosed herein, wherein the aromatic group is or becomes coupled through a carbonyloxy group (-OC(O)-). In some embodiments, the aromatic-carbonyloxy group is -OC(O)- R, in which R is an optionally substituted aromatic group, as defined herein.

[0107] 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-).Attorney Docket No. LAM1P062WO-11987-1WO In some embodiments, the aromatic-oxy group is -O-R, in which R is an optionally substituted aromatic group, as defined herein.

[0108] 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.

[0109] 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) C1-6alkanoyl (e.g., -C(O)-R, in which R is C1-6 alkyl); (2) C1-6 alkyl; (3) C1-6 alkoxy (e.g., -O-R, in which R is C1-6alkyl); (4) C1-6alkoxy-C1-6alkyl (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) C1-6 aminoalkyl (e.g., -L1-NR1R2or -L2- C(NR1R2)(R3)-R4, in which L1is C1-6alkyl; L2is a covalent bond or C1-6alkyl; 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 C1-6alkyl); (12) heteroaryl; (13) C4-18Attorney Docket No. LAM1P062WO-11987-1WO 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 C1-6 alkyl; L2is a covalent bond or C1-6 alkyl; X is fluoro, bromo, chloro, or iodo; and each of R1and R2is, independently, H or C1-6alkyl); (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) C1-6hydroxyalkyl (e.g., -L1-OH or -L2-C(OH)(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); (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, C1-6 alkyl); (36) -(CH2)rCO2R1, where r is an integer of from zero to four, and R1is selected from the group consisting of (a) hydrogen, (b) C1-6alkyl, (c) C4-18 aryl, and (d) C4-18 aryl-C1-6 alkyl (e.g., -L-R, in which L is C1-6 alkyl and R is C4-18 aryl); (37) -(CH2)rCONR1R2, where r is an integer of from zero to four and where each R1and R2is independently selected from the group consisting of (a) hydrogen, (b) C1-6 alkyl, (c) C4-18 aryl, and (d) C4-18aryl-C1-6alkyl (e.g., -L-R, in which L is C1-6alkyl and R is C4-18aryl); (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 C1-6 alkyl and R is C4-18 aryl); (40) -(CH2)rNR1R2, where r is an integer of from zero to four and where each of R1and R2is, independently, selected from the group consisting of (a) hydrogen, (b) an N-protecting group, (c) C1-6 alkyl, (d) C2-6 alkenyl, (e) C2-6 alkynyl, (f) C4-18 aryl, (g) C4-18 aryl- C1-6alkyl (e.g., -L-R, in which L is C1-6alkyl and R is C4-18aryl), (h) C3-8cycloalkyl, and (i) C3-8cycloalkyl-C1-6 alkyl (e.g., -L-R, in which L is C1-6 alkyl and R is C3-8 cycloalkyl), wherein in one embodiment no two groups are bound to the nitrogen atom through a carbonyl group or a sulfonyl group; (41) thiol (e.g., -SH); (42) perfluoroalkyl (e.g., -(CF2)nCF3, in which n is an integer from 0 to 10); (43) perfluoroalkoxy (e.g., -O-(CF2)nCF3, in which n is an integer from 0 to 10); (44)Attorney Docket No. LAM1P062WO-11987-1WO 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.

[0110] 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 (C7-16aryl-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- C2-6 alkynyl). In some embodiments, the aryl-alkyl group is -L-R, in which L is an alkyl group or an alkylene group, as defined herein, and R is an aryl group, as defined herein. In some embodiments, the aryl-alkenyl group is -L-R, in which L is an alkenyl group or an alkenylene group, as defined herein, and R is an aryl group, as defined herein. In some embodiments, the aryl-alkynyl group is -L-R, in which L is an alkynyl group or an alkynylene group, as defined herein, and R is an aryl group, as defined herein.

[0111] 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.

[0112] By “arylalkoxy” is meant an aryl-alkyl group, as defined herein, attached to the parent molecular group through an oxygen atom. In some embodiments, the arylalkoxy group is -O-L- R, in which L is an alkyl group, as defined herein, and R is an aryl group, as defined herein.

[0113] By “aryloxy” is meant -OR, where R is an optionally substituted aryl group, as described herein. In some embodiments, an unsubstituted aryloxy group is a C4-18 or C6-18 aryloxy group. InAttorney Docket No. LAM1P062WO-11987-1WO other embodiments, R is an aryl group that is optionally substituted with alkyl, alkanoyl, amino, hydroxyl, and the like.

[0114] By “aryloxycarbonyl” is meant an aryloxy group, as defined herein, that is attached to the parent molecular group through a carbonyl group. In some embodiments, an unsubstituted aryloxycarbonyl group is a C5-19 aryloxycarbonyl group. In other embodiments, the aryloxycarbonyl group is -C(O)O-R, in which R is an aryl group, as defined herein.

[0115] 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.

[0116] 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 C5-19aryloyloxy group. In other embodiments, the aryloyloxy group is -OC(O)-R, in which R is an aryl group, as defined herein.

[0117] By “azido” is meant an -N3group.

[0118] 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.

[0119] By “azo” is meant an -N=N- group.

[0120] 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.

[0121] 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 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.Attorney Docket No. LAM1P062WO-11987-1WO

[0122] 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.

[0123] By “carbonyl” is meant a -C(O)- group, which can also be represented as >C=O.

[0124] By “carboxyl” is meant a -CO2H group or an anion thereof.

[0125] 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.

[0126] By “cyanato” is meant a -OCN group.

[0127] By “cyano” is meant a -CN group.

[0128] By “cycloaliphatic” is meant an aliphatic group, as defined herein, that is cyclic.

[0129] 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.

[0130] 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.

[0131] 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.

[0132] By “cycloheteroaliphatic” is meant a heteroaliphatic group, as defined herein, that is cyclic.

[0133] 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, or optionally substituted amino.Attorney Docket No. LAM1P062WO-11987-1WO

[0134] By “disulfide” is meant -SSR, where R is selected from hydrogen, aliphatic, heteroaliphatic, haloaliphatic, haloheteroaliphatic, aromatic, as defined herein, or any combination thereof.

[0135] 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.

[0136] 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.

[0137] By “halo” is meant F, Cl, Br, or I.

[0138] 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.

[0139] 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 -CX3group, 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.

[0140] 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.

[0141] 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.

[0142] 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. LAM1P062WO-11987-1WO

[0143] 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.

[0144] 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.

[0145] 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.

[0146] 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.

[0147] By “heteroalkylene,” “heteroalkenylene,” and “heteroalkynylene” is meant a multivalent (e.g., bivalent) form of a heteroalkyl, heteroalkenyl, or heteroalkynyl group, respectively, as described herein.

[0148] 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.

[0149] 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.

[0150] 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-carbonyloxyAttorney Docket No. LAM1P062WO-11987-1WO group is -OC(O)-R, in which R is an optionally substituted heteroaromatic group, as defined herein.

[0151] 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.

[0152] 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.

[0153] 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.

[0154] By “heteroarylene” is meant a multivalent (e.g., bivalent) form of a heteroaryl group, as described herein.

[0155] 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.

[0156] 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 includeAttorney Docket No. LAM1P062WO-11987-1WO thiiranyl, thietanyl, tetrahydrothienyl, thianyl, thiepanyl, aziridinyl, azetidinyl, pyrrolidinyl, piperidinyl, azepanyl, pyrrolyl, pyrrolinyl, pyrazolyl, pyrazolinyl, pyrazolidinyl, imidazolyl, imidazolinyl, imidazolidinyl, pyridyl, homopiperidinyl, pyrazinyl, piperazinyl, pyrimidinyl, pyridazinyl, oxazolyl, oxazolidinyl, oxazolidonyl, isoxazolyl, isoxazolidiniyl, morpholinyl, thiomorpholinyl, thiazolyl, thiazolidinyl, isothiazolyl, isothiazolidinyl, indolyl, quinolinyl, isoquinolinyl, benzimidazolyl, benzothiazolyl, benzoxazolyl, furyl, thienyl, thiazolidinyl, isothiazolyl, isoindazoyl, triazolyl, tetrazolyl, oxadiazolyl, uricyl, thiadiazolyl, pyrimidyl, tetrahydrofuranyl, dihydrofuranyl, dihydrothienyl, dihydroindolyl, tetrahydroquinolyl, tetrahydroisoquinolyl, pyranyl, dihydropyranyl, tetrahydropyranyl, dithiazolyl, dioxanyl, dioxinyl, dithianyl, trithianyl, oxazinyl, thiazinyl, oxothiolanyl, triazinyl, benzofuranyl, benzothienyl, and the like.

[0157] 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.

[0158] 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.

[0159] 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.

[0160] By “hydroxyl” is meant -OH.

[0161] 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.Attorney Docket No. LAM1P062WO-11987-1WO

[0162] By “imidoyl” is meant a moiety including a carbonimidoyl group. In some embodiments, 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.

[0163] 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.

[0164] By “isocyanato” is meant a -NCO group.

[0165] By “isocyano” is meant a -NC group.

[0166] 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.

[0167] By “nitro” is meant an -NO2group.

[0168] 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.

[0169] By “oxo” is meant an =O group.

[0170] By “oxy” is meant -O-.

[0171] By “perfluoroalkyl” is meant an alkyl group, as defined herein, having each hydrogen atom substituted with a fluorine atom. Exemplary perfluoroalkyl groups include trifluoromethyl,Attorney Docket No. LAM1P062WO-11987-1WO pentafluoroethyl, etc. In some embodiments, the perfluoroalkyl group is -(CF2)nCF3, in which n is an integer from 0 to 10.

[0172] 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.

[0173] 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 hereinAttorney Docket No. LAM1P062WO-11987-1WO (e.g., optionally substituted isoxazolium, optionally substituted oxazolium, optionally substituted thiazolium, optionally substituted pyrrolium, optionally substituted furanium, optionally substituted thiophenium, optionally substituted imidazolium, optionally substituted pyrazolium, optionally substituted isothiazolium, optionally substituted triazolium, optionally substituted tetrazolium, optionally substituted furazanium, optionally substituted pyridinium, optionally substituted pyrimidinium, optionally substituted pyrazinium, optionally substituted triazinium, optionally substituted tetrazinium, optionally substituted pyridazinium, optionally substituted oxazinium, optionally substituted pyrrolidinium, optionally substituted pyrazolidinium, optionally substituted imidazolinium, optionally substituted isoxazolidinium, optionally substituted oxazolidinium, optionally substituted piperazinium, optionally substituted piperidinium, optionally substituted morpholinium, optionally substituted azepanium, optionally substituted azepinium, optionally substituted indolium, optionally substituted isoindolium, optionally substituted indolizinium, optionally substituted indazolium, optionally substituted benzimidazolium, optionally substituted isoquinolinum, optionally substituted quinolizinium, optionally substituted dehydroquinolizinium, optionally substituted quinolinium, optionally substituted isoindolinium, optionally substituted benzimidazolinium, and optionally substituted purinium).

[0174] 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.

[0175] 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 substitutedAttorney Docket No. LAM1P062WO-11987-1WO aryloxy, optionally substituted alkyl-aryl, optionally substituted aryl-alkyl, or optionally substituted amino. In other embodiments, the silyloxy group is -O-Si(R)a(OR)b(NR2)c, in which each R is, independently, H, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, or optionally substituted heteroaromatic; each of a, b, and c ≥ 0; and a + b + c = 3. In particular embodiments, each R is, independently, H, optionally substituted alkyl, optionally substituted aryl, optionally substituted alkyl-aryl, or optionally substituted aryl- alkyl

[0176] By “sulfinyl” is meant an -S(O)- group.

[0177] By “sulfo” is meant an -S(O)2OH group.

[0178] 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.

[0179] By “thioalkyl” is meant an alkyl group, as defined herein, attached to the parent molecular group through a sulfur atom. Exemplary unsubstituted thioalkyl groups include C1-6 thioalkyl. In some embodiments, the thioalkyl group is -S-R, in which R is an alkyl group, as defined herein.

[0180] By “thiol” is meant an -SH group.

[0181] 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.

[0182] 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.

[0183] 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.

[0184] Other features and advantages of the invention will be apparent from the following description and the claims. ADDITIVE EXAMPLES

[0185] The additive can any useful silicon-containing compound (Si-containing compound). In some embodiments, the compound includes a structure of formula (I): Si(Rʹ)4(I), wherein at least one Rʹ includes a carbon 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 RʹAttorney Docket No. LAM1P062WO-11987-1WO includes a carbon atom and a heteroatom (e.g., nitrogen, oxygen, and / or silicon). In particular embodiments, Rʹ does not include a halogen atom.

[0186] In other embodiments, the compound includes a structure of formula (II): (Rʹ)3Si−[L−Si(Rʹ)2]−Rʹ (II), wherein at least one Rʹ includes a carbon 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.

[0187] 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.

[0188] 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.

[0189] 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.

[0190] 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).

[0191] 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), carbamoylAttorney Docket No. LAM1P062WO-11987-1WO (e.g., -C(O)NRN1RN2), carbamoyloxy (e.g., -OC(O)NRN1RN2), 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), 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.

[0192] 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.

[0193] 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.

[0194] 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.

[0195] 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 substitutedAttorney Docket No. LAM1P062WO-11987-1WO 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 alkylsilyl groups include -SiH2RAk, -SiH[RAk]2, or -Si[RAk]3, in which RAkis any provided herein.

[0196] 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.

[0197] 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.

[0198] 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.

[0199] 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,Attorney Docket No. LAM1P062WO-11987-1WO heteroaromatic, 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 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.

[0200] 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.

[0201] 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-Attorney Docket No. LAM1P062WO-11987-1WO Si(R)a(ORAr)b, -O-Si(R)a(NRN1RN2)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; 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).

[0202] 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)c or -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.

[0203] 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 whichAttorney Docket No. LAM1P062WO-11987-1WO RN1and RN2can be taken together, with the nitrogen atom to which each is attached, to form an optionally substituted heterocyclyl; each of a and b ≥ 0; and a + b = 3.

[0204] 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.

[0205] 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).

[0206] 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.

[0207] 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.

[0208] 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 substitutedAttorney Docket No. LAM1P062WO-11987-1WO heteroaromatic), aromatic (e.g., aryl or -RAr), 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(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.

[0209] 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.

[0210] 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-NH2 or -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.Attorney Docket No. LAM1P062WO-11987-1WO

[0211] 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 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.

[0212] 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.

[0213] 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).

[0214] The organic silicon-containing compound may be selected from the group consisting of silane, disilane, trisilane, tetrasilane, amine-substituted versions of any of the foregoing silanes, and trisilylamine.

[0215] Examples of organic silicon-containing compounds 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 andAttorney Docket No. LAM1P062WO-11987-1WO organo silanes such as methylsilane, ethylsilane, isopropylsilane, t-butylsilane, dimethylsilane, diethylsilane, di-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.

[0216] 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)3and 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).

[0217] Examples of silicon-containing compounds 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.

[0218] Yet other examples of organic silicon-containing compounds 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 compounds 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 compounds include monosilanes substituted with one or more alkyl, alkene,Attorney Docket No. LAM1P062WO-11987-1WO and / or alkyne groups containing, e.g., 1-5 carbon atoms. Examples include but are not limited to trimethylsilane (3MS), dimethylsilane (2MS), triethylsilane (TES), and 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 compounds 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).

[0219] In the Si-containing compounds described herein, different kinds of Rʹ can be attached to the silicon atom. Further Si-containing compounds are described herein. Aminosilanes

[0220] A silicon-containing compound can include one or more optionally substituted amino groups, thereby providing a non-limiting amino silane. In one embodiment, the compound 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.

[0221] In another embodiment, the compound 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-),Attorney Docket No. LAM1P062WO-11987-1WO 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.

[0222] 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.

[0223] 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.

[0224] In particular embodiments, at least one Rʹ or Rʺ is not H. The compound can have any useful combination of Rʹ groups and amino groups (NRʺ2) attached to one or more silicon atoms.

[0225] 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 substitutedAttorney Docket No. LAM1P062WO-11987-1WO 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.

[0226] 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.

[0227] The compound can include at least one Rʹ group attached to the silicon atom. In one embodiment, the compound 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 compound has a formula of (Rʹ)(H)2Si(NRʺ2), wherein Rʹ and Rʺ can be any described herein. In one embodiment, the compound has a formula of (Rʹ)(H)Si(NRʺ2)2, wherein Rʹ and Rʺ can be any described herein. In another embodiment, the compound has a formula of (Rʹ)2(H)Si(NRʺ2), wherein Rʹ and Rʺ can be any described herein. In yet another embodiment, the compound has a formula of (Rʹ)2Si(NRʺ2)2, wherein Rʹ and Rʺ can be any described herein. In one embodiment, the compound has a formula of (Rʹ)3Si(NRʺ2), wherein Rʹ and Rʺ can be any described herein.

[0228] The compound can lack an Rʹ group attached to the silicon atom. In one embodiment, the compound 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 compound 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.

[0229] The compound can include one or more hydrogen atoms attached to the silicon atom. In one embodiment, the compound has a formula of (H)3Si(NRʺ2) or (H)2Si(NRʺ2)2or (H)Si(NRʺ2)3,Attorney Docket No. LAM1P062WO-11987-1WO 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.

[0230] The compound 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 compound has a formula of , in which the heterocyclyl group can be optionally substituted (e.g., with any substituent described herein as a substitution for alkyl), and wherein n is 1,2, 3, 4, or 5. In one embodiment, the formula has a formula of Rʹ3Si-Het, in which Het is an optionally substituted heterocyclyl including at least one nitrogen atom, and each Rʹ can independently be any described herein. In particular embodiments, the compound 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.

[0231] In some instances, the compound can have two or more silicon atoms, in which the compound can include a Si-Si bond. In a particular embodiment, the compound 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 compound has a formula of (Rʺ2N)(Rʹ)2Si−Si(Rʹ)2(NRʺ2), wherein Rʹ and Rʺ can be any described herein. In another embodiment, the compound 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 compound has a formula of (Rʺ2N)3Si−Si(NRʺ2)3, wherein each Rʺ can independently be any described herein.

[0232] The compound can include differing groups attached to the silicon atoms. In one instance, the compound has a formula of (Rʺ2N)x(Rʹ)3-xSi−SiH3, wherein Rʹ and Rʺ can be any described herein.

[0233] A linker can be present between two silicon atoms. In one instance, the compound 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 compound 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.

[0234] The compound can include a combination of Rʹ groups with a linker having a heteroatom. In one instance, the compound has a formula of (Rʹ)3Si−NR−Si(Rʹ)3, wherein R and Rʹ can be any described herein. In another instance, the compound has a formula of (Rʹ)3Si−L−Si(Rʹ)3, whereinAttorney Docket No. LAM1P062WO-11987-1WO 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-).

[0235] The compound can include any useful combination of Rʹ and NRʺ2 groups in combination with two silicon atoms. In one instance, the compound has a formula of (Rʺ2N)(Rʹ)2Si−L−Si(Rʹ)2(NRʺ2)x, wherein L, Rʹ, and Rʺ can be any described herein.

[0236] The compound can include heterocyclic groups including the silicon and nitrogen atoms. In one embodiment, the compound has a , wherein Rʹ and Rʺ can be any described herein, and wherein n is 1, 2, 3, or

[0237] In another embodiment, the compound has a , wherein Rʹ and Rʺ can be any described herein, and wherein n is 1, 2, 3, or embodiment, thecompound has a which each Rʺ can independently be any described herein; and wherein n isIn another embodiment, the compound has a , wherein Rʹ and Rʺ can be any described herein, and wherein n is 1, 2, 3, or 4. Inthe compound has a , wherein Rʺ can independently be any described herein, and wherein n is 1,

[0238] In any compound herein, two Rʺ can be taken together, with the nitrogen atom to which each is attached, to form an optionally substituted heterocyclyl.

[0239] compounds 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), 4, InH,Attorney Docket No. LAM1P062WO-11987-1WO 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, 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.

[0240] Non-limiting examples of compound 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]2or BDMAS); bis(dimethylamino)Attorney Docket No. LAM1P062WO-11987-1WO methylsilane (SiMeH[NMe2]2); bis(dimethylamino)dimethylsilane (SiMe2[NMe2]2 or BDMADMS); bis(dimethylamino)diethylsilane (SiEt2[NMe2]2); bis(dimethylamino) methylvinylsilane (SiMeVi[NMe2]2); bis(ethylamino)dimethylsilane (SiMe2[NHEt]2); bis(ethylmethylamino)silane (SiH2[NMeEt]2); bis(ethylmethylamino)dimethylsilane (SiMe2[NMeEt]2); bis(ethylmethylamino)diethylsilane (SiEt2[NMeEt]2); bis(ethylmethylamino) methylvinylsilane (SiMeVi[NMeEt]2); bis(diethylamino)silane (SiH2[NEt2]2, C8H22N2Si, or BDEAS); bis(diethylamino)dimethylsilane (SiMe2[NEt2]2); bis(diethylamino)methylvinylsilane (SiMeVi[NEt2]2); bis(diethylamino)diethylsilane (SiEt2[NEt2]2); bis(iso-propylamino) dimethylsilane (SiMe2[NHiPr]2); bis(iso-propylamino)diethylsilane (SiEt2[NHiPr]2); bis(iso- propylamino)methylvinylsilane (SiMeVi[NHiPr]2); bis(di-iso-propylamino)silane (SiH2[NiPr2]2); bis(di-iso-propylamino)dimethylsilane (SiMe2[NiPr2]2); bis(di-iso-propylamino) diethylsilane (SiEt2[NiPr2]2); bis(di-iso-propylamino)methylvinylsilane (SiMeVi[NiPr2]2); bis(methylamino)silane (SiH2[NHMe]2); bis(sec-butylamino)silane (SiH2[NHsBu]2); bis(sec- butylamino)methylsilane (SiHMe[NHsBu]2); bis(sec-butylamino)ethylsilane (SiHEt[NHsBu]2); bis(tert-butylamino)silane (SiH2[NHtBu]2or 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

[0241] A silicon-containing compound can include one or more isocyanato groups, thereby providing a non-limiting isocyanato silane. In one embodiment, the compound 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,Attorney Docket No. LAM1P062WO-11987-1WO 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.

[0242] In another embodiment, the compound 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 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.

[0243] In yet another embodiment, the compound 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.Attorney Docket No. LAM1P062WO-11987-1WO

[0244] 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.

[0245] 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.

[0246] compounds 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,Attorney Docket No. LAM1P062WO-11987-1WO optionally substituted alkoxy, optionally substituted aromatic, optionally substituted heteroaromatic, optionally substituted aryl, or optionally substituted heteroaryl. Azido silanes

[0247] A silicon-containing compound can include one or more azido groups, thereby providing a non-limiting azido silane. In one embodiment, the compound 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.

[0248] In another embodiment, the compound 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 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.

[0249] In yet another embodiment, the compound 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 substitutedAttorney Docket No. LAM1P062WO-11987-1WO 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.

[0250] 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.

[0251] 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 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.Attorney Docket No. LAM1P062WO-11987-1WO

[0252] compounds 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 compounds also include tris(dimethylamino)silylazide ([Me2N]3SiN3); di-tert-butyl diazidosilane (tBu2Si(N3)2); ethylsilicon triazide (EtSi(N3)3); and the like. Hydrazino silanes

[0253] A silicon-containing compound can include one or more optionally substituted hydrazino groups, thereby providing a non-limiting hydrazino silane. In one embodiment, the compound 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.

[0254] In another embodiment, the compound 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 beAttorney Docket No. LAM1P062WO-11987-1WO taken together, with the nitrogen atom to which each is attached, to form an optionally substituted heterocyclyl.

[0255] In yet another embodiment, the compound 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.

[0256] 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 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).

[0257] 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.

[0258] The compound can include any useful combination of Rʹ and hydrazino groups. In one embodiment, the compound has a formula of (Rʹ)3Si(NRʺ-L-NRʺ2) or (Rʹ)3Si(NRʺ-NRʺ2), wherein L, Rʹ, and Rʺ can be any described herein.

[0259] The compound can include a plurality of hydrazino groups. In one embodiment, the compound 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.

[0260] The compound can include at least two silicon atoms. In one embodiment, the compound has a formula of (NRʺ2-NRʺ)(Rʹ)2Si−Si(Rʹ)2(NRʺ-NRʺ2), wherein each Rʹ and Rʺ can be any described herein.

[0261] Non-limiting compounds can include bis(tert-butylhydrazino)diethylsilane (SiEt2[NH−NHtBu]2); tris(dimethylhydrazino)silane (SiH[NH−NMe2]3); and the like. Siloxanes and derivatives thereof

[0262] A silicon-containing compound 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 moreAttorney Docket No. LAM1P062WO-11987-1WO Si-O, O-Si-O, or Si-O-Si bonds. In one embodiment, the compound 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, 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.

[0263] In another embodiment, the compound 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.

[0264] 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.Attorney Docket No. LAM1P062WO-11987-1WO

[0265] 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.

[0266] 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.

[0267] 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.Attorney Docket No. LAM1P062WO-11987-1WO

[0268] The compound can include one or more hydrogen atoms attached to the silicon atom. In one embodiment, the compound has a formula of H3Si(OR‴), H2Si(OR‴)2, or HSi(OR‴)3, wherein each R‴ can independently be any described herein.

[0269] The compound can include any combination of Rʹ and OR‴ groups within the compound. In one embodiment, the compound 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 compound can include alkyl groups, such as in the compound having a formula of (RAk)3Si(ORAk), (RAk)2Si(ORAk)2, or (RAk)Si(ORAk)3, in which RAkis optionally substituted alkyl.

[0270] In some instances, the compound can have two or more silicon atoms, in which the compound can include a Si-Si bond. In a particular embodiment, the compound 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 compound has a formula of (R‴O)(Rʹ)2Si−Si(Rʹ)2(OR‴), wherein Rʹ and R‴ can be any described herein.

[0271] The compound can include a combination of Rʹ groups with a linker having a heteroatom. In one instance, the compound has a formula of (Rʹ)3Si−O−Si(Rʹ)3, wherein Rʹ can be any described herein. In another instance, the compound 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 compound 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 compound 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.

[0272] The compound can include any useful combination of Rʹ and OR‴ groups in combination with two silicon atoms. In one instance, the compound 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 compound 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.

[0273] Non-limiting compounds 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); diethoxysilaneAttorney Docket No. LAM1P062WO-11987-1WO (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-butoxydiethylsilane (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]2 or 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

[0274] A silicon-containing compound 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 compound 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 substitutedAttorney Docket No. LAM1P062WO-11987-1WO heterocyclyl; and each R‴ is, independently, H, aliphatic, heteroaliphatic, aromatic, heteroaromatic, silyl, or silyloxy, in which any of these may be optionally substituted.

[0275] In another embodiment, the compound 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); 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.

[0276] Non-limiting examples of Rʹ, Rʺ, and R‴ are described herein, e.g., such as for amino silane, siloxane, or derivatives thereof.

[0277] The compound can include any combination of Rʹ, NRʺ2, and OR‴ groups. In one embodiment, the compound 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 compound 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.Attorney Docket No. LAM1P062WO-11987-1WO

[0278] The compound can include only amino and oxy-containing groups attached to the silicon atom. In one embodiment, the compound 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 compounds 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- 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

[0279] A silicon-containing compound 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 compound 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.

[0280] In another embodiment, the compound has a formula of (Rʹ3Si)y(Rʺ)2-yN−L− N(Rʺ)2-y(SiRʹ3)y, wherein:Attorney Docket No. LAM1P062WO-11987-1WO 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- 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.

[0281] 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.

[0282] 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,Attorney Docket No. LAM1P062WO-11987-1WO 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).

[0283] 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.

[0284] The compound can include at least one Rʺ group attached to the nitrogen atom. In one embodiment, the compound has a formula of (Rʺ)N(SiRʹ3)2 or (Rʺ)2N(SiRʹ3), wherein Rʹ and Rʺ can be any described herein. In another embodiment, the compound 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.

[0285] The compound can include at least one hydrogen atom attached to the nitrogen atom. In one embodiment, the compound has a formula of (H)N(SiRʹ3)2, wherein Rʹ can be any described herein. In another embodiment, the compound has a formula of (H)N(SiRAk3)2, wherein RAkcan be optionally substituted aliphatic, optionally substituted alkyl, optionally substituted alkenyl, or optionally substituted alkynyl.

[0286] The compound can include three silicon atoms attached to the nitrogen atom. In one embodiment, the compound has a formula of N(SiRʹ3)3, wherein Rʹ can be any described herein.Attorney Docket No. LAM1P062WO-11987-1WO In another embodiment, the compound has a formula of N(SiH3)(SiRʹ3)2, wherein Rʹ can be any described herein. In yet another embodiment, the compound has a formula of N(SiH3)(SiRAk3)2, wherein RAkcan be optionally substituted aliphatic, optionally substituted alkyl, optionally substituted alkenyl, or optionally substituted alkynyl.

[0287] The compound can have two or more nitrogen atoms, in which the compound includes a N-N bond. In one instance, the compound has a formula of (Rʹ3Si)2N−N(SiRʹ3)2, wherein Rʹ can be any described herein.

[0288] A linker can be present between nitrogen atoms. In one instance, the compound 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 compound has a formula of (H3Si)(Rʺ)N−L−N(Rʺ)(SiH3), wherein Rʺ can be any described herein.

[0289] The linker can include a silicon atom. In one instance, the compound has a formula of (Rʹ3Si)2N−SiRʹ2−N(SiRʹ3)2, wherein Rʹ can be any described herein. In another instance, the compound 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.

[0290] The linker can include a SiH2group. In one instance, the compound has a formula of (Rʹ3Si)2N−SiH2−N(SiRʹ3)2, wherein Rʹ can be any described herein. In another instance, the compound 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.

[0291] A plurality of nitrogen- and silicon-containing moieties may be present within the compound. In one embodiment, the compound has a formula of (Rʹ3Si)(Rʺ)N−SiRʹ2−N(Rʺ)− SiRʹ2−N(Rʺ)(SiRʹ3), wherein Rʹ and Rʺ can be any described herein.

[0292] Non-limiting compounds 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]); diisopropylsilylamineAttorney Docket No. LAM1P062WO-11987-1WO (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

[0293] A silicon-containing compound can include one or more amino, silyl, and / or imino groups, 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 compound 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.

[0294] In another embodiment, the compound 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.

[0295] In yet another embodiment, the compound 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.

[0296] In one embodiment, the compound 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,Attorney Docket No. LAM1P062WO-11987-1WO 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.

[0297] In another embodiment, the compound 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.

[0298] 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.

[0299] 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 optionallyAttorney Docket No. LAM1P062WO-11987-1WO 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).

[0300] 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.

[0301] The compound can include one or more disilanyl groups and amino groups. In one embodiment, the compound has a formula of Rʺ2N−SiRʹ2−SiRʹ3, wherein L, Rʹ, and Rʺ can be any described herein. In other embodiments, the compound has a formula of Rʺ2N−SiH2−SiH3, wherein Rʺ is any described herein. In another embodiment, the compound 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 compound has a formula of (Rʺ)3-yN−(SiH2−SiH3)y, wherein y and Rʺ can be any described herein.

[0302] The compound can include a bivalent disilanyl group. In one embodiment, the compound has a formula of Rʺ2N−SiRʹ2−SiRʹ2−L−NRʺ2, wherein L, Rʹ, and Rʺ can be any described herein. In another embodiment, the compound has a formula of Rʺ2N−SiRʹ2−SiRʹ2−NRʺ2, wherein Rʹ and Rʺ can be any described herein.

[0303] A linker L can be present between two silyl group. In one embodiment, the compound 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 compound has a formula of Rʺ2N−SiRʹ2−L− SiRʹ2−NRʺ2, wherein L, Rʹ, and Rʺ can be any described herein. In yet another embodiment, the compound has a formula of (Rʺ)3-yN−(SiRʹ2−L−SiH3)y, wherein y, L, Rʹ, and Rʺ can be any described herein.

[0304] The compound can include −SiH3as the silyl group. In one embodiment, the compound has a formula of Rʺ2N−SiH2−SiH3, wherein Rʺ can be any described herein. In anotherAttorney Docket No. LAM1P062WO-11987-1WO embodiment, the compound 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.

[0305] The compound 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 compound 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 compound has a formula of H2Si(NRʺ−SiRʹ3)3, wherein Rʹ and Rʺ can be any described herein.

[0306] The compound can include a bis-trisilylamino group, such as, e.g., -N(SiRʹ3)2 in which Rʹ can be any described herein. In one embodiment, the compound has a formula of Rʺ2N−SiRʹ2− N(SiRʹ3)2, in which Rʹ and Rʺ can be any described herein. In another embodiment, the compound has a formula of Rʺ2N−SiH2−N(SiH3)2, in which Rʹ can be any described herein. In yet another embodiment, the compound 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.

[0307] The compound can include a linker L disposed between a silicon atom and a nitrogen atom. In one embodiment, the compound has a formula of Rʺ2N−SiRʹ2−L−NRʺ2, wherein L, Rʹ, and Rʺ can be any described herein.

[0308] The compound can include a linker L disposed between two nitrogen atoms. In one embodiment, the compound has a formula of Rʹ3Si−SiRʹ2−NRʺ−L−NRʺ−SiRʹ2−SiRʹ3, wherein L, Rʹ, and Rʺ can be any described herein.

[0309] 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 compound has a formula of Rʺ2N−[SiRʹ2−N(SiRʹ3)]z−SiRʹ3or Rʺ2N−[N(SiRʹ3)]z−SiRʹ3, in which z is 1, 2, 3, or more; and wherein Rʹ and Rʺ can be any described herein.

[0310] The linker can include both a silyl group and an imino group. In one embodiment, the compound 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.

[0311] Non-limiting compounds 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.Attorney Docket No. LAM1P062WO-11987-1WO Mixed amines including silicon and oxygen

[0312] A silicon-containing compound can include one or more amino groups substituted with a silyl group, thereby providing a non-limiting mixed amine. In one embodiment, the compound 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; 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.

[0313] Non-limiting examples of Rʹ, Rʺ, and R‴ are described herein, e.g., such as for amino silane, siloxane, silyl amine, or derivatives thereof.

[0314] The compound can include any combination of Rʺ groups and silicon-containing groups. In one embodiment, the compound has a formula of (Rʺ)3-yN[Si(ORAk)xRAk3-x]yor (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 compound has a formula of (Rʺ)3-yN [Si(ORAk)xH3-x]yor (Rʺ)3-yN[Si(ORAk)H(RAk)]y, in which Rʺ, RAk, x, and y is any described herein.

[0315] The compound can include two silicon-containing groups. In one embodiment, the compound 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.

[0316] The compound can include a hydrogen atom attached to the nitrogen atom. In one embodiment, the compound has a formula of (H)3-yN[Si(ORAk)xRAk3-x]yor (H)3-yN[Si(ORAk)xH3-x]y or (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.

[0317] Non-limiting compounds include, e.g., bis(dimethoxysilyl)amine (NH[Si(OMe)2H]2); bis(diethoxysilyl)amine (NH[Si(OEt)2H]2); N-iso-propylbis(diethoxysilyl)amineAttorney Docket No. LAM1P062WO-11987-1WO (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

[0318] A silicon-containing compound can include a cyclic group having one or more nitrogen atoms. In one embodiment, the compound 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, 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.

[0319] In one embodiment, the compound 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.Attorney Docket No. LAM1P062WO-11987-1WO

[0320] In another embodiment, the compound 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.

[0321] In yet another embodiment, the compound 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).

[0322] In one embodiment, the compound has a , wherein Rʹ and Rʺ can be any described herein, and wherein n is 1, 2, 3, or 4.

[0323] In another embodiment, the compound has a formula , wherein Rʹ and Rʺcan be any described herein, and wherein n is 1, 2, 3, or 4.

[0324] In yet another embodiment, the compound has a formula of , wherein Rʺ and R‴ can be any described herein, and wherein n is 1, 2, 3, or 4. In particular embodiments, each R‴ is, independently, H, aliphatic, heteroaliphatic, aromatic, heteroaromatic, silyl, or silyloxy, in which any of these may be optionally substituted.

[0325] In one embodiment, the compound has a formula , wherein Rʹ can includea heteroatom (e.g., a nitrogen atom, such as in optionallyazido, isocyanato, or optionally substituted hydrazino), and wherein n is 1, 2, 3, or 4.

[0326] 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 substitutedAttorney Docket No. LAM1P062WO-11987-1WO heteroaliphatic, optionally substituted aromatic, optionally substituted aryl, and optionally substituted heteroaromatic.

[0327] 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.

[0328] 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.

[0329] 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, optionally substituted aryl, optionally substituted heteroaromatic, or optionally substituted heteroaryl.

[0330] Non-limiting compounds include 1,3,3-trimethylcyclodisilazane ([NH−SiMe2][NH−SiMeH]); hexamethylcyclotrisilazane ([NH−SiMe2]3); octamethylcyclotetrasilazane ([NH−SiMe2]4); and the like. Cyclic siloxanes

[0331] A silicon-containing compound can include a cyclic group having one or more oxygen atoms. In one embodiment, the compound 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.

[0332] In one embodiment, the compound 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,Attorney Docket No. LAM1P062WO-11987-1WO 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.

[0333] In another embodiment, the compound 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.

[0334] In yet another embodiment, the compound 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-), 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., oxygen atoms).

[0335] In one embodiment, the compound has a formula , wherein Rʹ can be any described herein, and wherein n is 1, 2, 3, or 4.

[0336] In another embodiment, the compound has a formula , wherein Rʹ and Rʺcan be any described herein, and wherein n is 1, 2, 3, or 4.

[0337] In yet another embodiment, the compound has a formula of , wherein R‴ can be any described herein, and wherein n is 1, 2, 3, or 4. In particular embodiments, each R‴ is, independently, H, aliphatic, heteroaliphatic, aromatic, heteroaromatic, silyl, or silyloxy, in which any of these may be optionally substituted.

[0338] In one embodiment, the compound has a formula of , wherein Rʹ can includea heteroatom (e.g., an oxygen atom, such as in optionally substituted aliphatic-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.Attorney Docket No. LAM1P062WO-11987-1WO

[0339] 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.

[0340] Non-limiting compounds 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

[0341] A silicon-containing compound can include siloxane or a derivative thereof and having one or more amino substitutions, thereby providing a siloxane or a derivative thereof having one or more Si-O, O-Si-O, or Si-O-Si bonds and having one or more -NR2 substitutions. In one embodiment, the compound 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.

[0342] In another embodiment, the compound has a formula of (Rʺ)3-yN [(SiRʹ2−O)z−SiRʹ3]y, wherein Rʹ, Rʺ, y, and z can be any described herein.

[0343] The compound can include an optionally substituted amino group with an optionally substituted silyl group. In one embodiment, the compound 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 compound has a formula of Rʺ2N(SiRʹ2−O)z−SiRʹ3, wherein Rʹ, Rʺ, and z can be any described herein.Attorney Docket No. LAM1P062WO-11987-1WO

[0344] The compound can include two optionally substituted amino group. In one embodiment, the compound has a formula of Rʺ2N−SiRʹ2−(OSiRʹ2)z−NRʺ2, wherein Rʹ, Rʺ, and z can be any described herein.

[0345] 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.

[0346] Non-limiting compounds 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 silanols

[0347] A silicon-containing compound can include one or more hydroxyl groups, thereby providing a non-limiting silanol. In one embodiment, the compound 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.

[0348] In other embodiments, the compound 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, orAttorney Docket No. LAM1P062WO-11987-1WO silyloxy, in which any of these may be optionally substituted.

[0349] The compound can have one hydroxyl group. In one embodiment, the compound has a formula of (Rʹ)3Si(OH), in which each Rʹ can be any described herein. In another embodiment, the compound 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.

[0350] Non-limiting compounds include, e.g., tri(t-butoxy)silanol (SiOH[OtBu]3); tri(t- pentoxy)silanol (SiOH[OtPe]3); and the like. Carbonyloxy silanes

[0351] A silicon-containing compound can include one or more optionally substituted aliphatic- carbonyloxy groups, thereby providing a non-limiting carbonyloxy silane. In one embodiment, the compound 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- 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.

[0352] In another embodiment, the compound 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.

[0353] 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.,Attorney Docket No. LAM1P062WO-11987-1WO 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.

[0354] In some embodiments, R^ is H, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted alkoxy, optionally substituted aryloxy, optionally substituted amino, or optionally substituted aminooxy.

[0355] Non-limiting compounds include those having a formula of (Rʹ)2Si(OC(O)-R^)2, wherein Rʹ and R^ can be any described herein. CONCLUSION

[0356] 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

1. Attorney Docket No. LAM1P062WO-11987-1WO CLAIMS What is claimed is:

1. A method for processing substrates, the method comprising: providing a substrate having a polysilicon material over a contrast material; generating a plasma using a gas mixture to a process chamber housing the substrate, the gas mixture comprising a halogen-containing gas, a carbon-containing gas, and one or more additives; and exposing the substrate to the plasma to selectively etch the polysilicon material relative to the contrast material, wherein the one or more additives comprises a silicon-containing gas.

2. The method of claim 1, wherein the silicon-containing gas comprises silicon tetrafluoride.

3. The method of claim 1, wherein the silicon-containing gas comprises a silane.

4. The method of claim 1, wherein the halogen-containing gas comprises nitrogen trifluoride.

5. The method of claim 1, wherein the halogen-containing gas comprises carbon tetrafluoride.

6. The method of claim 1, wherein the halogen-containing gas is nitrogen-free.

7. The method of claim 1, wherein the carbon-containing gas comprises methane.

8. The method of claim 1, wherein the gas mixture further comprises hydrogen gas.

9. The method of claim 1, wherein the gas mixture further comprises a dilution gas.

10. The method of any one of claims 1-9, wherein the plasma is pulsed.

11. The method of any one of claims 1-9, further comprising biasing the substrate during exposure of the substrate to the plasma.

12. The method of any one of claims 1-9, wherein the silicon-containing gas is flowed at a flow rate of about 1 sccm to about 150 sccm.

13. The method of any one of claims 1-9, wherein the substrate further comprises a patternedAttorney Docket No. LAM1P062WO-11987-1WO SiGe material underlying the contrast material.

14. The method of any one of claims 1-9, wherein the contrast material is a dielectric material.

15. The method of any one of claims 1-9, wherein the contrast material is selected from the group consisting of oxygen-containing material, nitrogen-containing material, and carbon- containing material.

16. The method of claim 15, wherein the contrast material is silicon oxide.

17. The method of any one of claims 1-9, wherein the plasma is generated remotely.

18. The method of any one of claims 1-9, wherein the substrate is exposed to the plasma for at least 120 seconds.

19. The method of any one of claims 1-9, wherein the substrate is exposed to the plasma for a duration sufficient to etch at least about 1000Å of polysilicon.

20. A method for processing substrates, the method comprising: providing a substrate having a germanium material over a contrast material; generating a plasma using a gas mixture to a process chamber housing the substrate, the gas mixture comprising a halogen-containing gas, a carbon-containing gas, and one or more additives; and exposing the substrate to the plasma to selectively etch the germanium material relative to the contrast material, wherein the one or more additives comprises a germanium-containing gas.

21. 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; a plasma generator; 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 oneAttorney Docket No. LAM1P062WO-11987-1WO processor to at least control the flow-control hardware to: cause generation of a plasma in the plasma generator using a gas mixture to a process chamber housing the substrate, the gas mixture comprising a halogen-containing gas, a carbon-containing gas, and a silicon-containing additive gas; and cause delivery of the plasma to the one or more process chambers to etch a substrate in the one or more process chambers using the plasma.

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