Deposition of silicon oxide in trenches

Abstract

Methods for forming void-free dielectric material in high aspect ratio trenches on a semiconductor substrate using an alternating deposition and inhibition process are provided.

Description

Attorney Docket No. 12306-1WO / LAM1P120WODEPOSITION OF SILICON OXIDE IN TRENCHES BACKGROUND

[0001] Semiconductor device fabrication involves deposition of materials into large areas, such as in gapfill applications for fabrication of memory devices, including 3D-NAND devices. As devices shrink, structures for fabricating efficient and multiple memory cells are used to maximize density of memory cells in a memory device. 3D-NAND technology addresses challenges associated with two-dimensional NAND technology by stacking memory cells vertically in layers.

[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 in a chamber, the method including: providing a semiconductor substrate having a feature to a chamber; and depositing dielectric material in the feature on the semiconductor substrate by: exposing the semiconductor substrate including a deposition precursor and a reactant and form the dielectric material, and introducing a passivation gas to the chamber and igniting a passivation plasma in a passivation gas ambient.

[0004] In various embodiments, exposing the semiconductor substrate includes introducing the deposition precursor and introducing the reactant.

[0005] In various embodiments, the method also includes purging after introducing the deposition precursor.

[0006] In various embodiments, the method also includes purging after introducing the reactant.

[0007] In various embodiments, the method also includes purging after introducing the passivation gas.

[0008] In various embodiments, the deposition precursor includes a silane. In some embodiments, the silane is an aminosilane. In some embodiments, the aminosilane is selected from the group consisting of bis(t-butylamino) silane and diisopropylaminosilane.

[0009] In various embodiments, the reactant is an oxidizer. In some embodiments, the oxidizer includes oxygen. In some embodiments, the oxygen is ignited in a plasma.

[0010] In various embodiments, the exposing of the semiconductor substrate is performed in a plasma free environment.Attorney Docket No. 12306-1WO / LAM1P120WO

[0011] In various embodiments, the passivation gas ambient inhibits deposition on one or more regions of the semiconductor substrate.

[0012] In various embodiments, depositing the dielectric material is performed in supercycles, where a supercycle includes performing a first cycle n times, the first cycle including the introducing of the deposition precursor (“A”) and the introducing the reactant (“B”) in n cycles, and performing the introducing of the passivation gas to the chamber and the igniting of the passivation plasma (“C”) every m cycles of performing the n cycles, where the supercycle is optionally given by the expression [(AB)nC]m.

[0013] In various embodiments, performing about 50 to about 1000 cycles of introducing the deposition precursor and introducing the reactant results in a deposition growth rate of about 1.25 Å / cycle.

[0014] In various embodiments, performing multiple m cycles of introducing the passivation gas every n cycles of alternating between introducing the deposition precursor and introducing the reactant results in a growth rate of about 0.1 Å / cycle or less, wherein the passivation gas includes NF3.

[0015] In various embodiments, m is about 2 to about 1000. In various embodiments, m is about 100 to about 150.

[0016] In various embodiments, n is about 1 to about 25. In various embodiments, n is about 5 to about 10.

[0017] In various embodiments, the passivation gas includes one or more gases selected from the group consisting of ammonia, nitrogen, argon, oxygen, nitrous oxide, and nitrogen trifluoride.

[0018] In various embodiments, the passivation gas is introduced for a duration sufficient to reach a saturation limit. In various embodiments, at the saturation limit, the dielectric material grows at a growth rate of about 0.13 Å / cycle.

[0019] In various embodiments, the passivation gas is introduced for a duration of about 0.5 seconds to about 1 second.

[0020] In various embodiments, plasma power during the igniting of the passivation plasma inhibits deposition of the dielectric material to a depth of about 10 nm to about 15 μm or about 3.8 μm.

[0021] In various embodiments, after depositing the dielectric material in the feature, the feature is void-free.

[0022] In various embodiments, the feature has an aspect ratio of about 20:1 to about 60:1. In various embodiments, the feature has an aspect ratio of about 20:1 to about 200:1.Attorney Docket No. 12306-1WO / LAM1P120WO

[0023] These and other aspects are described further below with reference to the drawings.BRIEF DESCRIPTION OF THE DRAWINGS

[0024] Figure 1 is a process flow diagram depicting operations for a method performed in accordance with certain disclosed embodiments.

[0025] Figure 2 is a timing sequence diagram showing an example of cycles in a method in accordance with certain disclosed embodiments.

[0026] Figure 3A shows a flow diagram of an example process for depositing a silicon oxide film using thermal ALD and PEALD according to some implementations.

[0027] Figure 3B shows a flow diagram of an example process for depositing a silicon oxide film using thermal ALD according to some implementations.

[0028] Figure 4 illustrates an example timing sequence diagram showing a thermal ALD cycle and a PEALD cycle for depositing a silicon oxide film according to some implementations.

[0029] Figure 5 illustrates an example timing sequence diagram showing thermal ALD cycles for depositing a silicon oxide film with co-flowed hydrogen and an oxygen-containing reactant according to some implementations.

[0030] Figure 6 illustrates an example timing sequence diagram showing thermal ALD cycles for depositing a silicon oxide film with low RF plasma power according to some implementations.

[0031] Figure 7 illustrates an example timing sequence diagram showing thermal ALD cycles for depositing a silicon oxide film with pulsing hydrogen flow during oxidation according to some implementations.

[0032] Figure 8 illustrates an example timing sequence diagram showing thermal ALD cycles for depositing a silicon oxide film with oxygen radicals generated from a remote plasma source during oxidation according to some implementations.

[0033] Figure 9 illustrates an example timing sequence diagram showing a thermal ALD cycle with co-flowed hydrogen and oxygen followed by a PEALD cycle with plasma oxidation / nitridation for depositing a silicon oxide film according to some implementations.

[0034] Figure 10 illustrates an example timing sequence diagram showing thermal CVD with co-flowed silicon-containing precursor, hydrogen, and oxygen-containing reactant for depositing a silicon oxide film according to some implementations.

[0035] Figure 11 is a schematic diagram of an example plasma processing apparatus for depositing a silicon oxide film using thermal ALD according to some implementations.

[0036] Figure 12 is a schematic diagram of an example process tool for performing the disclosed implementations.Attorney Docket No. 12306-1WO / LAM1P120WODETAILED DESCRIPTION

[0037] 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.

[0038] Semiconductor fabrication processes involve deposition of dielectric material. Dielectric material may include silicon oxide material in various embodiments. Dielectric material may be doped. In some embodiments, dielectric material may be doped silicon oxide. Examples of dielectric material include but are not limited to nitrogen-doped silicon oxide, carbon-doped silicon oxide, nitrogen-and-carbon-doped silicon oxide, phosphorous-doped silicon oxide, and boron-doped silicon oxide. Additional examples include silicon oxynitride, silicon oxycarbide, and silicon oxycarbonitride. Examples include SiON, SiOC, SiOCN, SiO(P), or SiO(B). Dielectric material may be deposited onto a variety of topography on a partially fabrication semiconductor device, such as features, gaps, and other areas. The term “feature” used herein refers to negative features, which have a feature opening. Example features include large areas, gaps, trenches, and other holes in a partially fabricated semiconductor device. Dielectric material may be deposited to form pillars, to fill high aspect ratio features, to cover large areas of a substrate, or fill other regions of a partially fabricated semiconductor device.

[0039] High aspect ratio features may include features having an aspect ratio of at least about 3:1 or at least about 1:5 or at least about 1:7 or at least about 1:10 or at least about 1:20 or at least about 1:50 or greater or at least about 1:200 or greater. In some embodiments, the aspect ratio is about 20:1 to about 60:1. High aspect ratio features may also be referred to as “vias.” Vias vary in depth and may have a depth of at least about 1 micron, or about 1 micron to about 50 microns. The depth varies and scales with the number of steps. Shallow vias may be defined as having a depth less than 3.0 microns, such as between about 1.5 microns and 3.0 microns. Deep vias may have a depth greater than 3.0 microns. The critical dimension of vias formed in the oxide may be between about 50 nm and about 500 nm. Vias may be etched using a dry etch process which may involve masking operations to pattern the oxide.

[0040] Current gapfill deposition in large areas may involve a sub-atmospheric chemical vapor deposition process, PECVD tetraethyl orthosilicate (TEOS) deposition process, or an atomic layer deposition (ALD) process. However, SACVD results in a tensile film that is prone to crackingAttorney Docket No. 12306-1WO / LAM1P120WOand may be unable to fill reentrant features. It may be challenging to use SACVD to fill features having an aspect ratio of more than about 6:1. Low density films tends to shrink due to thermal treatment and may have more tensile stress. It is generally believed that tensile stress is used for crack propagation and shrinkage provides a driving force for cracking. PECVD TEOS can fill features having an aspect ratio of up to about 0.8:1. While PECVD TEOS does not result in cracking when deposited with enough compressive stress, there are limitations to its application.

[0041] Provided herein are methods of depositing dielectric materials by thermal CVD in combination with passivation and / or inhibition operations. Certain disclosed embodiments involve performing thermal or plasma CVD with a thermal or plasma-based passivation operation. Passivation operations may be performed periodically. Certain disclosed embodiments involve cycling between CVD and passivation using a plasma. Certain disclosed embodiments can be used to fill an entire structure, partially fill a structure, deposit material after liner deposition, or at any other portion of a semiconductor substrate processing scheme. Periodic passivation in combination with thermal CVD may also be referred to as “dep-etch-dep,” where passivation constitutes “etch” and thermal CVD constitutes “dep,” although passivation may not necessarily involve etching. In some embodiments, passivation reduces nucleation rate or reduces deposition rate of material on a surface without etching the surface. In some embodiments, “passivation” is referred to as “inhibition” or passivating a surface inhibits deposition on the surface.

[0042] In some embodiments, the deposition growth rate is about 0.1 Å / cycle or less on a passivated surface or is below the threshold at which film thickness increase can be measured by certain spectral methods. In some embodiments, passivation is performed using a passivation gas such as ammonia or nitrogen trifluoride (NF3). In some embodiments, deposition growth rate overall is about 1.25 Å / cycle. In some embodiments, a passivation gas is introduced for a duration of about 0.5 seconds to about 10 seconds or about 0.5 seconds to about 1 second. In some embodiments, passivation plasma power is adjusted in such way to inhibit deposition of the dielectric material to a depth of about 10 nm to about 15 μm or about 3.8 μm. In some embodiments, deposition using a passivation gas using certain disclosed embodiments results in void-free fill.

[0043] In some embodiments, dielectric material deposited using certain disclosed embodiments have improved wet etch rate. Some films deposited using certain disclosed embodiments may be conformal and / or may have high step coverage. Conformality of films may be measured by the step coverage. “Step coverage” as used herein is calculated by dividing the average thickness of the deposited film on the sidewall by the average thickness of the deposited film at the top of theAttorney Docket No. 12306-1WO / LAM1P120WOfeature and multiplying it by 100 to obtain a percentage. Disclosed embodiments may deposit films having a step coverage of at least about 50%, or at least about 95%, or about 100%, or 100%. In some embodiments, features are completely filled using certain disclosed embodiments alone or in combination with thermal CVD without passivation.

[0044] Deposition may be performed in cycles. Multiple cycles within a cycle may be referred to as a “supercycle.” A supercycle may be given by the expression [(AB)nC]mwhich means an operation A and B is performed for n cycles, followed by performing C, whereby the full cycle of performing A and B for n cycles and C for after performing A and B for n cycles is performed for a total of m cycles. In some embodiments, n is about 1 to about 25, or about 5 to about 10. In certain embodiments, m is about 2 to about 1000, about 100 to about 150.

[0045] For example, A may be an operation for introducing a silicon-containing precursor, B may be an operation for introducing an oxidizer, which may be an oxygen-containing reactant (such as oxygen, nitrous oxide, carbon dioxide, sulfur oxide, hydrogen peroxide, ozone, and combinations thereof), and A and B may be performed in temporally separated alternating operations for n times, then after A and B are performed for n cycles, C, an inhibition or passivation operation, maybe performed, and then the overall supercycle is performed for m cycles. For example, if n is 3 and m is 2, then the supercycle involves the following:1. Introduce silicon-containing reactant2. Introduce an oxidizer3. Repeat 1 and 2 three (n) times4. Perform inhibition / passivation5. Repeat 3 and 4 two (m) times

[0046] Other variations of such examples may be used and additional operations may also be added (such as purging, densification, adjusting plasma power, adjusting pressure, and other operations as described herein).

[0047] Figure 1 provides a process flow diagram depicting operations that may be performed in accordance with certain disclosed embodiments. Operations in Figure 1 may be performed in any order and some operations may be omitted. In some embodiments, operations may be performed in cycles. Non-limiting examples of cycles include the following: (1) operation 106, then operation 108, then operation 112; (2) operation 108, then operation 106, then operation 112; and (3) operation 108, then operation 112, then operation 106. Additionally, operation 108 may be performed for longer durations after passivation and / or densification, without periodic passivation or densification.Attorney Docket No. 12306-1WO / LAM1P120WO

[0048] Process conditions can affect the deposition rate of the dielectric material. For example, chamber pressure may be modulated to affect the deposition rate of the dielectric material deposited into the large gap. For example, as chamber pressure increase, deposition rate of the dielectric material increases. Fast deposition may involve increasing the chamber pressure such that the chamber pressure may be at least about 10 Torr, or at least about 15 Torr, or at least about 20 Torr. Chamber pressure for operations 102-118 may be at least about 10 Torr, or at least about 15 Torr, or at least about 20 Torr. In some embodiments, chamber pressure is about 0.1 Torr to about 200 Torr or about 0.1 Torr to about 30 Torr. Chamber pressure may be modified between operations and may be different or the same in any operation in Figure 1, such as in operation 110. In some embodiments, chamber pressure is maintained constant throughout operations 102-118. In some embodiments, the chamber pressure is the same during operation 105 and 106.

[0049] In operation 102, a substrate is provided to a process chamber. The substrate may have a feature. The feature may be a large gap which may have an aspect ratio of at least about 5:1 and may have a depth of at least about 10 microns. The feature may have a feature opening of up to about 5000 nm, up to about 2500 nm, between about 70 nm and about 5 microns, or between about 70 nm and about 5 microns, or between about 70 nm and about 500 nm, or between about 5 nm to 500 nm, or between about 25 nm and about 300 nm, or about 2 microns, or at least about 2 microns.

[0050] In some embodiments, the feature may have an aspect ratio of at least about 2:1, at least about 3:1, at least about 4:1, at least about 6:1, at least about 10:1, or higher. A via, trench, or other recessed feature may be referred to as an unfilled feature or a feature.

[0051] In some embodiments, the substrate includes a partially fabricated structure, such as a partially fabricated 3D-NAND structure having a staircase topography. In some embodiments, the substrate includes a deep multi-layer stack with one or more features etched therein. In some embodiments, the substrate includes a top deck stack with a feature etched therein. In some embodiments, the substrate includes a dual deck stack with a feature etched therein. In some embodiments, the substrate includes a bottom deck stack with a feature etched therein.

[0052] Certain disclosed embodiments described herein refer a temporal processing mode, but certain disclosed embodiments can also be performed on a spatial ALD reactor as well. For example, in a spatial ALD reactor, each operation such as those described herein may be separated into zones of the reactor and the wafer is brought into each zone for a particular amount of time whereby the overall process sequence is performed in different zones of a reactor.

[0053] The substrate may be provided to a process chamber equipped to generate a plasma. The substrate may be provided to a process chamber without a plasma generator. The process chamberAttorney Docket No. 12306-1WO / LAM1P120WOmay include a heated pedestal for holding the semiconductor substrate and may include a showerhead for delivering one or more gases to a processing environment within the process chamber such that the processing environment is between the showerhead and the substrate on the pedestal during processing in the chamber. Further examples of features of the process chamber are described below with respect to Figures 3 and 4.

[0054] In an optional operation 104, an inert gas may be introduced to stabilize the temperature of the substrate prior to deposition. In various embodiments, the inert gas may be any of helium, argon, nitrogen, oxygen, nitrous oxide, hydrogen, and combinations thereof. The inert gas may be continuously flowed during all, any, most, or at least one of operations 106, 108, 110, 112, and 114. In some embodiments, the inert gas is continuously flowed throughout all of operations 106, 108, 110, 112, and 114. In some embodiments involving dep-etch-dep, the inert gas is also flowed during an etching operation. In some embodiments, the inert gas may also be used as a carrier gas to deliver gases to the process chamber. In some embodiments, the inert gas may also be used as a purge gas to remove excess byproducts or gases between particular operations. In some embodiments, the inert gas may include one or more gases that are used during operation 106, 108, 110, 112, and / or 114. In some embodiments, one or more gases used in the inert gas may be used in operation 106, 112, 114, and / or 116. In some embodiments, the inert gas is the same as one or more gases used in operation 106, 108, 110, 112, and / or 114. In some embodiments, the inert gas is different from one or more gases used in operation 106, 108, 110, 112, and / or 114.

[0055] In various embodiments, during operation 104, an inert gas is delivered and the pedestal temperature is set to a desired temperature to heat the substrate. The inert gas may be selected to facilitate heating of the substrate. For example, the pedestal may be set to a temperature to heat the substrate to a temperature or at least about 350°C, or at least about 450°C, or at least about 550°C, or at least about 650°C. Substrate temperature affects the deposition rate of the dielectric material. Deposition rates can vary depending on the relative gas flows. In one non-limiting example, at a temperature of about 550°C, little to no deposition may occur, while at a deposition temperature of about 650°C, a deposition rate of at least about 2 Å / s, or at least about 10 Å / s can be achieved, or at least about 20 Å / s can be achieved.

[0056] Deposition temperature may also be selected depending on the particular application, the particular gases selected, as well as the presence of other materials on the substrate so as not to degrade or damage materials on the substrate. For some logic applications, the substrate may withstand a temperature of up to about 650°C. For some memory applications, the substrate may withstand a temperature of up to about 650°C.Attorney Docket No. 12306-1WO / LAM1P120WO

[0057] In operation 106, a passivation gas and / or plasma is introduced to the process chamber. In some embodiments, a liner may be deposited in situ prior to igniting the passivation gas. In various embodiments, a passivation gas is used. In various embodiments, a passivation gas is ignited with a plasma and introduced to the chamber from a remote plasma chamber or generated in the chamber. The passivation gas composition depends on the material to be deposited. In some embodiments, for deposition of dielectric material, the passivation gas is a halogen-containing gas. In some embodiments, the passivation gas is a fluorine-containing gas. Non-limiting examples of gases that may be used for inhibiting deposition include nitrogen trifluoride (NF3) and nitrogen (N2). Plasma etching and / or passivation plasma operations may involve flowing NF3 and igniting a plasma. “Directional” or “preferential” as used herein may be defined as etching more material at or near the top of the feature than in the rest of the feature, such as inside or interior of the feature. Operation 106 may be used to preferentially passivate the feature openings. Operation 106 may be used to preferentially etch material at or near the feature openings. In some embodiments, preferential etching may be performed by etching material deposited at or near the feature openings, followed by depositing additional material, which results in a higher nucleation rate in the interior of the feature than at the feature openings. In some embodiments, preferential passivation may be performed by passivating surfaces using a passivation gas and / or plasma to reduce deposition and / or nucleation rate of material to be deposited at or near the feature openings, followed by depositing additional material, which results in a higher nucleation rate in the interior of the feature than at the feature openings.

[0058] Both gas flow and passivation exposure duration in operation 106 may be modulated to increase tunability of the deposited film. The greater the gas flow, the more likely the passivation gas may exhibit etching characteristics which can, in some embodiments, help open a feature opening or reduce gaps of a partially filled feature to allow bottom-up deposition. The flow rate may be modulated to deposit material to achieve fill in various features. For example, deposition of material at the bottom, top, or all of a feature of a multi-layer stack, or a dual deck substrate, may be modulated by varying the flow rate of the passivation gas during passivation. In some embodiments, for a 4-station chamber, the passivation gas may be flowed at a flow rate about 6000 seem or less, or about 5 seem to about 6 slm, or about 200 seem to about 5000 seem, or about 400 seem to about 1000 seem. In some embodiments, the passivation gas is diluted. For example, about 10 seem to about 30 seem of passivation gas may be diluted in a total flow of gases of about 120 slm to about 160 slm. The percentage of flow of the passivation gas in the total flow of all gases may be about 0.001% to about 0.003%.Attorney Docket No. 12306-1WO / LAM1P120WO

[0059] During operation 106, one or more other added gases may also be flowed. Example added gases include inert gases such as hydrogen, nitrogen, argon, helium, oxygen, and combinations thereof. In some embodiments, nitrogen may be flowed at a flow rate for a 4-station chamber of about 1000 seem to about 40 slm, or about 25 slm to about 45 slm. In some embodiments, hydrogen may be flowed at a flow rate for a 4-station chamber of about 0 slm to about 5 slm. In some embodiments, argon may be flowed at a flow rate for a 4-station chamber of about 25 slm to about 45 slm. In some embodiments, oxygen may be flowed at a flow rate for a 4-station chamber of about 0 slm to about 5 slm. In some embodiments, helium may be flowed at a flow rate for a 4-station chamber of about 0 slm to about 20 slm.

[0060] Pedestal temperature during operation 106 may be about 400°C to about 800°C. Pressure may be between about 0 Torr to about 100 Torr.

[0061] In various embodiments, a plasma is ignited during operation 106. The plasma is generated by igniting the passivation gas. The plasma may be generated remotely or in situ. In some embodiments, a combination of low frequency (LF) and high frequency (HF) plasma is used to generate a plasma for which one can modulate characteristics of the deposited film by affecting the level of passivation of a substrate surface during operation 106. The plasma may be generated with a radio frequency plasma power of about 0W to about 6000W for high frequency plasma, and about 0W to about 5000W for low frequency plasma. Plasma power may be about 250 W to about 10000 W, or about 5500 W. Operation 106 may be performed for a duration between about 0.1 seconds to about 500 seconds or more. The duration depends on the film being deposited, the deposition conditions and passivation process conditions, and the feature characteristics (e.g., feature width, feature depth, etc.) In general, longer exposures to plasma can be used in conjunction with longer deposition (e.g., longer durations of operation 108).

[0062] If HF and LF plasmas are used, then the HF power may be about 0W to about 10000W, or about 0W to about 6000W, at a frequency of 13.6 MHz and LF power may be about 0W to about 5000W, or about 0W to about 3000W, at a frequency of about 430 MHz. If a single-frequency plasma is used, HF is used at a frequency of 13.6 MHz with HF power up to about 6000W. Additional frequencies of plasmas that may be used include but are not limited to 50 KHz to 300 MHz, or 300 MHz to 30 GHz, or 915 MHz to 2.45 GHz, or 2,440 MHz to 2,470 MHz, or 2 MHz, or 13.56 MHz, or 27 MHz.

[0063] Other tunable characteristics of operation 106 include but are not limited to chamber pressure, pedestal temperature, gas flow dilution amount, plasma power, and plasma frequency. Passivation in operation 106 may be referred to as an “etch” operation in a dep-etch-dep processAttorney Docket No. 12306-1WO / LAM1P120WOwhere dep refers to operation 108. Variations of dep-etch-dep may be used, such as performing alternating cycles of deposition and passivation; performing cycles including deposition, then passivation, then deposition, then passivation, then deposition followed by only deposition without passivation; and performing deposition, followed by multiple cycles of alternating cycles of passivation and deposition. Variations of dep-etch-dep may be used to reduce overhang caused by deposition or by the underlying structure. Dep-etch-dep may be used for depositing material into reentrant features. Dep-etch-dep may be used to deposit materials into features to slope the sidewalls to reduce reentrancy. In some embodiments, operation 106 is omitted.

[0064] In some embodiments, after operation 106, a purge operation (not shown) is performed. In some embodiments, before operation 108, a purge operation (not shown) is performed.

[0065] In operation 108, the substrate is exposed to a deposition precursor and reactant to deposit a dielectric material on the substrate surface. In operation 108, a deposition precursor and reactant may be flowed simultaneously and continuously to the process chamber housing the substrate. The surface on the substrate that is exposed to the deposition precursor and reactant depends on the particular application of certain disclosed embodiments. In some embodiments, the surface includes silicon, poly-silicon, amorphous silicon, silicon dioxide, silicon nitride, silicon carboxide, silicon carbonitride, other materials, and combinations thereof.

[0066] The deposition precursor may be any Group IV-containing precursor, such as a silicon-containing precursor. In some embodiments, the deposition precursor may be a germanium-containing precursor. In some embodiments, hydrogen gas is co-flowed to the chamber in addition to the deposition precursor and reactant. In various embodiments, the deposition precursor is an aminosilane. Example silicon-containing precursors are described elsewhere herein. Examples include but are not limited to bis(t-butylaminosilane) (BTBAS) and diisopropylsilane.

[0067] As noted above, in some embodiments, the silicon-containing precursor may be an aminosilane, with hydrogen atoms, such as bisdiethylaminosilane, diisopropylaminosilane, tertbutylamino silane (BTBAS), or tris(dimethylamino)silane (3DMAS). Aminosilane precursors include, but are not limited to, the following: Hx-Si-(NR)ywhere x = 1-3, x + y = 4 and R is an organic or hydride group.

[0068] In some embodiments, a halogen-containing silane may be used such that the silane includes at least one hydrogen atom. Such a silane may have a chemical formula of SiXaHywhere y > 1. For example, dichloro silane (H2SiCl2) may be used in some embodiments.

[0069] The reactant used to react with the deposition precursor is selected based on material to be deposited in the large gaps and depending on the deposition precursor selected. For example,Attorney Docket No. 12306-1WO / LAM1P120WOfor deposition of silicon oxide, one option is to use a silicon-containing precursor as the deposition precursor and to use an oxidant or an oxidizing agent as the reactant. Example oxidizing agents include but are not limited to oxygen, ozone, peroxides, nitric oxide, nitrous oxide, water, and combinations thereof. The reactant gas flow for a 4-station chamber may be about 200 seem to about 5000 seem. Example flow rates for the first reactant may be between about 200-500 seem, and example dose times for the first reactant may be between about 0.2-2 seconds. In some cases, a carrier gas may be provided at a flow between about 1000-2000 seem, for example about 1500 seem.

[0070] Both the deposition precursor and reactant may be simultaneously delivered to the process chamber to generate a processing environment in the chamber that includes both the deposition precursor and the reactant. In some embodiments, the deposition precursor and reactant flow are turned on at different times, but there is at least some duration for which both flow of the deposition precursor and flow of the reactant are on at the same time, thereby creating a processing environment in the process chamber that includes both the deposition precursor and the reactant. In some embodiments, delivering the precursor and reactant involves turning on the flow of the deposition precursor and turning on the flow of the reactant at the same time, or about at the same time, or at a time such that both flows are on during at least a duration of time. These gases may be delivered to a showerhead which then delivers the gases to the processing environment in the process chamber, where the gases can react to deposit a film on the semiconductor substrate. In some embodiments, delivery of each process gas may be delivered using different lines to the showerhead so as to avoid reacting before reaching the processing environment.

[0071] Operation 1108 may be performed for any suitable duration. The duration of operation 1108 as described herein means the duration in which the substrate is exposed to the processing environment that includes both the deposition precursor and the reactant. That is, in some embodiments, the duration of keeping the flow of the deposition precursor on and the duration of keeping the flow of the reactant on may be different. In some embodiments, the flow of the deposition precursor and the flow of the reactant are on for the same amount of time.

[0072] In some embodiments, the duration of operation 108 may be about 1 second, or at least about 1 second. The deposition rate of operation 108 depends on the flow of the reactant gases as well as the particular precursor and reactant gases chosen and process conditions under which the gases are delivered to the substrate. In some embodiments, the deposition rate may be about 3 Å / s to about 60 Å / s, or at least about 50 Å / s.Attorney Docket No. 12306-1WO / LAM1P120WO

[0073] The pressure of the process chamber may be about 9 Torr to about 40 Torr, or at least about 30 Torr. If and when a pressure within the reaction chamber exceeds a limit of a high-pressure limit switch during deposition, the high-pressure limit switch trips and sends a signal to a controller to cause the controller to stop or restrict the flow of reactants into the reaction chamber. In various embodiments, the high-pressure limit switch may trip at a pressure greater than 10 Torr and equal to or less than about 40 Torr, in some cases equal to or less than about 30 Torr, or equal to or less than about 20 Torr.

[0074] The gas flow rates depend on the gases being used. In some embodiments, the deposition precursor is flowed at a range between about 1000 seem and about 3000 seem, and the oxidant is flowed at a range between about 2000 seem and about 5000 seem. In some embodiments, H2is co-flowed with the oxidant at a flow rate of between 0 sccm and about 5000 sccm. Where H2is H2not co-flowed, flow rate of H2is 0 sccm. As noted previously, the inert gas may be continuously flowed during operation 1006. In some embodiments, the inert gas is flowed at a flow rate between about 2000 seem and about 12000 seem.

[0075] In features that include constrictions or are otherwise susceptible to pinch-off, operation 1006 can be performed at least until the feature is pinched off in some embodiments. Features having different sizes may pinch off at different times. In conformal deposition, deposition starts from each surface and progresses with growth generally orthogonal to the surface. Dielectric growth in features starts from each sidewall and progresses until the growth pinches off the feature.

[0076] In various embodiments, operation 108 may be performed until the opening of the feature is closed. In some embodiments, a seam may be formed at or near the opening of the feature. For the purposes of this description, “near the opening” is defined as an approximate position or an area within the feature (i.e., along the side wall of the feature) corresponding to about 0% to about 20% of the feature depth measured from the field region. In certain embodiments, the area near the opening corresponds to the area at the opening. Further, “inside the feature” or the “interior of the feature” is defined as an approximate position or an area within the feature corresponding to about 20% to about 60% of the feature depth measured from the field region on the top of the feature. Typically, when values for certain parameters (e.g., thicknesses) are specified “near the opening” or “inside the feature”, these values represent a measurement or an average of multiple measurements taken within these positions / areas.

[0077] In operation 110, the process chamber is optionally purged. Purging may be performed when the flows of the deposition precursor and reactant(s) in operation 110 are reduced and / or turned off. Purging may be performed depending on plasma process conditions used forAttorney Docket No. 12306-1WO / LAM1P120WOsubsequent operations. In some embodiments, purge time is longer than the duration between operation 112 described below and a repeated operation of 108. Typically, the precursor flow is turned off or diverted during the purge, and only purge gas flows. Purging the chamber may involve flowing a purge gas or a sweep gas, which may be a carrier gas used in other operations or may be a different gas. In some embodiments, purging may involve evacuating the chamber. Example purge gases include argon, nitrogen, hydrogen, helium, and combinations thereof. In some embodiments, operation 110 may include one or more evacuation subphases for evacuating the process chamber. Alternatively, it will be appreciated that operation 110 may be omitted in some embodiments. Operation 110 may have any suitable duration, such as between about 0 seconds and about 60 seconds, for example about 0.01 seconds. In some embodiments, increasing a flow rate of one or more purge gases may decrease the duration of operation 110. For example, a purge gas flow rate may be adjusted according to various reactant thermodynamic characteristics and / or geometric characteristics of the process chamber and / or process chamber plumbing for modifying the duration of operation 110. In one non-limiting example, the duration of a purge phase may be adjusted by modulating purge gas flow rate. This may reduce deposition cycle time, which may improve substrate throughput. In some embodiments, operations 106-110 are optionally repeated in several cycles.

[0078] In an optional operation 112, densification is performed. In some embodiments, densification is performed by introducing a plasma generated from an inert gas. In some embodiments, densification is performed by introducing a plasma generated from gas that is not an inert gas. A plasma may be generated using a noble gas, oxidizing gas, or other gas. Nonlimiting examples of gases include argon, nitrogen, hydrogen, oxygen, nitrous oxide, helium, and combinations thereof. The plasma may be generated in situ, or within the chamber, in a processing environment above the substrate. In some embodiments, the plasma is generated in a processing environment between the substrate and the showerhead of a process chamber. The plasma is generated under process conditions selected to modulate features of the film deposited in operation 112. In some embodiments, a capacitively coupled plasma is used to generate the plasma. In some embodiments, an inductively coupled plasma is used to generate the plasma.

[0079] For example, in some embodiments, a high-pressure radio frequency plasma is generated so as to form a film that has uniform within wafer wet etch rate. A high pressure may be a pressure of at least about 10 Torr, or about 10 Torr to about 50 Torr, or about 10 Torr to about 35 Torr, or about 10 Torr to about 25 Torr.

[0080] In some embodiments, a low-pressure radio frequency plasma is generated to modulateAttorney Docket No. 12306-1WO / LAM1P120WOthe deposited material to make it dome-shaped with a particular within wafer wet etch rate. A dome- shaped layer may include a convex region in at or near the center of the wafer. A low pressure may be a pressure of less than about 10 Torr, or about 2 Torr to about 10 Torr.

[0081] The within-wafer thickness non-uniformity of a film and etch rate can be tuned by modulating the pressure. In one non-limiting example, a dome-shaped film can be changed to a dish-shaped film by modulating pressure, such as using a pressure of about 6 Torr, a flat film at about 18 Torr, and a dish shaped film at a pressure of about 20 Torr. Specifically, deposition at about 10-40 Torr has been shown to produce silicon oxide with a relatively low, relatively uniform wet etch rate (as compared to silicon oxide deposited at < 10 Torr). Further, deposition at higher pressure allows for increased throughput. Typically, techniques that produce lower wet etch rate also have the effect of decreasing throughput. It was unexpected to find a technique that both lowered the wet etch rate of the film and provided for increased throughput. In various cases, at the time the reaction is initiated, the pressure in the reaction chamber may be at least about 10 Torr, at least about 12 Torr, at least about 15 Torr, at least about 20 Torr, at least about 25 Torr, or at least about 30 Torr. The upper limit on the chamber pressure at the time of initiating the reaction depends on the particular high-pressure limit switch that is used.

[0082] In some embodiments, a combination of low frequency (LF) and high frequency (HF) plasma is used to generate a plasma for which one can modulate whether the resulting film has a dome or dish shape. The plasma may be generated with a radio frequency plasma power of about 1000 W to about 10000 W, or about 5500 W. Duration of operation 112 depends on the application for which certain disclosed embodiments are used. In some embodiments, operation 112 may be performed for a duration about 0.1 seconds to about 500 seconds or about 1 second to about 3 seconds.

[0083] If HF and LF plasmas are used, then the HF power may be about 0W to about 10000 W, at a frequency of 13.6 MHz and LF power may be about 0W to about 3000W, at a frequency of about 430 MHz. If a single-frequency plasma is used, HF is used at a frequency of 13.6 MHz with HF power up to about 6000W.

[0084] Temperature during this operation may be the same as during operation 1106 and / or operation 108 or both. In some embodiments, temperature during operation 112 is about 550°C to about 650°C, or about 650°C.

[0085] In operation 114, the chamber is optionally purged. Purge gases and purge conditions may be any of those described above with respect to operation 110.

[0086] In operation 118, it is determined whether the film has been deposited as desired, whetherAttorney Docket No. 12306-1WO / LAM1P120WOto the desired thickness or a desired film property, such as wet etch rate, concavity, uniformity, or conformality. If not, many variations of operations 106-114 may be performed. Although certain optionally repeated operations are depicted in Figure 1, it will be understood that any variation of repeating one or more of operations 106-114 may be used. In some embodiments, operations 108-118 are repeated in cycles. In some embodiments, operations 106-114 are repeated in cycles. Operations may be repeated for at least about 2 cycles or more, or about 2 cycles to about 2000 cycles, or about 100 cycles and about 1500 cycles.

[0087] In one example of repeated cycles, operation 108 may be performed for about x seconds and operation 112 may be performed for about y seconds, where x and y depend on the particular properties desired for the resulting film. In some embodiments, x is about 0.1 seconds to about 10 seconds. In some embodiments, y is about 0.1 seconds to about 3 seconds. In some embodiments, x is about 0.1 seconds to about 10 seconds, and y is about 0.1 seconds to about 3 seconds. In some embodiments, x and y may each be at least about 1 second. In some embodiments, x may be about 1 second and y may be about 3 seconds. In some cases, continuous deposition may be used whereby y=0. In continuous deposition, operations 110 and 114 are not performed. In some embodiments, operations 110 and 114 are not performed in one or more repeated cycles. Film properties can be tuned by adjusting ratio of duration of operation 106 to duration of operation 108 to duration of operation 112. That is, film properties can be tuned by adjusting ratio of passivation time to deposition time to densification time. In some embodiments, if a deposition cycle includes an increased duration of operation 108, the duration of operation 112 may likewise be increased. In some embodiments, operations 104-118 are performed without breaking vacuum. In some embodiments, operations 104-118 are performed in the same chamber.

[0088] In various embodiments, shifting between operation 106, operation 108, and operation 112 may be performed by fast switching. Fast switching may be performed by utilizing particular valving and / or plasma turn on techniques and components. In some embodiments, fast switching valves are operable to quickly open and close to without pressure surges or flow instabilities of gases. Fast switching valves can open and close within 100 milliseconds, or within 80 milliseconds, or within 60 milliseconds, or within 40 milliseconds, or within 30 milliseconds, or within 20 milliseconds or faster. Fast switching vales may be operably connected to receive signals from a controller to open or close. In various embodiments, switching is performed quickly with minimal pressure changes between operations. In some embodiments, two or more of operations 104-114 are performed in the same chamber, or in the same station. Switching may be performed by using multi-plenum showerheads, whereby one or more source gases are separatelyAttorney Docket No. 12306-1WO / LAM1P120WOdistributed to the showerhead before being delivered to the process chamber or station housing the substrate. In some embodiments, a volume of a gas composition in a confined region within a vacuum chamber, such as a plasma confinement zone, can be replaced (i.e., flushed out) by another gas composition introduced into the vacuum chamber within a short period of time. Such gas replacement can be achieved in less than about Is, more preferably within less than about 200 ms, by providing valves having a fast switching capability in the gas distribution system. In various embodiments, the gas switching section (not shown) includes a fast switching valve arrangement configured to receive signals to (iii) open a first group of fast switching valves and close a second group of fast switching valves to supply a first process gas to the inner and outer zones while a second process gas is diverted to the bypass line via a first group of the first gas passages, and (iv) to close the first group of fast switching valves and open the second group of fast switching valves to switch the first and second process gas flows to supply the second process gas to the inner and outer zones while the first process gas is diverted to the bypass line via a second group of the first gas passages. In some embodiments, two or more operations 104-114 are performed such that a first process gas is introduced into the process chamber while diverting a second (and optionally third, fourth, or more) process gas to one or more bypass-lines. The first process gas is then ignited to generate a first plasma. In some cases, this first plasma may be a passivation plasma, such as an NF3plasma. In some embodiments, the first process gas is introduced and a plasma is not generated in this operation (such as if the first process gas is a precursor or reactant used for thermal or plasma-free deposition). The flows of the first and second process gases are switched so that the second process gas is supplied into the process chamber while diverting the first process gas to the by-pass line. For example, this second process gas may be a thermal deposition precursor gas. In some embodiments, the second process gas may be a densification gas. The first process gas may be replaced in a confinement zone of the process chamber by the second process gas within a period of less than about 1 s, or less than about 200 ms. In some embodiments, the second process gas is ignited to produce a second plasma, such as for densification or passivation or inhibition. In some embodiments, the second process gas is not ignited and is flowed thermally, such as for thermal deposition. The flows of the first and second process gases may be switched so that the first process gas is supplied into the plasma processing chamber while diverting the second process gas to the by-pass line, with the second process gas being substantially replaced in a confinement zone of the process chamber by the first process gas within a period of less than about 1 s, or less than about 200 ms. In some embodiments, flows of second and third process gases may be switched. Any number of process gas flows may be switched in a similar manner asAttorney Docket No. 12306-1WO / LAM1P120WOdescribed in the above example. Gas delivery systems designed for fast gas switching are disclosed in commonly-owned U. S. Pat. Nos. 7,459,100; 7,708,859; and 8,088,248; and U. S. Patent Publication No. 2007 / 0066038, the disclosures of which are hereby incorporated by reference.

[0089] Temperature of components of the chamber can be modulated so as to selectively deposit material on the substrate without substantially depositing material on components of the chamber. For example, temperature of components in the process chamber other than the pedestal may be set at a temperature of less than about 300°C, and deposition using CVD and densification as described herein achieves deposition on the substrate on the pedestal substantially faster than deposition of material on surfaces of the process chamber. Where the temperature of the components is less than about 550°C, film accumulation does not occur on the components. This selectivity results in no flaking at higher accumulation when material accumulates on surfaces of the process chamber from processing numerous wafers in the same chamber, which allows the process chamber to be used until the accumulation on non-pedestal components of the chamber has a tolerable thickness. In general, process chambers can withstand more than 3 times the accumulation caused by atomic layer deposition processes. Overall, this is highly advantageous so as to reduce the cost of ownership and reduce the frequency of chamber cleaning.

[0090] In some embodiments, the pedestal is made of aluminum or aluminum nitride. In some embodiments, the pedestal is ceramic. In some cases, a tool may be retrofitted by replacing the pedestal with a ceramic pedestal and heaters and cooling components may be modified to be able to cool other components while maintaining a pedestal temperature of greater than about 550 °C or between about 550°C and about 650°C. In some embodiments, the showerhead is made of aluminum.

[0091] Figure 2 shows a timing scheme diagram showing one example of a method performed in accordance with certain disclosed embodiments. Although a specific order of operations is shown, it will be understood that operations may be performed in any order. Process 200 includes a first cycle 201a and a second cycle 201b. Inert gas shown in Figure 2 can, depending on the gas composition, refer to one or more of an inert gas as carrier gas, inert gas, dilution gas, or other gas used during various operations. The inert gas may be Ar or He. In lieu of the inert gas, other gases that may be used include H2, N2, 02, or combinations thereof. Although the “on” phase shows constant amounts, it will be understood that an “on” phase may have different levels or amounts used in each phase. Although not shown, in various embodiments, a purging operation may be performed between densification phase 212A and passivation phase 206 A and densification phaseAttorney Docket No. 12306-1WO / LAM1P120WO212B and passivation phase 206B.

[0092] First cycle 201A includes four phases - deposition phase 208A, optional densification phase 212A, passivation phase 206A, and purge phase 210A. Deposition phase 208A may correspond to operation 108 of Figure 1. During deposition phase 208 A, the inert gas flow continues to be on, the deposition precursor flow is turned on, and the reactant flow is turned on, while passivation gas flow is off and plasma is off. In this example, the deposition precursor flow is turned on at the start of the reactant flow, but it will be understood that in some embodiments, the deposition precursor flow may be turned on shortly before the reactant flow, or the reactant flow may be turned on shortly before the deposition precursor flow.

[0093] Densification phase 212A may correspond to operation 112 of Figure 1. During densification phase 212A, the deposition precursor flow is off and the plasma is turned on while reactant flow is off. In some cases, an inert gas such as Ar may also be flowed during densification phase 212A as shown as an example inert gas. Note inert gas herein may refer to either carrier gases and / or gases flowed during plasma exposure phase.

[0094] Passivation phase 206A may correspond to operation 106 of Figure 1. Curing passivation phase 206A, the deposition precursor flow is off, the reactant flow is off, the passivation gas flow is on, and plasma is turned on. The inert gas may continue to flow.

[0095] Purge phase 210A may correspond to operation 110 of Figure 1, whereby inert gas flow may continue to be on while deposition precursor gas flow is turned off, reactant gas flow is off, passivation gas flow is off, and the plasma is turned off.

[0096] In this example, it is determined in operation 118 of Figure 1 that the film has not been sufficiently deposited and the cycle of operations is repeated.

[0097] Second cycle 201B includes four phases - deposition phase 208B, densification phase 212B, passivation phase 206B, and purge phase 210B. Deposition phase 208B may correspond to a repeated operation 108 of Figure 1. During deposition phase 208B, the inert gas flow continues to be on, the deposition precursor flow is turned on, and the reactant flow is turned on, while passivation gas flow is off and plasma is off. In this example, the deposition precursor flow is turned on at the start of the reactant flow, but it will be understood that in some embodiments, the deposition precursor flow may be turned on shortly before the reactant flow, or the reactant flow may be turned on shortly before the deposition precursor flow.

[0098] Densification phase 212B may correspond to a repeated operation 112 of Figure 1. During densification phase 212B, the deposition precursor flow is off and the plasma is turned on while reactant flow is off. In some cases, an inert gas such as Ar may also be flowed duringAttorney Docket No. 12306-1WO / LAM1P120WOdensification phase 212B as shown as an example inert gas. Note inert gas herein may refer to either carrier gases and / or gases flowed during plasma exposure phase.

[0099] Passivation phase 206B may correspond to operation 106 of Figure 1. Curing passivation phase 206B, the deposition precursor flow is off, the reactant flow is off, the passivation gas flow is on, and plasma is turned on. The inert gas may continue to flow.

[0100] Purge phase 210B may correspond to operation 110 of Figure 1, whereby inert gas flow may continue to be on while deposition precursor gas flow is turned off, reactant gas flow is off, passivation gas flow is off, and the plasma is turned off.

[0101] Figure 3A shows a flow diagram of an example process for depositing a silicon oxide film using thermal (or plasma- free) ALD and PEALD according to some implementations. As used herein, the term “silicon oxide film” may refer to undoped silicon oxide (e.g., SiOx) films as well as doped silicon oxide (e.g., SiOxNy) films. The operations in a process 300a of Figure 3A may be performed in different orders and / or with different, fewer, or additional operations. The operations in the process 300a may be performed by a plasma processing apparatus shown in Figure 11 and / or the process tool shown in Figure 12. In some implementations, the operations of the process 300a may be implemented, at least in part, according to software stored in one or more non-transitory computer readable media. Figures 3 A and 4 may be described together below.

[0102] At block 310 of the process 300a, a substrate is provided in a plasma processing chamber. The plasma processing chamber may be a single wafer plasma reactor configured to perform thermal ALD processes, PEALD processes, or combinations thereof. The substrate may be a silicon substrate, such as a 200-mm, 300-mm, or 450-mm substrate, including substrates having one or more layers of material, such as dielectric, conducting, or semiconducting material. In some implementations, the substrate on which silicon oxide films are deposited may include a material that is sensitive to plasma damage / oxidation by PEALD. For example, the material may include but is not limited to silicon (Si), germanium (Ge), silicon-germanium (Si-Ge), carbon (C), and metals, where example metals include molybdenum (Mo), tungsten (W), copper (Cu), cobalt (Co), ruthenium (Ru), rhodium (Rh), iridium (Ir), titanium (Ti), tantalum (Ta), titanium nitride (TiN), tantalum nitride (TaN), and combinations thereof. The substrate on which the silicon oxide films are deposited may include one or more features, which may refer to non-planar structures of a substrate. For example, the one or more features may include vertical structures such as fins or pillars. In some implementations, the one or more features may include an under-layer such as a barrier layer, liner layer, or adhesion layer.

[0103] At block 320 of the process 300a, a first silicon oxide layer is deposited via thermalAttorney Docket No. 12306-1WO / LAM1P120WO(plasma-free) ALD in the plasma processing chamber. Any suitable number of thermal ALD cycles may be performed at block 320 prior to performing PEALD. Each thermal ALD cycle may be broken down into a series of phases, including a dose phase, a first purge phase, a thermal oxidation phase, and a second purge phase. It will be understood that one or both of the first purge phase and the second purge phase may be optionally performed in each thermal ALD cycle. Depositing a thin film via thermal ALD includes: heating the substrate to an elevated temperature, exposing the substrate to a precursor to adsorb onto a surface of the substrate, and exposing the substrate to one or more gas reactants to drive a surface reaction between the one or more gas reactants and the precursor, thereby forming the thin film via thermal ALD. Specifically, depositing the first silicon oxide layer via thermal ALD includes: heating the substrate to an elevated temperature, exposing the substrate to a silicon-containing precursor to adsorb onto a surface of the substrate, and exposing the substrate to an oxygen-containing reactant or an oxidizer to drive a reaction between the oxygen-containing reactant or the oxidizer and the silicon-containing precursor, thereby forming the first silicon oxide layer via thermal ALD.

[0104] Figure 4 illustrates an example timing sequence diagram showing a thermal ALD cycle and a PEALD cycle for depositing a silicon oxide film according to some implementations. Figure 4 shows phases in a thermal ALD cycle 410A followed by phases in a PEALD cycle 410B. However, it will be understood that phases in the PEALD cycle 410B may be followed by phases in the thermal ALD cycle 410A. Figure 4 shows various process parameters, such as carrier gas or purge gas flow, plasma, silicon-containing precursor flow, and oxygen-containing reactant or oxidizer flow. The lines indicate when the flow is turned on / off, or when plasma is turned on / off. As shown in Figure 4, during the thermal ALD cycle 410A, the substrate is exposed to a silicon-containing precursor during a dose phase 457A. In some implementations, the silicon-containing precursor includes a silane, such as an aminosilane. 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 may include bis(tert-butylamino)silane (BTBAS), N-(diethylaminosilyl)-N-ethylethanamine (SAM-24), tris(dimethylamino)silane (3DMAS), tetrakis(dimethylamino)silane (4DMAS), and diisopropylamino silane. During the dose phase 457A, plasma is turned off, oxygen-containing reactant flow is turned off, and a carrier gas may be flowed towards the substrate. However, it will be understood that the substrate may be heated to an elevated temperature during the dose phase 457A. In some implementations, the substrate may be exposed to the silicon-containing precursor during the dose phase 457A for a duration between about 0.1 seconds and about 60 seconds, between about 0.2 seconds and about 6 seconds,Attorney Docket No. 12306-1WO / LAM1P120WOor between about 0.3 seconds and about 2 seconds, such as about 0.75 seconds, depending on the flow rate and substrate surface area. In some implementations, the silicon-containing precursor adsorbs onto the surface of the substrate in a self-limiting manner such that once active sites are occupied by the silicon-containing precursor, little or no additional silicon-containing precursor will be adsorbed on the surface of the substrate. When the silicon-containing precursor adsorbs onto active sites of the surface of the substrate, a thin layer of the silicon-containing precursor forms on the surface. Unlike a CVD or CVD-like process, the silicon-containing precursor does not decompose to form a silicon layer.

[0105] In some implementations, the plasma processing chamber may be purged between operations of exposing the substrate to the silicon-containing precursor and exposing the substrate to the oxidizer or oxygen-containing reactant. In addition, the plasma processing chamber may be purged after exposing the substrate to the oxidizer or oxygen-containing reactant. Purging may involve a sweep gas, which may be a carrier gas used in other operations / phases or a different gas. Purging may remove excess species in the vapor phase that did not adsorb or react on the surface of the substrate. As shown in Figure 4, the plasma processing chamber undergoes purging during purge phases 459A and 463A. Silicon-containing precursor flow is turned off, plasma is turned off, and oxidizer or oxygen-containing reactant flow is turned off. However, the carrier gas may continue to flow towards the substrate. In some implementations, the purge phases 459A and 463A may each include one or more evacuation sub-phases for evacuating the plasma processing chamber. Alternatively, it will be appreciated that each of the purge phases 459A and 463A may be omitted in some implementations. Each purge phase 459A and 463A may have a suitable duration, such as between about 0 seconds and about 60 seconds or between about 0.01 seconds and about 6 seconds.

[0106] As shown in Figure 4, during the thermal ALD cycle 410A, the substrate may be exposed to the oxidizer or oxygen-containing reactant and the elevated temperature during a thermal oxidation phase 461 A. Process conditions during the thermal oxidation phase 461 A may be tuned to promote deposition of the first silicon oxide layer by thermal ALD at an appreciable or adequate deposition rate. For example, the deposition rate of the first silicon oxide layer by thermal ALD can be equal to or greater than about 0.2 Å / cycle, equal to or greater than about 0.3 Å / cycle, equal to or greater than about 0.5 Å / cycle, or equal to or greater than about 0.75 Å / cycle. This may be an appreciable deposition rate when the first silicon oxide layer is used to protect a surface against oxidation / damage.

[0107] In some implementations, the oxidizer or oxygen-containing reactant can include anAttorney Docket No. 12306-1WO / LAM1P120WOoxidant gas such as oxygen (O2), ozone (O3), hydrogen peroxide (H2O2), water (H2O), sulfur oxide (SO3), carbon dioxide (CO2), or combinations thereof. In some implementations, exposing the substrate to the oxidizer or oxygen-containing reactant includes flowing hydrogen and oxygen to the substrate to react in situ within the plasma processing chamber to cause an exothermic reaction. In some implementations, it is believed that water may be formed in situ by a reaction between the hydrogen and oxygen. Water vapor is not flowed into the plasma processing chamber as a starting reactant, but may or may not be formed in situ within the plasma processing chamber. As used herein, flowing “hydrogen” refers to flowing molecular hydrogen and flowing “oxygen” refers to flowing molecular oxygen. The hydrogen and oxygen may be flowed towards the substrate in the plasma processing chamber simultaneously. The exothermic reaction involving hydrogen and oxygen may release energy for driving a surface reaction with the adsorbed silicon-containing precursor to form the first silicon oxide layer. A flow rate of hydrogen during the thermal oxidation phase 461 A may be between about 0 slm and about 20 slm, between about 1 slm and about 10 slm, between about 2 slm and about 6 slm, greater than about 3 slm, such as about 4 slm. A flow rate of oxygen during the thermal oxidation phase 461 A may be between about 0.5 slm and about 20 slm, between about 1 slm and about 10 slm, or between about 2 slm and about 8 slm, such as about 5 slm. A flow rate ratio between hydrogen and oxygen may be equal to or less than about 1.2:1, such as between about 0.5:1 and about 1.2:1.

[0108] The substrate may be exposed to the oxidizer or oxy gen-containing reactant and exposed to an elevated temperature for a suitable duration during the thermal oxidation phase 461 A. Ordinarily, thermal oxidation in furnace or batch reactors in thermal ALD / CVD chambers may last at least 10 seconds to obtain an appreciable deposition rate, particularly for silicon oxide films. However, the duration of thermal oxidation in the plasma processing chamber of the present disclosure may be less than about 10 seconds. In some implementations, the duration of thermal oxidation in the thermal oxidation phase 361 A may be between about 0.1 seconds and about 6 seconds, between about 0.2 seconds and about 4 seconds, or between about 0.5 seconds and about 3 seconds.

[0109] The substrate may be exposed to an elevated temperature during the thermal oxidation phase 461 A and / or prior to the thermal oxidation phase 461 A. The substrate may be operating at the elevated temperature simultaneously with exposing the substrate to the oxidizer or oxygencontaining reactant. In some implementations, the elevated temperature may be between about 500°C and about 750°C, between about 500°C and about 700°C, between about 500°C and about 650°C, or between about 550°C and about 650°C. Ordinarily, temperatures in furnace or batchAttorney Docket No. 12306-1WO / LAM1P120WOreactors in thermal ALD / CVD chambers may be greater than 700°C in driving surface reactions for deposition of silicon oxide films. However, temperatures may be equal to or less than about 700°C in driving surface reactions for deposition of silicon oxide films by thermal ALD in a plasma processing chamber of the present disclosure. Furthermore, many conventional plasma processing chambers for PEALD do not operate at temperatures equal to or greater than about 400°C. Deposition by thermal ALD in the plasma processing chamber at the elevated temperature may be equal to or greater than about 0.2 Å / cycle.

[0110] The substrate may be exposed to increased chamber pressure during the thermal oxidation phase 461 A. Increased chamber pressure may increase deposition rate and drive the surface reaction between the silicon-containing precursor and the oxidizer or oxygen-containing reactant. In some implementations, the chamber pressure of the plasma processing chamber may be equal to or greater than about 7 Torr, equal to or greater than about 10 Torr, equal to or greater than about 12 Torr, or between about 10 Torr and about 20 Torr. Ordinarily, a pressure in a furnace or batch reactor in thermal ALD / CVD chambers may be less than about 5 Torr. However, chamber pressure may be equal to or greater than about 5 Torr for deposition by thermal ALD in the plasma processing chamber of the present disclosure. In addition, some conventional plasma processing chambers for PEALD do not typically operate at pressures equal to or greater than 5 Torr.

[0111] The process conditions to achieve an appreciable deposition rate may be different during the thermal oxidation phase 461 A depending on the selected gas reactants. In some implementations, where the gas reactant consists of oxygen, a deposition rate greater than about 0.2 Å / cycle may be achieved at temperatures between about 550°C and about 700°C and chamber pressures equal to or greater than about 12 Torr. Such implementations may be referred to as an oxygen-only flow. In some implementations, where the gas reactants consist of hydrogen and oxygen, a deposition rate equal to or greater than about 0.7 Å / cycle may be achieved at temperatures between about 500°C and about 700°C and chamber pressures equal to or greater than about 7 Torr. Such implementations may be referred to as a co-flow of hydrogen and oxygen (H2 / O2). The co-flow of hydrogen and oxygen may enable higher deposition rates even at lower temperatures and pressures in the plasma processing chamber. Specifically, thermal oxidation may occur at a faster rate using the co-flow of hydrogen and oxygen compared to an oxygen-only flow.

[0112] A plurality of thermal ALD cycles 410A may be performed to form the first silicon oxide layer on the substrate. In some implementations, the first silicon oxide layer deposited by thermal ALD may serve as a liner layer prior to deposition by PEALD. The liner layer may protectAttorney Docket No. 12306-1WO / LAM1P120WOunderlying layers from substrate damage and / or provide a high quality liner in high aspect ratio structures. In some implementations, the first silicon oxide layer may be relatively thin and be between about 1 Å and about 100 Å, such as between about 10 Å and about 100 Å. For such thicknesses involving an oxygen-only flow, the number of thermal ALD cycles may be between about between about 5 cycles and about 50 cycles, between about 5 cycles and about 20 cycles, or between about 5 cycles and about 10 cycles.

[0113] The first silicon oxide layer deposited by the plurality of thermal ALD cycles 410A may cause little to no damage to the substrate and little to no oxidation to the substrate. For example, an amount of silicon substrate oxidation may be between about 1 Å and about 3 Å when using oxygen-only flow of thermal ALD process, whereas a typical PEALD process results in silicon substrate oxidation between about 15 Å and about 35 Å. Where the first silicon oxide layer is deposited on vertical structures of the substrate, little to no bending occur on the vertical structures. The wet etch rate of the first silicon oxide layer along the depth of the vertical structures is uniform. Furthermore, where the substrate includes one or more features, a step coverage of the first silicon oxide layer is highly conformal. For example, the step coverage of the first silicon oxide layer may be equal to or greater than about 85%, equal to or greater than about 90%, or equal to or greater than about 95%. Figure 13 shows an image of silicon oxide film deposited on fin structures at 650°C using thermal ALD, where the deposited silicon oxide film exhibits high conformality and limited bending of the fin structures.

[0114] At block 330 of the process 300, a second silicon oxide layer is deposited on the substrate via PEALD in the plasma processing chamber. The thermal ALD operation at block 320 and the PEALD operation at block 330 are performed in the same plasma processing chamber. Any suitable number of PEALD cycles may be performed at block 330 after performing thermal ALD. Each PEALD cycle may be broken down into a series of phases, including a dose phase, a first purge phase, a plasma exposure phase, and a second purge phase. It will be understood that one or both of the first purge phase and the second purge phase may be optionally performed in each PEALD cycle. Depositing a thin film via PEALD includes: exposing the substrate to a precursor to adsorb onto a surface of the substrate, and exposing the substrate to plasma generated from one or more gas reactants, where the plasma drives a reaction between reactive species of the one or more gas reactants and the precursor, thereby forming the thin film via PEALD. Specifically, depositing the second silicon oxide layer by PEALD includes: exposing the substrate to a silicon-containing precursor to adsorb onto the surface of the substrate, and exposing the substrate to plasma generated from an oxidizer or oxygen-containing reactant, where the plasma drives aAttorney Docket No. 12306-1WO / LAM1P120WOreaction between reactive species of the oxidizer or oxygen-containing reactant and the silicon-containing precursor, thereby forming the second silicon oxide layer via PEALD. The silicon-containing precursor in the PEALD cycles may or may not be the same as the silicon-containing precursor in the thermal ALD cycles. In addition, the oxygen-containing reactant in the PEALD cycles may or may not be the same as the oxidizer or oxygen-containing reactant in the thermal ALD cycles. For example, the oxidizer or oxygen-containing reactant may include oxygen, ozone, or combinations thereof.

[0115] As shown in Figure 4, during the PEALD cycle 410B, the substrate is exposed to a silicon-containing precursor during a dose phase 457B. In some implementations, the silicon-containing precursor includes a silane, such as an aminosilane. During the dose phase 457B, plasma is turned off, oxidizer or oxygen-containing reactant flow is turned off, and a carrier gas may be flowed towards the substrate. In some implementations, the silicon-containing precursor adsorbs onto the surface of the substrate in a self-limiting manner such that once active sites are occupied by the silicon-containing precursor, little or no additional silicon-containing precursor will be adsorbed on the surface of the substrate.

[0116] In some implementations, the plasma processing chamber may be purged between operations of exposing the substrate to the silicon-containing precursor and exposing the substrate to an oxidizer or oxy gen-containing reactant. In addition, the plasma processing chamber may be purged after exposing the substrate to the oxidizer or oxygen-containing reactant. Purging may involve a sweep gas, which may be a carrier gas used in other operations / phases or a different gas. Purging may remove excess species in the vapor phase that did not adsorb or react onto the surface of the substrate. As shown in Figure 4, the plasma processing chamber undergoes purging during purge phases 459B and 463B. Silicon-containing precursor flow is turned off, plasma is turned off, and oxidizer or oxygen-containing reactant flow is turned off. However, the carrier gas may continue to flow towards the substrate. In some implementations, the purge phases 459B and 463B may each include one or more evacuation sub-phases for evacuating the plasma processing chamber. Alternatively, it will be appreciated that each of the purge phases 459B and 463B may be omitted in some implementations.

[0117] As shown in Figure 4, during the PEALD cycle 410B, the substrate may be exposed to the plasma generated from the oxidizer or oxygen-containing reactant during a plasma exposure phase 461B. An oxygen plasma may be ignited during the plasma exposure phase 461B. The plasma may include ions, radicals, charged neutrals, and other reactive species generated from the oxidizer or oxygen-containing reactant. The reactive species from the oxidizer or oxygen-Attorney Docket No. 12306-1WO / LAM1P120WOcontaining reactant may react with the adsorbed silicon-containing precursor to form the second silicon oxide layer over the first silicon oxide layer. The plasma may be generated in situ or remotely. Flow of the silicon-containing precursor is turned off while flow of the oxidizer or oxygen-containing reactant is turned on during the plasma exposure phase 461B.

[0118] Process conditions in the plasma processing chamber may vary for the oxygen plasma during the plasma exposure phase 461B. In some implementations, the substrate temperature may be maintained between about 0°C and about 750°C or between about 20° and about 200°C. In some implementations, the chamber pressure in the plasma processing chamber may be relatively low and between about 10 mTorr and about 200 mTorr, or may be relatively high and between about 1 Torr and about 7 Torr. An RF field is applied to the plasma processing chamber to generate ions and radicals of the oxidizer or oxygen-containing reactant. In various implementations, the RF frequency used to generate the plasma may be at least about 13.56 MHz, at least about 27 MHz, at least about 40 MHz, or at least about 60 MHz, though other frequencies may also be used. In some implementations, the RF power may be a few hundred Watts, for example about 500 W or less, about 400 W or less, or about 300 W or less, though it will be understood that other RF powers may be applied depending on substrate area. In some implementations, the duration of the plasma exposure phase 461B may be between about 0.1 seconds and about 120 seconds or between about 1 second and about 60 seconds.

[0119] A plurality of PEALD cycles 410B may be performed to form the second silicon oxide layer on the first silicon oxide layer. The first silicon oxide layer deposited by thermal ALD cycles 410A may provide a liner layer of silicon oxide film to protect underlying layers. In some implementations, the liner layer may be relatively thin and between about 10 Å and about 100 Å thick. In some implementations, the liner layer may serve as a protective liner on soft layers to eliminate or otherwise reduce substrate damage. In some implementations, the liner layer may serve as a high quality liner on high aspect ratio structures. Such high aspect ratio structures may include fins and pillars. The high aspect ratio structures may be prone to bending / damage when exposed to only PEALD operations. However, having the first silicon oxide layer deposited by thermal ALD prior to the second silicon oxide layer provides high conformality, high deposition rate, limited surface oxidation, limited bending of substrate features (e.g., pillars, fins), and uniform wet etch rate on sidewalls. The second silicon oxide layer deposited by PEALD cycles 410B may follow as bulk deposition of silicon oxide film on the liner layer. Accordingly, in various implementations, nucleation of silicon oxide film may be performed by thermal ALD and bulk deposition may be performed by PEALD in the same plasma processing chamber.Attorney Docket No. 12306-1WO / LAM1P120WO

[0120] In some implementations, the process 300a further includes exposing the substrate to plasma generated from a nitrogen-containing reactant in the plasma processing chamber, where the plasma drives a reaction between reactive species of the nitrogen-containing reactant and at least the second silicon oxide layer, thereby converting at least the second silicon oxide layer to a silicon oxynitride layer. In some implementations, the nitrogen-containing reactant may include nitrogen (N2), ammonia (NH3), or combinations thereof. A nitrogen plasma may cause nitridation of one or both of the first and second silicon oxide layer to form the silicon oxynitride layer.

[0121] In addition or in the alternative to the aforementioned nitridation of silicon oxide, the process 300a may include depositing a silicon nitride layer on the first and second silicon oxide layer by thermal ALD or PEALD in the plasma processing chamber. Thus, the combination of the first silicon oxide layer, the second silicon oxide layer, and the silicon nitride layer collectively form a silicon oxynitride film. In various implementations, silicon oxide and silicon nitride layers may be deposited in alternating fashion to form nanolaminates of silicon oxide / silicon nitride. In some implementations, the process 300a further includes annealing the substrate to form the silicon oxynitride film from the first silicon oxide layer, the second silicon oxide layer, and the silicon nitride layer.

[0122] Figure 3B shows a flow diagram of an example process for depositing a silicon oxide film using thermal ALD according to some implementations. The operations in a process 300b of Figure 3B may be performed in different orders and / or with different, fewer, or additional operations. The operations in the process 300b may be performed by a plasma processing apparatus shown in Figure 11 and / or the process tool shown in Figure 12. In some implementations, the operations of the process 300b may be implemented, at least in part, according to software stored in one or more non-transitory computer readable media. Figures 3B and 5-10 may be described together below.

[0123] At block 350 of the process 300b, a substrate is heated to an elevated temperature. The substrate may be heated to the elevated temperature before and during thermal ALD. This allows the substrate to be heated to the elevated temperature to drive surface reactions between precursors and reactants in thermal ALD. In some implementations, the elevated temperature applied to the substrate may be between about 500°C and about 750°C, between about 500°C and about 700°C, between about 500°C and about 650°C, or between about 550°C and about 650°C. In some implementations, a pressure of a plasma processing chamber may be equal to or greater than about 7 Torr, equal to or greater than about 10 Torr, or equal to or greater than about 12 Torr. Chamber pressure may provide a further knob to control the deposition rate of the layer of silicon oxide film.Attorney Docket No. 12306-1WO / LAM1P120WO

[0124] In some implementations, prior to heating the substrate to the elevated temperature, the substrate may be provided into the plasma processing chamber. The plasma processing chamber may be a single wafer plasma reactor configured to perform thermal ALD processes, PEALD processes, or combinations thereof. The substrate may be a silicon substrate, such as a 200-mm, 300-mm, or 450-mm substrate, including substrates having one or more layers of material, such as dielectric, conducting, or semiconducting material. In some implementations, the substrate on which silicon oxide films are deposited may include a material that is sensitive to plasma damage by PEALD. For example, the material may include but is not limited to silicon, germanium, silicon-germanium, carbon, and metals, where example metals may include molybdenum, tungsten, copper, cobalt, ruthenium, rhodium, and iridium. The substrate on which the silicon oxide films are deposited may include one or more features such as fins or pillars. In some implementations, the one or more features may include an under-layer such as a barrier layer, liner layer, or adhesion layer.

[0125] At block 360 of the process 300b, the substrate is exposed to a silicon-containing precursor to adsorb onto a surface of the substrate in the plasma processing chamber. In some implementations, the silicon-containing precursor includes a silane, such as an aminosilane. 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 may include BTBAS, N-SAM-24, 3DMAS, and 4DMAS. In some implementations, the substrate is exposed to the silicon-containing precursor while the substrate is heated to the elevated temperature.

[0126] Figure 5 illustrates an example timing sequence diagram showing thermal ALD cycles for depositing a silicon oxide film with co-flowed hydrogen and an oxidizer or oxygen-containing reactant according to some implementations. A first thermal ALD cycle 510A may include a dose phase 557A, followed by a first purge phase 559A, followed by a thermal oxidation phase 561 A, and followed by a second purge phase 563A. A second thermal ALD cycle 510B may include a dose phase 557B, followed by a first purge phase 559B, followed by a thermal oxidation phase 561B, and followed by a second purge phase 563B. As shown in Figure 5, the substrate may be exposed to the silicon-containing precursor during the dose phase 557A / 557B of the thermal ALD cycle 510A / 510B, where a duration of the dose phase 557A / 557B may be between about 0.1 seconds and about 60 seconds, between about 0.2 seconds and about 6 seconds, or between about 0.3 seconds and about 2 seconds, such as about 0.75 seconds, depending on the flow rate and the substrate surface area. The silicon-containing precursor adsorbs onto the surface of the substrate in a self-limiting manner such that once active sites are occupied by the silicon-containingAttorney Docket No. 12306-1WO / LAM1P120WOprecursor, little or no additional silicon-containing precursor will be adsorbed on the surface of the substrate. During the dose phase 557A / 557B, plasma is turned off, no oxidizer or oxygencontaining reactant is flowed to the substrate, and a carrier gas may be flowed towards the substrate.

[0127] In some implementations, the plasma processing chamber may be purged between operations of exposing the substrate to the silicon-containing precursor and flowing hydrogen and an oxidizer or oxygen-containing reactant into the plasma processing chamber. In addition, the plasma processing chamber may be purged after the flow of hydrogen and oxidizer or oxy gencontaining reactant has ceased. Purging may involve a sweep gas, which may be a carrier gas used in other operations / phases or a different gas. Purging may remove excess species in the vapor phase that did not adsorb or react on the surface of the substrate. As shown in Figure 5, the plasma processing chamber undergoes purging during purge phases 559A, 563A, 559B, and 563B. Silicon-containing precursor flow is turned off, plasma is turned off, hydrogen flow is turned off, and oxidizer or oxygen-containing reactant flow is turned off. However, the carrier gas may continue to flow towards the substrate. In some implementations, the purge phases 559A, 563A, 559B, and 563B may each include one or more evacuation sub-phases for evacuating the plasma processing chamber. Alternatively, it will be appreciated that each of the purge phases 559A, 563 A, 559B, and 563B may be omitted in some implementations. Each purge phase 559 A, 563 A, 559B, and 563B may have a suitable duration, such as between about 0 seconds and about 60 seconds or between about 0.01 seconds and about 6 seconds.

[0128] Returning to Figure 3B, at block 370 of the process 300b, hydrogen and oxidizer or oxygen-containing reactant are flowed towards the substrate in the plasma processing chamber. The hydrogen and the oxidizer or oxy gen-containing reactant react within the plasma processing chamber, where a layer of a silicon oxide film is formed on the substrate. The hydrogen and oxidizer or oxy gen-containing reactant may be flowed simultaneously into the plasma processing chamber. In some implementations, the oxidizer or oxy gen-containing reactant includes oxygen or ozone. For example, the oxidizer or oxygen-containing reactant includes oxygen, thereby providing a co-flow of hydrogen and oxygen (H2 / O2). Without being limited by any theory, the hydrogen and the oxidizer or oxygen-containing reactant react in situ with one another within the plasma processing chamber in an exothermic reaction. It is possible that the reaction between the hydrogen and the oxidizer or oxygen-containing reactant forms water in the exothermic reaction. The exothermic reaction releases energy that may drive the thermal oxidation of the adsorbed silicon-containing precursor to form silicon oxide film. The flow rate of hydrogen and the flowAttorney Docket No. 12306-1WO / LAM1P120WOrate of the oxidizer or oxygen-containing reactant may be controlled according to a desired flow rate ratio to promote thermal oxidation. In some implementations, a flow rate ratio between hydrogen and the oxidizer or oxygen-containing reactant may be equal to or less than about 1.2:1, such as between about 0.5:1 and about 1.2:1. In some implementations, a flow rate of hydrogen may be between about 0 slm and about 20 slm, between about 1 slm and about 10 slm, between about 2 slm and about 6 slm, greater than about 3 slm, such as about 4 slm. A flow rate of oxidizer or oxygen-containing reactant may be between about 0.5 slm and about 20 slm, between about 1 slm and about 10 slm, or between about 2 slm and about 8 slm, such as about 5 slm.

[0129] During the flow of hydrogen and the oxidizer or oxygen-containing reactant, the substrate is maintained at the elevated temperature. The substrate is at the elevated temperature while the hydrogen and oxidizer or oxygen-containing reactant are flowing towards the substrate to drive a reaction with the adsorbed silicon-containing precursor in the plasma processing chamber, thereby forming the layer of the silicon oxide film. The elevated temperature may promote formation of the layer of the silicon oxide film at an appreciable deposition rate. Without being limited by any theory, the in situ exothermic reaction between hydrogen and the oxidizer or oxygen-containing reactant along with the heated substrate at the elevated temperature may provide sufficient energy to drive the formation of the layer of the silicon oxide film at an appreciable deposition rate. In some implementations, the deposition rate of the layer of the silicon oxide film using co-flowed hydrogen and oxidizer or oxygen-containing reactant may be equal to or greater than about 0.7 Å / cycle.

[0130] As shown in Figure 5, hydrogen and oxidizer or oxygen-containing reactant may be flowed towards the substrate while the substrate is heated at the elevated temperature during a thermal oxidation phase 561A / 561B of the thermal ALD cycle 510A / 510B. The in situ exothermic reaction between the hydrogen and oxidizer or oxygen-containing reactant combined with the substrate heated at the elevated temperature may provide energy for driving oxidation during the thermal oxidation phase 561A / 561B. Moreover, temperature and pressure in the plasma processing chamber may be controlled to enable the deposition of the layer of the silicon oxide film at a deposition rate equal to or greater than about 0.7 Å / cycle during the thermal oxidation phase 561A / 561B. A duration of the thermal oxidation phase 561A / 561B may be between about 0.1 seconds and about 6 seconds, between about 0.2 seconds and about 4 seconds, or between about 0.5 seconds and about 3 seconds. For example, the duration of the thermal oxidation phase 561A / 561B with co-flowed hydrogen and oxidizer or oxygen-containing reactant may be between about 0.5 seconds and about 1 second, such as about 0.8 seconds. During the thermal oxidationAttorney Docket No. 12306-1WO / LAM1P120WOphase 561A / 561B, plasma is turned off and silicon-containing precursor flow is turned off. However, carrier gas, hydrogen, and oxidizer or oxygen-containing reactant flow may be turned on.

[0131] Example process times and process conditions are shown in Table 1 for co-flowed hydrogen and oxygen in thermal ALD.Table 1Process Times Dose 0.2 - 2 seconds Post-Dose Purge 0.15 -2 seconds Conversion Time 0.5 - 2 seconds Post- Oxidation Time 0- 1 second Process Silicon-Containing Precursor Flow 1500 seem Conditions Purge Gas Flow 25000 - 65000 seem 02 Flow 2000 - 5000 seem H2 flow 2000 - 5000 seem Pressure 9 Torr - 17.5 Torr Temperature 500°C - 750°C Purge Gas Ar and / or N2

[0132] In some implementations, the process 300b further includes applying plasma power to the plasma processing chamber to ignite plasma generated from the hydrogen and oxidizer or oxygen-containing reactant in the plasma processing chamber. In some implementations, the plasma may include ions, radicals, and other reactive species of hydrogen and oxygen (e.g., H* and O*). In some implementations, the plasma may further include ions, radicals, and other reactive species of the carrier gas (e.g., Ar+). The plasma power applied to the plasma processing chamber may be relatively small. In some implementations, the plasma power applied to the plasma processing chamber is equal to or less than about 300 W, equal to or less than about 200 W, or between about 10 W and about 200 W. That way, the plasma may include more radicals and fewer ions. In various implementations, the RF frequency used to generate the plasma may be at least about 13.56 MHz, at least about 27 MHz, at least about 40 MHz, or at least about 60 MHz, though other frequencies may also be used.

[0133] Without being limited by any theory, low RF power may ignite low RF plasma with energy from the exothermic reaction between the hydrogen and the oxidizer or oxygen-containing reactant. Without an in situ exothermic reaction between hydrogen and the oxidizer or oxygen-containing reactant, plasma may not be ignited at relatively low RF powers. In other words, aAttorney Docket No. 12306-1WO / LAM1P120WOcombustion reaction of hydrogen and the oxidizer or oxygen-containing reactant may contribute to generating low RF plasma in the plasma processing chamber. A stable plasma may be maintained at relatively low RF powers. The low RF plasma may limit damage to the substrate and particularly limit damage to any sensitive substrate. The low RF plasma may enhance or at least modulate deposition and properties of the layer of silicon oxide film. In some implementations, the low RF plasma may modulate deposition rate and provide higher wet etch rates. In some implementations, the low RF plasma may provide more conformal films, lower operating temperatures, and / or higher deposition rates.

[0134] Figure 6 illustrates an example timing sequence diagram showing thermal ALD cycles for depositing a silicon oxide film with low RF plasma power according to some implementations. Figure 6 shows a first thermal ALD cycle 610A that includes a dose phase 657A, first purge phase 659A, thermal oxidation phase 661A, and second purge phase 663A. Figure 6 also shows a second thermal ALD cycle 610B that includes a dose phase 657B, first purge phase 659B, thermal oxidation phase 66 IB, and second purge phase 663B. Aspects of the phases for each of the thermal ALD cycles 610A / 610B of Figure 6 can be described in the thermal ALD cycles 510A / 510B of Figure 5.

[0135] In the thermal oxidation phase 661A / 661B, plasma is turned on rather than off. The plasma power can be a low RF plasma power that is equal to or less than about 300 W, equal to or less than about 200 W, or between about 10 W and about 200 W. Application of the low RF plasma power occurs while hydrogen and oxidizer or oxygen-containing reactant are being flowed toward the substrate and while the substrate is heated at the elevated temperature. Reactive species in the plasma such as radicals of oxygen may react with the adsorbed silicon-containing precursor to form silicon oxide.

[0136] In some implementations at block 370 of the process 300b, flowing hydrogen and oxidizer or oxygen-containing reactant towards the substrate may include flowing the oxidizer or oxygen-containing reactant continuously into the plasma processing chamber and pulsing hydrogen at regular intervals into the plasma processing chamber. The hydrogen may be pulsed at regular intervals while the oxidizer or oxygen-containing reactant is simultaneously and continuously flowed towards the substrate. For example, a constant oxygen flow may be combined with pulsed hydrogen flow into the plasma processing chamber. In some implementations, pulses of hydrogen may be introduced into the plasma processing chamber at regular intervals that last between about 0.1 seconds and about 1 second, between about 0.1 seconds and about 0.8 seconds, or between about 0.2 seconds and about 0.6 seconds. Pulsing hydrogen may facilitate combustionAttorney Docket No. 12306-1WO / LAM1P120WOreactions of hydrogen and oxidizer or oxy gen-containing reactant that occur in pulses rather than continuously. Pulsing hydrogen may affect the deposition and properties of the layer of silicon oxide film. When pulsing hydrogen, the duration of the thermal oxidation phase may be longer. Without being limited by any theory, this permits pulsed exothermic reaction(s) to proceed for as long as desired to drive film properties.

[0137] Figure 7 illustrates an example timing sequence diagram showing thermal ALD cycles for depositing a silicon oxide film with pulsing hydrogen flow during oxidation according to some implementations. Figure 7 shows a first thermal ALD cycle 710A that includes a dose phase 757A, first purge phase 759A, thermal oxidation phase 761A, and second purge phase 763A. Figure 7 also shows a second thermal ALD cycle 710B that includes a dose phase 757B, first purge phase 759B, thermal oxidation phase 761B, and second purge phase 763B. Aspects of the phases for each of the thermal ALD cycles 710A / 710B of Figure 7 can be described in the thermal ALD cycles 510A / 510B of Figure 5.

[0138] In the thermal oxidation phase 761A / 761B, hydrogen flow is pulsed rather than continuous. Oxidizer or oxy gen-containing reactant flow is continuous and simultaneous with the pulsed hydrogen flow. Typically, pulses in the pulsed hydrogen flow can be in the form of a square waveform. The pulses in the pulsed hydrogen flow can occur in regular intervals, where each of the regular intervals can last between about 0.1 seconds and about 1 second, between about 0.1 seconds and about 0.8 seconds, or between about 0.2 seconds and about 0.6 seconds. In some implementations, a total duration of the thermal oxidation phase 761A / 761B may be equal to or greater than 0.5 seconds, equal to or greater than 1 second, or between about 1 second and about 30 seconds. It will be understood that the total duration of the thermal oxidation phase 761A / 761B may be longer to permit pulsed exothermic reactions to drive film properties. A duty cycle can refer to the percentage of on time (Ton) that flow is turned on during the total of on and off time, where T = Ton+ Toffduring the thermal oxidation phase 761A / 761B. In some implementations, the duty cycle of the pulsed hydrogen flow can be between about 1% and about 99%, between about 5% and about 95%, between about 15% and about 90%, or between about 25% and about 75%.

[0139] In some implementations at block 370 of the process 300b, flowing hydrogen and oxidizer or oxygen-containing reactant towards the substrate may include generating oxygen radicals from the oxidizer or oxygen-containing reactant in a remote plasma source, introducing the radicals of oxygen into the plasma processing chamber, and flowing the hydrogen into the plasma processing chamber. Instead of pure oxygen gas, the radicals of oxygen may provide moreAttorney Docket No. 12306-1WO / LAM1P120WOreactive species to react with the hydrogen and the adsorbed silicon-containing precursor. Without being limited by any theory, the radicals of oxygen may react with hydrogen to form hydroxyl radicals or water, where the hydroxyl radicals or water may promote oxidation of the adsorbed silicon-containing precursor. In some implementations, the oxygen radicals are generated from oxygen gas or ozone. In some implementations, remote plasma source is located upstream of the plasma processing chamber, where the remote plasma source can be any suitable plasma generator such as an inductively-coupled plasma generator or capacitively-coupled plasma generator.

[0140] Figure 8 illustrates an example timing sequence diagram showing thermal ALD cycles for depositing a silicon oxide film with oxygen radicals generated from a remote plasma source during oxidation according to some implementations. Figure 8 shows a first thermal ALD cycle 810A that includes a dose phase 857A, first purge phase 859A, thermal oxidation phase 861 A, and second purge phase 863 A. Figure 8 also shows a second thermal ALD cycle 810B that includes a dose phase 857B, first purge phase 859B, thermal oxidation phase 861B, and second purge phase 863B. Aspects of the phases for each of the thermal ALD cycles 810A / 810B of Figure 8 can be described in the thermal ALD cycles 510A / 510B of Figure 5.

[0141] In the thermal oxidation phase 861A / 861B, oxygen radicals are introduced into the plasma processing chamber instead of pure oxygen gas. Hydrogen flow may be continuous and simultaneous with the flow of oxygen radicals into the plasma processing chamber. However, it will be understood that in some implementations, hydrogen flow may be pulsed. In the thermal oxidation phase 861A / 861B, remote plasma power is turned on rather than off. RF power may be applied to a remote plasma source to generate the oxygen radicals upstream from the plasma processing chamber.

[0142] In some implementations, at block 380 of the process 300b, the process 300b further includes performing PEALD in the plasma processing chamber. For example, the process 300b can include depositing one or more additional layers of the silicon oxide film on the substrate via PEALD in the plasma processing chamber. In addition or in the alternative, the process 300b can include depositing one or more layers of a silicon nitride film on the layer of the silicon oxide film by thermal ALD or PEALD in the plasma processing chamber to ultimately form a silicon oxynitride film. In some implementations, at block 380 of the process 300b, a PEALD cycle can include exposing the substrate to plasma of a nitrogen-containing reactant to convert the layer of the silicon oxide film to a silicon oxynitride film during a plasma exposure phase. The layer of silicon oxide film deposited by thermal ALD may serve as a liner layer protecting underlying layers of the substrate, and subsequent layers of silicon oxide and / or silicon nitride may beAttorney Docket No. 12306-1WO / LAM1P120WOdeposited in bulk over the liner layer. The layer of silicon oxide film deposited by thermal ALD may exhibit high conformality, high deposition rate, limited surface oxidation, limited bending of substrate features (e.g., pillars, fins), and uniform wet etch rate on sidewalls. In some implementations, however, performing PEALD in the plasma processing chamber may occur before thermal ALD in the plasma processing chamber. In other words, layers of silicon oxide film may be deposited by PEALD and followed by additional layers of silicon oxide film deposited by thermal ALD.

[0143] Figure 9 illustrates an example timing sequence diagram showing a thermal ALD cycle with co-flowed hydrogen and oxygen followed by a PEALD cycle with plasma oxidation / nitridation for depositing a silicon-containing film according to some implementations. However, it will be understood that the PEALD cycle may be performed prior to the thermal ALD cycle in some implementations. Figure 9 shows a thermal ALD cycle 910A that includes a dose phase 957A, a first purge phase 959A, a thermal oxidation phase 961A, and a second purge phase 963A. Figure 9 also shows a PEALD cycle 910B that includes a dose phase 957B, first purge phase 959B, plasma oxidation / nitridation phase 961B, and second purge phase 963B. Aspects of the phases for the thermal ALD cycle 910A of Figure 9 can be described in the thermal ALD cycle 510A / 510B of Figure 5. Aspects of the phases for the PEALD cycle 910B of Figure 9 can be described in the PEALD cycle 410B of Figure 4.

[0144] In the plasma oxidation / nitridation phase 961B, the substrate may be exposed to an oxygen plasma or nitrogen plasma. If plasma nitridation takes place, one or more nitrogencontaining reactants may be flowed towards the substrate and plasma turned on. For example, the one or more nitrogen-containing reactants may include N2 / NH3. The plasma nitridation may deposit a layer of silicon nitride film over the layer of silicon oxide film. In some implementations, the plasma nitridation may convert silicon oxide to silicon oxynitride. If plasma oxidation takes place, one or more oxidizer or oxygen-containing reactants maybe flowed towards the substrate and plasma turned on. For example, the one or more oxidizer or oxygen-containing reactants may include O2. The plasma oxidation may deposit an additional layer of silicon oxide film over the layer of silicon oxide film.

[0145] In some implementations, at blocks 360 and 370 of the process 300b, exposing the substrate to the silicon-containing precursor and flowing the hydrogen and oxidizer or oxygencontaining reactant may occur in a continuous manner rather than in a cyclic manner. Specifically, exposing the substrate to the silicon-containing precursor and flowing the hydrogen and oxidizer or oxygen-containing reactant occurs in a thermal CVD process instead of a thermal ALD process.Attorney Docket No. 12306-1WO / LAM1P120WOBriefly, thermal ALD reactions involve cyclically performing (a) delivery of precursor to form an adsorbed precursor layer, (b) optional purge operation, (c) delivery of reactant(s) on a heated substrate, (d) optional purge operation, and (e) repeating operations (a)-(d) until the film reaches a desired thickness. However, thermal CVD reactions involve delivering the precursor and reactant(s) continuously while the substrate is heated. CVD reactions are gas phase reactions, which deposition reaction products on the substrate surface. Hence, the reaction mechanism of the present disclosure may involve thermal CVD using silicon-containing precursor, hydrogen, and oxidizer or oxygen-containing reactant being delivered continuously rather than cyclically in thermal ALD.

[0146] Figure 10 illustrates an example timing sequence diagram showing thermal CVD with co-flowed silicon-containing precursor, hydrogen, and oxidizer or oxygen-containing reactant for depositing a silicon-containing film according to some implementations. A thermal CVD process 1010 is not broken down into a series of phases in cycles. Carrier gas is continuously flowed to the substrate, silicon-containing precursor is continuously flowed to the substrate, hydrogen gas is continuously flowed to the substrate, and oxidizer or oxygen-containing reactant is continuously flowed to the substrate. Delivery of the silicon-containing precursor, delivery of hydrogen, and delivery of the oxidizer or oxygen-containing reactant do not occur sequentially and do not occur in separate phases. Plasma is turned off during the thermal CVD process 1010.

[0147] It will be understood that any of the foregoing techniques described in Figures 4-10 may be mixed together in a series of ALD cycles and / or CVD reactions. In other words, deposition of a silicon-containing film by thermal ALD may involve one or more cycles with pulsed hydrogen flow, one or more cycles with co-flowed hydrogen and oxidizer or oxygen-containing reactant, one or more cycles with application of low RF power, one or more cycles with oxygen radicals, one or more PEALD cycles for plasma oxidation / nitridation, and one or more periods of thermal CVD reactions with a silicon-containing precursor, hydrogen, and oxidizer or oxygen-containing reactant. Such techniques may be applied in any sequence when depositing the silicon-containing film.APPARATUS

[0148] The methods described herein may be performed by any suitable apparatus or combination of apparatus. A suitable apparatus includes hardware for accomplishing the process operations and a system controller having instructions for controlling process operations in accordance with the present disclosure. For example, in some implementations, the hardware may include one or more process stations included in a process tool. In the present disclosure, theAttorney Docket No. 12306-1WO / LAM1P120WOthermal ALD / CVD and PEALD / PECVD may be performed in a single station / chamber.

[0149] Figure 11 is a schematic diagram of an example plasma processing apparatus for depositing a silicon-containing film using thermal ALD according to some implementations. The plasma apparatus or process station 1100a includes a plasma processing chamber 1102 for maintaining a low-pressure environment. A plurality of plasma apparatuses or process stations 1100a may be included in a common low-pressure process tool environment. For example, Figure 12 depicts an implementation of a multi-station processing tool 1200. In some implementations, one or more hardware parameters of the plasma apparatus or process station 1100a including those discussed in detail below may be adjusted programmatically by one or more system controllers 1150. The plasma apparatus or process station 1100a can be configured to perform thermal ALD and PEALD, thermal CVD and PEALD, thermal ALD and PECVD, or thermal CVD and PECVD. In some implementations, the plasma apparatus or process station 1100a can be configured to perform one or more PEALD cycles and one or more thermal ALD cycles to deposit a silicon oxide film on a substrate 1112.

[0150] The apparatus or process station 1100a fluidly communicates with reactant delivery system 1101a for delivering process gases to a distribution showerhead 1106. Reactant delivery system 1101a includes a mixing vessel 1104 for blending and / or conditioning process gases, such as a silicon-containing precursor in the vapor phase, for delivery to showerhead 1106. In some implementations, the reactant delivery system 1101a includes a mixing vessel 1104 for blending and / or conditioning an oxidizer or oxygen-containing reactant (e.g., oxygen) for delivery to the showerhead 1106. In some implementations, the reactant delivery system 1101a includes a mixing vessel 1104 for blending and / or conditioning hydrogen and an oxidizer or oxygen-containing reactant (e.g., oxygen) for delivery to the showerhead 1106. One or more mixing vessel inlet valves 1120 may control introduction of process gases to mixing vessel 1104. Plasma of the oxidizer or oxygen-containing reactant may also be delivered to the showerhead 1106 or may be generated in the plasma apparatus or process station 1100a. The showerhead 1106 may be fluidly coupled to the plasma processing chamber 1102 for delivery of silicon-containing precursors and reactants into the plasma processing chamber 1102.

[0151] As an example, the implementation of Figure 11 includes a vaporization point 1103 for vaporizing liquid reactant to be supplied to the mixing vessel 1104. In some implementations, vaporization point 1103 may be a heated vaporizer. In some implementations, delivery piping downstream of vaporization point 1103 may be heat traced. In some examples, the mixing vessel 1104 may also be heat traced. In one non-limiting example, piping downstream of vaporizationAttorney Docket No. 12306-1WO / LAM1P120WOpoint 1103 has an increasing temperature profile extending from approximately 100°C to approximately 150°C at the mixing vessel 1104. In some implementations, liquid precursor or liquid reactant may be vaporized at a liquid injector. For example, a liquid injector may inject pulses of a liquid reactant into a carrier gas stream upstream of the mixing vessel 1104. In one implementation, a liquid injector may vaporize the reactant by flashing the liquid from a higher pressure to a lower pressure. In another example, a liquid injector may atomize the liquid into dispersed microdroplets that are subsequently vaporized in a heated delivery pipe. Smaller droplets may vaporize faster than larger droplets, reducing a delay between liquid injection and complete vaporization. Faster vaporization may reduce a length of piping downstream from vaporization point 1103. In one scenario, a liquid injector may be mounted directly to mixing vessel 1104. In another scenario, a liquid injector may be mounted directly to showerhead 1106.

[0152] In some implementations, a liquid flow controller (LFC) upstream of vaporization point 1103 may be provided for controlling a mass flow of liquid for vaporization and delivery to the plasma apparatus or process station 1100a. For example, the LFC may include a thermal mass flow meter (MFM) located downstream of the LFC. A plunger valve of the LFC may then be adjusted responsive to feedback control signals provided by a proportional-integral-derivative (PID) controller in electrical communication with the MFM. However, it may take one second or more to stabilize liquid flow using feedback control. This may extend a time for dosing a liquid reactant. Thus, in some implementations, the LFC may be dynamically switched between a feedback control mode and a direct control mode. In some implementations, this may be performed by disabling a sense tube of the LFC and the PID controller.

[0153] The showerhead 1106 distributes process gases toward a substrate 1112. In the implementation shown in Figure 11, the substrate 1112 is located beneath the showerhead 1106 and is shown resting on a substrate support 1108, where the substrate support 1108 is configured to support the substrate 1112. The substrate support 1108 may include a chuck, a fork, or lift pins (not shown) to hold and transfer the substrate 1112 during and between the deposition operations. The chuck may be an electrostatic chuck, a mechanical chuck, or various other types of chuck as are available for use in the industry and / or for research. The showerhead 1106 may have any suitable shape, and may have any suitable number and arrangement of ports for distributing process gases to the substrate 1112.

[0154] In some implementations, the substrate support 1108 may be raised or lowered to expose the substrate 1112 to a volume between the substrate 1112 and the showerhead 1106. It will be appreciated that, in some implementations, substrate support height may be adjustedAttorney Docket No. 12306-1WO / LAM1P120WOprogrammatically by a suitable system controller 1150.

[0155] In another scenario, adjusting a height of the substrate support 1108 may allow a plasma density to be varied during plasma activation cycles included in the process. At the conclusion of a processing phase, the substrate support 1108 may be lowered during another substrate transfer phase to allow removal of the substrate 1112 from the substrate support 1108.

[0156] In some implementations, the substrate support 1108 may be configured to be heated to an elevated temperature via a heater 1110. In some implementations, the substrate support 1108 may be heated to a temperature less than about 700°C, such as about between about 500°C and about 750°C or between about 500°C and about 650°C, during deposition of silicon oxide films as described in the disclosed implementations. Further, in some implementations, pressure control for the apparatus or process station 700a may be provided by a butterfly valve 1118. As shown in the implementation of Figure 11, the butterfly valve 1118 throttles a vacuum provided by a downstream vacuum pump (not shown). However, in some implementations, pressure control of the plasma processing chamber 1102 may also be adjusted by varying a flow rate of one or more gases introduced to the plasma processing chamber 1102. In some implementations, the pressure in the plasma processing chamber 1102 may be controlled to be equal to or greater than about 7 Torr, equal to or greater than about 10 Torr, or equal to or greater than about 12 Torr during deposition of silicon oxide films as described in the disclosed implementations.

[0157] In some implementations, a position of the showerhead 1106 may be adjusted relative to the substrate support 1108 to vary a volume between the substrate 1112 and the showerhead 1106. Further, it will be appreciated that a vertical position of substrate support 1108 and / or showerhead 1106 may be varied by any suitable mechanism within the scope of the present disclosure. In some implementations, the substrate support 1108 may include a rotational axis for rotating an orientation of the substrate 1112. It will be appreciated that, in some implementations, one or more of these example adjustments may be performed programmatically by one or more suitable system controllers 1150.

[0158] In some implementations where plasma may be used as discussed above, showerhead 1106 and substrate support 1108 electrically communicate with a radio frequency (RF) power supply 1114 and matching network 1116 for powering a plasma in the plasma processing chamber 1102. In some implementations, the plasma energy may be controlled by controlling one or more of a process station pressure, a gas concentration, an RF source power, an RF source frequency, and a plasma power pulse timing. For example, RF power supply 1114 and matching network 1116 may be operated at any suitable power to form a plasma having a desired composition ofAttorney Docket No. 12306-1WO / LAM1P120WOradical species. In some implementations, the RF power supply 1114 and matching network 1116 may be operated to apply plasma power to the plasma processing chamber 1102 to ignite plasma generated from hydrogen and oxidizer or oxygen-containing reactant in the plasma processing chamber 1102. Example plasma powers applied by the RF power supply 1114 may be equal to or less than about 300 W, equal to or less than about 200 W, or between about 10 W and about 200 W. Likewise, RF power supply 1114 may provide RF power of any suitable frequency. In some implementations, RF power supply 1114 may be configured to control high- and low-frequency RF power sources independently of one another. Example low-frequency RF frequencies may include, but are not limited to, frequencies between 0 kHz and 500 kHz. Example high-frequency RF frequencies may include, but are not limited to, frequencies between 1.8 MHz and 2.45 GHz, or at least about 13.56 MHz, or at least about 27 MHz, or at least about 40 MHz, or at least about 60 MHz. It will be appreciated that any suitable parameters may be modulated discretely or continuously to provide plasma energy for the surface reactions.

[0159] In some implementations, the plasma may be monitored in-situ by one or more plasma monitors. In one scenario, plasma power may be monitored by one or more voltage, current sensors (e.g., VI probes). In another scenario, plasma density and / or process gas concentration may be measured by one or more optical emission spectroscopy sensors (OES). In some implementations, one or more plasma parameters may be programmatically adjusted based on measurements from such in situ plasma monitors. For example, an OES sensor may be used in a feedback loop for providing programmatic control of plasma power. It will be appreciated that, in some implementations, other monitors may be used to monitor the plasma and other process characteristics. Such monitors may include, but are not limited to, infrared (IR) monitors, acoustic monitors, and pressure transducers.

[0160] In some implementations, instructions for a controller 1150 may be provided via input / output control (IOC) sequencing instructions. In one example, the instructions for setting conditions for a process phase may be included in a corresponding recipe phase of a process recipe. In some cases, process recipe phases may be sequentially arranged, so that all instructions for a process phase are executed concurrently with that process phase. In some implementations, instructions for setting one or more reactor parameters may be included in a recipe phase. For example, a first recipe phase may include instructions for setting a flow rate of an inert and / or a precursor gas (e.g., the silicon-containing precursor), instructions for setting a flow rate of a carrier gas (such as argon), and time delay instructions for the first recipe phase. A second, subsequent recipe phase may include instructions for modulating or stopping a flow rate of an inert and / or aAttorney Docket No. 12306-1WO / LAM1P120WOprecursor gas, and instructions for modulating a flow rate of a carrier or purge gas and time delay instructions for the second recipe phase. A third recipe phase may include instructions for modulating a flow rate of an oxidizer or oxygen-containing reactant gas such as oxygen, instructions for modulating a flow rate of hydrogen gas, instructions for modulating the flow rate of a carrier or purge gas, and time delay instructions for the third recipe phase. A fourth, subsequent recipe phase may include instructions for modulating or stopping a flow rate of an inert and / or a reactant gas, and instructions for modulating a flow rate of a carrier or purge gas and time delay instructions for the fourth recipe phase. The fourth recipe, in some implementations, may include instructions for igniting plasma of the oxidizer or oxygen-containing reactant. It will be appreciated that these recipe phases may be further subdivided and / or iterated in any suitable way within the scope of the disclosed implementations.

[0161] In certain implementations, the controller 1150 has instructions to perform the operations described in the present disclosure. For example, the controller 1150 may be configured with instructions to perform the following operations: expose a substrate 1112 to a silicon-containing precursor to adsorb onto a surface of the substrate 1112 in the plasma processing chamber 1102, flow hydrogen and oxidizer or oxygen-containing reactant towards the substrate 1112 in the plasma processing chamber 1102, and heat the substrate 1112 to an elevated temperature, where the hydrogen and oxidizer or oxygen-containing reactant react with one another in the plasma processing chamber 1102, where a layer of silicon oxide film is formed on the substrate 1112. In some implementations, the elevated temperature is between about 500°C and about 650°C and the oxidizer or oxygen-containing reactant is oxygen. In some implementations, the controller 1150 is further configured with instructions to perform the following operation: deposit one or more additional layers of the silicon oxide film on the substrate 1112 via PEALD in the plasma processing chamber 1102. In some implementations, the controller 1150 configured with instructions for flowing the hydrogen and oxidizer or oxygen-containing reactant is configured with instructions for performing the following operations: flow the oxidizer or oxy gen-containing reactant continuously into the plasma processing chamber 1102, and pulse hydrogen at regular intervals into the plasma processing chamber 1102. In some implementations, the controller 1150 may include any of the features described below with respect to system controller 1250 of Figure 12.

[0162] Figure 12 is a schematic diagram of an example process tool for performing the disclosed implementations. A multi-station processing tool 1200 may include a transfer module 1203. The transfer module 1203 provides a clean, pressurized environment to minimize the risk ofAttorney Docket No. 12306-1WO / LAM1P120WOcontamination of substrates being processed as they are moved between various reactor modules. Mounted on the transfer module 1203 are multi-station reactors 1207, 1208, and 1209, referred to in this context as processing chambers or reactors or tool modules or modules. Each reactor is capable of performing deposition processes such as PEALD, thermal ALD, PECVD, or thermal CVD. One or more of the reactors 1207, 1208, and 1209 may be capable of performing soaking / cleaning, plasma treatment, etching, annealing, or other operations. The reactors 1207, 1208, and 1209 may include multiple stations 1211, 1213, 1215, and 1217 that may sequentially or non- sequentially perform operations in accordance with the disclosed implementations. While a depicted reactor 1207, 1208, or 1209 is depicted with four stations, it will be understood that a reactor according to the present disclosure may have any suitable number of stations. For example, in some implementations, a reactor may have five or more stations, while in other implementations, a reactor may have three or fewer stations. Each station may be configured for deposition by PEALD, thermal ALD, PECVD, or thermal CVD, or configured for different phases of a deposition process. Each station may include a substrate support configured to be heated to an elevated temperature as well as a showerhead or gas inlets for delivering gases.

[0163] The multi- station processing tool 1200 also includes one or more substrate source modules 1201 where substrates are stored before and after processing. An atmospheric robot 1204 in the atmospheric transfer chamber 1219 first removes substrates from the one or more substrate source modules 1201 to load locks 1221. While the implementation depicted includes load locks 1221, it will be appreciated that, in some implementations, direct entry of a substrate into a process station may be provided. A substrate transfer device 1205, such as a robot arm unit, in the transfer module 1203 moves the substrates from the load locks 1221 to and among the reactors 1207, 1208, and 1209. This can be done in a pressurized (e.g., vacuum) environment. The multi-station processing tool 1200 may perform one or more of the processes described in the present disclosure as well as other operations such as soaking / cleaning, plasma treatment, annealing, etc. Such processes may be performed in the multi-station processing tool 1200 without introducing a vacuum break.

[0164] Figure 12 may also include a system controller 1250 employed to control process conditions and hardware states of multi-station processing tool 1200. System controller 1250 may include one or more memory devices, one or more mass storage devices, and one or more processors. Processor may include a CPU or computer, analog and / or digital input / output connections, stepper motor controller boards, etc.

[0165] In some implementations, a controller is part of a system, which may be part of the above-Attorney Docket No. 12306-1WO / LAM1P120WOdescribed 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, 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.

[0166] Broadly speaking, the controller may be defined as electronics having various integrated circuits, logic, memory, and / or software that receive instructions, issue instructions, control operation, enable cleaning operations, enable endpoint measurements, and the like. The integrated circuits may include chips in the form of firmware that store program instructions, digital signal processors (DSPs), chips defined as application specific integrated circuits (ASICs), and / or one or more microprocessors, or microcontrollers that execute program instructions (e.g., software). Program instructions may be instructions communicated to the controller 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 implementations, be part of a recipe defined by process engineers to accomplish one or more processing operations during the fabrication of one or more layers, materials, metals, oxides, silicon, silicon dioxide, surfaces, circuits, and / or dies of a wafer.

[0167] The controller, 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 may be in the “cloud” or all or a part of a fab host computer system, which can allow for remote access of the wafer processing. The computer may enable remote access to the system to monitor current progress of fabrication operations, examine a history of past fabrication operations, examine trends or performance metrics from a plurality of fabrication operations, to change parameters of current processing, to set processing operations to follow a current processing, or to start a new process. In some examples, a remote computer (e.g.Attorney Docket No. 12306-1WO / LAM1P120WOa 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 receives instructions in the form of data, which specify parameters for each of the processing operations to be performed during one or more operations. It should be understood that the parameters may be specific to the type of process to be performed and the type of tool that the controller is configured to interface with or control. Thus as described above, the controller 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.

[0168] 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.

[0169] As noted above, depending on the process operation or operations to be performed by the tool, the controller 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.

[0170] Returning to the implementation of Figure 12, in some implementations, system controller 1250 controls all of the activities of multi-station processing tool 1200. System controller 1250 executes system control software stored in mass storage device, loaded into memory device, and executed on processor. Alternatively, the control logic may be hard coded in the controller 1250. Applications Specific Integrated Circuits, Programmable Logic Devices (e.g., field-programmable gate arrays, or FPGAs) and the like may be used for these purposes. In theAttorney Docket No. 12306-1WO / LAM1P120WOfollowing discussion, wherever “software” or “code” is used, functionally comparable hard coded logic may be used in its place. System control software 1258 may include instructions for controlling the timing, mixture of gases, chamber and / or station pressure, chamber and / or station temperature, wafer temperature, target power levels, RF power levels, RF exposure time, substrate pedestal, chuck and / or susceptor position, and other parameters of a particular process performed by multi-station processing tool 1200. System control software may be configured in any suitable way. For example, various process tool component subroutines or control objects may be written to control operation of the process tool components necessary to carry out various process tool processes. System control software may be coded in any suitable computer readable programming language.

[0171] In some implementations, system control software may include input / output control (IOC) sequencing instructions for controlling the various parameters described above. For example, each phase of a thermal ALD cycle or each phase of a PEALD cycle may include one or more instructions for execution by system controller 1250. The instructions for setting process conditions for an ALD process phase may be included in a corresponding ALD recipe phase. In some implementations, the ALD recipe phases may be sequentially arranged, so that all instructions for an ALD process phase are executed concurrently with that process phase.

[0172] Other computer software and / or programs stored on mass storage device and / or memory device associated with system controller 1250 may be employed in some implementations. Examples of programs or sections of programs for this purpose include a substrate positioning program, a process gas control program, a pressure control program, a heater control program, and a plasma control program.

[0173] A substrate positioning program may include program code for process tool components that are used to load the substrate onto pedestal and to control the spacing between the substrate and other parts of multi-station processing tool 1200.

[0174] A process gas control program may include code for controlling gas composition and flow rates and optionally for flowing gas into one or more process stations prior to deposition in order to stabilize the pressure in the process station. In some implementations, the controller includes instructions for depositing a first silicon oxide layer by thermal ALD in a plasma processing chamber and depositing a second silicon oxide layer by PEALD in the same plasma processing chamber. In some implementations, the controller includes instructions for depositing a layer of silicon oxide by delivering silicon-containing precursor to a substrate in a dose phase and co-flowing hydrogen and oxygen towards the substrate in a thermal oxidation phase.Attorney Docket No. 12306-1WO / LAM1P120WO

[0175] A pressure control program may include code for controlling the pressure in the process station by regulating, for example, a throttle valve in the exhaust system of the process station, a gas flow into the process station, etc. In some implementations, the controller includes instructions for providing a chamber pressure in the plasma processing chamber to be at least about 7 Torr prior to performing thermal ALD of silicon oxide layer.

[0176] A heater control program may include code for controlling the current to a heating unit that is used to heat the substrate. Alternatively, the heater control program may control delivery of a heat transfer gas (such as helium) to the substrate. In certain implementations, the controller includes instructions for heating the substrate to an elevated temperature during a thermal oxidation phase of a thermal ALD cycle, where the elevated temperature is between about 500°C and about 650°C.

[0177] A plasma control program may include code for setting RF power levels and exposure times in one or more process stations in accordance with the implementations herein. In some implementations, the controller includes instructions for igniting plasma at an RF power level between about 10 W and about 200 W during a thermal oxidation phase of a thermal ALD cycle when hydrogen and oxygen are being co-flowed.

[0178] In some implementations, there may be a user interface associated with system controller 1250. The user interface may include a display screen, graphical software displays of the apparatus and / or process conditions, and user input devices such as pointing devices, keyboards, touch screens, microphones, etc.

[0179] In some implementations, parameters adjusted by system controller 1250 may relate to process conditions. Non-limiting examples include process gas composition and flow rates, temperature, pressure, plasma conditions (such as RF power levels and exposure times), etc. These parameters may be provided to the user in the form of a recipe, which may be entered utilizing the user interface.

[0180] Signals for monitoring the process may be provided by analog and / or digital input connections of system controller 1250 from various process tool sensors. The signals for controlling the process may be output on the analog and digital output connections of multi-station processing tool 1200. Non-limiting examples of process tool sensors that may be monitored include mass flow controllers, pressure sensors (such as manometers), thermocouples, etc. Appropriately programmed feedback and control algorithms may be used with data from these sensors to maintain process conditions.

[0181] System controller 1250 may provide program instructions for implementing the above-Attorney Docket No. 12306-1WO / LAM1P120WOdescribed deposition processes. The program instructions may control a variety of process parameters, such as DC power level, RF bias power level, pressure, temperature, gas flow composition, flow rates, etc. The instructions may control the parameters to operate thermal ALD or thermal CVD of silicon oxide film according to various implementations described herein.

[0182] The system controller 1250 will typically include one or more memory devices and one or more processors configured to execute the instructions so that the apparatus will perform a method in accordance with the disclosed implementations. Machine-readable, non-transitory media containing instructions for controlling process operations in accordance with the disclosed implementations may be coupled to the system controller.

[0183] The various hardware and method implementations described above may be used in conjunction with lithographic patterning tools or processes, for example, for the fabrication or manufacture of semiconductor devices, displays, LEDs, photovoltaic panels and the like. Typically, though not necessarily, such tools / processes will be used or conducted together in a common fabrication facility.DEFINITIONS AND PRECURSORS DEFINITIONS

[0184] This section presents additional definitions that may be used herein. Some of the materials described in this section may overlap with those presented elsewhere in the application.

[0185] 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, acetyl, 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.

[0186] By “acyl halide” is meant -C(O)X, where X is a halogen, such as Br, F, I, or Cl.

[0187] By “aldehyde” is meant a -C(O)H group.

[0188] By “aliphatic” is meant a hydrocarbon group having at least one carbon atom to 50 carbon atoms (C1-50), such as one to 25 carbon atoms (C1-25), or one to ten carbon atoms (C1-10), and which includes alkanes (or alkyl), alkenes (or alkenyl), alkynes (or alkynyl), including cyclic versions thereof, and further including straight- and branched-chain arrangements, and all stereo and position isomers as well. An aliphatic group is unsubstituted or substituted, e.g., by a functional group described herein. For example, the aliphatic group can be substituted with one or more substitution groups, as described herein for alkyl.Attorney Docket No. 12306-1WO / LAM1P120WO

[0189] By “alkyl-aryl,” “alkenyl-aryl,” and “alkynyl-aryl” 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 alkyl-aryl, alkenyl-aryl, or alkynyl-aryl group can be substituted or unsubstituted. For example, the alkyl-aryl, alkenyl-aryl, or alkynyl-aryl group can be substituted with one or more substitution groups, as described herein for alkyl, alkenyl, alkynyl, or aryl. Example unsubstituted alkyl-aryl groups are of from 7 to 16 carbons (C7-16 alkyl-aryl), as well as those having an alkyl group with 1 to 6 carbons and an aryl group with 4 to 18 carbons (i.e., C1-6 alkyl-C4-18 aryl). Example 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). Example unsubstituted alkynyl-aryl groups are of from 7 to 16 carbons (C7-16 alkynyl-aryl), as well as those having an alkynyl group with 2 to 6 carbons and an aryl group with 4 to 18 carbons (i.e., C2-6 alkynyl-C4-18 aryl). In some embodiments, the alkyl-aryl group is -L-R, in which L is an alkyl group, as defined herein, and R is an aryl group, as defined herein. In some embodiments, the alkenyl-aryl group is -L-R, in which L is an alkenyl group, as defined herein, and R is an aryl group, as defined herein. In some embodiments, the alkynyl-aryl group is -L-R, in which L is an alkynyl group, as defined herein, and R is an aryl group, as defined herein.

[0190] 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 example 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.

[0191] By “alkyl-heteroaryl” is meant a heteroaryl group, as defined herein, attached to the parent molecular group through an alkyl group, as defined herein. In some embodiments, the alkyl-heteroaryl group is -L-R, in which L is an alkyl group, as defined herein, and R is a heteroaryl group, as defined herein.

[0192] By “alkyl-heterocyclyl,” “alkenyl-heterocyclyl,” and “alkynyl-heterocyclyl” is meant aAttorney Docket No. 12306-1WO / LAM1P120WOheterocyclyl 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 alkyl-heterocyclyl, alkenyl-heterocyclyl, or alkynyl-heterocyclyl group can be substituted or unsubstituted. For example, the alkyl-heterocyclyl, alkenyl-heterocyclyl, or alkynyl-heterocyclyl group can be substituted with one or more substitution groups, as described herein for alkyl, alkenyl, alkynyl, or heterocyclyl. Example unsubstituted alkyl-heterocyclyl groups are of from 2 to 16 carbons (C2-16 alkyl-heterocyclyl), as well as those having an alkyl group with 1 to 6 carbons and a heterocyclyl group with 1 to 18 carbons (i.e., C1-6 alkyl-C1-18 heterocyclyl). Example unsubstituted alkenyl-heterocyclyl groups are of from 3 to 16 carbons (C3-16 alkenyl-heterocyclyl), as well as those having an alkenyl group with 2 to 6 carbons and a heterocyclyl group with 1 to 18 carbons (i.e., C2-6 alkenyl-C1-18 heterocyclyl). Example unsubstituted alkynyl-heterocyclyl groups are of from 3 to 16 carbons (C3-16 alkynyl-heterocyclyl), as well as those having an alkynyl group with 2 to 6 carbons and a heterocyclyl group with 1 to 18 carbons (i.e., C2-6 alkynyl-C1-18 heterocyclyl). In some embodiments, the alkyl-heterocyclyl group is -L-R, in which L is an alkyl group, as defined herein, and R is a heterocyclyl group, as defined herein. In some embodiments, the alkenyl-heterocyclyl group is -L-R, in which L is an alkenyl group, as defined herein, and R is a heterocyclyl group, as defined herein. In some embodiments, the alkynyl-heterocyclyl group is -L-R, in which L is an alkynyl group, as defined herein, and R is a heterocyclyl group, as defined herein.

[0193] By “alkoxy” is meant -OR, where R is an optionally substituted aliphatic group, as described herein. Example 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. Example unsubstituted alkoxy groups include C1-3, C1-6, C1-12, C1-16, C1-18, C1-20, or C1-24 alkoxy groups.

[0194] By “alkyl” is meant a saturated monovalent hydrocarbon having at least one carbon atom to 50 carbon atoms (C1-50), such as one to 25 carbon atoms (C1-25), or one to ten carbon atoms (C1-10), wherein the saturated monovalent hydrocarbon can be derived from removing one hydrogen atom from one carbon atom of a parent compound (e.g., alkane). An alkyl group can be branched, straight-chain, or cyclic (e.g., cycloalkyl). An exemplary alkyl includes a branched or unbranched saturated hydrocarbon group of 1 to 24 carbon atoms, such as methyl (Me), ethyl (Et), n-propyl (nPr), iso-propyl (iPr), n-butyl (nBu), iso-butyl (iBu), sec-butyl (sBu), tert-butyl (tBu), pentyl (Pe),Attorney Docket No. 12306-1WO / LAM1P120WOn-pentyl (nPe), isopentyl (iPe), s-pentyl (sPe), neopentyl (neoPe), tert-pentyl (tPe), hexyl, heptyl, octyl, nonyl, decyl, 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) Ci-6 alkoxy (e.g., -O-R, in which R is Ci-6 alkyl); (2) Ci-6 alkylsulfinyl (e.g., -S(O)-R, in which R is Ci-6 alkyl); (3) Ci-6 alkylsulfonyl (e.g., -SO2-R, in which R is C1-6 alkyl); (4) amine (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) C3-8 cycloalkyl; (12) halo; (13) heterocyclyl (e.g., as defined herein, such as a 5-, 6- or 7-membered ring containing one, two, three, or four non-carbon heteroatoms); (14) heterocyclyloxy (e.g., -O-R, in which R is heterocyclyl, as defined herein); (15) heterocyclyloyl (e.g., -C(O)-R, in which R is heterocyclyl, as defined herein); (16) hydroxyl (e.g., -OH); (17) A-protected amino; (18) nitro (e.g., -NO2); (19) oxo (e.g., =0); (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) C1-6 alkyl, (c) C4-18 aryl, and (d) C1-6 alkyl-C4-18 aryl (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) C1-6 alkyl, (c) C4-18 aryl, and (d) C1-6 alkyl-C4-18 aryl (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) C1-6 alkyl, (b) C4-18 aryl, and (c) C1-6 alkyl-C4-18 aryl (e.g., -L-R, in which L is C1-6 alkyl and R is C4-18 aryl); (25) SO2NR1R2, where each of R1and R2is, independently, selected from the group consisting of (a) hydrogen, (b) C1-6 alkyl, (c) C4-18 aryl, and (d) C1-6 alkyl-C4-18 aryl (e.g., -L-R, in which L is C1-6 alkyl and R is C4-18 aryl); and (26) NR1R2, where each of R1and R2is, independently, selected from the group consisting of (a) hydrogen, (b) an N-protecting group, (c) C1-6 alkyl, (d) C2-6 alkenyl, (e) C2-6 alkynyl, (f) C4-18 aryl, (g) C1-6 alkyl-C4-18 aryl (e.g., -L-R, in which L is C1-6 alkyl and R is C4-18 aryl), (h) C3-8 cycloalkyl, and (i) C1-6 alkyl-C3-8 cycloalkyl (e.g., -L-R, in which L is C1-6 alkyl and R is C3-8 cycloalkyl), wherein in one embodiment no two groupsAttorney Docket No. 12306-1WO / LAM1P120WOare 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, Ci-12, C116, C1-18, C1-20, or Ci-24 alkyl group.

[0195] 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.

[0196] 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 perfluoro alkyl).

[0197] 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 example 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.

[0198] By “amide” is mean -C(O)NR1R2or -NHCOR1, 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, form a heterocyclyl group, as defined herein.

[0199] By “amine” or “amino” is meant -NR1R2, where each of R1and R2is, independently, selected from hydrogen, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted haloaliphatic, optionally substituted haloheteroaliphatic, optionallyAttorney Docket No. 12306-1WO / LAM1P120WOsubstituted aromatic, 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, 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.

[0200] By “aminoalkyl” is meant an alkyl group, as defined herein, substituted by an amine 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, haloaliphatic, haloheteroaliphatic, aromatic, as defined herein, or any combination thereof, or R1and R2, taken together with the nitrogen atom to which each are attached, form a heterocyclyl group, as defined herein. In other embodiments, the aminoalkyl group is -L-C(NR1R2)(R3)-R4, in which L is a covalent bond or an alkyl group, as defined herein; each of R1and R2is, independently, selected from hydrogen, aliphatic, heteroaliphatic, haloaliphatic, haloheteroaliphatic, aromatic, as defined herein, or any combination thereof, or R1and R2, taken together with the nitrogen atom to which each are attached, form a heterocyclyl group, as defined herein; and each of R3and R4is, independently, H or alkyl, as defined herein.

[0201] 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 7t-electron system. Typically, the number of out of plane 7t-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.

[0202] 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. Example aryl groups include, but are not limited to, benzyl, naphthalene, phenyl,Attorney Docket No. 12306-1WO / LAM1P120WObiphenyl, 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) Ci6 alkanoyl (e.g., -C(O)-R, in which R is Ci-6 alkyl); (2) Ci6 alkyl; (3) Ci6 alkoxy (e.g., -O-R, in which R is Ci-6 alkyl); (4) Ci6 alkoxy-Ci6 alkyl (e.g., -L-O-R, in which each of L and R is, independently, Ci-6 alkyl); (5) Ci6 alkylsulfinyl (e.g., -S(O)-R, in which R is Ci-6 alkyl); (6) Ci6 alkylsulfinyl-Ci6 alkyl (e.g., -L-S(O)-R, in which each of L and R is, independently, Ci-6 alkyl); (7) Ci6 alkylsulfonyl (e.g., -SO2-R, in which R is C1-6 alkyl); (8) Ci6 alkylsulfonyl-Ci6 alkyl (e.g., -L-SO2-R, in which each of L and R is, independently, C1-6 alkyl); (9) aryl; (10) amine (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, form a heterocyclyl group, as defined herein); (11) Ci6 aminoalkyl (e.g., -L1-NR1R2or -L2-C(NR1R2)(R3)-R4, in which L1is C1-6 alkyl; L2 is a covalent bond or C1-6 alkyl; each of R1and R2is, independently, selected from hydrogen, aliphatic, heteroaliphatic, haloaliphatic, haloheteroaliphatic, aromatic, as defined herein, or any combination thereof, or R1and R2, taken together with the nitrogen atom to which each are attached, form a heterocyclyl group, as defined herein; and each of R3and R4is, independently, H or C1-6 alkyl); (12) heteroaryl; (13) Ci6 alkyl-C4is aryl (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) Ci6 azidoalkyl (e.g., -L-N3, in which L is C1-6 alkyl); (18) aldehyde (e.g., C(O)H); (19) aldehyde-Ci6 alkyl (e.g., -L-C(O)H, in which L is C1-6 alkyl); (20) C38 cycloalkyl; (21) Ci6 alkyl-C38 cycloalkyl (e.g., -L-R, in which L is C1-6 alkyl and R is C3-8 cycloalkyl); (22) halo; (23) Ci6haloalkyl (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 C1-6 alkyl); (24) heterocyclyl (e.g., as defined herein, such as a 5-, 6- or 7-membered ring containing one, two, three, or four non-carbon heteroatoms); (25) heterocyclyloxy (e.g., -O-R, in which R is heterocyclyl, as defined herein); (26) heterocyclyloyl (e.g., -C(O)-R, in which R is heterocyclyl, as defined herein); (27) hydroxyl (-OH); (28) Ci6hydroxyalkyl (e.g., -L1-OH or -L2-C(OH)(R1)-R2, in which L1is C1-6 alkyl; L2is a covalent bond or alkyl; and each of R1and R2is, independently,Attorney Docket No. 12306-1WO / LAM1P120WOH or Ci-6 alkyl, as defined herein); (29) nitro; (30) Ci6 nitroalkyl (e.g., -L1-NO2or -L2-C(NO)(R1)-R2, in which L1is Ci-6 alkyl; L2is a covalent bond or alkyl; and each of R1and R2is, independently, H or Ci-6 alkyl, as defined herein); (31) N-protected amino; (32) N-protected amino-Ci6 alkyl; (33) oxo (e.g., =0); (34) Ci6 thioalkoxy (e.g., -S-R, in which R is Ci-6 alkyl); (35) thio-Ci6 alkoxy-Ci6 alkyl (e.g., L-S-R, in which each of L and R is, independently, Ci-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) Ci6 alkyl, (c) C4-18 aryl, and (d) Ci6 alkyl-C4i8 aryl (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) Ci6 alkyl, (c) C418 aryl, and (d) Ci6 alkyl-C4-i8 aryl (e.g., -L-R, in which L is C1-6 alkyl and R is C4-18 aryl); (38) -(CH2)rSO2R1, where r is an integer of from zero to four and where R1is selected from the group consisting of (a) Ci6 alkyl, (b) C4-18 aryl, and (c) Ci6 alkyl-C4-i8 aryl (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) Ci6 alkyl, (c) C4-18 aryl, and (d) Ci6 alkyl-C4is aryl (e.g., -L-R, in which L is Ci-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) Ci6 alkyl, (d) C2-6 alkenyl, (e) C2-6 alkynyl, (f) C418 aryl, (g) Ci6 alkyl-C4-i8 aryl (e.g., -L-R, in which L is C1-6 alkyl and R is C4-18 aryl), (h) C3-8 cycloalkyl, and (i) Ci6 alkyl-C3-8 cycloalkyl (e.g., -L-R, in which L is C1-6 alkyl and R is C3-8 cycloalkyl), wherein in one embodiment no two groups are bound to the nitrogen atom through a carbonyl group or a sulfonyl group; (41) thiol (e.g., -SH); (42) perfluoroalkyl (e.g., -(CF2)nCF3, in which n is an integer from 0 to 10); (43) perfluoroalkoxy (e.g., -O-(CF2)nCF3, in which n is an integer from 0 to 10); (44) aryloxy (e.g., -O-R, in which R is aryl); (45) cycloalkoxy (e.g., -O-R, in which R is cycloalkyl); (46) cycloalkylalkoxy (e.g., -O-L-R, in which L is alkyl and R is cycloalkyl); and (47) arylalkoxy (e.g., -O-L-R, in which L is alkyl and R is aryl). In particular embodiments, an unsubstituted aryl group is a C4-18, C4-14, C4-12, C4-10, Ce-18, Ce-i4, C6-12, or Ce-io aryl group.

[0203] By “arylalkoxy” is meant an alkyl-aryl 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.

[0204] 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 Ce-18 aryloxy group.

[0205] By “aryloyl” is meant an aryl group that is attached to the parent molecular group throughAttorney Docket No. 12306-1WO / LAM1P120WOa 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.

[0206] By ‘ ‘azido” is meant an -N3 group.

[0207] 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. By “azo” is meant an -N=N- group.

[0208] By ‘ ‘carbene” is meant H2C: and derivatives thereof having carbon bearing two nonbonding electrons or (C:). In some embodiments, the carbene is R1R2(C:), where each of R1and R2is, independently, selected from hydrogen, aliphatic, hetero aliphatic, haloaliphatic, haloheteroaliphatic, aromatic, as defined herein, or any combination thereof, or R1and R2, taken together with the atom to which each are attached, form a cycloaliphatic group, as defined herein.

[0209] By ‘ ‘carbenium cation” is meant H3C+and derivatives thereof having carbon bearing a +1 formal charge or C+. In some embodiments, the carbenium cation is R1-C+(R)-R2, where each of R, R1, and R2is, independently, selected from hydrogen, aliphatic, heteroaliphatic, haloaliphatic, haloheteroaliphatic, aromatic, as defined herein, or any combination thereof, or R1and R2and optionally R, taken together with the atom to which each are attached, form a cycloaliphatic group, as defined herein.

[0210] By “carbonyl” is meant a -C(O)- group, which can also be represented as > C=O.

[0211] By “carboxyl” is meant a CO2H group or an anion thereof.

[0212] By “cyano” is meant a -CN group.

[0213] By “cycloaliphatic” is meant an aliphatic group, as defined herein, that is cyclic.

[0214] 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.

[0215] By “cycloalkylalkoxy” is meant an alkyl-cycloalkyl group, as defined herein, attached to the parent molecular group through an oxygen atom. In some embodiments, the cycloalkylalkoxy group is O-L-R, in which L is an alkyl group, as defined herein, and R is a cycloalkyl group, as defined herein.

[0216] 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 cycloalkylAttorney Docket No. 12306-1WO / LAM1P120WOgroup can be substituted with one or more groups including those described herein for alkyl.

[0217] By “cycloheteroaliphatic” is meant a heteroaliphatic group, as defined herein, that is cyclic.

[0218] By “ester” is meant -C(O)OR or -OC(O)R, where R is selected from aliphatic, heteroaliphatic, haloaliphatic, haloheteroaliphatic, aromatic, as defined herein, or any combination thereof.

[0219] By “halo” is meant F, Cl, Br, or I.

[0220] 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.

[0221] By “haloalkyl” is meant an alkyl group, as defined herein, where one or more hydrogen atoms, such as one to 10 hydrogen atoms, independently is replaced with a halogen atom, such as fluoro, bromo, chloro, or iodo. In an independent embodiment, haloalkyl can be a -CX3 group, wherein each X independently can be selected from fluoro, bromo, chloro, or iodo. In some embodiments, the haloalkyl group is -L-X, in which L is an alkyl group, as defined herein, and X is fluoro, bromo, chloro, or iodo. In other embodiments, the haloalkyl group is -L-C(X)(R1)-R2, in which L is a covalent bond or an alkyl group, as defined herein; X is fluoro, bromo, chloro, or iodo; and each of R1and R2is, independently, H or alkyl, as defined herein.

[0222] 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.

[0223] 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.

[0224] By “heteroalkyl,” “heteroalkenyl,” and “hetero alky nyl” 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.

[0225] By “heteroalkyl-aryl,” “heteroalkenyl-aryl,” and “heteroalkynyl-aryl” is meant an aryl group, as defined herein, that is or can be coupled to a compound disclosed herein, where the aryl group is or becomes coupled through a heteroalkyl, heteroalkenyl, or heteroalkynyl group,Attorney Docket No. 12306-1WO / LAM1P120WOrespectively, as defined herein. In some embodiments, the heteroalkyl-aryl group is -L-R, in which L is a heteroalkyl group, as defined herein, and R is an aryl group, as defined herein. In some embodiments, the heteroalkenyl-aryl group is -L-R, in which L is a heteroalkenyl group, as defined herein, and R is an aryl group, as defined herein. In some embodiments, the heteroalkynyl-aryl group is -L-R, in which L is a heteroalkynyl group, as defined herein, and R is an aryl group, as defined herein.

[0226] By “heteroalkyl-heteroaryl,” “heteroalkenyl-heteroaryl,” and “heteroalkynyl-heteroaryl” is meant a heteroaryl group, as defined herein, that is or can be coupled to a compound disclosed herein, where the heteroaryl group is or becomes coupled through a heteroalkyl, heteroalkenyl, or heteroalkynyl group, respectively, as defined herein. In some embodiments, the heteroalkyl-heteroaryl group is -L-R, in which L is a heteroalkyl group, as defined herein, and R is a heteroaryl group, as defined herein. In some embodiments, the heteroalkenyl-heteroaryl group is -L-R, in which L is a heteroalkenyl group, as defined herein, and R is a heteroaryl group, as defined herein. In some embodiments, the heteroalkynyl-heteroaryl group is -L-R, in which L is a heteroalkynyl group, as defined herein, and R is a heteroaryl group, as defined herein.

[0227] 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 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 example 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.

[0228] 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.

[0229] By “heterocycle” is meant a compound having one or more heterocyclyl moieties. Nonlimiting heterocycles include optionally substituted imidazole, optionally substituted triazole, optionally substituted tetrazole, optionally substituted pyrazole, optionally substituted imidazoline, optionally substituted pyrazoline, optionally substituted imidazolidine, optionally substituted pyrazolidine, optionally substituted pyrrole, optionally substituted pyrroline, optionallyAttorney Docket No. 12306-1WO / LAM1P120WOsubstituted pyrrolidine, optionally substituted tetrahydrofuran, optionally substituted furan, optionally substituted thiophene, optionally substituted oxazole, optionally substituted isoxazole, optionally substituted isothiazole, optionally substituted thiazole, optionally substituted oxathiolane, optionally substituted oxadiazole, optionally substituted thiadiazole, optionally substituted sulfolane, optionally substituted succinimide, optionally substituted thiazolidinedione, optionally substituted oxazolidone, optionally substituted hydantoin, optionally substituted pyridine, optionally substituted piperidine, optionally substituted pyridazine, optionally substituted piperazine, optionally substituted pyrimidine, optionally substituted pyrazine, optionally substituted triazine, optionally substituted pyran, optionally substituted pyrylium, optionally substituted tetrahydropyran, optionally substituted dioxine, optionally substituted dioxane, optionally substituted dithiane, optionally substituted trithiane, optionally substituted thiopyran, optionally substituted thiane, optionally substituted oxazine, optionally substituted morpholine, optionally substituted thiazine, optionally substituted thiomorpholine, optionally substituted cytosine, optionally substituted thymine, optionally substituted uracil, optionally substituted thiomorpholine dioxide, optionally substituted indene, optionally substituted indoline, optionally substituted indole, optionally substituted isoindole, optionally substituted indolizine, optionally substituted indazole, optionally substituted benzimidazole, optionally substituted azaindole, optionally substituted azaindazole, optionally substituted pyrazolopyrimidine, optionally substituted purine, optionally substituted benzofuran, optionally substituted isobenzofuran, optionally substituted benzothiophene, optionally substituted benzisoxazole, optionally substituted anthranil, optionally substituted benzisothiazole, optionally substituted benzoxazole, optionally substituted benzthiazole, optionally substituted benzthiadiazole, optionally substituted adenine, optionally substituted guanine, optionally substituted tetrahydroquinoline, optionally substituted dihydroquinoline, optionally substituted dihydroisoquinoline, optionally substituted quinoline, optionally substituted isoquinoline, optionally substituted quinolizine, optionally substituted quinoxaline, optionally substituted phthalazine, optionally substituted quinazoline, optionally substituted cinnoline, optionally substituted naphthyridine, optionally substituted pyridopyrimidine, optionally substituted pyridopyrazine, optionally substituted pteridine, optionally substituted chromene, optionally substituted isochromene, optionally substituted chromenone, optionally substituted benzoxazine, optionally substituted quinolinone, optionally substituted isoquinolinone, optionally substituted carbazole, optionally substituted dibenzofuran, optionally substituted acridine, optionally substituted phenazine, optionally substituted phenoxazine, optionally substituted phenothiazine,Attorney Docket No. 12306-1WO / LAM1P120WOoptionally substituted phenoxathiine, optionally substituted quinuclidine, optionally substituted azaadamantane, optionally substituted dihydroazepine, optionally substituted azepine, optionally substituted diazepine, optionally substituted oxepane, optionally substituted thiepine, optionally substituted thiazepine, optionally substituted azocane, optionally substituted azocine, optionally substituted thiocane, optionally substituted azonane, optionally substituted azecine, etc. Optional substitutions include any described herein for aryl. Heterocycles can also include cations or salts of any of these.

[0230] By “heterocyclyl” is meant a 5-, 6- or 7-membered ring, unless otherwise specified, containing one, two, three, or four non-carbon heteroatoms (e.g., independently selected from the group consisting of nitrogen, oxygen, phosphorous, sulfur, or halo). The 5-membered ring has zero to two double bonds and the 6- and 7-membered rings have zero to three double bonds. The term “heterocyclyl” also includes bicyclic, tricyclic and tetracyclic groups in which any of the above heterocyclic rings is fused to one, two, or three rings independently selected from the group consisting of an aryl ring, a cyclohexane ring, a cyclohexene ring, a cyclopentane ring, a cyclopentene ring, and another monocyclic heterocyclic ring, such as indolyl, quinolyl, isoquinolyl, tetrahydroquinolyl, benzofuryl, benzothienyl and the like. Heterocyclics include thiiranyl, thietanyl, tetrahydrothienyl, thianyl, thiepanyl, aziridinyl, azetidinyl, pyrrolidinyl, piperidinyl, azepanyl, pyrrolyl, pyrrolinyl, pyrazolyl, pyrazolinyl, pyrazolidinyl, imidazolyl, imidazolinyl, imidazolidinyl, pyridyl, homopiperidinyl, pyrazinyl, piperazinyl, pyrimidinyl, pyridazinyl, oxazolyl, oxazolidinyl, oxazolidonyl, isoxazolyl, isoxazolidiniyl, morpholinyl, thiomorpholinyl, thiazolyl, thiazolidinyl, isothiazolyl, isothiazolidinyl, indolyl, quinolinyl, isoquinolinyl, benzimidazolyl, benzothiazolyl, benzoxazolyl, furyl, thienyl, thiazolidinyl, isothiazolyl, isoindazoyl, triazolyl, tetrazolyl, oxadiazolyl, uricyl, thiadiazolyl, pyrimidyl, tetrahydrofuranyl, dihydrofuranyl, dihydrothienyl, dihydroindolyl, tetrahydroquinolyl, tetrahydroisoquinolyl, pyranyl, dihydropyranyl, tetrahydropyranyl, dithiazolyl, dioxanyl, dioxinyl, dithianyl, trithianyl, oxazinyl, thiazinyl, oxothiolanyl, triazinyl, benzofuranyl, benzothienyl, and the like.

[0231] 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.

[0232] 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.Attorney Docket No. 12306-1WO / LAM1P120WO

[0233] By “hydroxyl” is meant -OH.

[0234] 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.

[0235] By “ketone” is meant -C(O)R, where R is selected from aliphatic, heteroaliphatic, aromatic, as defined herein, or any combination thereof.

[0236] By “nitro” is meant an -NO2group.

[0237] 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.

[0238] By “oxo” is meant an =0 group.

[0239] By “oxy” is meant -O-.

[0240] By “perfluoroalkyl” is meant an alkyl group, as defined herein, having each hydrogen atom substituted with a fluorine atom. Example perfluoroalkyl groups include trifluoromethyl, pentafluoroethyl, etc. In some embodiments, the perfluoroalkyl group is -(CF2)nCF3, in which n is an integer from 0 to 10.

[0241] 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.

[0242] 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 anAttorney Docket No. 12306-1WO / LAM1P120WOanionic 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 amine cations, including, but not limited to ammonium, tetramethylammonium, tetraethylammonium, methylamine, dimethylamine, trimethylamine, triethylamine, ethylamine, pyridinium, and the like. Other cationic salts include organic salts, such as chloroprocaine, choline, dibenzylethylenediamine, diethanolamine, ethylenediamine, methylglucamine, and procaine. Yet other salts include ammonium, sulfonium, sulfoxonium, phosphonium, iminium, imidazolium, benzimidazolium, amidinium, guanidinium, phosphazinium, phosphazenium, pyridinium, etc., as well as other cationic groups described herein (e.g., optionally substituted isoxazolium, optionally substituted oxazolium, optionally substituted thiazolium, optionally substituted pyrrolium, optionally substituted furanium, optionally substituted thiophenium, optionally substituted imidazolium, optionally substituted pyrazolium, optionally substituted isothiazolium, optionally substituted triazolium, optionally substituted tetrazolium, optionally substituted furazanium, optionally substituted pyridinium, optionally substituted pyrimidinium, optionally substituted pyrazinium, optionally substituted triazinium, optionally substituted tetrazinium, optionally substituted pyridazinium, optionally substituted oxazinium, optionally substituted pyrrolidinium, optionally substituted pyrazolidinium, optionally substituted imidazolinium, optionally substituted isoxazolidinium, optionally substituted oxazolidinium, optionally substituted piperazinium, optionally substituted piperidinium, optionally substituted morpholinium, optionally substituted azepanium, optionally substitutedAttorney Docket No. 12306-1WO / LAM1P120WOazepinium, 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).

[0243] 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.

[0244] 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 hetero aliphatic, optionally substituted aromatic, optionally substituted hetero aromatic, 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 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

[0245] By ‘ ‘sulfo” is meant an -S(O)2OH group.

[0246] By “sulfonyl” or “sulfonate” is meant an -S(O)2- group or a -SO2R, where R is selectedAttorney Docket No. 12306-1WO / LAM1P120WOfrom hydrogen, aliphatic, heteroaliphatic, haloaliphatic, haloheteroaliphatic, aromatic, as defined herein, or any combination thereof.

[0247] By “thioalkoxy” is meant an alkyl group, as defined herein, attached to the parent molecular group through a sulfur atom. Example unsubstituted thioalkoxy groups include Ci-6 thioalkoxy. In some embodiments, the thioalkoxy group is -S-R, in which R is an alkyl group, as defined herein.

[0248] By “thiol” is meant an -SH group.

[0249] 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.

[0250] As used herein, the term “or” is used to link alternatives provided within a list. The use of this term does not exclude the use of such alternatives together, such as in a combination; and the use of this term does not indicate or require that an alternative must be used alone. The use of this term can indicate that the alternative can be used alone or can be used together with any other alternative within the list.

[0251] 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.

[0252] Any of the example materials described herein include unsubstituted or substituted forms of the compound (e.g., halogen source, additive, carrier gas, precursors, and the like). Nonlimiting example substituents include, e.g., one, two, three, four, or more substituents independently selected from the group consisting of: (1) Ci6 alkoxy (e.g., O-R, in which R is Ci-6 alkyl); (2) Ci6 alkylsulfinyl (e.g., -S(O)-R, in which R is Ci-6 alkyl); (3) Ci6 alkylsulfonyl (e.g., -SO2-R, in which R is C1-6 alkyl); (4) amine (e.g., C(O)NR1R2or -NHCOR1, 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, 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) C38 cycloalkyl; (12) halo; (13) heterocyclyl (e.g., as defined herein, such as a 5-, 6-or 7-membered ring containing one, two, three, or four non-carbon heteroatoms); (14) heterocyclyloxy (e.g., -O-R, in which R is heterocyclyl, as defined herein); (15) heterocyclyloyl (e.g., -C(O)-R, in which R is heterocyclyl, as defined herein); (16) hydroxyl (e.g., -OH); (17) N-protected amino; (18) nitro (e.g., -NO2); (19) oxo (e.g., =0); (20) Ci6 thioalkoxyAttorney Docket No. 12306-1WO / LAM1P120WO(e.g., -S-R, in which R is Ci-6 alkyl); (21) thiol (e.g., -SH); (22) CO2R1, where R1is selected from the group consisting of (a) hydrogen, (b) Ci6 alkyl, (c) C418 aryl, and (d) Ci6 alkyl-C4-i8 aryl (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) Ci6 alkyl, (c) C418 aryl, and (d) Ci6 alkyl-C4i8 aryl (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) Ci6 alkyl, (b) C418 aryl, and (c) C1-6 alkyl-C4is aryl (e.g., -L-R, in which L is C1-6 alkyl and R is C4-18 aryl); (25) SO2NR1R2, where each of R1and R2is, independently, selected from the group consisting of (a) hydrogen, (b) Ci6 alkyl, (c) C418 aryl, and (d) Ci6 alkyl-C4-i8 aryl (e.g., -L-R, in which L is C1-6 alkyl and R is C4-18 aryl); and (26) NR1R2, where each of R1and R2is, independently, selected from the group consisting of (a) hydrogen, (b) an N-protecting group, (c) C1-6 alkyl, (d) C2-6 alkenyl, (e) C2-6 alkynyl, (f) C4-18 aryl, (g) C1-6 alkyl-C4-18 aryl (e.g., -L-R, in which L is C1-6 alkyl and R is C4-18 aryl), (h) C3-8 cycloalkyl, and (i) C1-6 alkyl-Ca-s cycloalkyl (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.PRECURSORS

[0253] The implementations disclosed herein describe deposition of a material on a substrate such as a wafer, substrate, or other work piece. The work piece may be of various shapes, sizes, and materials. In this application, the terms “semiconductor wafer,” “wafer,” “substrate,” “wafer substrate,” and “partially fabricated integrated circuit” are used interchangeably. The substrate can have any useful property, such as a diameter of more than about 150 mm, 200 mm, 300 mm, 450 mm, or larger.

[0254] Silicon-containing precursors suitable for use in accordance with disclosed embodiments include polysilanes (H3Si-(SiH2)n-SiH3), where n > 0. Examples of silanes are silane (SiH4), disilane (Si2H6), and organosilanes such as methylsilane, ethylsilane, isopropylsilane, t-butylsilane, dimethylsilane, diethylsilane, di-t-butylsilane, allylsilane, sec-butylsilane, thexylsilane, isoamylsilane, t-butyldisilane, di-t-butyldisilane, and the like.

[0255] A halosilane includes at least one halogen group and may or may not include hydrogens and / or carbon groups. Examples of halosilanes are iodosilanes, bromosilanes, chlorosilanes and fluorosilanes. Although halosilanes, particularly fluorosilanes, may form reactive halide species that can etch silicon materials when a plasma is struck, a halosilane may not be introduced to the chamber when a plasma is struck in some embodiments, so formation of a reactive halide species from a halosilane may be mitigated. Specific chlorosilanes are tetrachloro silane, trichlorosilane,Attorney Docket No. 12306-1WO / LAM1P120WOdichlorosilane, monochlorosilane, chloroallylsilane, chloromethylsilane, dichloromethylsilane, chlorodimethylsilane, chloroethylsilane, t-butylchlorosilane, di-t-butylchlorosilane, chloroisopropylsilane, chloro- sec-butylsilane, t-butyldimethylchlorosilane, thexyldimethylchlorosilane, and the like.

[0256] 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), 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, bi(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 and the like. A further example of an aminosilane is trisilylamine (N(SiH3)).

[0257] The film can be deposited using any useful silicon-containing precursor (Si-containing precursor). In some embodiments, the precursor includes a structure of formula (I):Si(R')4(I), wherein at least one R' includes a carbon atom. In other embodiments, at least one R' includes a heteroatom (e.g., nitrogen, oxygen, and / or silicon). In yet other embodiments, at least one R' includes a carbon atom and a heteroatom (e.g., nitrogen, oxygen, and / or silicon). In particular embodiments, R' does not include a halogen atom.

[0258] In other embodiments, the precursor includes a structure of formula (II):(R')3Si-[L-Si(R')2]-R' (II), wherein at least one R' includes a carbon atom and L is a linker. In some embodiments, at least one R' includes a heteroatom (e.g., nitrogen, oxygen, and / or silicon). In yet other embodiments, at least one R' includes a carbon atom and a heteroatom (e.g., nitrogen, oxygen, and / or silicon). In particular embodiments, R' does not include a halogen atom.

[0259] 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.

[0260] For any formula herein (e.g., for formula (I) or (II)), R' can be H, aliphatic, heteroaliphatic, aromatic, heteroaromatic, amino, hydrazino, azido, hydroxyl, silyl (e.g., aminosilyl, alkoxysilyl, and the like), silyloxy (e.g., amino silyloxy, alkoxy silyloxy, and the like), cyanato (-OCN), isocyanato (-NCO), cyano (-CN), or isocyano (-NC), in which any of these may be optionally substituted.Attorney Docket No. 12306-1WO / LAM1P120WO

[0261] In particular embodiments, at least one, two, three, four, or more R' 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.

[0262] In some embodiments, at least one, two, three, four, or more R' in any formula herein (e.g., for formula (I) or (II)) includes an optionally substituted heteroaliphatic. A hetero aliphatic group can include any including one or more carbon atoms and one or more heteroatoms (e.g., oxygen, nitrogen, and the like).

[0263] Non-limiting heteroaliphatic groups includes aliphatic-carbonyl (e.g., alkanoyl or -C(O)RAk), aliphatic-carbonyloxy (e.g., alkanoyloxy or -OC(O)RAk), aliphatic-oxy (e.g., alkoxy or -ORAk), aliphatic-oxycarbonyl (e.g., alkoxycarbonyl or -C(O)ORAk), amino(e.g., -NRN1RN2), aromatic-carbonyl (e.g., aryloyl or -C(O)RAr), aromatic-carbonyloxy (e.g., aryloyloxy or -OC(O)RAr), aromatic-oxy (e.g., aryloxy or -ORAr), aromatic-oxycarbonyl (e.g., aryloxycarbonyl or -C(O)ORAr), imidoyl (e.g., -C(NRN1)H, -C(NRN1)RAk, or -C(NRN1)RAr), carbamoyl (e.g., -C(O)NRN1RN2), carbamoyloxy (e.g., -OC(O)NRN1RN2), carboxyl (-CO2H), 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., -SiRslRS2RS3), and silyloxy (e.g., -O-SiRslRS2RS3). Each of these groups can be optionally substituted with any substituent described herein (e.g., as described herein for alkyl). Hetero aliphatic groups can include linear, branched, cyclic (e.g., heterocyclyl), saturated, or unsaturated forms thereof.

[0264] 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.Attorney Docket No. 12306-1WO / LAM1P120WO

[0265] 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.

[0266] 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.

[0267] 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 groupis -Si(R)a(RAk)b, in which R is, independently, H, aromatic, hetero aromatic, 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 alkylsilyl groupsinclude -SiH2RAk, -SiH[RAk]2, or -Si[RAk]3, in which RAkis any provided herein.

[0268] 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., amino silyloxy, 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, orAttorney Docket No. 12306-1WO / LAM1P120WOoptionally 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.

[0269] 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., amino silyloxy, alkoxy silyloxy, 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.

[0270] 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., amino silyloxy, 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 aryloxy silyl groupsinclude -SiH2[ORAr], -SiH[ORAr]2, or -S i [ ORAr|3, in which RAris any described herein.

[0271] 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 groupis -Si(R)a(NRN1RN2)b, in which R is, independently, H, aliphatic, heteroaliphatic, aromatic, heteroaromatic, hydrazino, azido, hydroxyl, silyl (e.g., aminosilyl, alkoxysilyl, and the like), silyloxy (e.g., amino silyloxy, alkoxy silyloxy, 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],Attorney Docket No. 12306-1WO / LAM1P120WO-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[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.

[0272] In some embodiments, the silyl group is -Si(R')a(OR)b(NR2)c, in which each R' 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.

[0273] 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(R')a(OR)b(NR2)c, in which each R 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. Yet other non-limiting silyloxy groups include -O-Si(R)a(RAk)b, -O-Si(R)a(ORAk)b, -O-Si(R)a(RAr)b, -O-Si(R)a(ORAr)b, -O-Si(R)a(NRN1RN2)b, in which R is, independently, H, aromatic, heteroaromatic, amino, hydrazino, azido, hydroxyl, silyl (e.g., aminosilyl, alkoxysilyl, and the like), silyloxy (e.g., amino silyloxy, 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, orAttorney Docket No. 12306-1WO / LAM1P120WOoptionally 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-SiEhR^, -O-SiH[RAk]2, or -O-SitR^h); alkoxysilyloxy (e.g., -O-SiH2[ORAk], -O-SiH[ORAk]2, or -O-S i [ ORAkla); arylsilyloxy (e.g., -O-SiH2RAr, -O-SiH[RAr]2, or -O-S i [ RA1]3); oraryloxy silyloxy (e.g., -O-SiEhfOR^], -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||NRIR2|,-O-Si[RAk]2[NRN1RN2], -O-SiH[NRN1RN2]2, -O-Si[RAk][NRN1RN2]2, or -O-Si[NRN1RN2]3).

[0274] 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, hetero aromatic, amino, hydrazino, azido, hydroxyl, silyl (e.g., aminosilyl, alkoxysilyl, and the like), silyloxy (e.g., amino silyloxy, alkoxy silyloxy, 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.

[0275] 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, hetero aromatic, amino, hydrazino, azido, hydroxyl, silyl (e.g., aminosilyl, alkoxysilyl, and the like), silyloxy (e.g., aminosilyloxy, alkoxysilyloxy, and the like), cyanato, isocyanato, cyano, or isocyano, in which any of these may be optionally substituted; each of RN1and RN2is, independently, H, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, optionally substituted heteroaromatic, optionally substituted silyl, or optionally substituted silyloxy, in which RN1and RN2can be taken together, with the nitrogen atom to which each is attached, to form an optionally substituted heterocyclyl; each of a and b ≥ 0; and a + b = 3.

[0276] 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, R^, and RArare any described herein; and a, b, and c are any described herein.Attorney Docket No. 12306-1WO / LAM1P120WO

[0277] In some embodiments, at least one, two, three, four, or more R' in any formula herein (e.g., for formula (I) or (II)) includes an optionally substituted aliphatic-oxy, hetero aliphatic -oxy, aromatic-oxy, or heteroaromatic-oxy. For instance, R' 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., -SiRslRS2RS3or -Si(R')a(OR)b(NR2)c, including any described herein), or optionally substituted amino (e.g., -NRN1RN2, including any described herein).

[0278] In particular embodiments, at least one, two, three, four, or more R' 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.

[0279] In particular embodiments, at least one, two, three, four, or more R' in any formula herein (e.g., for formula (I) or (II)) includes an optionally substituted amino (e.g., -NFh, -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.

[0280] Non-limiting instances of RN1and RN2can include H, aliphatic, alkyl (e.g., -R^), alkenyl, alkynyl, aliphatic carbonyl (e.g., alkanoyl or -C(O)RAk), aliphatic-carbonyloxy (e.g., alkanoyloxy or -OC(O)RAk), aliphatic-oxy (e.g., alkoxy or -ORAk), aliphatic-oxycarbonyl (e.g., alkoxycarbonyl or -C(O)ORAk), amino (e.g., -NR2, in which each R is, e.g., H, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, or optionally substituted heteroaromatic), aromatic (e.g., aryl or -R^), 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.,Attorney Docket No. 12306-1WO / LAM1P120WO-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(0)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., -0C(0)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., -SiRslRS2RS3or -Si(R')a(OR)b(NR2)c), and silyloxy (e.g., -O-SiRslRS2RS3or -O-Si(R')a(OR)b(NR2)c). For any of these groups, where indicated, RAk, R^, R', R, RS1, RS2, RS3, a, b, and c can be any described herein.

[0281] 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, -NHfSiHMeEt], -NMe[SiH2Me], -NMe[SiHMe2], -NMe[SiH2Et], -NMe[SiHEt2]2, -NMefSiHMeEt], and the like.

[0282] In particular embodiments, at least one, two, three, four, or more R' 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. 12306-1WO / LAM1P120WO

[0283] In some embodiments, at least one, two, three, four, or more R' in any formula herein (e.g., for formula (I) or (II)) includes an optionally substituted silyl. In one embodiment, silyl is -SiRslRS2RS3, 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(R)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.

[0284] In other embodiments, at least one, two, three, four, or more R' 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(R')a(OR)b(NR2)c, and the like. Yet other nonlimiting 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.

[0285] In yet other embodiments, at least one, two, three, four, or more R' in any formula herein (e.g., for formula (I) or (II)) includes azido (-Na), hydroxyl (-OH), cyanato (-OCN), isocyanato (-NCO), cyano (-CN), and / or isocyano (-NC).

[0286] The organic silicon-containing precursor may be selected from the group consisting of silane, disilane, trisilane, tetrasilane, amine-substituted versions of any of the foregoing silanes, and trisilylamine.

[0287] Examples of organic silicon-containing precursors include, but are not limited to, silanes, poly silanes, halosilanes, and aminosilanes. A silane contains hydrogen and / or carbonAttorney Docket No. 12306-1WO / LAM1P120WOgroups, but does not contain a halogen. A polysilane may have the formula (H3Si-(SiH2)n-SiH3), where n > 1. Examples of silanes include silane (SiH₄), disilane (Si₂H₆), trisilane, tetrasilane and organo silanes such as methylsilane, ethylsilane, isopropylsilane, t-butylsilane, dimethylsilane, diethylsilane, di-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.

[0288] 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), H₂Si(NH₂)₂, HSi(NH₂)₃ and Si(NH₂)₄, respectively), as well as substituted mono-, di-, tri- and tetra-aminosilanes, for example, t-butylaminosilane, methylaminosilane, tert-butylsilanamine, bis(tertiarybutylamino)silane (SiH2(NHC(CH3)3)2 (BTBAS), tert-butyl silylcarbamate, SiH(CH3)-(N(CH3)2)2, SiHCl-(N(CH3)2)2, (Si(CH3)2NH)3, di(sec-butylamino)silane (DSBAS), di(isopropylamido)silane (DIPAS), bis(diethylamino)silane (BDEAS), and the like. A further example of an aminosilane is trisilylamine (N(SiH3)3).

[0289] Examples of silicon-containing precursors for depositing silicon carbide include siloxanes, alkyl silane or hydrocarbon-substituted silane, or a nitrogen-containingcarbon-containing reactant. Examples of siloxanes include 2,4,6, 8 -tetramethylcyclo tetrasiloxane (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.

[0290] Yet other examples of organic silicon-containing precursors can include siloxanes such as cyclotetrasiloxanes such as heptamethylcyclotetrasiloxane (HMCTS) and tetramethyl cyclo tetrasiloxane. Other cyclic siloxanes can also include but are not limited toAttorney Docket No. 12306-1WO / LAM1P120WOcyclotrisiloxanes and cyclopentasiloxanes. Other examples of suitable precursors include linear siloxanes such as, but not limited to, disiloxanes, such as pentamethyldisiloxane (PMDSO), tetramethyldisiloxane (TMDSO), hexamethyl trisiloxane, and heptamethyl trisiloxane. For undoped silicon carbide, examples of suitable precursors include monosilanes substituted with one or more alkyl, alkene, and / or alkyne groups containing, e.g., 1-5 carbon atoms. Examples include but are not limited to trimethylsilane (3MS), dimethylsilane (2MS), triethylsilane (TES), 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 precursors include, e.g., alkyldisilazanes and possibly compounds including amino (-NH2) and alkyl groups separately bonded to one or more silicon atoms. Alkyldisilazanes include silizanes and alkyl groups bonded to two silicon atoms. An example includes 1,1,3,3-tetramethyldisilazane (TMDSN).

[0291] In the Si-containing precursors described herein, different kinds of R' can be attached to the silicon atom. Further Si-containing precursors are described herein.Amino silanes

[0292] A silicon-containing precursor can include one or more optionally substituted amino groups, thereby providing a non-limiting amino silane. In one embodiment, the precursor has a formula of (R')4-xSi(NR"2)x, wherein:x is 1, 2, 3, or 4;each R' is, independently, H, aliphatic, aliphatic-carbonyl, aliphatic-carbonyloxy, aliphatic-oxy, aliphatic-oxycarbonyl, heteroaliphatic, heteroaliphatic-carbonyl, hetero aliphatic -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; andeach R" is, independently, H, aliphatic, heteroaliphatic, aromatic, heteroaromatic, or amino, in which any of these may be optionally substituted; or optionally in which two R" can be taken together, with the nitrogen atom to which each is attached, to form an optionallyAttorney Docket No. 12306-1WO / LAM1P120WOsubstituted heterocyclyl.

[0293] In another embodiment, the precursor has a formula of (R"2N)x(R')3-xSi-L-Si(R')3-X(NR"2)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 R' is, independently, H, aliphatic, aliphatic-carbonyl, aliphatic-carbonyloxy, aliphatic-oxy, aliphatic-oxycarbonyl, heteroaliphatic, heteroaliphatic-carbonyl, hetero aliphatic -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; andeach R" is, independently, H, aliphatic, heteroaliphatic, aromatic, heteroaromatic, or amino, in which any of these may be optionally substituted; or optionally in which two R" can be taken together, with the nitrogen atom to which each is attached, to form an optionally substituted heterocyclyl.

[0294] 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.

[0295] 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.

[0296] In particular embodiments, at least one R' or R" is not H. The precursor can have any useful combination of R' groups and amino groups (NRA) attached to one or more silicon atoms.Attorney Docket No. 12306-1WO / LAM1P120WO

[0297] In some embodiments, R' is H, optionally substituted amino (e.g., -NR2), aliphatic-oxy (e.g., alkoxy or -OR), aliphatic-carbonyl (e.g., alkanoyl or -C(O)R), aliphatic-carbonyloxy (e.g., alkanoyloxy or -OC(O)R), aliphatic-oxycarbonyl (e.g., alkoxycarbonyl or -C(O)OR), silyl (e.g., -SiR3), aliphatic-oxy-silyl (e.g., alkoxy silyl or -Si(R)a(OR)b), aminosilyl(e.g., -Si(R)a(NR2)b), silyloxy (e.g., -O-SiR3), aliphatic-oxy- silyloxy (e.g., alkoxy silyloxy 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.

[0298] In other embodiments, R" is H, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted alkyl, optionally substituted silyl, or optionally substituted silyloxy. In some embodiments, R" is optionally substituted alkyl (e.g., Me, Et, nPr, iPr, sBu, or tBu). In other embodiments, R" is -SiR'3, -SiRa, -Si(R')a(OR)b, -Si(R)a(OR)b, -Si(R')a(NR2)b, -Si(R)a(NR2)b, -Si(R')a(OR)b(NR2)c, -Si(R)a(OR)b(NR2)c, -O-SiR'3, -O-SiR3, -O-Si(R')a(OR)b, -O-Si(R)a(OR)b, -O-Si(R')a(NR2)b, -O-Si(R)a(NR2)b, -O-Si(R')a(OR)b(NR2)c, or-O-Si(R)a(OR)b(NR2)cin which each R' 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.

[0299] The precursor can include at least one R' group attached to the silicon atom. In one embodiment, the precursor has a formula of (R')(H)3-xSi(NR"2)x, wherein R' and R" can be any described herein, and wherein x is 1, 2, or 3. In another embodiment, the precursor has a formula of (R')(H)2Si(NR"2), wherein R' and R" can be any described herein. In one embodiment, the precursor has a formula of (R')(H)Si(NR"2)2, wherein R' and R" can be any described herein. InAttorney Docket No. 12306-1WO / LAM1P120WOanother embodiment, the precursor has a formula of (R')2(H)Si(NR"2), wherein R' and R" can be any described herein. In yet another embodiment, the precursor has a formula of (R')2Si(NR"2)2, wherein R' and R" can be any described herein. In one embodiment, the precursor has a formula of (R')3Si(NR"2), wherein R' and R" can be any described herein.

[0300] The precursor can lack an R' group attached to the silicon atom. In one embodiment, the precursor has a formula of (H)4-xSi(NR"2)x, wherein each R" can independently be any described herein, and wherein x is 1, 2, 3, or 4. In another embodiment, the precursor has a formula of Si(NR″₂)x, wherein each R" can independently be any described herein. In particular embodiments, each R" is, independently, aliphatic, heteroaliphatic, aromatic, or hetero aromatic.

[0301] The precursor can include one or more hydrogen atoms attached to the silicon atom. In one embodiment, the precursor has a formula of (H)3Si(NR"2) or (H)2Si(NR"2)2 or (H)Si(NR"2)3, wherein each R" can independently be any described herein. In particular embodiments, each R" is, independently, aliphatic, heteroaliphatic, aromatic, heteroaromatic, or amino, in which any of these may be optionally substituted.

[0302] The precursor can include a heterocyclyl group having a nitrogen atom. In one embodiment, the formula has a formula of H₃Si-Het, in which Het is an optionally substituted heterocyclyl including at least one nitrogen atom. In particular embodiments, the precursor has a H3Si— NH>)nformula ofv, 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 R′₃Si-Het, in which Het is an optionally substituted heterocyclyl including at least one nitrogen atom, and each R' can independently be R’3Si— N >)nany described herein. In particular embodiments, the precursor has a formula of, in which the heterocyclyl group can be optionally substituted (e.g., with any substituent described herein as a substitution for alkyl); each R' can independently be any described herein; and wherein n is 1,2, 3, 4, or 5.

[0303] In some instances, the precursor can have two or more silicon atoms, in which the precursor can include a Si-Si bond. In a particular embodiment, the precursor has a formula of (R"2N)x(R')3-xSi-Si(R')3-x(NR"2)x, wherein R' and R" can be any described herein. In one embodiment, the precursor has a formula of (R"2N)(R')2Si-Si(R')2(NR"2), wherein R' and R" can be any described herein. In another embodiment, the precursor has a formula of (R"2N)2(R')Si-Si(R')(NR"2)2, wherein R' and R" can be any described herein. In yet another embodiment, theAttorney Docket No. 12306-1WO / LAM1P120WOprecursor has a formula of (R"2N)3Si-Si(NR"2)3, wherein each R" can independently be any described herein.

[0304] The precursor can include differing groups attached to the silicon atoms. In one instance, the precursor has a formula of (R"2N)x(R')3-xSi-SiH3, wherein R' and R" can be any described herein.

[0305] A linker can be present between two silicon atoms. In one instance, the precursor has a formula of (R"2N)x(R')3-xSi-NR-Si(R')3-x(NR"2)x, wherein R' and R" can be any described herein, and in which R is H, optionally substituted aliphatic, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, or optionally substituted aromatic. In another instance, the precursor has a formula of (R"2N)x(H)3-xSi-NR-Si(H)3-x(NR"2)x, wherein R, R', and R" can be any described herein.

[0306] The precursor can include a combination of R' groups with a linker having a heteroatom. In one instance, the precursor has a formula of (R')3Si-NR-Si(R')3, wherein R and R' can be any described herein. In another instance, the precursor has a formula of(R')3Si-L-Si(R')3, wherein L and R' 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-).

[0307] The precursor can include any useful combination of R' and NRA groups in combination with two silicon atoms. In one instance, the precursor has a formula of (R"2N)(R')2Si-L-Si(R')2(NR"2)x, wherein L, R', and R" can be any described herein.

[0308] The precursor can include heterocyclic groups including the silicon and nitrogen atoms.R" R"i iIn one embodiment, the precursor has a formula of R" R", wherein R' and R" can be any described herein, and wherein n is 1, 2, 3, or 4.SVR’-Si— Si— R'

[0309] In another embodiment, the precursor has a formula of 'n, wherein R' and R" can be any described herein, and wherein n is 1, 2, 3, or 4. In yet another embodiment, theAttorney Docket No. 12306-1WO / LAM1P120WOSiiSiprecursor has a formulaof3, in which each R" can independently be any described herein; and wherein n is 1,2, 3, or 4.R"iR'2s< )nNinIn another embodiment, the precursor has a formula ofR", wherein R' and R" can be any described herein, and wherein n is 1, 2, 3, or 4. In yet another embodiment, the precursor(rrNR" NR'S.'vn \ / F'nR" N- Si- Si- NR"I \R-'V -R"has a formula of n, wherein R" can independently be any described herein, and wherein n is 1, 2, 3, or 4.

[0310] In any precursor herein, two R" can be taken together, with the nitrogen atom to which each is attached, to form an optionally substituted heterocyclyl.

[0311] Precursors can include any of the following, e.g., (RAk)Si(NH2)(NRAk2)2, (RAk)Si(NRAk2)3, (RAk)2Si(NHRAk2)2, (RAk)(H)Si(NHRAk)2, (R^ SiCNR^), (RAk)3Si(NHRAk), H2Si(NHRAk2)2, (RAk)(H)Si(NRAk2)2, HSi(NH2)(NRAk2)2, HSi(NRAk2)3, Si(NRAk2)4, (R')(H)Si(NR"2)2, (R')2Si(NRAk2)2, (R')2Si(N[SiH3]2)2, (R')2Si(N[SiR"3]2)2, or (R' SiCNHR^). In some embodiments, each of R' and R", independently, can be any described herein (e.g., H, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted alkyl, optionally substituted alkenyl, or optionally substituted alkynyl). In other embodiments, each RAkis, independently, H, optionally substituted aliphatic, optionally substituted heteroaliphatic, 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.

[0312] Non-limiting examples of precursor include any of the following: methylaminotrimethylsilane (SiMe3[NHMe]); dimethylaminodimethylsilane (SiMe2H[NMe2]); dimethylaminotrimethylsilane (SiMe3[NMe2]); dimethylaminodiethylsilane (SiHEt2[NMe2]); dimethylaminotriethylsilane (SiEt3[NMe2] ); ethylmethylaminodimethylsilane (SiHMe2[NMeEt]); ethylmethylaminotrimethylsilane (SiMe3[NMeEt]); ethylmethylaminodiethylsilane (SiHEt2[NMeEt]); ethylmethylaminotriethylsilane (SiEt3[NMeEt]); diethylaminomethylsilane (SiH2Me[NEt2]); diethylaminoethylsilaneAttorney Docket No. 12306-1WO / LAM1P120WO(SiH2Et[NEt2]); ethylaminotrimethylsilane (SiMeafNHEt]); diethylaminodimethylsilane (SiHMe2[NEt2]); diethylaminodiethylsilane (SiHEt2[NEt2]); diethylaminotrimethylsilane (SiMe3[NEt2]); diethylaminotriethylsilane (SiEt3[NEt2]); iso-propylaminodimethylsilane (SiHMe2[NHiPr]); iso-propylaminotrimethylsilane (SiMe3[NHiPr]); iso-propylamino diethylsilane (SiHEt2[NHiPr]); iso-propylaminotriethylsilane (SiEt3[NHiPr]); di-isopropyl aminotrimethylsilane (SiMe3[NiPr2]); di-iso-propylaminosilane (SiH3[NiPr2], C6H17NSi, or DIPAS); di-iso-propylaminomethylsilane (SiH2Me[NiPr2]); di-isopropylaminodimethylsilane (SiHMe2[NiPr2]); di-isopropylaminodiethylsilane (SiHEt2[NiPr2]); di-isopropylamino triethylsilane (SiEt3[NiPr2]); n-propylaminotrimethylsilane (SiMe3[NHnPr]); di-sec -butylamino silane (SiH3[NsBu2] or DSBAS); di-sec -butylaminomethylsilane (SiH2Me[NsBu2]); isobutylaminotrimethylsilane (SiMe3[NHiBu]); n-butylaminotrimethylsilane (SiMe3[NHnBu]); tertbutylaminodimethylsilane (SiHMe2[NHtBu]); tert-butylaminotrimethylsilane (SiMe3[NHtBu]); tert-butylaminodiethylsilane (SiHEt2[NHtBu]); tert-butylaminotriethylsilane (SiEt3[NHtBu]); dicyclohexylaminosilane (SiH3[NCy2], in which Cy is cyclohexyl); N-propylisopropyl aminosilane (SiH3[NiPrnPr]); N-methylcyclohexylaminosilane (SiH3[NMeCy]); N-ethyl cyclohexylaminosilane (SiH3[NEtCy]); allylphenylaminosilane (SiH3[NAllPh]); N-isopropyl cyclohexylaminosilane (SiH3[NiPrCy]); allylcyclopentylaminosilane (SiH3[NAllCp]); phenylcyclohexylaminosilane (SiH3[NPhCy]); cyclohexylaminotrimethylsilane (SiMe3[NHCy], in which Cy is cyclohexyl); pyrrolyltrimethylsilane (SiMe3[NHPy], in which Py is pyrrolyl); pyrrolidinotrimethylsilane (SiMe3[NHPyr], in which Pyr is pyrrolindyl); piperidino trimethylsilane (SiMe3[NHPip], in which Pip is piperidinyl); piperazinotrimethylsilane (SiMe3[NHPz], in which Pz is piperazinyl); imidazolyltrimethylsilane (SiMe3[NHIm], in which Im is imidazolyl); bis(dimethylamino)silane (SiH2[NMe2]2 or BDMAS); bis(dimethylamino) methylsilane (SiMeH[NMe2]2); bis(dimethylamino)dimethylsilane (SiMe2[NMe2]2 or BDMADMS); bis(dimethylamino)diethylsilane (SiEt2[NMe2]2); bis(dimethylamino) methylvinylsilane (SiMeVi[NMe2]2); bis(ethylamino)dimethylsilane (SiMe2[NHEt]2); bis(ethylmethylamino)silane (SiH2[NMeEt]2); bis(ethylmethylamino)dimethylsilane (SiMe2[NMeEt]2); bis(ethylmethylamino)diethylsilane (SiEt2[NMeEt]2); bis(ethylmethylamino) methylvinylsilane (SiMeVi[NMeEt]2); bis(diethylamino)silane (SiH2[NEt2]2, C8H22N2Si, or BDEAS); bis(diethylamino)dimethylsilane (SiMe2[NEt2]2); bis(diethylamino)methylvinylsilane (SiMeVi[NEt2]2); bis(diethylamino)diethylsilane (SiEt2[NEt2]2); bis(iso-propylamino) dimethylsilane (SiMe2[NHiPr]2); bis(iso-propylamino)diethylsilane (SiEt2[NHiPr]2); bis(iso-propylamino)methylvinylsilane (SiMeVi[NHiPr]2); bis(di-iso-propylamino)silaneAttorney Docket No. 12306-1WO / LAM1P120WO(SiH2[NiPr2]2); bis(di-iso-propylamino)dimethylsilane (SiMe2[NiPr2]2); bis(di-iso-propylamino) diethylsilane (SiEt2[NiPr2]2); bis(di-iso-propylamino)methylvinylsilane (SiMeVi[NiPr2]2); bis(methylamino)silane (SiH2[NHMe]2); bis(sec-butylamino)silane (SiH2[NHsBu]2); bis(sec-butylamino)methylsilane (SiHMe[NHsBu]2); bis(sec-butylamino)ethylsilane (SiHEt[NHsBu]2); bis(tert-butylamino)silane (SiH2[NHtBu]2 or BTBAS); bis(tert-butylamino)dimethylsilane (SiMe2[NHtBu]2); bis(tert-butylamino) methylvinylsilane (SiMeVi[NHtBu]2); bis(tert-butylamino)diethylsilane (SiEt2[NHtBu]2); bis(l-imidazolyl)dimethylsilane (SiMe2[Im]2, in which Im is imidazolyl); tris(dimethylamino)silane (SiH[NMe2]3 or 3DMAS); tris(dimethylamino)phenylsilane (SiPh[NMe2]3); tris(dimethylamino) methylsilane (SiMe[NMe2]3); tris(dimethylamino)ethylsilane (SiEt[NMe2]3); tris(ethylmethylamino)silane (SiH[NEtMe]3); tris(diethylamino)silane (SiH[NEt2]3); tris(iso-propylamino)silane (SiH[NHiPr]3, C9H25N3Si, or TIPAS); tris(dimethylamino)silylamide (Si[NMe2]3[NH2]); tetrakis(dimethylamino)silane (Si[NMe2]4); tetrakis(ethylmethylamino)silane (Si[NEtMe]4); tetrakis(diethylamino)silane (Si[NEt2]4); l,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

[0313] A silicon-containing precursor can include one or more isocyanato groups, thereby providing a non-limiting isocyanato silane. In one embodiment, the precursor has a formula of (R')4-xSi(NCO)x, wherein:x is 1, 2, 3, or 4; andeach R' is, independently, H, aliphatic, aliphatic-carbonyl, aliphatic-carbonyloxy, aliphatic-oxy, aliphatic-oxycarbonyl, heteroaliphatic, heteroaliphatic-carbonyl, hetero aliphatic -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.

[0314] In another embodiment, the precursor has a formula of (R')zSi(NCO)x(NR"2)y, wherein:x is 1, 2, 3, or 4;each of y and z is, independently, 0, 1, 2, or 3;Attorney Docket No. 12306-1WO / LAM1P120WOx + y + z = 4;each R' is, independently, H, aliphatic, aliphatic-carbonyl, aliphatic-carbonyloxy, aliphatic-oxy, aliphatic-oxycarbonyl, heteroaliphatic, heteroaliphatic-carbonyl, hetero aliphatic -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; andeach R" is, independently, H, aliphatic, hetero aliphatic, aromatic, heteroaromatic, or amino, in which any of these may be optionally substituted; or optionally in which two R" can be taken together, with the nitrogen atom to which each is attached, to form an optionally substituted heterocyclyl.

[0315] In yet another embodiment, the precursor has a formula of (NCO)x(R')3-xSi-L-Si(R')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; andeach R' is, independently, H, aliphatic, aliphatic-carbonyl, aliphatic-carbonyloxy, aliphatic-oxy, aliphatic-oxycarbonyl, heteroaliphatic, heteroaliphatic-carbonyl, hetero aliphatic -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.

[0316] In some embodiments, R' is H, optionally substituted amino (e.g., -NR2), aliphatic-oxy (e.g., alkoxy or -OR), aliphatic-carbonyl (e.g., alkanoyl or -C(O)R), aliphatic-carbonyloxy (e.g., alkanoyloxy or -OC(O)R), aliphatic-oxycarbonyl (e.g., alkoxycarbonyl or -C(O)OR), silyl (e.g., -SiRs), aliphatic-oxy-silyl (e.g., alkoxysilyl or -Si(R)a(OR)b), aminosilyl (e.g., -Si(R)a(NR2)b), silyloxy (e.g., -O-SiR,), aliphatic-oxy- silyloxy (e.g., alkoxysilyloxyor -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 particularAttorney Docket No. 12306-1WO / LAM1P120WOembodiments, 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.

[0317] In other embodiments, R" is H, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted alkyl, optionally substituted silyl, or optionally substituted silyloxy. In some embodiments, R" is optionally substituted alkyl (e.g., Me, Et, nPr, iPr, sBu, or tBu). In other embodiments, R" is -SiR'3, -SiRa, -Si(R')a(OR)b, -Si(R)a(OR)b, -Si(R')a(NR2)b, -Si(R)a(NR2)b, -Si(R')a(OR)b(NR2)c, -Si(R)a(OR)b(NR2)c, -O-SiR'3, -O-SiR3, -O-Si(R')a(OR)b, -O-Si(R)a(OR)b, -O-Si(R')a(NR2)b, -O-Si(R)a(NR2)b, -O-Si(R')a(OR)b(NR2)c, or-O-Si(R)a(OR)b(NR2)cin which each R' 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.

[0318] Precursors can include any of the following, e.g., (R')Si(NCO)(NR"2)2, (R')2Si(NCO)(NR"2), (R')2Si(NCO)(N[SiR3]2), or tetraisocyanatosilane (Si[NCO]4). In some embodiments, each of R' and R", independently, can be any described herein (e.g., H, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted alkyl, optionally substituted alkenyl, or optionally substituted alkynyl). In other embodiments, each R is, independently, H, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted alkoxy, optionally substituted aromatic, optionally substituted heteroaromatic, optionally substituted aryl, or optionally substituted heteroaryl.Attorney Docket No. 12306-1WO / LAM1P120WOAzido silanes

[0319] A silicon-containing precursor can include one or more azido groups, thereby providing a non-limiting azido silane. In one embodiment, the precursor has a formula of (R')4-xSi(N3)x, wherein:x is 1, 2, 3, or 4; andeach R' is, independently, H, aliphatic, aliphatic-carbonyl, aliphatic-carbonyloxy, aliphatic-oxy, aliphatic-oxycarbonyl, heteroaliphatic, heteroaliphatic-carbonyl, hetero aliphatic -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.

[0320] In another embodiment, the precursor has a formula of (R')zSi(N3)x(NR"2)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 R' is, independently, H, aliphatic, aliphatic-carbonyl, aliphatic-carbonyloxy, aliphatic-oxy, aliphatic-oxycarbonyl, heteroaliphatic, heteroaliphatic-carbonyl, hetero aliphatic -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; andeach R" is, independently, H, aliphatic, hetero aliphatic, aromatic, heteroaromatic, or amino, in which any of these may be optionally substituted; or optionally in which two R" can be taken together, with the nitrogen atom to which each is attached, to form an optionally substituted heterocyclyl.

[0321] In yet another embodiment, the precursor has a formula of (N3)x(R')3-xSi-L-Si(R')3-x(N3)x, wherein:each x is, independently, 0, 1, 2, or 3;L is a linker, such as a covalent bond, optionally substituted aliphatic, optionally substituted alkylene, optionally substituted alkenylene, optionally substituted alkynylene, optionally substituted heteroaliphatic, optionally substituted heteroalkylene, optionally substituted heteroalkenylene, optionally substituted heteroalkynylene, optionally substituted aromatic, optionally substituted arylene, optionally substituted heteroaromatic, optionally substituted heteroarylene, oxy (-O-), imino, or silyl; andAttorney Docket No. 12306-1WO / LAM1P120WOeach R' is, independently, H, aliphatic, aliphatic-carbonyl, aliphatic-carbonyloxy, aliphatic-oxy, aliphatic-oxycarbonyl, heteroaliphatic, heteroaliphatic-carbonyl, hetero aliphatic -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.

[0322] In some embodiments, R' is H, optionally substituted amino (e.g., -NR2), aliphatic-oxy (e.g., alkoxy or -OR), aliphatic-carbonyl (e.g., alkanoyl or -C(O)R), aliphatic-carbonyloxy (e.g., alkanoyloxy or -OC(O)R), aliphatic-oxycarbonyl (e.g., alkoxycarbonyl or -C(O)OR), silyl (e.g., -SiR3), aliphatic-oxy-silyl (e.g., alkoxysilyl or -Si(R)a(OR)b), aminosilyl (e.g., -Si(R)a(NR2)b), silyloxy (e.g., -O-SiR3), aliphatic-oxy- silyloxy (e.g., alkoxy silyloxy 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.

[0323] In other embodiments, R" is H, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted alkyl, optionally substituted silyl, or optionally substituted silyloxy. In some embodiments, R" is optionally substituted alkyl (e.g., Me, Et, nPr, iPr, sBu, or tBu). In other embodiments, R" is -SiR'3, -SiRa, -Si(R')a(OR)b, -Si(R)a(OR)b, -Si(R')a(NR2)b, -Si(R)a(NR2)b, -Si(R')a(OR)b(NR2)c, -Si(R)a(OR)b(NR2)c, -O-SiR'3, -O-SiR3, -O-Si(R')a(OR)b, -O-Si(R)a(OR)b, -O-Si(R')a(NR2)b, -O-Si(R)a(NR2)b, -O-Si(R')a(OR)b(NR2)c, or-O-Si(R)a(OR)b(NR2)cin which each R 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 ora + 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. 12306-1WO / LAM1P120WO

[0324] Precursors can include any of the following, e.g., (R')3Si(N3), (R')2Si(N3)2, (R')Si(N3)3, or Si(N3)(NR"2)3. In some embodiments, each of R' and R", independently, can be any described herein (e.g., H, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted alkyl, optionally substituted alkenyl, or optionally substituted alkynyl). Non-limiting examples of precursors also include tris(dimethylamino)silylazide ([Me2N]3SiN3); di-tert-butyl diazidosilane (tBu2Si(N3)2); ethylsilicon triazide (EtSi(N3)3); and the like.Hydrazino silanes

[0325] A silicon-containing precursor can include one or more optionally substituted hydrazino groups, thereby providing a non-limiting hydrazino silane. In one embodiment, the precursor has a formula of (R')4-xSi(NR"-NR"2)x, wherein:x is 1, 2, 3, or 4;each R' is, independently, H, aliphatic, aliphatic-carbonyl, aliphatic-carbonyloxy, aliphatic-oxy, aliphatic-oxycarbonyl, heteroaliphatic, heteroaliphatic-carbonyl, hetero aliphatic -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; andeach R" is, independently, H, aliphatic, heteroaliphatic, aromatic, heteroaromatic, or amino, in which any of these may be optionally substituted; or optionally in which two R" can be taken together, with the nitrogen atom to which each is attached, to form an optionally substituted heterocyclyl.

[0326] In another embodiment, the precursor has a formula of (NR"2-NR")x(R')3-xSi-L-Si (R')3-X(NR"-NR"2)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 R' is, independently, H, aliphatic, aliphatic-carbonyl, aliphatic-carbonyloxy, aliphatic-oxy, aliphatic-oxycarbonyl, heteroaliphatic, heteroaliphatic-carbonyl, hetero aliphatic -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; andAttorney Docket No. 12306-1WO / LAM1P120WOeach R" is, independently, H, aliphatic, heteroaliphatic, aromatic, heteroaromatic, or amino, in which any of these may be optionally substituted; or optionally in which two R" can be taken together, with the nitrogen atom to which each is attached, to form an optionally substituted heterocyclyl.

[0327] In yet another embodiment, the precursor has a formula of (R')4-xSi(NR"-L-NR"2)x, wherein: x is 1, 2, 3, or 4; and each L, R', and R" can be any described herein.

[0328] 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).

[0329] 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.

[0330] The precursor can include any useful combination of R' and hydrazino groups. In one embodiment, the precursor has a formula of (R')3Si(NR"-L-NR"2) or (R')3Si(NR"-NR"2), wherein L, R', and R" can be any described herein.

[0331] The precursor can include a plurality of hydrazino groups. In one embodiment, the precursor has a formula of (R')2Si(NR"-L-NR"2)2, (R')2Si(NR"-NR"2)2, or (R')2Si(NH-NHR")2, wherein L, R', and R" can be any described herein.

[0332] The precursor can include at least two silicon atoms. In one embodiment, the precursor has a formula of (NR"2-NR")(R')2Si-Si(R')2(NR"-NR"2), wherein each R' and R" can be any described herein.

[0333] Non-limiting precursors can include bis(tert-butylhydrazino)diethylsilane (SiEt2[NH-NHtBu]2); tris(dimethylhydrazino)silane (SiH[NH-NMe2]3); and the like.Attorney Docket No. 12306-1WO / LAM1P120WOSiloxanes and derivatives thereof

[0334] A silicon-containing precursor can include one or more aliphatic-oxy, aromatic-oxy groups, and / or oxy groups, thereby providing a siloxane or a derivative thereof having one or more Si-O, O-Si-O, or Si-O-Si bonds. In one embodiment, the precursor has a formula of (R')4-xSi(OR"')x, wherein:x is 1, 2, 3, or 4;each R' is, independently, H, aliphatic, aliphatic-carbonyl, aliphatic-carbonyloxy, aliphatic-oxy, aliphatic-oxycarbonyl, heteroaliphatic, heteroaliphatic-carbonyl, hetero aliphatic -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; andeach R"' is, independently, H, aliphatic, hetero aliphatic, aromatic, heteroaromatic, silyl, or silyloxy, in which any of these may be optionally substituted.

[0335] In another embodiment, the precursor has a formula of (R"'O)x(R')3-xSi-L-Si(R')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 R' is, independently, H, aliphatic, aliphatic-carbonyl, aliphatic-carbonyloxy, aliphatic-oxy, aliphatic-oxycarbonyl, heteroaliphatic, heteroaliphatic-carbonyl, hetero aliphatic -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; andeach R"' is, independently, H, aliphatic, hetero aliphatic, aromatic, heteroaromatic, silyl, or silyloxy, in which any of these may be optionally substituted.

[0336] 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-L-O-,Attorney Docket No. 12306-1WO / LAM1P120WOin which L' 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.

[0337] 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.

[0338] In some embodiments, R' is H, optionally substituted amino (e.g., -NR2), aliphatic-oxy (e.g., alkoxy or -OR), aliphatic-carbonyl (e.g., alkanoyl or -C(O)R), aliphatic-carbonyloxy (e.g., alkanoyloxy or -OC(O)R), aliphatic-oxycarbonyl (e.g., alkoxycarbonyl or -C(O)OR), silyl (e.g., -SiR3), aliphatic-oxy-silyl (e.g., alkoxy silyl or -Si(R)a(OR)b), aminosilyl(e.g., -Si(R)a(NR2)b), silyloxy (e.g., -O-SiR3), aliphatic-oxy- silyloxy (e.g., alkoxy silyloxy 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.

[0339] In other embodiments, R"' is H, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted alkyl, optionally substituted silyl, or optionally substituted silyloxy. In some embodiments, R"' is optionally substituted alkyl (e.g., Me, Et, nPr, iPr, sBu, or tBu). In other embodiments, R"' is -SiR'3, -SiRa, -Si(R')a(OR)b, -Si(R)a(OR)b, -Si(R')a(NR2)b, -Si(R)a(NR2)b, -Si(R')a(OR)b(NR2)c, -Si(R)a(OR)b(NR2)c, -O-SiR'3, -O-SiR3, -O-Si(R')a(OR)b, -O-Si(R)a(OR)b, -O-Si(R')a(NR2)b, -O-Si(R)a(NR2)b, -O-Si(R')a(OR)b(NR2)c, or -O-Si(R)a(OR)b(NR2)cin which each R is, independently, H, aliphatic, heteroaliphatic, aromatic,Attorney Docket No. 12306-1WO / LAM1P120WOheteroaromatic, 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.

[0340] The precursor can include one or more hydrogen atoms attached to the silicon atom. In one embodiment, the precursor has a formula of H3Si(OR"'), H2Si(OR"')2, or HSi(OR"')3, wherein each R"' can independently be any described herein.

[0341] The precursor can include any combination of R' and OR"' groups within the precursor. In one embodiment, the precursor has a formula of (R')3Si(OR"'), (R')2Si(OR"')2, or (R')Si(OR"')3, wherein each of R' and R"' can independently be any described herein. The precursor can include alkyl groups, such as in the precursor having a formula of (RAk)3Si(ORAk), (RAk)2Si(ORAk)2, or (RAk)Si(ORAk)3, in which RAkis optionally substituted alkyl.

[0342] In some instances, the precursor can have two or more silicon atoms, in which the precursor can include a Si-Si bond. In a particular embodiment, the precursor has a formula of (R"'O)x(R')3-xSi-Si(R')3-x(OR"')x, wherein R' and R"' can be any described herein. In one embodiment, the precursor has a formula of (R"'O)(R')2Si-Si(R')2(OR"'), wherein R' and R"' can be any described herein.

[0343] The precursor can include a combination of R' groups with a linker having a heteroatom. In one instance, the precursor has a formula of (R')3Si-O-Si(R')3, wherein R' can be any described herein. In another instance, the precursor has a formula of (R')3Si-O-L'-O-Si(R')3, wherein L' and R' can be any described herein. In yet another instance, the precursor has a formula of (R')3Si-(OSiR'2)z-R', wherein R' can be any described herein; and in which z is 1, 2, 3, 4, or more. In another instance, the precursor has a formula of (R')4-xSi-[(OSiR'2)z-R']x, wherein R' can be any described herein; x is 1, 2, 3, or 4; and z is 1, 2, 3, 4, or more.

[0344] The precursor can include any useful combination of R' and OR"' groups in combination with two silicon atoms. In one instance, the precursor has a formula of (R"'O)x(R')3-xSi-O-Si(R')3-x(OR"')x, wherein R' and R"' can be any described herein. In another instance, the precursor has a formula of (R"'O)x(R')3-xSi-O-L'-O-Si(R')3-x(OR"')x, wherein L', R', and R"' can be any described herein.

[0345] Non-limiting precursors can include methoxydimethylsilane (SiHMe2[OMe]); ethoxydimethylsilane (SiHMe2[OEt]); iso-propoxydimethylsilane (SiHMe2[OiPr]); t-Attorney Docket No. 12306-1WO / LAM1P120WObutoxydimethylsilane (SiHMe2[OtBu]); t-pentoxydimethylsilane (SiHMe2[OtPe]); phenoxy dimethylsilane (SiHMe2[OPh]); acetoxydimethylsilane (SiHMe2[0Ac]); methoxytrimethylsilane (SiMe3[OMe]); ethoxytrimethylsilane (SiMe3[OEt]); iso-propoxytrimethylsilane (SiMe3[OiPr]); t-butoxytrimethylsilane (SiMe3[OtBu]); t-pentoxytrimethylsilane (SiMe3[OtPe]); phenoxytrimethylsilane (SiMe3[OPh]); acetoxytrimethylsilane (SiMe3[OAc]); methoxytriethylsilane (SiEt3[OMe]); ethoxy triethylsilane (SiEt3[OEt]); iso-propoxy triethylsilane (SiEt3[OiPr]); t-butoxytriethylsilane (SiEt3[OtBu]); t-pentoxytriethylsilane (SiEt3[OtPe]); phenoxytriethylsilane (SiEt3[OPh]); acetoxytriethylsilane (SiEt3[OAc]); dimethoxysilane (SiH2[OMe]2); diethoxysilane (SiH2[OEt]2); di-iso-propoxysilane (SiH2[OPr]2); di-tert-butoxysilane (SiH2[OtBu]2 or DTBOS); di-tert-pentoxysilane (SiH2[OtPe]2 or 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[0Me]2); diethoxymethylvinylsilane (SiMeVi[OEt]2); di-iso-propoxymethylvinylsilane (SiMeVi[0iPr]2); di-tert-butoxymethylvinylsilane (SiMeVi[0tBu]2); diacetoxymethylvinylsilane (SiMeVi[0Ac]2); triethoxysilane (SiH[OEt]3 or TES); trimethoxyethylsilane (SiEt[OMe]3); triethoxymethylsilane (SiMe[OEt]3); triethoxyphenylsilane (SiPh[OEt]3); tetramethoxysilane (Si[0Me]4); tetraethoxysilane (Si[OEt]4 or TEOS); tetra-n-propoxysilane (Si[OnPr]4); tetra-iso-propoxysilane (Si[OiPr]4); tetra-n-butoxysilane (Si[0nBu]4); tetra- t-butoxy silane (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

[0346] A silicon-containing precursor can include one or more optionally substituted amino groups with either aliphatic-oxy or aromatic-oxy groups, thereby providing a non-limiting mixed silane. In one embodiment, the precursor has a formula of (R')zSi(OR"')x(NR"2)y, wherein:each of x and y is, independently, 1, 2, 3, or 4;z is 0, 1, or 2;Attorney Docket No. 12306-1WO / LAM1P120WOx + y + z = 4;each R' is, independently, H, aliphatic, aliphatic-carbonyl, aliphatic-carbonyloxy, aliphatic-oxy, aliphatic-oxycarbonyl, heteroaliphatic, heteroaliphatic-carbonyl, hetero aliphatic -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 R" is, independently, H, aliphatic, heteroaliphatic, aromatic, heteroaromatic, or amino, in which any of these may be optionally substituted; or optionally in which two R" can be taken together, with the nitrogen atom to which each is attached, to form an optionally substituted heterocyclyl; andeach R"' is, independently, H, aliphatic, hetero aliphatic, aromatic, heteroaromatic, silyl, or silyloxy, in which any of these may be optionally substituted.

[0347] In another embodiment, the precursor has a formula of (R"2N)y(R"'O)x(R')zSi-L-Si(R')z(OR"')x(NR"2)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 R' is, independently, H, aliphatic, aliphatic-carbonyl, aliphatic-carbonyloxy, aliphatic-oxy, aliphatic-oxycarbonyl, heteroaliphatic, heteroaliphatic-carbonyl, hetero aliphatic -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 R" is, independently, H, aliphatic, heteroaliphatic, aromatic, heteroaromatic, or amino, in which any of these may be optionally substituted; or optionally in which two R" can be taken together, with the nitrogen atom to which each is attached, to form an optionallyAttorney Docket No. 12306-1WO / LAM1P120WOsubstituted heterocyclyl; andeach R"' is, independently, H, aliphatic, hetero aliphatic, aromatic, heteroaromatic, silyl, or silyloxy, in which any of these may be optionally substituted.

[0348] Non-limiting examples of R', R", and R"' are described herein, e.g., such as for amino silane, siloxane, or derivatives thereof.

[0349] The precursor can include any combination of R', NR "2, and OR"' groups. In one embodiment, the precursor has a formula of (R')Si(OR"')2(NR"2) or (R')2Si(OR"')2(NR"2), wherein each of R', R", and R"' can independently be any described herein. In other embodiments, the precursor has a formula of (R')2Si(OR"')(N[SiR3]2), wherein each of R' 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.

[0350] The precursor can include only amino and oxy-containing groups attached to the silicon atom. In one embodiment, the precursor has a formula of Si(OR"')3(NR"2), Si(OR"')2(NR"2)2, or Si(OR"')(NR"2)3, wherein each of R" and R"' can independently be any described herein. Nonlimiting precursors can include, e.g., diethoxy(iso-propylamino)silane (SiH[NHiPr][OEt]2); diethoxy(tert-butylamino)silane (SiH[NHtBu][OEt]2); diethoxy(tert-pentylamino)silane (SiH[NHtPe][OEt]2); di-tert-butoxy(methylamino)silane (SiH[NHMe][OtBu]2); di-tert-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 (SiMe[NPhMe][OEt]2); and the like.Attorney Docket No. 12306-1WO / LAM1P120WOSilyl amines

[0351] A silicon-containing precursor can include one or more optionally substituted silyl groups attached to a nitrogen atom, thereby providing a non-limiting silyl amine. In one embodiment, the precursor has a formula of (R")3-yN(SiR'3)y, wherein:y is 1, 2, or 3;each R' is, independently, H, aliphatic, aliphatic-carbonyl, aliphatic-carbonyloxy, aliphatic-oxy, aliphatic-oxycarbonyl, heteroaliphatic, heteroaliphatic-carbonyl, hetero aliphatic -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; andeach R" 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 R" can be taken together, with the nitrogen atom to which each is attached, to form an optionally substituted heterocyclyl.

[0352] In another embodiment, the precursor has a formula of (R'3Si)y(R")2-yN-L-N(R")2-y(SiR'3)y, wherein:each y is, independently, 0, 1, or 2;L is a linker, such as a covalent bond, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, optionally substituted heteroaromatic, oxy (-O-), imino, or silyl;each R' is, independently, H, aliphatic, aliphatic-carbonyl, aliphatic-carbonyloxy, aliphatic-oxy, aliphatic-oxycarbonyl, heteroaliphatic, heteroaliphatic-carbonyl, hetero aliphatic -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; andeach R" is, independently, H, aliphatic, heteroaliphatic, aromatic, heteroaromatic, or amino, in which any of these may be optionally substituted; or optionally in which two R" 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.

[0353] 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 includesAttorney Docket No. 12306-1WO / LAM1P120WOoptionally 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(SiRa)-), 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 hetero aliphatic, optionally substituted aromatic, optionally substituted aryl, and optionally substituted heteroaromatic.

[0354] In some embodiments, R' is H, optionally substituted amino (e.g., -NR2), aliphatic-oxy (e.g., alkoxy or -OR), aliphatic-carbonyl (e.g., alkanoyl or -C(O)R), aliphatic-carbonyloxy (e.g., alkanoyloxy or -OC(O)R), aliphatic-oxycarbonyl (e.g., alkoxycarbonyl or -C(O)OR), silyl (e.g., -SiR3or -SiR2-L-SiRa), aliphatic-oxy-silyl (e.g., alkoxy silyl or -Si(R)a(OR)b), aminosilyl (e.g., -Si(R)a(NR2)b), silyloxy (e.g., -O-SiR3), aliphatic-oxy- silyloxy (e.g., alkoxy silyloxy or -O-Si(R)a(OR)b), aminosilyloxy (e.g., -O-Si(R)a(NR2)b), aromatic (e.g., aryl), aromatic-oxy (e.g., aryloxy or -OR), hydroxyl (-OH), formyl (-C(O)H), and the like. In particular embodiments, each R is, independently, H, optionally substituted aliphatic, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted heteroaliphatic, optionally substituted aromatic, optionally substituted aryl, and optionally substituted heteroaromatic; a ≥ 0; b ≥ 1; and a + b = 3. In some embodiments, two R groups can be taken together, with the nitrogen atom to which each is attached, to form an optionally substituted heterocyclyl. In other embodiments, each R is, independently, H, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, or optionally substituted aryl. L can be any useful linker (e.g., a covalent bond, optionally substituted alkylene, optionally substituted heteroalkylene, oxy, imino, silyl, or the like).

[0355] 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 -SiRa, -SiR3, -Si(R')a(OR)b, -Si(R)a(OR)b, -Si(R')a(NR2)b, -Si(R)a(NR2)b, -Si(R')a(OR)b(NR2)c, -Si(R)a(OR)b(NR2)c, -O-SiR'3, -O-SiRa, -O-Si(R')a(OR)b, -O-Si(R)a(OR)b, -O-Si(R')a(NR2)b, -O-Si(R)a(NR2)b, -O-Si(R')a(OR)b(NR2)c, or-O-Si(R)a(OR)b(NR2)cin which each R is, independently, H, aliphatic, heteroaliphatic, aromatic,Attorney Docket No. 12306-1WO / LAM1P120WOheteroaromatic, 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.

[0356] The precursor can include at least one R" group attached to the nitrogen atom. In one embodiment, the precursor has a formula of (R")N(SiR'3)2 or (R")2N(SiR'3), wherein R' and R" can be any described herein. In another embodiment, the precursor has a formula of (R")2N(SiH3) or (R")N(SiH3)2, wherein R" can be any described herein. In particular embodiments, R' is optionally substituted alkyl, amino, or alkoxy; and R" is optionally substituted alkyl or amino, optionally wherein two R" are taken together, with the nitrogen atom to which each are attached, to form a heterocyclyl.

[0357] The precursor can include at least one hydrogen atom attached to the nitrogen atom. In one embodiment, the precursor has a formula of (H)N(SiR'3)2, wherein R' can be any described herein. In another embodiment, the precursor has a formula of (H)N(SiRAk3)2, wherein RAkcan be optionally substituted aliphatic, optionally substituted alkyl, optionally substituted alkenyl, or optionally substituted alkynyl.

[0358] The precursor can include three silicon atoms attached to the nitrogen atom. In one embodiment, the precursor has a formula of NCSiRS) ’- wherein R' can be any described herein. In another embodiment, the precursor has a formula of N(SiH3)(SiR'3)2, wherein R' can be any described herein. In yet another embodiment, the precursor has a formula of N(SiH3)(SiRAk3)2, wherein RAkcan be optionally substituted aliphatic, optionally substituted alkyl, optionally substituted alkenyl, or optionally substituted alkynyl.

[0359] The precursor can have two or more nitrogen atoms, in which the precursor includes a N-N bond. In one instance, the precursor has a formula of (R'3Si)2N-N(SiR'3)2, wherein R' can be any described herein.

[0360] A linker can be present between nitrogen atoms. In one instance, the precursor has a formula of (R'3Si)(R")N-L-N(R")(SiR'3) or (R'3Si)2N-L-N(SiR'3)2, wherein R' and R" 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 R" is not H. In another instance, the precursor has a formula of(H3Si)(R")N-L-N(R")(SiH3), wherein R" can be any described herein.Attorney Docket No. 12306-1WO / LAM1P120WO

[0361] The linker can include a silicon atom. In one instance, the precursor has a formula of (R'3Si)2N-SiR'2-N(SiR'3)2, wherein R' can be any described herein. In another instance, the precursor has a formula of (R'3Si)(R")N-SiR'2-N(R")(SiR'3) or (R'3Si)2N-SiR'2-N(R")2, wherein R' and R" can be any described herein.

[0362] The linker can include a Si H group. In one instance, the precursor has a formula of (R'3Si)2N-SiH2-N(SiR'3)2, wherein R' can be any described herein. In another instance, the precursor has a formula of (R'3Si)HN-SiH2-NH(SiR'3) or (R'3Si)2N-SiH2-N(R")2, wherein R' and R" can be any described herein.

[0363] A plurality of nitrogen- and silicon-containing moieties may be present within the precursor. In one embodiment, the precursor has a formula of (R'3Si)(R")N-SiR'2-N(R")-SiR'2-N(R")(SiR'3), wherein R' and R" can be any described herein.

[0364] Non-limiting precursors can include, e.g., 1,1,3,3-tetramethyldisilazane (NH[SiHMe2]2 or TMDS); 1,1,2,3,3-pentamethyldisilazane (NMe[SiHMe2]2); 1,1,1,3,3,3-hexamethyldisilazane (NH[SiMe3]2 or HMDS); heptamethyldisilazane (NMe[SiMe3]2); 1,1, 1,3,3, 3-hexamethyl-2-ethyldisilazane (NEt[SiMe3]2); l,l,l,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); l,l,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); l,l,l,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); nonamethyl trisilazane (N[SiMe3]3); di-iso-propylsilylamine (NiPr2[SiH3]); diethylsilylamine (NEt2[SiH3]); diisopropylsilylamine (NiPr2[SiH3]); di-sec -butylsilylamine (NsBu2[SiH3]); di-tert-butyl silylamine (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

[0365] A silicon-containing precursor 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 precursor has a formula of (R")3-yN(SiR'2-L-SiR'3)y, wherein:y is 1, 2, or 3;L is a linker, such as a covalent bond, optionally substituted aliphatic, optionallyAttorney Docket No. 12306-1WO / LAM1P120WOsubstituted heteroaliphatic, optionally substituted aromatic, optionally substituted heteroaromatic, oxy (-O-), imino, or silyl, as well as combinations thereof;each R' is, independently, H, aliphatic, aliphatic-carbonyl, aliphatic-carbonyloxy, aliphatic-oxy, aliphatic-oxycarbonyl, heteroaliphatic, heteroaliphatic-carbonyl, hetero aliphatic -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; andeach R" 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 R" can be taken together, with the nitrogen atom to which each is attached, to form an optionally substituted heterocyclyl.

[0366] In another embodiment, the precursor has a formula of (R")3-yN(SiR'2-L-SiR'2-NR"2)y, wherein y is 1, 2, or 3; and each of L, R', and R" can be any described herein.

[0367] In yet another embodiment, the precursor has a formula of (R")3-yN (SiR'2-L-NR"2)y, wherein y is 1, 2, or 3; and each of L, R', and R" can be any described herein.

[0368] In one embodiment, the precursor has a formula of (R')4-xSi(NR"-L-SiR'3)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 R' is, independently, H, aliphatic, aliphatic-carbonyl, aliphatic-carbonyloxy, aliphatic-oxy, aliphatic-oxycarbonyl, heteroaliphatic, heteroaliphatic-carbonyl, hetero aliphatic -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; andeach R" 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 R" can be taken together, with the nitrogen atom to which each is attached, to form an optionally substituted heterocyclyl.

[0369] In another embodiment, the precursor has a formula of (R"2N)-(SiR'2-L)z-SiR'3, wherein z is 1, 2, or 3; and each of L, R', and R" can be any described herein.Attorney Docket No. 12306-1WO / LAM1P120WO

[0370] 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(SiRa)-), 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.

[0371] In some embodiments, R' is H, optionally substituted amino (e.g., -NR2), aliphatic-oxy (e.g., alkoxy or -OR), aliphatic-carbonyl (e.g., alkanoyl or -C(O)R), aliphatic-carbonyloxy (e.g., alkanoyloxy or -OC(O)R), aliphatic-oxycarbonyl (e.g., alkoxycarbonyl or -C(O)OR), silyl (e.g., -SiR3 or -SiR3-L-SiR3), aliphatic-oxy-silyl (e.g., alkoxy silyl or -Si(R)a(OR)b), aminosilyl (e.g., -Si(R)a(NR2)b), silyloxy (e.g., -O-SiR3), aliphatic-oxy- silyloxy (e.g., alkoxy silyloxy or -O-Si(R)a(OR)b), aminosilyloxy (e.g., -O-Si(R)a(NR2)b), aromatic (e.g., aryl), aromatic-oxy (e.g., aryloxy or -OR), hydroxyl (-OH), formyl (-C(O)H), and the like. In particular embodiments, each R is, independently, H, optionally substituted aliphatic, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted heteroaliphatic, optionally substituted aromatic, optionally substituted aryl, and optionally substituted heteroaromatic; a ≥ 0; b ≥ 1; and a + b = 3. In some embodiments, two R groups can be taken together, with the nitrogen atom to which each is attached, to form an optionally substituted heterocyclyl. In other embodiments, each R is, independently, H, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, or optionally substituted aryl. L can be any useful linker (e.g., a covalent bond, optionally substituted alkylene, optionally substituted heteroalkylene, oxy, imino, silyl, or the like).

[0372] In other embodiments, R" is H, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted alkyl, optionally substituted silyl, or optionally substituted silyloxy. In some embodiments, R" is optionally substituted alkyl (e.g., Me, Et, nPr, iPr, sBu, or tBu). In other embodiments, R" is -SiR'3, -SiRa, -Si(R')a(OR)b, -Si(R)a(OR)b, -Si(R')a(NR2)b, -Si(R)a(NR2)b, -Si(R')a(OR)b(NR2)c, -Si(R)a(OR)b(NR2)c, -O-SiR'3, -O-SiR3, -O-Si(R')a(OR)b, -O-Si(R)a(OR)b, -O-Si(R')a(NR2)b, -O-Si(R)a(NR2)b, -O-Si(R')a(OR)b(NR2)c, orAttorney Docket No. 12306-1WO / LAM1P120WO-O-Si(R)a(OR)b(NR2)c in which each R 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.

[0373] The precursor can include one or more disilanyl groups and amino groups. In one embodiment, the precursor has a formula of R"2N-SiR'2-SiR'3, wherein L, R', and R" can be any described herein. In other embodiments, the precursor has a formula of R"2N-SiH2-SiH3, wherein R" is any described herein. In another embodiment, the precursor has a formula of (R")3-yN-(SiR'2-SiR'3)y, wherein y, R', and R" can be any described herein. In yet another embodiment, the precursor has a formula of (R")3-yN-(SiH2-SiH3)y, wherein y and R" can be any described herein.

[0374] The precursor can include a bivalent disilanyl group. In one embodiment, the precursor has a formula of R"2N-SiR'2-SiR'2-L-NR"2, wherein L, R', and R" can be any described herein. In another embodiment, the precursor has a formula of R"2N-SiR'2-SiR'2-NR"2, wherein R' and R" can be any described herein.

[0375] A linker L can be present between two silyl group. In one embodiment, the precursor has a formula of R"2N-SiR'2-L-SiR'3 or R" N-(SiR'2-L-SiR'3)2, wherein L, R', and R" can be any described herein. In another embodiment, the precursor has a formula of R"2N-SiR'2-L-SiR'2-NR"2, wherein L, R', and R" can be any described herein. In yet another embodiment, the precursor has a formula of (R")3-yN-(SiR'2-L-SiH3)y, wherein y, L, R', and R" can be any described herein.

[0376] The precursor can include −SiH3 as the silyl group. In one embodiment, the precursor has a formula of R"2N-SiH2-SiH3, wherein R" can be any described herein. In another embodiment, the precursor has a formula of (R")N-(SiH2-L-SiH3)2 or (R")2N-(SiH2-L-SiH3), wherein L and R" can be any described herein.

[0377] The precursor can include a silyl-substituted amino group, such as, e.g., -NR"-SiR'3, in which R' and R" can be any described herein. In one embodiment, the precursor has a formula of (R')4-xSi(NR"-SiR'3)xor (R')4-xSi(NH-SiR'3)x, wherein x is 1, 2, 3, or 4; and in which R' and R" can be any described herein. In another embodiment, the precursor has a formula of H2Si(NR"-SiR'3)3, wherein R' and R" can be any described herein.Attorney Docket No. 12306-1WO / LAM1P120WO

[0378] The precursor can include a bis-trisilylamino group, such as, e.g., -N(SiR'3)2 in which R' can be any described herein. In one embodiment, the precursor has a formula of R"2N-SiR'2-N(SiR'3)2, in which R' and R" can be any described herein. In another embodiment, the precursor has a formula of R"2N-SiH2-N(SiH3)2, in which R' can be any described herein. In yet another embodiment, the precursor has a formula of (R'3Si)2N-[SiR'2-N(SiR'3)]z(SiR'3), wherein z is 0, 1, 2, or 3; and in which R' and R" can be any described herein.

[0379] The precursor can include a linker L disposed between a silicon atom and a nitrogen atom. In one embodiment, the precursor has a formula of R"2N-SiR'2-L-NR"2, wherein L, R', and R" can be any described herein.

[0380] The precursor can include a linker L disposed between two nitrogen atoms. In one embodiment, the precursor has a formula of R'3Si-SiR'2-NR"-L-NR"-SiR'2-SiR'3, wherein L, R', and R" can be any described herein.

[0381] The linker can include a silylimino group, such as, e.g., -N(SiR'3)-, in which R' can be any described herein. In one embodiment, the precursor has a formula ofR"2N-[SiR'2-N(SiR'3)]z-SiR'3 or R"2N-[N(SiR'3)]z-SiR'3, in which z is 1, 2, 3, or more; and wherein R' and R" can be any described herein.

[0382] The linker can include both a silyl group and an imino group. In one embodiment, the precursor has a formula of R"2N-[SiR'2-NR"]z-SiR'3, in which z is 1, 2, 3, or more; and wherein R' and R" can be any described herein.

[0383] Non-limiting precursors include, e.g., di-iso-propylaminodisilane ([iPr2N]-SiH2-SiH3); di-sec-butylaminodisilane ([sBu2N]-SiH2-SiH3); methylcyclohexylaminodisilane ([MeCyN]-SiH2-SiH3); methylphenylaminodisilane ([MePhN]-SiH2-SiH3); piperidinodisilane; 3,5-dimethylpiperidinodisilane; di-iso-propylaminotrisilylamine ([iPr2N]-SiH2-N[SiH3]2); diethyl aminotrisilylamine ([Et2N]-SiH2-N[SiH3]2); iso-propylaminotrisilylamine ([iPrHN]-SiH2-N[SiH3]2); and the like.Mixed amines including silicon and oxygen

[0384] A silicon-containing precursor can include one or more amino groups substituted with a silyl group, thereby providing a non-limiting mixed amine. In one embodiment, the precursor has a formula of (R")3-yN[Si(OR"')xR'3-x]y, wherein:each of x and y is, independently, 1, 2, or 3;each R' is, independently, H, aliphatic, aliphatic-carbonyl, aliphatic-carbonyloxy, aliphatic-oxy, aliphatic-oxycarbonyl, heteroaliphatic, heteroaliphatic-carbonyl, hetero aliphatic -carbonyloxy, heteroaliphatic-oxy, heteroaliphatic-oxycarbonyl, aromatic, aromatic-carbonyl,Attorney Docket No. 12306-1WO / LAM1P120WOaromatic-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 R" is, independently, H, aliphatic, heteroaliphatic, aromatic, heteroaromatic, or amino, in which any of these may be optionally substituted; or optionally in which two R" can be taken together, with the nitrogen atom to which each is attached, to form an optionally substituted heterocyclyl; andeach R"' is, independently, H, aliphatic, hetero aliphatic, aromatic, heteroaromatic, silyl, or silyloxy, in which any of these may be optionally substituted.

[0385] Non-limiting examples of R', R", and R"' are described herein, e.g., such as for amino silane, siloxane, silyl amine, or derivatives thereof.

[0386] The precursor can include any combination of R" groups and silicon-containing groups. In one embodiment, the precursor has a formula of (R")3-yN[Si(ORAk)xRAk3-x]y or (RAk)3-yN [Si(ORAk)xRAk3-x]y, in which R ", x, and y is any described herein; and wherein RAkis H, optionally substituted aliphatic, or optionally substituted heteroaliphatic. In particular embodiments, RAkis H, optionally substituted alkyl, optionally substituted alkylene, or optionally substituted alkynyl. In other embodiments, the precursor has a formula of (R")3-yN[Si(ORAk)xH3-x]y or (R")3-yN[Si(ORAk)H(RAk)]y, in which R", R^, x, and y is any described herein.

[0387] The precursor can include two silicon-containing groups. In one embodiment, the precursor has a formula of (R")N[Si(ORAk)xRAk3-x]2 or (RAk)N[Si(ORAk)xRAk3-x]2, in which R", R^, x, and y is any described herein. In particular embodiments, x is 1 or 2.

[0388] The precursor can include a hydrogen atom attached to the nitrogen atom. In one embodiment, the precursor has a formula of (H)3-yN[Si(ORAk)xRAk3-x]y or (H)3-yN[Si(ORAk)xH3-x]y or (H)3-yN[Si(ORAk)H(RAk)]y, in which R^, x, and y is any described herein. In particular embodiments, x is 1 or 2.

[0389] Non-limiting precursors include, e.g., bis(dimethoxysilyl)amine (NH[Si(OMe)2H]2); bis(diethoxysilyl)amine (NH[Si(OEt)2H]2); N-iso-propylbis(diethoxysilyl)amine (NiPr[Si(OEt)2H]2); bis(methoxymethylsilyl)amine (NH[Si(OMe)MeH]2); tris(di...

Claims

Attorney Docket No. 12306-1WO / LAM1P120WOCLAIMSWhat is claimed is:

1. A method for processing substrates in a chamber, the method comprising:providing a semiconductor substrate having a feature to a chamber; anddepositing dielectric material in the feature on the semiconductor substrate by:exposing the semiconductor substrate comprising a deposition precursor and a reactant and form the dielectric material, andintroducing a passivation gas to the chamber and igniting a passivation plasma in a passivation gas ambient.

2. The method of claim 1, wherein exposing the semiconductor substrate comprises introducing the deposition precursor and introducing the reactant.

3. The method of claim 1, further comprising purging after introducing the deposition precursor.

4. The method of any one of claims 1-3, further comprising purging after introducing the reactant.

5. The method of any one of claims 1-4, further comprising purging after introducing the passivation gas.

6. The method of any one of claims 1-5, wherein the deposition precursor comprises a silane.

7. The method of claim 6, wherein the silane is selected from the group consisting of bis(t-butylamino)silane, bis(diethylamino)silane, tris(dimethylamino)silane, and diisopropylaminosilane.

8. The method of any one of claims 1-5, wherein the reactant comprises an oxidizer.

9. The method of any one of claims 1-8, wherein the exposing of the semiconductor substrate is performed in a plasma- free environment.

10. The method of claim 8, wherein the oxidizer is ignited in a plasma.

11. The method of any one of claims 1-10, wherein the passivation gas ambient inhibits deposition on one or more regions of the semiconductor substrate.Attorney Docket No. 12306-1WO / LAM1P120WO12. The method of claim 2, wherein depositing the dielectric material is performed in supercycles, wherein a supercycle comprises performing a first cycle n times, the first cycle comprising the introducing of the deposition precursor (“A”) and the introducing the reactant (“B”) in n cycles, and performing the introducing of the passivation gas to the chamber and the igniting of the passivation plasma (“C”) every m cycles of performing the n cycles, wherein the supercycle is optionally given by the expression [(AB)nC]m.

13. The method of claim 2, wherein performing about 50 to about 1000 cycles of introducing the deposition precursor and introducing the reactant results in a deposition growth rate of about 1.25 Å / cycle.

14. The method of claim 2, wherein performing multiple m cycles of introducing the passivation gas every n cycles of alternating between introducing the deposition precursor and introducing the reactant results in a growth rate of about 0.1 A / cycle or less, wherein the passivation gas comprises NF3.

15. The method of claim 14, wherein m is about 2 to about 1000.

16. The method of claim 14, wherein n is about 1 to about 25.

17. The method of claim 14, wherein the passivation gas comprises one or more gases selected from the group consisting of ammonia, nitrogen, argon, oxygen, nitrous oxide, and nitrogen trifluoride.

18. The method of claim 1, wherein the passivation gas is introduced for a duration sufficient to reach a saturation limit.

19. The method of claim 18, wherein at the saturation limit, the dielectric material grows at a growth rate of about 0.13 Å / cycle.

20. The method of claim 1, wherein the passivation gas is introduced for a duration of about 0.5 seconds to about 1 second.

21. The method of claim 1, wherein plasma power during the igniting of the passivation plasma inhibits deposition of the dielectric material to a depth of about 10 nm to about 15 pm.

22. The method of claim 1, wherein after depositing the dielectric material in the feature, the feature is void-free.Attorney Docket No. 12306-1WO / LAM1P120WO23. The method of claim 1, wherein the feature has an aspect ratio of about 20:1 to about 200:1.

24. The method of any of claims 1-23, wherein the semiconductor substrate is processed in a temporal atomic layer deposition tool.

25. The method of any of claims 1-23, wherein the semiconductor substrate is processed in a spatial atomic layer deposition tool.

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